CN101054466A - Super branched polyamine/montmorillonite/graphite nano composite material and preparation thereof - Google Patents
Super branched polyamine/montmorillonite/graphite nano composite material and preparation thereof Download PDFInfo
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- CN101054466A CN101054466A CN 200710017938 CN200710017938A CN101054466A CN 101054466 A CN101054466 A CN 101054466A CN 200710017938 CN200710017938 CN 200710017938 CN 200710017938 A CN200710017938 A CN 200710017938A CN 101054466 A CN101054466 A CN 101054466A
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- polynite
- graphite
- hyperbranched polyurethane
- montmorillonite
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Abstract
The invention provides a producing material of a hyperbranched poly(amine-ester)/montmorillonite/graphite nano compound material, including mixing the hyperbranched poly(amine-ester) and modified montmorillonite with a mass ratio of 1:0.1-1:0.6, adding the initiator 1-3% to the hyperbranched poly(amine-ester) monomer mass, blending for 3-6 hours at 100-120 DEG C constant temperature, getting hyperbranched poly(amine-ester)/montmorillonite compound; then adding nano graphite powder, 1-6% to the hyperbranched poly(amine-ester), blending by machine for 3-6 hours, getting hyperbranched poly(amine-ester)/montmorillonite/graphite nano compound material. The inventive compound material plays the advantages of the hyperbranched poly(amine-ester), montmorillonite and nano graphite, and has the rigidity of the mineral and a good processability, thermal conductivity, electrical conductivity properties of the organic macromolecule.
Description
Technical field
The invention belongs to technical field of composite materials, relate to a kind of polymer-montmorillonoid/graphite nanometer composite material, particularly a kind of hyperbranched polyurethane/polynite/graphite nanometer composite material and preparation thereof.
Background technology
Hyperbranched polymer be last century the eighties just begin the type material that grows up.Because the close packed structure of its height and approaching perfectly geometric configuration make it become new research direction in the fields such as topology, biology, materialogy.Hyperbranched polymer also is that a class is three-dimensional, the novel high polymer of high-sequential, compare with traditional polymer, this family macromolecule can design its bulk of molecule, shape, 26S Proteasome Structure and Function group when synthetic as required, on molecular level, give strict control, the general symmetry height of product, monodispersity is good, thereby has potential use widely.The hyperbranched dendrimer of higher algebraically has three-dimensional symmetric class globosity, and dispersion coefficient is near 1, molecular memory is at the cavity that can hold nanoparticle, a large amount of active functional groups are carried in the molecule outside, both can fetter nanoparticle, and can realize the dissolving of quantum dot in water again, increase its biocompatibility, can also carry quantum dot other material is carried out mark, perhaps be directly used in the assembling of nano-cluster.
Polynite belongs to 2: 1 type layered silicates, and each unit cell is carried a silica octahedron secretly by two tetrahedrons and constituted, and connects with shared Sauerstoffatom between the two, and every layer thickness is 1nm, has very high rigidity; Interlamellar spacing is 1nm, and tetrahedral sheet in the crystal layer and octahedral sheet can be substituted by extensive isomorph, as the Si in the tetrahedron
4+By Al
3+, Fe
3+Substitute the Al in the octahedron
3+By Mg
2+, Fe
2+, Ni
2+, Zn
2+, Mn
2+Substitute, make a layer inner surface belt negative charge.So hydrated cation (Na
+, K
+, Ca
2+, Mg
2+) can occupy interlamination region with the superfluous negative charge that neutralizes.Polynite has very strong ion-exchange capacity, and loading capacity (CEC) is generally between 80-150mmol/100g.
Because a large amount of mineral ions are arranged between cheating engaging layer, so organic compound is thin property, utilize the interchangeability of metal ion between cheating engaging layer, from the exchange metal ion, make organ-mmt with organic sun.The polynite of handling through organising increases the cheating engaging layer spacing because the bigger organic cation of volume has exchanged original metal ion, is covered by organic cation because of the montmorillonite layer surface simultaneously, and polynite becomes lipophilicity by wetting ability.So the polynite of handling through organising and the organic polymer or the organic micromolecule compound of intercalation have had good affinity, like this organic compound more easily intercalation enter between cheating engaging layer.
Nano-graphite is the more inorganic nonmetallic nanometer material of a kind of Recent study.It possesses excellent chemical stability, heat conduction, conduction, the self-lubricating property of common graphite on the one hand, at self-lubricating material, and antifriction, aspects such as fire extinguishing flame-proof composite material and field emmision material have all embodied good effect.
Summary of the invention
The objective of the invention is to utilize the special construction and the performance of hyperbranched polyurethane, polynite and Nano graphite, a kind of hyperbranched polyurethane/polynite/graphite nanometer composite material of performance optimization is provided.
Another object of the present invention provides the preparation method of a kind of hyperbranched polyurethane/polynite/graphite nanometer composite material.
The preparation method of hyperbranched polyurethane/polynite of the present invention/graphite nanometer composite material is to be finished by following processing step:
1. the mass ratio of the organo montmorillonite after a certain amount of hyperbranched polyurethane and the modification with 1: 0.1～1: 0.5 mixed, the toluenesulphonic acids that adds hyperbranched polyurethane quality 1～3% again in mixture is an initiator, stirred 3～6 hours in 100 ℃～120 ℃ following constant temperature, obtain hyperbranched polyurethane/montmorillonite composite;
2. the Nano graphite powder that adds hyperbranched polyurethane quality 1～6% carried out mechanical stirring 3～6 hours, promptly got hyperbranched polymer/polynite/graphite nanometer composite material.
Described hyperbranched polyurethane is N, and N-dihydroxy ethyl-3-amido methyl propionate monomer can make with following method: diethanolamine and the methyl acrylate mol ratio with 1: 1 is dissolved in the methyl alcohol, at N
2Protection is warming up to 30～40 ℃ down behind stirring at room 30～40min, isothermal reaction 3～6h promptly.
Above-mentioned steps 1. in the modified technique of polynite as follows:
A, a certain amount of na montmorillonite is dissolved in the deionized water, stirring forms montmorillonite suspension liquid 1;
B, the properties-correcting agent cetyl trimethylammonium bromide of na montmorillonite quality 2～4% fully is dissolved in the water, solution 2;
C, step B gained solution 2 is joined in the montmorillonite suspension liquid 1 of steps A in batches, at 70～90 ℃ of following vigorous stirring 4～6h, suction filtration and water repeated washing (are not used Ag to there being chlorion
+Check has or not Cl
-1);
D, in 50～70 ℃ of following vacuum-dryings, grind, sieve montmorillonite modified.
In hyperbranched polyurethane/polynite/graphite nanometer composite material by method preparation of the present invention, hyperbranched polyurethane, polynite and graphite particle are in conjunction with tight, and polynite is dispersed in the hyperbranched polyurethane matrix with the microplate stratiform, and graphite particle is dispersed in the polymeric matrix with nano-scale; Hyperbranched polyurethane, polynite and graphite particle shared pbw in polymkeric substance is as follows:
100 parts of hyperbranched polyurethanes
10～60 parts of polynites
1～6 part of graphite particle
Hyperbranched polyurethane/polynite/the graphite nanometer composite material of the present invention's preparation, be to have particular structure and performance hyperbranched polymer as matrix, have little, the easy film forming performance of viscosity, introduce polynite and make matrix material possess the rigidity and the good workability of organic polymer of inorganics; Introduce thermostability, electroconductibility that the nano-graphite particle improves matrix material.
The preparation of matrix material of the present invention, be that montmorillonite layer is mutually compound with nanoscale with polymeric matrix, the adding nano-graphite carries out mechanical blending and gets, this intercalation blending method carries out the generation of hyperbranched polyurethane and the intercalation composite sync of polynite, simultaneously introduce the nano-graphite particle in the simplest mechanical blending mode again, simplified the Composite Preparation program greatly, shortened the preparation time of matrix material, reduce the preparation cost of matrix material, improved production efficiency.
Below with hyperbranched polyurethane N, the matrix material of N-dihydroxy ethyl-3-amido methyl propionate monomer, polynite and graphite particle preparation is an example, and by infrared spectrogram, electron diffraction photo figure, SEM photo, TG curve matrix material is tested and characterized.Test result is as follows:
Fig. 1 (a) is that hyperbranched polyurethane/polynite/graphite amplifies 2.5 * 10
4Times SEM photo figure, Fig. 1 (b) is hyperbranched polyurethane/polynite/graphite X electron diffraction photo figure.From Fig. 1 (a), can clearly be seen that, in hyperbranched polyurethane/polynite/graphite composite material system, montmorillonite layer, polymkeric substance, and graphite particle in conjunction with closely, present white, grey and black three-phase.White plates is the polynite phase, and grey form and aspect are polymkeric substance, and black is nano-graphite mutually.Montmorillonite layer dispersive in polymkeric substance is more even, but is still keeping laminated structure.The point diffraction arrangement is regular as can be seen from figure (b), and can infer has uniform laminated structure in the matrix material, and this and Fig. 1 (a) result match, and also can infer to have formed undersized nano-graphite particle in the matrix material.
Fig. 2 is the infrared spectrogram of hyperbranched polyurethane/polynite/graphite nanometer composite material.As can be seen from Figure 2, at 1047cm
-1For the charateristic avsorption band of polynite, at 513cm
-1It is the little absorption peak of interior Al-O stretching vibration of polynite and Si-O flexural vibration.At 1720cm
-1The absorption peak of carbonyl on the ester group has appearred in the place, at 3300-3500cm
-1The absorption peak of hydroxyl has appearred in the place, and this is consistent with hyperbranched polyurethane infrared spectrogram (Fig. 3) in the document, N in this proof mixture, and N-dihydroxy ethyl-3-amido methyl propionate monomer polymerization has generated hyperbranched polyurethane.Through the contrast of infrared spectrogram, and in conjunction with above analysis revealed: the product of formation is hyperbranched polyurethane/polynite/Nano graphite mixture.The existence of graphite does not have influence substantially to its infrared spectrogram in the product simultaneously.
Fig. 4 is the TG curve of hyperbranched polyurethane and hyperbranched polyurethane/polynite/graphite nanometer composite material.(curve a) temperature of initial decomposition is 70 ℃ to our pure as can be seen hyperbranched polyurethane from Fig. 4,510 ℃ of maximum heat weightless temperatures, and hyperbranched polymer/polynite/graphite nanometer composite material (curve b) temperature of initial decomposition is 140 ℃, the maximum heat weightless temperature is 575 ℃, and the matrix material thermostability increases by contrast.Its reason is: (1) has tangible restriction with nano-scale dispersive stratiform montmorillonite layer to the reactivity of polymer molecular chain in polymeric matrix, thereby makes polymer molecular chain have higher decomposition temperature in decomposes than molecular chain fully freely.In addition, because the effect of the physical crosslinking point of stratiform polynite makes to show better flame retardant properties by matrix material easier maintenance original shape when burning.(2) because the stratiform montmorillonite layer that is distributed in the polymeric matrix has good gas-liquid barrier property, when matrix material burns, the stratiform montmorillonite layer that is positioned at burning surface just can possess the ability of the inner flammable small molecules that produces because polymer molecular chain decomposes to the combustion boundary migration that intercept, thereby the carrying out of retarded combustion plays fire-retardant effect.(3) owing to have strong molecular interaction between a large amount of surface atom of nano-graphite particle and the hyperbranched polyurethane, limited the mass motion of polymer macromolecule chain, the nano-graphite particle also may cause the degree of crosslinking of polymer molecular chain to increase simultaneously.Improved the required energy of thermolysis based on above reason, promptly the thermotolerance of matrix material increases.
Fig. 5 is that hyperbranched polyurethane/polynite/graphite composite material specific conductivity is with the content of graphite variation diagram.Its electroconductibility of carbon containing electro-conductive material mainly connects into by conducting particles and constitutes between conductive network and conducting particles enough hour of distance, and electronics passes through polymer film layer and forms the common decision of conductive channel.As can be seen from the figure the specific conductivity of matrix material is in rising trend with the increase of content of graphite.This is because of the adding along with graphite, forms the conductive channel that is interconnected in polymeric matrix, has increased conductive path or has increased contact area, and specific conductivity increases thereupon.But graphite particle can not add too much, influences its electroconductibility on the contrary otherwise can take place to reunite.
Description of drawings
Fig. 1 is the transmission electron microscope photo of hyperbranched polyurethane/polynite/graphite composite material
Fig. 2 is hyperbranched polyurethane/polynite/graphite composite material infrared spectrogram
Fig. 3 is the hyperbranched polyurethane infrared spectrogram
Fig. 4 is the thermogravimetric curve figure of hyperbranched polyurethane/polynite/graphite nanometer composite material
Fig. 5 is that hyperbranched polyurethane/polynite/graphite composite material specific conductivity is with the content of graphite variation diagram
Embodiment
1, N, the N-dihydroxy ethyl-monomeric preparation of 3-amido methyl propionate: diethanolamine and the methyl acrylate mol ratio with 1: 1 is dissolved in the methyl alcohol, at N
2Protection is warming up to 30～40 ℃ down behind stirring at room 30～40min, isothermal reaction 3～6h promptly.
2, the modification of polynite:
A, a certain amount of na montmorillonite is dissolved in the deionized water, stirring forms montmorillonite suspension liquid 1;
B, the properties-correcting agent cetyl trimethylammonium bromide of na montmorillonite quality 2～4% fully is dissolved in the water, solution 2;
C, step B gained solution 2 is joined in the montmorillonite suspension liquid 1 of steps A in batches, at 70～90 ℃ of following vigorous stirring 4～6h, suction filtration and water repeated washing (are not used Ag to there being chlorion
+Check has or not Cl
-1);
D, in 50～70 ℃ of following vacuum-dryings, grind, sieve montmorillonite modified.
3, the mass ratio of the organo montmorillonite after a certain amount of hyperbranched polyurethane monomer and the modification with 1: 0.1～1: 0.6 mixed, the initiator that in mixture, adds hyperbranched polyurethane monomer mass 1～3% again, stirred 3～6 hours in 100 ℃～120 ℃ following constant temperature, obtain hyperbranched polyurethane/montmorillonite composite.
4, the Nano graphite powder that adds hyperbranched polyurethane monomer mass 1～6% carried out mechanical stirring 3～6 hours, promptly got hyperbranched polymer/polynite/graphite nanometer composite material.
In the hyperbranched polyurethane/polynite of method for preparing/graphite nanometer composite material, hyperbranched polyurethane, polynite and graphite particle are in conjunction with tight, and polynite is dispersed in the hyperbranched polyurethane matrix with the microplate stratiform, and graphite particle is dispersed in the polymeric matrix with nano-scale; Hyperbranched polyurethane, polynite and graphite particle shared pbw in polymkeric substance is as follows:
100 parts of hyperbranched polyurethanes
10～60 parts of polynites
1～6 part of graphite particle.
Claims (7)
1, the preparation method of a kind of hyperbranched polyurethane/polynite/graphite nanometer composite material is to be finished by following processing step:
1. the mass ratio of the organo montmorillonite after a certain amount of hyperbranched polyurethane monomer and the modification with 1: 0.1～1: 0.6 mixed, the initiator that in mixture, adds hyperbranched polyurethane monomer mass 1～3% again, stirred 3～6 hours in 100 ℃～120 ℃ following constant temperature, obtain hyperbranched polyurethane/montmorillonite composite;
2. the Nano graphite powder that adds hyperbranched polyurethane monomer mass 1～6% carried out mechanical stirring 3～6 hours, promptly got hyperbranched polymer/polynite/graphite nanometer composite material.
2, the preparation method of hyperbranched polyurethane/polynite according to claim 1/graphite nanometer composite material is characterized in that: described hyperbranched polyurethane monomer is N, N-dihydroxy ethyl-3-amido methyl propionate monomer.
3, as the preparation method of hyperbranched polyurethane/polynite/graphite nanometer composite material as described in the claim 2, it is characterized in that: described N, N-dihydroxy ethyl-3-amido methyl propionate monomer is to be made by following method: diethanolamine and the methyl acrylate mol ratio with 1: 1 is dissolved in the methyl alcohol, at N
2Protection is warming up to 30～40 ℃ down behind stirring at room 30～40min, isothermal reaction 3～6h vacuumizes and removes methanol solvate promptly.
4, the preparation method of hyperbranched polyurethane/polynite according to claim 1/graphite nanometer composite material is characterized in that: the modified technique of described polynite is:
1. a certain amount of na montmorillonite is dissolved in the deionized water, stirs, form montmorillonite suspension liquid 1;
2. the properties-correcting agent with na montmorillonite quality 2～4% fully is dissolved in the water, and gets solution 2;
3. with step 2. gained solution 2 join in the step montmorillonite suspension liquid 1 1. in batches, at 70～90 ℃ of following vigorous stirring 3～5h, suction filtration and water repeated washing are to there not being chlorion;
4. in 50～70 ℃ of following vacuum-dryings, grind, sieve montmorillonite modified.
5, as the preparation method of hyperbranched polyurethane/polynite/graphite nanometer composite material as described in the claim 4, it is characterized in that: described properties-correcting agent is cetyl trimethylammonium bromide.
6, the preparation method of hyperbranched polyurethane/polynite according to claim 1/graphite nanometer composite material is characterized in that: described initiator is a tosic acid.
7, the hyperbranched polyurethane/polynite/graphite nanometer composite material of the method for claim 1 preparation, it is characterized in that: hyperbranched polyurethane, polynite and graphite particle are in conjunction with tight, and polynite is dispersed in the hyperbranched polyurethane matrix with the microplate stratiform, and graphite particle is dispersed in the polymeric matrix with nano-scale; Hyperbranched polyurethane, polynite and graphite particle shared pbw in polymkeric substance is as follows:
100 parts of hyperbranched polyurethanes
10～60 parts of polynites
1～6 part of graphite particle.
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Cited By (7)
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| WO2011081659A1 (en) * | 2009-12-15 | 2011-07-07 | Massachusetts Institute Of Technology | Degradable polymer nanostructure materials |
| CN102436862A (en) * | 2011-09-08 | 2012-05-02 | 西北师范大学 | Graphene/nanometer copper electric conducting composite material and preparation thereof |
| CN103408764A (en) * | 2013-07-15 | 2013-11-27 | 中山大学 | Photo-convertible hyperbranched polymer and preparation method thereof |
| CN104231430A (en) * | 2014-08-26 | 2014-12-24 | 广东红旗家具有限公司 | Preparation method and product of stain-resistant anti-aging wood-plastic material |
| CN105694283A (en) * | 2016-02-24 | 2016-06-22 | 东莞市国贤塑胶有限公司 | High-strength PVC (polyvinyl chloride) elastomer for electromobile charging cables and preparation process thereof |
| CN110627968A (en) * | 2019-09-20 | 2019-12-31 | 中国林业科学研究院木材工业研究所 | Aqueous organic montmorillonite modifier emulsion, preparation method and application thereof |
| CN114672035A (en) * | 2022-03-18 | 2022-06-28 | 湖南工业大学 | Hyperbranched polymer delustering agent and preparation method and application thereof |
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2007
- 2007-05-19 CN CNB2007100179384A patent/CN100489031C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011081659A1 (en) * | 2009-12-15 | 2011-07-07 | Massachusetts Institute Of Technology | Degradable polymer nanostructure materials |
| CN102436862A (en) * | 2011-09-08 | 2012-05-02 | 西北师范大学 | Graphene/nanometer copper electric conducting composite material and preparation thereof |
| CN103408764A (en) * | 2013-07-15 | 2013-11-27 | 中山大学 | Photo-convertible hyperbranched polymer and preparation method thereof |
| CN103408764B (en) * | 2013-07-15 | 2015-11-25 | 中山大学 | A kind of can the hyperbranched polymer and preparation method thereof of light conversion |
| CN104231430A (en) * | 2014-08-26 | 2014-12-24 | 广东红旗家具有限公司 | Preparation method and product of stain-resistant anti-aging wood-plastic material |
| CN104231430B (en) * | 2014-08-26 | 2016-09-07 | 广东红运家具有限公司 | The preparation method of anti-soiling aging-resisting Wood-plastic material and goods |
| CN105694283A (en) * | 2016-02-24 | 2016-06-22 | 东莞市国贤塑胶有限公司 | High-strength PVC (polyvinyl chloride) elastomer for electromobile charging cables and preparation process thereof |
| CN110627968A (en) * | 2019-09-20 | 2019-12-31 | 中国林业科学研究院木材工业研究所 | Aqueous organic montmorillonite modifier emulsion, preparation method and application thereof |
| CN110627968B (en) * | 2019-09-20 | 2021-12-17 | 中国林业科学研究院木材工业研究所 | Aqueous organic montmorillonite modifier emulsion, preparation method and application thereof |
| CN114672035A (en) * | 2022-03-18 | 2022-06-28 | 湖南工业大学 | Hyperbranched polymer delustering agent and preparation method and application thereof |
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Granted publication date: 20090520 Termination date: 20110519 |