CN1752154A - Amine silane surface modified micro crystal isinglass active filler and its preparation method - Google Patents
Amine silane surface modified micro crystal isinglass active filler and its preparation method Download PDFInfo
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- CN1752154A CN1752154A CN 200510021668 CN200510021668A CN1752154A CN 1752154 A CN1752154 A CN 1752154A CN 200510021668 CN200510021668 CN 200510021668 CN 200510021668 A CN200510021668 A CN 200510021668A CN 1752154 A CN1752154 A CN 1752154A
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Abstract
A process for preparing the active filler from the microcrystalline muscovite through modifying its surface by aminosilane includes such steps as baking said microcrystalline muscovite, loading it in a mixer, using glacial acetic acid to regulate pH value of alcohol to 3-7 to obtain deluent, proportionally mixing the aminosilane as coupling agent with said deluent to obtain surface modifier, spraying it onto the microcrystalline mascovite in mixer, high-speed mixing, and drying.
Description
One, technical field
Microcrystal muscovite is a kind of novel non-metallic minerals resource.The present invention relates to a kind of preparation method of amine silane surface modified micro crystal isinglass active filler, applicable to plastics, rubber, coating, industry such as tackiness agent, especially be suitable as Resins, epoxy (EP), resol (PF), aminoresin, Synolac, unsaturated polyester resin (UPR), Phthalic acid, diallyl ester (DAP), polyimide resin (PI), thermosetting resins such as trimeric cyanamide, polyamide (PA), polycarbonate (PC), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polyphenylene sulfide (PPS), polyethylene terephthalate (PETP), polybutylene terephthalate (PBT), polyphenylene oxide (PPO), thermoplastic resins such as polyacrylic ester, and nitrocellulose (CN), the functional stuffing of chloroprene rubber etc., and can give or improve the acid and alkali-resistance of institute's filled high polymer material or superpolymer based composites, antiultraviolet, anti-aging, insulativity, wear resistance, thermotolerance, weathering resistance, full of elasticity, performances such as physical strength, for example, at heavy antiseptic project plastics, the effect of performance functional stuffing in automobile engineering plastics and the High Performance Insulation material.
Two, technical background
1, white mica and Application Areas thereof
White mica (Muscovite) is the important member of mica family, white mica subtribe mineral, is 2: 1 type dioctahedron layered struture silicate mineralss of a kind of rich K, Al.The ideal composition formula of white mica is: K{Al
2[AlSi
3010] (OH)
2, its Chemical Composition is: K
2O 11.8%, Al
2O
338.5%, SiO
245.2%, H
2O 4.5%.The white mica isomorph substitutes more extensive, therefore has mutation such as roscoelite, fuchsite, phengite.Si: Al in four coordinations of phengite＞3: 1, six coordinate Al are by more Mg and Fe
2+Replace.In addition, so-called sericite generally is meant some very tiny white micas (the normally white mica or the mica of receiving).
White mica has 1Md (unordered type), 1M, 2M
1Many types of with 3T etc., the white mica majority of nature output is 2M
1Type.The white mica crystalline form forms false hexagon or rhombus outward usually in the form of sheets or tabular, sees that sometimes the white mica single crystal is the taper cylinder.The tiny person of crystal is flakey, and big person has hundreds of square centimeters, and maximum can reach 2000cm
2
White mica has many good physical and chemical performances.At first, has very outstanding electrical properties.It is good that it mainly shows as electrical insulating property, is the desirable feedstock of producing the premium insulation material.Secondly, have good thermotolerance, in the time of 100～600 ℃, can keep its a series of good physical.The 3rd, have excellent elasticity and wear resistance, its wear resisting property is better than copper.The 4th, have good chemical stability.Alkali works hardly to white mica, does not dissolve in hot acid, but can decompose under boiling vitriolic long duration of action.The 5th, have the premium properties that shielding ultraviolet rays, counter infrared ray radiation etc. resist various x radiation xs.The 6th, have excellent waterproofness.The white mica water absorbability is 0～0.37%, and water-absorbent is 0～0.23%, is the damp-proof material of excellent waterproof.
The above-mentioned physical and chemical performance of white mica makes it to have purposes very widely.White mica industrial application and its wafer size and crystal chemistry feature have relation nearly.Large stretch of white mica (useful area 24cm
2The person) is mainly used in hard-core technology fields such as electrical industry, electronic industry and Aeronautics and Astronautics.
On the other hand, along with the finiteness of scientific-technical progress and big mica splitting resource is obvious day by day, the Application and Development of garrulous mica (waste material and the natural little mica splitting that comprise fragment mica, big mica splitting processing) has obtained remarkable progress.At first, the mica powder of super-fine processing can be used as the good filler of plastics.White mica powder is easy to mix with Plastic Resin behind surface actives such as coupling agent, and processing characteristics is good, can be used for filling multiple plastics such as PE, PP, PVC, PA, PET, ABS, and can improve the modulus of plastic substrate, improves dielectric properties.Simultaneously, white mica powder has bidimensional enhancing property, can improve thermotolerance, reduces creep, prevents the goods warpage, reduces molding shrinkage.In addition, white mica powder also has the excellent electric insulating energy, and the processing units wearing and tearing are few, and heat-drawn wire improves, the flammable reduction, and perviousness reduces and advantages such as weather-resistant and acid-alkali-corrosive-resisting.The matrix material that obtains with mica enhancing PP/EPDM co-mixing system not only has good impact property but also have higher modulus in flexure, has been widely used in injection moulding hardness fascia and other plastic automotive parts.The second, the mica powder of super-fine processing also is the good filler of rubber and paint, multiple coating.Add mica powder in the rubber, can make the tubeless rubber tire.Add ultra-fine mica powder in the paint and can improve Chinese People's Anti-Japanese Military and Political College's gas, frost resistance, preservative property, closely knit wear resistance, can reduce perviousness, reduce paint film yellowing and be full of cracks.Mix the mica ultrafine powder in the coating and can improve the weather resistance of building appearance, increase water-repellancy, elasticity, plasticity, adhesivity and the non-corrosibility of coating.The 3rd, hot pressing moulding or injection molding are mica ceramics behind mica powder and the glass powder mixing.Mechanical workouts such as this pottery can bore, mill can prepare the special-shaped products complex-shaped, that dimensional precision is high and instrument skeleton plug connector elements and thyristor shell etc.The 4th, the mica paper with fragment mica and mica powder are made all is gradually improved aspect quality and variety, has replaced natural flaky shape mica in a large number, and extensive use is arranged.Pull with mica paper very extensive as mica ply of paper pressure in the industrial application of Electrical and Electronic.Replace the natural flaky mica in a large number although should be pointed out that mica paper, the large stretch of white mica of high-quality does not still have substitute material in sophisticated technology Application for Field such as robot calculator, radar, guided missile, man-made satellites.
2, microcrystal muscovite and application prospect thereof
Microcrystal muscovite (Microcrystal muscovite) is a newcomer of mica family, white mica subtribe mineral, is a kind of novel non-metallic minerals resource.The crystalline structure of microcrystal muscovite, crystal chemistry, Chemical Composition, crystal habit and mineral physics feature of being showed thereof etc. are all identical with white mica or basic identical, thereby should have the physical and chemical performance identical or similar with white mica.With white mica very inequality be, the mineral crystal of microcrystal muscovite is very little, only has micron-sized crystal or wafer (be called for short " crystallite "), its size is generally at 1～10 micron.The origin of title that Here it is " microcrystal muscovite ".
Formation and its origin cause of formation of microcrystal muscovite this distinctive " crystallite " structure have substantial connection.1997, the super-huge microcrystal muscovite mineral deposit of at first being found in somewhere, China Sichuan by applicant (Chengdu University of Technology) was exactly typical example.This mineral deposit is to be formed through diagenesis or later hydrothermal alteration transformation by dignified limestone, and large stretch of white mica of known various uses is mainly derived from the granitic pegmatite-type mineral deposit.In the world, except that near Nevada, USA Luo Qisite, found in 1933 with similar agalmatolite ore deposit, this mineral deposit, do not find the report in other place of production so far.Thereby this mineral deposit is the domestic new mica group genetic type of ore deposit of finding first, also is a kind of novel non-metallic minerals resource.
The physical and chemical performance of mineral is must reflecting of mineral self crystalline structure, crystal chemistry.As mentioned above, because features such as the crystalline structure of microcrystal muscovite and crystal chemistry are all basic identical with white mica, thereby it also should have the very good physical and chemical performance identical or similar with white mica, comprising: resistivity height, physical strength height, chemically stable, acid and alkali-resistance, wear resistance, thermotolerance, weathering resistance, antiultraviolet, anti-aging, full of elasticity etc.Simultaneously, microcrystal muscovite removes also has characteristics such as natural superfine, whiteness height, frangible easy mill processing, is easy to be processed into varigrained microcrystal muscovite superfine powdery material.Toughness is big, wear resistance is the good physical and chemical performance that white mica has well.Therefore, adopt the difficulty of white mica or garrulous mica processing mica powder and ultra-fine mica powder big, cost is high, restricted its widespread use as functional stuffing.In addition, microcrystal muscovite also has the bigger characteristics of radius-thickness ratio, has tangible strengthening action as rubber filling.In a word, the microcrystal muscovite excellent property, aboundresources is easy to exploitation, and low processing cost has the incomparable advantage of other white non-metallic minerals filler in many industrial application.
This shows, microcrystal muscovite is the good raw mineral materials of preparation mica powder and ultra-fine mica powder, at industrial sectors such as plastics, rubber, electric, electronics, space flight, aviation, automobiles very wide application prospect will be arranged by the functional stuffing of its preparation, and might in Application Areass such as automobile engineering plastics, anti-soda acid plastics, anticorrosive coating and High Performance Insulation material, exhibit one's skill to the full as functional stuffing.And along with the minimizing day by day of large stretch of white mica mineral wealth and the restriction of broken white mica super-fine processing cost, the searching of natural microcrystal muscovite mineral wealth will seem with development and use and become more and more important.
3, the technical problem underlying of microcrystal muscovite in polymer materials is used
In industry such as modern macromolecular material such as plastics, rubber, tackiness agent, polymer matrix composite and functional materials, inorganic nonmetal mineral fillers is occupied very consequence.These inorganic nonmetal mineral fillers, as lime carbonate, kaolin, wollastonite, talcum, mica, pyrophyllite, rhombspar, the tremolite etc., not only can reduce the cost of macromolecular material, superpolymer based composites, and can also improve rigidity, hardness, the dimensional stability of material, and give material some special physicochemical performance, as erosion resistance, flame retardant resistance, insulativity etc.Because these inorganic nonmetal mineral fillers are different with the surface properties of polymer matrix material, be that the inorganic nonmetal mineral fillers surface has hydrophilic oleophobic property usually, the situation of polymer matrix material is just in time opposite, usually has lipophilic-hydrophobic property, therefore, carry out compound tense when the two, consistency is poor, make inorganic non-metallic mineral powder material in the polymer packing body material, be difficult to disperse, directly or in a large number fill some degradation that often causes material easily.Therefore, for the non-metallic minerals filler, except carrying out processing treatment such as the broken or superfine grinding of fine powder, also must carry out surface modification, make it have surfactivity, to improve the consistency of it and polymeric matrix it, thereby improve the dispersiveness of non-metallic minerals filler in body material, improve the over-all propertieies such as physical strength of composite material interface bonding force and material, and increase the loading level of non-metallic minerals filler, reduce cost.
Modern macromolecular materials such as plastics, rubber, tackiness agent and polymer matrix composite will be the of paramount importance Application Areass of microcrystal muscovite filler.Because natural microcrystal muscovite is the hydrophilic mineral of a kind of polarity, and organic polymers such as plastics, rubber have nonpolar hydrophobic surface.Therefore, if they are directly lumped together, polarity difference each other then, consistency is poor, is difficult to mutual homodisperse, thereby causes the boundary defect of two phase materials, the organic polymer material property is descended or fills restricted greatly.If will make microcrystal muscovite in above-mentioned polymer materials, bring into play the effect of function powder material, must at first carry out the microcrystal muscovite Research on Surface Modification, solve the surface bonding problem of microcrystal muscovite filler and polymer matrix material, give microcrystal muscovite powder filler due surfactivity, to improve its application performance.But because microcrystal muscovite is a kind of novel metalloid raw mineral materials of just finding in recent years, research also is in blank about the micro crystal isinglass active filler process for modifying surface, thereby restricts its industrial application.
In sum, microcrystal muscovite is a kind of novel non-metallic minerals resource, have tangible quality price than advantage as feedstock production mica powder and ultra-fine mica powder,, wide application prospect will be arranged if can adopt process for modifying surface to improve the consistency of it and organic polymer matrix.By retrieval, do not find with the microcrystal muscovite to be raw material, prepare a kind of bibliographical information or patent application of amine silane surface modified micro crystal isinglass active filler.
The objective of the invention is, according to microcrystal muscovite filler and industrial application characteristics thereof, carry out the research of amino silicane coupling agent process for modifying surface, develop a kind of micro crystal isinglass active filler with functions such as obvious reinforcement, applicable to plastics, rubber, coating, industry such as tackiness agent, especially be suitable as Resins, epoxy (EP), resol (PF), aminoresin, Synolac, unsaturated polyester resin (UPR), Phthalic acid, diallyl ester (DAP), polyimide resin (PI), thermosetting resins such as trimeric cyanamide, polyamide (PA), polycarbonate (PC), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polyphenylene sulfide (PPS), polyethylene terephthalate (PETP), polybutylene terephthalate (PBT), polyphenylene oxide (PPO), thermoplastic resins such as polyacrylic ester, and nitrocellulose (CN), the functional stuffing of chloroprene rubber etc., and can give or improve the acid and alkali-resistance of institute's filled high polymer material or superpolymer based composites, antiultraviolet, anti-aging, insulativity, wear resistance, thermotolerance, weathering resistance, full of elasticity, performances such as physical strength, for example, at heavy antiseptic project plastics, the effect of performance functional stuffing in automobile engineering plastics and the High Performance Insulation material.
Two, technical scheme
For achieving the above object, the present invention has adopted following technical scheme:
At present, the method that is used for the non-metallic minerals stuffing surface modification mainly contains surface chemistry coating modification method, mechanochemical modification method and high energy modification method etc.
Surface chemistry coating modification method is present the most frequently used surface modifying method, and it is a kind ofly to utilize the functional group in the organic molecule filler particles surface to be coated the method that it is organised in filling surface absorption or chemical reaction.For this method, the selection of chemical modifier has conclusive effect to the modification result, and the consumption of chemical modifier, modified technique also are the keys that influences modified effect.Present chemical modifier has tensio-active agent and coupling agent two big classes, and modified effect is preferably the coupling agent that can play molecule bridge coupled action on non-metallic minerals filler and organic materials interface.
According to microcrystal muscovite and industrial application characteristics thereof, the method that this patent adopted is a surface chemistry coating modification method, and chemical modifier is a coupling agent.Putting before this, the related gordian technique of the art of this patent scheme has: the definite and consumption of (1) coupling agent; (2) the coupling agent thinner determines and consumption; (3) surface modification technology etc.
1, coupling agent kind and consumption
Coupling agent is a kind of surface-modifying agent most widely used, with fastest developing speed in the non-metallic minerals stuffing surface modification, various in style, the type complexity mainly contains series product such as silane, titanic acid ester, aluminic acid ester, zircoaluminate, organic complex, phosphoric acid ester, boric acid ester, stannic acid ester, aluminium titanium composite coupler.Wherein, it is more that first three plants serial kind, uses also the widest.And silane coupling agent is to study the earliest, and kind is maximum, consumption maximum a kind of.It not only can improve the mechanical property of plastics, can also improve performances such as its electric property, thermotolerance, water tolerance and weathering resistance.
Silane coupling agent is the low molecule silicoorganic compound that a class has special construction.Its general formula is RSiX
3, in the formula: R representative and polymer molecule have the organo-functional group of avidity or response capacity, as amino, epoxy group(ing), methacryloxy, sulfydryl, vinyl and cyano group etc.; X representative can with the hydrolyzable group of inorganic mineral surface action, as alkoxyl group, acyloxy, halogen etc.
Silane at first is that the hydrolysis of X base forms silanol when carrying out coupled action, and then with the hydroxyl reaction of inorganic filler surface, form hydrogen bond and also be condensed into-Si-M covalent linkage (M represents inorganic filler surface).Simultaneously, the oligomerisation of associating mutually again of the silanol of each molecule of silane forms cancellated film and covers filling surface, and mineral filler is organised, and reaches the purpose of surface modification.
The research and development of silane coupling agent start from 1945, and after half a century, the kind of amino silicane coupling agent has developed into over one hundred kind.Press the structure of R functional group in the molecule, organo silane coupling agent is divided into three types of silane coupling agents such as alpha-functional group, β-functional group and γ-functional group.Substituting group separates the position of Siliciumatom in their corresponding respectively R carbochains, and a carbon atom claims the alpha-functional group silane coupling agent at interval, and two and three carbon atoms in interval divide another name β-functional group and γ-functional group's coupling agent.
β-coupling agent mechanism of functional group instability has no value for use.
γ-functional group's coupling agent structure is the most stable, and using value is big, and series product are all arranged both at home and abroad, according to substituent different amino, the types such as the carbonyl alkoxyl oxygen alkyl ethyl amino of urea groups of dividing.γ-functional group's coupling agent is used for the mineral surface modification that thermoplasticity and thermosetting resin fill to be handled, and it is very remarkable to improve effect such as product strength.
Alpha-functional group coupling agent structural stability is used for rubber, plastics, coating and adhesives industry between β and γ-functional group, effect is obvious.Except that the mechanical property that strengthens goods, the alpha-functional group coupling agent also makes the electric property of goods and humidity resistance be improved.
Because γ-functional silanes coupling agent Application Areas is extensive, be applicable to that the mineral surface modification of filling in thermoplasticity and the thermosetting resin handles, very remarkable to improving effect such as product strength.According to the purpose of this patent, this patent has been selected γ-functional groups amino silane coupling agent for use.Simultaneously, according to pertinent data, for the micaceous surface modification, amine silane surface modified dose of effect is good.So this patent has been selected the surface-modifying agent of aminosilane as the microcrystal muscovite filler.
Aminosilane, full name are γ-An Bingjisanyiyangjiguiwan, and code name is KH-550 (domestic) or A-1100 (abroad), and molecular formula is C
3H
6(NH
2) Si (OC
2H
5)
3, its infrared spectrogram as shown in Figure 1.For sake of convenience, this patent abbreviates the gamma-aminopropyl-triethoxy-aminosilane as: aminosilane (KH-550), perhaps aminosilane.
Aminosilane (KH-550) is a kind of colourless transparent liquid, and relative molecular weight is 221.3, relative density 0.946,217 ℃ of boiling points (101324.72Pa), specific refractory power 1.420 (25 ℃), 96 ℃ of flash-points; Can be water-soluble fully, pure immediately, aromatic series and aliphatic hydrocarbon compounds, and hydrolysis in water is alkalescence.
Aminosilane is a kind of mineral powder, especially coupling agent of silicate minerals powder surface modification of being widely used in.This coupling agent is widely used, be applicable to many thermoplastic resins and thermosetting resins such as mineral-filled Resins, epoxy, polypropylene, polyvinyl chloride, melmac, resol, polyethylene, polycarbonate, nylon, polymethylmethacrylate, polysulfones, can improve wettability and the dispersiveness of filler in polymkeric substance, and can increase substantially and physical and mechanical property and hygrometric state electric properties such as the dried hygrometric state bending strength of reinforced plastics, ultimate compression strength, shearing resistance.
For some coupling agent, can calculate its theoretical consumption by following formula:
W=(W
1* S
1)/S
2(formula 1)
In the formula: W---coupling agent consumption (g);
W
1---desire the mineral filler weight (g) of modification;
S
1---the specific surface area (m of mineral filler
2/ g);
S
2---the minimum of coupling agent coats area (m
2/ g), can provide data with reference to manufacturer.
But what calculated by above-mentioned formula is theoretical consumption.During practical application, because crystal chemistry, crystal habit, granular size and the surface characteristic etc. of different non-metallic minerals fillers all have bigger difference, so theoretical consumption and actual amount also have than big difference.The coupling agent actual amount is generally the 0.5-3% of mineral quantity.In general, mineral granularity is thin more, and specific surface area is big more, and the consumption of required properties-correcting agent is big more.Therefore, this patent determines that the method for coupling agent consumption is: calculate the theoretical consumption of different grain size microcrystal muscovite filler earlier by above-mentioned formula, observation and test analysis are verified and are revised by experiment again, sift out optimum amount at last.Aminosilane (KH-550) consumption of different grain size microcrystal muscovite filler will provide in the example of this patent.
2, the thinner kind and the consumption of coupling agent
Coupling agent is very important with solvent cut, and it can make coupling agent evenly be coated on the surface of microcrystal muscovite filler.
Aminosilane (KH-550) can be water-soluble fully, pure immediately, aromatic series and aliphatic hydrocarbon compounds, but acetone, tetracol phenixin are not suitable for releasing agent.According to the characteristics of microcrystal muscovite, consider factors such as modification cost and modified technique, this patent has been selected water and alcohol (90% industrial spirit, the i.e. water 10%+ alcohol 90%) thinner as aminosilane (KH-550) coupling agent.Its consumption determines that by the surface modification experiment thinner consumption of the aminosilane (KH-550) of different grain size microcrystal muscovite filler will provide in the example of this patent.
3, amino silicane coupling agent surface modification technology
The technology approach of surface chemistry coating modification method has two kinds: (1) method for pretreating: earlier filler is carried out surface modification treatment, be added to then and remove to form matrix material in the base-material; (2) whole blending method:, after forming process, form matrix material in that filler and polymkeric substance are added surface-modifying agent when mixing.In general, the pre-treatment modified effect is better than whole blending method.Because when having resin to exist, coupling agent is diluted, but also may lump mutually because of the effect of resin.To reach the identical modified effect of method for pretreating with whole fusion method, must use the coupling agent that is several times as much as the method for pretreating consumption.In addition, in whole fusion method, factors such as the ratio of coupling agent kind, using method, superpolymer binder types, superpolymer and coupling agent, mixing time, temperature all can influence physical properties of articles.In order to help the micro crystal isinglass active filler that enterprise produces a kind of aminosilane (KH-550) surface modification, this patent has adopted the pre-treatment modified technique.
Pre-treatment modification method also has two kinds of methods: a kind of is dry method, promptly coupling agent with solvent cut after, promptly spray in the microcrystalline white mica powder powerful stir (about stirring velocity 2000r/min).A kind of is wet method, is about to coupling agent and is mixed with dilute solution by 1～3% of microcrystalline white mica powder weight, makes microcrystalline white mica powder fully effect in solution, dries then, encapsulates.According to applicant's experimental result, for aminosilane (KH-550) surface modification of microcrystalline white mica filler, comprehensively each face factor has adopted dry method, and has obtained satisfied modified effect.
This patent is a raw material with the microcrystal muscovite powder, adopts heated at high speed to mix (kneading) machine and dry surface modification technology, and its specific embodiment is:
(1) oven dry material: microcrystal muscovite powder material is dried under 110 ℃ of constant temperatures in heating unit, remove whole adsorption moistures in the material.It is definite that drying time should be done wet situation according to material, generally at 3 hours;
(2) take by weighing material: take by weighing the microcrystal muscovite powder oven dry material of certainweight, certain particle size, and the material that takes by weighing is packed in the mixing kettle of modified device heated at high speed mixing machine by the operational requirement of this equipment;
(3) prepared and diluted agent: the amino silicane coupling agent thinner is mixed by distilled water and ethanol, and the volume ratio of the two is 1: 9, and is promptly formulated by the ethanol of 10% distilled water and 90%; Perhaps directly adopting ethanol content is that 90% industrial spirit is as thinner.Then, and thinner pH value is adjusted to 3～7, is beneficial to the hydrolysis of coupling agent with Glacial acetic acid;
(4) take by weighing coupling agent: weight is in microcrystal muscovite powder material: the ratio of aminosilane (KH-550)=100: 0.5～5 claims (amount) to get a certain amount of aminosilane (KH-550) coupling agent;
(5) preparation surface-modifying agent: will measure the mixing diluents of aminosilane (KH-550) coupling agent and preparation, the volume ratio of the two is 1: 3, and stirs, and promptly obtains aminosilane (KH-550) surface-modifying agent of being prepared.It should be noted that aminosilane (KH-550) surface modification solution should promptly join i.e. usefulness, influence result of use to prevent chemical reaction;
(6) add surface-modifying agent: will mix amine silane surface modified dose is sprayed in the microcrystal muscovite powder material in the mixing kettle uniformly with atomizer.Powder material should manually constantly be stirred, so that properties-correcting agent is evenly distributed therebetween, in powder material;
(7) high-speed mixing material: set the surface modification temperature, open the heated at high speed mixing machine, make powder material high-speed mixing (the powerful stirring) 30～90 minutes under 90～130 ℃ of conditions.Therebetween, under the less situation of powder material, shut down once (about 15 minutes) at regular intervals, in time mixing kettle wall, the powder that covers adhesion is swept mixing kettle, makes surface-modifying agent and powder uniform mixing;
(8) drying of modification material: by the time after the setting high-speed mixing time, take out material by operational requirement.Then, material is dry under 110 ℃ of constant temperatures in heating unit, with combining of further promotion coupling agent and mineral surface.Should determine according to the material particular case time of drying,, promptly obtain the active powder filler of amine silane surface modified microcrystal muscovite generally at 3 hours;
(9) modified effect detects: microcrystal muscovite powder material is after the amino silicane coupling agent surface modification, and its surface properties will become " oleophilic drainage " by " hydrophilic oleophobic ".Can adopt methods such as penetration time, viscosity test and Infrared spectroscopy, surface modification effect is done further detection and evaluation.
4, surface modification effect characterizes and estimates
The characterizing method of non-metallic minerals stuffing surface modification effect has two kinds of direct method and indirect methods.Direct method is powder filled in corresponding plastics, rubber, coating, tackiness agent with after the surface modification, fills the physical and chemical performance of back material by test analysis and estimates modified effect.Indirect method is to estimate by the correlated performance of test analysis modified powder itself.Because the industrial application of aminosilane (KH-550) surface modified micro crystal isinglass active filler is wider, applicable multiple polymers material, thereby adopt indirect method to carry out the surface modification effect sign.
Forefathers' result of study and applicant's experiment shows that the indirect method of silane surface modified effect is a relatively problem of difficulty.According to the characteristics of aminosilane (KH-550) surface modified micro crystal isinglass active filler, this patent adopts methods such as penetration time method, viscosimetry to characterize and estimate, and has obtained better effects.
The penetration time characterizing method is a quality of representing modified effect with the speed that water droplet is penetrated into the powder medium velocity fully.Under normal conditions, under identical experiment condition, the mineral powder modified effect is good more, and penetration time is long more; The mineral powder modified effect is poor more, and then penetration time is short more.The practical significance of penetration time characterizing method is: (1) can characterize or estimate in advance the mineral powder modified effect indirectly.When the modified mineral powder capillary time is longer, illustrate that modified effect is better.On the contrary, illustrate that modified effect is relatively poor.Therefore, the penetration time characterizing method can be in order to instruct modified technique.(2) can characterize or estimate in advance the effect of modified mineral powder in polymer matrix composite indirectly.When the modified mineral powder capillary time is longer, mean with the polymer phase capacitive good.On the contrary, when the modified mineral powder capillary time more in short-term, mean with the polymer phase capacitive relatively poor.
The viscosity analysis is to utilize the viscosity variation characteristic of powder filler in a constant volume mineral oil (white oil) to estimate the compatibility performance of powder filler in nonpolar medium quantitatively.Under normal conditions, for the good powder filler of modified effect, good consistency is arranged with the mineral oil nonpolar medium.Therefore, along with the increase gradually of modified powder filler content, less to the influence of viscosity number.On the contrary, viscosity number will increase rapidly along with the increase gradually of powder filler.
Three, technical superiority
Compared with prior art, this patent modified effect excellence, modified product quality height, technology is convenient, and its end-use is extensive, can produce tangible economy and society benefit.The advantage and the effect of this patent are embodied in:
(1) modified effect excellence.The microcrystal muscovite filler of long time without surface modification is a kind of polarity inorganics, has " hydrophilic oleophobic " surface characteristic, relatively poor with the affinity of organic polymer matrix, directly filling cause easily in machine superpolymer base-material, disperse inhomogeneous, thereby cause the boundary defect of two phase materials.The modified effect detected result shows, aminosilane (KH-550) surface modified micro crystal isinglass active filler has " oleophilic drainage " surface characteristic, demonstration is good with the affinity of organic polymer matrix, can be filled in the machine superpolymer base-material by homodisperse the effect of performance function powder filler.
(2) modified product quality height.The surface modified product of this patent can increase substantially and physical and mechanical property and hygrometric state electric properties such as the dried hygrometric state bending strength of reinforced plastics, ultimate compression strength, shearing resistance, and can give or improve institute's filled high polymer material or superpolymer based composites wear resistance, insulativity, thermotolerance, weathering resistance, full of elasticity, physical strength big, acid and alkali-resistance, antiultraviolet, performance such as anti-aging.
(3) modified technique is convenient.The dry method modification technology that this patent adopted, technical process is simple, and the mechanization degree height is easy to operate, is suitable for large-scale mass production.
(4) modified product is of many uses.Aminosilane (KH-550) is widely used, especially be suitable as Resins, epoxy (EP), resol (PF), aminoresin, Synolac, unsaturated polyester resin (UPR), Phthalic acid, diallyl ester (DAP), polyimide resin (PI), thermosetting resins such as trimeric cyanamide, polyamide (PA), polycarbonate (PC), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polyphenylene sulfide (PPS), polyethylene terephthalate (PETP), polybutylene terephthalate (PBT), polyphenylene oxide (PPO), thermoplastic resins such as polyacrylic ester, and nitrocellulose (CN), the functional stuffing of chloroprene rubber etc.
(5) economic benefit is obvious.Above-mentioned advantage shows that this patent can obviously improve the physical and chemical performance of microcrystal muscovite filler, increases substantially and strengthens the plastics of being filled, the performances such as intensity of rubber item, widens its industrial application, and makes its obvious increment; Simultaneously, this patent technology is convenient, and production cost is cheaper.Thereby this patent can produce tangible economy and society benefit.
Four, description of drawings
Accompanying drawing 1: the infrared absorpting light spectra (IR) of aminosilane (KH-550);
Accompanying drawing 2: the X-ray powder crystal diffraction analysis (XRD) of somewhere, Sichuan microcrystal muscovite (measuring unit: Chengdu University of Technology material engineering experimental center; Laboratory apparatus: Japanese Rotafiex D/max C type x x ray diffractometer x of science; Experiment condition: CuK α radiation, the filtering of Ni sheet, operating voltage 35KV, electric current are 25mA, sweep velocity is 4deg/min);
Accompanying drawing 3: the infrared absorpting light spectra (IR) of somewhere, Sichuan microcrystalline white mica powder (600 order);
Accompanying drawing 4: the thermal analysis curve of somewhere, Sichuan microcrystal muscovite (measuring unit: advanced material of construction Sichuan Province key lab of Xinan Science and Technology Univ.);
Accompanying drawing 5: the scanning electronic microscope (SEM) of somewhere, Sichuan microcrystal muscovite is analyzed (measuring unit: Chengdu University of Technology material engineering experimental center);
Accompanying drawing 6: the unmodified microcrystal muscovite powder (600 order) of different mass and loading level and the viscosity changing conditions thereof of aminosilane KH-550 surface modification of microcrystalline white mica powder body (600 order) in white oil.
Five, embodiment
Example 1:
A kind of preparation method of amine silane surface modified micro crystal isinglass active filler (600 order).The microcrystal muscovite powder sample that this example adopted originates from super-huge microcrystal muscovite mineral deposit, somewhere, Sichuan.As mentioned above, this mineral deposit is at first found in 1997 by the author.In the past few years, Sichuan Xinju Mineral Resource Development Co., Ltd and the scientific and technical personnel of Chengdu University of Technology have done certain work with regard to aspects such as Sichuan microcrystal muscovite ore type, chemical ingredients, mineralogical composition, structure construction and ore dressing experiments, and have succeeded in developing varigrained prosperous torch board microcrystal muscovite powder product series such as 200 orders, 325 orders, 400 orders, 600 orders, 800 orders, 1250 orders and 2500 orders in view of the above.The varigrained microcrystal muscovite sample of all examples of this patent is all taken from the prosperous torch board microcrystalline white mica powder of institute of Sichuan Xinju Mineral Resource Development Co., Ltd process for processing, and its Chemical Composition and physical and chemical performance are as shown in Table 1 and Table 2.
The chemical ingredients (%) of somewhere, table 1 Sichuan microcrystalline white mica powder
| SiO 2 | Al 2O 3 | K 2O | Fe 2O 3 | MgO | Na 2O | CaO | TiO 2 | MnO | P 2O 5 |
| 45.7 | 30.51 | 11.63 | 2.50 | 1.65 | 0.12 | 0.59 | 0.07 | 0.09 | 0.03 |
Annotate: this table draws the product description from Sichuan Xinju Mineral Resource Development Co., Ltd
The physical and chemical performance of somewhere, table 2 Sichuan microcrystalline white mica powder
Annotate: this table draws the product description from Sichuan Xinju Mineral Resource Development Co., Ltd
The author adopts X-ray powder crystal diffraction analysis (XRD, Fig. 2), infrared absorption spectrum (IR, Fig. 3), heat analyze (DTA-TG, Fig. 4) and scanning electronic microscope (SEM, Fig. 5) wait technological method, the microcrystalline white mica powder sample used to this example carried out test analysis.The result shows that prosperous torch board microcrystalline white mica powder mainly is made up of microcrystal muscovite, and contains mineral such as a small amount of quartz, celedonite and micro-feldspar; The mineral of microcrystal muscovite are many types of to be 2M
1, its crystal all is fine lamellar crystal, and particle diameter is less than 10 μ m, general 1～5 μ m, average 5.5 μ m, the average 0.8 μ m of thickness, the radius-thickness ratio value is little, and is average 6.9, has typical " crystallite " feature.
In addition, this patent has carried out infrared absorption spectrum analysis to aminosilane (KH-550) coupling agent that example adopted (IR, Fig. 1), its feature is identical with the standard spectrogram.
This example is a raw material with 600 purpose microcrystal muscovite powders, adopts heated at high speed to mix (kneading) machine and dry surface modification technology, and its specific embodiment is:
(1) oven dry material: microcrystal muscovite powder material is dried under 110 ℃ of constant temperatures in heating unit, remove whole adsorption moistures in the material.It is definite that drying time should be done wet situation according to material, generally at 3 hours;
(2) take by weighing material: take by weighing the microcrystal muscovite powder oven dry material of certainweight, certain particle size, and the material that takes by weighing is packed in the mixing kettle of modified device heated at high speed mixing machine by the operational requirement of this equipment;
(3) prepared and diluted agent: adopting ethanol content is that 90% industrial spirit is as the amino silicane coupling agent thinner.And thinner pH value is adjusted to 3～7 with Glacial acetic acid, be beneficial to the hydrolysis of coupling agent;
(4) take by weighing coupling agent: weight is in microcrystal muscovite powder material: the ratio of aminosilane (KH-550)=100: 1.1～1.6 (1.4) claims (amount) to get a certain amount of aminosilane (KH-550) coupling agent.The calculating consumption of aminosilane (KH-550) and amount ranges (%) are as shown in table 3;
The consumption (wt%) of table 3 aminosilane (KH-550) coupling agent in the microcrystalline white mica powder surface modification
| Microcrystal muscovite granularity (order) | 200 | 325 | 400 | 600 | 800 | 1250 | 2500 |
| Specific surface area (m 2/cm 3) *Aerated density (g/cm 3) *Coupling agent calculates consumption (%) **Coupling agent amount ranges (%) | 0.60 0.36 0.47 0.5-0.7 | 0.80 0.24 0.94 0.9-1.3 | 1.0-1.4 | 1.00 0.25 1.13 1.1-1.6 | 1.20 0.23 1.47 1.5-2.1 | 2.10 0.22 2.70 2.5-3.8 | 2.59 0.20 3.65 3.5-5.0 |
Annotate: (1) "
*" data draw from Sichuan Xinju Mineral Resource Development Co., Ltd's product description (table 2); (2) "
*" data are according to formula (1) W=(W
1* S
1)/S
2Result calculated, wherein W
1=100g, S
1=specific surface area (m
2/ cm
3)/aerated density (g/cm
3), S
2=354m
2/ g
(5) preparation surface-modifying agent: will measure the mixing diluents of aminosilane (KH-550) coupling agent and preparation, the volume ratio of the two is 1: 3, and stirs, and promptly obtains aminosilane (KH-550) surface-modifying agent of being prepared.It should be noted that aminosilane (KH-550) surface modification solution should promptly join i.e. usefulness, influence result of use to prevent chemical reaction;
(6) add surface-modifying agent: will mix amine silane surface modified dose is sprayed in the microcrystal muscovite powder material in the mixing kettle uniformly with atomizer.Powder material should manually constantly be stirred, so that properties-correcting agent is evenly distributed therebetween, in powder material;
(7) high-speed mixing material: set the surface modification temperature, open the heated at high speed mixing machine, make powder material high-speed mixing (the powerful stirring) 30～90 minutes under 90～130 ℃ of conditions.Therebetween, under the less situation of powder material, shut down once (15 minutes) at regular intervals, in time mixing kettle wall, the powder that covers adhesion is swept mixing kettle, makes surface-modifying agent and powder uniform mixing;
(8) drying of modification material: by the time after the setting high-speed mixing time, take out material by operational requirement.Then, material is dry under 110 ℃ of constant temperatures in heating unit, with combining of further promotion coupling agent and mineral surface.Should determine according to the material particular case time of drying,, promptly obtain the active powder filler of amine silane surface modified microcrystal muscovite generally at 3 hours;
(9) modified effect detects: microcrystal muscovite powder material is after the amino silicane coupling agent surface modification, and its surface properties will become " oleophilic drainage " by " hydrophilic oleophobic ".Can adopt methods such as penetration time, viscosity test and Infrared spectroscopy, surface modification effect is done further detection and evaluation.
Fig. 6 is the unmodified microcrystal muscovite powder (600 order) and loading level and the viscosity changing conditions thereof of aminosilane KH-550 surface modification of microcrystalline white mica powder body (600 order) in white oil of different mass.Illustrate that the microcrystal muscovite powder has good consistency with the mineral oil nonpolar medium after aminosilane KH-550 surface modification, reached the ideal modified effect.
Example 2:
A kind of preparation method of amine silane surface modified micro crystal isinglass active filler (200 order).The features such as the place of production, mineralogical composition, chemical ingredients and mineral physics of the microcrystal muscovite filler that this example adopted (200 order) are all identical with this patent example 1; Its physical and chemical performance is as shown in table 2.
The aminosilane that this example adopted (KH-550) coupling agent, thinner etc. are all identical with this patent example 1; Its surface modification technology is also identical with this patent example 1, as shown in table 3, the consumption of different is this example coupling agent is by microcrystal muscovite powder material: aminosilane (KH-550)=100: 0.5～0.7, the calculating consumption of aminosilane (KH-550) and amount ranges (%) are as shown in table 3.
This example adopts and example 1 same procedure, and surface modification effect is characterized and estimates, and shows to have reached the ideal surface modification effect.
Example 3:
A kind of preparation method of amine silane surface modified micro crystal isinglass active filler (325 order).The features such as the place of production, mineralogical composition, chemical ingredients and mineral physics of the microcrystal muscovite filler that this example adopted (325 order) are all identical with this patent example 1; Its physical and chemical performance is as shown in table 2.
The aminosilane that this example adopted (KH-550) coupling agent, thinner etc. are all identical with this patent example 1; Its surface modification technology is also identical with this patent example 1, as shown in table 3, the weight of this example connection agent that different is is by microcrystal muscovite powder material: aminosilane (KH-550)=100: 0.9～1.3, the calculating consumption of aminosilane (KH-550) and amount ranges (%) are as shown in table 3.
This example adopts and example 1 same procedure, and surface modification effect is characterized and estimates, and shows to have reached the ideal surface modification effect.
Example 4:
A kind of preparation method of amine silane surface modified micro crystal isinglass active filler (400 order).The features such as the place of production, mineralogical composition, chemical ingredients and mineral physics of the microcrystal muscovite filler that this example adopted (400 order) are all identical with this patent example 1; Its physical and chemical performance is as shown in table 2.
The aminosilane that this example adopted (KH-550) coupling agent, thinner etc. are all identical with this patent example 1; Its surface modification technology is also identical with this patent example 1, as shown in table 3, the weight of different is this example coupling agent is by microcrystal muscovite powder material: aminosilane (KH-550)=100: 1.0～1.4, the calculating consumption of aminosilane (KH-550) and amount ranges (%) are as shown in table 3.
This example adopts and example 1 same procedure, and surface modification effect is characterized and estimates, and shows to have reached the ideal surface modification effect.
Example 5:
A kind of preparation method of amine silane surface modified micro crystal isinglass active filler (800 order).The features such as the place of production, mineralogical composition, chemical ingredients and mineral physics of the microcrystal muscovite filler that this example adopted (800 order) are all identical with this patent example 1; Its physical and chemical performance is as shown in table 2.
The aminosilane that this example adopted (KH-550) coupling agent, thinner etc. are all identical with this patent example 1; Its surface modification technology is also identical with this patent example 1, as shown in table 3, the weight of different is this example coupling agent is by microcrystal muscovite powder material: aminosilane (KH-550)=100: 1.5～2.1, the calculating consumption of aminosilane (KH-550) and amount ranges (%) are as shown in table 3.
This example adopts and example 1 same procedure, and surface modification effect is characterized and estimates, and shows to have reached the ideal surface modification effect.
Example 6:
A kind of preparation method of amine silane surface modified micro crystal isinglass active filler (1250 order).The features such as the place of production, mineralogical composition, chemical ingredients and mineral physics of the microcrystal muscovite filler that this example adopted (1250 order) are all identical with this patent example 1; Its physical and chemical performance is as shown in table 2.
The aminosilane that this example adopted (KH-550) coupling agent, thinner etc. are all identical with this patent example 1; Its surface modification technology is also identical with this patent example 1, as shown in table 3, the weight of different is this example coupling agent is by microcrystal muscovite powder material: aminosilane (KH-550)=100: 2.5～3.8, the calculating consumption of aminosilane (KH-550) and amount ranges (%) are as shown in table 3.
This example adopts and example 1 same procedure, and surface modification effect is characterized and estimates, and shows to have reached the ideal surface modification effect.
Example 7:
A kind of preparation method of amine silane surface modified micro crystal isinglass active filler (2500 order).The features such as the place of production, mineralogical composition, chemical ingredients and mineral physics of the microcrystal muscovite filler that this example adopted (2500 order) are all identical with this patent example 1; Its physical and chemical performance is as shown in table 2.
The aminosilane that this example adopted (KH-550) coupling agent, thinner etc. are all identical with this patent example 1; Its surface modification technology is also identical with this patent example 1, as shown in table 3, the weight of different is this example coupling agent is by microcrystal muscovite powder material: aminosilane (KH-550)=100: 3.5～5.0, the calculating consumption of aminosilane (KH-550) and amount ranges (%) are as shown in table 3.
This example adopts and example 1 same procedure, and surface modification effect is characterized and estimates, and shows to have reached the ideal surface modification effect.
Express one's thanks to
This work is Sichuan Province's applied basic research fund (03JY029-026-1) and state natural sciences fund (40472028; 40272029) subsidize.
Claims (2)
1, a kind of amine silane surface modified micro crystal isinglass active filler and preparation method thereof is a raw material with the microcrystal muscovite powder, adopts heated at high speed mixing machine and dry surface modification technology, it is characterized in that:
A, oven dry material adopt drying plant oven dry microcrystal muscovite powder material, dry under 110 ℃ of conditions, and drying time is generally at 3 hours;
B, take by weighing material, take by weighing microcrystal muscovite powder material, and material is packed in the heated at high speed mixing machine mixing kettle by the operational requirement of this equipment;
C, prepared and diluted agent, with ethanol content be 90% industrial spirit as thinner, and thinner pH value is adjusted to 3～7 with Glacial acetic acid;
D, take by weighing coupling agent, amount is by microcrystal muscovite powder material: the ratio of aminosilane (KH-550)=100: 0.5～5, and a certain amount of aminosilane (KH-550) coupling agent got in title (amount);
E, preparation surface-modifying agent are measured the mixing diluents of aminosilane (KH-550) coupling agent and preparation, and the volume ratio of the two is 1: 3, and stirs;
F, adding surface-modifying agent, amine silane surface modified dose of mixing are sprayed in the interior microcrystal muscovite powder material of mixing kettle uniformly;
G, high-speed mixing material are set the surface modification temperature, open high-speed mixer, make powder material high-speed mixing 30～90 minutes under 90～130 ℃ of conditions;
The drying of H, modification material, the mixed material of heated at high speed are dry under 110 ℃ of conditions in heating unit, and promptly obtain amine silane surface modified microcrystal muscovite active powder filler generally at 3 hours time of drying.
2, the preparation method of the micro crystal isinglass active filler of a kind of aminosilane according to claim 1 (KH-550) surface modification is characterized in that:
A, said aminosilane (KH-550), full name is the gamma-aminopropyl-triethoxy-aminosilane, molecular formula is C
3H
6(NH
2) Si (OC
2H
5)
3
B, for the varigrained micro crystal isinglass active filler series product of aminosilane (KH-550) surface modification, aminosilane (KH-550) with respect to the percentage consumption of microcrystal muscovite is respectively: 200 orders, 0.5～0.7%; 325 orders, 0.9～1.3%; 400 orders, 1.0～1.4%; 600 orders, 1.1～1.6%; 800 orders, 1.5～2.1%; 1250 orders, 2.5～3.8%; 2500 orders, 3.5～5.0%;
C, this preparation method are suitable equally for garrulous mica, sericite, illitic surface modification.
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