CN101041742B - Over-branched polyamine ester/lanthanum/montmorillonite nano composite material and preparation thereof - Google Patents
Over-branched polyamine ester/lanthanum/montmorillonite nano composite material and preparation thereof Download PDFInfo
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- CN101041742B CN101041742B CN200710017703A CN200710017703A CN101041742B CN 101041742 B CN101041742 B CN 101041742B CN 200710017703 A CN200710017703 A CN 200710017703A CN 200710017703 A CN200710017703 A CN 200710017703A CN 101041742 B CN101041742 B CN 101041742B
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Abstract
The invention discloses a preparing method of super branched polyamine ester/lanthanum/montmorillonite ternary nanometer composite material, which comprises the following steps: choosing super branched polyamine ester (HPAE) tree molecule as organic phase; coating rare earth particle lanthanum (La); intercalation-compositing with montmorillonite (MMT); getting the product. This product possesses good stability and even dispersion showed through tests of TEM, TGA, DSC, UV-vis and FT-IR, which can be used to produce rare earth permanent magnet material and fluorescent material.
Description
Technical field
The invention belongs to technical field of macromolecules, relate to a kind of preparation of polymer composite, relate in particular to a kind of hyperbranched polyurethane/lanthanum/Nanometer Composite Material Of Montmorillonite And Its Preparation Method.
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, can fetter nanoparticle, 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.
Hyperbranched dendrimer is a kind of good optically active space symmetric form material that has.In recent years, dendrimer and metal ion is compound, make network filled-type polymeric optical matrix material appear in the newspapers repeatly to, greatly expanded the range of application of dendrimer, but, still existing greatly limitation aspect dendrimer preparation and performance optimization, the product development, the profound level that has directly influenced branch type macromolecular compound is used.
Rare earth element has the 4fx5d16s2 electronic structure, the electricity price height, radius is big, polarization force is strong, chemical property vivaciously reach can hydrolysis etc. factor, so its application is very extensive.The application of rare earth element in matrix material mainly is character such as the light that utilizes the rare earth uniqueness, electricity, magnetic, be used as painted or help the chromogen material, and be important element or the core element that constitutes new function materials such as light, electricity, magnetic.As: preparation rare earth permanent-magnetic material, fluorescent material, magnetostriction materials, photoelectric conversion material, hydrogen storage material etc.Select for use dendrimer as template for preparing rare earth ion nano-cluster, make rare earth ion and dendrimer generation coordination, obtained being evenly distributed, thermally-stabilised good, with this new type nanocomposites of rare earth ion nano-cluster/dendrimer that nano level distributes, have broad application prospects.
In recent years, polymer/laminated compound nano matrix material has been owing to overcome the shortcoming of traditional composite organic-inorganic material, and enjoys the extensive concern of academia and industry member.For polymer/laminated compound compound system, the interfacial effect between lamellar compound and the matrix polymer is the principal element that influences composite property.Because hydrophilic lamellar compound can not disperse the dispersion of more inaccessible nano-scale equably in the non-polar polymer matrix.People have considerable time to the research of lamellar compound and intercalation chemistry, and have obtained some achievements.Compare with straight polymer or traditional in the past matrix material (microscopic dimensions), the mechanical property of stratiform polynite/polymer nanocomposites, thermal characteristics, optical property and physical and chemical performance etc. all increase significantly.
Summary of the invention
The objective of the invention is to utilize the performance such as light, electricity, magnetic of the uniqueness of special laminate structure of the special space structure of hyperbranched dendrimer and physicals, polynite and rare earth ion, providing a kind of is organic phase with hyperbranched polyurethane (HPAE) dendrimer, coat rare earth ion lanthanum (La), and take place with polynite (MMT) that intercalation is compound to be prepared into a kind of method with hyperbranched polyurethane/lanthanum/polynite (HPAE/La/MMT) ternary nano composite material of good optical property.
The present invention prepares the method for hyperbranched polyurethane/lanthanum/polynite (HPAE/La/MMT) ternary nano composite material, comprises following processing step:
1. a certain amount of hyperbranched polyurethane fully is dissolved in the dispersion medium, ultrasonic agitation is fully dissolved it;
2. slowly add 0.5～5 times of hyperbranched polyurethane quality, concentration was the inorganic lanthanum salt brine solution of 0.2～0.5mol/L, and adds the tensio-active agent of 0.015～0.03 times of hyperbranched polyurethane quality, 30～60 ℃ of following ultra-sonic dispersion reactions 4～6 hours;
3. slowly add 0.8～5 times of hyperbranched polyurethane quality to become concentration through ultra-sonic dispersion be the aqueous solution of 5%～25% organo montmorillonite, and adding the intercalator of 0.03～0.08 times of hyperbranched polyurethane quality, ultrasonic agitation was carried out intercalation compound 3～8 hours at normal temperatures;
4. the initiator that adds 0.02～0.06 times of hyperbranched polyurethane quality under agitation reacted 2～7 hours;
5. treat that solution becomes oyster white, wash, be drying to obtain hyperbranched polyurethane/lanthanum/polynite ternary nano composite material.
Dissolve better for the ease of HPAE/La, after the 1. middle hyperbranched polyurethane of step is dissolved in dispersion agent, need HPAE to be preheated to 100～120 ℃.
Hyperbranched polyurethane of the present invention is end-NH
2The base hyperbranched polyurethane, it can directly be bought from the market, also can get by following method preparation:
Adopt methyl acrylate, diethanolamine synthetic N in methanol solution earlier, N-dihydroxy ethyl-3-alanine methylmethacrylate monomer, took by weighing tetramethylolmethane and N again in 1: 20 in molar ratio, N-dihydroxy ethyl-3-alanine methylmethacrylate monomer is a solvent with methyl alcohol then, with p-methyl benzenesulfonic acid as catalyzer, stir reaction down 3～5 hours in 100～120 ℃ of constant temperature, removal of solvent under reduced pressure methyl alcohol obtains faint yellow viscous liquid, is end-NH
2The base hyperbranched polyurethane.
The dispersion medium of step in 1. can adopt ethanol or chloroform.
The inorganic lanthanum salt of step in 2. can adopt Lanthanum trichloride; Tensio-active agent can adopt polyoxyethylene glycol-400 or hexadecyl trimethyl ammonium bromide.
The 3. middle intercalator of step can use the vitriol oil or hydrogen peroxide or Potcrate.
The initiator of step in 4. is ammonium persulphate or Diisopropyl azodicarboxylate or p-methyl benzenesulfonic acid iron.
Used organo montmorillonite (MMT) among the present invention makes and adopts supersonic method that it is disperseed fully common polynite.Characteristics such as wavelength is short because ultrasonic wave has, near linear is propagated, energy is concentrated easily, it can improve polynite the chemical reaction yield, shorten the reaction times, improve the selectivity of reaction, and can also excite the chemical reaction that when not having ultrasonic wave to exist, can not take place.The present invention joins common MMT in the middle of the certain density ethanolic soln, be placed in the ultrasonic field, with the ultrasonic wave of suitable frequency and power handled and organo montmorillonite.Nano-powder is under its effect, and surface energy is weakened, can effectively prevent to reunite to make it abundant dispersion.
In the hyperbranched polyurethane/lanthanum/polynite ternary nano composite material of method preparation of the present invention, hyperbranched polyurethane, lanthanum particle and polynite are in conjunction with tight, and polynite is dispersed in the hyperbranched polyurethane matrix with the microplate stratiform, and the lanthanum particle is dispersed in the polymeric matrix with nano-scale.The mass percent of hyperbranched polyurethane, lanthanum, polynite is as follows in the matrix material:
Hyperbranched polyurethane 15～40%
Polynite 45～75%.
The present invention has been applied to the solution intercalation compounding technology in the building-up process of carrying out the HPAE/La/MMT trielement composite material.The distinguishing feature of this method is that step is simple, quick, can improve so inorganicly to be uniformly dispersed in reaction process with organic phase, efficiently solves the agglomeration traits of nanoparticle, and reaches the homodisperse of nanoscale, has simplified preparation procedure.So method of the present invention is simple to operate, production efficiency height, product have superior performance.
Owing between HPAE/La matrix and MMT disperse phase very strong interaction is arranged among the present invention, toughness, workability that abundant high strength with inorganics, high heat resistance and polymer are good combine, and have obtained the matrix material of excellent performance.Selected in addition HPAE has the good optical performance, has expanded the application of HPAE/La/MMT ternary nano composite material in the optical property field widely.
The microtexture and the physicals of the hyperbranched polyurethane/lanthanum/polynite trielement composite material of the present invention's preparation can be passed through transmission electron microscope observing, and characterize through TEM, TGA, DSC, UV-vis and FT-IR.Test result shows; rare earth ion La with the super branched molecule protection is inserted between cheating engaging layer; and distribute with nano level equably; these nanoparticles all can stably exist in the aqueous solution; has good thermostability; the thermal weight loss temperature is higher than 350 ℃, than HPAE/La binary material thermostability increase significantly (referring to Fig. 1, Fig. 3).
In the HPAE/La/MMT ternary nano composite material, can add the amount of MMT with control, measure the influence of different substances amount concentration MMT to this trielement composite material optical property.Result of study shows that by HPAE/La/MMT ternary nano composite material FT-IR contrast map analysis under the different MMT content is shown (see figure 2), different MMT content has bigger influence to the optical property of HPAE/La matrix material.In the HPAE/La mixture ,-CONH
2The weakening of stretching vibration absorption peak shows this compound-NH
2Intensive takes place with rare earth ion La and interacts in base, and-CO-NH-absorption peak is from 1670 and 1470cm
-1Move to 1731cm
-1, these significant addings that change explanation MMT are further strengthened the interaction between the HPAE/La, have formed the HPAE/La/MMT ternary nano composite material.
The tem analysis of different MMT content HPAE/La/MMT ternary nano composite materials shows (see figure 3), the polynite of different mass fractional plays a decisive role to the microscopic appearance of material, polynite content is hour (massfraction is less than 20%), rare earth ion La distributes equably, it is less to reunite, and particle diameter is 10-15nm, and along with the increase (massfraction is greater than 70%) of polynite content, the rare earth ion dispersity is relatively poor, and particle diameter increases to 30nm.
TGA contrast figure (see figure 4) by the HPAE/La/MMT ternary nano composite material, as can be seen, HPAE/La/MMT ternary nano composite material of the present invention gets nanoparticle and all can stably exist in the aqueous solution, and good thermostability is just arranged, the thermal weight loss temperature is higher than 350 ℃, increases significantly than HPAE/La binary material thermostability.Therefore, a spot of MMT can improve stability and the thermostability of HPAE/La binary material in the aqueous solution, and optical activity liquid is played significant booster action; Greatly expanded dendrimer, and the application of clay material aspect optical activity.Experimental result shows that when the content of polynite was 30%, the thermostability of this material was best.
Hyperbranched polyurethane/lanthanum/polynite trielement composite material also has stronger optical activity, the UV-Vis analysis of spectra shows (see figure 5), hyperbranched polyurethane/lanthanum/polynite trielement composite material has the last one absorption peak at the 280nm place, along with the increase of super branched molecule algebraically, the intensity of its maximum absorption band increases thereupon.One new absorption peak appears in hyperbranched polyurethane/lanthanum/polynite trielement composite material at the 370nm place, be metal La
3+Characteristic absorbance, along with the increase of super branched molecule algebraically, the intensity of maximum absorption band increases thereupon, and slight blue shift takes place, and the interaction of super branched polyurethane and polynite is described, has strengthened the optical activity of rare earth ion La.
Hyperbranched polyurethane/lanthanum/polynite the trielement composite material of the present invention's preparation is because its good thermostability and stronger optical activity can be widely used in preparing rare earth permanent-magnetic material and fluorescent material.
Description of drawings
Fig. 1 is different algebraically HPAE/La nano particle TEM contrast figure, and (a) is 2.0GHPAE/La among the figure, (b) is 3.0G HPAE/La, (b) is 4.0G HPAE/La.
Fig. 2 is different MMT content HPAE/La/MMT ternary nano composite material FT-IR comparison diagrams, and (a) is HPAE/La/5%-MMT among the figure, and (b) HPAE/La/10%-MMT (c) is HPAE/La/20%-MMT, (d) is HPAE/La/70%-MMT.
Fig. 3 is different MMT content HPAE/La/MMT ternary nano composite material TEM contrast figure, and (a) is 3.0G HPAE/La/5%-MMT among the figure, and (b) 3.0G HPAE/La/10%-MMT (c) is 3.0G HPAE/La/20%-MMT.
Fig. 4 is different MMT content HPAE/La/MMT ternary nano composite material TGA contrast figure, and (a) is HPAE/La/10%-MMT, (b) HPAE/La/30%-MMT among the figure.
Fig. 5 is different algebraically HPAE/La nano composite material UV-vis comparison diagrams, (a) 2.0GHPAE/La among the figure, and (b) 3.0G HPAE/La (c) is 4.0G HPAE/La/20%MMT, (d) is 5.0GHPAE/La.
Embodiment
The preparation of embodiment 1, hyperbranched polyurethane/lanthanum/polynite ternary nano composite material:
1. a certain amount of hyperbranched polyurethane fully is dissolved in the ethanol, adopts the ultrasonic echography stirring of 30～40KHZ that it is fully dissolved; Each material is uniformly dispersed in the mixed solution in order to make, and HPAE solution is preheated to 100～120 ℃.
2. the concentration that adds 2 times of hyperbranched polyurethane quality is the aqueous solution of 0.4mol/L Lanthanum trichloride, and adds the polyoxyethylene glycol-400 of 0.025 times of hyperbranched polyurethane quality, at 40 ℃～60 ℃ following ultrasonic agitation reaction 4～6h;
3. slowly add 1.5 times of hyperbranched polyurethane quality to become concentration through ultra-sonic dispersion be the aqueous solution of 5% organo montmorillonite, and add the vitriol oil of 0.05 times of hyperbranched polyurethane quality, ultrasonic agitation is carried out the compound 4～6h of intercalation at normal temperatures; The general ultrasonic wave intercalation that adopts 30～40KHZ.
4. the ammonium persulphate that adds 0.02 times of hyperbranched polyurethane quality continues to stir about 3～5 hours, makes the polymer monomer initiated polymerization;
5. treat that solution becomes oyster white, wash, be drying to obtain hyperbranched polyurethane/lanthanum/polynite ternary nano composite material.
The preparation of embodiment 2, hyperbranched polyurethane/lanthanum/polynite ternary nano composite material:
1. certain amount of H PAE is preheated to 100～120 ℃, fully is dissolved in the chloroform, adopt the ultrasonic echography stirring of 30～40KHZ that it is fully dissolved;
2. add 5 times of hyperbranched polyurethane quality, concentration is the aqueous solution of 0.2mol/L Lanthanum trichloride, and adds the hexadecyl trimethyl ammonium bromide of 0.03 times of hyperbranched polyurethane quality, under 50～70 ℃ without ultrasonic agitation reaction 7～9h;
3. slowly add 5 times of hyperbranched polyurethane quality to become concentration through ultra-sonic dispersion be the aqueous solution of 15% organo montmorillonite, and add the hydrogen peroxide of 0.08 times of hyperbranched polyurethane quality, ultrasonic agitation is carried out the compound 6～8h of intercalation at normal temperatures.The general ultrasonic wave intercalation that adopts 30～40KHZ.
4. the p-methyl benzenesulfonic acid iron that adds 0.06 times of hyperbranched polyurethane quality continues to stir 5～7h, makes the polymer monomer initiated polymerization;
5. treat that solution becomes oyster white, wash, be drying to obtain hyperbranched polyurethane/lanthanum/polynite ternary nano composite material.
The preparation of embodiment 3, hyperbranched polyurethane/lanthanum/polynite ternary nano composite material:
1. a certain amount of hyperbranched polyurethane fully is dissolved in the ethanol, adopts the ultrasonic echography stirring of 30～40KHZ that it is fully dissolved.Each material is uniformly dispersed in the mixed solution in order to make, and HPAE solution is preheated to 100～120 ℃.
2. add 0.5 times of hyperbranched polyurethane quality, concentration is the aqueous solution of 0.5mol/L Lanthanum trichloride, and adds the polyoxyethylene glycol-400 of 0.015 times of hyperbranched polyurethane quality, at 30～50 ℃ of following ultrasonic agitation reaction 2～4h;
3. slowly add 0.8 times of hyperbranched polyurethane quality to become concentration through ultra-sonic dispersion be the aqueous solution of 25% organo montmorillonite, and add the Potcrate of 0.035 times of hyperbranched polyurethane quality, ultrasonic agitation is carried out the compound 3～5h of intercalation at normal temperatures; The general ultrasonic wave intercalation that adopts 30～40KHZ.
4. the Diisopropyl azodicarboxylate that adds 0.02 times of hyperbranched polyurethane quality continues to stir 2～4h, makes the polymer monomer initiated polymerization;
5. treat that solution becomes oyster white, wash, be drying to obtain hyperbranched polyurethane/lanthanum/polynite ternary nano composite material.
Claims (9)
1. the preparation method of hyperbranched polyurethane/lanthanum/polynite ternary nano composite material comprises following processing step:
1. a certain amount of hyperbranched polyurethane fully is dissolved in the dispersion medium, ultrasonic agitation is fully dissolved it;
2. slowly add 0.5～5 times of hyperbranched polyurethane quality, concentration was the inorganic lanthanum salt brine solution of 0.2～0.5mol/L, and adds the tensio-active agent of 0.015～0.03 times of hyperbranched polyurethane quality, 30～60 ℃ of following ultra-sonic dispersion reactions 4～6 hours;
3. slowly add 0.8～5 times of hyperbranched polyurethane quality to become concentration through ultra-sonic dispersion be the aqueous solution of 5%～25% polynite, and adding the intercalator of 0.03～0.08 times of hyperbranched polyurethane quality, ultrasonic agitation was carried out intercalation compound 3～8 hours at normal temperatures;
4. the initiator that adds 0.02～0.06 times of hyperbranched polyurethane quality under agitation reacted 2～7 hours;
5. treat that solution becomes oyster white, wash, be drying to obtain hyperbranched polyurethane/lanthanum/polynite ternary nano composite material;
The 1. described hyperbranched polyurethane of step is to be got by following method preparation: adopt methyl acrylate, diethanolamine synthetic N in methanol solution earlier, N-dihydroxy ethyl-3-alanine methylmethacrylate monomer, took by weighing tetramethylolmethane and N again in 1: 20 in molar ratio, N-dihydroxy ethyl-3-alanine methylmethacrylate monomer, be solvent then with methyl alcohol, with p-methyl benzenesulfonic acid as catalyzer, stir reaction down 3～5 hours in 100～120 ℃ of constant temperature, removal of solvent under reduced pressure methyl alcohol, obtain faint yellow viscous liquid, be described hyperbranched polyurethane.
2. the preparation method of hyperbranched polyurethane/lanthanum as claimed in claim 1/polynite ternary nano composite material is characterized in that: after the 1. middle hyperbranched polyurethane of described step is dissolved in dispersion agent, be preheated to 100 ℃～120 ℃.
3. the preparation method of hyperbranched polyurethane/lanthanum/polynite ternary nano composite material as claimed in claim 1 or 2, it is characterized in that: the 1. described dispersion medium of step is ethanol or chloroform.
4. the preparation method of hyperbranched polyurethane/lanthanum/polynite ternary nano composite material as claimed in claim 1 or 2, it is characterized in that: the 2. described inorganic lanthanum salt of step is Lanthanum trichloride.
5. the preparation method of hyperbranched polyurethane/lanthanum/polynite ternary nano composite material as claimed in claim 1 or 2, it is characterized in that: the 2. described tensio-active agent of step is polyoxyethylene glycol-400 or hexadecyl trimethyl ammonium bromide.
6. the preparation method of hyperbranched polyurethane/lanthanum/polynite ternary nano composite material as claimed in claim 1 or 2, it is characterized in that: the 3. described intercalator of step is the vitriol oil or hydrogen peroxide or Potcrate.
7. the preparation method of hyperbranched polyurethane/lanthanum/polynite ternary nano composite material as claimed in claim 1 or 2, it is characterized in that: the 4. described initiator of step is ammonium persulphate or Diisopropyl azodicarboxylate or p-methyl benzenesulfonic acid iron.
8. according to the hyperbranched polyurethane/lanthanum/polynite ternary nano composite material of the described method of claim 1 preparation, it is characterized in that: hyperbranched polyurethane, lanthanum particle and polynite are in conjunction with tight, the lanthanum particle is dispersed in the polymeric matrix with nano-scale, and polynite is dispersed in the hyperbranched polyurethane matrix with the microplate stratiform.
9. according to the hyperbranched polyurethane/lanthanum/polynite ternary nano composite material of the described method preparation of claim 1, it is characterized in that: the mass percent of hyperbranched polyurethane, lanthanum, polynite is as follows in the trielement composite material:
Hyperbranched polyurethane 15～40%
Lanthanum 10～35%
Polynite 45～75%.
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| CN114672035A (en) * | 2022-03-18 | 2022-06-28 | 湖南工业大学 | Hyperbranched polymer delustering agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1248586A (en) * | 1999-08-06 | 2000-03-29 | 中国科学技术大学 | Radiation-curable amino superbranching polyester and preparation process thereof |
| CN1390871A (en) * | 2002-07-01 | 2003-01-15 | 北京理工大学 | Process for preparing poly (amine-ester) with superbranching of ester terminal group |
| CN1775850A (en) * | 2005-12-05 | 2006-05-24 | 西北师范大学 | Montmorillonite/rare-earth particle/polymer ternary nano composite material and its preparing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1248586A (en) * | 1999-08-06 | 2000-03-29 | 中国科学技术大学 | Radiation-curable amino superbranching polyester and preparation process thereof |
| CN1390871A (en) * | 2002-07-01 | 2003-01-15 | 北京理工大学 | Process for preparing poly (amine-ester) with superbranching of ester terminal group |
| CN1775850A (en) * | 2005-12-05 | 2006-05-24 | 西北师范大学 | Montmorillonite/rare-earth particle/polymer ternary nano composite material and its preparing method |
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