CN102816461B - Quaternary ammonium cation and quaternary phosphonium cation-containing modified clay, its preparation and application - Google Patents
Quaternary ammonium cation and quaternary phosphonium cation-containing modified clay, its preparation and application Download PDFInfo
- Publication number
- CN102816461B CN102816461B CN201210308868.9A CN201210308868A CN102816461B CN 102816461 B CN102816461 B CN 102816461B CN 201210308868 A CN201210308868 A CN 201210308868A CN 102816461 B CN102816461 B CN 102816461B
- Authority
- CN
- China
- Prior art keywords
- halide
- ammonium
- quaternary
- phosphonium
- cation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
Belonging to the field of organic-inorganic hybrid materials, the invention provides a quaternary ammonium cation and quaternary phosphonium cation-containing organic cation modified clay, its preparation method and application. The preparation method comprises: reacting a suspending solution of a sodium base treated clay mineral with quaternary ammonium cations and quaternary phosphonium cations, conducting filtering, washing, drying and crushing, thus obtaining the quaternary ammonium cation and quaternary phosphonium cation-containing organic cation modified clay with a synergistic effect. The organic cation modified clay provided in the invention has good stability, excellent weather resistance, and no toxicity. The organic cation modified clay contains quaternary ammonium cation modified clay and quaternary phosphonium cation modified clay simultaneously, and shows a synergistic antibacterial activity, so that it can be applied to plastics, rubber, fibers, coatings, adhesives, paper, wood-plastic composite materials and a variety of polymer materials to improve the antibacterial property, the flame retardance and the barrier property of polymers, and has no influence on the mechanical properties of the polymers.
Description
Technical field
The present invention relates to hybrid inorganic-organic materials field, particularly a kind of quaternary ammonium cation that contains is with cationic modified clay of quaternary phosphine and preparation method thereof and application.
Background technology
Organic cation refers to what the hydrophobic group in organic molecule was connected with positively charged hydrophilic group by covalent linkage, to reach the ionic species of relatively stable structure.Organic cation, because its special structure presents unique performance as static resistance, bactericidal properties, flexibility etc., is widely used in the aspects such as papermaking, oil field, water treatment, washing, has good society and economic benefit.The machine positively charged ion of common are has quaternary ammonium salt ion, quaternary alkylphosphonium salt ion, imidazole salts ion and pyrroles's salt ion etc., wherein again with quaternary ammonium salt ion with quaternary alkylphosphonium salt ion is the most conventional, having the features such as foam is low, clay stripping ability strong, the pH value scope of application is wide, is the excellent activity group of preparing functional materials.
Clay is 2:1 layer mineral mostly, interlayer has tradable hydrated cation, absorption property is strong, it is the good carrier of functional substance, functional organism (organic cation) is inserted between clay seam, make itself and clay form the compound of molecular level, can obtain insoluble organic cation modified clay.Because the organic cations thermotolerance in organic cation modified clay increases substantially, toxicity declines, become stable long-acting matrix material, present unique performance, can in polymkeric substance (plastics, rubber, fiber, coating, tackiness agent, paper, wood plastic composite), apply, give polymkeric substance antibacterial, fire-retardant and barrier property, and within the scope of certain interpolation, the mechanical property of polymkeric substance is not being had a significant effect.
At antibiosis: quaternary alkylphosphonium salt has similar structure with quaternary ammonium salt, due to P element in the periodic table of elements, be positioned at N element below, phosphorus atom is larger than the ionic radius of nitrogen-atoms, polarized action is strong, a little less than electronegativity, therefore quaternary alkylphosphonium salt molecular structure is more stable, be difficult to and general Oxidizing and Reducing Agents and acid, alkali reaction, can in the water in the scope of pH=2～12, use, have efficient, fast, wide spectrum, easily degraded, low toxicity and the advantage such as easy to use, can algae, to iron oxygen bacterium, heterotrophic bacterium, sulphate reducing bacteria has good sterilization effect, therefore, quaternary alkylphosphonium salt has than quaternary ammonium salt antibacterial applications widely.(the Liu Renfu such as Liu Renfu, Liang Guanke, Chen Yin, Tan Shao early, Xie Yushan, Ou Yangyousheng, Shi Qingshan. the preparation and characterization [J] of quaternary alkylphosphonium salt pillared montmorillonite. Ji'nan University's journal (natural science edition), 2009,30 (5): 534-538.) ten alkyl tributyl phosphonium bromides of different components are intercalation into and in polynite, prepare quaternary alkylphosphonium salt pillared montmorillonite.The compound ， quaternary alkylphosphonium salt that forms molecular level due to quaternary alkylphosphonium salt between silicate can stably be present in the microenvironment between silicate layer, thereby improves long-lasting, thermostability, becomes a kind of environmental protection, long-acting anti-biotic material.
Aspect fire-retardant: quaternary ammonium salt-modified clay has the features such as aboundresources, adsorptive power are strong, amphiphilic and renewable, the aspects such as the anti-settling and reinforcing rubber of pollutent absorption, algae flocculation, coating are applied in.At present halogen-free flame retardant for plastics efficiency low, affect the mechanical properties; And quaternary ammonium salt-modified clay also can be made fire retardant, but efficiency is lower, heat-resisting poor, is difficult to meet actual needs.Quaternary alkylphosphonium salt and quaternary ammonium cation structural similitude, but relatively better (the Omatete O O of thermotolerance, Pollinger J P.Gelcasting and aquous injection molding for silicon nitride structural ceramics[A] F.6th International Conference of Ceramic Processing[C of .In:Fed L], USA:Materials Reserch Laboratory at UCSB, 1997.11.), as quaternary phosphine positively charged ion is inserted between cheating engaging layer, the thermotolerance of the modified montmorillonoid obtaining has greatly improved, its heat resisting temperature can reach 220 DEG C of (Tan Shaozao, Zhang Kuihua, Li Duxin, Liu Yingliang, Zhang Yuanming. the preparation of quaternary alkylphosphonium salt modified montmorillonoid and performance [J]. Central South University's journal (natural science edition), 2006, 37 (2): 280-285.).Quaternary alkylphosphonium salt modified montmorillonoid resistance toheat is better compared with the modified montmorillonoid of quaternary ammonium salt, and decomposition temperature is higher, is so more conducive to the processing of material.Set it as fire retardant and add in the middle of the macromolecular materials such as polypropylene, can prepare the polymer composite with flame retardant properties.
Aspect obstruct: (the Thellen C. such as Thellen, Orroth C., Froio D., et al.Influence of montmorillonite layered silicate on plasticized poly (L-lactide) blown films[J] .Polymer, 2005,46 (25): 11716-11727) prepared the plastics film of PLA and quaternary ammonium salt modified montmorillonoid, the rejection rate that compares oxygen with pure PLA film has improved 48%, and the rejection rate of water vapour has been improved to 50%.Heat decomposition temperature has also improved nearly 9 DEG C.(the Vaia R A such as Richard, Teukolsky R K, Giannelis E P.Interlayer structure and molecular environment of alkylammonium layered silicates[J] .Chem Mater, 1994,6 (7): 1017-1022.) quaternary ammonium salt is inserted between cheating engaging layer, make to form between quaternary ammonium salt and silicate the compound of molecular level, in the microenvironment of quaternary ammonium salt energy stable existence between silicate layer, thereby improve thermostability and long-lasting.
As seen from the above analysis, quaternary ammonium cation modified clay is with the cation-modified clay of quaternary phosphine respectively has relative merits, as quaternary ammonium cation and quaternary phosphine positively charged ion are inserted to layer mineral (polynite, vermiculite, attapulgite, illite, rectorite leng) interlayer simultaneously, to obtain the novel organic cation modified clay of a class, this class material yet there are no relevant report at present.
Summary of the invention
Primary and foremost purpose of the present invention is that the shortcoming that overcomes prior art is with not enough, provides a kind of quaternary ammonium cation that contains with the preparation method of the cationic modified clay of quaternary phosphine.
Another object of the present invention is to provide prepare by above-mentioned preparation method containing quaternary ammonium cation with the cationic modified clay of quaternary phosphine.
A further object of the present invention is to provide the above-mentioned quaternary ammonium cation that contains with the application of the cationic modified clay of quaternary phosphine.
Object of the present invention is achieved through the following technical solutions: a kind of containing quaternary ammonium cation He the preparation method of the cationic modified clay of quaternary phosphine comprise the following steps:
(1) sodium laminated clay (Na-sheet minerals) is added to the water, stirs and make it be dispersed into suspension, then add quaternary ammonium salt with quaternary alkylphosphonium salt reacts, filter and collect solid substance;
(2) wash to halogen ion-free with the solid substance that aqueous ethanolic solution is prepared step (1), dry, obtain head product;
(3) head product step (2) being obtained is pulverized, and obtains containing quaternary ammonium cation with the cationic modified clay of quaternary phosphine.
Sodium laminated clay described in step (1) is that clay mineral obtains through the processing of sodium base, and operation steps is: 100g clay mineral is joined in 1L water, add 10g Sodium hexametaphosphate 99, be heated to 75 DEG C, add 20g Na
2cO
3; Induction stirring 60rpm 3h, uses deionized water centrifuge washing 4 times after standing 24h, removes bottom insolubles, reclaims solids; At 105 DEG C, after dry 48h, obtain sodium laminated clay (Xu J, Li RKY, Xu Y, Li L, Meng YZ.Preparation of poly (propylene carbonate)/organo-vermiculite nano-composites via direct melt intercalation[J] .European Polymer Journal, 2005,41 (4): 881-888.); Described clay mineral is polynite, vermiculite, attapulgite, illite or rectorite leng, its cation exchange capacity is different with the variation in clay mineral type and the place of production, measuring method reference (Chen Jimei. about the measuring method [J] of wilkinite cation exchange capacity. GEOLAB, 1992,8 (6): 372-376.); Described sodium laminated clay is sodium-based montmorillonite, sodium base vermiculite, sodium base attapulgite, sodium base illite or sodium base rectorite leng; The cation exchange capacity (CEC) of described sodium laminated clay is respectively: sodium-based montmorillonite 100～160mmol/100g, sodium base vermiculite 90～140mmol/100g, sodium base attapulgite 70～100mmol/100g, sodium base illite 30～60mmol/100g, sodium base rectorite leng 30～60mmol/100g.
Stirring described in step (1) is preferably 40 DEG C and stirs 0.5h.
The concentration of the suspension described in step (1) is preferably 5～10wt%; Preferred, the concentration of suspension is 8wt%;
Quaternary ammonium salt described in step (1) is suc as formula at least one in the quaternary ammonium salt shown in I or formula II:
Formula I
Formula II
Wherein, n
1be 8～16 integer, n
2be 8～12 integer, R
1for methyl, ethyl, butyl, phenyl, R
2for methyl, ethyl, butyl, phenyl or benzyl, R
3for methyl, ethyl, X is Cl or Br;
Preferred, described quaternary ammonium salt is ten alkyl trimethyl ammonium halides, undecyl trimethyl-ammonium halide, dodecyl trimethyl-ammonium halide, tridecyl trimethyl-ammonium halide, tetradecyl trimethyl-ammonium halide, pentadecyl trimethyl-ammonium halide, cetyl trimethyl ammonium halide, heptadecyl trimethyl-ammonium halide, octadecyl trimethyl-ammonium halide, ten alkyl tributyl ammonium halides, undecyl tributyl ammonium halide, dodecyl tributyl ammonium halide, tridecyl tributyl ammonium halide, tetradecyl tributyl ammonium halide, pentadecyl tributyl ammonium halide, hexadecyl tributyl ammonium halide, heptadecyl tributyl ammonium halide, octadecyl tributyl ammonium halide, ten alkyl-dimethyl benzyl ammonium halides, undecyl dimethyl benzyl ammonium halide, dodecyl dimethyl benzyl ammonium halide, tridecyl dimethyl benzyl ammonium halide, tetradecyl dimethyl benzyl ammonium halide, pentadecyl dimethyl benzyl ammonium halide, cetyl dimethyl benzyl ammonium halide, heptadecyl dimethyl benzyl ammonium halide, octadecyl dimethyl benzyl ammonium halide, two ten alkyl methyl ethyl ammonium halides, two undecyl methylethyl ammonium halides, two dodecyl methyl ethyl ammonium halides, double tridecyl methylethyl ammonium halide, two tetradecyl methylethyl ammonium halides, didecyl Dimethy ammonium halide, two undecyl dimethyl ammonium halides, two dodecyl dimethyl ammonium halides, at least one in double tridecyl dimethyl ammonium halide or two tetradecyl dimethyl ammonium halide.
Quaternary alkylphosphonium salt described in step (1) is suc as formula at least one in the quaternary alkylphosphonium salt of shown in III:
Formula III
Wherein, n
3be 8～14 integer, R
1for methyl, ethyl, butyl, phenyl, R
2for methyl, ethyl, butyl, phenyl or benzyl, X is Cl or Br;
Preferred, described quaternary alkylphosphonium salt is ten alkyl trimethyl phosphonium halides, undecyl trimethylammonium phosphonium halide, dodecyl trimethylammonium phosphonium halide, tridecyl trimethylammonium phosphonium halide, tetradecyl trimethylammonium phosphonium halide, pentadecyl trimethylammonium phosphonium halide, cetyl trimethyl phosphonium halide, ten alkyl tributyl phosphonium halides, undecyl tributyl phosphonium halide, dodecyl tributyl phosphonium halide, tridecyl tributyl phosphonium halide, tetradecyl tributyl phosphonium halide, pentadecyl tributyl phosphonium halide, hexadecyl tributyl phosphonium halide, ten alkyl triphenyl phosphonium halides, undecyl triphenyl phosphonium halide, dodecyl triphenyl phosphonium halide, tridecyl triphenyl phosphonium halide, tetradecyl triphenyl phosphonium halide, pentadecyl triphenyl phosphonium halide, hexadecyl triphenyl phosphonium halide, ten alkyl dimethyl benzyl phosphonium halides, hendecane base dimethyl benzyl phosphonium halide, dodecyl dimethyl benzyl phosphonium halide, tridecyl dimethyl benzyl phosphonium halide, tetradecyl dimethyl benzyl phosphonium halide, at least one in pentadecyl dimethyl benzyl phosphonium halide or hexadecyldimethyl benzyl ammonium benzyl phosphonium halide.
Above-mentioned quaternary ammonium salt or quaternary alkylphosphonium salt open up Chemical Co., Ltd. by Guangzhou Rui Yang tensio-active agent company limited, upper Haikang or Changzhou Ai Sheng Chemical Co., Ltd. produces.
Quaternary ammonium salt described in step (1) is with the mole number sum of quaternary alkylphosphonium salt is preferably 0.5～1.5 times of sodium laminated clay CEC, and described quaternary ammonium salt is with the mol ratio of quaternary alkylphosphonium salt is preferably 3:7～5:5; Preferred, described quaternary ammonium salt is with the mole number sum of quaternary alkylphosphonium salt is 1 times of sodium laminated clay CEC, and described quaternary ammonium salt is with the mol ratio of quaternary alkylphosphonium salt is 1:1.
The condition optimization of the reaction described in step (1) is 50～70 DEG C of stirring reaction 3～5h; Preferred, the condition of described reaction is 60 DEG C of stirring reaction 4h.
Aqueous ethanolic solution described in step (2) is preferably the aqueous ethanolic solution of the 50wt% of 50 DEG C.
Halide-ions described in step (2) refers to bromide anion and chlorion.
Dry described in step (2) is preferably in the air atmosphere of 110 DEG C more than dry 24h.
Pulverizing described in step (3) is preferably superfine grinding and head product is crushed to median size is less than 10 microns.
One contains quaternary ammonium cation with the cationic modified clay of quaternary phosphine prepares by above-mentioned preparation method.
The above-mentioned quaternary ammonium cation that contains is with the application of the cationic modified clay of quaternary phosphine in polymkeric substance, comprise the steps: 1～5 mass parts to contain quaternary ammonium cation with the cationic modified clay of quaternary phosphine and 0～40 mass parts magnesium hydroxide join in the corresponding polymkeric substance of 55～99 mass parts by different complete processings, obtain polymer-modified.
Described magnesium hydroxide is preferably chemical pure, 3000 object magnesium hydroxides, before use 120 DEG C of dry 10h.
Described polymkeric substance is plastics, rubber, fiber, coating, tackiness agent, paper or wood plastic composite etc.
Described complete processing, according to the difference of polymkeric substance, its complete processing is also different.Wherein, when polymkeric substance is plastics, rubber or wood plastic composite, complete processing technique of injection moulding again after being preferably and mixing in high-speed mixer; When polymkeric substance is fiber, complete processing technique of wire drawing again after being preferably in high-speed mixer and mixing; When polymkeric substance is coating or tackiness agent, complete processing is preferably dispersed with stirring technique; When polymkeric substance is paper, complete processing technique of copy paper again after being preferably in high-speed mixer and mixing.
In described high-speed mixer, mixing preferred condition is: first stirring at low speed 2min under 160rpm, then under 1200rpm high-speed stirring 4.5min.
, with can improving antibacterial, the fire-retardant and barrier property of polymkeric substance, the cationic modified clay of quaternary phosphine and mechanical properties of polymer is had no significant effect containing quaternary ammonium cation.
The present invention has following advantage and effect with respect to prior art:
(1) long-lasting: quaternary ammonium cation and quaternary phosphine positively charged ion insert the interlayer of laminated clay, due to its closely compound with clay formation molecular level, therefore its good stability, weathering resistance is good, is stable long-acting matrix material.
(2) Synergistic antimicrobial: prepared contains quaternary ammonium cation with the cationic modified clay of quaternary phosphine is all better than the anti-microbial activity of the single cation-modified clay of quaternary ammonium cation Huo quaternary phosphine, shows obvious Synergistic antimicrobial.
(3) multifunctionality: prepared contains quaternary ammonium cation with the cationic modified clay of quaternary phosphine can be applied in polymkeric substance (plastics, rubber, fiber, coating, tackiness agent, paper, wood plastic composite), can improve antibacterial, the fire-retardant and barrier property of polymkeric substance, there is multifunctionality.
(4) nontoxicity: should be containing quaternary ammonium cation with the LD of the cationic modified clay material of quaternary phosphine
50>5000mg/g, for the nontoxic level of reality material, without mutagenicity, to skin nonirritant.
(5) polymer machinery mechanical property is not affected: owing to containing quaternary ammonium cation with the addition of the cationic modified clay of quaternary phosphine is low, be only 1.0～5.0%, therefore its mechanical property to polymer materials has no significant effect.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
10g sodium-based montmorillonite (CEC is 120mmol/100g) is added in 115mL water, stir 0.5h at 40 DEG C, make it be dispersed into the suspension of 8wt%, then 6mmol tetradecyl tributyl ammonium chloride and 6mmol dodecyl tributyl phosphonium bromide are joined in above-mentioned solution, in 60 DEG C of stirring reaction 4h, then filter, and the solid substance of collecting is extremely detected to filtrate halogen ion-free with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic modified montmorillonoid of quaternary phosphine, simultaneous test is to add respectively 12mmol tetradecyl tributyl ammonium chloride, 12mmol dodecyl tributyl phosphonium bromide, and other condition test is identical.Its analytical test the results are shown in Table 1.
Embodiment 2
10g sodium base vermiculite (CEC is 120mmol/100g) is added in 115mL water, stir 0.5h at 40 DEG C, make it be dispersed into the suspension of 8wt%, then 6mmol ten alkyl trimethyl ammonium bromides and 6mmol phosphonium hexadecanyl-3-butyl chloride are joined in above-mentioned solution, in 60 DEG C of stirring reaction 4h, then filter, and the solid substance of collecting is extremely detected to filtrate halogen ion-free with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic PERFORMANCE OF MODIFIED VERMICULITE of quaternary phosphine, simultaneous test is to add respectively 12mmol ten alkyl trimethyl ammonium bromides, 12mmol phosphonium hexadecanyl-3-butyl chloride, and other condition test is identical.Its analytical test the results are shown in Table 1.
Embodiment 3
10g sodium base attapulgite (CEC is 85mmol/100g) is added in 115mL water, stir 0.5h at 40 DEG C, make it be dispersed into the suspension of 8wt%, then 4.25mmol hexadecyl tributyl ammonium chloride and 4.25mmol ten alkyl three phenyl phosphonium bromides are joined in above-mentioned solution, in 60 DEG C of stirring reaction 4h, then filter, and the solid substance of collecting is extremely detected to filtrate halogen ion-free with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic modified attapulgite of quaternary phosphine, simultaneous test is to add respectively 8.5mmol hexadecyl tributyl ammonium chloride, 8.5mmol ten alkyl three phenyl phosphonium bromides, and other condition test is identical.Its analytical test the results are shown in Table 1.
Embodiment 4
10g sodium base illite (CEC is 45mmol/100g) is added in 115mL water, 40 DEG C are stirred 0.5h, make it be dispersed into the suspension of 8wt%, then 2.25mmol dodecyl tributyl brometo de amonio and 2.25mmol pentadecyl triphenyl phosphonium chloride are joined in above-mentioned solution, in 60 DEG C of stirring reaction 4h, then filter, and the solid substance of collecting is extremely detected to filtrate halogen ion-free with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic modification illite of quaternary phosphine, simultaneous test is to add respectively 4.5mmol dodecyl tributyl brometo de amonio, 4.5mmol pentadecyl triphenyl phosphonium chloride, and other condition test is identical.Its analytical test the results are shown in Table 1.
Embodiment 5
10g sodium base rectorite leng (CEC is 45mmol/100g) is added in 115mL water, stir 0.5h at 40 DEG C, make it be dispersed into the suspension of 8wt%, then 2.25mmol ten alkyl dimethyl benzyl ammonium chlorides and 2.25mmol Shi six alkyl trimethyl phosphonium bromides are joined in above-mentioned solution, in 60 DEG C of stirring reaction 4h, then filter, and the solid substance of collecting is extremely detected to filtrate halogen ion-free with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic property of modified rectorite of quaternary phosphine, simultaneous test is to add respectively 4.5mmol ten alkyl dimethyl benzyl ammonium chlorides, 4.5mmol Shi six alkyl trimethyl phosphonium bromides, and other condition test is identical.Its analytical test the results are shown in Table 1.
Embodiment 6
10g sodium-based montmorillonite (CEC is 100mmol/100g) is added in 190mL water, stir 0.5h at 40 DEG C, make it be dispersed into the suspension of 5wt%, then two 4.0mmol tetradecyl methylethyl brometo de amonios and 6.0mmol ten alkyl dimethyl benzyl phosphonium chlorides are joined in above-mentioned solution, in 70 DEG C of stirring reaction 3h, then filter, and the solid substance of collecting is extremely detected to filtrate halogen ion-free with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic modified montmorillonoid of quaternary phosphine, simultaneous test is to add respectively the two tetradecyl methylethyl brometo de amonios of 10mmol, 10mmol ten alkyl dimethyl benzyl phosphonium chlorides, and other condition test is identical.Its analytical test the results are shown in Table 1.
Embodiment 7
10g sodium-based montmorillonite (CEC is 160mmol/100g) is added in 90mL water, stir 0.5h at 40 DEG C, make it be dispersed into the suspension of 10wt%, then 2.4mmol pentadecyl dimethyl benzyl ammonium chloride and 5.6mmol undecyl trimethylammonium phosphonium bromide are joined in above-mentioned solution, in 50 DEG C of stirring reaction 5h, then filter, and the solid substance of collecting is extremely detected to filtrate halogen ion-free with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic modified montmorillonoid of quaternary phosphine, simultaneous test is to add respectively 8mmol pentadecyl dimethyl benzyl ammonium chloride, 8mmol undecyl trimethylammonium phosphonium bromide, and other condition test is identical.Its analytical test the results are shown in Table 1.
Embodiment 8
10g sodium-based montmorillonite (CEC is 120mmol/100g) is added in 115mL water, stir 0.5h at 40 DEG C, make it be dispersed into the suspension of 8wt%, then two 6mmol dodecyl methyl ethyl brometo de amonios and 6mmol tetradecyl tributyl phosphonium chloride are joined in above-mentioned solution, in 60 DEG C of stirring reaction 4h, then filter, and the solid substance of collecting is extremely detected to filtrate without bromide anion with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic modified montmorillonoid of quaternary phosphine, simultaneous test is to add respectively the two dodecyl methyl ethyl brometo de amonios of 12mmol, 12mmol tetradecyl tributyl phosphonium chloride, and other condition test is identical.Its analytical test the results are shown in Table 1.
Embodiment 9
10g sodium-based montmorillonite (CEC is 120mmol/100g) is added in 115mL water, stir 0.5h at 40 DEG C, make it be dispersed into the suspension of 8wt%, then two 6mmol ten alkyl methyl ethyl ammonium chlorides and 6mmol pentadecyl dimethyl benzyl phosphonium bromide are joined in above-mentioned solution, in 60 DEG C of stirring reaction 4h, then filter, and the solid substance of collecting is extremely detected to filtrate halogen ion-free with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic modified montmorillonoid of quaternary phosphine, simultaneous test is to add respectively the two ten alkyl methyl ethyl ammonium chlorides of 12mmol, 12mmol pentadecyl dimethyl benzyl phosphonium bromide, and other condition test is identical.Its analytical test the results are shown in Table 1.
Prepared by table 1 embodiment 1～embodiment 9 contains quaternary ammonium cation with the detected result of the cationic modified clay of quaternary phosphine
Note:
a: the content of quaternary ammonium salt in every 100g layer mineral matrix; Content according to nitrogen element in the organic cation modified clay of Kjeldahl nitrogen determination is determined, reference literature (An Xuebin, Wang Yunshan, Zhang Jinping, Yang Gang. the nitrogen in humic acid complex fertilizer, phosphorus, potassium content analysis [J]. chemical analysis metering, 2010,19 (6): 29-32.) carry out.
b: the content of every 100g layer mineral matrix Zhong quaternary alkylphosphonium salt; Content according to phosphoric in the organic cation modified clay of phospho-molybdic acid quinoline volumetric determination is determined, reference literature (An Xuebin, Wang Yunshan, Zhang Jinping, Yang Gang. the nitrogen in humic acid complex fertilizer, phosphorus, potassium content analysis [J]. chemical analysis metering, 2010,19 (6): 29-32.) carry out.
c: adopt film adherence method (Japanese SIAA (SIAA) " the antimicrbial power evaluation test method of antimicrobial prod---film adherence the method ") minimum inhibitory concentration of working sample to intestinal bacteria (ATCC25292) and streptococcus aureus (ATCC6538).
d: adopt GB 15193.3-2003 to carry out the acute oral toxicity experiment of sample, adopt GB15193-94 to carry out the mutagenicity experiment of sample.Adopt GB/T 21604-2008 to carry out the skin irritation test of sample.
Embodiment 10
10g sodium-based montmorillonite (CEC is 120mmol/100g) is added in 115mL water, stir 0.5h at 40 DEG C, make it be dispersed into the suspension of 8wt%, then 6mmol dodecyl dimethyl benzyl ammonium bromide and 6mmol tridecyl San Jia Ji phosphonium chloride are joined in above-mentioned solution, in 60 DEG C of stirring reaction 4h, then filter, and the solid substance of collecting is extremely detected to filtrate halogen ion-free with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic modified montmorillonoid of quaternary phosphine, simultaneous test is to add respectively 12mmol dodecyl dimethyl benzyl ammonium bromide, 12mmol tridecyl San Jia Ji phosphonium chloride, and other condition test is identical.Its analytical test the results are shown in Table 2.
Embodiment 11
By 10g sodium-based montmorillonite (CEC is 120mmol/100g), add in 115mL water, stir 0.5h at 40 DEG C, make it be dispersed into the suspension of 8wt%, then 6mmol pentadecyl trimethyl ammonium chloride and 6mmol dodecyl dimethyl benzyl phosphonium bromide are joined in above-mentioned solution, in 60 DEG C of stirring reaction 4h, then filter, and the solid substance of collecting is extremely detected to filtrate halogen ion-free with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic modified montmorillonoid of quaternary phosphine, simultaneous test is to add respectively 12mmol pentadecyl trimethyl ammonium chloride, 12mmol dodecyl dimethyl benzyl phosphonium bromide, and other condition test is identical.Its analytical test the results are shown in Table 2.
Embodiment 12
By 10g sodium-based montmorillonite (CEC is 120mmol/100g), add in 115mL water, stir 0.5h at 40 DEG C, make it be dispersed into the suspension of 8wt%, then 6mmol Cetyltrimethylammonium bromide and 6mmol hexadecyldimethyl benzyl ammonium benzyl phosphonium chloride are joined in above-mentioned solution, in 60 DEG C of stirring reaction 4h, then filter, and the solid substance of collecting is extremely detected to filtrate halogen ion-free with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic modified montmorillonoid of quaternary phosphine, simultaneous test is to add respectively 12mmol Cetyltrimethylammonium bromide, 12mmol hexadecyldimethyl benzyl ammonium benzyl phosphonium chloride, and other condition test is identical.Its analytical test the results are shown in Table 2.
Embodiment 13
By 10g sodium-based montmorillonite (CEC is 120mmol/100g), add in 115mL water, stir 0.5h at 40 DEG C, make it be dispersed into the suspension of 8wt%, then by 6mmol cetalkonium chloride, 3mmol tetradecyl tributyl phosphonium bromide and 3mmol ten alkyl dimethyl benzyl phosphonium bromides join in above-mentioned solution, in 60 DEG C of stirring reaction 4h, then filter, and the solid substance of collecting is extremely detected to filtrate halogen ion-free with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic modified montmorillonoid of quaternary phosphine, simultaneous test is to add respectively 12mmol cetalkonium chloride, 12mmol tetradecyl tributyl phosphonium bromide, 12mmol ten alkyl dimethyl benzyl phosphonium bromides, and other condition test is identical.Its analytical test the results are shown in Table 2.
Embodiment 14
By 10g sodium-based montmorillonite (CEC is 120mmol/100g), add in 115mL water, stir 0.5h at 40 DEG C, make it be dispersed into the suspension of 8wt%, then by 6mmol double tridecyl methylethyl brometo de amonio, 3mmol ten alkyl three phenyl phosphonium bromides and 3mmol hexadecyldimethyl benzyl ammonium benzyl phosphonium chloride join in above-mentioned solution, in 60 DEG C of stirring reaction 4h, then filter, and the solid substance of collecting is extremely detected to filtrate halogen ion-free with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic modified montmorillonoid of quaternary phosphine, simultaneous test is to add respectively 12mmol double tridecyl methylethyl brometo de amonio, 12mmol ten alkyl three phenyl phosphonium bromides, 12mmol hexadecyldimethyl benzyl ammonium benzyl phosphonium chloride, and other condition test is identical.Its analytical test the results are shown in Table 2.
Embodiment 15
By 10g sodium-based montmorillonite (CEC is 120mmol/100g), add in 115mL water, stir 0.5h at 40 DEG C, make it be dispersed into the suspension of 8wt%, then by 3mmol octadecyl trimethyl ammonium chloride, 3mmol ten Alkyl dimethyl benzyl ammonium bromides and 6mmol dodecyl tributyl phosphonium chloride join in above-mentioned solution, in 60 DEG C of stirring reaction 4h, then filter, and the solid substance of collecting is extremely detected to filtrate halogen ion-free with silver nitrate solution with 50wt% aqueous ethanolic solution (50 DEG C) washing, dry 24h in the air atmosphere of 110 DEG C, then superfine grinding to median size is less than 10 μ m(employing laser particle analyzers mensuration), obtain containing quaternary ammonium cation with the cationic modified montmorillonoid of quaternary phosphine, simultaneous test is to add respectively 12mmol octadecyl trimethyl ammonium chloride, 12mmol ten Alkyl dimethyl benzyl ammonium bromides, 12mmol dodecyl tributyl Lu Lv Phosphonium, and other condition test is identical.Its analytical test the results are shown in Table 2.
Prepared by table 2 embodiment 10～embodiment 15 contains quaternary ammonium cation with the detected result of the cationic modified clay of quaternary phosphine
Note:
a: the content of quaternary ammonium salt in every 100g layer mineral matrix; Content according to nitrogen element in the organic cation modified clay of Kjeldahl nitrogen determination is determined, reference literature (An Xuebin, Wang Yunshan, Zhang Jinping, Yang Gang. the nitrogen in humic acid complex fertilizer, phosphorus, potassium content analysis [J]. chemical analysis metering, 2010,19 (6): 29-32.) carry out.
b: the content of every 100g layer mineral matrix Zhong quaternary alkylphosphonium salt; Content according to phosphoric in the organic cation modified clay of phospho-molybdic acid quinoline volumetric determination is determined, reference literature (An Xuebin, Wang Yunshan, Zhang Jinping, Yang Gang. the nitrogen in humic acid complex fertilizer, phosphorus, potassium content analysis [J]. chemical analysis metering, 2010,19 (6): 29-32.) carry out.
c: adopt film adherence method (Japanese SIAA (SIAA) " the antimicrbial power evaluation test method of antimicrobial prod---film adherence the method ") minimum inhibitory concentration of working sample to intestinal bacteria (ATCC25292) and streptococcus aureus (ATCC6538).
d: adopt GB 15193.3-2003 to carry out the acute oral toxicity experiment of sample, adopt GB15193-94 to carry out the mutagenicity experiment of sample.Adopt GB/T 21604-2008 to carry out the skin irritation test of sample.
e: in embodiment 13,14 and 15, insert two kinds of quaternary ammonium salt Huo quaternary alkylphosphonium salts, with its putting in order in an embodiment, mark (1) and (2) after content.
Can find out from table 1, table 2, although modified clay quaternary ammonium cation prepared by embodiment 1～embodiment 15 is different with kind with the cationic content of quaternary phosphine, it is all less than 500mgL to the minimum inhibitory concentration of intestinal bacteria and streptococcus aureus
-1, show good anti-microbial activity; With the single cation-modified clay-phase ratio of quaternary ammonium cation Huo quaternary phosphine, its anti-microbial activity obviously improves, and shows synergetic antibacterial effect; Meanwhile, its Oral toxicity LD
50all be greater than 5000mg/kg, and to human body skin there is no pungency, without mutagenicity, be the very high material of a class security.
Embodiment 16～embodiment 23 for containing quaternary ammonium cation with the application of the cationic modified clay of quaternary phosphine in polymkeric substance, can improve the performance such as antibacterial, fire-retardant, obstruct of polymkeric substance.Adopt film adherence method (Japanese SIAA (SIAA) " the antimicrbial power evaluation test method of antimicrobial prod---film adherence method ") to measure its anti-microbial property to intestinal bacteria (ATCC25292) and streptococcus aureus (ATCC6538); Carry out fluorescent ultraviolet lamp exposure test 240 hours by GB/T 14522-1993, light source is UV-A lamp (351nm), carries out aberration detection by GB/T 3979-1997, GB/T 7921-1997; Demarcate limiting oxygen index(LOI) (LOI) according to GB/T2406-93, sample is of a size of 100mm × 6.5mm × 3.0mm; The vertical combustion method that adopts 94V-0,94V-1,94V-2, by ASTM-63S working sample flame retardant resistance, sample size is 130mm × 13mm × 3.0mm.Press GBIT 1040-92 standard testing tensile property, draw speed 100mm/min; Press GB/T1043-93 standard testing impact property.
Embodiment 16
Get prepared by embodiment 1 containing quaternary ammonium cation with cationic modified montmorillonoid 5 mass parts of quaternary phosphine, magnesium hydroxide (3000 orders, chemical pure, is used front 120 DEG C of dry 10h) 40 mass parts, PE plastics, PP plastics or ABS plastic 55 mass parts, put into high-speed mixer, first stirring at low speed 2min under 160rpm, then high-speed stirring 4.5min under 1200rpm, discharging, then be injection molded into modified PE plastics, PP plastics or ABS plastic sample, analytical test the results are shown in Table 3.
As can be seen from Table 3, what interpolation embodiment 1 was prepared contains quaternary ammonium cation with after the cationic modified montmorillonoid of quaternary phosphine, the limiting oxygen index(LOI) of modified PE plastics, PP plastics and ABS plastic reaches more than 29.4, UL-94 reaches V-0 level, the antibiotic rate of intestinal bacteria and streptococcus aureus is all greater than to 99.9%, chromatic aberration is little, and the tensile strength of PE, PP or ABS plastic, elongation at break and notched Izod impact strength obviously do not reduce.
The performance of table 3 modified plastics
Embodiment 17
First prepared by PE resin and embodiment 1～embodiment 10 containing quaternary ammonium cation with the cationic modified clay of quaternary phosphine ratio extruding pelletization on parallel dual-screw extruding machine of 99:1～95:5 in mass ratio obtains matrix material pellet, extrusion temperature is 170 DEG C; Then matrix material pellet is dry, go out blown film unit blowing up film at 3 layers of plastic co-extrusion, matrix material is as middle layer and the skin of 3 layers of coextrusion composite fluid food packaging film.The packing film obtaining is carried out to the test of barrier property, steam penetrating capacity is undertaken by GB/T1037-1988, adopts cup type method; Oxygen transit dose is tested by GB/T 1038-2000, adopts pressure differential method.Analytical test the results are shown in Table 4.
As can be seen from Table 4, what interpolation embodiment 1～embodiment 15 was prepared contains quaternary ammonium cation with after the cationic modified montmorillonoid of quaternary phosphine, the horizontal and vertical tensile strength of modification packing film all increases, the antibiotic rate of intestinal bacteria and streptococcus aureus is all greater than to 98%, and barrier obviously improves.
The performance of table 4 modification packing film
A.1m
2in 24h, water vapour sees through grams; B.1m
2the cubic centimetre number that in 24h, oxygen sees through under 0.1MPa.
Embodiment 18
Get prepared by embodiment 3 containing quaternary ammonium cation with cationic modified attapulgite 5 mass parts of quaternary phosphine, magnesium hydroxide (3000 orders, chemical pure, is used front 120 DEG C of dry 10h) 40 mass parts, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber or paracril 55 mass parts, put into high-speed mixer, first stirring at low speed 2min under 160rpm, then high-speed stirring 4.5min under 1200rpm, discharging, then be injection molded into styrene-butadiene rubber(SBR), isoprene-isobutylene rubber or paracril sample, analytical test the results are shown in Table 5.
As can be seen from Table 5, add embodiment 3 prepared containing quaternary ammonium cation with after the cationic modified attapulgite of quaternary phosphine; the limiting oxygen index(LOI) of styrene-butadiene rubber(SBR), isoprene-isobutylene rubber or paracril reaches more than 29.0; UL-94 reaches V-0 level; the antibiotic rate of intestinal bacteria and streptococcus aureus is all greater than to 99.9%; chromatic aberration is little, and the notched Izod impact strength of butylbenzene, butyl or paracril obviously raises, and elongation at break and tensile strength obviously do not reduce.
The performance of table 5 modified rubber
Embodiment 19
Get prepared by embodiment 2 containing quaternary ammonium cation with 2 parts of the PERFORMANCE OF MODIFIED VERMICULITE of quaternary phosphine cation A BS, 98 parts of the PP resin of spinning-grade or PET resins.First PERFORMANCE OF MODIFIED VERMICULITE, PP resin or PET resin are put into high-speed mixer, first stirring at low speed 2min under 160rpm, high-speed stirring 4.5min under 1200rpm again, then, by twin screw melt extruder extruding pelletization, obtains modified PP fiber or modified PET fiber finally by melt-spinning.The extruding pelletization of PP and the temperature of melt-spinning are all controlled at 165-185 DEG C, and the extruding pelletization of PET and the temperature of melt-spinning are all controlled at 255-275 DEG C.Analytical test the results are shown in Table 6.
The performance of table 6 modified fibre
As can be seen from Table 6, what interpolation embodiment 3 was prepared contains quaternary ammonium cation with after the cationic PERFORMANCE OF MODIFIED VERMICULITE of quaternary phosphine, PP fiber or PET fiber are all greater than 99.9% to the antibiotic rate of intestinal bacteria and streptococcus aureus, chromatic aberration is little, and breaking tenacity, draw ratio and the elongation at break of PP fiber or PET fiber obviously do not reduce.
Embodiment 20
Get prepared by embodiment 1～embodiment 15 containing quaternary ammonium cation with cationic modified clay 5 mass parts of quaternary phosphine, magnesium hydroxide (3000 orders, chemical pure are used front 120 DEG C of dry 10h) 20 mass parts, styrene-acrylic latex coating 75 mass parts, put into high-speed mixer, first stirring at low speed 2min, then high-speed stirring 4.5min under 1200rpm under 160rpm, discharging, use No. 8 scrapers that prepared coating is coated on respectively to paper, on plastic plate and plank, form 100g/m
2film.Prepared film is tested, and set time, cured film hardness was with reference to GB/T6739-86(pencil method with referring to dry method), cured film sticking power is with reference to GB/T9286-88(cross-hatching).Analytical test the results are shown in Table 7.
As can be seen from Table 7, add containing quaternary ammonium cation with after the cationic modified clay of quaternary phosphine, the limiting oxygen index(LOI) of modification styrene-acrylic latex coating reaches more than 29.4, UL-94 reaches V-0 level, the antibiotic rate of intestinal bacteria and streptococcus aureus is all greater than to 99.9%, chromatic aberration is little, and sticking power to film etc. does not have a significant effect.
The performance of table 7 modification styrene-acrylic latex coating
Embodiment 21
Get prepared by embodiment 1～embodiment 15 containing quaternary ammonium cation with cationic modified clay 3 mass parts of quaternary phosphine, aqueous polyvinyl acetate emulsion 97 mass parts, by the abundant dispersed with stirring of mulser, obtain modified latex.Its frost resistance testing method: sample and glue after solidifying are placed in to refrigerator, and freezing 24h under-5 DEG C～3 DEG C conditions, measures shearing resistance and observation and freeze situation.Analytical test the results are shown in Table 8.
As can be seen from Table 8, add and contain quaternary ammonium cation with after the cationic modified clay of quaternary phosphine, modified latex is all greater than 96.8% to the antibiotic rate of intestinal bacteria and streptococcus aureus, the more blank white glue with vinyl of its mechanical property and frost resistance all has clear improvement.
The performance of table 8 modified latex
Embodiment 22
Get prepared by embodiment 13 containing quaternary ammonium cation with cationic modified montmorillonoid 1～5 mass parts of quaternary phosphine, magnesium hydroxide (3000 orders, chemical pure, is used front 120 DEG C of dry 10h) 20 mass parts, straw pulp fiber, wood pulp cellulose or bamboo pulp fiber 75～79 mass parts, put into high-speed mixer, first stirring at low speed 2min under 160rpm, then high-speed stirring 4.5min under 1200rpm, discharging, then manual handsheet, makes straw pulp paper, wood pulp paper or bamboo pulp paper sample.Analytical test the results are shown in Table 9, testing method reference (Yao Yunzhen, Huang Yiwang, analogy enlightening, Wang Yi, Hu Jian, Liang Yun. the impact [J] of staple length on aramid fiber paper structure and mechanical property. paper and papermaking, 2010,29 (12): 29-32.).
As can be seen from Table 9, what interpolation embodiment 4 was prepared contains quaternary ammonium cation with after the cationic modified montmorillonoid of quaternary phosphine, straw pulp paper, wood pulp paper or bamboo pulp paper are all greater than 97.5% to the antibiotic rate of intestinal bacteria and streptococcus aureus, chromatic aberration is little, and the tensile strength of paper, tearability, pop strength and elongation obviously do not reduce.
The performance of table 9 modification paper
Embodiment 23
Get Modified Montmorillonite with Organic Cations 5 mass parts prepared by embodiment 15, magnesium hydroxide (3000 orders, chemical pure are used front 120 DEG C of dry 10h) 40 mass parts, plastics 33 mass parts, wood powder or bamboo powder 22 mass parts (its median size is less than 10 μ m(and crosses 1250 objects sieves, aperture be 10 μ m), put into high-speed mixer, first stirring at low speed 2min under 160rpm, then high-speed stirring 4.5min under 1200rpm, discharging, is then injection molded into wood and plastic composite material samples.Analytical test the results are shown in Table 10.
As can be seen from Table 10, the limiting oxygen index(LOI) of modified composite material of woods and plastics reaches more than 25.5, UL-94 reaches V-0 level, the antibiotic rate of intestinal bacteria and streptococcus aureus is all greater than to 99.9%, aberration does not have considerable change, and the reduction amplitude of its tensile strength, elongation at break and notched Izod impact strength is also little.
The performance of table 10 modified composite material of woods and plastics
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (9)
1. containing a preparation method for quaternary ammonium cation and the cationic modified clay of quaternary phosphine, it is characterized in that comprising the following steps:
(1) sodium laminated clay is added to the water, stirs and make it be dispersed into suspension, then add quaternary ammonium salt with quaternary alkylphosphonium salt reacts, filter and collect solid substance;
(2) wash to halogen ion-free with the solid substance that aqueous ethanolic solution is prepared step (1), dry, obtain head product;
(3) head product step (2) being obtained is pulverized, and obtains containing quaternary ammonium cation with the cationic modified clay of quaternary phosphine;
Sodium laminated clay described in step (1) is sodium-based montmorillonite, sodium base vermiculite, sodium base attapulgite, sodium base illite or sodium base rectorite leng;
Stirring described in step (1) is 40 DEG C and stirs 0.5h;
The concentration of the suspension described in step (1) is 5～10wt%;
The condition of the reaction described in step (1) is 50～70 DEG C of stirring reaction 3～5h;
Quaternary ammonium salt described in step (1) is suc as formula at least one in the quaternary ammonium salt shown in I or formula II:
Wherein, n
1be 8～16 integer, n
2be 8～12 integer, R
1for methyl, ethyl, butyl, phenyl, R
2for methyl, ethyl, butyl, phenyl or benzyl, R
3for methyl, ethyl, X is Cl or Br;
Quaternary alkylphosphonium salt described in step (1) is suc as formula at least one in the quaternary alkylphosphonium salt of shown in III:
Wherein, n
3be 8～14 integer, R
1for methyl, ethyl, butyl, phenyl, R
2for methyl, ethyl, butyl, phenyl or benzyl, X is Cl or Br;
Quaternary ammonium salt described in step (1) is with the mole number sum of quaternary alkylphosphonium salt is 0.5～1.5 times of sodium laminated clay cation exchange capacity, and described quaternary ammonium salt is with the mol ratio of quaternary alkylphosphonium salt is 3:7～5:5.
According to claim 1 containing quaternary ammonium cation He the preparation method of the cationic modified clay of quaternary phosphine it is characterized in that:
The cation exchange capacity of described sodium laminated clay is respectively: sodium-based montmorillonite 100～160mmol/100g, sodium base vermiculite 90～140mmol/100g, sodium base attapulgite 70～100mmol/100g, sodium base illite 30～60mmol/100g, sodium base rectorite leng 30～60mmol/100g;
The concentration of described suspension is 8wt%;
The condition of described reaction is 60 DEG C of stirring reaction 4h;
Described quaternary ammonium salt is ten alkyl trimethyl ammonium halides, undecyl trimethyl-ammonium halide, dodecyl trimethyl-ammonium halide, tridecyl trimethyl-ammonium halide, tetradecyl trimethyl-ammonium halide, pentadecyl trimethyl-ammonium halide, cetyl trimethyl ammonium halide, heptadecyl trimethyl-ammonium halide, octadecyl trimethyl-ammonium halide, ten alkyl tributyl ammonium halides, undecyl tributyl ammonium halide, dodecyl tributyl ammonium halide, tridecyl tributyl ammonium halide, tetradecyl tributyl ammonium halide, pentadecyl tributyl ammonium halide, hexadecyl tributyl ammonium halide, heptadecyl tributyl ammonium halide, octadecyl tributyl ammonium halide, ten alkyl-dimethyl benzyl ammonium halides, undecyl dimethyl benzyl ammonium halide, dodecyl dimethyl benzyl ammonium halide, tridecyl dimethyl benzyl ammonium halide, tetradecyl dimethyl benzyl ammonium halide, pentadecyl dimethyl benzyl ammonium halide, cetyl dimethyl benzyl ammonium halide, heptadecyl dimethyl benzyl ammonium halide, octadecyl dimethyl benzyl ammonium halide, two ten alkyl methyl ethyl ammonium halides, two undecyl methylethyl ammonium halides, two dodecyl methyl ethyl ammonium halides, double tridecyl methylethyl ammonium halide, two tetradecyl methylethyl ammonium halides, didecyl Dimethy ammonium halide, two undecyl dimethyl ammonium halides, two dodecyl dimethyl ammonium halides, at least one in double tridecyl dimethyl ammonium halide or two tetradecyl dimethyl ammonium halide,
Described quaternary alkylphosphonium salt is ten alkyl trimethyl phosphonium halides, undecyl trimethylammonium phosphonium halide, dodecyl trimethylammonium phosphonium halide, tridecyl trimethylammonium phosphonium halide, tetradecyl trimethylammonium phosphonium halide, pentadecyl trimethylammonium phosphonium halide, cetyl trimethyl phosphonium halide, ten alkyl tributyl phosphonium halides, undecyl tributyl phosphonium halide, dodecyl tributyl phosphonium halide, tridecyl tributyl phosphonium halide, tetradecyl tributyl phosphonium halide, pentadecyl tributyl phosphonium halide, hexadecyl tributyl phosphonium halide, ten alkyl triphenyl phosphonium halides, undecyl triphenyl phosphonium halide, dodecyl triphenyl phosphonium halide, tridecyl triphenyl phosphonium halide, tetradecyl triphenyl phosphonium halide, pentadecyl triphenyl phosphonium halide, hexadecyl triphenyl phosphonium halide, ten alkyl dimethyl benzyl phosphonium halides, hendecane base dimethyl benzyl phosphonium halide, dodecyl dimethyl benzyl phosphonium halide, tridecyl dimethyl benzyl phosphonium halide, tetradecyl dimethyl benzyl phosphonium halide, at least one in pentadecyl dimethyl benzyl phosphonium halide or hexadecyldimethyl benzyl ammonium benzyl phosphonium halide,
Described quaternary ammonium salt is with the mole number sum of quaternary alkylphosphonium salt is 1 times of sodium laminated clay cation exchange capacity, and described quaternary ammonium salt is with the mol ratio of quaternary alkylphosphonium salt is 1:1.
According to claim 1 containing quaternary ammonium cation He the preparation method of the cationic modified clay of quaternary phosphine it is characterized in that:
Aqueous ethanolic solution described in step (2) is the aqueous ethanolic solution of the 50wt% of 50 DEG C;
Halide-ions described in step (2) refers to bromide anion and chlorion;
Being dried as more than dry 24h in the air atmosphere of 110 DEG C described in step (2).
According to claim 1 containing quaternary ammonium cation He the preparation method of the cationic modified clay of quaternary phosphine it is characterized in that: the pulverizing described in step (3) is that superfine grinding is crushed to median size by head product and is less than 10 microns.
5. containing quaternary ammonium cation and the cationic modified clay of quaternary phosphine, it is characterized in that being prepared by the preparation method described in claim 1～4 any one.
6. the quaternary ammonium cation that contains claimed in claim 5 is with the application of the cationic modified clay of quaternary phosphine in polymkeric substance.
7. the quaternary ammonium cation that contains according to claim 6 is with the application of the cationic modified clay of quaternary phosphine in polymkeric substance, it is characterized in that comprising the steps: 1～5 mass parts is contained to quaternary ammonium cation with the cationic modified clay of quaternary phosphine and 0～40 mass parts magnesium hydroxide join in the corresponding polymkeric substance of 55～99 mass parts by different complete processings, obtain polymer-modified.
According to claim 7 containing quaternary ammonium cation He the application of the cationic modified clay of quaternary phosphine in polymkeric substance it is characterized in that:
Described magnesium hydroxide is chemical pure, 3000 object magnesium hydroxides, before use 120 DEG C of dry 10h;
Described polymkeric substance is plastics, rubber, fiber, coating, tackiness agent, paper or wood plastic composite;
In the time that polymkeric substance is plastics, rubber or wood plastic composite, described complete processing is the technique of injection moulding again after mixing in high-speed mixer;
In the time that polymkeric substance is fiber, described complete processing is the technique of wire drawing again after mixing in high-speed mixer;
In the time that polymkeric substance is coating or tackiness agent, described complete processing is dispersed with stirring technique;
In the time that polymkeric substance is paper, described complete processing is the technique of copy paper again after mixing in high-speed mixer.
According to claim 8 containing quaternary ammonium cation He the application of the cationic modified clay of quaternary phosphine in polymkeric substance it is characterized in that:
The condition of mixing in described high-speed mixer is: first stirring at low speed 2min under 160rpm, then under 1200rpm high-speed stirring 4.5min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210308868.9A CN102816461B (en) | 2012-08-27 | 2012-08-27 | Quaternary ammonium cation and quaternary phosphonium cation-containing modified clay, its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210308868.9A CN102816461B (en) | 2012-08-27 | 2012-08-27 | Quaternary ammonium cation and quaternary phosphonium cation-containing modified clay, its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102816461A CN102816461A (en) | 2012-12-12 |
| CN102816461B true CN102816461B (en) | 2014-10-29 |
Family
ID=47300927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210308868.9A Active CN102816461B (en) | 2012-08-27 | 2012-08-27 | Quaternary ammonium cation and quaternary phosphonium cation-containing modified clay, its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102816461B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103451993B (en) * | 2013-08-01 | 2015-10-28 | 安徽省安邦矿物有限公司 | A kind of attapulgite clay paper making additive and preparation method thereof |
| CN105131653A (en) * | 2015-07-25 | 2015-12-09 | 铜陵瑞莱科技有限公司 | Iron oxide black pigment used for printing ink and preparation method thereof |
| CN105111794A (en) * | 2015-07-27 | 2015-12-02 | 安徽明珠颜料科技有限公司 | Black iron oxide pigment containing tourmalinite powder and preparation method thereof |
| CN105086518A (en) * | 2015-07-27 | 2015-11-25 | 安徽明珠颜料科技有限公司 | Black iron oxide pigment containing bamboo charcoal powder and preparation method thereof |
| CN105766994A (en) * | 2016-04-15 | 2016-07-20 | 佛山市聚成生化技术研发有限公司 | Preparation method of biodegradable bactericide and prepared biodegradable bactericide |
| CN106675534B (en) * | 2017-02-10 | 2019-08-13 | 中国石油化工股份有限公司 | A kind of heat-resistant salt-resistant type prevents swollen clay stabilizer and its synthetic method |
| CN108676347A (en) * | 2018-05-18 | 2018-10-19 | 许水仙 | A kind of preparation method of the special antistatic agent of polyurethane plastics |
| CN108752728A (en) * | 2018-06-25 | 2018-11-06 | 安徽省创安体育用品有限公司 | A kind of elastic processing method of raising foamed shoe sole |
| CN113718363B (en) * | 2021-09-06 | 2023-12-01 | 浙江戴乐无纺新材料有限公司 | Water-jet composite non-woven fabric and preparation method thereof |
| CN114479371A (en) * | 2021-12-24 | 2022-05-13 | 上海普利特复合材料股份有限公司 | Antibacterial degradable gas barrier material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724415A (en) * | 2009-12-18 | 2010-06-09 | 暨南大学 | Non-halogen flame retardant containing phosphonium actericide modified montmorillonite, preparation method and application thereof |
| CN101932641A (en) * | 2008-01-30 | 2010-12-29 | 昭和电工株式会社 | Transparent composite |
-
2012
- 2012-08-27 CN CN201210308868.9A patent/CN102816461B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101932641A (en) * | 2008-01-30 | 2010-12-29 | 昭和电工株式会社 | Transparent composite |
| CN101724415A (en) * | 2009-12-18 | 2010-06-09 | 暨南大学 | Non-halogen flame retardant containing phosphonium actericide modified montmorillonite, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102816461A (en) | 2012-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102816461B (en) | Quaternary ammonium cation and quaternary phosphonium cation-containing modified clay, its preparation and application | |
| Fukushima et al. | Properties of poly (lactic acid) nanocomposites based on montmorillonite, sepiolite and zirconium phosphonate. | |
| Xu et al. | An overview of alginates as flame-retardant materials: Pyrolysis behaviors, flame retardancy, and applications | |
| EP2729552B1 (en) | Fire-resistant cellulosic material | |
| Idumah et al. | Emerging trends in eco-compliant, synergistic, and hybrid assembling of multifunctional polymeric bionanocomposites | |
| Mahmoodi et al. | High-strength, low-permeable, and light-protective nanocomposite films based on a hybrid nanopigment and biodegradable PLA for food packaging applications | |
| CA2797927C (en) | A composition comprising microfibrillated cellulose and a process for the production of a composition | |
| CN101492572B (en) | Antimicrobial macromolecule material and method for preparing the same | |
| Fox et al. | Char-forming behavior of nanofibrillated cellulose treated with glycidyl phenyl POSS | |
| CN102268750B (en) | Antibiotic fiber, preparation method thereof, and pillow core and quilt core containing antibiotic fiber | |
| CN101926358B (en) | Quaternary phosphonium salt pillared layered zirconium phosphate material, and preparation method and application thereof | |
| CN101302318A (en) | Polychloroethylene / organic modified sheet silicate nano-composite material | |
| Villanueva et al. | Comparative study of nanocomposites of polyolefin compatibilizers containing kaolinite and montmorillonite organoclays | |
| CN103643332B (en) | A kind of functional composite fiber and preparation method thereof | |
| CN108794931A (en) | A kind of method of modifying of flame retardant type PVC board timber-used nano-calcium carbonate and its application | |
| CN105924757A (en) | Halogen-free and high-flame-retardancy cable material and preparation method thereof | |
| CN106120020A (en) | A kind of preparation method of ageing resistance polypropylene fiber | |
| CN105419258A (en) | Method of preparing degradable flame-retarding composite material with surface-modified magnesium salt crystal whisker | |
| JP5934064B2 (en) | Additive for thermoplastic resin | |
| Gao et al. | Composite based on poly (acrylic acid)/modified attapulgite/zinc oxide as a flame retardant of cotton fabrics | |
| CN110066293A (en) | A kind of aminotrimethylenephosphonic acid aluminium and its preparation method and application | |
| Kilinc | Silicon based flame retardants | |
| Micó-Vicent et al. | A combination of three surface modifiers for the optimal generation and application of natural hybrid nanopigments in a biodegradable resin | |
| Kabiri et al. | Highly rapid preparation of a bio-modified nanoclay with chitosan | |
| Badritala et al. | Morphology and mechanical properties of zinc borate-pretreated poplar wood flour/plastic composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |