CN104610050B - One kind hydration o-chloromandelic acid ferromanganese sulfate ferroelectric functional material and preparation method thereof - Google Patents
One kind hydration o-chloromandelic acid ferromanganese sulfate ferroelectric functional material and preparation method thereof Download PDFInfo
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- CN104610050B CN104610050B CN201310554089.1A CN201310554089A CN104610050B CN 104610050 B CN104610050 B CN 104610050B CN 201310554089 A CN201310554089 A CN 201310554089A CN 104610050 B CN104610050 B CN 104610050B
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- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 12
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 230000036571 hydration Effects 0.000 title claims description 15
- 238000006703 hydration reaction Methods 0.000 title claims description 15
- RWOLDZZTBNYTMS-UHFFFAOYSA-N 2-(2-chlorophenyl)-2-hydroxyacetic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1Cl RWOLDZZTBNYTMS-UHFFFAOYSA-N 0.000 title claims description 11
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- -1 (R)-o-chloromandelic acid sodium Chemical compound 0.000 claims description 16
- RWOLDZZTBNYTMS-SSDOTTSWSA-N (2r)-2-(2-chlorophenyl)-2-hydroxyacetic acid Chemical compound OC(=O)[C@H](O)C1=CC=CC=C1Cl RWOLDZZTBNYTMS-SSDOTTSWSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229940071125 manganese acetate Drugs 0.000 claims description 9
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 8
- 230000005621 ferroelectricity Effects 0.000 claims description 7
- VQWQYXBWRCCZGX-UHFFFAOYSA-N acetic acid;manganese Chemical compound [Mn].CC(O)=O.CC(O)=O VQWQYXBWRCCZGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000011437 Amygdalus communis Nutrition 0.000 claims description 3
- 241000220304 Prunus dulcis Species 0.000 claims description 3
- 235000020224 almond Nutrition 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 3
- PGWAQGPKHFVSPC-UHFFFAOYSA-N chloro 2-hydroxy-2-phenylacetate Chemical compound ClOC(=O)C(O)C1=CC=CC=C1 PGWAQGPKHFVSPC-UHFFFAOYSA-N 0.000 abstract 1
- 230000010287 polarization Effects 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
O-chloromandelic acid ferromanganese sulfate ferroelectric functional material and its preparation method of crystal are hydrated the invention discloses a kind of.The ferroelectric function material molecular formula is [Mn (H2O)(Cl‑ma)2]n, it is that one kind can be by 100 mesh sieves, purity is not less than 99% pink powder, belongs to monoclinic system, with P21Space group structure, the cell parameter of its crystal is：α=90 °, β=101.75 (3) °, γ=90 °, its ferroelectric characteristicses parameter is respectively：2Pr=0.02 μ C/cm2, 2Ec=1.52kV/cm, Ps=0.22 μ C/cm2.The preparation method of the present invention has the advantages that simple for process, low for equipment requirements, cost of material is low, yield is high, pollution-free.
Description
Technical field
The present invention relates to ferroelectric function material, and in particular to one kind hydration o-chloromandelic acid ferromanganese sulfate ferroelectric functional material and its system
Preparation Method.
Background technology
Ferroelectric material has the characteristics such as good ferroelectricity, piezoelectricity, pyroelectric and nonlinear optics, is current state
One of research field very active in the new and high technology material of border.Meanwhile, it is wide that the outstanding electric property of ferroelectric material has bred it
Wealthy application prospect, its electronic component has many merits such as integrated level height, the small, fast response time of energy consumption, and studies at present
Ferroelectric material is combined by person with other technologies, makes the integrated ferroelectric material property being newly born more outstanding, therefore ferroelectric material
The positive practical development of study hotspot.
So far, the research of ferroelectric material can be broadly divided into four-stage：First stage (1920-1939), sieve
Cease salt (NaKC4H4O6·4H2) and potassium dihydrogen phosphate (KH O2PO4) ferroelectric structures discovery；Second stage (1940-1958),
First not hydrogen bonds, with multiple ferroelectricity phase barium titanate (BaTiO3) discovery, the foundation of ferroelectricity phenomenological theory；Phase III
(1959-1970), ferroelectricity microscopic theory occurs and substantially perfect, referred to as the soft mode stage；Fourth stage (1980 are so far), it is main
If studying the nonhomogeneous system such as ferroelectric thin film and ferroelectric superlattice.In recent years, hybrid inorganic-organic metal organic complex
Develop into the design synthesis of novel ferroelectric functional material and prepare and its develop and provide brand-new thinking.In addition, its component is numerous
Many, structure diversification, it is contemplated that can therefrom excavate out more ferroelectrics, so as to extend the research field of feroelectronics, is developed
New application.Therefore the research of metal organic complex ferroelectric material has caused the broad interest of chemist and physicist,
And the development of material science has been promoted significantly.
Research shows that its crystal structure of the material of tool ferroelectric properties belongs to ten polarity point group (C1, Cs, C2, C2v, C3, C3v,
C4, C4v, C6, C6vOne of).Present invention selection (R)-o-chloromandelic acid is raw material：First, (R)-o-chloromandelic acid has a hand-type
Carbon atom, belongs to chiral organic carboxyl acid, can improve and prepare ferroelectric probability；2nd, (R)-o-chloromandelic acid is important medicine
Thing synthetic intermediate, the product prepared has bioactivity, becomes the possibility of multifunctional material offer；3rd, it is so far
Only, the present invention is complex of the first case using (R)-o-chloromandelic acid as raw material, at the same the present invention be also first case utilize (R)-
O-chloromandelic acid is the ferroelectric property that part probes into product.
The content of the invention
The technical problems to be solved by the invention are to provide hydration o-chloromandelic acid ferromanganese sulfate ferroelectric functional material.The ferroelectricity function
Material is a kind of to be not less than 99% by the pink powders of 100 mesh sieves, purity.Its molecular formula is Mn (H2O)(Cl-ma)2
(Cl-ma=(R)-o-chloromandelic acid), belongs to monoclinic system, P21Space group (C1Point group), cell parameter is：α=90 °, β=101.75 (3) °, γ=90 °.The ferroelectricity function
Material ferroelectric characteristicses parameter is respectively：Remanent polarization 2Pr=0.02 μ Ccm-2, coercive electric field 2Ec=1.52kvcm-1, saturated polarization Ps=0.22 μ Ccm-2.The ferroelectric saturated polarization rate ceases salt close to typical ferroelectric sieve
NaKC4H4O6·4H2O saturated polarization Ps=0.25 μ Ccm-2, show that it has good ferroelectric properties.
Present invention also offers the hydration ferroelectric preparation method of o-chloromandelic acid manganese, the preparation method has flow few,
Technique is simple, low for equipment requirements, and raw material (R)-o-chloromandelic acid and manganese acetate environmental pollution are few, it is excellent to be easy to industrialization etc.
Point.
The preparation method of above-mentioned ferroelectric function material crystal, comprises the steps：
1) preparation of (R)-o-chloromandelic acid sodium：(R)-o-chloromandelic acid is dissolved in deionized water, stirred to completely molten
Solution, then in sodium hydroxide and the ratio that (R)-o-chloromandelic acid mol ratio is 1: 1, sodium hydroxide dissolving is added, being made into concentration is
0.050~0.500mol/L (R)-o-chloromandelic acid sodium solution is stand-by；
2) configuration of acetic acid manganese solution：Manganese acetate is dissolved in deionized water, stirred to being completely dissolved, being made into concentration is
0.025~0.250mol/L manganese acetate solution for later use；
3) configuration of o-chloromandelic acid manganese solution：It is 1 by (R)-o-chloromandelic acid sodium and manganese acetate solution's solute mol ratio
~4: 1 ratio, by above-mentioned steps 1) (the R)-o-chloromandelic acid sodium solution and the step 2 that prepare) the acetic acid manganese solution for preparing mixes
Close.After several weeks, just there are pink bulk crystals to be separated out from mother liquor, and can keep stable in atmosphere.
4) the red bulk crystals of hydration o-chloromandelic acid manganese powder are ground, 100 mesh sieves can be passed through.
Compared with prior art, the advantage of the invention is that the ferroelectric function material molecular formula is Mn (H2O)(Cl-ma)2,
The ferroelectric function material is can be by the pink powder of 100 mesh sieves, and purity is not less than 99%, belongs to P21Space group structure, crystal
Cell parameter be： α=90 °, β=101.75 (3) °, γ=
90°.Its ferroelectric characteristicses parameter is respectively：Remanent polarization 2Pr=0.02 μ Ccm-2, coercive electric field 2Ec=1.52kv
cm-1, saturated polarization Ps=0.22 μ Ccm-2.The ferroelectric saturated polarization rate is slightly above typical ferroelectric sieve breath salt
NaKC4H4O6·4H2O saturated polarization Ps=0.25 μ Ccm-2, with good ferroelectric properties.
The preparation method of the present invention is molten by normal temperature using the low manganese acetate of cost (the R)-o-chloromandelic acid small with pollution
Liquid reacts, and synthesis obtains that yield is higher, purity is higher, better performances hydration o-chloromandelic acid manganese ferroelectric powders.The present invention's
Synthetic method has flow few, and technique is simple, and low for equipment requirements, the raw acetic acid manganese cost used is low, it is easy to industrialization
Advantage.
Brief description of the drawings
Fig. 1 is hydrated the molecular structure of o-chloromandelic acid ferromanganese sulfate ferroelectric functional material for the present invention；
Fig. 2 simulates PXRD collection of illustrative plates for the PXRD collection of illustrative plates of present invention hydration o-chloromandelic acid ferromanganese sulfate ferroelectric functional material with monocrystalline
Comparison diagram；
Fig. 3 is hydrated the TG-DTA curve maps of o-chloromandelic acid ferromanganese sulfate ferroelectric functional material for the present invention；
Fig. 4 is hydrated the ferroelectric hysteresis loop figure of o-chloromandelic acid ferromanganese sulfate ferroelectric functional material for the present invention.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing embodiment.
Embodiment 1
0.186g (1.0mmol) (R)-o-chloromandelic acid is dissolved in 10mL deionized waters, stirring and dissolving, formed colourless molten
Liquid, separately measures 1.0mL (1M) NaOH solution and is added dropwise in above-mentioned solution, prepares (R)-adjacent chlorine almond sodium solution stand-by.Separately weigh
0.123g(0.5mmol)Mn(CH3COO)2·4H2O is dissolved in 10mL deionized waters, stirring and dissolving, forms colourless solution, and will
In (the R)-adjacent chlorine almond sodium solution of its place of adding to stirring, continue to stir a period of time.Reaction equation is as follows：
2HClma+2NaOH+Mn(CH3COO)2→Mn(H2O)(Cl-ma)2+2CH3COONa+H2O is block to gained pink
Crystal is ground, can be by 100 mesh sieves, and purity is not less than 99%.
Embodiment 2
It is substantially the same manner as Example 1, the difference is that (the R)-o-chloromandelic acid quality weighed is 0.093g (0.5mmol).
Embodiment 3
It is substantially the same manner as Example 1, the difference is that (the R)-o-chloromandelic acid quality weighed is 0.372g (2.0mmol).
Embodiment 4
It is substantially the same manner as Example 1, except that the Mn (CH weighed3COO)2·4H2O is 0.246g (1.0mmol).
The hydration o-chloromandelic acid ferromanganese sulfate ferroelectric functional material molecular formula that above-described embodiment is obtained is Mn (H2O)(Cl-ma)2, it is
A kind of purity is not less than 99% pink powder.The ferroelectric properties parameter of the ferroelectric function material is respectively：2Pr=0.02 μ
C·cm-2, 2Ec=1.52kvcm-1, Ps=0.22 μ Ccm-2。
The hydration o-chloromandelic acid manganese obtained using Rigaku R-Axis Rapid single crystal diffractometers to above-described embodiment is brilliant
Body carries out Advances in crystal X-ray diffraction, obtains the structure of the hydration o-chloromandelic acid manganese, as shown in Figure 1.
The θ angular ranges of Bruker D8 Focus powder diffractometers 2 are used for 5-50 °, with 8 °/min sweep speed to upper
State the hydration o-chloromandelic acid manganese ferroelectric that embodiment obtains to be scanned, the powder diffraction spectrum of sample is collected at room temperature
(PXRD), and with monocrystalline simulation PXRD figures contrast, as shown in Figure 2.
Using the type Differential Thermal Analysis instrument of Seiko TG/DTA 6300, with α-Al2O3For reference substance, in 200mL/min N2
Air-flow protection, heating rate be 10 DEG C/min under conditions of, by pink crystal grind into powder, determine its TG-DTA curve,
As shown in Figure 3.
The ferroelectric properties of the powder for the hydration o-chloromandelic acid ferromanganese sulfate ferroelectric functional material that above-described embodiment is obtained is determined, is obtained
Ferroelectric hysteresis loop figure as shown in Figure 4, as can be seen from Figure 4 its ferroelectric properties characteristic parameter be respectively：2Pr=0.02 μ C
cm-2, 2Ec=1.52kvcm-1, Ps=0.22 μ Ccm-2, illustrate that there is good ferroelectric properties.
Claims (5)
1. one kind hydration o-chloromandelic acid ferromanganese sulfate ferroelectric functional material, it is characterised in that the molecular formula of the ferroelectric function material is Mn
(H2O)(Cl-ma)2, Cl-ma=(R)-o-chloromandelic acid, category monoclinic system, P21Space group (C1Point group), cell parameter is：α=90 °, β=101.75 (3) °, γ=90 °, the ferroelectricity work(
Can material for 99% can be not less than by the pink powders of 100 mesh sieves, purity.
2. the preparation method of the ferroelectric function material described in claim 1, it is characterised in that comprise the steps：
1) preparation of (R)-o-chloromandelic acid sodium：(R)-o-chloromandelic acid is dissolved in deionized water, stirs to being completely dissolved, presses
Sodium hydroxide and (R)-o-chloromandelic acid mol ratio are 1: 1 ratio, add sodium hydroxide dissolving, be made into concentration for 0.050~
0.500mol/L (R)-o-chloromandelic acid sodium solution is stand-by；
2) configuration of acetic acid manganese solution：Manganese acetate is dissolved in deionized water, stirred to being completely dissolved, it is 0.025 to be made into concentration
~0.250mol/L manganese acetate solution for later use；
3) configuration of o-chloromandelic acid manganese solution：It is 1~4: 1 by (R)-o-chloromandelic acid sodium and manganese acetate solution's solute mol ratio
Ratio, by above-mentioned steps 1) (the R)-o-chloromandelic acid sodium solution and the step 2 that prepare) the acetic acid manganese solution of preparation mixes, several
Zhou Hou, just has pink bulk crystals to be separated out from mother liquor, and can keep stable in atmosphere；
4) to step 3) in the red bulk crystals of hydration o-chloromandelic acid manganese powder that obtain be ground to can be by 100 mesh sieves.
3. the preparation method of ferroelectric function material as claimed in claim 2, it is characterised in that in step 1) in, sodium hydroxide with
(R)-o-chloromandelic acid mol ratio is 1: 1, and (R)-o-chloromandelic acid sodium solution concentration is 0.050~0.500mol/L.
4. the preparation method of ferroelectric function material as claimed in claim 2, it is characterised in that in step 2) in, acetic acid manganese solution
Concentration is 0.025~0.250mol/L.
5. the preparation method of ferroelectric function material as claimed in claim 2, it is characterised in that in step 3) in, (R)-adjacent chlorine almond
Sour sodium is 1~4 with manganese acetate solution's solute mol ratio.
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Non-Patent Citations (1)
| Title |
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| Syntheses, Structures and Magnetic Properties of Layered Metal(II) Mandelates;Adel Beghidja，et al.;《Eur. J. Inorg. Chem.》;20051231;662-669 * |
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