CN1831049A - Method for producing compound and modified quartz powder by using aluminate ester and methyl acryloxyl silicane - Google Patents
Method for producing compound and modified quartz powder by using aluminate ester and methyl acryloxyl silicane Download PDFInfo
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- CN1831049A CN1831049A CN 200510021672 CN200510021672A CN1831049A CN 1831049 A CN1831049 A CN 1831049A CN 200510021672 CN200510021672 CN 200510021672 CN 200510021672 A CN200510021672 A CN 200510021672A CN 1831049 A CN1831049 A CN 1831049A
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Abstract
This invention relates to a technique method of compound modification powder quartz of aluminic acid couplant and gamma- methyl acryloyl oxygen group propyl lumiflavin oxygen group silicane, it belongs to mineral materials field. The two materials are used as modifier, the couplant is complex modified by mutual enwind and crosslinked action of the two materials. Comparing to the modified conite by single material of the two, the compatibility, processing fluidity and dispersibility of complex modified conite to organic polymer can be obviously improved, and the mechanical capability of filling things can also be largely improved. The ultra-red absorbing spectrum of the modified conite indicates that aluminic acid ester and gamma- methyl acryloyl oxygen group propyl lumiflavin oxygen group silicane have been couple activated with conite powder material.
Description
One, technical field
The present invention relates to adopt the processing method of aluminate coupling agent and the composite modified konilite of a kind of methacryloxy silane coupling agent.Utilize the dry process mechanical force and chemical modification, prepare the active konilite of high-quality functional stuffing, belong to the mineral material field.Suitable middle and high shelves filler and the whitening agent of making epoxy resin encapsulating material and matrix materials such as rubber, plastics, coating and nylon of the modification konilite product of the present invention's preparation is significantly improved the over-all properties of matrix material.
Two, technical background
Powder quartz ore is a kind of flint mineral deposit of natural output, a kind of novel silicon raw material that forms by microlitic quartzite weathering [Yu Zhiwei coats with lacquer little roc, Hu Xiaoping etc. western powder quartz ore development and use researchs [J]. and Chinese non-metallic mineral industry is led, 2002, (3)].China's powder quartz ore aboundresources, according to incompletely statistics, only ground powder quartz ore prospective reservess such as Jiangxi, Hunan and Guizhou just reach 1.5 hundred million tons of [Mu Guodong, Shi Nicheng, the horse Zhe is living etc. the reactive behavior research [J] of konilite under different curing conditions. and silicate circular, 2002, (1)].Konilite has a series of good physicochemical property, at many industrial circles wide application prospect is arranged.The konilite structural formula is SiO
2, be white in color, canescence or yellowish white, the general 2～10um of granularity, 50～75 ° of whiteness are neutral, and Mohs' hardness is 7, density 2.55～2.65g/cm
3, unit weight 1.96g/ml, pH are 6.3,1730 ℃ of refractoriness [Yu Zhiwei, Deng Huiyu. a kind of infant industry raw mineral materials-konilite [J]. Chinese non-metallic mineral industry periodical, 1999, (1)].Its chemical ingredients is slightly variant according to the place of production, general SiO
2All more than 98%, impurity has Fe to content
2O
3, Al
2O
3, CaO, MgO, K
2O, Na
2O, TiO
2Deng, do not contain Mn, Cu etc. and cause aging element and poisonous elements such as Pb, As, Hg, other micronutrient levels all is near or below detection limit, do not contain crystal water [Yu Zhiwei. the application [J] of konilite filler in the vulcanite goods. nonmetalliferous ore, 2001,24 (2)].
Natural powdery quartz is during directly as the organism filler, unsatisfactory in many cases, mainly be because affinity is poor between konilite and the macromolecular material, disperse uneven when making filler, even it is agglomerating, quality product there is considerable influence, thereby is necessary konilite is carried out surface modification, make it to become filler with reactive behavior.Surface modification is by changing the original surface properties (lipophilicity of mineral filler, oil absorbency, wetting property, mixture viscosity etc.), reach the affinity of improving mineral filler and organic polymer, consistency and processing fluidity and dispersiveness, improve the bonding force between filler and the polymer phase interface, the over-all properties that makes matrix material is to be significantly improved, and increase loading level, the purpose that reduces production costs, thereby the mineral filler that makes NOT-function change into functional stuffing [Yu Zhiwei. mineral filler modified technique research [J]. chemical industry mineral and processing, 2001 (4); Yang Huaming. the preparation of active konilite and application [J]. nonmetalliferous ore, 2002,25 (5); Yu Zhiwei. konilite Research on Surface Modification [J]. inorganic chemicals industry, 1999,31 (1)].
The konilite surface modification is that konilite character is optimized, and opens up new Application Areas, improves one of the effective way of new industrial value and added value and most important technology.The modification konilite is as the high-quality functional stuffing, to affinity, consistency and processing fluidity and the dispersiveness of improving konilite filler and organic polymer, improve the bonding force between konilite filler and the polymer phase interface, increase loading level, reduce production costs, and the advantage of performance konilite mineral products resource, the economic technology value of raising product etc. are all significant.The modification konilite have broad application prospects at industrial circles such as epoxy resin encapsulating material and rubber, plastics and coating [Yu Zhiwei. konilite modification and effect research [J]. nonmetalliferous ore, 1999,22 (4)].
Character, means and the purpose of pressing modifying function are different, and the method that is used for the non-metallic minerals stuffing surface modification at present can be divided into surface chemical modification, mechanical-chemical modification, surface active and coating and handle four classes.Chemical modification method is to utilize surface-modifying agent and mineral surface generation chemical reaction, perhaps in mineral surface generation chemisorption, makes polymer substance or other organism cover mineral surface, thereby changes the surface chemical property of mineral or mineral powder.Mechanical-chemical modification, comprise through pulverize, grind, friction etc. and act on the surfactivity that strengthens powder particle, make that molecular lattice is subjected to displacement, interior can the increase, particle temperature raises, the local fusion or thermolysis, the active powder surface that is produced is easy to react or adhewsive action with other material, that is changed crystalline structure, solubility property (surperficial amorphization), chemisorption and the reactive behavior (increase surfactivity point or active group) etc. of particle surface to a certain extent, thereby reach the purpose of change surface properties.In fact, mechanical-chemical modification has two layers of meaning: at first, in the superfine grinding process of mineral, the interaction energy of mechanical stress activates the mineral grain surface, and the surface crystal structure and the physicochemical property of mineral are changed, thereby realizes modification; Its two, utilize activation and consequent ion and the radical of mechanical stress to the mineral grain surface, cause polymer monomer in the particle surface polymerization, or make lipid acid and other surface-modifying agent adhere to and realize modification at particle surface generation highly effective reaction.Obviously, the mechanical-chemical modification method provides more useful condition for modifying process, so modification efficiency height, effective.Mechanical-chemical modification is a kind of independently method of modifying, also can regard as the realization of chemical modification method and promotion means [Zheng Shuilin. powder surface modification [M]. Beijing: Chinese building material industry press, 2003].Surface active is to use chemical reaction or high-energy physical action to change the inferior component of mineral kingdom surface layer, gives mineral surface with new functional group, and the basic crystalline structure of mineral is not touched in the process, and the powder behind surface active can show the function that makes new advances.It is to adopt multiple means such as brushing, spraying, electroplating chemical vapour deposition, chemical precipitation reaction and ionic membrane coating that coating is handled, make mineral surface coating last layer or several layers of novel substance, be coated on mineral surface he plant the surface property that the material film can change mineral, thereby give mineral with new technology physics performance or decoration functions [Xu Zesheng, Yang Qiaowen, Wang Xinguo etc. Pingxiang, Jiangxi konilite characteristic reaches the research [J] as loading material of rubber. mineral products comprehensive utilization, 1998, (1)].Contrast above-mentioned four kinds of method of modifying, surface chemical modification be present powder quartz ore powder surface modification main method [Chen Quanshui. konilite surface modification and effect research [J] thereof. nonmetalliferous ore, 2001,24 (2); Yu Zhiwei. konilite modification and effect research [J]. nonmetalliferous ore, 1999,22 (4)].And mechanical-chemical modification combines mechanical stress effect and the surface-modifying agent chemical action at powder surface, thereby the specific surface chemical modification has certain advantage; In addition, apparent surface's activation method and coating facture, the mechanical-chemical modification technology is easy, and cost is lower, and konilite is had more specific aim.Therefore, this patent utilizes the mechanical-chemical modification method to carry out surface modification for the powder quartz ore powder.
At present, the properties-correcting agent that is used for powder quartz ore powder surface modification have silane series coupling agent, aluminic acid ester series coupling agent, titanic acid ester series coupling agent etc. [Chen Quanshui. konilite surface modification and effect research [J] thereof. nonmetalliferous ore, 2001,24 (2); Yang Huaming, Tan Dingqiao, Tran Duc Luong etc. the preparation of active konilite and application [J]. nonmetalliferous ore, 2002,25 (5); Li Jintao, Lin Jinhui. the sign of konilite surface modification and effect thereof [J]. nonmetalliferous ore, 2004,27 (3)].By retrieval, do not find to adopt the patent application or the bibliographical information of aluminate coupling agent and γ-composite modified konilite processing method of methacryloxypropyl trimethoxy silane coupling agent.
Three, summary of the invention
The objective of the invention is, a kind of constructional feature that fully utilizes aluminate coupling agent and a kind of methacryloxy silane coupling agent is provided, by mutual winding and crosslinked action between aluminate coupling agent and the methacryloxy silane coupling agent konilite is carried out composite modified processing method, prepare the active konilite of high-quality functional stuffing.Because the interaction between aluminate coupling agent and the methacryloxy silane coupling agent, solved the simple few situation of group of twining with the polymer macromolecule chain in the system during with the methacryloxy silane coupling agent, thereby can under the situation that reduces methacryloxy silane coupling agent consumption, guarantee the mechanical property and the processing characteristics of infill system.The related gordian technique of the art of this patent scheme has: (1) coupling agent kind and consumption; (2) processing method of composite coupler modification konilite.
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, and is various in style, the type complexity.Wherein more with the kind of silane, aluminic acid ester, three kinds of coupling agent series of titanic acid ester, use also the widest.
The coupling agent breed selection except that the modified effect of considering coupling agent itself, also will be considered the industrial application and the Financial cost of modified product, and composite factor such as easy to operate.At present, the properties-correcting agent that is used for powder quartz ore powder surface modification has single silane coupling agent, single aluminate coupling agent, single titanate coupling agent, silane series coupling agent to make up with titanate coupling agent.Because the methacryloxy silane coupling agent can be applicable to multiple thermoplasticity and thermosetting resin, can increase substantially the dried hygrometric state bending strength of plastics, ultimate compression strength, mechanical property and hygrometric state electric properties such as shearing resistance, and improve wetting property and the dispersiveness of filler in polymkeric substance, and the methacryloxy silane coupling agent is at vibrin, suitability and specific aim in Resins, epoxy and the PE film, this patent adopt a kind of methacryloxy silane coupling agent-γ-methacryloxypropyl trimethoxy silane as to one of properties-correcting agent of konilite mineral stuffing surface modification.Consider that γ-methacryloxypropyl trimethoxy silane coupling agent price is higher, make the modification cost improve.Therefore, this patent adopts the cheaper aluminate coupling agent of price as second kind of properties-correcting agent to konilite mineral stuffing surface modification, with γ-compound use of methacryloxypropyl trimethoxy silane coupling agent.Compare with γ-methacryloxypropyl trimethoxy silane coupling agent, titanate coupling agent, aluminate coupling agent has tangible viscosity reduction effect to powder quartz ore powder filler/organism dispersion system except having price advantage.By twining mutually and crosslinked action between aluminate coupling agent and the γ-methacryloxypropyl trimethoxy silane coupling agent, promptly by the C in the aluminate coupling agent
3H
7In γ after O-group and the hydrolysis-methacryloxypropyl trimethoxy silane coupling agent-the OH radical reaction, thereby take place to twine konilite is carried out surface modification with crosslinked action mechanism, on the basis that reduces the modification cost, prepare the active konilite of high-quality functional stuffing, its filling over-all properties in organic polymer is had clear improvement.
Determining of coupling agent consumption 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
1The mineral filler weight (g) of-desire modification;
S
1Specific surface area (the m of-mineral filler
2/ g);
S
2The minimum parcel area (m of-coupling agent
2/ g);
But, just its theoretical consumption that calculates by above-mentioned formula (formula 1).During practical application, owing to be subjected to the influence of factors such as mineral filler crystal habit, surface characteristic, crystal chemistry, the actual amount of coupling agent and theoretical consumption have certain difference.The actual amount of coupling agent is generally 0.50～3.0% of mineral filler weight.This patent determines that the method for coupling agent actual amount is: earlier by utilizing above-mentioned formula (formula 1) to calculate its theoretical consumption, observation and test analysis are verified theoretical consumption and are revised by experiment again, the actual amount of the coupling agent that filters out at last, promptly the aluminate coupling agent of different grain size konilite and the total consumption of the methacryloxy silane coupling agent weight percent that accounts for the konilite consumption is respectively: 0.7～1.0% of 400 order konilites, 0.9～1.3% of 600 order konilites, 1.1～1.5% of 800 order konilites, 1.8～2.6% of 1250 order konilites.
2. the processing method of composite coupler modification konilite
The present invention adopts the processing method of aluminic acid ester and the composite modified konilite of methacryloxy silane, and following processing step is arranged:
(1) konilite is carried out preheating and drying, time of drying 60min, 90～110 ℃ of drying temperatures.
(2) be 1.0 ‰ of konilite consumption by ammonia volume, ammoniacal liquor: the ratio preparation modified additive of water=1: 3.
(3) by aluminate coupling agent and the total consumption of methacryloxy silane composite coupler account for konilite weight percent 0.7～2.6% take by weighing coupling agent, and press aluminate coupling agent: methacryloxy silane coupling agent=1: 1, coupling agent: dehydrated alcohol: the ratio preparation coupling agent diluent of water=1: 2: 1.
(4) will be set by step (1) preparation konilite put into ball mill, add the modified additive ammonia soln of (2) preparation set by step, the coupling agent diluent that adds (3) dilution preparation set by step simultaneously carries out mechanical-chemical modification, modification time 60min, 100～120 ℃ of modification temperatures.
(5) will be set by step the modification konilite discharging of (4) preparation, and remove aggregated particles in the modified powder with sub-sieve.
The chemical general formula of the said aluminate coupling agent of above-mentioned processing step (3) is: (RO) xAl (Dn) (OCOR '), wherein Dn represents coordinating group, RO is the group with the effect of the active proton of inorganic powder surface or functional group, and COR ' is the group with the effect of superpolymer base-material.Said a kind of methacryloxy silane is γ-methacryloxypropyl trimethoxy silane, and its molecular formula is: CH
2=C (CH
3) COO (CH
2)
3Si (OCH
3)
3
With above-mentioned processing method, the modification konilite product that makes is through viscosity, activation index, mechanical property, the infrared absorption spectrum test, the result is, with accounting for system weight per-cent is that to mix the system viscosity that forms in epoxy resin E-44 be 3370～5720mPas for 65% modification konilite, activation index is 96.2～99.8%, in the modification konilite: polyethylene: polyethylene wax=20g: 20g: the mechanical property of the goods of 0.5g ratio preparation is: ultimate tensile strength 9.746～11.070MPa, breaking tenacity 7.746～11.000MPa, yield strength 9.746～10.270MPa, elongation at break 8.617～23.110%.And will account for system weight per-cent is that to mix the system viscosity that forms in epoxy resin E-44 be 12720mPas for 65% unmodified konilite, activation index is 0.0%, in unmodified konilite: polyethylene: polyethylene wax=20g: 20g: the mechanical property of the goods of 0.5g ratio preparation is: ultimate tensile strength 7.542～8.181MPa, breaking tenacity 7.507～8.038MPa, yield strength 7.507～8.818MPa, elongation at break 9.369～12.240%; With accounting for system weight per-cent is that to mix the system viscosity that forms in epoxy resin E-44 be 4410～7780mPas for the konilite of 65% the single aluminate coupling agent of usefulness (coupling agent consumption 0.5～2.0%) modification, activation index is 80.5～99.0%, in single aluminate coupling agent modification konilite: polyethylene: polyethylene wax=20g: 20g: the mechanical property of the goods of 0.5g ratio preparation is: ultimate tensile strength 7.577～8.582MPa, breaking tenacity 7.577～8.115MPa, yield strength 7.865～8.118MPa, elongation at break 8.886～11.970%; With accounting for system weight per-cent is that to mix the system viscosity that forms in epoxy resin E-44 be 3000～4200mPas for 65% the single γ of the usefulness-konilite of methacryloxypropyl trimethoxy silane coupling agent (coupling agent consumption 0.5～2.0%) modification, activation index is 95.4～99.7%, in the coupling agent modified konilite of single γ-methacryloxypropyl trimethoxy silane: polyethylene: polyethylene wax=20g: 20g: the mechanical property of the goods of 0.5g ratio preparation is: ultimate tensile strength 9.847～10.480MPa, breaking tenacity 9.847～10.440MPa, yield strength 9.847～10.480MPa, elongation at break 13.100～25.050%.Compare with unmodified konilite raw material, the modification konilite product of the present invention's preparation and affinity, consistency and processing fluidity and the dispersiveness of organic polymer have obtained tangible improvement, and the mechanical property of filled articles also is significantly improved.Viscosity, activation index, the mechanical property of the modification konilite product of the present invention preparation obviously is better than utilizing the konilite product of single aluminate coupling agent modification, and coupling agent modified konilite is suitable with utilizing γ-methacryloxypropyl trimethoxy silane.Utilize aluminate coupling agent and γ-composite modified konilite of methacryloxypropyl trimethoxy silane coupling agent, owing to twine mutually and crosslinked action between aluminate coupling agent and the γ-methacryloxypropyl trimethoxy silane coupling agent, solved the simple few situation of group of twining with the polymer macromolecule chain in the system during with γ-methacryloxypropyl trimethoxy silane coupling agent, thereby can under the situation that reduces γ-methacryloxypropyl trimethoxy silane coupling agent consumption, guarantee the mechanical property and the processing characteristics of infill system.Simultaneously, in the infrared absorption spectrum of the modification konilite product of the present invention's preparation, 1090cm
-1～1125cm
-1And 1682cm
-1～1689cm
-1New absorption peak has appearred in the wave-number range, show aluminic acid ester and γ-methacryloxypropyl trimethoxy silane coupling agent in some way with konilite powder material generation coupling activation.
Four, embodiment
Following examples further specify the present invention, but do not limit the present invention.
Embodiment 1:
The present invention adopts the processing method of a kind of aluminate coupling agent and γ-composite modified konilite of methacryloxypropyl trimethoxy silane coupling agent (400 order), and its processing step is as follows:
(1) 400 order konilites are carried out preheating and drying, time of drying 60min, 100 ℃ of drying temperatures.
(2) be 1.0 ‰ of konilite consumption by ammonia volume, ammoniacal liquor: the ratio preparation modified additive of water=1: 3.
(3) be 0.7% to take by weighing coupling agent by aluminate coupling agent and γ-total consumption of methacryloxypropyl trimethoxy silane coupling agent by the weight percent that accounts for the konilite consumption, and press the aluminic acid ester: γ-methacryloxypropyl trimethoxy silane=1: 1, coupling agent: dehydrated alcohol: the ratio preparation coupling agent diluent of water=1: 2: 1.
(4) will be set by step the konilite of (1) preparation put into ball mill, add the modified additive ammonia soln of (2) preparation set by step, to adjust the surface potential of konilite.The coupling agent diluent that adds (3) preparation set by step simultaneously carries out mechanical-chemical modification, modification time 60min, 110 ℃ of modification temperatures.
(5) will be set by step the modification konilite discharging of (4) preparation, and remove aggregated particles in the modified powder with sub-sieve.
With above-mentioned processing step, the modification konilite product (400 order) that makes is through viscosity, wetting property, activation index, mechanical property, the infrared absorption spectrum test, the result shows, with accounting for system weight per-cent is that to mix the system viscosity that forms in epoxy resin E-44 be 3370mPas for 65% modification konilite, activation index is 97.5%, in the modification konilite: polyethylene: polyethylene wax=20g: 20g: the mechanical property of the goods of 0.5g ratio preparation is: ultimate tensile strength 10.220MPa, breaking tenacity 10.210MPa, yield strength 10.008MPa, elongation at break 15.000%.And will account for system weight per-cent is that to mix the system viscosity that forms in epoxy resin E-44 be 12720mPas for 65% unmodified konilite (400 order), activation index is 0.0%, in unmodified konilite: polyethylene: polyethylene wax=20g: 20g: the mechanical property of the goods of 0.5g ratio preparation is: ultimate tensile strength 7.944MPa, breaking tenacity 7.858MPa, yield strength 7.929MPa, elongation at break 10.830%.With accounting for system weight per-cent is that to mix the system viscosity that forms in epoxy resin E-44 be 4720mPas for 65% konilite (400 order) product that utilizes single aluminate coupling agent (coupling agent optimum amount 1.2%) modification, activation index is 89.5%, in utilizing single aluminate coupling agent modification konilite: polyethylene: polyethylene wax=20g: 20g: the mechanical property of the goods of 0.5g ratio preparation is: ultimate tensile strength 7.961MPa, breaking tenacity 7.894MPa, yield strength 8.077MPa, elongation at break 10.250%.With accounting for system weight per-cent is that to mix the system viscosity that forms in epoxy resin E-44 be 3870mPas for 65% konilite (400 order) product that utilizes single γ-methacryloxypropyl trimethoxy silane coupling agent (coupling agent optimum amount 1.5%) modification, activation index is 96.6%, in utilizing the coupling agent modified konilite of single γ-methacryloxypropyl trimethoxy silane: polyethylene: polyethylene wax=20g: 20g: the mechanical property of the goods of 0.5g ratio preparation is: ultimate tensile strength 10.260MPa, breaking tenacity 10.250MPa, yield strength 10.250MPa, elongation at break 22.380%.Compare with unmodified konilite raw material, the modification konilite product of the present invention's preparation and affinity, consistency and processing fluidity and the dispersiveness of organic polymer have obtained tangible improvement, and the mechanical property of filled articles also is significantly improved.Viscosity, activation index, the mechanical property of the modification konilite product of the present invention's preparation obviously is better than utilizing the konilite product of single aluminate coupling agent (coupling agent optimum amount 1.2%) modification, and suitable with the konilite that utilizes single γ-methacryloxypropyl trimethoxy silane coupling agent (coupling agent optimum amount 1.5%) modification.Simultaneously, in the infrared absorption spectrum, 1090cm
-1～1125cm
-1And 1682cm
-1～1689cm
-1New absorption peak has appearred in the wave-number range, show aluminic acid ester and γ-methacryloxypropyl trimethoxy silane coupling agent in some way with konilite powder material generation coupling activation.
This modification konilite product can be used as the middle and high shelves filler and the whitening agent of epoxy resin encapsulating material and matrix materials such as rubber, plastics, coating and nylon.
Embodiment 2:
The present invention is the processing method of a kind of employing aluminate coupling agent and the composite modified konilite of γ-methacryloxypropyl trimethoxy silane (600 order), its raw material, coupling agent kind and proportioning, modified additive type and proportioning, preparation method are similar to embodiment 1, but the konilite of modification is 600 orders, and aluminate coupling agent and γ-total consumption of methacryloxypropyl trimethoxy silane coupling agent is 1.0% of a konilite consumption.The modification konilite product (600 order) that makes is through viscosity, wetting property, activation index, mechanical property, infrared absorption spectrum test, the result shows, with accounting for system weight per-cent is that to mix the system viscosity that forms in epoxy resin E-44 be 3880mPas for 65% modification konilite, activation index reaches 98.8%, in the modification konilite: polyethylene: polyethylene wax=20g: 20g: the mechanical property of the goods of 0.5g ratio preparation is: ultimate tensile strength 10.270MPa, breaking tenacity 10.270MPa, yield strength 10.270MPa, elongation at break 18.470%.And will account for system weight per-cent is that to mix the system viscosity that forms in epoxy resin E-44 be 12720mPas for 65% unmodified konilite (600 order), activation index is 0.0%, in unmodified konilite: polyethylene: polyethylene wax=20g: 20g: the mechanical property of the goods of 0.5g ratio preparation is: ultimate tensile strength 8.181MPa, breaking tenacity 7.971MPa, yield strength 8.181MPa, elongation at break 12.240%.With accounting for system weight per-cent is that to mix the system viscosity that forms in epoxy resin E-44 be 4410mPas for 65% konilite (600 order) product that utilizes single aluminate coupling agent (coupling agent optimum amount 1.4%) modification, activation index is 98.5%, in utilizing single aluminate coupling agent modification konilite: polyethylene: polyethylene wax=20g: 20g: the mechanical property of the goods of 0.5g ratio preparation is: ultimate tensile strength 8.282MPa, breaking tenacity 8.115MPa, yield strength 8.248MPa, elongation at break 10.740%.With accounting for system weight per-cent is that to mix the system viscosity that forms in epoxy resin E-44 be 3820mPas for 65% konilite (600 order) product that utilizes single γ-methacryloxypropyl trimethoxy silane coupling agent (coupling agent optimum amount 1.8%) modification, activation index is 98.8%, in utilizing the coupling agent modified konilite of single γ-methacryloxypropyl trimethoxy silane: polyethylene: polyethylene wax=20g: 20g: the mechanical property of the goods of 0.5g ratio preparation is: ultimate tensile strength 10.360MPa, breaking tenacity 10.320MPa, yield strength 10.320MPa, elongation at break 21.150%.Compare with unmodified konilite raw material, the modification konilite product of the present invention's preparation and affinity, consistency and processing fluidity and the dispersiveness of organic polymer have obtained tangible improvement, and the mechanical property of filled articles also is significantly improved.Viscosity, activation index, the mechanical property of the modification konilite product of the present invention's preparation obviously is better than utilizing the konilite product of single aluminate coupling agent (coupling agent optimum amount 1.4%) modification, and suitable with the konilite that utilizes single γ-methacryloxypropyl trimethoxy silane coupling agent (coupling agent optimum amount 1.8%) modification.Simultaneously, in the infrared absorption spectrum, 1090cm
-1～1125cm
-1And 1682cm
-1～1689cm
-1New absorption peak has appearred in the wave-number range, show aluminic acid ester and γ-methacryloxypropyl trimethoxy silane coupling agent in some way with konilite powder material generation coupling activation.
This modification konilite product can be used as the middle and high shelves filler and the whitening agent of epoxy resin encapsulating material and matrix materials such as rubber, plastics, coating and nylon.
Claims (6)
1. the processing method of an aluminate coupling agent and the composite modified konilite of a kind of methacryloxy silane coupling agent, it is characterized in that fully utilizing the constructional feature of aluminate coupling agent and methacryloxy silane coupling agent, by twining mutually and crosslinked action between aluminate coupling agent and the methacryloxy silane coupling agent, adopt the dry process mechanical force and chemical method to carry out composite modified to konilite.Under the situation that reduces methacryloxy silane coupling agent consumption, guarantee the mechanical property and the processing characteristics of its infill system.
2. the technology of an aluminate coupling agent and the composite modified konilite of a kind of methacryloxy silane coupling agent, its feature has following processing step:
(1) konilite is carried out preheating and drying, time of drying 60min, 90～110 ℃ of drying temperatures.
(2) be 1.0 ‰ of konilite consumption by ammonia volume, ammoniacal liquor: the ratio preparation modified additive of water=1: 3.
(3) by aluminate coupling agent and the total consumption of methacryloxy silane composite coupler account for konilite weight percent 0.7～2.6% take by weighing coupling agent, and press aluminate coupling agent: methacryloxy silane coupling agent=1: 1, coupling agent: dehydrated alcohol: the ratio preparation coupling agent diluent of water=1: 2: 1.
(4) will be set by step (1) preparation konilite put into ball mill, add the modified additive ammonia soln of (2) preparation set by step, the coupling agent diluent that adds (3) preparation set by step simultaneously carries out mechanical-chemical modification, modification time 60min, 100～120 ℃ of modification temperatures.
(5) will be set by step the modification konilite discharging of (4) preparation, and remove aggregated particles in the modified powder with sub-sieve.
3. the described konilite modified technique of konilite method of modifying according to claim 1 and claim 2, the chemical general formula that it is characterized in that said aluminate coupling agent is: (RO) xAl (Dn) (OCOR '), wherein Dn represents coordinating group, RO is the group with the effect of the active proton of inorganic powder surface or functional group, and COR ＇ is the group with the effect of superpolymer base-material.Described a kind of methacryloxy silane is γ-methacryloxypropyl trimethoxy silane, and its molecular formula is: CH
2=C (CH
3) COO (CH
2)
3Si (OCH
3)
3
4. the described konilite modified technique of konilite method of modifying according to claim 1 and claim 2, when it is characterized in that the composite modified konilite of aluminate coupling agent and γ-methacryloxypropyl trimethoxy silane coupling agent, the weight percent that the aluminate coupling agent of different grain size konilite and γ-total consumption of methacryloxypropyl trimethoxy silane coupling agent accounts for the total consumption of konilite is respectively: 0.7～1.0% of 400 order konilites, 0.9～1.3% of 600 order konilites, 1.1～1.5% of 800 order konilites, 1250 purpose konilites 1.8～2.6%.
5. the described konilite modified technique of konilite method of modifying according to claim 1 and claim 2, after it is characterized in that aluminate coupling agent and γ-composite modified konilite of methacryloxypropyl trimethoxy silane coupling agent, the affinity of modification konilite product and organic polymer, consistency and processing fluidity and dispersiveness have obtained tangible improvement, and the mechanical property of filled articles improves a lot.With accounting for system weight per-cent is that to mix the system viscosity that forms in epoxy resin E-44 be 3370～5720mPas for 65% modification konilite, activation index is 96.2～99.8%, in the modification konilite: polyethylene: polyethylene wax=20g: 20g: the mechanical property of the goods that the 0.5g ratio is prepared is: ultimate tensile strength 9.746～11.070MPa, breaking tenacity 7.746～11.000MPa, yield strength 9.746～10.270MPa, elongation at break 8.617～23.110%.
6. the described konilite modified technique of konilite method of modifying according to claim 1 and claim 2, after it is characterized in that aluminate coupling agent and γ-composite modified konilite of methacryloxypropyl trimethoxy silane coupling agent, in the infrared absorption spectrum of modification konilite product, 1090cm
-1～1125cm
-1And 1682cm
-1～1689cm
-1New absorption peak has appearred in the wave-number range, show aluminic acid ester and γ-methacryloxypropyl trimethoxy silane coupling agent in some way with konilite powder material generation coupling activation.
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