CN108299799A - The layered double hydroxide and its preparation method and application that cagelike silsesquioxane is modified - Google Patents
The layered double hydroxide and its preparation method and application that cagelike silsesquioxane is modified Download PDFInfo
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Abstract
The invention discloses the layered double hydroxides and its preparation method and application that a kind of cagelike silsesquioxane is modified, preparation method is specially using cagelike silsesquioxane, soluble metallic salt, water and inorganic base as raw material, using mechanochemistry method, it is prepared through step modification；The cagelike silsesquioxane is selected from the cagelike silsesquioxane containing anionic group.The layered double hydroxide POSS LDH that the cagelike silsesquioxane being prepared using this method is modified belong to one kind completely new in LDH families.The novel POSS LDH have nanoscale lamellar structure, and primary grain size is approximately less than 100nm, while having excellent thermal stability and flame retardant property.
Description
Technical field
The present invention relates to the technical fields of modified layered double-metal hydroxide, and in particular to a kind of cagelike silsesquioxane
Modified layered double hydroxide and its preparation method and application.
Background technology
Layered double hydroxide (Layered double hydroxides, LDHs) is a kind of typically with layer
The Subjective and Objective functional material of shape structure.Its structure is similar to natural brucite Mg (OH)2Crystal, divalent metal in main layer board from
Subdivision is replaced by trivalent metal ion, and the octahedral structure unit that hydroxide ion is constituted around metal ion is total to side and extends shape
At 2D layer structures, laminate positive charge is balanced with interlayer anion so that LDHs is in integrally the electroneutral of stabilization
(Mineralogical Magazine,1973,39,377).The general structure of LDHs is [M2+ 1-xM3+ x(OH)2]x+·An- x/n·
yH2O, wherein M2+, M3+And An-Respectively represent bivalent metal ion (such as Mg2+,Zn2+,Ni2+,Co2+), trivalent metal ion is (such as
Al3+,Fe3+,Mn3+,Cr3+) and interlayer anion (such as NO3 -,Cl-,CO3 2-), the value range of stoichiometric coefficient x usually 0.17~
Between 0.33.The composition of the flexible modulations of LDHs and the uniform sequential structure feature of molecular level, assign its various physical chemistry
Property, and the characteristics of show type various Various Functions (Solid State Ionics, 1986,22,135；
Chem.Mater.,2002,14,4286；Chem.Rev.2012,112,4124).
Height Modulatory character based on LDHs structures and performance and the potentiality that flame retardance of polymer can be significantly improved, in recent years
Come it and is widely used in all kinds of polymer materials as Nano filling.Due to the dimensional effect of LDHs itself and stronger hydrophilic
Characteristic and interlaminar action power are difficult to be dispersed in polymeric matrix, therefore carried out to it organically-modified most important.It cuts
Only currently, having intercalation and modification that a large amount of organic modifiers are employed successfully in LDHs, the most commonly used is detergent alkylates
Sodium sulfonate (SDBS) (Polymer, 2005,46,4447, Chem.Mater., 2009,21,4490), other include all kinds of sulfuric acid
Salt and phosphate surfactant active (Appl.Clay Sci., 2008,38,153；J.Solid State Chem.,2011,184,
171；J.Mater.Chem., 2011,21,8085), aliphatic or aromatic carboxylic acid (Solid State Ionics, 1997,
98,73；J.Microw.Power Electromagn.Energy, 2013,47,12), amino acid (Eur.J.Inorg.Chem.,
2015,925), ionic dye (ACS Appl.Mater.Interfaces, 2013,5,8991) and biology base modifying agent is (such as
Cyclodextrin and eugenol etc. and its derivative) (J.Mater.Chem.A, 2013,1,11376；J.Mater.Chem.A,2015,
3,3471；J.Mater.Chem.A,2015,3,6819；J.Mater.Chem.A, 2016,4,2147) etc..
However, regrettably, the thermal stability and anti-flammability of most organic modifiers itself used at present are equal
It is unsatisfactory so that the performance of the modification LDHs of preparation and application are restricted.
Invention content
The present invention is in view of the above-mentioned problems, provide a kind of layered double hydroxide that cagelike silsesquioxane is modified
The preparation method of (being denoted as POSS-LDH), the POSS-LDH being prepared belong to one kind completely new in LDH families.This is novel
POSS-LDH has nanoscale lamellar structure, primary grain size about 10~50nm, while having excellent thermal stability and anti-flammability
Energy.
Specific technical solution is as follows：
A kind of preparation method for the layered double hydroxide that cagelike silsesquioxane is modified, steps are as follows：
(1) soluble magnesium salt, aluminum soluble salt and water are mixed to get solution A, by cagelike silsesquioxane (POSS) with
Water is mixed to get solution B；
The cagelike silsesquioxane is selected from the cagelike silsesquioxane containing anionic group；
(2) solution A is mixed with solution B, and keeps the pH value of reaction system in mixed process constant between 9~11；
(3) stratiform that the cagelike silsesquioxane is modified is obtained after crude product obtained by step (2) is aged and post-processing
Double-metal hydroxide.
It is gone in the present invention by selecting the cagelike silsesquioxane for containing anionic group to be used as functional organic modifiers
Intercalation modifying LDH, the anionic group and positively charged LDH piece layer equilibrations being rich in using anionic POSS molecules surface layer,
Prepare novel POSS-LDH nano-hybrid materials.
In step (1)：
Preferably, the soluble magnesium salt be selected from magnesium nitrate and/or magnesium chloride, aluminum soluble salt be selected from aluminum nitrate and/
Or aluminium chloride, magnalium molar ratio are 0.20~0.50；Further preferably, in the solution A, metal ion total concentration be 0.05~
1mol/L。
Preferably, the anionic group is carboxyl or sulfonic group；Further preferably, described containing anionic group
Cagelike silsesquioxane is selected from poly- (the carboxyethyl carbonyl amino propyl) silsesquioxane of cage type eight or its metal salt, cage type eight poly- (third
P-methoxybenzoic acid) silsesquioxane or its metal salt, eight carboxy phenyl cagelike silsesquioxanes or its metal salt, eight benzene sulfonic acid base cages
At least one of shape silsesquioxane or its metal salt.
The metal salt includes sodium salt, sylvite, ammonium salt etc..
Since the water solubility containing carboxyl or sulfonic POSS is bad, when using it as raw material, NaOH, KOH can be used
It is adjusted to alkalinity promotion dissolving etc. common inorganic base.The above-mentioned gold containing carboxyl or sulfonic POSS can also directly be used
Category salt is raw material.
Further preferably, it is segment containing flexible alkyl that the cagelike silsesquioxane containing anionic group, which is selected from side group,
POSS, the backbone atoms number of the flexible alkyl segment is no more than 12.It is found through experiment that the flexible carbochain of suitable length is conducive to
Intercalation efficiency is improved, while the compatibility of modified LDH and polymeric matrix can be improved；Side chain is long or rigidity is excessive,
It is unfavorable for nucleation and the crystallization of LDH, to influence intercalation efficiency.Much further preferably from poly- (the carboxyethyl carbonyl amino of cage type eight
Propyl) silsesquioxane (structural formula such as following formula (Ι)) or its metal salt.
Preferably, a concentration of 0.005~0.1mol/L of the solution B；
The total mole number of the metal ion and the mole ratio of cagelike silsesquioxane are 1~40.
In step (2)：
Preferably, solution A is added dropwise in solution B, reaction system is kept by the way that alkaline solution is added during dropwise addition
PH value it is constant.
The inorganic alkali solutions such as common sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide may be used in the alkaline solution,
It is added purpose and is ensuring that the pH value of reaction system is constant.
Preferably, along with being vigorously stirred during being added dropwise, stir speed (S.S.) is preferably controlled in 400~600rpm.
In step (3)：
Preferably, the temperature of the ageing is 60~90 DEG C, the time is 10~30h.
Preferably, the post-processing includes being filtered, washed and dried.
On the basis of above-mentioned raw materials and process conditions, further preferably：
In step (1), metal ion total concentration is 0.1~0.5mol/L in the solution A, and magnalium molar ratio is 0.5；Institute
State cagelike silsesquioxane be selected from poly- (the carboxyethyl carbonyl amino propyl) silsesquioxane of cage type eight, solution B a concentration of 0.01~
0.05mol/L；The total mole number of the metal ion and the mole ratio of cagelike silsesquioxane are 10~15.
In step (2), solution A is added dropwise in solution B, reaction system is kept by the way that alkaline solution is added during dropwise addition
PH value be 10 ± 0.5.
The invention also discloses the laminated type bimetal hydroxides that the cagelike silsesquioxane prepared according to the above method is modified
Object, it is 0.8~2.4nm, primary partical size which, which has typical layered double hydroxide structure, interlamellar spacing,
For 10~100nm, polygon or subcircular lamella pattern is presented.
The POSS-LDH has excellent thermal stability and flame retardant property, can be applied to prepare flame-retardant polymer.
Compared with prior art, the invention has the advantages that：
1, the present invention is using soluble magnesium salt, aluminium salt as raw material, in the effect of anionic cage-type silsesquioxane intercalator
Under, the layer structure that piece interlamellar spacing is Nano grade is formed, the preparation process is simple, and new system is provided for organically-modified LDH
Preparation Method.
2, cage-type silsesquioxane (POSS) is introduced LDH by the present invention, gained be modified the primary partical grain size of LDH 10~
Between 50nm, and there is excellent thermal stability and flame retardant property, belongs to a kind of novel LDH, change for heat-resisting flame-retardant is organic
Property LDH provides new member.
Description of the drawings
Fig. 1 is the X-ray diffraction comparison diagram for the NLDH that POSS-LDH prepared by embodiment 1 is prepared with comparative example 1；
Fig. 2 is POSS-LDH and poly- (the carboxyethyl carbonyl amino propyl) silsesquioxane of intercalator cage type eight prepared by embodiment 1
The XPS spectrum figure of NLDH three prepared by alkane (OCPS) and comparative example 1；
Fig. 3 is NLDH Fourier-infrared comparison spectrogram that POSS-LDH prepared by embodiment 1 is prepared with comparative example 1；
Fig. 4 is the NLDH scanning electron microscope comparison diagrams that POSS-LDH prepared by embodiment 1 is prepared with comparative example 1；
Fig. 5 is the structural schematic diagram of POSS-LDH prepared by embodiment 1；
Fig. 6 is POSS-LDH and intercalator OCPS prepared by embodiment 1 and the thermal weight loss of NLDH prepared by comparative example 1 is bent
Line comparison diagram (nitrogen atmosphere, 10 DEG C/min of heating rate)；
Fig. 7 is the burning behavior (miniature calorimetric) for the DBS-LDH that POSS-LDH prepared by embodiment 1 is prepared with comparative example 2
Comparison diagram.
Specific implementation mode
Embodiment 1
At room temperature, 0.2mol/L magnesium nitrates and 0.1mol/L aluminum nitrates mixed solution (200ml) are slowly added dropwise into dense
In poly- (carboxyethyl carbonyl amino propyl) the silsesquioxane alkaline solution of 200mL cage types eight that degree is 0.025mol/L (pH=10),
Reaction system is kept to be vigorously stirred during being added dropwise, and the sodium hydroxide solution by the way that 1mol/L is added dropwise makes the pH value of system keep
10 ± 0.1, continues to stir 30nin after being added dropwise, be then aged 20 hours under the conditions of 60 DEG C, through being filtered, washed, drying
And etc. can obtain white powder product, the layered double hydroxide that as cagelike silsesquioxane is modified is named as POSS-
LDH。
XRD, XPS, FTIR and TEM characterize (Fig. 1~Fig. 4) display, and intercalator OCPS is successively inserted into LDH, is prepared
POSS-LDH there is typical layered double hydroxide structure, interlamellar spacing 1.33nm, primary partical size 10~
Between 50nm.Its structural schematic diagram is as shown in Figure 5.
Comparative example 1
At room temperature, 0.2mol/L magnesium nitrates and 0.1mol/L aluminum nitrates mixed solution (200ml) are slowly added dropwise into pH
In=10 NaOH aqueous solutions, reaction system is kept to be vigorously stirred during being added dropwise, and the sodium hydroxide by the way that 1mol/L is added dropwise
Solution makes the pH value of system be maintained at 10 ± 0.1, continues to stir 30min after being added dropwise, is then aged 20 under the conditions of 60 DEG C
Hour, through being filtered, washed, drying and other steps can obtain white powder product, be named as NLDH.
NLDH is unmodified LDH, relevant characterization (Fig. 1~Fig. 4) display, interlamellar spacing 0.90nm, primary partical ruler
It is very little between 100~200nm.
Comparative example 2
At room temperature, by 0.2mol/L magnesium nitrates and 0.1mol/L aluminum nitrates mixed solution (200ml) be slowly added dropwise into
In 200mL neopelexes (SDBS) aqueous solution of 0.1mol/L, reaction system is kept to be vigorously stirred during being added dropwise,
And the sodium hydroxide solution by the way that 1mol/L is added dropwise makes the pH value of system be maintained at 10 ± 0.1, continues to stir after being added dropwise
30min is then aged 20 hours under the conditions of 60 DEG C, through being filtered, washed, drying and other steps can obtain white powder product, name
For DBS-LDH.DBS-LDH is current most popular organically-modified LDH.
Heat resistance is tested
Fig. 6 is POSS-LDH and intercalator OCPS prepared by embodiment 1 and NLDH prepared by comparative example 1 is in nitrogen atmosphere
In thermogravimetric curve comparison diagram, data show OCPS intercalations after LDH thermal stability be substantially better than intercalator OCPS and do not change
Property purely inorganic NLDH, the temperature of initial decomposition of POSS-LDH improves 97 DEG C compared with NLDH, decomposes peak value corresponding temperature and improve
83 DEG C, 800 DEG C of remaining carbons improve 10%, synergy highly significant.(note：LDH thermal stability meetings after tradition is organically-modified
Decrease to some degree, such as Chem.Mater., 2009,21,4490；Appl.Clay Sci.,2008,38,153；
J.Mater.Chem.A,2013,1,11376；J.Mater.Chem.A,2016,4,2147).
Flame retardant property is tested
Fig. 7 is the burning behavior (miniature calorimetric) for the DBS-LDH that POSS-LDH prepared by embodiment 1 is prepared with comparative example 2
Comparison diagram, specific data are as shown in table 1.The results show that 3 important parameter peak heat releases of characterization material combustion performance
(pHRR), heat release capacity (HRC), the corresponding numerical value of total heat release (THR) have compared with DBS-LDH significantly declines, and shows
The flame retardant property of POSS-LDH itself is significantly better than the organically-modified LDH of tradition.
Table 1
Application examples
It is to introduce LDH by the way of blending using matrix, it is nano combined to prepare fire-retardant epoxy resin with epoxy resin
Material.It is as follows：
Using Exakt 80E (Exact Technologies) three rollers by LDH and epoxy resin ground and mixed, mixed process
Middle roll spacing is gradually reduced from 20 μm to 5 μm, to improve ground and mixed effect.It is mixed that acetone progress solution is then added into system
It closes, is stirred at 60 DEG C and 80 DEG C promote within two hours LDH dispersions respectively.Desolventizing is heated later, and 120 DEG C are evacuated to constant weight.To
Appropriate 3,3- diaminodiphenylsulfones curing agent (N-H is added in system：Epoxy group (molar ratio)=1:1), 115 DEG C of heating stirrings
30min, poured into after vacuum outgas (115 DEG C) tetrafluoro mold and in convection oven solidification (140 DEG C/2h, 160 DEG C/2h, 180
℃/2h).Batten is taken out after solidification is placed at room temperature for 48h or more.
Prepare the NLDH/ epoxy resin (NLDH/ of pure epoxy resin (EP), 4wt% additive amounts respectively according to the method described above
) and the POSS-LDH/ epoxy resin of 4wt% additive amounts (POSS-LDH/EP) EP.Batten size be 100 × 100 ×
2.9mm3, taper calorimetric test is carried out according to ISO5660 testing standards.
Test result is as follows shown in table 2, data show POSS-LDH/EP general flame-retardant index be significantly better than EP and
NLDH/EP shows that POSS-LDH has good application potential in terms of flame retardance of polymer.
Table 2
The preparation method for the layered double hydroxide that cagelike silsesquioxane provided by the present invention is modified above
It is described in detail.Specific case used herein is expounded the principle of the present invention, embodiment and application, with
Upper embodiment and application examples, which are only to aid in, understands the method for the present invention and key point.The content of the present specification should not be construed as to the present invention
Limitation.
Claims (10)
1. a kind of preparation method for the layered double hydroxide that cagelike silsesquioxane is modified, which is characterized in that step is such as
Under：
(1) soluble magnesium salt, aluminum soluble salt and water are mixed to get solution A, cagelike silsesquioxane and water is mixed to get
Solution B；
The cagelike silsesquioxane is selected from the cagelike silsesquioxane containing anionic group；
(2) solution A is mixed with solution B, and keeps the pH value of reaction system in mixed process constant between 9~11；
(3) the double gold of stratiform that the cagelike silsesquioxane is modified are obtained after crude product obtained by step (2) is aged and post-processing
Belong to hydroxide.
2. the preparation method for the layered double hydroxide that cagelike silsesquioxane according to claim 1 is modified,
It is characterized in that, in step (1), the soluble magnesium salt is selected from magnesium nitrate and/or magnesium chloride, and aluminum soluble salt is selected from aluminum nitrate
And/or aluminium chloride, magnalium molar ratio are 0.20~0.50.
3. the preparation method for the layered double hydroxide that cagelike silsesquioxane according to claim 1 is modified,
It is characterized in that, in step (1), in the solution A, metal ion total concentration is 0.05~1mol/L.
4. the preparation method for the layered double hydroxide that cagelike silsesquioxane according to claim 1 is modified,
It is characterized in that, in step (1)：
A concentration of 0.005~0.1mol/L of the solution B；
The total mole number of the metal ion and the mole ratio of cagelike silsesquioxane are 1~40.
5. the preparation method for the layered double hydroxide that cagelike silsesquioxane according to claim 1 is modified,
It is characterized in that, in step (1), the anionic group is carboxyl or sulfonic group.
6. the preparation method for the layered double hydroxide that cagelike silsesquioxane according to claim 5 is modified,
It is characterized in that, the cagelike silsesquioxane containing anionic group is selected from poly- (the carboxyethyl carbonyl amino propyl) sesquialter of cage type eight
Siloxanes or poly- (propoxy benzoic acid) silsesquioxane of its metal salt, cage type eight or its metal salt, eight carboxy phenyl cage type sesquialters
At least one of siloxanes or its metal salt, eight benzene sulfonic acid base cagelike silsesquioxanes or its metal salt.
7. the preparation method for the layered double hydroxide that cagelike silsesquioxane according to claim 1 is modified,
It is characterized in that, in step (2), solution A is added dropwise in solution B, reactant is kept by the way that alkaline solution is added during dropwise addition
The pH value of system is constant.
8. the preparation method for the layered double hydroxide that cagelike silsesquioxane according to claim 1 is modified,
It is characterized in that, in step (3), the temperature of the ageing is 60~90 DEG C, and the time is 10~30h.
9. the layer that cagelike silsesquioxane prepared by a kind of method according to claim 1~8 any claim is modified
Shape double-metal hydroxide.
10. a kind of layered double hydroxide that cagelike silsesquioxane according to claim 9 is modified is as fire-retardant
The application of agent in the polymer.
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| CN110551357B (en) * | 2019-09-29 | 2022-04-15 | 陕西科技大学 | Flame-retardant magnesium-aluminum hydrotalcite/carboxyl POSS composite material and preparation method thereof |
| CN112159594A (en) * | 2020-09-25 | 2021-01-01 | 华东理工大学 | Cage type silsesquioxane nucleating agent and preparation method and application thereof |
| CN114561019A (en) * | 2022-03-21 | 2022-05-31 | 国科广化精细化工孵化器(南雄)有限公司 | Amphiphilic polymer taking cage-shaped silsesquioxane as core and modified LMHs |
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