CN1511865A - Process for preparing nano fiber reinforcing agent - Google Patents
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- CN1511865A CN1511865A CNA02159287XA CN02159287A CN1511865A CN 1511865 A CN1511865 A CN 1511865A CN A02159287X A CNA02159287X A CN A02159287XA CN 02159287 A CN02159287 A CN 02159287A CN 1511865 A CN1511865 A CN 1511865A
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Abstract
The preparation process of nano fiber reinforcing agent with natural needle silicate, including attapulgite, sepiolite and palygorskite, includes the steps of: purifying with salt of organic acid in the amount 0.5-10 wt% of natural needle silicate; dissociation via stirring to disperse purified natural needle silicate in polar medium to form concentration of 5-30 wt%; activating modification via reaction with activating modifier in the amount of 3-50 wt% of natural needle silicate at 50-80 deg.c for 0.5-6 hr; coating isolation with organic surface isolator in the amount of 5-80 wt% of natural needle silicate; and drying at 80-150 deg.c. The nano fiber reinforcing agent may be used in preparing nano composite polymer material with high performance and low cost.
Description
Technical field
The present invention relates to the natural fibrillar silicate of a kind of usefulness through the method for purifying, dissociating, modification, coating isolation obtaining nano fiber reinforcing agent, this nano fiber reinforcing agent can be used for preparing the polymer nanocomposites of high-performance and low-cost.
Background technology
Nano filling comprises nano-calcium carbonate, nano silicon, nano zine oxide, nano titanium oxide, nano-sized magnesium hydroxide, carbon nanotube, various Nano metal powders etc.A very important characteristic of nano material is a surface effects.Therefore, the easy reunion of nano-powder reduces surface energy and is tending towards than steady state.And the surface tension of polymkeric substance is generally lower, differs far away with the surface tension of most nano-powders, lacks thermodynamic driving force when causing the two to mix.Therefore, adopt conventional polymer blending working method (polymer melt, solution or emulsion are mixed), be difficult to make filler to reach the nano level dispersion level, and can only prepare a kind of microcosmic dispersive matrix material, do not reach the ideal reinforced effects.
In order effectively to solve the fine dispersion problem of Nano filling in polymeric matrix, people have proposed in-situ polymerization compound novel method, promptly on the filler of polymolecularity, be written into component, on this filling surface, carry out polyreaction then and prepare nano composite material with catalytic activity.
" nanocomposite of a kind of polyolefine and clay " (Chinese invention patent ZL98125042.4, publication number 1255510) described a kind of fiber rod stone kind clay by 1～99% reunion ethene and 0.1～60% weight and formed, described clay is selected from fiber rod stone kind clay-sepiolite or attapulgite.This nanocomposite adopts the situ aggregation method preparation, and has excellent mechanical property and thermotolerance.Yet situ aggregation method is because complicated polymerization technique and high preparation cost are difficult to realize industrialization promotion.
Natural fibrillar silicate is the aqueous aluminium magensium silicate of a class.The natural fibrillar silicate of this class comprises sepiolite, attapulgite and polygorskite.Natural fibrillar silicate has the double-stranded wafer of upper and lower 2 or 3 silicon-oxy tetrahedrons at each unit layer, therebetween 5 or 8 aluminum-oxygen tetrahedrons, each unit layer connects into the crystalline structure of duct formula each other by oxygen, all belong to the crystalline structure of a kind of chain to the stratiform transition.Its monocrystalline is different fibrous, bar-shaped, a needle-like of development degree, and diameter mostly is 10～100 nanometers greatly, and length is several microns to tens microns.
Attapulgite (AT) is subspecies of polygorskite, has identical chemical constitution and crystalline structure with polygorskite, and difference is the polygorskite good crystallinity, and single crystal fibre is long, and iron level is low, the outward appearance softness.Its ideal chemical structure is: Mg
5[Al] Si
8O
20(OH)
2(OH
2)
4.4H
2O.Its crystalline structure is: each unit layer has the double-stranded wafer of upper and lower 2 silicon-oxy tetrahedrons, 5 aluminum-oxygen tetrahedrons of therebetween, each unit layer connects into the crystalline structure of duct formula each other by oxygen, form fibrous monocrystalline (being straight needle-like, bar-shaped or fibrous) more, single crystal diameter mostly is 10～25 nanometers greatly, length is generally 100～2000 nanometers, monocrystalline length even reach 3～5 microns in the AT kind that has.Monocrystalline is called layer of structure I.Monocrystalline generally can closely be arranged in parallel, and becomes brilliant restraint (layer of structure II), and brilliant bundle is assembled and the AT particle (layer of structure III) of formation micron level again mutually.Because monocrystalline inside is pore passage structure, simultaneously, also formed numerous Parallel Tunnel spaces between the nano crystal fiber that is arranged in parallel naturally, thereby the intragranular void volume of the AT of micron level accounts for more than 30% of particle cumulative volume, inside has huge surface-area.
AT is found in the concavo-convex fort of the U.S. the earliest, contains abundant, cheap in China.AT is widely used as sorbent material, support of the catalyst, drilling mud thickening material, binding agent, fodder additives etc. at present, and using value is lower.
Sepiolite and attapulgite are two independent mineral with gang, and its structure is roughly similar, and the structure of its monocrystalline is slightly different.Each unit layer of sepiolite has the double-stranded wafer of upper and lower 3 silicon-oxy tetrahedrons, 8 aluminum-oxygen tetrahedrons of therebetween, and each unit layer connects into the crystalline structure of duct formula each other by oxygen.Its chemical structural formula is Mg
8[Al] Si
12O
30(OH)
4(OH
2)
4.8H
2O.
Contain a large amount of carbonate, quartz and polynite etc. in the natural fibrillar silicate mineral, these materials are difficult to further disperse in the conventional course of processing of polymkeric substance, and its size is bigger, and the mechanical property of material is had a strong impact on.Should purify before use." a kind of cracking catalyst that contains sepiolite " (Chinese invention patent ZL 89100692, publication number 1044772) relates to a kind of cracking catalyst that contains sepiolite, adopt mineral acid (hydrochloric acid, sulfuric acid, phosphoric acid) purification processes sepiolite, can effectively remove carbonate." attapulgite clay of purifying " (US 6130179) provide a kind of preparation method of attapulgite clay, this method adopts poly-Sodium Propionate purification processes, can fully disperse the attapulgite particle to form suspension, effectively remove the carbonate, quartz and the polynite that contain in the attapulgite raw ore, the content of attapulgite is about 90% behind the purifying.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing nano fiber reinforcing agent by natural fibrillar silicate, when this nano fiber reinforcing agent is mixed with polymer melt, solution and emulsion, can form the disperse phase of nanoscale, realization is to the efficient enhancing of polymkeric substance, thus the polymer nanocomposites of preparation high-performance and low-cost.
The preparation method of a kind of nano fiber reinforcing agent of the present invention comprises following five preparation processes:
A purifies: natural fibrillar silicate through organic acid salt agitator treating, sedimentation and drying, is obtained the purifying natural fibrillar silicate, and the consumption of organic acid salt is 0.5%～10% of a natural fibrillar silicate weight;
B dissociates: with purifying natural fibrillar silicate dispersed with stirring in polarizable medium, the weight concentration of fibrillar silicate is 5%～30%;
The C activation modification: add surface active properties-correcting agent to B, reacted 0.5～6 hour down at 50～80 ℃, surface active properties-correcting agent consumption is 3%～50% of a purifying fibrillar silicate weight;
D coats isolation: add organic surperficial separant to C, coat isolation, isolation agent is 5%～80% of a purifying fibrillar silicate weight;
E with the product of D 80～150 ℃ of dryings;
Obtain nano fiber reinforcing agent at last.
The used natural fibrillar silicate of the present invention is any one in attapulgite, sepiolite or the polygorskite.
At the used organic acid salt of above-mentioned A is sodium polyacrylate, polyacrylic acid potassium, copolymerization maleic acid anhydride-propenoic acid sodium or copolymerization maleic acid anhydride-propenoic acid potassium.
At the used polarizable medium of above-mentioned B is water, ethanol, Virahol or their mixing solutions.
At the used surface active properties-correcting agent of above-mentioned C is titanate coupling agent, aluminate coupling agent, silane coupling agent, anionic surface properties-correcting agent, C
4～C
20Aliphatic hydrocarbon quaternary ammonium salt or their mixture.
At the used organic surperficial separant of above-mentioned D is nature rubber latex, SBR emulsion, acrylonitrile-butadiene rubber latex, carboxy nitrile rubber emulsion, polyacrylic acid emulsion, sodium stearate, potassium stearate, calcium stearate, Magnesium Stearate, ammonium stearate or sulfonated castor oil.
Preferred dodecyl dimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, octadecyl pivalic ammonium or octadecyl trimethylammonium bromide in the used aliphatic hydrocarbon quaternary ammonium salt of the present invention.
Natural fibrillar silicate of the present invention is selected from attapulgite, sepiolite or polygorskite.Because a large amount of silicon hydroxyls is contained on fibrillar silicate nano crystal surface, the interaction between the monocrystalline is mainly Van der Waals force, hydrogen bond force; Although shared cationic situation between a spot of monocrystalline is arranged, plane of action very little (cross section of monocrystalline is bordering on circle, is line of action theoretically between monocrystalline), so the reactive force between nano crystal is little far beyond the power between the phyllosilicate nano crystal layer.Because piling up, the geometry of nano crystal formed a large amount of spaces simultaneously, thereby may or be dissociated in some polarizable medium under strong shearing force or peeled off dispersion, so natural needle-like silicic acid is expected on nanoscale to carry out compoundly with polymkeric substance, realizes the efficient enhancing to polymkeric substance.
The method that the present invention proposes is for the used organic acid salt of natural fibrillar silicate purification, not only available polyacrylate, can also select copolymerization maleic acid anhydride-propenoic acid salt for use, because the latter has intensive multiviscosisty and dissemination, can disperse fibrillar silicate looser, both can effectively remove impurity such as the carbonate that contains in the raw ore and quartz, can remove layered silicate-polynite again.
The method that the present invention proposes, the purifying fibrillar silicate disperses in polarizable medium when dissociating, because fibrillar silicate list intergranular reactive force is less, under the effect that intense mechanical stirs, the nano crystal that the fibrillar silicate that is scattered in the polarizable medium can be included dissociates.Preferably water of the present invention or ethanol are dispersion medium, not only economy but also nontoxic.In order further to strengthen the dissociation effect of fibrillar silicate, stablize the dispersion state of fibrillar silicate in dispersion medium, unlikely generation sedimentation is beneficial to the surface active modification of next step nanofiber, and key is the concentration of control purifying fibrillar silicate.Purifying fibrillar silicate concentration is too low, mechanical agitation power is difficult for passing to fibrillar silicate, be unfavorable for that the nano crystal fiber that fibrillar silicate includes dissociates, and sedimentation takes place in dissociated single crystal fibre easily, influence next step surface active modification single crystal fibre.Purifying fibrillar silicate concentration is too high, and fibrillar silicate is not easy to be dispersed in the polarizable medium, and the slurry viscosity height stirs difficulty.
The surface active modification of nano crystal fiber is in order to reduce its surface tension, the affinity of increase and polymkeric substance, the interface interaction of reinforcing filler and polymkeric substance.The present invention selects to contain the surface active properties-correcting agent of reactive functionality, as have carboxyl, ester group, epoxy group(ing), the titanate coupling agent of alkoxyl group isoreactivity functional group, aluminate coupling agent, silane coupling agent, an aliphatic hydrocarbon quaternary ammonium salt, can with the silicon hydroxyl generation intensive physics or the chemical action of nano crystal fiber, but chemical reaction can not take place rapidly with dispersion medium in it, this activation modifier contains long organic chain simultaneously, preferably contain the carbon atom more than 12, to form certain thickness modified layer.The surface active key in modified treatment is control activation temperature, soak time and an activator level.The activation temperature height, soak time is short, on the contrary activation temperature is low, and soak time is long.But when being ethanol or Virahol, preferably be no more than its critical volatilization temperature for dispersion medium.
The coating isolation is the aggregation force for the nano crystal fiber that further weakens, and reduces the secondary aggregation extent of monocrystalline, is dissociated into the nano crystal fiber in the course of processing afterwards easily again.
The removal methods of dispersion medium comprises vacuum-drying, fluidized drying or spraying drying etc., and temperature is controlled at 80-150 ℃.
Used purificant, surface active properties-correcting agent, the organic separant of method of the present invention all belongs to the commercial goods, and cost is low, and is safe in utilization.Preparation process simple possible of the present invention, process stabilizing.The nano fiber reinforcing agent of the present invention's preparation is dissociated into the nano crystal fiber easily again in the polymer processing of routine, realize the dispersion of nanoscale in polymeric matrix, to prepare the polymer nanocomposites of a series of high-performance and low-costs.
Can observe the deployment conditions of nano fiber reinforcing agent of the present invention in polymeric matrix by transmission electron microscope, observe nano fiber reinforcing agent and in polymeric matrix, have the one dimension size at least, and be uniformly dispersed less than 100nm; By sem observation fracture of composite materials face, disclose nano fiber reinforcing agent and combine situation with the interface of polymer matrix.It is fuzzy to observe the fracture of composite materials interface, and nanofiber is embedded in the polymkeric substance.Adopt the mechanical property of Instron electronic universal tester according to national standard test compound material, matrix material has good 300% stress at definite elongation, tensile strength and tear strength, shows good reinforced effects.
Description of drawings
Fig. 1 is that the nano fiber reinforcing agent of the embodiment of the invention 3 preparations is dispersed in the electronic transmission Electronic Speculum figure (magnification is 30000 times) in the styrene-butadiene rubber(SBR).
Fig. 2 is that the purifying attapulgite of Comparative Examples 1 preparation is dispersed in the electronic transmission Electronic Speculum figure (magnification is 10000 times) in the styrene-butadiene rubber(SBR).
Embodiment
Embodiment 1
Be 20 liters at internal volume and be with 10 premium on currency of packing in the reactive tank that stirs, adding 3000g attapulgite mineral stirs, add the copolymerization maleic acid anhydride-propenoic acid potassium of attapulgite mineral weight 0.5%, after fully stirring, through washing, centrifugal settling, drying obtains purifying attapulgite 2250g, and the yield of purification is 75%.At internal volume is the 10 liters of deionized waters of packing in the reactive tank that stirs of 20 liters of bands, and getting above-mentioned purifying attapulgite, to be made into concentration be 5% slurries.Under violent stirring, the nano crystal fiber that the attapulgite that dissociates includes, slurry viscosity rises rapidly, and last viscosity tends to be steady.Heat to 80 ℃ of constant temperature when slurries stir, add two (dioctyl pyrophosphoryl oxygen base) ethylene titanate coupling agent of purifying attapulgite weight 3% this moment, priming reaction stopped to stir after 30 minutes, and sedimentation does not take place slurries.The sulfonated castor oil that adds purifying attapulgite weight 5% then continues to stir 20 minutes.Slurry is put into vacuum drying oven remove moisture content, pulverize the dry thing that obtains, cross 325 mesh sieves, obtain nano fiber reinforcing agent at 80 ℃.Nano fiber reinforcing agent is loose, and is broken easily.Can observe its not sedimentation in water, and good dispersiveness and stability are arranged in ethanol.
Embodiment 2
Operation steps is with embodiment 1, and processing parameter sees Table 1, and used purificant is a sodium polyacrylate, and the yield of purification is 73.5%.Used polarity dispersion medium is an ethanol, and final slurries directly obtain pulverous nano fiber reinforcing agent 150 ℃ of following spraying dryings, and quality is loose soft.Can be observed its not sedimentation in water, and good dispersiveness and stability are arranged in ethanol
Embodiment 3
Operation steps is with embodiment 1, and processing parameter sees Table 1, and used purificant is a copolymerization maleic acid anhydride-propenoic acid sodium, and the yield of purification is 78.5%.Used polarity dispersion medium is water and alcoholic acid mixed solution, and final slurries directly obtain Powdered, the loose softish nano fiber reinforcing agent of quality at 120 ℃ of following fluidized dryings.Can be observed its not sedimentation in water, and good dispersiveness and stability are arranged in ethanol.This nano fiber reinforcing agent is directly mixed with styrene-butadiene rubber(SBR) and (is filled 40phr attapulgite/100phrSBR), can be evenly dispersed in the rubber matrix with the nano unit yardstick, (see figure 1), and have good reinforced effects (seeing Table 2).
Comparative Examples 1
Operation steps is only purified and drying step.Used purificant is a sodium polyacrylate, and the yield of purification is 74%.Final slurries obtain the Powdered dry thing of purifying at 120 ℃ of following fluidized dryings, and outward appearance is hard closely knit.This drying thing mixes with styrene-butadiene rubber(SBR) directly that (fill 40phr attapulgite/100phrSBR), disperses inhomogeneously, dispersion size is (see figure 2) greatly, reinforced effects poor (seeing Table 2).
Table 1
| Preparation technology | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | |
| Natural fibrillar silicate | Attapulgite | Polygorskite | Attapulgite | Attapulgite | |
| Purify | Purificant and consumption, % (weight ratio) | Copolymerization maleic acid anhydride-propenoic acid potassium 0.5 | Sodium polyacrylate 10 | Copolymerization maleic acid anhydride-propenoic acid sodium 3 | Sodium polyacrylate 3 |
| Dissociate | Polarizable medium and concentration (%) | Water 5 | Ethanol 15 | Water and ethanol 30 | / |
| The surface active modification | Properties-correcting agent and consumption, % (weight ratio) | Two (dioctyl pyrophosphoryl oxygen base) ethylene titanate coupling agent 3 | Cetyl trimethylammonium bromide 50 | γ-An Bingjisanyiyangjiguiwan 20 | / |
| Temperature (℃) | ??80 | ?50 | 60 | / | |
| Time (hr) | ??0.5 | ?6 | 1.5 | / | |
| Coat and isolate | Separant and consumption (% weight ratio) | Sulfonated castor oil 5 | Sodium stearate 30 | SBR emulsion 80 | / |
Table 2
Performance embodiment 3 Comparative Examples 1
Shao A hardness 64 56
300% stress at definite elongation, MPa 7.4 1.9
Tensile strength, MPa 12.5 6.1
Elongation at break, % 556 972
Tensile deformation, % 20 48
Tear strength, KN.m
-134.9 21.7
Claims (7)
1. the preparation method of a nano fiber reinforcing agent comprises following preparation process:
A purifies: natural fibrillar silicate through organic acid salt agitator treating, sedimentation and drying, is obtained the purifying natural fibrillar silicate, and the consumption of organic acid salt is 0.5%～10% of a natural fibrillar silicate weight;
B dissociates: with purifying natural fibrillar silicate dispersed with stirring in polarizable medium, the weight concentration of fibrillar silicate is 5%～30%;
The C activation modification: add surface active properties-correcting agent to B, reacted 0.5～6 hour down at 50～80 ℃, surface active properties-correcting agent consumption is 3%～50% of a purifying fibrillar silicate weight;
D coats isolation: add organic surperficial separant to C, coat isolation, isolation agent is 5%～80% of a purifying fibrillar silicate weight;
E with the product of D 80～150 ℃ of dryings;
Obtain nano fiber reinforcing agent at last.
2. method according to claim 1 is characterized in that: natural fibrillar silicate is any one in attapulgite, sepiolite or the polygorskite.
3. method according to claim 1 is characterized in that: at the used organic acid salt of A is sodium polyacrylate, polyacrylic acid potassium, copolymerization maleic acid anhydride-propenoic acid sodium or copolymerization maleic acid anhydride-propenoic acid potassium.
4. method according to claim 1 is characterized in that: at the used polarizable medium of B is water, ethanol, Virahol or their mixing solutions.
5. method according to claim 1 is characterized in that: at the used surface active properties-correcting agent of C is titanate coupling agent, aluminate coupling agent, silane coupling agent, anionic surface properties-correcting agent, C
4～C
20Aliphatic hydrocarbon quaternary ammonium salt or their mixture.
6. method according to claim 1 is characterized in that: at the used organic surperficial separant of D is nature rubber latex, SBR emulsion, acrylonitrile-butadiene rubber latex, carboxy nitrile rubber emulsion, polyacrylic acid emulsion, sodium stearate, potassium stearate, calcium stearate, Magnesium Stearate, ammonium stearate or sulfonated castor oil.
7. method according to claim 5 is characterized in that: the aliphatic hydrocarbon quaternary ammonium salt is dodecyl dimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, octadecyl pivalic ammonium or octadecyl trimethylammonium bromide.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333004C (en) * | 2004-11-16 | 2007-08-22 | 北京化工大学 | Method for preparing nano silicate fiber and rubber composite material |
| CN101240089B (en) * | 2008-03-11 | 2010-06-30 | 江苏江昕轮胎有限公司 | Rubber activity cut staple |
| CN101691275B (en) * | 2009-08-31 | 2012-01-04 | 河北工业大学 | Method for preparing nano mineral fiber |
| CN101508801B (en) * | 2009-03-19 | 2012-09-05 | 兰州大学 | Method for preparing oil-filled styrene butadiene rubber SBR1712/attapulgite stone nano-composite material |
| CN105579495A (en) * | 2013-09-24 | 2016-05-11 | 纳幕尔杜邦公司 | Fibrous pulp and use thereof in a composite |
| CN105733047A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Nitrile-butadiene rubber/attapulgite nanocomposite, vulcanized rubber and preparation method thereof |
| CN107938393A (en) * | 2017-11-01 | 2018-04-20 | 浙江圣山科纺有限公司 | A kind of Non-water washing pigment printing umbrella cloth |
| CN107964781A (en) * | 2017-11-01 | 2018-04-27 | 浙江圣山科纺有限公司 | A kind of preparation method of short route padding machine dyeing umbrella cloth |
| CN111944231A (en) * | 2020-08-24 | 2020-11-17 | 安徽省康利亚股份有限公司 | Low-smoke halogen-free flame-retardant super-flexible oil-resistant cable material |
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2002
- 2002-12-30 CN CN 02159287 patent/CN1195009C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333004C (en) * | 2004-11-16 | 2007-08-22 | 北京化工大学 | Method for preparing nano silicate fiber and rubber composite material |
| CN101240089B (en) * | 2008-03-11 | 2010-06-30 | 江苏江昕轮胎有限公司 | Rubber activity cut staple |
| CN101508801B (en) * | 2009-03-19 | 2012-09-05 | 兰州大学 | Method for preparing oil-filled styrene butadiene rubber SBR1712/attapulgite stone nano-composite material |
| CN101691275B (en) * | 2009-08-31 | 2012-01-04 | 河北工业大学 | Method for preparing nano mineral fiber |
| CN105579495A (en) * | 2013-09-24 | 2016-05-11 | 纳幕尔杜邦公司 | Fibrous pulp and use thereof in a composite |
| CN105579495B (en) * | 2013-09-24 | 2017-11-21 | 纳幕尔杜邦公司 | Fibre pulp and its purposes in the composite |
| CN105733047A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Nitrile-butadiene rubber/attapulgite nanocomposite, vulcanized rubber and preparation method thereof |
| CN107938393A (en) * | 2017-11-01 | 2018-04-20 | 浙江圣山科纺有限公司 | A kind of Non-water washing pigment printing umbrella cloth |
| CN107964781A (en) * | 2017-11-01 | 2018-04-27 | 浙江圣山科纺有限公司 | A kind of preparation method of short route padding machine dyeing umbrella cloth |
| CN111944231A (en) * | 2020-08-24 | 2020-11-17 | 安徽省康利亚股份有限公司 | Low-smoke halogen-free flame-retardant super-flexible oil-resistant cable material |
| CN111944231B (en) * | 2020-08-24 | 2024-04-12 | 安徽省康利亚股份有限公司 | Low-smoke halogen-free flame-retardant super-flexible oil-resistant cable material |
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