CN108299799B - The modified layered double hydroxide and its preparation method and application of cagelike silsesquioxane - Google Patents
The modified layered double hydroxide and its preparation method and application of cagelike silsesquioxane Download PDFInfo
- Publication number
- CN108299799B CN108299799B CN201810079939.XA CN201810079939A CN108299799B CN 108299799 B CN108299799 B CN 108299799B CN 201810079939 A CN201810079939 A CN 201810079939A CN 108299799 B CN108299799 B CN 108299799B
- Authority
- CN
- China
- Prior art keywords
- silsesquioxane
- cagelike silsesquioxane
- solution
- cagelike
- preparation
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 125000000129 anionic group Chemical group 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003063 flame retardant Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- -1 carboxyethyl carbonyl amino propyl Chemical group 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 159000000003 magnesium salts Chemical class 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910001051 Magnalium Inorganic materials 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 150000004679 hydroxides Chemical class 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 102000040954 LDH family Human genes 0.000 abstract description 2
- 108091077232 LDH family Proteins 0.000 abstract description 2
- 150000007529 inorganic bases Chemical class 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000003822 epoxy resin Substances 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 239000000138 intercalating agent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000002687 intercalation Effects 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 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 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a kind of modified layered double hydroxides and its preparation method and application of cagelike silsesquioxane, 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 modified layered double hydroxide POSS-LDH of the cagelike silsesquioxane being prepared using this method belongs to one kind completely new in LDH family.The novel POSS-LDH has nanoscale lamellar structure, and primary partial 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 technique
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 hydroxide ion is total to side around the octahedral structure unit that metal ion is constituted and extends shape
At 2D layer structure, laminate positive charge and interlayer anion are balanced so that LDHs is integrally in stable electroneutral
(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 and the uniform sequential structure feature of molecular level of the flexible modulation of LDHs, assign the physical chemistry of its multiplicity
Property, and the characteristics of show many kinds of Various Functions (Solid State Ionics, 1986,22,135；
Chem.Mater.,2002,14,4286；Chem.Rev.2012,112,4124).
Height Modulatory character based on LDHs structure and performance and the potentiality that flame retardance of polymer can be significantly improved, in recent years
Come it as nanofiller and is widely used in all kinds of polymer materials.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 carry 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.
Summary of the invention
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 family.This is novel
POSS-LDH has nanoscale lamellar structure, primary partial 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) the modified stratiform of the cagelike silsesquioxane is obtained after crude product obtained by step (2) is aged and post-processing
Double-metal hydroxide.
By selecting the cagelike silsesquioxane for containing anionic group to go as functional organic modifiers in the present invention
Intercalation modifying LDH, the anionic group being rich in using anionic POSS molecule surface layer and positively charged LDH piece layer equilibration,
Prepare novel POSS-LDH nano-hybrid material.
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
Alkalinity, which is adjusted to, etc. common inorganic base promotes dissolution.Also the above-mentioned gold containing carboxyl or sulfonic POSS can be directly 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 too long or rigidity is excessive,
It is unfavorable for the nucleation and 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, the concentration of the solution B is 0.005~0.1mol/L；
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 being added dropwise
PH value it is constant.
The alkaline solution can use the inorganic alkali solutions such as common sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide,
It is added purpose and is ensuring that the pH value of reaction system is constant.
Preferably, stirring rate is preferably controlled in 400~600rpm along with being vigorously stirred during being added dropwise.
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
It states cagelike silsesquioxane and is selected from poly- (the carboxyethyl carbonyl amino propyl) silsesquioxane of cage type eight, the concentration of solution B is 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, keeps reaction system by the way that alkaline solution is added during being added dropwise
PH value be 10 ± 0.5.
The invention also discloses the modified laminated type bimetal hydroxides of the cagelike silsesquioxane prepared according to the above method
Object, the POSS-LDH have typical layered double hydroxide structure, and interlamellar spacing is 0.8~2.4nm, primary partical size
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 present invention has the advantage 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 step 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, the primary partical partial size of the modified LDH of gained 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.
Detailed description of the invention
The X-ray diffraction comparison diagram for the NLDH that Fig. 1 is POSS-LDH prepared by embodiment 1 and prepared by 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；
NLDH Fourier-infrared comparison spectrogram that Fig. 3 is POSS-LDH prepared by embodiment 1 and prepared by comparative example 1；
The NLDH scanning electron microscope comparison diagram that Fig. 4 is POSS-LDH prepared by embodiment 1 and prepared by comparative example 1；
Fig. 5 is the structural schematic diagram of POSS-LDH prepared by embodiment 1；
Fig. 6 is that the thermal weight loss of the NLDH of POSS-LDH prepared by embodiment 1 and intercalator OCPS and the preparation of comparative example 1 is bent
Line comparison diagram (nitrogen atmosphere, 10 DEG C/min of heating rate)；
The burning behavior (miniature calorimetric) for the DBS-LDH that Fig. 7 is POSS-LDH prepared by embodiment 1 and prepared by comparative example 2
Comparison diagram.
Specific embodiment
Embodiment 1
At room temperature, 0.2mol/L magnesium nitrate and 0.1mol/L aluminum nitrate mixed solution (200ml) are slowly added dropwise into dense
Degree is (pH=10) in poly- (carboxyethyl carbonyl amino propyl) the silsesquioxane alkaline solution of 200mL cage type eight of 0.025mol/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 keeps the pH value of system
10 ± 0.1, continues to stir 30min after being added dropwise, be then aged 20 hours under the conditions of 60 DEG C, be filtered, washed, dried
And etc. can obtain white powder product, the as modified layered double hydroxide of cagelike silsesquioxane is named as POSS-
LDH。
XRD, XPS, FTIR and TEM characterize (FIG. 1 to 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 nitrate and 0.1mol/L aluminum nitrate mixed solution (200ml) are slowly added dropwise into pH
In=10 NaOH aqueous solution, 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, it is filtered, washed, drying and other steps can obtain white powder product, is named as NLDH.
NLDH is unmodified LDH, relevant characterization (FIG. 1 to 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 nitrate and 0.1mol/L aluminum nitrate mixed solution (200ml) be slowly added dropwise into
In 200mL neopelex (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, is 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 test
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 intercalation after LDH thermal stability be substantially better than intercalator OCPS and do not change
Property pure 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: the LDH thermal stability meeting 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 test
The burning behavior (miniature calorimetric) for the DBS-LDH that Fig. 7 is POSS-LDH prepared by embodiment 1 and prepared by 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 sharp fall compared with DBS-LDH, show
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.Specific step 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, stirs promotion LDH dispersion in two hours at 60 DEG C and 80 DEG C respectively.Desolventizing is heated later, and 120 DEG C are evacuated to constant weight.To
Appropriate 3,3- diaminodiphenylsulfone curing agent (N-H: epoxy group (molar ratio)=1:1), 115 DEG C of heating stirrings are added in system
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 amount respectively according to the method described above
) and the POSS-LDH/ epoxy resin (POSS-LDH/EP) of 4wt% additive amount EP.Batten having a size of 100 × 100 ×
2.9mm3, taper calorimetric test is carried out according to ISO5660 testing standard.
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 of the layered double hydroxide modified to cagelike silsesquioxane provided by the present invention 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 (8)
1. a kind of preparation method of the modified layered double hydroxide of cagelike silsesquioxane, 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 total mole number of metal ion and the mole ratio of cagelike silsesquioxane are 1~40；
The cagelike silsesquioxane is selected from the cagelike silsesquioxane containing anionic group, 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；
(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 the modified stratiform of the cagelike silsesquioxane are obtained after crude product obtained by step (2) is aged and post-processing
Belong to hydroxide.
2. the preparation method of the modified layered double hydroxide of cagelike silsesquioxane according to claim 1,
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 of the modified layered double hydroxide of cagelike silsesquioxane according to claim 1,
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 of the modified layered double hydroxide of cagelike silsesquioxane according to claim 1,
It is characterized in that, in step (1):
The concentration of the solution B is 0.005~0.1mol/L.
5. the preparation method of the modified layered double hydroxide of cagelike silsesquioxane according to claim 1,
It is characterized in that, in step (2), solution A is added dropwise in solution B, keep reactant by the way that alkaline solution is added during being added dropwise
The pH value of system is constant.
6. the preparation method of the modified layered double hydroxide of cagelike silsesquioxane according to claim 1,
It is characterized in that, in step (3), the temperature of the ageing is 60~90 DEG C, and the time is 10~30h.
7. the modified layer of the cagelike silsesquioxane of method preparation described in a kind of any claim according to claim 1~6
Shape double-metal hydroxide.
8. a kind of layered double hydroxide that cagelike silsesquioxane according to claim 7 is modified is as fire retardant
Application in the polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810079939.XA CN108299799B (en) | 2018-01-27 | 2018-01-27 | The modified layered double hydroxide and its preparation method and application of cagelike silsesquioxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810079939.XA CN108299799B (en) | 2018-01-27 | 2018-01-27 | The modified layered double hydroxide and its preparation method and application of cagelike silsesquioxane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108299799A CN108299799A (en) | 2018-07-20 |
| CN108299799B true CN108299799B (en) | 2019-09-20 |
Family
ID=62866829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810079939.XA Active CN108299799B (en) | 2018-01-27 | 2018-01-27 | The modified layered double hydroxide and its preparation method and application of cagelike silsesquioxane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108299799B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109354878B (en) * | 2018-08-03 | 2020-07-28 | 华南理工大学 | Organic ceramic precursor modified bimetallic hydroxide nanosheet and preparation method and application thereof |
| CN111777766B (en) * | 2019-04-04 | 2022-10-28 | 北京化工大学 | Metal-containing amino polyhedral oligomeric silsesquioxane as well as preparation method and application thereof |
| 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 |
| CN114561019B (en) * | 2022-03-21 | 2023-07-07 | 国科广化精细化工孵化器(南雄)有限公司 | Amphiphilic polymer with cage-shaped silsesquioxane as core and modified LMHs |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492172A (en) * | 2011-12-08 | 2012-06-13 | 山东春潮色母料有限公司 | Preparation method and application of nanometer organic-layered composite metal hydroxide |
| WO2012081133A1 (en) * | 2010-12-17 | 2012-06-21 | L'oreal | Make-up cosmetic composition comprising a layered double hydroxide |
| CN103333366A (en) * | 2013-06-24 | 2013-10-02 | 西南科技大学 | Layered double metal hydroxide based antiflaming smoke suppressant, preparation method thereof and antiflaming smoke suppressing compound material modified by using antiflaming smoke suppressant |
| CN103613845A (en) * | 2013-11-21 | 2014-03-05 | 浙江大学宁波理工学院 | Flame retardant polypropylene composite compounded by layered thermometal hydroxide and intumescent flame retardant and preparation method of flame retardant polypropylene composite |
| CN104829864A (en) * | 2015-05-08 | 2015-08-12 | 广西经正科技开发有限责任公司 | Preparation method of polyhedral oligomeric silsesquioxane-aluminum hydroxide composite flame-resistant material |
| CN104829865A (en) * | 2015-05-08 | 2015-08-12 | 广西经正科技开发有限责任公司 | Preparation method of polyhedral oligomeric silsesquioxane-calcium hydroxide composite flame-resistant material |
| CN104830067A (en) * | 2015-05-08 | 2015-08-12 | 广西经正科技开发有限责任公司 | Preparation method of a polyhedral oligomeric silsesquioxane-magnesium hydroxide composite flame-resistant material |
-
2018
- 2018-01-27 CN CN201810079939.XA patent/CN108299799B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012081133A1 (en) * | 2010-12-17 | 2012-06-21 | L'oreal | Make-up cosmetic composition comprising a layered double hydroxide |
| CN102492172A (en) * | 2011-12-08 | 2012-06-13 | 山东春潮色母料有限公司 | Preparation method and application of nanometer organic-layered composite metal hydroxide |
| CN103333366A (en) * | 2013-06-24 | 2013-10-02 | 西南科技大学 | Layered double metal hydroxide based antiflaming smoke suppressant, preparation method thereof and antiflaming smoke suppressing compound material modified by using antiflaming smoke suppressant |
| CN103613845A (en) * | 2013-11-21 | 2014-03-05 | 浙江大学宁波理工学院 | Flame retardant polypropylene composite compounded by layered thermometal hydroxide and intumescent flame retardant and preparation method of flame retardant polypropylene composite |
| CN104829864A (en) * | 2015-05-08 | 2015-08-12 | 广西经正科技开发有限责任公司 | Preparation method of polyhedral oligomeric silsesquioxane-aluminum hydroxide composite flame-resistant material |
| CN104829865A (en) * | 2015-05-08 | 2015-08-12 | 广西经正科技开发有限责任公司 | Preparation method of polyhedral oligomeric silsesquioxane-calcium hydroxide composite flame-resistant material |
| CN104830067A (en) * | 2015-05-08 | 2015-08-12 | 广西经正科技开发有限责任公司 | Preparation method of a polyhedral oligomeric silsesquioxane-magnesium hydroxide composite flame-resistant material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108299799A (en) | 2018-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108299799B (en) | The modified layered double hydroxide and its preparation method and application of cagelike silsesquioxane | |
| Gong et al. | Superior thermal and fire safety performances of epoxy-based composites with phosphorus-doped cerium oxide nanosheets | |
| TWI593787B (en) | Flame retardant, flame retardant composition and compact | |
| US20080157029A1 (en) | Method of producing copper nanoparticles and copper nanoparticles produced thereby | |
| EP2431374B1 (en) | Method for producing phosphonic acid metal salt fine particles | |
| JP5128882B2 (en) | Magnesium hydroxide fine particles and method for producing the same | |
| TW200734275A (en) | Process for preparing organically modified layered double hydroxide | |
| KR20080081973A (en) | Magnesium hydroxide nanoparticles, methods of making same and compositions incorporating same | |
| TW201442946A (en) | Method for preparing lithium iron phosphate nanopowder | |
| Yan et al. | Fabrication of green and scalable N/P/S/Mn containing biobased layered double hydroxide as a novel flame retardant and efficient char forming agent for polypropylene | |
| KR20070116902A (en) | Surface modified nanoparticle and method of preparing same | |
| CN112812372B (en) | Tannin-phosphazene network functionalized hydrotalcite-based flame retardant and preparation method thereof | |
| Liao et al. | Enhanced ionic conductivity in poly (ethylene oxide)/layered double hydroxide nanocomposite electrolytes | |
| KR102086628B1 (en) | Surface-modified cathode materials with nano-metal oxides for lithium secondary batteries and methods for preparing the same | |
| Zhou et al. | Facile preparation of layered double hydroxide/MoS2/poly (vinyl alcohol) composites | |
| CN107603589A (en) | A kind of calcium carbonate-base terbium coordination compound and preparation method thereof | |
| JP2009007215A (en) | Spherical magnesium oxide particles and method for producing the same | |
| JP2008303110A (en) | Low-soda fine particle aluminum hydroxide and its production method | |
| JP6279199B2 (en) | Resin composite material and method for producing resin composite material | |
| WO2017080336A1 (en) | Hydrotalcite used in polymer and preparation method therefor | |
| KR100995401B1 (en) | Hollow magnesium fluoride particle, preparing process thereof and anti-reflection coating solution comprising the same | |
| CN110627079A (en) | Ternary borate hydrotalcite flame retardant and preparation method and application thereof | |
| Kędzierski et al. | Graphite oxide as an intumescent flame retardant for polystyrene | |
| CN113150440B (en) | Preparation method of flame-retardant polypropylene | |
| KR102085040B1 (en) | Fine particle composite metal hydroxide, its baked material, its manufacturing method, and its resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |