CN103467777A - Lanthanum-based organic acid montmorillonite and water phase one-step preparation technology thereof - Google Patents
Lanthanum-based organic acid montmorillonite and water phase one-step preparation technology thereof Download PDFInfo
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Abstract
The invention relates to lanthanum-based organic acid montmorillonite and a water phase one-step preparation technology thereof. The lanthanum-based organic acid montmorillonite is characterized in that: the crystal structure of the lanthanum-based organic acid montmorillonite is montmorillonite lamellar structure; part of the plurality of ionic bonds of rare earth lanthanum ions among the sheets of montmorillonite are combined with the montmorillonite sheets, and the rest of the ionic bonds are combined with acid groups of long-chain organic acids; and different organic acids are employed so as to obtain a plurality of kinds of lanthanum-based organic acid montmorillonite. According to the one-step preparation technology, Na-montmorillonite, rare earth lanthanum inorganic salts and the long-chain organic acids are taken as raw materials; Na-montmorillonite, the rare earth lanthanum inorganic salts and the long-chain organic acids are reacted in water phase so as to obtain the lanthanum-based organic acid montmorillonite. The water phase one-step preparation technology is simple for operation, is safe, and is friendly to the environment. Acting force between the organic acids and montmorillonite, and acting force between the rare earth lanthanum element and montmorillonite are strong; thermal performance is stable; form is uniform; organic content is more that 20%, and interlamellar spacing of montmorillonite is increased obviously. The lanthanum-based organic acid montmorillonite can be used in the fields such as preparation of polymer nanocomposites and polymer modification.
Description
Technical field
The present invention relates to a kind of lanthanum base organic acid polynite and preparation technology thereof, belong to chemical technology field, specifically for polymer nanocomposites preparation or polymer processing modification.
Background technology
Polynite (montmorillonite, be called for short MMT) because mining deposits is abundant, excellent property, cheap and be subject to people's favor, industrial, be of wide application, as the sorbent material of the additive of polymkeric substance, toxic substance, support of the catalyst, coating-forming agent etc., by people, be described as " universal material ".Add mechanical property, flame retardant properties and thermal stability that a small amount of organically-modified polynite can improve material greatly in polymeric matrix.
Polynite (MMT) is a kind of inorganic non-metallic layer silicate mineral, and its interlayer has tradable positively charged ion, and this special laminate structure is given the character of polynite uniqueness, as large as surface polarity, cation exchange capacity (CEC) is strong, interlayer surface is moisture etc.A large amount of mineral ions are arranged between cheating engaging layer and show hydrophilic oleophobic property, be unfavorable for its dispersion in polymeric matrix, therefore will carry out organically-modified to polynite.Carrying out organically-modified purpose is the high polarity that changes the polynite surface, make montmorillonite layer change lipophilicity into by wetting ability, reduce its surface energy, make the interlamellar spacing of polynite increase simultaneously, make polymer chain or monomer enter interlayer, thus the nano composite material of preparing.Conclusive effect is played in the organically-modified preparation to nano composite polymer-montmorillonoid material of polynite.
Traditional polynite is organically-modified is that ion exchange reaction by quaternary cationic surfactant obtains, but the organic quaternary ammonium salt price that the method is used than high, toxicity is large, kind is limited, and relevant research shows, common quaternary ammonium salt-modified polynite thermostability is poor, and its range of application is very limited.As in polyvinyl chloride (PVC) fusion intercalation or following process process, PVC easily removes the HCl reaction, and adding of quaternary ammonium salt modified montmorillonoid at high temperature can be decomposed generation amine, further promoted the dehydrochlorination process of PVC molecular chain, cause accelerated degradation and the variable color of PVC material.
In order to solve, traditional organo montmorillonite high temperature easily decomposes and the modified montmorillonoid interlamellar spacing increases limited problem, Chinese patent [application (patent) number] CN201210046490.X discloses the organically-modified sodium-based montmorillonite of a kind of ricinolic acid sodium salt and the application in hard polyaminoester thereof, the method uses sodium-based montmorillonite through emulsification and sodium ricinoleate reactant salt, the modified montmorillonoid stable chemical nature obtained, improved the consistency of organo montmorillonite and urethane, and the activity hydroxy on the ricinolic acid sodium salt and isocyanate reaction, realize the polynite secondary intercalation, the matrix material of preparation has higher thermostability, flame retardant resistance and mechanical property.
With quaternary ammonium salt modified organo montmorillonite, compare, the organic acid wide material sources, various in style, different types of product contains the organic group that function is different, has made up the deficiency of original organo montmorillonite function singleness, and the Application Areas of polynite is widened greatly.Chinese patent [application (patent) number] CN200710027154.X discloses bentonite of organic acid and preparation method thereof, this bentonite of organic acid be take alkaline calcium bentonite as raw material, azeotropic in organic solvent, the hydroxide radical generation neutralization reaction of organic acidity group and calcium-base bentonite interlayer, the water generated is removed by component distillation, obtain bentonite of organic acid, heat-resisting, anti-oxidant and uvioresistant ability improves greatly, can be used for preparing various organism/bentonite nano composite materials.This invention adopts two-step approach first by sodium bentonite, to prepare alkaline calcium bentonite, and then is organised, and organic dehydrated solvent that preparation process is used is unfavorable for energy-conservation and environmental protection.
Rare earth compound has unique effects aspect the processing of improvement polymer materials and use properties, as as stablizer, strengthening agent, promotor, coupling agent, pigment, siccative etc., aspect special functional application, also can be used as magnetic agent, antiseptic-germicide, fire retardant, phototransformation agent etc.There are some researches show, rare earth compound be applied to plastics have toughness reinforcing, increased just, improved heat-drawn wire, promoted the effects such as crystallization, high-efficiency lubricating; The rare earth functional agent can extend rubber work-ing life, improve its mechanical property, thermotolerance and wear resistance, make the multiple performance generation qualitative leap of rubber, significantly promote the added value of rubber item.
In recent years, many scholars carry out rare earth compound applied research in polymer materials in conjunction with polynite, have obtained a series of achievements.Chinese patent [application (patent) number] CN200810242658.8 discloses montmorillonite/rare-earth stabilizer and preparation method thereof for PVC, and the method is first by longer chain fatty acid, calcium oxide, catalyst Z n
2+, group of the lanthanides or cerium be inorganic salt reaction, dehydration, dry, pulverize the organic rare-earth salts of preparation, then carry out polynite organic intercalation and surface modification.The montmorillonite/rare-earth stabilizer of preparation is applicable to the requirement of the thermally-stabilised and reinforcing property of the PVC material higher to requirement of mechanical strength.
Chinese patent [application (patent) number] CN02134846.4 discloses rare earth modified polyolefin/montmorillonite composite and preparation method thereof, by original montmorillonoid soil, rare-earth modifier, synergist (being mainly the organic carboxyl acid class) etc. and polyolefin blend, carry out mixing or extrude and prepare polymer composites.Polynite is dispersed the raising obviously in polymeric matrix, and composite materials property correspondingly also significantly improves.
Above-mentioned patent relates to the preparation technology of rare earth modified polynite, is all first to form step by step organic rare-earth salts or rare-earth modifier, then is used for the organic-treating polynite, and the preparation system is selected dehydration of organic solvent.Its shortcoming is: this processing mode can not guarantee that organise reagent enters between cheating engaging layer fully, and quite a few organise reagent exists with physical adsorption way; In preparing polymer nanocomposites and the course of processing, though the organise reagent that physical adsorption way exists can improve the consistency of polynite and polymeric matrix, but also be easy to because of the strong polarity of montmorillonite layer and interact not strong with polymeric matrix, and causing montmorillonite layer to reassemble, the matrix material homogeneity of preparation is unstable.The invention provides a kind of lanthanum base organic acid polynite and water one-step preparation process thereof, the preparation method is green simple, the intercalation effect that organises is good, organic degree is controlled, the introducing organifying reagent of Rare Earth Lanthanum and montmorillonite layer reactive force strengthen, thermostability improves, and the possibility application of more specific functions is provided.
Summary of the invention
The invention provides a kind of lanthanum base organic acid polynite and water one-step preparation process thereof, introduce the Rare Earth Lanthanum element when organising and enter between cheating engaging layer, enlarge the interlamellar spacing of polynite, and the rear earth organic phosphonate physical adsorption is few, the product form homogeneous obtained, stable performance.The water one-step preparation process is simple, lower to the requirement of equipment, and the water react single stage method completes not only cost-saving but also be conducive to environmental protection.
Lanthanum base organic acid of the present invention polynite, its crystalline structure is the montmorillonite layer structure, a plurality of ionic linkages of interlayer lanthanum ion, part is combined with montmorillonite layer, and all the other are combined with the acidic-group of long chain organic acid salt.
Lanthanum base organic acid polynite of the present invention adopts La-salt hydrochlorate or the nitrate of solubility.
The described long chain organic acid salt of lanthanum base organic acid of the present invention polynite can be the sodium salt of the compounds such as undecylenic acid, lauric acid, dodecyl sodium sulfonate, dodecylphosphoric acid, end aminolauric acid, oxystearic acid.
The preparation method of lanthanum base organic acid of the present invention polynite is that to take sodium-based montmorillonite, Rare Earth Lanthanum inorganic salt and long chain organic acid sodium salt be raw material, and in water, reaction Dehydration obtain, and its preparation process as shown in Figure 1.Preparation method of the present invention puts into sodium-based montmorillonite in the water of 20～50 times of its quality and disperses slurrying, be heated to 40～90 ℃ and high-speed stirring, regulate pH5～8 activation 2～4h, by consumption, it is 1～4CEC Rare Earth Lanthanum inorganic salt solution, the constant temperature high-speed stirring, after reaction for some time, regulate pH, evenly adding consumption is 1～4CEC organic acid sodium solution, maintenance system pH is in 5～11 scopes, continue reaction 2～4 hours, product is through washing, dehydration, drying makes, organise content more than 20% in the polynite of lanthanum base organic acid, and the cheating engaging layer spacing increases obviously.
In lanthanum base organic acid polynite preparation process of the present invention, reaction is carried out in aqueous systems, all adopt Rare Earth Lanthanum inorganic salt and the organic acid sodium salt of solubility, by the complex coordination effect, lanthanum ion and organic acid fully react with electronegative montmorillonite layer, the adjusting of pH value promote the to organise formation of intercalated montmorillonite, reduce the physical adsorption of organise reagent on the polynite surface.This preparation process completes by the water single stage method, the simple and environmental protection and energy saving of technique, quality product homogeneous.
The preparation principle of lanthanum base organic acid of the present invention polynite is the Rare Earth Lanthanum inorganic salt solution with after the sodium-based montmorillonite suspension liquid mixes, lanthanum ion first partly enters between cheating engaging layer by cationic exchange, the preliminary interlamellar spacing of expanding montmorillonite layer, after the long chain organic acid salt that adds dissociate organic acid and rare earth ion enters between cheating engaging layer by the complex coordination effect, further organise and increase the cheating engaging layer spacing, making the polynite of lanthanum base organic acid.
Advantage of the present invention is:
[1] adopt the modified with organic acids polynite, kinds of organic acids is various, and different types of product contains the organic group that function is different, has made up the deficiency of original organo montmorillonite function singleness, and the Application Areas of polynite is widened greatly.
[2] adopt single stage method water preparation technology, simple to operate, lower to the requirement of equipment.Reaction is carried out in aqueous systems, safety and environmental protection, and also raw material all adopts Rare Earth Lanthanum inorganic salt and the organic acid sodium salt of solubility, sufficient reacting, and aftertreatment is simple, obtains the product homogeneous, effectively guarantees quality product.
[3] the Rare Earth Lanthanum element is the important component part of lanthanum base organic acid polynite, and its introducing makes organic montmorillonoid have unusual effect at aspects such as improving macromolecular material thermostability and mechanical property, and the possibility application of more specific functions is provided.
[4] adopt the synthetic lanthanum base organic acid polynite of the method, the physical adsorption of organic acid lanthanum salt is few, and organic acid and rare earth element and montmorillonite layer reactive force are strong, thermal characteristics is stable, and the quality homogeneous, organic content is more than 20%, and the cheating engaging layer spacing increases obviously.
The accompanying drawing explanation
Fig. 1 is the process flow sheet for preparing the polynite of lanthanum base organic acid that the present invention proposes.
Fig. 2 is the XRD spectra that lanthanum base organic acid polynite prepared by the present invention contrasts original polynite: Na-MMT (a), SDS-La-MMT (b), SDD-La-MMT (c) and SMDP-La-MMT (d).
Fig. 3 is the XRD spectra that lanthanum base organic acid polynite prepared by the present invention contrasts original polynite: the SADD-La-MMT (g, h) of Na-MMT (a), SU-La-MMT (e), SHS-La-MMT (f) and different intercalator consumptions.
Fig. 4 is the TGA spectrogram that lanthanum base organic acid polynite prepared by the present invention contrasts original polynite: Na-MMT (a), SDS-La-MMT (b), SDD-La-MMT (c) and SMDP-La-MMT (d).
Fig. 5 is the TGA spectrogram that lanthanum base organic acid polynite prepared by the present invention contrasts original polynite: the SADD-La-MMT (g, h) of Na-MMT (a), SU-La-MMT (e), SHS-La-MMT (f) and different intercalator consumptions.
Embodiment
Embodiment 1:
Lanthanum base dodecyl sodium sulfonate polynite (SDS-La-MMT) preparation: cation exchange capacity (CEC) is put in the water that consumption is 30 times of polynite quality for the 145meq/100g sodium-based montmorillonite, dispersed with stirring 1 hour, the rear thermostatically heating that is uniformly dispersed stirs 2 hours, regulate pH to 5, constant temperature stirs 2 hours, the lanthanum chloride solution that adds 2CEC, constant temperature stirs 2 hours, regulate pH to 8, the sodium dodecyl sulfate aqueous solution that adds 2CEC, continue stirring reaction 2 hours, product, through washing, dehydration, dry, grinding, is made lanthanum base dodecyl sodium sulfonate polynite product.Through XRD and TGA, analyze, it the results are shown in Figure 2-b, Fig. 4-b.
Embodiment 2:
Lanthanum base lauric acid polynite (SDD-La-MMT) preparation: cation exchange capacity (CEC) is put in the water that consumption is 30 times of polynite quality for the 145meq/100g sodium-based montmorillonite, dispersed with stirring 1 hour, the rear thermostatically heating that is uniformly dispersed stirs 4 hours, the lanthanum chloride solution that adds 2CEC, under constant temperature, stir 2 hours, regulate pH to 7, add the sodium laurate aqueous solution of 2CEC to regulate pH to 10, continue stirring reaction 2 hours, product is through washing, and dehydration, dry, grinding, make lanthanum base lauric acid polynite product.Through XRD and TGA, analyze, it the results are shown in Figure 2-c, Fig. 4-c.
Embodiment 3:
Lanthanum base dodecylphosphoric acid polynite (SMDP-La-MMT) preparation: cation exchange capacity (CEC) is put in the water that consumption is 30 times of polynite quality for the 145meq/100g sodium-based montmorillonite, dispersed with stirring 1 hour, the rear thermostatically heating that is uniformly dispersed stirs 2 hours, regulate pH to 5, constant temperature stirs 2 hours, the lanthanum chloride solution that adds 2CEC, constant temperature stirs 2 hours, regulate pH to 8, the dodecylphosphoric acid monoesters sodium water solution that adds 2CEC, continue stirring reaction 2 hours, product is through washing, dehydration, dry, grind, make lanthanum base dodecylphosphoric acid polynite product.Through XRD and TGA, analyze, it the results are shown in Figure 2-d, Fig. 4-d.
Embodiment 4:
Lanthanum base undecylenic acid polynite (SU-La-MMT) preparation: cation exchange capacity (CEC) is put in the water that consumption is 30 times of polynite quality for the 145meq/100g sodium-based montmorillonite, dispersed with stirring 1 hour, the rear thermostatically heating that is uniformly dispersed stirs 4 hours, the lanthanum chloride solution that adds 2CEC, under constant temperature, stir 2 hours, the undecylenic acid sodium water solution that adds 2CEC, regulate pH to 10, continue the constant temperature stirring reaction 2 hours, product, through washing, dehydration, dry, grinding, is made lanthanum base undecylenic acid polynite product.Through XRD and TGA, analyze, it the results are shown in Figure 3-e, Fig. 5-e.
Embodiment 5:
Lanthanum base oxystearic acid polynite (SHS-La-MMT) preparation: cation exchange capacity (CEC) is put in the water that consumption is 30 times of polynite quality for the 145meq/100g sodium-based montmorillonite, dispersed with stirring 1 hour, the rear thermostatically heating that is uniformly dispersed stirs 4 hours, the lanthanum chloride solution that adds 1.5CEC, under constant temperature, stir 2 hours, add the ten dihydroxystearic acid sodium water solutions of 1.5CEC to regulate pH to 10, continue stirring reaction 2 hours, product, through washing, dehydration, dry, grinding, is made lanthanum base oxystearic acid polynite product.Through XRD and TGA, analyze, it the results are shown in Figure 3-f, Fig. 5-f.
Embodiment 6:
Lanthanum cardinal extremity aminolauric acid polynite (SADD-La-MMT) preparation: cation exchange capacity (CEC) is put in the water that consumption is 30 times of polynite quality for the 145meq/100g sodium-based montmorillonite, dispersed with stirring 1 hour, the rear thermostatically heating that is uniformly dispersed stirs 2 hours, regulate pH to 5, constant temperature stirs 2 hours, the lanthanum chloride solution that adds 1CEC, under constant temperature, stir 2 hours, pH to 8, the end aminolauric acid sodium water solution that adds 1CEC, regulate pH to 5, continue stirring reaction 2 hours, product is through washing, dehydration, dry, grind, make lanthanum cardinal extremity aminolauric acid polynite product.Through XRD and TGA, analyze, it the results are shown in Figure 3-g, Fig. 5-g.
Embodiment 7:
Lanthanum cardinal extremity aminolauric acid polynite (SADD-La-MMT) preparation: cation exchange capacity (CEC) is put in the water that consumption is 30 times of polynite quality for the 145meq/100g sodium-based montmorillonite, dispersed with stirring 1 hour, the rear thermostatically heating that is uniformly dispersed stirs 2 hours, regulate pH to 5, constant temperature stirs 2 hours, the lanthanum chloride solution that adds 2CEC, under constant temperature, stir 2 hours, regulate pH to 8, the end aminolauric acid sodium water solution that adds 2CEC, regulate pH to 5, continue stirring reaction 2 hours, product is through washing, dehydration, dry, grind, make lanthanum cardinal extremity aminolauric acid polynite product.Through XRD and TGA, analyze, it the results are shown in Figure 3-h, Fig. 5-h.
Embodiment 8:
Embodiment chooses PVC and has contrasted the polynite of lanthanum base organic acid to the impact of macromolecular material thermostability, gets 100 parts of PVC, and 1 part of polynite, carry out Congo red test (testing method is with reference to national standard) after fully mixing, the results are shown in Table 1.
The Congo red experimental result of table 1
As shown in table 1, adding of lanthanum base organic acid polynite makes the Congo red time of PVC material improve, and illustrates that the thermostability to the PVC material has promoter action, and the promotion degree is relevant with properties-correcting agent content in polynite with the properties-correcting agent kind.
Embodiment 9:
Embodiment investigates the polynite of lanthanum base organic acid to the PVC Effect on Mechanical Properties, adopt suspension polymerization to prepare PVC/ lanthanum base organic acid Nano composite material of montmorillonite, get 100 parts of VCM, 1 part of SU-La-MMT, 200 parts of water, 0.1 part of initiator, 3 parts of dispersion agents, be warming up to 57.5 ℃ after all materials are fully mixed in polymeric kettle, pressure rise is to 0.8MPa, and pressure drop is discharging afterwards obviously.Polymer material is its mechanical property of test through plasticating, after pressing plate, sample preparation, the results are shown in 2.
Table 2PVC and PVC/MMT nano composite material mechanical experimental results
As shown in table 2, the shock strength of PVC/1phr MMT nano composite material improves 46.92% than PVC, tensile strength improves 12.71%, and Young's modulus improves 13.72%, illustrates that the polynite of lanthanum base organic acid can be applied in the preparation and mechanical property modification thereof of polymer nanocomposites.
Claims (8)
1. lanthanum base organic acid polynite is characterized in that its crystalline structure is the montmorillonite layer structure, a plurality of ionic linkages of interlayer lanthanum ion, part is combined with montmorillonite layer, and all the other are combined with the acidic-group of long chain organic acid salt, forms the polynite of lanthanum base organic acid.The lanthanum base organic acid polynite gross weight of take is benchmark, and polynite content is 50～80%, and lanthanum element content is 5～15%, and organic content is 20～40%.
2. lanthanum base organic acid according to claim 1 polynite, it is characterized in that, described polynite mineralogical composition content is no less than 85%, the sodium-based montmorillonite that preferably 95% interlayer exchangable ion is sodium ion, its cation exchange capacity (CEC) is 50～200meq/100g, and preferably CEC is 90～150meq/100g.
3. lanthanum base organic acid according to claim 1 polynite, is characterized in that, described Rare Earth Lanthanum element, La-salt hydrochlorate or the nitrate of employing solubility.
4. lanthanum base organic acid according to claim 1 polynite is characterized in that described long chain organic acid salt is C
10～C
24, long-chain is saturated or wherein a kind of of undersaturated fatty acid sodium salt or derivatives thereof, described fatty acid sodium salt comprises aliphatic carboxylic acid, sulfonic acid, sodium phosphate salt, described derivative is with hydroxyl, ether, carbonyl or amino organic acid sodium salt on carbochain.
5. a lanthanum base organic acid polynite and water one-step preparation process thereof, is characterized in that, described method comprises the steps:
(1) polynite is placed in to a certain amount of water, dispersed with stirring 1～2 hour, the rear thermostatically heating that is uniformly dispersed stirs 4～6 hours;
The mass ratio of described polynite and water is, 1: 20～50;
(2) add the Rare Earth Lanthanum inorganic salt solution, high-speed stirring 2～4 hours, make it fully to exchange with the sodium-based montmorillonite interlayer cation;
Described Rare Earth Lanthanum inorganic salt solution amount of substance concentration is 0.1～0.5mol/L, and the Rare Earth Lanthanum inorganic salt with the amount of substance ratio of sodium-based montmorillonite cation exchange capacity are, 1～4: 1;
(3) add the long chain organic acid salts solution, regulate the pH value, stir and continue reaction 2～4 hours, make long chain organic acid root and interlayer rare earth ion form fine coordination-intercalation;
Described long chain organic acid salt with the amount of substance ratio of Rare Earth Lanthanum inorganic salt is, 1～4: 1;
(4) through washing, dehydration, dry, grinding, make the polynite of lanthanum base organic acid.
6. preparation method according to claim 5, is characterized in that, the introducing of Rare Earth Lanthanum element and the step that organises, for single stage method is carried out continuously.
7. preparation method according to claim 5, is characterized in that, described Heating temperature is 40～90 ℃.
8. preparation method according to claim 5, is characterized in that, described adjusting pH scope is 5～11, and the mineral acid of utilization is hydrochloric acid or sulfuric acid, and mineral alkali is sodium hydroxide.
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| CN108752632A (en) * | 2018-06-20 | 2018-11-06 | 江苏海明斯新材料科技有限公司 | A kind of preparation method of the quaternary ammonium salt-modified nanometer organic montmorillonite of easily disperse |
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