CN114015242A - Nano-attapulgite composite flame retardant and preparation method thereof - Google Patents
Nano-attapulgite composite flame retardant and preparation method thereof Download PDFInfo
- Publication number
- CN114015242A CN114015242A CN202111367427.1A CN202111367427A CN114015242A CN 114015242 A CN114015242 A CN 114015242A CN 202111367427 A CN202111367427 A CN 202111367427A CN 114015242 A CN114015242 A CN 114015242A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- attapulgite
- composite flame
- nano composite
- 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.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 118
- 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 title claims abstract description 114
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 67
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title claims description 23
- 239000002114 nanocomposite Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920002627 poly(phosphazenes) Polymers 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- -1 phosphazene compound Chemical class 0.000 claims abstract 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 239000003822 epoxy resin Substances 0.000 claims description 25
- 229920000647 polyepoxide Polymers 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000010907 mechanical stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 3
- 229960001553 phloroglucinol Drugs 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 238000013508 migration Methods 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 12
- 230000002195 synergetic effect Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012264 purified product Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention provides an attapulgite nano composite flame retardant and a preparation method thereof, the flame retardant is prepared by a one-step polymerization method by using natural mineral-nano attapulgite and phosphazene compound, and has good chemical stability, thermal stability and flame retardant property. The flame retardant is added into a polymer material, has better compatibility with a polymer matrix, can effectively improve the comprehensive performance of the material while resisting flame, and can play a role in enhancing the mechanical property of the material. The flame retardant has the advantages of simple preparation process, low cost, recyclable solvent, high efficiency, environmental protection, migration resistance, hydrolysis resistance and the like. The multifunctional efficient nano composite flame retardant is prepared by combining the unique structure of the attapulgite and the characteristics of high phosphorus and nitrogen contents and hydrolysis resistance of the polyphosphazene through a one-step method, solves the problems of high preparation cost, low flame retardant efficiency, poor migration resistance, poor compatibility of a base body and the like of the traditional flame retardant, and has good market application prospect.
Description
Technical Field
The invention relates to a nano attapulgite composite flame retardant and a preparation method thereof, in particular to a nano composite flame retardant prepared by compounding natural nano attapulgite and polyphosphazene materials.
Technical Field
At present, the halogen flame retardant is still the organic flame retardant with the largest output in the world, especially the bromine-containing flame retardant product, and is most widely used in the field of electronic and electric appliances. However, a large amount of corrosive and toxic gases are generated in the use and recovery processes of the halogen flame retardant, so that the environment is polluted, the halogen flame retardant is eliminated with the promotion of the green development concept, the halogen-free flame retardant is imperative, and the development of novel low-smoke low-toxicity halogen-free environment-friendly flame retardant and flame retardant polymer materials to replace the halogen flame retardant is urgently needed. For halogen-free flame retardant, the research focus in recent years is mainly on the flame retardant with structure of phosphorus, nitrogen, silicon, etc., wherein the phosphorus-containing flame retardant has become the focus of research in recent years.
One of the latest research and development hotspots of international halogen-free flame retardants is to make up for the deficiency of a single flame retardant element by utilizing the synergistic effect of multiple flame retardant elements, so as to better balance the relationship between the dosage, performance and cost of the flame retardant, and meet the increasing environmental protection and safety requirements, and researchers have made a great deal of research on the synergistic effect of multiple systems of flame retardants, such as hydroxide synergistic flame retardant, phosphorus-nitrogen synergistic flame retardant, phosphorus-silicon synergistic flame retardant, nano particle compound synergistic flame retardant systems, and the like.
The attapulgite is applied to various industries due to the special structure and properties of the attapulgite. For example: the polymer field, the sewage treatment field, the organic product decoloration field, the multifunctional carrier material field, the catalysis field, the drilling mud and dye adsorption or gas separation and other fields. The attapulgite is compounded with rubber as a rubber additive to prepare a concave-convex rod/polymer nano composite material; the mechanical property, heat resistance, flame retardant property, crystallization property and the like of the plastic can be improved by compounding the flame retardant with the plastic; the attapulgite is compounded with the flame retardant, so that a good flame retardant can be prepared, and the heat absorption function, the covering function and the like of the flame retardant material can be effectively improved. In combination with the research of scholars at home and abroad in recent years, the functional application of the attapulgite is still an important trend of future development, and the direction of how to develop high-performance materials with green environmental protection, high added value and low cost is the direction of the common efforts of people.
Disclosure of Invention
The invention designs and prepares a nano attapulgite composite flame retardant, which is a nano composite flame retardant prepared by compounding natural nano materials, namely attapulgite and polyphosphazene, and emphasizes the compounding and functionalization of the natural nano materials, namely the attapulgite and the polyphosphazene flame retardant, and is suitable for flame retardance and reinforcement of an epoxy resin system. The invention has the advantages of simple preparation process, low cost, recyclable solvent, high efficiency, environmental protection, migration resistance, hydrolysis resistance and the like. In addition, so far, no accurate and detailed report that the attapulgite-polyphosphazene nano composite flame retardant is directly used for the flame retardance and the mechanical property enhancement of the epoxy resin after being functionalized exists.
The attapulgite nano mineral is rich natural mineral resources, and has special physical and chemical properties due to the unique structural characteristics. Firstly, the microscopic morphology of the material is fine needle fibrous, the diameter is in the order of magnitude of 0.01 mu m, the length can reach the order of magnitude of 0.1-1 mu m, and the material has a better length-diameter ratio, so that the potential capability of enhancing the mechanical property of the material is determined; secondly, the surface of the attapulgite crystal has rich pore channel structures, contains a large amount of crystal water (adsorbed water, zeolite water, combined water, structural water and the like), can lose water at high temperature when the material is burnt with heat, and the generated steam can isolate oxygen to achieve the flame retardant effect, so the material has better flame retardant capability; the attapulgite is a magnesium-aluminum-rich silicate material, and can form MgO and Al at high temperature (above 350℃)2O3The compact heat insulation layer plays a role in isolating oxygen and achieving the purpose of flame retardance.
The invention carries out reasonable and scientific experimental design aiming at the problem of flammability of the current epoxy resin flame retardant, and prepares the nano-composite flame retardant by compounding the natural attapulgite and the polyphosphazene flame retardant, thereby not only effectively improving the flame retardant property and the mechanical property of the epoxy resin material, but also achieving the purpose of environmental protection while retarding flame. The attapulgite clay is close to micron-sized, is in a fine needle shape, contains a large amount of hydroxyl on the surface, and can be well compatible with epoxy resin after being compounded with polyphosphazene, so that the mechanical property and curing shrinkage of the epoxy resin are improved; on the other hand, as a natural mineral rich in magnesium and aluminum, attapulgite can form MgO and Al under high temperature conditions2O3The oxide isolating layer has good thermal stability and has flame retardant function. In addition, the addition of the attapulgite can improve the heat resistance and the flame retardance of the epoxy resin and simultaneously has small influence on the mechanical property of the material, and the implementation of the technology can expand the application range of the attapulgite nano material and drive the regional economic development.
The purpose of the invention is realized by the following technical scheme:
the attapulgite nano composite flame retardant is prepared by compounding natural mineral-nano attapulgite and macromolecular polyphosphazene through a one-step polymerization method, and the structure of the flame retardant contains ATP and polyphosphazene materials.
The preparation of the flame retardant is carried out by four steps:
firstly, smashing and coarsely screening attapulgite ore, and removing impurities to obtain coarse and purified ATP.
And secondly, dispersing the ATP roughly purified in the first step in a good solvent, finishing the reaction for a period of time by mechanical stirring and ultrasonic dispersion at a certain temperature, and settling, separating, washing and drying the product to obtain off-white solid powder.
And thirdly, dispersing the purified ATP powder in a solvent, uniformly suspending the ATP powder in the solution through ultrasonic dispersion, adding 4'4 dihydroxy diphenol, adding a certain amount of acid-binding agent, dissolving hexachlorocyclotriphosphazene in a specific solvent, placing the solution in a constant-pressure dropping funnel, controlling the dropping rate, reacting at normal temperature, continuing to react for a period of time after the dropping is complete, and naturally cooling to room temperature after the reaction is finished.
And fourthly, after the reaction is finished, centrifuging, separating, washing and drying the product after the reaction to obtain the composite flame retardant.
The natural attapulgite is mainly from areas such as Gansu, Jiangsu, inner Mongolia, Sichuan and Shanxi.
The fifth step, the method for using the flame retardant in the epoxy resin is as follows: weighing a proper amount of epoxy resin and a flame retardant, adding the epoxy resin and the flame retardant into a beaker, heating and stirring the mixture uniformly to form a gray emulsion, continuously adding a curing agent, stirring the mixture uniformly, pouring the mixture into a mold for curing and molding at a high temperature, and naturally cooling and demolding the mixture to test the flame retardant performance and the mechanical performance.
The polyphosphazene material is polymerized by hexachlorocyclotriphosphazene and 1 or more of hydroquinone, resorcinol, phloroglucinol, 4 '4-dihydroxy diphenyl sulfone, 4' 4-dihydroxy diphenyl methane, 4 '4-diamino diphenyl sulfone and 4' 4-diamino diphenyl methane.
The solvent used in the second purification step of the preparation of the flame retardant is any one or a mixture of any several of methanol, ethanol, acetonitrile, DMF, acetone and water (for example, ethanol: water: 0: 1000-1000: 0).
The time used in the second step of modification is 0-24 h; the mechanical stirring speed is 10-10000 r/min, and the ultrasonic dispersion power is 50-300W; the temperature used during drying is-50 to 150 ℃.
In the third step, the solvent used for preparing the composite flame retardant is any one or a mixture of any several of dioxane, methanol, ethanol, acetonitrile, DMF, acetone and chlorobenzene in any proportion (for example, methanol: ethanol is 0: 200-200: 0); the acid-binding agent is any one of triethylamine and pyridine.
The raw materials used in the third step of preparing the composite flame retardant are 1 or more of hexachlorocyclotriphosphazene, hydroquinone, resorcinol, phloroglucinol, 4 '4-dihydroxy diphenyl sulfone, 4' 4-dihydroxy diphenyl methane, 4 '4-diamino diphenyl sulfone and 4' 4-diamino diphenyl methane. (since the starting materials are more numerous, only some of them are listed here and not all of them are represented).
The use method of the flame retardant in the epoxy resin comprises the following steps: weighing a proper amount of epoxy resin and a flame retardant, adding the epoxy resin and the flame retardant into a beaker, heating and stirring the mixture uniformly to form a gray emulsion, continuously adding a curing agent, stirring the mixture uniformly, pouring the mixture into a mold for curing and molding at a high temperature, and naturally cooling and demolding the mixture to test the flame retardant performance and the mechanical performance.
The invention has the advantages and effects that:
1. the attapulgite nano-composite flame retardant and the preparation method thereof provided by the invention have good chemical stability, thermal stability and flame retardant property.
2. The attapulgite nano-composite flame retardant and the preparation method thereof provided by the invention can effectively improve the comprehensive performance of the material while being added into a matrix polymer material for flame retardance, and the nano particles and the polymer matrix have better compatibility and can play a role in enhancing the mechanical property of the material.
3. The attapulgite nano composite flame retardant and the preparation method thereof have the advantages of simple preparation process, low cost, recyclable solvent, high efficiency, environmental protection, migration resistance, hydrolysis resistance and the like.
4. According to the attapulgite nano composite flame retardant and the preparation method thereof provided by the invention, the unique structure of attapulgite and the characteristics of high phosphorus and nitrogen contents and hydrolysis resistance of polyphosphazene are combined, and the multifunctional efficient nano composite flame retardant is prepared by a one-step method, so that the problems of high preparation cost, low flame retardant efficiency, poor migration resistance, poor substrate compatibility and the like of the traditional flame retardant are solved, and the attapulgite nano composite flame retardant has a good market application prospect.
Drawings
FIG. 1 is a comparison graph of infrared spectra of nanocomposite flame retardants;
FIG. 2 XRD contrast of nanocomposite flame retardant;
FIG. 3 is a SEM comparison of attapulgite and a nanocomposite flame retardant;
Detailed Description
The following detailed description is provided to enable those skilled in the art to more clearly understand the advantages and features of the present invention, and to further define the scope of the invention.
Example 1:
attapulgite purification: adding 30g of attapulgite powder into a 500ml two-necked bottle with mechanical stirring, adding 0.6g of sodium hexametaphosphate modifier, adding 300ml of deionized water as a solvent, controlling the temperature to be 35-55 ℃ for reaction for 4 hours, cooling to room temperature after the reaction is finished, standing the product to remove large-particle impurities, centrifuging, washing and drying, and drying the obtained purified product in a 60 ℃ oven for 12 hours to obtain an off-white solid.
Preparing a composite flame retardant: taking 10g of the attapulgite solid powder, dispersing the attapulgite solid powder in 500ml of absolute ethanol, adding 8.6g of 4, 4-dihydroxy diphenyl sulfone (BPS), adding 14ml of Triethylamine (TEA) after fully dissolving, accurately weighing 4g of Hexachlorocyclotriphosphazene (HCCP) to dissolve in 80ml of absolute ethanol, placing in a 100ml constant pressure dropping funnel, starting mechanical stirring, beginning to drop the mixed solution, controlling the reaction temperature at 60 ℃ after the dropping is finished, continuing to react for 6h, ending the reaction, naturally cooling to room temperature, filtering, washing and drying the product, thus obtaining the composite flame retardant.
Example 2:
attapulgite purification: adding 30g of attapulgite powder into a 500ml two-mouth bottle with mechanical stirring, adding 5ml of concentrated hydrochloric acid as a modifier, adding 300ml of deionized water as a solvent, controlling the temperature to 35-55 ℃ for reaction for 4 hours, cooling to room temperature after the reaction is finished, standing the product to remove large-particle impurities, centrifuging, washing, drying, and drying the obtained purified product in an oven at 60 ℃ for 12 hours to obtain an off-white solid.
Preparing a composite flame retardant: taking 10g of the attapulgite solid powder, dispersing the attapulgite solid powder in 500ml of absolute ethanol, adding 8.6g of 4, 4-dihydroxy diphenyl sulfone (BPS) to fully dissolve the attapulgite solid powder, adding 14ml of Triethylamine (TEA), accurately weighing 4g of Hexachlorocyclotriphosphazene (HCCP) to dissolve the 4g of BPS in 80ml of absolute ethanol, placing the mixture in a 100ml constant-pressure dropping funnel, starting mechanical stirring, beginning to drop the mixed solution, controlling the reaction temperature to be 60 ℃ after the dropping is finished, continuing to react for 6 hours, ending the reaction, naturally cooling to room temperature, filtering, washing and drying the product to obtain the composite flame retardant.
Preparing an epoxy resin flame-retardant composite material: weighing 50g of epoxy resin E-51, adding 25g of the prepared composite flame retardant, heating to fully disperse the flame retardant into the matrix resin, uniformly dispersing to obtain gray emulsion, continuously adding 15g of curing agent D230, uniformly stirring, quickly pouring into a mold, curing and molding at 80 ℃, naturally cooling and demolding to test the flame retardant performance and other comprehensive properties.
Example 2:
attapulgite purification: adding 30g of attapulgite powder into a 500ml two-mouth bottle with mechanical stirring, adding 5ml of concentrated hydrochloric acid as a modifier, adding 300ml of deionized water as a solvent, controlling the temperature to 35-55 ℃ for reaction for 4 hours, cooling to room temperature after the reaction is finished, standing the product to remove large-particle impurities, centrifuging, washing, drying, and drying the obtained purified product in an oven at 60 ℃ for 12 hours to obtain an off-white solid.
Preparing a composite flame retardant: taking 10g of the attapulgite solid powder, dispersing the attapulgite solid powder in 500ml of absolute ethanol, adding 5.6g of hydroquinone for full dissolution, adding 14ml of Triethylamine (TEA), accurately weighing 4g of Hexachlorocyclotriphosphazene (HCCP) for dissolving in 80ml of absolute ethanol, placing in a 100ml constant pressure dropping funnel, starting mechanical stirring, beginning to drop the mixed solution, controlling the reaction temperature at 60 ℃ after the dropping is finished, continuing to react for 6h, finishing the reaction, naturally cooling to room temperature, filtering, washing and drying the product, thus obtaining the composite flame retardant.
Preparing an epoxy resin flame-retardant composite material: weighing 50g of epoxy resin E-51, adding 20g of the prepared composite flame retardant, heating to fully disperse the flame retardant into the matrix resin, uniformly dispersing to obtain gray emulsion, continuously adding 15g of curing agent D230, uniformly stirring, quickly pouring into a mold, curing and molding at 80 ℃, naturally cooling and demolding to test the flame retardant performance and other comprehensive properties.
The above-described embodiments are only a part of the method of the present invention, and improvements and modifications can be made to the method without departing from the scope of the invention, and these improvements and modifications should be considered within the scope of the invention.
Example 3:
attapulgite purification: adding 30g of attapulgite powder into a 500ml two-mouth bottle with mechanical stirring, adding 50ml of 10% NaOH as a modifier, adding 300ml of deionized water as a solvent, controlling the temperature to 35-55 ℃ for reaction for 4 hours, cooling to room temperature after the reaction is finished, standing the product to remove large-particle impurities, centrifuging, washing, drying, and drying the obtained purified product in a 60 ℃ oven for 12 hours to obtain an off-white solid.
Preparing a composite flame retardant: taking 10g of the attapulgite solid powder, dispersing the attapulgite solid powder in 500ml of absolute ethanol, adding 7.8g of 4, 4-dihydroxy diphenylmethane (DADPM), fully dissolving, adding 14ml of Triethylamine (TEA), accurately weighing 4g of Hexachlorocyclotriphosphazene (HCCP), dissolving in 80ml of absolute ethanol, placing in a 100ml constant-pressure dropping funnel, starting mechanical stirring, beginning to drop the mixed solution, controlling the reaction temperature at 60 ℃ after the dropping is finished, continuing to react for 6h, ending the reaction, naturally cooling to room temperature, filtering, washing and drying the product, thus obtaining the composite flame retardant.
Preparing an epoxy resin flame-retardant composite material: weighing 50g of epoxy resin E-51, adding 25g of the prepared composite flame retardant, heating to fully disperse the flame retardant into the matrix resin, uniformly dispersing to obtain gray emulsion, continuously adding 15g of curing agent D230, uniformly stirring, quickly pouring into a mold, curing and molding at 80 ℃, naturally cooling and demolding to test the flame retardant performance and other comprehensive properties.
The above-described embodiments are only a part of the method of the present invention, and improvements and modifications can be made to the method without departing from the scope of the invention, and these improvements and modifications should be considered within the scope of the invention.
Claims (9)
1. The attapulgite nano composite flame retardant is characterized in that the flame retardant is prepared by compounding nano attapulgite and a phosphazene compound, and the structure of the flame retardant is except thatAttapulgiteBesides, it also contains polyphosphazene material.
2. The attapulgite nano composite flame retardant according to claim 1, characterized in that the attapulgite and the phosphazene compound are prepared by compounding by a one-step polymerization method, and the attapulgite adopts natural ore-nano attapulgite.
3. The attapulgite nano composite flame retardant of claim 1, wherein the preparation method of the attapulgite nano composite flame retardant comprises the following steps:
firstly, smashing and coarsely screening attapulgite ore, and removing impurities to obtain coarse and purified ATP.
And secondly, dispersing the ATP roughly purified in the first step in a solvent, finishing the reaction for a period of time by mechanical stirring and ultrasonic dispersion at a certain temperature, and settling, separating, washing and drying the product to obtain off-white solid powder.
And thirdly, dispersing the purified ATP powder in a solvent, uniformly suspending the ATP powder in the solution through ultrasonic dispersion, adding a polyhydroxy compound, adding a certain amount of an acid-binding agent, dissolving hexachlorocyclotriphosphazene in a specific solvent, placing the solution in a constant-pressure dropping funnel, controlling the dropping rate, reacting at normal temperature, continuing to react for a period of time after the dropping is finished, and naturally cooling to room temperature. And fourthly, after the reaction is finished, centrifugally separating, washing and drying the product after the reaction to obtain the nano composite flame retardant.
The fifth step, the method for using the flame retardant in the epoxy resin is as follows: weighing a proper amount of epoxy resin and a flame retardant, adding the epoxy resin and the flame retardant into a beaker, heating and stirring the mixture uniformly to form a gray emulsion, continuously adding a curing agent, stirring the mixture uniformly, pouring the mixture into a mold for curing and molding at a high temperature, and naturally cooling and demolding the mixture to test the flame retardant performance and the mechanical performance.
4. The attapulgite nano composite flame retardant according to claim 3, characterized in that the polyhydroxy compounds used in the third step of the preparation of the flame retardant are: 1 or more of catechol, resorcinol, hydroquinone, phloroglucinol, 4 '4-dihydroxy diphenyl sulfone and 4' 4-dihydroxy diphenyl methane.
5. The attapulgite nano composite flame retardant according to claim 3, characterized in that the solvent used in the second purification of the preparation of the flame retardant is any one or a mixture of any several proportions of methanol, ethanol, acetonitrile, DMF, acetone and water.
6. The attapulgite nano composite flame retardant according to claim 3, characterized in that the time used in the second step of modification is 0-12 h; the mechanical stirring speed is 10-10000 r/min, and the ultrasonic dispersion power is 50-300W; the temperature used during drying is-50 to 150 ℃.
7. The attapulgite nano composite flame retardant according to claim 3, characterized in that the solvent used in the preparation of the composite flame retardant in the third step is any one or a mixture of any several proportions of dioxane, methanol, ethanol, acetonitrile, DMF, acetone and chlorobenzene.
8. The attapulgite nano composite flame retardant according to claim 3, wherein in the third step of the preparation of the composite flame retardant, the acid-binding agent is any one of triethylamine and pyridine, and the molar ratio of the acid-binding agent to the hexachlorocyclotriphosphazene is acid-binding agent: hexachlorocyclotriphosphazene is 6:1 to 20: 1.
9. The attapulgite nano composite flame retardant of claim 1, wherein the use method of the flame retardant in epoxy resin is as follows: the using amount of the epoxy resin is 100 parts, the using amount of the prepared flame retardant is 20-200 parts, the adding amount of the curing agent is 20-100 parts, and the temperature for pouring the epoxy resin into a mould for curing and molding is (room temperature-200 ℃).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111367427.1A CN114015242A (en) | 2021-11-18 | 2021-11-18 | Nano-attapulgite composite flame retardant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111367427.1A CN114015242A (en) | 2021-11-18 | 2021-11-18 | Nano-attapulgite composite flame retardant and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114015242A true CN114015242A (en) | 2022-02-08 |
Family
ID=80065019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111367427.1A Pending CN114015242A (en) | 2021-11-18 | 2021-11-18 | Nano-attapulgite composite flame retardant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114015242A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6130179A (en) * | 1998-11-12 | 2000-10-10 | Itc, Inc. | Purified attapulgite clay |
| US20100256268A1 (en) * | 2009-04-01 | 2010-10-07 | National Taiwan University | Phosphorous flame retardant and application thereof to polymer |
| CN106674597A (en) * | 2016-12-31 | 2017-05-17 | 华南理工大学 | Nitrogen and phosphorus synergistic flame retardant modified layered inorganic matter and preparation method and application thereof |
| CN107011501A (en) * | 2017-04-16 | 2017-08-04 | 西北师范大学 | A kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material |
| CN107641958A (en) * | 2017-10-11 | 2018-01-30 | 陕西科技大学 | Bafta is fire-retardant attapulgite modified and preparation method thereof with hexachlorocyclotriph,sphazene |
| CN108912336A (en) * | 2018-08-01 | 2018-11-30 | 河北大学 | A kind of active amino cross-linking type phosphazene derivative, preparation method and application and fire retarding epoxide resin |
| CN110591157A (en) * | 2019-08-30 | 2019-12-20 | 厦门大学 | Preparation method and application of polyphosphazene polymer modified halloysite nanotube composite material with different coating thicknesses |
| CN113307280A (en) * | 2021-06-23 | 2021-08-27 | 西北师范大学 | Method for normalizing quality of attapulgite product |
-
2021
- 2021-11-18 CN CN202111367427.1A patent/CN114015242A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6130179A (en) * | 1998-11-12 | 2000-10-10 | Itc, Inc. | Purified attapulgite clay |
| US20100256268A1 (en) * | 2009-04-01 | 2010-10-07 | National Taiwan University | Phosphorous flame retardant and application thereof to polymer |
| CN106674597A (en) * | 2016-12-31 | 2017-05-17 | 华南理工大学 | Nitrogen and phosphorus synergistic flame retardant modified layered inorganic matter and preparation method and application thereof |
| CN107011501A (en) * | 2017-04-16 | 2017-08-04 | 西北师范大学 | A kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material |
| CN107641958A (en) * | 2017-10-11 | 2018-01-30 | 陕西科技大学 | Bafta is fire-retardant attapulgite modified and preparation method thereof with hexachlorocyclotriph,sphazene |
| CN108912336A (en) * | 2018-08-01 | 2018-11-30 | 河北大学 | A kind of active amino cross-linking type phosphazene derivative, preparation method and application and fire retarding epoxide resin |
| CN110591157A (en) * | 2019-08-30 | 2019-12-20 | 厦门大学 | Preparation method and application of polyphosphazene polymer modified halloysite nanotube composite material with different coating thicknesses |
| CN113307280A (en) * | 2021-06-23 | 2021-08-27 | 西北师范大学 | Method for normalizing quality of attapulgite product |
Non-Patent Citations (3)
| Title |
|---|
| JAU-YU CHIOU 等: "Fine dispersion of phosphazene-amines and silicate platelets in epoxy nanocomposites and the synergistic fire-retarding effect", 《JOURNAL OF POLYMER RESEARCH》 * |
| 张冲 等: "环交联聚磷腈包覆羟基锡酸锶杂化纳米棒的合成及阻燃环氧树脂研究", 《无机材料学报》 * |
| 赵师师 等: "含磷/氮/硫环交联磷腈微纳米管的合成及对环氧树脂的阻燃作用", 《高等学校化学学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107266685B (en) | Phosphorus and silicon containing polymeric flame retardant and preparation method thereof | |
| CN109438925B (en) | Preparation method of intrinsic halogen-free low-smoke flame-retardant epoxy resin composite material | |
| CN104592549A (en) | Phosphorus-containing reaction-type fire retardant as well as synthesis method and application thereof | |
| CN114380947B (en) | Halogen-free phosphorus-free flame-retardant shape memory bismaleimide resin and preparation method thereof | |
| CN107011501A (en) | A kind of preparation method of phosphor-containing halogen-free low-smoke and flame retardant epoxy resin composite material | |
| CN112142953A (en) | Dielectric and heat conduction enhanced bio-based high-temperature-resistant epoxy resin and preparation method and application thereof | |
| CN101659677B (en) | Triphosphazene epoxy resin and preparation method thereof | |
| CN104448830A (en) | Phosphorus-silicon composite flame retardant as well as preparation method and application thereof | |
| CN105348742A (en) | Thermosetting resin composition containing melamine type benzoxazine resin, prepreg and laminated board | |
| CN103194063B (en) | Trapezoidal polysiloxane modified thermosetting resin and preparation method thereof | |
| CN103834169A (en) | Flame-retardant benzoxazine resin and preparation method thereof | |
| CN107663278B (en) | A kind of epoxy resin highly effective flame-retardant agent dispersing liquid and preparation method thereof | |
| CN111100332B (en) | Preparation method and application of dumbbell type fluorine-containing polyphosphazene modified halloysite nanotube | |
| CN114015242A (en) | Nano-attapulgite composite flame retardant and preparation method thereof | |
| CN112194822B (en) | Phosphorus-containing flame retardant, preparation method and modified epoxy resin | |
| CN102643517B (en) | Method for preparing composite material by blending PHQEP/montmorillonite and modified epoxy resin | |
| Agag et al. | Reinforcement of polybenzoxazine matrix with organically modified mica | |
| CN113292823B (en) | Preparation method of terephthalonitrile derivative flame-retardant epoxy resin composite material | |
| CN112694856B (en) | Two-component epoxy pouring sealant | |
| CN112723342B (en) | Phosphorus-containing functionalized graphene and preparation method and application thereof | |
| CN108948658B (en) | Preparation method of magnesium oxychloride whisker/epoxy resin composite material | |
| CN113429535A (en) | Degradable bio-based thermosetting resin containing isosorbide structure and preparation method thereof | |
| CN110643168A (en) | Black phosphorus nanosheet flame-retardant polyphenyl ether resin and preparation method thereof | |
| CN109880301A (en) | A kind of New-type long-acting heat-resistant fireproof material and preparation method thereof | |
| CN111518118B (en) | Benzoxazine monomer containing butterfly alkene structure and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220208 |
|
| RJ01 | Rejection of invention patent application after publication |