CN102532597A - 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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- CN102532597A CN102532597A CN2010106039897A CN201010603989A CN102532597A CN 102532597 A CN102532597 A CN 102532597A CN 2010106039897 A CN2010106039897 A CN 2010106039897A CN 201010603989 A CN201010603989 A CN 201010603989A CN 102532597 A CN102532597 A CN 102532597A
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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.
Background technology
Halloysite (halloysite) is a kind of nano silicone Barbiturates clay mineral.The basic structural unit of halloysite is claimed halloysite nanotubes, and being curled under natural condition by kaolinic lamella forms, and is micro-tube shaped structure, and chemical constitution is identical with kaolinite, has 1: 1 identical SiO
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 is curled by a plurality of kaolin lamellas and forms, and is natural many walls type nanotube, and O.D.T. 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, excellent in chemical and thermostability, the more important thing is that the halloysite mineral wealth are extremely abundant, cheap, and therefore, using for tool provides wide prospect.For example, Chinese patent CN1746216 discloses the method that a kind of halloysite nanotubes is used to prepare polymer composites.At first halloysite is carried out surface treatment with silane coupling agent, then halloysite of handling well and polymkeric substance are carried out the melt blending granulation, with injector the mixture that obtains is carried out extrusion moulding at last, obtain polymkeric substance/halloysite composite product.People such as the Judd people of South China Science & Engineering University have also carried out studying (Eur Polym J, 42 (2006) 1362-1369) to the thermal stability and the flame retardant properties of halloysite nanotubes modified polypropylene composite material.
Polynite reinforced modifier application as plastics in polymer arts is known by people.Organically-modified polynite is applied to can effectively improve in the polyamide resin physical strength and the resistance toheat of resin, referring to USP 4,739, and 007,4,810,734,5,385,776.Also can use organo montmorillonite to improve mechanical property for nonpolar polyolefin resin such as Vestolen PP 7052, referring to Chinese patent ZL 00105494.5, ZL 00104624.1.The method that polynite is carried out modification through organic intercalation agent has all been adopted in the application of above polynite in polymkeric substance, promptly all needs earlier the inorganic polynite processing that organises.And the method for using is main method with melt blending also generally; Because this method simply is easy to realize suitability for industrialized production; But because the thermotolerance of the long chain quaternary class intercalator that generally adopts at present is not good; Thermolysis taking place in the polymer melt extrusion easily, therefore can in the polymer melt course of processing, bring adverse consequencess such as variable color, generation smell, does not also have good solution at present.
Therefore, how modified montmorillonoid makes it not produce smell in physical strength and the nondiscoloration in the course of processing of stable on heating while of strengthening resin, is the present technical issues that need to address.
Summary of the invention
For solving the problem that exists in the prior art, the invention provides a kind of halloysite/montmorillonite Composite powder.Said composite powder does not contain the machine component, has good thermotolerance, and is carrying out not producing unpleasant odor in the melt blended course of processing with plastics, and nondiscoloration can make that matrix plastic has good comprehensive mechanical properties.
One of the object of the invention provides 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 preferred 25: 75～75: 25, said composite powder was prepared from the method that may further comprise the steps:
A, said polynite and water are mixed with suspension-s;
B, said halloysite and water are made into suspension-s, the montmorillonite suspension liquid that makes with step a mixes, and obtains mixed solution;
C, with the mixed solution spraying drying that step b makes, make said halloysite/montmorillonite Composite powder.
Above-described halloysite and polynite are in the 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 inorganic nano-particle composite powder that need not organise and handle; This powder does not contain the machine component, has good thermotolerance; Owing to do not contain long chain quaternary class organic intercalation agent, therefore carrying out not producing unpleasant odor in the melt blended course of processing with plastics.
Two of the object of the invention provides the preparation method of a kind of halloysite/montmorillonite Composite powder.
Comprise following steps:
A, said polynite and water are mixed with suspension-s;
B, said halloysite and water are made into suspension-s, and the montmorillonite suspension liquid that makes with step a mixes, and obtains mixed solution;
C, with the mixed solution spraying drying that step b makes, make said halloysite/montmorillonite Composite powder.
The mutual isolated state of flaky montmorillonite layer and piped halloysite nanotubes particle is to be determined by its preparation process in the inorganic nano-particle composite powder of the present invention.The present invention is through mixing montmorillonite slurry and halloysite slurries under liquid state; Make flaky montmorillonite layer and piped halloysite nanotubes particle in water, keep isolating mutually the dispersive state; Spray-dried then, can be fixed up fast through the mutual isolation dispersive state that the water rapid drying in the suspension-s is made montmorillonite layer and halloysite nanotubes.
In the concrete operations:
The concentration of the suspension-s of step a generally is about 5～20%wt to add polynite and fully still can keep flowability to be advisable after the dispersion; In order to make polynite abundant swelling in water, peel off, can preferably leave standstill montmorillonite suspension liquid, time of repose is more than the week, more preferably leaves standstill 7～15 days;
The concentration of the suspension-s of step b also to add the dust trachelospermum jasminoide and fully still can keep flowability to be advisable after the dispersion, generally is about 5～40%wt;
Polynite and water are mixed with certain density suspension-s in advance through the high-shear dispersion machine; Equally also halloysite and water are mixed with certain density suspension-s in advance through the high-shear dispersion machine; Getting the montmorillonite suspension liquid that configures in needed ratio then carries out slurries with halloysite suspension-s and mixes; To be mixed evenly after, prepare through spray-dired method.Formulated suspension can adopt that existing various whipping devices, emulsifying device carry out in the prior art, preferred high-shear dispersion machine.The same prior art of said spray-dired parameter condition can be adjusted as the case may be, realizes that rapid drying gets final product.
Wherein water can adopt zero(ppm) water, deionized water, preferred deionized water.
Three of the object of the invention provides the application of a kind of halloysite/montmorillonite Composite powder in preparation reinforced plastics.
The present invention adopts the spacer of inorganic nano clay halloysite as montmorillonite layer; Prepare a kind of inorganic nano-particle composite powder that need not organise and handle; This powder does not contain the machine component, has good thermotolerance; Can be used for improving the rigidity of resin, under identical addition, have than add independent polynite or add halloysite separately and have improved comprehensive mechanical performance.Add 1～20%wt that umber generally can be matrix plastic; Preferred 3～10%wt owing to do not contain long chain quaternary class organic intercalation agent, is therefore carrying out in the melt blended course of processing with plastics; Having and do not produce unpleasant odor, is a kind of mechanical property properties-correcting agent of ideal thermoplastic resin.
Embodiment
Below in conjunction with embodiment, further specify the present invention.
Embodiment 1:
Sodium-based montmorillonite (production of chemical plant, Qinghe, Zhangjiakou, Hebei) 1000 grams are mixed with 19000 milliliters of concentration by 5wt% of water; (FLUKO produces, model FA90 through the high-shear dispersion machine; Rotating speed is 3000 rpms) dispersed with stirring 1 hour and placing 7 days; So that polynite is abundant swelling in water, peel off.And then single pass high-shear dispersion machine disperses to obtain stable sheet interlayer and fully peels off suspension-s.With halloysite (Danjiangkou, Hubei natural resources kaolin ltd) 1000 gram and 19000 milliliters of halloysite suspension-s that were configured to 5wt% through high-shear dispersion machine (the same) dispersed with stirring in 1 hour of water.Suspension-s 1330 gram of getting scattered polynite and halloysite suspension-s 70 restrain promptly by 95: 5 proportionings of dry weight separately and mix; (FLUKO produces, model FA25 with the laboratory high-shearing dispersion emulsifying machine; Rotating speed is 10000 commentaries on classics/PMs) rotating speed stirred 30 minutes; Spraying in spray drying experiment device (QP-3X model, Beijing northization are ground petrochemical industry designing institute and produced), the inlet temperature of spray-dryer is 150 ℃; Temperature out is 60 ℃, and in cyclonic separator, collecting and obtaining obtaining after the drying polynite and halloysite part by weight is 95/5 1# composite powder.
Embodiment 2:
The preparation of montmorillonite suspension liquid and halloysite suspension-s is with embodiment 1; Difference only is that the time of repose of montmorillonite suspension liquid is 10 days; Getting montmorillonite suspension liquid 1050 gram and halloysite suspension-s 350 restrains promptly by 75: 25 proportionings of dry weight separately and mixes; All the other are identical with embodiment 1, and spray-dried polynite and the halloysite part by weight of obtaining is 75/25 2# composite powder.
Embodiment 3:
The preparation of montmorillonite suspension liquid and halloysite suspension-s is with embodiment 1; Getting montmorillonite suspension liquid 700 gram and halloysite suspension-s 700 restrains promptly by 50: 50 proportionings of dry weight separately and mixes; All the other are identical with embodiment 1, and spray-dried polynite and the halloysite part by weight of obtaining is 50/50 3# composite powder.
Embodiment 4
The preparation of montmorillonite suspension liquid and halloysite suspension-s is with embodiment 1; Difference only is that the time of repose of montmorillonite suspension liquid is 12 days; Getting montmorillonite suspension liquid 350 gram and halloysite suspension-s 1050 restrains promptly by 25: 75 proportionings of dry weight separately and mixes; All the other are identical with embodiment 1, and spray-dried polynite and the halloysite part by weight of obtaining is 25/75 4# composite powder.
Embodiment 5:
The preparation of montmorillonite suspension liquid and halloysite suspension-s is with embodiment 1; Difference only is that the time of repose of montmorillonite suspension liquid is 15 days; Getting montmorillonite suspension liquid 70 gram and halloysite suspension-s 1330 restrains promptly by 5: 95 proportionings of dry weight separately and mixes; All the other are identical with embodiment 1, and spray-dried polynite and the halloysite part by weight of obtaining is 5/95 5# composite powder.
Embodiment 6:
Adopting prepared polynite of embodiment 2 and halloysite part by weight is 75/25 2# composite powder and polypropylene powder (blue star group Plant of Tianjin Petrochemical Company 3
#Material, melt flow rate(MFR) 3.0-5.9g/10min), antioxidant 1010 and 168 (Switzerland vapour Ba Jiaji produces, the two mix use) mix with 1/1 part by weight, its concrete weight percentage consists of: Vestolen PP 7052 95%wt, 2# composite powder 5%wt, antioxidant 1010/168 mixtures that other sneaks in Vestolen PP 7052 and compound powder gross weight is 100 part of 0.2 weight part; In high speed agitator, mixed one minute; With PolylabOs twin screw extrusion system (length-to-diameter ratio 25: 1, diameter 16mm) the blend granulation of the U.S. thermoelectric Haake company, each section of forcing machine temperature is respectively 190 ℃, 200 ℃; 200 ℃; 200 ℃, 200 ℃, 195 ℃ (head temperature).Through mold pressing and adopt machine-tooled method to process the standard batten, the performance that obtains composite powder RPP plastics through test is listed in the table 1 with pellet.
Embodiment 7:
With polynite prepared among the embodiment 3 and halloysite part by weight is that 50/50 3# composite powder replaces the 2# composite powder among the embodiment 6; With polypropene blended preparation RPP; Each component ratio and processing, sample preparation condition are all identical with embodiment 6, and the test result of sample is listed in the table 1.
Embodiment 8:
With polynite prepared among the embodiment 4 and halloysite part by weight is that 25/75 4# composite powder replaces the 2# composite powder among the embodiment 6; With polypropene blended preparation RPP; Each component ratio and processing, sample preparation condition are all identical with embodiment 6, and the test result of sample is listed in the table 1.
Comparative example 1:
100 parts of polypropylene powders used among the embodiment 6 and 0.2 part of mixing granulation of oxidation inhibitor are extruded, processed identically with embodiment 6 with the sample preparation condition, the test result of sample is listed in the table 1.
Comparative example 2:
Get montmorillonite suspension liquid 1400 gram, all the other are identical with embodiment 1, spray-driedly obtain pure polynite powder.Prepared pure polynite powder is replaced the 2# composite powder among the embodiment 6, and with polypropene blended preparation RPP, each component ratio and processing, sample preparation condition are all identical with embodiment 6, and the test result of sample is listed in the table 1.
Comparative example 3:
Get halloysite suspension-s 1400 gram, all the other are identical with embodiment 1, spray-driedly obtain pure halloysite powder.Prepared pure halloysite powder is replaced the 2# composite powder among the embodiment 6, and with polypropene blended preparation RPP, each component ratio and processing, sample preparation condition are all identical with embodiment 6, and the test result of sample is listed in the table 1.
Table 1
Mechanical performance data can be found out from table; Adopt prepared polynite under different part by weight consumptions, can both well improve polypropene impact-resistant performance and heat-drawn wire with the composite powder of halloysite; Can also make simultaneously Vestolen PP 7052 obtain favorable rigidity, thereby make matrix plastic have good comprehensive performances.When polynite and halloysite are present in (being 2#, 3#, 4#) in the composite powder simultaneously; The shock resistance of PP composite material, thermal property compare pure polynite or pure halloysite all will more be improved; But also possess rigidity preferably simultaneously, when being described, dust trachelospermum jasminoide and polynite exist to have synergistic effect to improving polyacrylic performance.Shown in embodiment 6, weight ratio polynite/halloysite is 75/25 composite powder at addition is can make the shock strength of virgin pp improve 36% 5% time, and flexural strength improves 13%, and modulus in flexure improves 21%, and heat-drawn wire improves 6 ℃.In addition, because prepared composite powder of the present invention does not contain the machine component, so its thermotolerance is good, in the course of processing, does not produce peculiar smell, is a kind of ideal polymkeric substance reinforced modifier.
Claims (8)
1. halloysite/montmorillonite Composite powder includes halloysite and polynite, and the weight ratio of wherein said halloysite and polynite is 5: 95～95: 5, and said composite powder is prepared from the method that may further comprise the steps:
A, said polynite and water are mixed with suspension-s;
B, said halloysite and water are made into suspension-s, the montmorillonite suspension liquid that makes with step a mixes, and obtains mixed solution;
C, with the mixed solution spraying drying that step b makes, make said halloysite/montmorillonite Composite powder.
2. halloysite as claimed in claim 1/montmorillonite Composite powder is characterized in that:
The weight ratio of said halloysite and polynite is 25: 75～75: 25.
3. method for preparing halloysite/montmorillonite Composite powder according to claim 1 or claim 2 comprises following steps:
A, said polynite and water are mixed with suspension-s;
B, said halloysite and water are made into suspension-s, and the montmorillonite suspension liquid that makes with step a mixes, and obtains mixed solution;
C, with the mixed solution spraying drying that step b makes, make said halloysite/montmorillonite Composite powder.
4. the method for preparing halloysite/montmorillonite Composite powder as claimed in claim 3 is characterized in that:
Said 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 said montmorillonite suspension liquid, halloysite suspension-s, adopt the high dispersive shears to disperse.
6. the method for preparing halloysite/montmorillonite Composite powder as claimed in claim 3 is characterized in that:
Montmorillonite suspension liquid concentration is 5～20%wt among the step a;
The halloysite suspension concentration is 5～40%wt among the step b.
7. the method for preparing halloysite/montmorillonite Composite powder as claimed in claim 3 is characterized in that:
Polynite and water leave standstill more than the week after being mixed with suspension-s among the step a.
8. according to claim 1 or claim 2 halloysite/montmorillonite Composite powder is in the application of preparation in the reinforced plastics.
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| CN105603553A (en) * | 2015-11-03 | 2016-05-25 | 江苏擎宇化工科技有限公司 | Preparation method of HNTs, method used for preparing high polymer/HNTs mixed solution from HNTs, and method used for preparing high polymer nanofiber from high polymer/HNTs mixed solution |
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| CN105603553A (en) * | 2015-11-03 | 2016-05-25 | 江苏擎宇化工科技有限公司 | Preparation method of HNTs, method used for preparing high polymer/HNTs mixed solution from HNTs, and method used for preparing high polymer nanofiber from high polymer/HNTs mixed solution |
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| CN109694449A (en) * | 2017-10-20 | 2019-04-30 | 天津城建大学 | With mesoporous and micropore netted galapectite-montmorillonite Composite aerogel material and preparation method thereof |
| CN109988339A (en) * | 2018-01-03 | 2019-07-09 | 天津城建大学 | With mesoporous and micropore mesh carbon nanotube-montmorillonite Composite aerogel material and preparation method thereof |
| CN109912841A (en) * | 2019-01-25 | 2019-06-21 | 合肥工业大学 | A kind of additive and preparation method thereof and the composite material comprising the additive |
| CN109912841B (en) * | 2019-01-25 | 2021-07-16 | 合肥工业大学 | Additive, preparation method thereof and composite material containing additive |
| CN113512308A (en) * | 2020-04-09 | 2021-10-19 | 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 |
| 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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