CN116041791B - Naphthalene anhydride microencapsulated magnesium hydroxide composite powder and preparation method and application thereof - Google Patents
Naphthalene anhydride microencapsulated magnesium hydroxide composite powder and preparation method and application thereof Download PDFInfo
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- -1 Naphthalene anhydride Chemical class 0.000 title claims abstract description 141
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 title claims abstract description 134
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000000843 powder Substances 0.000 title claims abstract description 111
- 229910001862 magnesium hydroxide Inorganic materials 0.000 title claims abstract description 108
- 239000000347 magnesium hydroxide Substances 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 66
- 238000006482 condensation reaction Methods 0.000 claims abstract description 20
- 230000018044 dehydration Effects 0.000 claims abstract description 20
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000004108 freeze drying Methods 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 6
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000005577 anthracene group Chemical group 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 125000001041 indolyl group Chemical group 0.000 claims description 5
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 5
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 5
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 claims description 4
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical group N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 claims description 4
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 3
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims description 3
- 239000003094 microcapsule Substances 0.000 abstract description 4
- 230000015607 signal release Effects 0.000 abstract description 4
- 230000009977 dual effect Effects 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 57
- 238000012360 testing method Methods 0.000 description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 230000004044 response Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 230000008859 change Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000004631 polybutylene succinate Substances 0.000 description 10
- 229920002961 polybutylene succinate Polymers 0.000 description 10
- 230000035882 stress Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 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 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 229920000379 polypropylene carbonate Polymers 0.000 description 7
- 229920000954 Polyglycolide Polymers 0.000 description 6
- 229920001610 polycaprolactone Polymers 0.000 description 6
- 239000004632 polycaprolactone Substances 0.000 description 6
- 239000004633 polyglycolic acid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 229920000307 polymer substrate Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- 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
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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Abstract
The invention provides a naphthalene anhydride microencapsulated magnesium hydroxide composite powder and a preparation method and application thereof, belonging to the technical field of functional materials. The compound powder of the microencapsulated magnesium hydroxide of the anhydride derivative of naphthalene of the invention is composed of anhydride derivative of naphthalene and magnesium hydroxide, wherein the anhydride derivative of naphthalene is the shell of the compound powder, the magnesium hydroxide is the inner core of the compound powder, and the mole ratio of the magnesium hydroxide to the anhydride derivative of naphthalene is 1:1 to 100. The preparation process is carried out under the protective atmosphere, and the naphthalene anhydride derivative, the magnesium hydroxide and the inorganic salt are sequentially mixed in a solvent for dehydration condensation reaction, thus obtaining the microencapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative. The naphthalene anhydride microcapsule magnesium hydroxide composite powder has the dual characteristics of light signal release and flame retardance, is used for preparing degradable substrate film materials, and can greatly improve the comprehensive performance of the composite material.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a naphthalene anhydride microencapsulated magnesium hydroxide composite powder and a preparation method and application thereof.
Background
Sustainable development is one of the main propositions of this age, based on which various degradable materials are generated, and the degradable biological materials generally have better biocompatibility and environmental friendliness and are generally used in the fields of fiber preparation, adhesives, packaging materials, biomedical equipment and the like. At present, along with the rapid consumption of a large amount of traditional fossil energy, the traditional fossil energy cannot be regenerated in a short period, and degradable materials are permeated into aspects of daily life, including wearable devices, flexible solar cell substrates, mechanical force-induced optical materials, barrier devices and the like. The mechanical force induced stimulus response material is a functional material which is emerging in recent years, can generate photophysical response due to change of micro-area environment under the condition of external stress (stimulus), namely has change of luminous behavior, and can even recover to an initial state when the external stimulus disappears, and the reversible behavior enables the material to have the advantage of responding to the external stimulus, has great potential application value in the fields of sensing devices, anti-counterfeiting, data storage, drug delivery, cell imaging and the like, and draws wide attention.
At present, the application of the materials is mainly focused on organic micromolecules, metal-organic complexes and host-guest doped materials, and polymer substrates and even degradable substrates are rarely developed. Research shows that the materials are easy to synthesize, have various structures, relatively controllable performances and the like, but in most cases, the products still depend on macromolecular materials or macromolecular substrates as carriers. On the other hand, most degradable materials are unfortunately substantially easy to burn, have extremely poor flame retardant effects, and even when burned, can exhibit dripping, which can greatly promote flame propagation and can cause personal injury. Based on the above, development of a high-efficiency, sensitive, reliable and flame-retardant degradable base force-induced response material becomes particularly urgent, so that the application field of the mechanical force-induced stimulus response material can be greatly expanded, and better safety guarantee can be fully obtained.
As one of the core means for solving the problems, high-performance functional powder is developed into a preferred scheme for enhancing the functionality of various macromolecular materials in recent years, from the viewpoint of mechanical luminescence, the powder added into a polymer matrix can release stronger optical signals when the micro-area environment is changed, namely apparent luminescence performance can be observed through the change of a microstructure, and further visual response effect is realized; from the perspective of guaranteeing safety and stability, the flame retardant technology is taken as a passive protection technology, and the circulation path between three elements of combustion can be cut off at key time, so that the polymer substrate becomes a safe and controllable material, and the powder material without halogenation, smoke suppression and cleaning has been widely applied in the field. In summary, development of composite powder with two functions simultaneously and a preparation method thereof are imperative.
Disclosure of Invention
The invention aims to provide a naphthalene anhydride microencapsulated magnesium hydroxide composite powder, and a preparation method and application thereof, so as to solve the technical problems of poor response of a mechanical force-induced stimulus response material to external stimulus and poor flame retardant property in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder, which consists of naphthalene anhydride derivatives and magnesium hydroxide, wherein the naphthalene anhydride derivatives are shells of the composite powder, and the magnesium hydroxide is an inner core of the composite powder; the molar ratio of the magnesium hydroxide to the naphthalene anhydride derivative is 1:1 to 100.
Preferably, the particle size of the magnesium hydroxide composite powder microencapsulated by the naphthalene anhydride derivative is 0.9-4.0 mu m, wherein the particle size of the inner core is 0.8-3.0 mu m.
Preferably, the structural formula of the naphthalene anhydride derivative is shown as I:
wherein Y comprises one of a benzene ring, a methyl benzene ring, a benzene ring methyl ether, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, a phenylacetylene ring, a thiophene ring, a pyrazine ring, an indole ring, a quinoline ring, an isoquinoline ring, a pyridine ring, a furan ring, a pteridine ring, a quinoxaline ring, an acridine ring, a pyrimidine ring, and a quinazoline ring.
The invention provides a preparation method of a naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder, which comprises the following steps: under the protective atmosphere, the naphthalene anhydride derivative, magnesium hydroxide and inorganic salt are sequentially mixed in a solvent for dehydration condensation reaction, and the microencapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative can be obtained.
Preferably, the protective atmosphere is one of a nitrogen atmosphere, a helium atmosphere and an argon atmosphere.
Preferably, the concentration ratio of the naphthalene anhydride derivative, the magnesium hydroxide and the inorganic salt is 1 to 100mol/L:1mol/L:10 to 100mol/L; the inorganic salt comprises one or more of K 2CO3、Cs2CO3 and Ca (OH) 2.
Preferably, the solvent comprises one or more of ethanol, methanol, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, acetonitrile and ethyl acetate.
Preferably, the dehydration condensation reaction is carried out at a temperature of 30 to 80 ℃ for a time of 1 to 48 hours.
Preferably, the product of the dehydration condensation reaction is sequentially washed, centrifuged and freeze-dried; the freeze drying temperature is-60 to-10 ℃, and the freeze drying time is 1 to 72 hours.
The invention provides application of a naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder in a degradable base material, wherein the degradable base material and the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder are sequentially mixed in water and then dried, so that the degradable base material film material can be prepared.
Preferably, the concentration ratio of the degradable substrate to the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder is 1mol/L:1 to 30mol/L; the drying is carried out in two steps, wherein the temperature of the first step is 20-30 ℃, the drying time is 1-36 h, the temperature of the second step is 40-80 ℃, and the drying time is 1-36 h.
The invention has the beneficial effects that:
(1) The invention provides a micro-encapsulated magnesium hydroxide composite powder of a naphthalene anhydride derivative, which is prepared by skillfully combining a naphthalene anhydride small molecule derivative with a clean, efficient and halogen-free inorganic base (MH) to form organic-inorganic composite functional micro-nano particles. The naphthalene anhydride in the molecular structure can freely rotate in the environment with low micro-area stress, fluorescence signals become weak because of mechanical rotation dissipation excitation state energy, when micro-area stress gradually rises, the naphthalene anhydride rotation is gradually inhibited, and the fluorescence signals are released due to the fact that the naphthalene anhydride returns to a ground state through a channel of radiation transition, effective response to micro-area stress change can be achieved to a great extent, and visual detection of potential risks induced by local micro-environment stress change is achieved.
(2) According to the invention, organic naphthalene anhydride derivative functional molecules and superfine magnesium hydroxide powder (MH) are combined together through a microcapsule technology to prepare the naphthalene anhydride microencapsulated superfine MH composite powder, the naphthalene anhydride microcapsule superfine MH composite powder comprises a functionalized naphthalene anhydride derivative wall material and a superfine magnesium hydroxide inner core, the naphthalene anhydride derivative not only has response capability to micro-area stress, but also has good char formation property due to the large conjugated aromatic hydrocarbon structure, and the superfine MH has good smoke suppression and flame retardance characteristics, and the two are combined with each other, so that the visible detection of local micro-area stress change can be realized, the added value of the traditional superfine MH can be improved, and a good demonstration is made for high-value powder. Meanwhile, the functionalized naphthalene anhydride derivative can be used as a wall material to effectively improve the compatibility of superfine MH in a matrix, and can exert different effects in different combustion stages due to the existence of a core-shell structure, so that the improvement of flame retardant efficiency is promoted.
(3) The preparation process of the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder is simple and feasible, the process is environment-friendly, the yield is high, the raw material sources are wide and low, and the preparation method is suitable for large-scale production, preparation and application and has wide application prospect.
(4) According to the invention, the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder and part of degradable base materials are mixed together to prepare the degradable composite material, and the addition of the functional superfine MH enables the degradable base materials to have various characteristics of luminescence, flame retardance, enhancement and the like, namely, the degradable base materials can be improved in functions, safety, stability and mechanical properties.
Drawings
FIG. 1 is a schematic structural diagram of the microencapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative prepared in examples 1 to 5;
FIG. 2 is a schematic diagram showing the mechanism of micro-domain mechanical force induction of the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder prepared in examples 1 to 5;
FIG. 3 is a fluorescence spectrum of the micro-encapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative prepared in example 1 in solution environments with different micro-domains of mechanical force;
FIG. 4 is a graph showing the linear fitting of the fluorescence intensity of the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder prepared in example 1 to the logarithmic function of the mechanical force of different microcells;
FIG. 5 is a graph showing the absorption spectrum of the compound powder of the naphthalene anhydride derivative microencapsulated magnesium hydroxide prepared in example 1 in environments with different polarities.
Detailed Description
The invention provides a naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder, which consists of naphthalene anhydride derivatives and magnesium hydroxide, wherein the naphthalene anhydride derivatives are shells of the composite powder, and the magnesium hydroxide is an inner core of the composite powder; the molar ratio of the magnesium hydroxide to the naphthalene anhydride derivative is 1:1 to 100, preferably 1:20 to 80 percent.
In the present invention, the particle diameter of the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder is 0.9 to 4.0. Mu.m, preferably 1.1 to 3.5. Mu.m, and more preferably 1.2 to 3.0. Mu.m; wherein the particle diameter of the core is 0.8 to 3.0. Mu.m, preferably 1.0 to 2.8. Mu.m, more preferably 1.2 to 2.6. Mu.m.
In the present invention, it is preferable to use a mechanical method for preparing ultrafine magnesium hydroxide powder, and it is generally necessary to perform ball milling a plurality of times by a ball mill and to select magnesium hydroxide having a suitable particle size by air classification.
In the invention, the structural formula of the naphthalene anhydride derivative is shown as I:
Wherein the Y contains one of a benzene ring, a methyl benzene ring, a benzene ring methyl ether, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, a phenylacetylene ring, a thiophene ring, a pyrazine ring, an indole ring, a quinoline ring, an isoquinoline ring, a pyridine ring, a furan ring, a pteridine ring, a quinoxaline ring, an acridine ring, a pyrimidine ring, and a quinazoline ring, preferably one of a benzene ring, a methyl benzene ring, a benzene ring methyl ether, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, a phenylacetylene ring, a thiophene ring, a pyrazine ring, an indole ring, a quinoline ring, an isoquinoline ring, a pyridine ring, a furan ring, a pteridine ring, a quinoxaline ring, and an acridine ring, further preferably one of a benzene ring, a methyl benzene ring, a benzene ring methyl ether, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, a phenylacetylene ring, a thiophene ring, a pyrazine ring, an indole ring, a quinoline ring, an isoquinoline ring, and a pyridine ring.
The invention provides a preparation method of a naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder, which comprises the following steps: under the protective atmosphere, the naphthalene anhydride derivative, magnesium hydroxide and inorganic salt are sequentially mixed in a solvent for dehydration condensation reaction, and the microencapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative can be obtained.
In the invention, the protective atmosphere is one of a nitrogen atmosphere, a helium atmosphere and an argon atmosphere.
In the invention, the concentration ratio of the naphthalene anhydride derivative, the magnesium hydroxide and the inorganic salt is 1-100 mol/L:1mol/L:10 to 100mol/L, preferably 20 to 80mol/L:1mol/L:15 to 80mol/L, more preferably 20 to 80mol/L:1mol/L: 20-60 mol/L; the inorganic salt comprises one or more of K 2CO3、Cs2CO3 and Ca (OH) 2, preferably K 2CO3 and/or Cs 2CO3, more preferably K 2CO3.
In the present invention, the solvent contains one or more of ethanol, methanol, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, acetonitrile and ethyl acetate, preferably one or more of ethanol, methanol, tetrahydrofuran, N-dimethylformamide and dimethyl sulfoxide, more preferably one or more of ethanol, methanol and N, N-dimethylformamide.
In the present invention, the temperature of the dehydration condensation reaction is 30 to 80 ℃, preferably 40 to 70 ℃, and more preferably 50 to 60 ℃; the dehydration condensation reaction time is 1 to 48 hours, preferably 5 to 44 hours, more preferably 10 to 40 hours.
In the present invention, the product of the dehydration condensation reaction is sequentially washed, centrifuged and freeze-dried; the freeze-drying temperature is-60 to-10 ℃, preferably-50 to-20 ℃, and further preferably-40 to-30 ℃; the time for freeze-drying is 1 to 72 hours, preferably 12 to 60 hours, and more preferably 24 to 48 hours.
In the present invention, the centrifugation rate at the time of centrifugation is preferably 900 to 9000rpm, more preferably 1500 to 8000rpm; the centrifugation time is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.
The freeze drying process of the invention is to disperse the product of the dehydration condensation reaction in a small amount of water and freeze, and to make the product undergo solid sublimation at low temperature by a freeze dryer, thus obtaining the micro-encapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative.
The invention provides application of a naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder in a degradable base material, wherein the degradable base material and the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder are sequentially mixed in water and then dried, so that the degradable base material film material can be prepared.
In the present invention, the concentration ratio of the degradable substrate to the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder is 1mol/L, 1 to 30mol/L, preferably 1mol/L, 5 to 25mol/L, and more preferably 1mol/L, 10 to 20mol/L.
In the present invention, the degradable substrate includes one of polylactic acid (PLA), polybutylene adipate (PBAT), polybutylene succinate (PBS), polybutylene succinate (PBSA), polycaprolactone (PCL), polypropylene carbonate (PPC), polyglycolic acid (PGA), polyvinyl alcohol (PVA), and Polyhydroxyalkanoate (PHA), preferably one of polybutylene adipate (PBAT), polybutylene succinate (PBS), polybutylene succinate (PBSA), polycaprolactone (PCL), polypropylene carbonate (PPC), polyglycolic acid (PGA), and polyvinyl alcohol (PVA), and more preferably one of polybutylene succinate (PBS), polycaprolactone (PCL), polypropylene carbonate (PPC), polyglycolic acid (PGA), and polyvinyl alcohol (PVA).
In the present invention, when the degradable substrate is mixed with water, the stirring speed during the mixing is preferably 600 to 1600rpm, more preferably 800 to 1400rpm; the stirring time is preferably 1 to 24 hours, more preferably 5 to 20 hours; the temperature at the time of the mixing is 60 to 90 ℃, preferably 65 to 85 ℃, and more preferably 70 to 80 ℃.
In the present invention, when the compound powder of the microencapsulated magnesium hydroxide of the naphthalene anhydride derivative is mixed with water, the stirring speed during the mixing is preferably 400 to 1200rpm, and more preferably 600 to 1000rpm; the stirring time is preferably 1 to 36 hours, more preferably 9 to 27 hours; the temperature of the mixing is preferably 50 to 90 ℃, more preferably 60 to 80 ℃.
In the present invention, the drying is performed in two steps, and the temperature of the first drying is 20 to 30 ℃, preferably 22 to 28 ℃, and more preferably 25 ℃; the drying time is 1 to 36 hours, preferably 4 to 32 hours, and more preferably 8 to 24 hours; the temperature of the second drying step is 40-80 ℃, preferably 45-75 ℃, and more preferably 50-70 ℃; the drying time is 1 to 36 hours, preferably 4 to 32 hours, and more preferably 8 to 24 hours.
The thickness of the degradable substrate film material prepared by the invention is preferably controlled to be 0.1-0.6 mm, and more preferably 0.3-0.4 mm.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing 40mol of a naphthalene anhydride derivative, 1mol (58.3 g) of magnesium hydroxide and 20mol of K 2CO3 with 1L of ethanol in sequence, wherein the structural formula of the naphthalene anhydride derivative is shown as follows, carrying out dehydration condensation reaction for 24 hours under the condition of 50 ℃ in a nitrogen atmosphere, controlling the stirring speed in the reaction process to be 600rpm, washing a reaction product with deionized water after the reaction is finished, carrying out centrifugal treatment, wherein the centrifugal speed is 3000rpm, the centrifugal time is 30min, finally dispersing the centrifugal treated product in a small amount of water, carrying out freeze drying, and the freeze drying temperature is-30 ℃ and the freeze drying time is 36 hours, thus obtaining the microencapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative, wherein the D 50 of the magnesium hydroxide inner core is 1.165 mu m.
Dispersing 1mol of PVA degradable base material in 1L of water, wherein the stirring speed is 1000rpm, the stirring temperature is 80 ℃, the stirring time is 10 hours, then adding 20mol of naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder, controlling the stirring speed to be 900rpm, the stirring temperature to be 80 ℃, the stirring time to be 24 hours, pouring the mixed solution into a glass dish, drying the mixed solution in steps, wherein the drying temperature in the first step is 25 ℃, the drying time is 18 hours, the drying temperature in the second step is 50 ℃, and the drying time is 24 hours, thus obtaining the degradable base material film material with the thickness of 0.3 mm.
Example 2
Mixing 1mol of a naphthalene anhydride derivative, 1mol (58.3 g) of magnesium hydroxide and 10mol of K 2CO3 with 1L of ethanol in sequence, wherein the structural formula of the naphthalene anhydride derivative is shown as follows, carrying out dehydration condensation reaction for 48 hours at 30 ℃ under nitrogen atmosphere, controlling the stirring speed in the reaction process to be 100rpm, washing a reaction product with deionized water after the reaction is finished, carrying out centrifugal treatment, wherein the centrifugal speed is 900rpm, the centrifugal time is 60min, finally dispersing the centrifugal treated product in a small amount of water, carrying out freeze drying, wherein the freeze drying temperature is-10 ℃, and the freeze drying time is 72 hours, thus obtaining the microencapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative, wherein the D 50 of the magnesium hydroxide inner core is 1.418 mu m.
Dispersing 1mol of PVA degradable base material in 1L of water, wherein the stirring speed is 600rpm, the stirring temperature is 60 ℃, the stirring time is 24 hours, then adding 1mol of naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder, the stirring speed is 400rpm, the stirring temperature is 50 ℃, the stirring time is 36 hours, pouring the mixed solution into a glass dish, drying the mixed solution in steps, wherein the drying temperature in the first step is 25 ℃, the drying time is 36 hours, the drying temperature in the second step is 40 ℃, and the drying time is 36 hours, thus obtaining the degradable base material film material with the thickness of 0.3 mm.
Example 3
Mixing 100mol of naphthalene anhydride derivative, 1mol of magnesium hydroxide and 100mol of K 2CO3 with 1L of ethanol in sequence, wherein the structural formula of the naphthalene anhydride derivative is shown as follows, carrying out dehydration condensation reaction for 1h at 80 ℃ under nitrogen atmosphere, controlling the stirring speed in the reaction process to 600rpm, washing the reaction product with deionized water after the reaction is finished, carrying out centrifugal treatment, wherein the centrifugal speed is 9000rpm, the centrifugal time is 5min, finally dispersing the centrifugal treated product in a small amount of water, carrying out freeze drying, the freeze drying temperature is-60 ℃, and the freeze drying time is 1h, thus obtaining the microencapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative, wherein the D 50 of the magnesium hydroxide inner core is 1.356 mu m.
Dispersing 1mol of PVA degradable base material in 1L of water, wherein the stirring speed is 1600rpm, the stirring temperature is 90 ℃, the stirring time is 1h, then adding 30mol of naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder, controlling the stirring speed to be 1200rpm, the stirring temperature to be 90 ℃, the stirring time to be 1h, pouring the mixed solution into a glass dish, drying in steps, wherein the drying temperature in the first step is 25 ℃, the drying time is 1h, the drying temperature in the second step is 80 ℃, and the drying time is 1h, thus obtaining the degradable base material film material with the thickness of 0.3 mm.
Example 4
Mixing 80mol of naphthalene anhydride derivative, 1mol of magnesium hydroxide and 50mol of Cs 2CO3 with 1L of ethanol in sequence, wherein the structural formula of the naphthalene anhydride derivative is shown as follows, carrying out dehydration condensation reaction for 30 hours at 60 ℃ under nitrogen atmosphere, controlling the stirring speed in the reaction process to 1000rpm, washing a reaction product with deionized water after the reaction is finished, carrying out centrifugal treatment, wherein the centrifugal speed is 8000rpm, the centrifugal time is 10min, finally dispersing the centrifugal treated product in a small amount of water, carrying out freeze drying, the freeze drying temperature is-40 ℃, and the freeze drying time is 10 hours, thus obtaining the microencapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative, wherein the D 50 of the magnesium hydroxide inner core is 1.389 mu m.
Dispersing 1mol of PLA degradable base material in 1L of water, wherein the stirring speed is 1600rpm, the stirring temperature is 90 ℃, the stirring time is 1h, then adding 10mol of naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder, controlling the stirring speed to be 1200rpm, the stirring temperature to be 90 ℃, the stirring time to be 1h, pouring the mixed solution into a glass vessel, drying in steps, wherein the drying temperature in the first step is 25 ℃, the drying time is 1h, the drying temperature in the second step is 80 ℃, and the drying time is 1h, thus obtaining the degradable base material film material with the thickness of 0.4 mm.
Example 5
50Mol of naphthalene anhydride derivative, 1mol of magnesium hydroxide and 50mol of Ca (OH) 2 are sequentially mixed with 1L of ethanol, wherein the structural formula of the naphthalene anhydride derivative is shown as follows, Y is pyridine ring, then dehydration condensation reaction is carried out for 20 hours at 70 ℃ under nitrogen atmosphere, stirring speed is controlled at 1200rpm in the reaction process, reaction products are washed by deionized water after the reaction is finished, centrifugal treatment is carried out, wherein the centrifugal speed is 6000rpm, the centrifugal time is 20min, finally, the centrifugal treated products are dispersed in a small amount of water for freeze drying, the freeze drying temperature is-40 ℃, and the freeze drying time is 20 hours, so that the microencapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative can be prepared, wherein D 50 of a magnesium hydroxide inner core is 1.226 mu m.
Dispersing 1mol of PPC degradable base material in 1L of water, wherein the stirring speed is 1600rpm, the stirring temperature is 90 ℃, the stirring time is 1h, then adding 10mol of naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder, controlling the stirring speed to be 1200rpm, the stirring temperature to be 90 ℃, the stirring time to be 1h, pouring the mixed solution into a glass dish, drying in steps, wherein the drying temperature in the first step is 25 ℃, the drying time is 20h, the drying temperature in the second step is 50 ℃, and the drying time is 20h, thus obtaining the degradable base material film material with the thickness of 0.4 mm.
Comparative example 1
Mixing 0.5mol of a naphthalene anhydride derivative, 1mol of magnesium hydroxide and 40mol of K 2CO3 with 1L of ethanol in sequence, wherein the structural formula of the naphthalene anhydride derivative is shown as follows, carrying out dehydration condensation reaction for 32 hours at 45 ℃ under nitrogen atmosphere, washing a reaction product with deionized water after the reaction is finished, centrifuging at 4500rpm for 30 minutes, dispersing the centrifuged product in a small amount of water for freeze drying, wherein the freeze drying temperature is-30 ℃, and the freeze drying time is 36 hours, thus obtaining the microencapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative, wherein the D 50 of the magnesium hydroxide core is 1.345 mu m.
Dispersing 1mol of PVA degradable base material in 1L of water, wherein the stirring speed is 1000rpm, the stirring temperature is 80 ℃, the stirring time is 12h, then adding 20mol of naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder, the stirring speed is 800rpm, the stirring temperature is 70 ℃, the stirring time is 18h, pouring the mixed solution into a glass dish, drying the mixed solution in steps, wherein the drying temperature in the first step is 25 ℃, the drying time is 16h, the drying temperature in the second step is 60 ℃, and the drying time is 18h, thus obtaining the degradable base material film material with the thickness of 0.3 mm.
Comparative example 2
Sequentially mixing 120mol of naphthalene anhydride derivative, 1mol of magnesium hydroxide and 50mol of K 2CO3 with 1L of ethanol, wherein the structural formula of the naphthalene anhydride derivative is shown as follows, carrying out dehydration condensation reaction for 40 hours at 45 ℃ under nitrogen atmosphere, washing a reaction product with deionized water after the reaction is finished, carrying out centrifugal treatment, wherein the centrifugal speed is 5000rpm, the centrifugal time is 30 minutes, finally dispersing the centrifugal treated product in a small amount of water, carrying out freeze drying, the freeze drying temperature is-25 ℃, and the freeze drying time is 40 hours, thus obtaining the microencapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative, wherein the D 50 of the magnesium hydroxide core is 1.275 mu m.
Dispersing 1mol of PVA degradable base material in 1L of water, wherein the stirring speed is 1200rpm, the stirring temperature is 70 ℃, the stirring time is 14h, then adding 20mol of naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder, the stirring speed is 1000rpm, the stirring temperature is 50 ℃, the stirring time is 28h, pouring the mixed solution into a glass dish, drying the mixed solution step by step, wherein the drying temperature in the first step is 25 ℃, the drying time is 20h, the drying temperature in the second step is 65 ℃, and the drying time is 20h, thus obtaining the degradable base material film material with the thickness of 0.3 mm.
Comparative example 3
Dispersing 1mol of PVA degradable base material in 1L of water, wherein the stirring speed is 1200rpm, the stirring temperature is 70 ℃, the stirring time is 14 hours, then adding 20mol of mechanical ball-milled fine magnesium hydroxide powder, the stirring speed is 1000rpm, the stirring temperature is 50 ℃, the stirring time is 28 hours, pouring the mixed solution into a glass dish, drying the mixed solution in steps, wherein the drying temperature in the first step is 25 ℃, the drying time is 20 hours, the drying temperature in the second step is 65 ℃, and the drying time is 20 hours, thus obtaining the degradable base material film material with the thickness of 0.3 mm.
Performance test:
The microencapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative prepared in examples 1 to 5 and comparative examples 1 to 2 was subjected to particle size and oil absorption value tests on commercially available fine MH powder. The particle size testing method comprises the following steps: the laser particle distribution measuring instrument measures the particle size and distribution of the powder, the oil absorption is tested according to the DB/T5211.15-2014 standard, and the test results are shown in table 1:
table 1 particle size and oil absorption test results
| Numbering device | D50(μm) | Oil absorption value (mL/100 g) |
| Example 1 | 1.295 | 27 |
| Example 2 | 1.603 | 29 |
| Example 3 | 1.506 | 29 |
| Example 4 | 1.652 | 28 |
| Example 5 | 1.478 | 26 |
| Comparative example 1 | 2.121 | 33 |
| Comparative example 2 | 1.931 | 31 |
| Comparative example 3 | 3.278 | 38 |
From the test results in table 1, it can be seen that: after the functional naphthalene anhydride derivative and the superfine MH are added in a proper molar ratio for compounding, the median particle diameter D 50 of the obtained naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder shows a greatly reduced trend, and the oil absorption value is relatively low; in contrast, when the molar ratio of the added naphthalene anhydride derivative to MH is too low (lower than 1:1, as in comparative example 1), the surface of the MH powder cannot be well coated with the naphthalene anhydride derivative, and a complete wall material is difficult to form, namely, the exposure phenomenon occurs, the surface modification effect of the MH powder is limited, and the MH powder has a remarkable rising trend in both particle size and oil absorption value; however, when the molar ratio of the naphthalene anhydride derivative to the MH is too high (more than 100:1, such as comparative example 2), the naphthalene anhydride derivative may cause self-aggregation due to excessive addition, which not only causes the particle size of the composite powder to be too large, but also causes various small molecule aggregates to be filled therein, and the obtained product is difficult to play a comprehensive role with MH compounding. When the MH powder is not treated in any way, the above examples 1 to 5 and comparative examples 1 to 2 are very easy to agglomerate due to the large number of hydroxyl groups on the surface thereof, and the results are remarkably increased and the oil absorption value is remarkably increased in the median particle size test, which is not advantageous for improving the overall performance of the composite powder, as compared with comparative example 3. The results show that the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder provided by the invention can obviously improve the comprehensive performance of MH, and especially the surface performance of MH.
Spectroscopic testing:
the composite powder used in the spectroscopic test was the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder prepared in example 1.
(1) Luminescence performance test of fluorescent rotors in different solvents:
the composite powder is prepared into mother solution with 1mM, the final concentration is controlled to be 10 mu M during specific test, the mother solution is added into common six solvents including toluene, tetrahydrofuran, ethanol, dimethyl sulfoxide, glycerol and water respectively, the absorption spectrum of the composite powder in various conventional solvents is tested, the test results are shown in fig. 3 and table 2, the absorption spectrum peak values of the composite powder in various solvents are similar, the composite powder shows a slightly red shift trend, the composite powder is suitable for various solvents, and the composite powder has wider universality application potential.
Table 2 absorption spectrum peak value and absorbance data of the composite powder of example 1
(2) Response test of naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder to micro-domain mechanical force induction:
The physical environment of the solvent microdomains was changed by formulating different volume fractions of glycerol/deionized water mixed solutions, wherein the volume fractions of glycerol were 0%, 10%, 30%, 50%, 70%, 90%, 99%, respectively. When testing at room temperature, 10 mu M of naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder is added into the solution to be tested, and the excitation wavelength is set to 430nm, and the specific test result is shown in figure 4. As can be seen from fig. 4, as the physical viscosity of the micro-domain in the solution increases, the mechanical rotation of the naphthalene anhydride derivative becomes more difficult, the naphthalene anhydride derivative is restrained, the excited electrons return to the ground state through radiation transition, the released light signal is gradually enhanced, especially, the released light signal intensity reaches the maximum value when the micro-encapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative is added into 99% glycerol, and compared with the water with low physical viscosity, the released fluorescent signal intensity is increased by about 14 times (the specific test result is shown in table 3), and the detection effect is remarkable. Further, utilize The Hoffman equation quantifies the micro-region viscosity and the optical signal intensity to judge the response effect of the composite powder to the change of the micro-region stress, and the final fitting result is shown in fig. 5, so that the composite powder can be found to show an approximately linear result only in the environment of low micro-region viscosity and another linearly related result in the environment of high micro-region viscosity, and the slopes of the two results are different, which indicates that the composite powder has more obvious response effect to the change of the low micro-region stress and also has certain response effect to the change of the high micro-region stress, namely, the composite powder can be used for monitoring the change of various physical micro-region stresses.
TABLE 3 optical signal intensity of composite powders added to glycerol/deionized water solutions of different volume fractions
| Glycerol volume fraction | Fluorescence intensity |
| 0％ | 130.8 |
| 10％ | 401.9 |
| 30％ | 823.5 |
| 50％ | 1111.8 |
| 70％ | 1360.6 |
| 90％ | 1565.8 |
| 99％ | 1823.6 |
Testing the performance of the degradable substrate film material:
the PVA degradable substrate film materials prepared in examples 1 to 5 and comparative examples 1 to 3 were prepared into test specimens according to standard dimensions, and performance tests were conducted according to the following standards, and the results of the performance tests are shown in Table 4.
Vertical combustion test: testing was performed according to standard ASTM D4804-14;
total heat release: heat generated by heating from room temperature to 740 ℃ by using a microcalorimeter;
oxygen index test: the test was performed according to standard ASTM D2863-17.
TABLE 4 Performance test results of PVA degradable substrate film materials
The combustion performance of the degradable substrate film material is tested by comprehensively using a vertical combustor, a microcalorimeter and a limiting oxygen index, and the results shown in the table 4 show that when the molar ratio of the naphthalene anhydride derivative to the superfine MH is in a reasonable range, the prepared composite powder can exert better synergistic flame retardant effect in the combustion process after being added into a polymer matrix, and is particularly reflected in the grade capable of being combusted by VTM-0 vertically, the total heat release amount can be greatly reduced, and the limiting oxygen index can be kept at a higher level; in contrast, when the molar ratio of the naphthalene anhydride derivative to the ultrafine MH is too large or too small, or no naphthalene anhydride derivative is added, the vertical combustion grade in the polymer matrix is difficult to pass, the total heat release amount is high, and the limiting oxygen index is low, which may be attributed to the fact that the naphthalene anhydride derivative itself belongs to large conjugated aromatic molecules, is easy to form char in the combustion front carbon layer during the combustion process, and meanwhile, the inner ultrafine MH itself has better flame retardant performance, which can generate incombustible MgO inorganic matters to deposit on the combustion front during the combustion process, and can release more water vapor to dilute the degraded molecular fragments during the combustion, i.e. can block the combustion cycle path in the gas phase and the solid phase at the same time, and the large amount of char formation of the outer naphthalene anhydride molecules is matched, and the molar concentration of the two molecules is matched, and cannot be too large or too small.
The naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder provided by the invention has the dual characteristics of light signal release and flame retardance, the excitation wavelength required by the light signal release is just near 365nm of the emission wavelength of a common portable ultraviolet lamp, the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder is suitable for exciting the light signal through ultraviolet emission, and the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder has the effects of portability and rapid detection in various occasions and is very convenient; the interior is a superfine MH core, so that good smoke suppression and flame retardance can be provided; the naphthalene anhydride derivative can provide necessary surface modification performance to improve the dispersibility of superfine MH in a matrix, and has a great improvement effect on the comprehensive performance of the composite material; the obtained composite powder is prepared by a one-step method, has the characteristics of green preparation process, higher yield, wide range, low cost and the like, and is in accordance with the development concept of green low carbon.
From the above examples, the present invention provides a naphthalene anhydride microencapsulated magnesium hydroxide composite powder, and a preparation method and applications thereof. The compound powder of the microencapsulated magnesium hydroxide of the anhydride derivative of naphthalene of the invention is composed of anhydride derivative of naphthalene and magnesium hydroxide, wherein the anhydride derivative of naphthalene is the shell of the compound powder, the magnesium hydroxide is the inner core of the compound powder, and the mole ratio of the magnesium hydroxide to the anhydride derivative of naphthalene is 1:1 to 100. The preparation process is carried out under the protective atmosphere, and the naphthalene anhydride derivative, the magnesium hydroxide and the inorganic salt are sequentially mixed in a solvent for dehydration condensation reaction, thus obtaining the microencapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative. The naphthalene anhydride microcapsule magnesium hydroxide composite powder has the dual characteristics of light signal release and flame retardance, is used for preparing degradable substrate film materials, and can greatly improve the comprehensive performance of the composite material.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder is characterized by comprising naphthalene anhydride derivatives and magnesium hydroxide, wherein the naphthalene anhydride derivatives are shells of the composite powder, and the magnesium hydroxide is an inner core of the composite powder; the molar ratio of the magnesium hydroxide to the naphthalene anhydride derivative is 1:1 to 100;
the structural formula of the naphthalene anhydride derivative is shown as I:
Wherein Y comprises one of a benzene ring, a methyl benzene ring, a benzene ring methyl ether, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, a thiophene ring, a pyrazine ring, an indole ring, a quinoline ring, an isoquinoline ring, a pyridine ring, a furan ring, a pteridine ring, a quinoxaline ring, an acridine ring, a pyrimidine ring, and a quinazoline ring.
2. The naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder according to claim 1, wherein the particle size of the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder is 0.9 to 4.0 μm, and wherein the particle size of the inner core is 0.8 to 3.0 μm.
3. The method for preparing the micro-encapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative as claimed in claim 1 or 2, comprising the steps of: under the protective atmosphere, the naphthalene anhydride derivative, magnesium hydroxide and inorganic salt are sequentially mixed in a solvent for dehydration condensation reaction, and the microencapsulated magnesium hydroxide composite powder of the naphthalene anhydride derivative can be obtained.
4. The method according to claim 3, wherein the concentration ratio of the naphthalene anhydride derivative, magnesium hydroxide and inorganic salt is 1 to 100mol/L:1mol/L:10 to 100mol/L; the inorganic salt comprises one or more of K 2CO3、Cs2CO3 and Ca (OH) 2.
5. The method according to claim 4, wherein the solvent comprises one or more of ethanol, methanol, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, acetonitrile and ethyl acetate.
6. The method according to claim 4 or 5, wherein the dehydration condensation reaction is carried out at a temperature of 30 to 80℃for a time of 1 to 48 hours.
7. The method according to claim 3, wherein the product of the dehydration condensation reaction is washed, centrifuged and freeze-dried sequentially; the freeze drying temperature is-60 to-10 ℃, and the freeze drying time is 1 to 72 hours.
8. The application of the compound powder of the naphthalene anhydride derivative microencapsulated magnesium hydroxide in the degradable base material, which is characterized in that the degradable base material and the compound powder of the naphthalene anhydride derivative microencapsulated magnesium hydroxide are sequentially mixed in water and then dried, so that the degradable base material film material can be prepared.
9. The use according to claim 8, wherein the concentration ratio of the degradable substrate, the naphthalene anhydride derivative microencapsulated magnesium hydroxide composite powder is 1mol/L:1 to 30mol/L; the drying is carried out in two steps, wherein the temperature of the first step is 20-30 ℃, the drying time is 1-36 h, the temperature of the second step is 40-80 ℃, and the drying time is 1-36 h.
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| KR20110105210A (en) * | 2010-03-18 | 2011-09-26 | 경상대학교산학협력단 | Ultraefficient separation and sensing of mercury and methylmercury ions in drinking water by using aminonaphthalimide-functionalized fe3o4@sio2 core/shell magnetic nanoparticles |
| KR20150064345A (en) * | 2013-12-03 | 2015-06-11 | 주식회사 서흥 | Soft capsule composition showing improved stability and dissolution rate including naproxen ingredient |
| CN104804474A (en) * | 2015-05-19 | 2015-07-29 | 山东航通工贸有限公司 | Double-covered magnesium hydroxide fire retardant and preparation method thereof |
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| CN114058084A (en) * | 2021-11-29 | 2022-02-18 | 江西广源化工有限责任公司 | Molybdenum substrate layer modified magnesium hydroxide and preparation method and application thereof |
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| US7560161B2 (en) * | 2004-08-09 | 2009-07-14 | Xerox Corporation | Inorganic material surface grafted with charge transport moiety |
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| CN114058084A (en) * | 2021-11-29 | 2022-02-18 | 江西广源化工有限责任公司 | Molybdenum substrate layer modified magnesium hydroxide and preparation method and application thereof |
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