CN102532597B - Halloysite/montmorillonoid composite powder and preparation method and application thereof - Google Patents
Halloysite/montmorillonoid composite powder and preparation method and application thereof Download PDFInfo
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- CN102532597B CN102532597B CN201010603989.7A CN201010603989A CN102532597B CN 102532597 B CN102532597 B CN 102532597B CN 201010603989 A CN201010603989 A CN 201010603989A CN 102532597 B CN102532597 B CN 102532597B
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Abstract
The invention discloses halloysite/montmorillonoid composite powder and a preparation method and application of the halloysite/montmorillonoid composite powder. The composite powder contains halloysite and montmorillonoid with the weight proportion of 5:95 to 95:5. The composite powder is prepared by the method comprising the steps of: a) preparing montmorillonoid and water into a suspension; b) preparing halloysite and water into a suspension and mixing the suspension with the montmorillonoid suspension prepared by step a) to obtain a mixed solution; and c) spraying and drying the mixed solution prepared by step b) to prepare the halloysite/montmorillonoid composite powder. The composite powder provided by the invention does not contain organic components, has good heat resistance, can be used to improve the rigidity of resin, is free from objectionable odor and non-discoloring in the manufacturing process, and can be widely applied to reinforced plastics.
Description
Technical field
The present invention relates to a kind of inorganic powder, say further, relate to a kind of halloysite/montmorillonite Composite powder and its preparation method and application.
Background technology
Halloysite (halloysite) is a kind of nano silicone Barbiturates clay mineral.The basic structural unit of halloysite, claim halloysite nanotubes, by kaolinic lamella curling forming under natural condition, is micro-tube shaped structure, and chemical constitution is identical with kaolinite, has the identical SiO of 1: 1
2/ Al
2o
3ratio, laminated structure has been curled into SiO
2at skin, Al
2o
3at internal layer, so dust trachelospermum jasminoide nanotube has and SiO
2closely similar surface properties, and Al
2o
3similar internal layer character, in general halloysite nanotubes, by curling the forming of a plurality of kaolin lamellas, is natural many walls type nanotube, and the pipe external diameter is 20-100nm, and internal diameter is 5-30nm, and length is 150nm-2 μ m.Natural halloysite nanotubes has the similar hollow form structure of carbon nanotube, high specific surface area, good chemistry and thermostability, the more important thing is that the halloysite mineral wealth are extremely abundant, cheap, therefore, and for the tool application provides wide prospect.For example, Chinese patent CN1746216 discloses the method for a kind of halloysite nanotubes for the preparation of polymer composites.At first halloysite is carried out to surface treatment with silane coupling agent, then halloysite and the polymkeric substance handled well are carried out to the melt blending granulation, finally by injector, the mixture obtained is carried out to extrusion moulding, obtain polymkeric substance/halloysite composite material goods.The people such as the Judd people of South China Science & Engineering University also are studied (Eur Polym J, 42 (2006) 1362-1369) to thermal stability and the flame retardant properties of halloysite nanotubes modified polypropylene composite material.
Polynite reinforced modifier application as plastics in polymer arts is well known.Organically-modified polynite is applied to can effectively improve in polyamide resin physical strength and the resistance toheat of resin, referring to United States Patent (USP) 4,739, and 007,4,810,734,5,385,776.Also can improve mechanical property with organo montmorillonite for nonpolar polyolefin resin as polypropylene, referring to Chinese patent ZL 00105494.5, ZL 00104624.1.The application of above polynite in polymkeric substance all adopted carries out polynite the method for modification by organic intercalation agent, all need first inorganic polynite to be carried out to organic-treating.And the method for application generally also be take melt blending as main method, because the method simply is easy to realize suitability for industrialized production, but because the thermotolerance of the long chain quaternary class intercalator generally adopted at present is not good, thermolysis easily occurs in the polymer melt extrusion, therefore can in the polymer melt course of processing, bring the adverse consequencess such as variable color, generation smell, also there is no at present good solution.
Therefore, how modified montmorillonoid, make it in physical strength and the nondiscoloration in the course of processing of stable on heating while of strengthening resin, not produce smell, is the current technical issues that need to address.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of halloysite/montmorillonite Composite powder and its preparation method and application.Described composite powder does not contain organic constituent, has good thermotolerance, and, in plastics, carrying out the melt blended course of processing, does not produce unpleasant odor, and nondiscoloration, can make matrix plastic have good comprehensive mechanical property.
One of purpose of the present invention is to provide a kind of halloysite/montmorillonite Composite powder.
Include halloysite and polynite, the weight ratio of wherein said halloysite and polynite is 5: 95～95: 5, and preferably 25: 75～75: 25, described composite powder was prepared from by the method comprised the following steps:
A, described polynite and water are mixed with to suspension;
B, described halloysite and water are made into to suspension, the montmorillonite suspension liquid made with step a mixes, and obtains mixed solution;
C, the mixed solution spraying drying that step b is made, make described halloysite/montmorillonite Composite powder.
Above-described halloysite and polynite are in prior art various halloysites and the polynite without organic process.
The present invention adopts the spacer of inorganic nano clay halloysite as montmorillonite layer, prepare a kind of composite powder of the inorganic nano-particle without the need for the machine processing, this powder does not contain organic constituent, has good thermotolerance, owing to not containing long chain quaternary class organic intercalation agent, therefore in plastics, carrying out the melt blended course of processing, do not produce unpleasant odor.
Two of purpose of the present invention is to provide the preparation method of a kind of halloysite/montmorillonite Composite powder.
Comprise following steps:
A, described polynite and water are mixed with to suspension;
B, described halloysite and water are made into suspension, and the montmorillonite suspension liquid made with step a mixes, and obtains mixed solution;
C, the mixed solution spraying drying that step b is made, make described halloysite/montmorillonite Composite powder.
In inorganic nano-particle composite powder of the present invention, the state of the mutual isolation of the halloysite nanotubes particle of the montmorillonite layer of sheet and tubulose is to be determined by its preparation process.The present invention by mixing montmorillonite slurry and halloysite slurries under liquid state, make the montmorillonite layer of sheet and the halloysite nanotubes particle of tubulose keep the state that isolation disperses mutually in water, then spray-dried, the state that the mutual isolation of montmorillonite layer and halloysite nanotubes is disperseed by the water rapid drying by suspension can be fixed up fast.
In concrete operations:
The concentration of the suspension of step a, to add polynite and fully after dispersion, still can keep mobility to be advisable, generally is about 5～20%wt; In order to make polynite abundant swelling in water, peel off, can preferred standing montmorillonite suspension liquid, time of repose is more than one week, more preferably standing 7～15 days;
The concentration of the suspension of step b also, to add the dust trachelospermum jasminoide and fully after dispersion, still can keep mobility to be advisable, generally is about 5～40%wt;
Polynite and water are mixed with to certain density suspension in advance by the high-shear dispersion machine, equally also halloysite and water are mixed with to certain density suspension in advance by the high-shear dispersion machine, then getting in needed ratio the montmorillonite suspension liquid configured carries out slurries with halloysite suspension and mixes, to be mixed evenly after, by spray-dired method, prepare.Formulated suspension can adopt existing various whipping devices, emulsifying device in prior art to carry out, preferably the high-shear dispersion machine.Described spray-dired Parameter Conditions, with existing technology, can be adjusted as the case may be, realizes that rapid drying gets final product.
Wherein water can adopt distilled water, deionized water, preferably deionized water.
Three of purpose of the present invention is to provide a kind of halloysite/application of montmorillonite Composite powder in preparing reinforced plastics.
The present invention adopts the spacer of inorganic nano clay halloysite as montmorillonite layer, prepare a kind of composite powder of the inorganic nano-particle without the need for the machine processing, this powder does not contain organic constituent, has good thermotolerance, can be used for improving the rigidity of resin, under identical addition, have than adding independent polynite or adding separately halloysite and there is better comprehensive mechanical property.Add 1～20%wt that umber generally can be matrix plastic, preferred 3～10%wt, owing to not containing long chain quaternary class organic intercalation agent, therefore in plastics, carrying out the melt blended course of processing, having and do not produce unpleasant odor, is a kind of mechanical property properties-correcting agent of desirable thermoplastic resin.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment 1:
Sodium-based montmorillonite (production of chemical plant, body in Zhangjiakou Area, Hebei Province Qinghe) 19000 milliliters of concentration by 5wt% of 1000 grams and water are mixed, through the high-shear dispersion machine, (FLUKO produces, model FA90, rotating speed is 3000 rpms) dispersed with stirring 1 hour placing 7 days, so that polynite is abundant swelling in water, peel off.And then once by the high-shear dispersion machine, disperse to obtain stable sheet interlayer and fully peel off suspension.By halloysite (Danjiangkou, Hubei natural resources kaolin company limited) 1000 grams and 19000 milliliters of halloysite suspension that are configured to 5wt% through high-shear dispersion machine (the same) dispersed with stirring in 1 hour of water.Suspension 1330 grams of getting scattered polynite and halloysite suspension 70 grams mix by 95: 5 proportionings of dry weight separately, with the laboratory high-shearing dispersion emulsifying machine, (FLUKO produces, model FA25, rotating speed is 10000 turn/per minutes) rotating speed stirs 30 minutes, in spray drying experiment device (QP-3X model, Beijing North grinds petrochemical industry designing institute and produces) middle spraying, the inlet temperature of spray-dryer is 150 ℃, temperature out is 60 ℃, collects in cyclonic separator and obtains after drying obtaining the 1# composite powder that polynite and halloysite part by weight are 95/5.
Embodiment 2:
The preparation of montmorillonite suspension liquid and halloysite suspension is with embodiment 1, difference only is that the time of repose of montmorillonite suspension liquid is 10 days, getting montmorillonite suspension liquid 1050 grams and halloysite suspension 350 grams mixes by 75: 25 proportionings of dry weight separately, all the other are identical with embodiment 1, spray-driedly obtain the 2# composite powder that polynite and halloysite part by weight are 75/25.
Embodiment 3:
The preparation of montmorillonite suspension liquid and halloysite suspension is with embodiment 1, getting montmorillonite suspension liquid 700 grams and halloysite suspension 700 grams mixes by 50: 50 proportionings of dry weight separately, all the other are identical with embodiment 1, spray-driedly obtain the 3# composite powder that polynite and halloysite part by weight are 50/50.
Embodiment 4
The preparation of montmorillonite suspension liquid and halloysite suspension is with embodiment 1, difference only is that the time of repose of montmorillonite suspension liquid is 12 days, getting montmorillonite suspension liquid 350 grams and halloysite suspension 1050 grams mixes by 25: 75 proportionings of dry weight separately, all the other are identical with embodiment 1, spray-driedly obtain the 4# composite powder that polynite and halloysite part by weight are 25/75.
Embodiment 5:
The preparation of montmorillonite suspension liquid and halloysite suspension is with embodiment 1, difference only is that the time of repose of montmorillonite suspension liquid is 15 days, getting montmorillonite suspension liquid 70 grams and halloysite suspension 1330 grams mixes by 5: 95 proportionings of dry weight separately, all the other are identical with embodiment 1, spray-driedly obtain the 5# composite powder that polynite and halloysite part by weight are 5/95.
Embodiment 6:
Adopt 2# composite powder and polypropylene powder (blue star group Plant of Tianjin Petrochemical Company 3 that the prepared polynite of embodiment 2 and halloysite part by weight are 75/25
#material, melt flow rate (MFR) 3.0-5.9g/10min), (Switzerland vapour Ba Jiaji produces antioxidant 1010 and 168, the two mixes and uses with 1/1 part by weight) mix, its concrete weight percentage consists of: polypropylene 95%wt, 2# composite powder 5%wt, separately sneak into and take the antioxidant 1010 that polypropylene and compound powder gross weight be 100 part of 0.2 weight part/168 mixtures, in high speed agitator, mix one minute, PolylabOs twin-screw extrusion system (length-to-diameter ratio 25: 1 with U.S. thermoelectricity Haake company, diameter 16mm) blend granulation, each section temperature of forcing machine is respectively 190 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 195 ℃ (head temperature).By pellet, through mold pressing and adopt machine-tooled method to make the standard batten, the performance that obtains after tested composite powder Reinforced Polypropylene plastics is listed in table 1.
Embodiment 7:
The 3# composite powder that prepared polynite and halloysite part by weight are 50/50 in embodiment 3 of take replaces the 2# composite powder in embodiment 6, with polypropene blended preparation Reinforced Polypropylene, each component ratio and processing, sampling are all identical with embodiment 6, and the test result of sample is listed in table 1.
Embodiment 8:
The 4# composite powder that prepared polynite and halloysite part by weight are 25/75 in embodiment 4 of take replaces the 2# composite powder in embodiment 6, with polypropene blended preparation Reinforced Polypropylene, each component ratio and processing, sampling are all identical with embodiment 6, and the test result of sample is listed in table 1.
Comparative example 1:
100 parts of polypropylene powders used in embodiment 6 are extruded with 0.2 part of mixing granulation of oxidation inhibitor, and processing is identical with embodiment 6 with sampling, and the test result of sample is listed in table 1.
Comparative example 2:
Get montmorillonite suspension liquid 1400 grams, all the other are identical with embodiment 1, spray-driedly obtain pure polynite powder.Prepared pure polynite powder is replaced to the 2# composite powder in embodiment 6, and with polypropene blended preparation Reinforced Polypropylene, each component ratio and processing, sampling are all identical with embodiment 6, and the test result of sample is listed in table 1.
Comparative example 3:
Get halloysite suspension 1400 grams, all the other are identical with embodiment 1, spray-driedly obtain pure halloysite powder.Prepared pure halloysite powder is replaced to the 2# composite powder in embodiment 6, and with polypropene blended preparation Reinforced Polypropylene, each component ratio and processing, sampling are all identical with embodiment 6, and the test result of sample is listed in table 1.
Table 1
From table, mechanical performance data can be found out, adopt prepared polynite can well improve polypropene impact-resistant performance and heat-drawn wire from the composite powder of halloysite under different part by weight consumptions, can also make polypropylene obtain good rigidity, thereby make matrix plastic there is good over-all properties simultaneously.When polynite and halloysite are present in (being 2#, 3#, 4#) in composite powder simultaneously, the shock resistance of polypropylene composite material, thermal characteristics compare pure polynite or pure halloysite all will more be improved, but also possess rigidity preferably simultaneously, exist and there is synergistic effect to improving polyacrylic performance when dust trachelospermum jasminoide and polynite are described.As described in Example 6, weight ratio polynite/halloysite is that 75/25 composite powder is to make for 5% time the shock strength of virgin pp improve 36% at addition, and flexural strength improves 13%, and modulus in flexure improves 21%, and heat-drawn wire improves 6 ℃.In addition, the composite powder prepared due to the present invention do not contain organic constituent, so its thermotolerance is good, does not produce peculiar smell in the course of processing, is a kind of desirable enhancing by polymer properties-correcting agent.
Claims (8)
1. halloysite/montmorillonite Composite powder is characterized in that:
Described composite powder does not contain organic constituent,
Described composite powder includes halloysite and polynite, and the weight ratio of wherein said halloysite and polynite is 5: 95～95: 5, and described composite powder is prepared from by the method comprised the following steps:
A, described polynite and water are mixed with to suspension;
B, described halloysite and water are made into to suspension, the montmorillonite suspension liquid made with step a mixes, and obtains mixed solution;
C, the mixed solution spraying drying that step b is made, make described halloysite/montmorillonite Composite powder.
2. halloysite as claimed in claim 1/montmorillonite Composite powder is characterized in that:
The weight ratio of described halloysite and polynite is 25: 75～75: 25.
3. a method for preparing halloysite as claimed in claim 1 or 2/montmorillonite Composite powder comprises following steps:
A, described polynite and water are mixed with to suspension;
B, described halloysite and water are made into suspension, and the montmorillonite suspension liquid made with step a mixes, and obtains mixed solution;
C, the mixed solution spraying drying that step b is made, make described halloysite/montmorillonite Composite powder.
4. the method for preparing halloysite/montmorillonite Composite powder as claimed in claim 3 is characterized in that:
Described water is deionized water.
5. the method for preparing halloysite/montmorillonite Composite powder as claimed in claim 3 is characterized in that:
During the preparation of described montmorillonite suspension liquid, halloysite suspension, adopt the high dispersive shears to be disperseed.
6. the method for preparing halloysite/montmorillonite Composite powder as claimed in claim 3 is characterized in that:
In step a, montmorillonite suspension liquid concentration is 5～20%wt;
In step b, the halloysite suspension concentration is 5～40%wt.
7. the method for preparing halloysite/montmorillonite Composite powder as claimed in claim 3 is characterized in that:
In step a, polynite and water are mixed with after suspension standing more than one week.
8. the halloysite as claimed in claim 1 or 2/application of montmorillonite Composite powder in preparing reinforced plastics.
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| CN109912841B (en) * | 2019-01-25 | 2021-07-16 | 合肥工业大学 | Additive, preparation method thereof and composite material containing additive |
| CN113512308B (en) * | 2020-04-09 | 2022-07-05 | 中石化石油工程技术服务有限公司 | Preparation method of halloysite nanotube-surfactant composite intercalated montmorillonite fluid loss additive for drilling fluid |
| CN111825979A (en) * | 2020-07-27 | 2020-10-27 | 中国人民解放军海军工程大学 | Novel phthalonitrile resin composite material and preparation method thereof |
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