CN101926358A - Quaternary phosphonium salt pillared layered zirconium phosphate material, and preparation method and application thereof - Google Patents
Quaternary phosphonium salt pillared layered zirconium phosphate material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of quaternary phosphonium salt pillared layered zirconium phosphate materials and its preparation method and application. The chemical formula of quaternary phosphonium salt pillared layered zirconium phosphate material of the invention is
; R is the alkane of methyl, butyl, phenyl or carbochain a length of 8~20; X is Cl or Br; M is that 1, n is 0.00288~0.174462. The present invention is by being strutted the interlamellar spacing of basic zirconium phosphate using methylamine, obtain methylamine-basic zirconium phosphate presoma, then by the quaternary alkylphosphonium salt certain time that is added in methylamine-basic zirconium phosphate presoma that the reaction was continued, replace out the methylamine in presoma, appearance is obtained as white or grayish quaternary phosphonium salt pillared layered zirconium phosphate material, it is added prepares antibacterial or flame retarding function material in the materials such as plastics, rubber, fiber, coating, adhesive, paper, it also can remove the algae in water, for administering the red tide and fresh water bloom of large area.
Description
Technical field
The present invention relates to a kind of hybrid inorganic-organic materials and its production and application, particularly a kind of quaternary phosphonium salt pillared layered zirconium phosphate material and its production and application.
Background technology
Therefore lamellar clay is a kind of good carrier of functional materials because its interlayer has tradable hydrated cation, absorption property is strong.With the interlayer of functional organic matter insertion lamellar clay, make itself and lamellar clay form the compound of molecular level, obtain insoluble pillared compound.Pillared compound is because functional organic warm tolerance wherein increases substantially, toxicity descends, thus stable performance, long-acting.
Phosphate is the novel cationic lamellar compound of a class that development in recent years is got up, and its chemical formula can be used formula M (HPO4)
2H
2O (being abbreviated as MP, M=Zr, Ti, Sn, Hf etc.) expression (Zhang Rui, Hu Yuan, Song Lei etc. the synthetic extremely stability [J] of the hydro-thermal of layered phosphates. China YouSe Acta Metallurgica Sinica, 2001,11 (5): 895-899.).Because phosphate has regular veneer structure and can design and modulability, and heat endurance and resistance to acids and bases is good, ion-exchange performance and catalytic performance are good, be the good matrix of pillared compound of preparation or layer post catalysis material.
Quaternary ammonium salt and quaternary alkylphosphonium salt all are typical organic cation type bactericide.If directly use these organic cations to carry out sterilization, cause the pollution of water body easily, so the researcher attempt being fixed in the clay, to reach long acting antibiotic and purpose free from environmental pollution.Because organic cation type bactericide all contains chain alkyl, the molecule space volume is bigger, and phosphatic interlamellar spacing is little, so organic cation type bactericide can't directly insert phosphatic interlayer.In research process to phosphatic intercalation behavior and ion-exchange capacity, discovery is with little molecule of polarity such as alkylamine, hydramine and alkylamine alkali etc. can carry out colloidization to it to be handled, these little molecule insert layer chien shih interlamellar spacings are enlarged, reaction force attenuation between laminate, as presoma, other guest molecule is easy to enter interlayer and forms stable pillared compound or intercalation compound (H.Y. Wang, D.X.Han.A new method of immobilizing ionic liquids into layered zirciniumphosphates [J] .Chinese Chemical Letters, 2007,18:764-767.).So far the interlayer that successfully organic cations such as cetyl trimethyl quaternary ammonium cation is inserted basic zirconium phosphate has prepared pillared compound (R.A.Berm ú dez, Y. Col ó n, G. A.Tejada.Intercalation and photophysical characterization of1-pyrenemethylamine in zirconium phosphate layered materials[J] .Langmuir, 2005,21:890-895.).But the existing pillared compound of basic zirconium phosphate mostly is a quaternary ammonium cation, and its weak point is that temperature resistant capability is lower than 200 ℃, and therefore the processing and forming temperature of general plastics has limited its range of application all more than 200 ℃.
Quaternary alkylphosphonium salt is that a new generation is efficient, wide spectrum, the low toxicity bactericide, it is low to have foam, the foundry loam stripping ability is strong, characteristics (Omatete O O such as the wide and anti-flammability height of the pH value scope of application, Pollinger J P. Gelcasting andaquous injection molding for silicon nitride structural ceramics[A] .In:Fed L Conference of Ceramic Processing[C F.6thInternational], USA:Materials ReserchLaboratory at UCSB, 1997.11.), itself and quaternary ammonium cation structural similarity, but warm tolerance is better relatively.About preparing antimicrobial powder, yet there are no relevant report at present with the pillared basic zirconium phosphate of quaternary phosphine cation.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of quaternary phosphonium salt pillared layered zirconium phosphate material with not enough.The outward appearance of this material is white or light grey powder, has antibiotic, fire-retardant effect, can in materials such as plastics, rubber, fiber, coating, adhesive, paper and porcelain, obtain to use, also can remove the algae in the water, be used to administer large tracts of land red tide of sea, fresh water bloom, also be applicable to the removal of harmful algae in river course and the drinking water plant, have multifunctionality.
Another object of the present invention is to provide the preparation method of described quaternary phosphonium salt pillared layered zirconium phosphate material.
A further object of the present invention is to provide the application of described quaternary phosphonium salt pillared layered zirconium phosphate material.
Purpose of the present invention is achieved through the following technical solutions: a kind of quaternary phosphonium salt pillared layered zirconium phosphate material, chemical formula is
Wherein R is that methyl, butyl, phenyl or carbon chain lengths are 8～20 alkyl; X is Cl or Br; M is 1, and n is 0.00288～0.174462.
The preparation method of described quaternary phosphonium salt pillared layered zirconium phosphate material may further comprise the steps:
(1) (α-ZrP) be scattered in the water adds methylamine (MA) then, stirs 1～4h at 40～80 ℃, obtains MA-ZrP solution with alpha zirconium phosphate; Wherein the mol ratio of α-ZrP and MA is 1: 1～1: 10;
(2) quaternary alkylphosphonium salt with chloride ion-containing or bromide ion joins in the MA-ZrP solution, and stirring reaction 4～10h filters and collects solid content; Wherein the mol ratio of α-ZrP and quaternary alkylphosphonium salt is 1: 0.01～1: 10;
(3) wash to not having bromide ion or not having chlorion with the solid content of distilled water with step (2) preparation, drying obtains head product;
(4) head product with step (3) preparation grinds, and obtains the quaternary phosphonium salt pillared layered zirconium phosphate material of different-grain diameter.
In order to realize the present invention better, described quaternary alkylphosphonium salt is preferably suc as formula the quaternary alkylphosphonium salt shown in I or the formula II structure:
Formula I formula II
N, n
1And n
2Be respectively 8～14 even number;
R1 is methyl, butyl or phenyl;
R2 is methyl, butyl or phenyl;
R3 is methyl, butyl or phenyl;
X is Cl or Br;
The preferred ten alkyl trimethyl phosphonium chlorides of described quaternary alkylphosphonium salt, ten alkyl trimethyl phosphonium bromides, ten alkyl tributyl phosphorus chloride, ten alkyl tributyl phosphonium bromides, ten alkyl triphenyl phosphonium chlorides, ten alkyl, three phenyl phosphonium bromides, dodecyl San Jia Ji phosphonium chloride, dodecyl three methyl phosphonium bromides, dodecyl tributyl phosphorus chloride, dodecyl tributyl phosphonium bromide, the dodecyl triphenyl phosphonium chloride, dodecyl three phenyl phosphonium bromides, tetradecane base San Jia Ji phosphonium chloride, tetradecane base three methyl phosphonium bromides, myristyl tributyl phosphonium chloride, myristyl tributyl phosphonium bromide, the myristyl triphenyl phosphonium chloride, myristyl three phenyl phosphonium bromides, the cetyl trimethyl phosphonium chloride, Shi six alkyl trimethyl phosphonium bromides, phosphonium hexadecanyl-3-butyl chloride, hexadecyl tributyl phosphonium bromide, at least a in cetyl triphenyl phosphonium chloride or the cetyl three phenyl phosphonium bromides;
The temperature of stirring reaction is preferably 20～30 ℃ described in the step (2);
Drying described in the step (3) is preferably vacuum drying;
Described vacuum drying condition is preferably 60～120 ℃ of drying 12～48h, and vacuum is 1 * 10
4～3 * 10
4Pa;
Described quaternary phosphonium salt pillared layered zirconium phosphate material being applied as in materials such as plastics, rubber, fiber, coating, adhesive, paper is added on the antibiotic or anti-flaming function material of preparation in the materials such as plastics, rubber, fiber, coating, adhesive, paper;
Described quaternary phosphonium salt pillared layered zirconium phosphate material also can be used for removing the algae in the water, administers the harmful algae in large tracts of land red tide of sea, fresh water bloom and removal river course and the drinking water plant.
Principle of the present invention is to utilize methylamine that the interlamellar spacing of basic zirconium phosphate is strutted, obtain methylamine-basic zirconium phosphate presoma, then quaternary alkylphosphonium salt is joined in methylamine-basic zirconium phosphate presoma and to continue the reaction certain hour, replace out the methylamine in the presoma, and finally must arrive the phosphonium salt pillared layered zirconium phosphate material.
The present invention has following advantage and effect with respect to prior art:
(1) multifunctionality: the quaternary phosphonium salt pillared layered zirconium phosphate material that is synthesized has antibiotic, fire-retardant effect, can in materials such as plastics, rubber, fiber, coating, adhesive, paper porcelain, obtain to use, also can be used as the algae in antibiotic and the flocculation material removal water, be used to administer large tracts of land red tide of sea, fresh water bloom, also be applicable to the removal of harmful algae in river course and the drinking water plant, have multifunctionality.
(2) heat resisting temperature is higher: be that the quaternary phosphonium salt pillared basic zirconium phosphate compound of preparing carriers has than the higher heat resisting temperature of the pillared basic zirconium phosphate compound of quaternary ammonium salt with the basic zirconium phosphate, its heat endurance can be greater than 250 ℃, overcome the pillared basic zirconium phosphate temperature resistant capability of present quaternary ammonium cation and be lower than 200 ℃ shortcoming, helped it is added on great majority by in the macromolecular material of melt-processed.
(3) good weatherability: the quaternary phosphine cation inserts the interlayer of basic zirconium phosphate, because its closely compound with clay formation molecular level, so its good stability, weather resistance is good, is stable long-acting composite.
(4) toxicity is little: the LD of this material
50＞5000mg/g is the nontoxic level of reality material, and no mutagenicity is to the skin nonirritant.
(5) mechanical mechanics property there is not influence:, only be 0.5～3.0%, so can not have influence on the mechanical property of plastics and elastomeric material substantially because the addition of the cation-modified basic zirconium phosphate of quaternary phosphine is low.
Description of drawings
Fig. 1 is assembled to process schematic diagram between phosphate layer for organic cation.
Fig. 2 is the X-ray diffractogram of the embodiment of the invention 1.
Fig. 3 is the X-ray diffractogram of the embodiment of the invention 2.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Take by weighing 5.82g (0.02mol) stratiform α-ZrP and be scattered in the 300mL water, wait to disperse to finish, in this dispersion liquid, add methylamine (MA) solution (containing methylamine 0.10mol) of 12g 25%, stir 2h down, obtain MA-ZrP solution after the stirring at 60 ℃.Then 8.12g (0.02mol) dodecyl tributyl phosphonium bromide is joined in the MA-ZrP solution, stir, 25 ℃ are reacted 6h down, and product is filtered, solid content is washed with distilled water to detects filtrate with liquor argenti nitratis ophthalmicus and do not have bromide ion, (vacuum is 2 * 10 to 90 ℃ of vacuum
4Pa) dry 24h obtains head product, then ultra-fine grinding to average grain diameter less than 5 microns, (according to the TGA analysis result, chemical formula is to obtain quaternary phosphonium salt pillared layered zirconium phosphate material
).Testing result sees Table 1.
Embodiment 2
Take by weighing 5.82g (0.02mol) α-ZrP and be scattered in the 300mL water, wait to disperse to finish, in this dispersion liquid, add methylamine (MA) solution (containing methylamine 0.05mol) of 6g 25%, stir 3h down, obtain MA-ZrP solution after the stirring at 65 ℃.Then 32.48g (0.08mol) dodecyl tributyl phosphorus chloride is joined in the MA-ZrP solution, stir, 30 ℃ are reacted 5h down, and product is filtered, solid content is washed with distilled water to detects filtrate with liquor argenti nitratis ophthalmicus and do not have chlorion, (vacuum is 2 * 10 to 80 ℃ of vacuum
4Pa) dry 20h obtains head product, then ultra-fine grinding to average grain diameter less than 5 microns, (according to the TGA analysis result, chemical formula is to obtain quaternary phosphonium salt pillared zirconium phosphate material
).Testing result sees Table 1.
Embodiment 3
Take by weighing 5.82g (0.02mol) α-ZrP and be scattered in the 300mL water, wait to disperse to finish, in this dispersion liquid, add methylamine (MA) solution (containing methylamine 0.02mol) of 2.4g (0.02mol) 25%, stir 1h down, obtain MA-ZrP solution after the stirring at 40 ℃.Then 0.0894g (0.0002mol) ten alkyl tri-phenyl-phosphorus bromides are joined in the MA-ZrP solution, stir, 20 ℃ are reacted 4h down, and product is filtered, solid content is washed with distilled water to detects filtrate with liquor argenti nitratis ophthalmicus and do not have bromide ion, (vacuum is 2 * 10 to 80 ℃ of vacuum
4Pa) dry 24h obtains head product, then ultra-fine grinding to average grain diameter less than 3 microns, (according to the TGA analysis result, chemical formula is to obtain quaternary phosphonium salt pillared zirconium phosphate material
).Testing result sees Table 1.
Embodiment 4
Take by weighing 5.82g (0.02mol) α-ZrP and be scattered in the 300mL water, wait to disperse to finish, in this dispersion liquid, add methylamine (MA) solution (containing methylamine 0.2mol) of 24g (0.2mol) 25%, stir 4h down, obtain MA-ZrP solution after the stirring at 80 ℃.Then the two eicosyl diphenyl phosphorus chlorides of 158g (0.2mol) are joined in the MA-ZrP solution, stir, 30 ℃ are reacted 10h down, and product is filtered, solid content is washed with distilled water to detects filtrate with liquor argenti nitratis ophthalmicus and do not have chlorion, (vacuum is 2 * 10 to 120 ℃ of vacuum
4Pa) dry 22h obtains head product, then ultra-fine grinding to average grain diameter less than 5 microns, (according to the TGA analysis result, chemical formula is to obtain quaternary phosphonium salt pillared zirconium phosphate material
).Testing result sees Table 1.
Take by weighing 5.82g (0.02mol) α-ZrP and be scattered in the 300mL water, wait to disperse to finish, in this dispersion liquid, add methylamine (MA) solution (containing methylamine 0.15mol) of 18g (0.15mol) 25%, stir 3h down, obtain MA-ZrP solution after the stirring at 50 ℃.Then the two ten alkyl dibutyl phosphonium bromides of 46.8g (0.10mol) are joined in the MA-ZrP solution, stir, 25 ℃ are reacted 8h down, and product is filtered, solid content is washed with distilled water to detects filtrate with liquor argenti nitratis ophthalmicus and do not have bromide ion, (vacuum is 2 * 10 to 60 ℃ of vacuum
4Pa) dry 12h obtains head product, then ultra-fine grinding to average grain diameter less than 5 microns, (according to the TGA analysis result, chemical formula is to obtain quaternary phosphonium salt pillared zirconium phosphate material
).Testing result sees Table 1.
Embodiment 6:
Take by weighing 5.82g (0.02mol) α-ZrP and be scattered in the 300mL water, wait to disperse to finish, in this dispersion liquid, add methylamine (MA) solution (containing methylamine 0.04mol) of 4.8g (0.04mol) 25%, stir 3.5h down, obtain MA-ZrP solution after the stirring at 75 ℃.Then 0.812g (0.002mol) dodecyl tributyl phosphonium bromide is joined in the MA-ZrP solution, stir, 30 ℃ are reacted 9h down, and product is filtered, solid content is washed with distilled water to detects filtrate with liquor argenti nitratis ophthalmicus and do not have bromide ion, (vacuum is 2 * 10 to 115 ℃ of vacuum
4Pa) dry 46h obtains head product, then ultra-fine grinding to average grain diameter less than 5 microns, (according to the TGA analysis result, chemical formula is to obtain quaternary phosphonium salt pillared zirconium phosphate material
).Testing result sees Table 1.
Embodiment 7:
Take by weighing 5.82g (0.02mol) α-ZrP and be scattered in the 300mL water, wait to disperse to finish, in this dispersion liquid, add methylamine (MA) solution (containing methylamine 0.08mol) of 9.6g (0.08mol) 25%, stir 4h down, obtain MA-ZrP solution after the stirring at 65 ℃.Then the two ten alkyl dibutyl phosphorus chloride of 4.68g (0.01mol) are joined in the MA-ZrP solution, stir, 30 ℃ are reacted 9.5h down, and product is filtered, solid content is washed with distilled water to detects filtrate with liquor argenti nitratis ophthalmicus and do not have chlorion, (vacuum is 2 * 10 to 105 ℃ of vacuum
4Pa) dry 42h obtains head product, then ultra-fine grinding to average grain diameter less than 5 microns, (according to the TGA analysis result, chemical formula is to obtain quaternary phosphonium salt pillared zirconium phosphate material
).Testing result sees Table 1.
Embodiment 8:
Take by weighing 5.82g (0.02mol) α-ZrP and be scattered in the 300mL water, wait to disperse to finish, in this dispersion liquid, add methylamine (MA) solution (containing methylamine 0.16mol) of 19.2g (0.16mol) 25%, stir 1.5h down, obtain MA-ZrP solution after the stirring at 55 ℃.Then 16.24g (0.04mol) dodecyl tributyl phosphonium bromide is joined in the MA-ZrP solution, stir, 30 ℃ are reacted 5.5h down, and product is filtered, solid content is washed with distilled water to detects filtrate with liquor argenti nitratis ophthalmicus and do not have bromide ion, (vacuum is 2 * 10 to 120 ℃ of vacuum
4Pa) dry 20h obtains head product, then ultra-fine grinding to average grain diameter less than 5 microns, (according to the TGA analysis result, chemical formula is to obtain quaternary phosphonium salt pillared zirconium phosphate material
).Testing result sees Table 1.
The testing result of the quaternary phosphonium salt pillared zirconium phosphate material of table 1 embodiment 1～8 preparation
Annotate:
aWt%: the content of quaternary alkylphosphonium salt in every 100g basic zirconium phosphate matrix;
Adopt organic content and initial heat decomposition temperature (Onset decomposition temperature) in thermogravimetic analysis (TGA) (TGA) material, with the content of the weightlessness between 200～500 ℃ as quaternary alkylphosphonium salt, but concrete computational methods reference literature (Tan Shaozao, Zhang Kuihua, Li Duxin, Liu Yingliang, Zhang Yuanming. the preparation of phosphonium actericide modified montmorillonite and performance [J]. Central South University's journal (natural science edition), 2006,37 (2): 280-285.), heating rate is 10/min, nitrogen atmosphere, temperature range: 30-800 ℃; Adopt film adherence method (Japanese SIAA (SIAA) " the antimicrbial power evaluation test method of antibacterial product---film adherence method ") to measure it to Escherichia coli (ATCC25292, the Guangdong Microbes Inst provides) and the anti-microbial property of staphylococcus aureus (ATCC6538, the Guangdong Microbes Inst provides).
As can be seen from Table 1, although the quaternary phosphonium salt pillared zirconium phosphate material quaternary alkylphosphonium salt content difference of embodiment 1～8 preparation does not all have excitant to human body skin, and per os toxicity LD
50All greater than 5000, reality is to the human body non-toxic material.The initial heat decomposition temperature of all quaternary phosphonium salt pillared zirconium phosphate materials is all greater than 250 ℃, and its antibacterial activity increases and increases gradually along with quaternary alkylphosphonium salt content.
Embodiment 9
With the chemical formula of embodiment 1 preparation be
Quaternary phosphonium salt pillared zirconium phosphate material be prepared into PE (polyethylene), PP (polypropylene), ABS (acrylonitrile-butadiene-styrene copolymer) antibacterial plastic concentrate that contained for 20% (every 100g matrix material contains the mass percent of quaternary phosphonium salt pillared zirconium phosphate material) respectively, again antibacterial plastic concentrate is added in the corresponding plastics by 2.0wt% or 4.0wt%, is injection molded into PE, PP, ABS plastic sample then.For prepared sample, adopt film adherence method (Japanese SIAA (SIAA) " the antimicrbial power evaluation test method of antibacterial product---film adherence method ") to measure it to Escherichia coli (ATCC25292, the Guangdong Microbes Inst provides) and the anti-microbial property of staphylococcus aureus (ATCC6538, the Guangdong Microbes Inst provides); Carry out fluorescent ultraviolet lamp exposure test 240h by GB/T14522-1993, light source is UV-A lamp (351nm), carries out aberration by GB/T3979-1997, GB/T 7921-1997 and detects.The results are shown in Table 2.As can be seen from Table 2, the chemical formula of interpolation 2% is in plastics
Quaternary phosphonium salt pillared zirconium phosphate material, the anti-microbial property of plastics is reached more than 90% substantially, and does not change the color of plastics substantially.
The performance of table 2 antibiotic plastic
With the chemical formula of embodiment 8 preparations be
Quaternary phosphonium salt pillared zirconium phosphate material and OP-10 20: 1 in molar ratio add in the deionized water, be made into the emulsion that the composite antibiosis agent concentration is 20wt%, more than the ball milling 3h, add in the Silicone acrylic emulsion type interior wall coating in the ratio of 1wt%, 2wt%, 3wt% and 4wt% (every 100g matrix material contains the mass percent of quaternary phosphonium salt pillared zirconium phosphate material) respectively then and stir, obtain antibacterial inner wall paint.Method of testing is with embodiment 9, and result of the test sees Table 3.As can be seen from Table 3, the chemical formula of interpolation 4% is in interior wall coating
Quaternary phosphonium salt pillared zirconium phosphate material, the anti-microbial property of plastics is reached more than 90%, and does not change the color of coating substantially.
The performance of table 3 antibacterial inner wall paint
Embodiment 11
With the chemical formula of embodiment 8 preparations be
Quaternary phosphonium salt pillared zirconium phosphate material be added in the raw material of silicon rubber by 1wt%, 2wt%, 3wt% and 4wt% (every 100g matrix material contains the mass percent of quaternary phosphonium salt pillared zirconium phosphate material) and mix, be processed into the antimicrobial silicon rubbery sample then.Method of testing is with embodiment 9, and result of the test sees Table 4.As can be seen from Table 4, the chemical formula of interpolation 3% is in silicon rubber
Quaternary phosphonium salt pillared zirconium phosphate material, the anti-microbial property of silicon rubber is reached more than 99%, and does not change the color of plastics substantially.
The performance of table 4 antimicrobial silicon rubber
Embodiment 12
With the chemical formula of embodiment 1 preparation be
The preparation of no quaternary phosphonium salt pillared zirconium phosphate material become to contain 20% PP (polypropylene), PA (polyamide) antibacterial plastic concentrate respectively, again antibacterial plastic concentrate is added among PP, the PA of corresponding fibre-grade by 1wt% and 2wt% (every 100g matrix material contains the mass percent of quaternary phosphonium salt pillared zirconium phosphate material), obtains antibiotic PP, PA fiber through melt spinning then.For prepared sample, adopt film adherence method (Japanese SIAA (SIAA) " the antimicrbial power evaluation test method of antibacterial product---film adherence method ") to measure it to Escherichia coli (ATCC25292, the Guangdong Microbes Inst provides) and the anti-microbial property of staphylococcus aureus (ATCC6538, the Guangdong Microbes Inst provides); Carry out fluorescent ultraviolet lamp exposure test 120h by GB/T 14522-1993, light source is UV-A lamp (351nm), carries out aberration by GB/T 3979-1997, GB/T 7921-1997 and detects.Result of the test sees Table 5.As can be seen from Table 5, the chemical formula of interpolation 2% is in fiber
Quaternary phosphonium salt pillared zirconium phosphate material, the anti-microbial property of silicon rubber is reached more than 98%, and does not change the color of plastics substantially.
The performance of table 5 anti-bacterial fibre
Embodiment 13
With the chemical formula of embodiment 1 preparation be
Quaternary phosphonium salt pillared zirconium phosphate material add in the raw material of white glue with vinyl in the ratio of 0.5wt%, 1wt%, 2wt% and 3wt% (every 100g matrix material contains the mass percent of quaternary phosphonium salt pillared zirconium phosphate material) respectively, be uniformly dispersed, obtain antibiotic white glue with vinyl.Method of testing is with embodiment 9, and result of the test sees Table 6.As can be seen from Table 6, the chemical formula of interpolation 2% is in white glue with vinyl
Quaternary phosphonium salt pillared zirconium phosphate material, the anti-microbial property of white glue with vinyl is reached more than 99.9%, and does not change the color of plastics substantially.
The performance of the antibiotic white glue with vinyl of table 6
Embodiment 14
With the chemical formula of embodiment 8 preparations be
Quaternary phosphonium salt pillared zirconium phosphate material add in the raw material of paper in the ratio of 0.5wt%, 1wt%, 2wt% and 3wt% (every 100g matrix material contains the mass percent of quaternary phosphonium salt pillared zirconium phosphate material) respectively, after dispersed with stirring is even, copy sheet by hand, obtain antibiotic handmade paper through the squeezing oven dry.Method of testing the results are shown in Table 7 with embodiment 9.As can be seen from Table 7, the chemical formula of interpolation 3% is in paper
Quaternary phosphonium salt pillared zirconium phosphate material, the anti-microbial property of paper is reached more than 99.9%, and does not change the color of plastics substantially.
The performance of the antibiotic handmade paper of table 7
With the chemical formula of embodiment 1 preparation be
Quaternary phosphonium salt pillared zirconium phosphate material be prepared into PE (polyethylene), PP (polypropylene), ABS (acrylonitrile-butadiene-styrene copolymer) antibacterial plastic concentrate that contained for 20% (every 100g matrix material contains the mass percent of quaternary phosphonium salt pillared zirconium phosphate material) respectively, again antibacterial plastic concentrate is added in the corresponding plastics by 2.5wt% or 5.0wt%, is injection molded into PE, PP, ABS plastic sample then.Demarcate limited oxygen index (LOI) according to GB/T2406-93, sample is of a size of 100mm * 6.5mm * 3.0mm; Adopt the vertical combustion method of 94V-0,94V-1,94V-2, press ASTM-63S working sample anti-flammability, sample size is 130mm * 13mm * 3.0mm.Result of the test sees Table 8.As can be seen from Table 8, the chemical formula of interpolation 5% is in plastics
Quaternary phosphonium salt pillared zirconium phosphate material, the limited oxygen index of plastics is increased, and the carbon residual volume also increases.
The performance of table 8 flame retardant plastics
The antibacterial plastic concentrate addition has or not molten 500 ℃ of charcoal residual volumes
Antibiotic plastic limited oxygen index (LOI) UL-94 (3.0mm)
(wt%) drip (%)
PE 2.5 21.5 V-2 do not have 4.13
PE 5.0 24.1 V-2 do not have 8.31
PP 2.5 22.8 V-2 do not have 4.37
PP 5.0 24.3 V-2 do not have 8.95
ABS 2.5 19.7 V-2 do not have 3.54
ABS 5.0 23.4 V-2 do not have 7.56
Embodiment 16
With the chemical formula of embodiment 1 preparation be
The preparation of no quaternary phosphonium salt pillared zirconium phosphate material become to contain PP (polypropylene), PA (polyamide) antibacterial plastic concentrate of 20% (every 100g matrix material contains the mass percent of quaternary phosphonium salt pillared zirconium phosphate material) respectively, again antibacterial plastic concentrate is added into by 1wt% and 2wt% among PP, the PA of corresponding fibre-grade, obtains antibiotic PP, PA fiber through melt spinning then.Method of testing is with embodiment 15, and result of the test sees Table 9.As can be seen from Table 9, the chemical formula of interpolation 2% is in fiber
Quaternary phosphonium salt pillared zirconium phosphate material, the limited oxygen index of fiber is increased, and the carbon residual volume also increases.
The performance of table 9 fire resistance fibre
Antibacterial plastic concentrate adds limited oxygen index UL-94 and has or not 500 ℃ of charcoal remnants
Antibiotic plastic
Dosage (wt%) is (3.0mm) molten drop amount (%) (LOI)
PP 1.0 20.8 V-2 do not have 2.1/
PP 2.0 22.3 V-2 do not have 4.35
PE 1.0 19.9 V-2 do not have 2.01
PE 2.0 22.1 V-2 do not have 4.31
Embodiment 17
According to document (Huang Juan, Liu Jiesheng, Tan Shao early, Yang Weidong, Ceng Xiaohong, Li Hongye. the quaternary ammonium cation modified clay is to the removal effect [J] of two kinds of red tide algaes. Ji'nan University's journal (natural science edition), 2009,30 (3): 339-342.) method, get algae (ocean card shield algae (Cha ttonella m arina) and Alexandrium tamarense (A lexandrium tam a rense) are provided by Ji'nan University's red tide and Study of Water Environment center), be mixed with 5 * 10 with culture fluid (volume fraction is that 3.3% artificial seawater is made into according to f/2 culture fluid improved formulations Ensure Liquid salt, through 0.22 μ m fibrous filter membrane degerming gained)
6The algae liquid 1000ml of cell/ml, the amount by every liter of 150mg adds the quaternary phosphonium salt pillared zirconium phosphate material that example 3 prepares then, places to begin immediately on the electric blender to stir, and picks up counting.Mixing speed was 120rpm in preceding 3 minutes, was adjusted to 35rpm under the mixing speed then, stopped after 15 minutes stirring, and left standstill.According to the concentration of regular hour about 3cm place sampling and measuring frustule under liquid level, and calculate the frustule clearance in the whole process.The result is as shown in table 10.As can be seen from Table 10, (chemical formula is the cation-modified zirconium phosphate material of quaternary alkylphosphonium salt
) be used for removing the characteristics that algae has efficiently, action effective is long, be a kind of comparatively desirable red tide algae remover.
The performance that table 10 wawter bloom is handled
Time (min) 3 15 30 120 480
Clearance (%) 30 58 72 81 88%
Embodiment 18
According to document (Huang Juan, Liu Jiesheng, Tan Shao early, Yang Weidong, Ceng Xiaohong, Li Hongye. the quaternary ammonium cation modified clay is to the removal effect [J] of two kinds of red tide algaes. Ji'nan University's journal (natural science edition), 2009,30 (3): 339-342.) method, get algae (ocean card shield algae (Cha ttonella m arina) and Alexandrium tamarense (A lexandrium tam a rense) are provided by Ji'nan University's red tide and Study of Water Environment center), be mixed with 5 * 10 with culture fluid (volume fraction is that 3.3% artificial seawater is made into according to f/2 culture fluid improved formulations Ensure Liquid salt, through 0.22 μ m fibrous filter membrane degerming gained)
6The algae liquid 1000ml of cell/ml adds the prepared quaternary phosphonium salt pillared zirconium phosphate material of example 6 by the amount of every liter of 150mg then, places to begin immediately on the electric blender to stir, and picks up counting.Mixing speed was 120rpm in preceding 3 minutes, was adjusted to 35rpm under the mixing speed then, stopped after 15 minutes stirring, and left standstill.According to the concentration of regular hour about 5cm place sampling and measuring frustule under liquid level, and calculate the frustule clearance in the whole process.The result is as shown in table 11.As can be seen from Table 11, (chemical formula is the cation-modified zirconium phosphate material of quaternary alkylphosphonium salt
) be used for removing the characteristics that algae has efficiently, action effective is long, be a kind of comparatively desirable red tide algae remover.
The performance that table 11 wawter bloom is handled
Time (min) 3 15 30 120 480
Clearance (%) 39 66 78 85 91
Embodiment 19
According to document (Huang Juan, Liu Jiesheng, Tan Shao early, Yang Weidong, Ceng Xiaohong, Li Hongye. the quaternary ammonium cation modified clay is to the removal effect [J] of two kinds of red tide algaes. Ji'nan University's journal (natural science edition), 2009,30 (3): 339-342.) method, get algae (ocean card shield algae (Cha ttonella m arina) and Alexandrium tamarense (Alexandrium tam a rense) are provided by Ji'nan University's red tide and Study of Water Environment center), be mixed with 5 * 10 with culture fluid (volume fraction is that 3.3% artificial seawater is made into according to f/2 culture fluid improved formulations Ensure Liquid salt, through 0.22 μ m fibrous filter membrane degerming gained)
6The algae liquid 1000ml of cell/ml adds the prepared quaternary phosphonium salt pillared zirconium phosphate material material of example 7 by the amount of every liter of 150mg then, places to begin immediately on the electric blender to stir, and picks up counting.Mixing speed was 120rpm in preceding 3 minutes, was adjusted to 35rpm under the mixing speed then, stopped after 15 minutes stirring, and left standstill.According to the concentration of regular hour about 5cm place sampling and measuring frustule under liquid level, and calculate the frustule clearance in the whole process.The result is as shown in table 12.As can be seen from Table 12, (chemical formula is the cation-modified zirconium phosphate material of quaternary alkylphosphonium salt
) be used for removing the characteristics that algae has efficiently, action effective is long, be a kind of comparatively desirable red tide algae remover.
The performance that table 12 wawter bloom is handled
Time (min) 3 15 30 120 480
Clearance (%) 42 73 81 90 95
The foregoing description is a preferred implementation 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 spiritual essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. quaternary phosphonium salt pillared layered zirconium phosphate material, it is characterized in that: its chemical formula is
R is that methyl, butyl, phenyl or carbon chain lengths are 8～20 alkyl;
X is Cl or Br; M is 1, and n is 0.00288～0.174462.
2. the preparation method of the described quaternary phosphonium salt pillared layered zirconium phosphate material of claim 1 is characterized in that: may further comprise the steps:
(1) alpha zirconium phosphate is scattered in the water, adds methylamine then, stir 1～4h, obtain methylamine-basic zirconium phosphate solution at 40～80 ℃; Wherein the mol ratio of alpha zirconium phosphate and methylamine is 1: 1～1: 10;
(2) quaternary alkylphosphonium salt with chloride ion-containing or bromide ion joins in methylamine-basic zirconium phosphate solution, and stirring reaction 4～10h filters and collects solid content; Wherein the mol ratio of alpha zirconium phosphate and quaternary alkylphosphonium salt is 1: 0.01～1: 10;
(3) step (2) gained solid content is washed with distilled water to no bromide ion or does not have chlorion, drying obtains head product;
(4) step (3) gained head product is ground, obtain the quaternary phosphonium salt pillared layered zirconium phosphate material of different-grain diameter.
3. preparation method according to claim 2 is characterized in that: described quaternary alkylphosphonium salt is suc as formula the quaternary alkylphosphonium salt shown in I or the formula II structure:
N, n
1And n
2Be respectively 8～14 even number;
R1 is methyl, butyl or phenyl;
R2 is methyl, butyl or phenyl;
R3 is methyl, butyl or phenyl;
X is Cl or Br.
4. preparation method according to claim 3 is characterized in that: described quaternary alkylphosphonium salt is ten alkyl trimethyl phosphonium chlorides, ten alkyl trimethyl phosphonium bromides, ten alkyl tributyl phosphorus chloride, ten alkyl tributyl phosphonium bromides, ten alkyl triphenyl phosphonium chlorides, ten alkyl, three phenyl phosphonium bromides, dodecyl San Jia Ji phosphonium chloride, dodecyl three methyl phosphonium bromides, dodecyl tributyl phosphorus chloride, dodecyl tributyl phosphonium bromide, the dodecyl triphenyl phosphonium chloride, dodecyl three phenyl phosphonium bromides, tetradecane base San Jia Ji phosphonium chloride, tetradecane base three methyl phosphonium bromides, myristyl tributyl phosphonium chloride, myristyl tributyl phosphonium bromide, the myristyl triphenyl phosphonium chloride, myristyl three phenyl phosphonium bromides, the cetyl trimethyl phosphonium chloride, Shi six alkyl trimethyl phosphonium bromides, phosphonium hexadecanyl-3-butyl chloride, hexadecyl tributyl phosphonium bromide, at least a in cetyl triphenyl phosphonium chloride or the cetyl three phenyl phosphonium bromides.
5. preparation method according to claim 2 is characterized in that: the temperature of stirring reaction is 20～30 ℃ described in the step (2).
6. preparation method according to claim 2 is characterized in that: the drying described in the step (3) is vacuum drying.
7. preparation method according to claim 6 is characterized in that: described vacuum drying condition is 60～120 ℃ of drying 12～48h, and vacuum is 1 * 10
4～3 * 10
4Pa.
8. the described quaternary phosphonium salt pillared layered zirconium phosphate material of claim 1 is used to prepare anti-biotic material or fire proofing.
9. the described quaternary phosphonium salt pillared layered zirconium phosphate material of claim 1 algae that is used for removing water.
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| CN102874785A (en) * | 2012-10-12 | 2013-01-16 | 吉林大学 | Method for preparing aggregation induced emission (AIE) group functionalized laminar zirconium phosphate material by ion exchange method |
| CN102897737A (en) * | 2012-09-24 | 2013-01-30 | 常州大学 | Method for preparation of pillared zirconium phosphate material by self-assembly technology |
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| CN109336076A (en) * | 2018-11-13 | 2019-02-15 | 华南理工大学 | A kind of method of green high-efficient stripped laminar basic zirconium phosphate |
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