Summary of the invention
An object of the present invention is the polymeric system at ambient temperature range based on Tg, add inorganic multimode filler, be then rolled into sheet material.This material safety, environmental protection, has excellent damping capacity.Because the use of multimode filler, the damping capacity of material can get a promotion in very wide range of frequency, so that corresponding to the differing temps scope of same frequency.
" multimode " involved in the present invention, refers to the size distribution by controlling particle, and such as controlling the ratio of nanometer, submicron and micro-size particles, after polymer hybrid, tan δ can produce multimodal, can improve significantly the damping characteristics of material.Nanometer, submicron and micro-size particles yardstick involved in the present invention all present Gaussian distribution.Because the price of grade filler and the cost of attrition process are lower than Nano filling, its cost is lower than Nano filling.
Described damping material raw material comprises following substances: thermoplastic resin, multimode mineral filler.Wherein, multimode mineral filler is used special coupling agent treatment liquid to carry out surface treatment.
Described multimode mineral filler of crossing through coupling agent treatment is 1-80wt%, and all the other are thermoplastic resin.
Described thermoplastic resin be selected from PVC-polyvinyl acetate (PVA), esters of acrylic acid, polyvinyl chloride-vinyl acetate between to for plastic, EVA-Vinyl Acetate Copolymer-ethene, ethylene-acrylate copolymer, PU-polyurethanes PE-polyethylene, PVC-polyvinyl chloride, PS-polystyrene, PP-polypropylene, POM-polyoxymethylene, PET-thermoplasticity according to ethylene glycol terephthalate, PVA Vinyl Acetate Copolymer etc. any one or multiple.The principle of selection material is to expand glass transition temperature range as far as possible and improve tan δ.This invention relates to high fillibility macromolecule resin or its composite matrix of second-order transition temperature (Tg) near room temperature (30-80 ℃), by controlling component ratio, and even add multimode mineral filler, can easier regulate and control the visco-elasticity of microstructure.Preferably, selected thermoplastic resin is Vinyl Acetate Copolymer-ethene, is called for short EVA.
The multimode filler the present invention relates to also relates to the variation of different sorts filler.Described mineral filler comprises granulated mineral filler, the mineral filler of plate shape, any one in aciculiform mineral filler or multiple.
Described granulated weighting material can comprise silicon-dioxide, pottery, cenosphere, glass microsphere, aluminum oxide, Calucium Silicate powder, barium sulfate, one or more in calcium carbonate etc.; Preferably, selecting light calcium carbonate is granule filler;
Plate shape weighting material can comprise sheet mica, flake graphite, Schistose kaolinite, one or more in sheet zinc oxide etc.; Preferably, selecting sheet mica is plate shape weighting material;
Aciculiform weighting material can comprise sepiolite, wollastonite, attapulgite, glass fibre, one or more in short carbon fiber etc.; Preferably, selecting wollastonite is needle-like weighting material;
The size of filler has directly determined the interface contact area of filler and matrix, thereby affects the sound absorbing capabilities of material.The corresponding certain absorbing wavelength of certain filler grain yardstick, and corresponding generation absorption peak.In the time that the yardstick of filler approaches with corresponding vibration or wave length of sound, material is the strongest to corresponding mechanical wave attenuation.Big scale particle is corresponding to relatively low range of frequency; And small scale particle is corresponding to relatively high range of frequency.This is key involved in the present invention, i.e. multimode filler problem.In the present invention, if design the particle distribution of multimode filler, can find out, the absorption peak of matrix material can present " controllable state ".
Its comparative data is shown in embodiment 1-4, and Fig. 5.Can see, for identical resin matrix, when filler yardstick becomes multimode size distribution from nano level, (each particle size ratio is: Nano/micron/submillimeter=9.6/2.6/0.36) time, tan δ spectrogram absorption peak obviously broadens; When particle morphology is from spherical spherical, sheet, the needle-like multiform looks particle compound tense of becoming, absorption peak also obviously broadens.For spherical particle, polydispersion diminishes 0.2 than monodisperse sphere shape pattern maximum value, and peak moves to left, but when temperature below 27 degrees Celsius (47--24 ℃), the large 0.1-0.2 of tan δ;-24-20 ℃ scope, and be greater than 70 ℃ of scopes, the tan δ value of multimode yardstick is higher by 0.05 than Nano filling.For multiform looks situation, the value of multimode yardstick is better than the absorption of nanoscale filler in wide region more, the tan δ in whole temperature range almost all large 0.2.Multiform looks filler is with respect to spherical morphology particle, in whole temperature range tan δ all large 0.08.Multimode multiform looks filler is than the absorption of multimode spherical pattern particle, in the time of-100-0 ℃ large 0.05; In the time of 0-30 ℃ all large 0.1.
Described coupling agent can be selected from various silane coupling agents, aluminate, Borate Ester as Coupling, titante coupling agent; Silane coupling agent comprises KH550, KH560 KH792, DL602, DL171; Aluminate comprises DL2411, DL2410; Borate Ester as Coupling comprises PDR-180, PRA-101; Titante coupling agent comprises monoalkoxy pyrophosphate type titante coupling agent, chelating titanate class coupling agent, corrdination type titante coupling agent etc.Preferred in the present invention, use corrdination type titante coupling agent.Preferred, use sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester to make coupling agent, the 0.1-2.2% that coupling agent consumption is mineral filler.Preferably, the 0.8-1.2% that sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester consumption is mineral filler;
Coupling agent, especially sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester must select suitable thinner just can better bring into play powerful fillers dispersed or surface treatment effect.Conventional thinner comprises Witco 70, sherwood oil, and hexanaphthene, ethanol, Virahol, diglycidyl ether of ethylene glycol, acetone etc. are all suitable for.The present invention, through experimental results demonstrate, adopts composite thinning agent formula of the present invention much more remarkable than using single thinner effect, and inorganics disperses more uniform and stable.Preferably, use Witco 70, hexanaphthene and sherwood oil, its volume ratio is 5: 3: 2 o'clock best results, and thinner consumption is identical with coupling agent or bigger, preferably, and according to volume ratio coupling agent: thinner is 1: 0.8-1.5.
Can also comprise auxiliary agent, according to material character such as flame resistivity, resistance to deterioration, or the needs of over-all properties, the auxiliary agent that can suitably add comprises antioxidant, tackifier, softening agent, antioxidant, various fire retardants and stablizer, tinting material etc.
Tackifier are one or more of petroleum resin C9, petroleum resin C5, terpine resin, rosin, coumarone indene resin kind, preferably, select petroleum resin C9, and usage ratio is 0-5wt%;
Can suitably add a small amount of softening agent.The softening agent of addressing comprises DOP-dioctyl phthalate (DOP), DBP-dibutyl phthalate, DINP-diisononyl phthalate, one or more in DIDP-Di Iso Decyl Phthalate etc.Preferably, selecting DINP is external plasticizer, and usage ratio is 0-10wt%;
Described oxidation inhibitor is 2,6-ditertbutylparacresol, two (3, tri-grades of butyl-4-hydroxy phenyls of 5-) thioether, four (β-(3, tri-grades of butyl-4-hydroxy phenyls of 5-) propionic acid) a kind of or its compound system in pentaerythritol ester, two Lauryl Alcohol ester, two ten four carbon alcohols esters and two octadecanol ester, three (Lauryl Alcohol) esters and three (16 carbon alcohol) ester, tricresyl phosphite monooctyl ester, tridecyl phosphite, preferably, select 2,6-ditertbutylparacresol is antioxidant, and usage ratio is 0-5wt%;
Fire retardant comprises magnesium hydroxide, aluminium hydroxide, and TDCPP, ammonium polyphosphate, eight bromo ether, triphenylphosphate, hexabromocyclododecane, MPP, zinc borate, TDE, encapsulated red phosphorus, TBC etc., preferably, select triphenylphosphate, and usage ratio is 0-5wt%.
Stablizer comprises various soap salt (Zinic stearas/calcium stearate), organotin (dimercapto 2-ethyl hexyl ethanoate dioctyltin, DOTTG), antimony organic, phosphite ester stabilizer, and various auxiliary stabilizer and its mixture.Preferably, selecting Zinic stearas is stablizer, and usage ratio is 0-10wt%.
Related sound-proof material can be as required, adds appropriate tinting material, such as carbon black, and white carbon black, cobalt blue, iron oxide yellow, red iron oxide etc.
The size distribution of inorganic filler is polydisperse.For reaching good polydispersion effect, take micron order commercialization mineral filler as just expecting.
In damping material of the present invention, not only can filler particles shape weight weighting material, can also infill panel shape and aciculiform weight weighting material.Various shape, multiple yardstick particle can, to the generation of vibration effect of different frequency, improve the tan δ of system, and finally improve the cushioning ability of material in very wide range of frequency.
Described making method is carried out according to following technique:
1.) will just expect under shredder, to grind rear mixing, form mineral filler;
2.) with coupling agent treatment liquid treatment inorganic filling material;
3.) merge various raw materials, make this product.
The filler yardstick that uses according to nano level, submicron order, micron order, 10* micron order, any one in submillimeter level filler or the multiple use of arranging in pairs or groups.Preferably, select nano level, micron order, and submillimeter level yardstick particle, like this, for the polydisperse particle of commercially available non-strict boundary, filler yardstick still presents obvious multimode and distributes in time.Described 10* micron order refers to 10 times of micron-sized meanings.
The size distribution of mineral filler is polydisperse.For reaching good polydispersion effect, expect as first take grade or submillimeter level micron order commercialization mineral filler, grind, make the size of mineral filler contain nano level, micron order, and submillimeter level.
That is to say, in step 1, also comprise that grinding, described grinding select in grade or submillimeter level or micron order any one commercialization mineral filler for first material, carry out after the grinding of different time, after filler that will all types of each sizes of gained mixes, form mineral filler.The preparation of described sound-proof material is carried out according to following technique:
1.) will just expect to grind under shredder, according to different condition form all kinds and various size mineral filler, then mix;
2.) with coupling agent treatment liquid treatment inorganic filling material: add in mineral filler after thinner is mixed with coupling agent, select high-speed kneading machine high-speed stirring, after stirring, discharging is for subsequent use;
3.) merge various raw materials, make this product: adjust the temperature of melting pot to 70-85 ℃, add thermoplastic resin and various auxiliary agent, stir and be warming up to higher than in 2-5 ℃ of situation of thermoplastic resin melt temperature, after the complete melting of raw material, keep temperature, stir 10-60 minute, then add mineral filler to continue stirring mixing, until mineral filler is uniformly dispersed, by rolling press extrusion moulding, make this product.
To just expect to grind under shredder.Grind different time or change other abrasive parameters, the velocity of shear providing such as pulverizer, direction and the shear mode etc. of shearing force.Can cause final particle to present different particle distribution and yardstick, distribute to micron-sized particle size such as covering from nano level.Can use ball mill, with identical parameter configuration, as at constant rotational speed 50rpm, grind respectively more than 3 days, obtain ball sample 1, sheet sample 1, pin sample 1; 0.5 to 3 day, obtain ball sample 2, sheet sample 2, pin sample 2; 2 to 12 hours, obtain ball sample 3, sheet sample 3, pin sample 3.Then, the material that grinds different time is mixed with certain proportion, the type of mineral filler is more, size distribution span is larger, absorption to sound and isolation are better from theory, through great many of experiments, find that soundproof effect is best under the type range scale of the present invention's restriction and the condition of proportioning.
More specifically, described making method is carried out according to following technique:
Described step 1 by all kinds and various size mineral filler mix; In described granulated weighting material, the weight of ball sample 1 is 3-97%, and the weight fraction of ball sample 2 is 3-97%, and the weight fraction of ball sample 3 is 3-97%; Preferably, the weight fraction of ball sample 1 is 30-70%, and the weight fraction of ball sample 2 is 15-50%, and the weight fraction of ball sample 3 is 5-15%; Preferably, the weight fraction of ball sample 1 is 45-55%, and the weight fraction of ball sample 2 is 22-45%, ball sample 3. weight fraction is 5-20%; In described sheet weighting material, the weight of sheet sample 1 is 3-97%, and the weight fraction of sheet sample 2 is 3-97%, and the weight fraction of sheet sample 3 is 3-97%; Preferably, in option 4, the weight fraction of sheet sample 1 is 30-70%, and the weight fraction of sheet sample 2 is 15-50%, and the weight fraction of sheet sample 3 is 5-15%; Preferably, the weight fraction of sheet sample 1 is 45-55%, and the weight fraction of sheet sample 2 is 22-45%, and the weight fraction of sheet sample 3 is 5-20%; In described needle-like weighting material, the weight of pin sample 1 is 3-97%, and the weight fraction of pin sample 2 is 3-97%, and the weight fraction of pin sample 3 is 3-97%; Preferably, in option 6, the weight fraction of pin sample 1 is 30-70%, and the weight fraction of pin sample 2 is 15-50%, and the weight fraction of pin sample 3 is 5-15%; Preferably, the weight fraction of pin sample 1 is 45-55%, and the weight fraction of pin sample 2 is 22-45%, and the weight fraction of pin sample 3 is 5-20%.
By the polishing shown in above step, can obtain the multimode mineral filler of different-grain diameter, yardstick presents from nanometer to submillimeter level polydispersion and distributes.The size distribution of mineral filler can be used opticmicroscope to combine with electron microscope with shape characteristic, or powder diffractometer, powder size analyser make for characterizing.The filler of different-shape mixes and is compound with fluoropolymer resin, just forms the basis of multilayered structure sound-proof material.Certainly, multimode mineral filler also can partly or entirely be used commercialization sample.
The common variation that those skilled in the art carries out within the scope of of the present invention and multimode technical scheme and replacement all should be included in protection scope of the present invention.
Adjust the temperature to 75 ℃ of melting pot, add fluoropolymer resin and various auxiliary agent, keep temperature in tank to stir under the melt temperature higher than fluoropolymer resin, after the complete melting of raw material, stir 30 minutes, then add mineral filler to continue stirring mixing, until mineral filler is uniformly dispersed, by rolling press extrusion moulding, make final damping material.
Beneficial effect:
Damping material of the present invention, because contain a large amount of multimodes, different structure mineral filler, can keep good mechanical property, and the vibrations of different frequency are all had to good isolating power down to sound.In addition, it can improve the heat-resistant aging of material, ozone resistance, and impact strength, makes the effect of damping material aspect damping very good, can be applied to automobile, house ornamentation interior trim and movie theatre public place of entertainment etc.
When acoustic wave action is during in material, polymer network produces local expansion or compression, and filler grain is vibration thereupon also, and the non-binding effect power between can saboteur increases the relaxation assimilation effect of material to sound wave simultaneously.The main manifestations that affects of filler grain is that height frequency, especially low frequency absorption coefficient obviously improve, and certain deviation can occur frequency corresponding to feature sound absorption peak.
Suitably can effectively improve the sound absorbing capabilities of material and the factors such as the form of filler, size, content all have material impact to the underwater acoustic properties of this material adding of filler.Except the chemical constitution of filler, its form, content and yardstick disperse to become key factor.
The content of filler has material impact to material property.In the time that the content of filler increases, the feature sound absorption frequency of material moves to low frequency.The reflection coefficient of while material also changes corresponding reflection coefficient frequency spectrum with the variation of different sorts filler and also produces larger difference.
Laminal filler particle has scattering process in resin, thereby it adds the density that can change material to change the velocity of sound of material and the filler of different size is different to sound wave reflection and scattering process, the variation of therefore laminal filler size on the anti-acoustic performance of material to affect rule more complicated.
And needle-like filler grain is more complicated on the impact of material.Certainly, the present invention does not take pains in needle-like (or particle) affects and provides conclusion the quantification of acoustic wave action.
Therefore, in the damping material of being made up of multimode filler/polymer composites, the decay of vibration mechanical energy relates to non-binding effect power between saboteur increases internal friction, and the mass loading effect of heavy material.Bonding irregular between each particle, such structure has increased the internal friction of the multiple dimensioned scope of system effectively, can improve significantly out-of-phase modulus and tan δ, and that storage modulus increases is few, makes damping factor or loss tangent become large.The vibration of the corresponding different frequency of multimode filler, therefore more comprehensive to the consumption rate of different frequency vibration.
Embodiment
Enter-walk explanation the present invention below in conjunction with embodiment, but not as a limitation of the invention.
Embodiment 1
Sound-proof material shown in corresponding diagram 1/ table 1
Raw material
EVA?23.0kg
Linear low density polyethylene (LLDPE) 14.0kg
Polyethyl acrylate 4.0kg
Sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester 1.0kg
Witco 70 500ml
Hexanaphthene 300ml
Sherwood oil 200ml
Nano level light calcium carbonate fine powder 14.5kg
Petroleum resin C9 3.6kg
2,6 ditertiary butyl p cresol 2.0kg
Triphenylphosphate 1.0kg
Zinic stearas 1.7kg
Preparation and the pre-treatment of nanometer-submillimeter level inorganic fine powder
We select XMQ-350 × 160 ball mill, with identical parameter configuration, and as at constant rotational speed 280rpm, same sample treatment capacity (2kg), ball milling subparameter (consumption is 3kg, and diameter is 1cm), grinds respectively 10 days, obtains ball sample 1; 1.5 days, obtain ball sample 2; 5 hours, obtain ball sample 3.The size distribution of mineral filler and shape characteristic can characterize with Mastersizer 3000 powder size analysers.Then, yardstick is mixed with certain proportion at the multiform looks material of nanometer range.
The surface preparation of mineral filler
By coupling agent sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester and a certain amount of mixing diluents, preparation coupling agent dispersed liquid.Then calcium carbonate is mixed with coupling agent dispersed liquid, select high-speed kneading machine, by for subsequent use the discharging of filler high-speed stirring.
The preparation of damping material
Adjust the temperature of melting pot to 60-90 ℃, add the auxiliary agent such as fluoropolymer resin and 2,6 ditertiary butyl p cresol.Keep 110 ℃ of stirrings of temperature in tank.After the complete melting of raw material, stir 30 minutes, then add nano level light calcium carbonate to continue stirring mixing, until mineral filler is uniformly dispersed.
The test of dynamic properties
The test of employing dynamic thermomechanical analysis apparatus, 3.5 ℃/min of temperature rise rate, frequency 35Hz, measures temperature range-100~120 ℃, deformation quantity 0.8, pre-tension 0.01N.
Form 1
Temperature (℃) |
-100 |
-80 |
-60 |
-40 |
-20 |
0 |
tanδ |
0.0369 |
0.0410 |
0.0470 |
0.0591 |
0.0823 |
0.1494 |
Temperature (℃) |
20 |
40 |
60 |
80 |
100 |
120 |
tanδ |
0.3444 |
0.7900 |
0.3566 |
0.1402 |
0.0840 |
0.0600 |
Embodiment 2
Sound-proof material shown in corresponding diagram 2/ table 2
Raw material:
EVA?23.0kg
Linear low density polyethylene (LLDPE) 14.0kg
Polyethyl acrylate 4.0kg
Sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester 1.0kg
Witco 70 500ml
Hexanaphthene 300ml
Sherwood oil 200ml
Nano-calcium carbonate 9.6kg
Micron order calcium carbonate 2.6kg
Submillimeter level calcium carbonate 0.36kg
Petroleum resin C9 3.6kg
2,6 ditertiary butyl p cresol 2.0kg
Triphenylphosphate 1.0kg
Zinic stearas 1.7kg
The preparation of nanometer-submillimeter level inorganic fine powder, characterize and mix, the preparation of pre-treatment and damping material, and the test of dynamic properties is all with embodiment 1.
Form 2
Temperature (℃) |
-100 |
-80 |
-60 |
-40 |
-20 |
0 |
tanδ |
0.0473 |
0.0675 |
0.0973 |
0.1531 |
0.2510 |
0.4106 |
Temperature (℃) |
20 |
40 |
60 |
80 |
100 |
120 |
tanδ |
0.5958 |
0.5934 |
0.3607 |
0.0210 |
0.1361 |
0.0210 |
Embodiment 3
Sound-proof material shown in corresponding diagram 3/ table 3
Raw material
EVA?23.0kg
Linear low density polyethylene (LLDPE) 14.0kg
Polyethyl acrylate 4.0kg
Sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester 1.0kg
Witco 70 500ml
Hexanaphthene 300ml
Sherwood oil 200ml
Nano level light calcium carbonate 5.2kg
Nano level mica 3.5kg
Nano silicone lime stone 2.5
Petroleum resin C9 3.6kg
2,6 ditertiary butyl p cresol 2.0kg
Triphenylphosphate 1.0kg
Zinic stearas 1.7kg
The preparation of nanometer-submillimeter level inorganic fine powder, pre-treatment and damping material, and the test of dynamic properties is all with embodiment 1.
Form 3
Temperature (℃) |
-100 |
-80 |
-60 |
-40 |
-20 |
0 |
tanδ |
0.07704 |
0.0829 |
0.0950 |
0.1141 |
0.1527 |
0.2454 |
Temperature (℃) |
20 |
40 |
60 |
80 |
100 |
120 |
[0127]?
tanδ |
0.4885 |
0.7381 |
0.4166 |
0.2169 |
0.1419 |
0.1093 |
Embodiment 4
Sound-proof material shown in corresponding diagram 4/ table 4
Raw material
EVA?23.0kg
Linear low density polyethylene (LLDPE) 14.0kg
Polyethyl acrylate 4.0kg
Sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester 1.0kg
Witco 70 500ml
Hexanaphthene 300ml
Sherwood oil 200ml
Light calcium carbonate 3.5kg
Nano level light calcium carbonate 3.2kg
Micron order calcium carbonate 0.9kg
Submillimeter level calcium carbonate 0.12kg
Nano mica powder 3.2kg
Micron order mica powder 0.9kg
Submillimeter level mica powder 0.12kg
Nano-silicon lime stone 3.2kg
Micron silicon lime stone 0.9kg
Submillimeter level wollastonite 0.12kg
Petroleum resin C9 3.6kg
2,6 ditertiary butyl p cresol 2.0kg
Triphenylphosphate 1.0kg
Zinic stearas 1.7kg
The preparation of nanometer-submillimeter level inorganic fine powder, pre-treatment and damping material, and the test of dynamic properties is all with embodiment 1.
Form 4
Temperature (℃) |
-100 |
-80 |
-60 |
-40 |
-20 |
0 |
tanδ |
0.0737 |
0.0891 |
0.1153 |
0.1599 |
0.2425 |
0.4047 |
Temperature (℃) |
20 |
40 |
60 |
80 |
100 |
120 |
tanδ |
0.6371 |
0.6686 |
0.4368 |
0.2615 |
0.1694 |
0.1218 |
Embodiment 5-17:
Thermoplastic resin, coupling agent, diluent is selected respectively the material in following table, and consumption is thermoplastic resin 48kg, coupling agent 1kg, diluent 1kg, mineral filler 50kg, three kinds of shape mineral filler ratios are 1: 1: 1: all the other are with embodiment 4; In this form, all ratios that relate to are mass ratio.
The product performance that above-described embodiment product performance are basic and embodiment 3 is prepared approach.
Embodiment 18-29
Selection of auxiliary following substances, all the other are with embodiment 4