CN115246982A - Fire-resistant flame-retardant phenolic resin - Google Patents
Fire-resistant flame-retardant phenolic resin Download PDFInfo
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- CN115246982A CN115246982A CN202211027696.8A CN202211027696A CN115246982A CN 115246982 A CN115246982 A CN 115246982A CN 202211027696 A CN202211027696 A CN 202211027696A CN 115246982 A CN115246982 A CN 115246982A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 220
- 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 195
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 96
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 96
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 230000009970 fire resistant effect Effects 0.000 title claims abstract description 59
- 229920002748 Basalt fiber Polymers 0.000 claims abstract description 66
- 239000012745 toughening agent Substances 0.000 claims abstract description 42
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 244000226021 Anacardium occidentale Species 0.000 claims abstract description 28
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000020226 cashew nut Nutrition 0.000 claims abstract description 28
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 26
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 26
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011787 zinc oxide Substances 0.000 claims abstract description 18
- 238000013329 compounding Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 37
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 30
- 229960000892 attapulgite Drugs 0.000 claims description 23
- 229910052625 palygorskite Inorganic materials 0.000 claims description 23
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 21
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 21
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 21
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 21
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 21
- 229960003638 dopamine Drugs 0.000 claims description 18
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 17
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical compound NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 claims description 17
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 claims description 16
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 15
- NKFNBVMJTSYZDV-UHFFFAOYSA-N 2-[dodecyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCCCCCCCCCN(CCO)CCO NKFNBVMJTSYZDV-UHFFFAOYSA-N 0.000 claims description 15
- URJDFYQNAFUJJQ-UHFFFAOYSA-N tetrakis-decyl silicate Chemical compound CCCCCCCCCCO[Si](OCCCCCCCCCC)(OCCCCCCCCCC)OCCCCCCCCCC URJDFYQNAFUJJQ-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 238000000502 dialysis Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000000352 supercritical drying Methods 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 97
- 238000002360 preparation method Methods 0.000 description 79
- 239000011159 matrix material Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical group [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- FCZCIXQGZOUIDN-UHFFFAOYSA-N ethyl 2-diethoxyphosphinothioyloxyacetate Chemical compound CCOC(=O)COP(=S)(OCC)OCC FCZCIXQGZOUIDN-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 238000002679 ablation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000009528 severe injury Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- BGNTUSKZDOUZCZ-UHFFFAOYSA-N tris(1-butoxyethyl) phosphate Chemical compound CCCCOC(C)OP(=O)(OC(C)OCCCC)OC(C)OCCCC BGNTUSKZDOUZCZ-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- 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
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
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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
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
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- 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)
Abstract
The application relates to the technical field of high polymer materials, and particularly discloses a fire-resistant and flame-retardant phenolic resin which comprises the following raw materials in parts by weight: 60-80 parts of resorcinol, 30-40 parts of paraformaldehyde, 2-5 parts of cashew nut shell oil, 1-2 parts of succinic acid, 11-15 parts of a flame retardant and 16-20 parts of a toughening agent; the flame retardant is prepared by mixing a first flame retardant and a second flame retardant according to the mass ratio of 8 (7-11); the toughening agent is prepared by compounding zinc oxide whiskers and modified basalt fibers in a mass ratio of (3-8) to (1-6); the formula of the scheme is simple, the proportion is strict, and the obtained phenolic resin has excellent fire-resistant and flame-retardant properties and remarkable mechanical properties, and can better meet the high-performance requirement in a special environment.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a fire-resistant flame-retardant phenolic resin.
Background
Phenolic resin is synthetic resin which is the earliest to realize industrialization in the world, has the history of nearly one hundred years so far, is easy to obtain raw materials, low in price, simple in production process and equipment, and more importantly, has excellent mechanical property, heat resistance, ablation resistance, electrical insulation property, size stability, molding processability and flame retardance, and is widely applied to industries such as corrosion prevention engineering, adhesives, flame retardant materials, grinding wheel manufacturing and the like, so that the phenolic resin becomes an indispensable material for industrial departments.
In order to enable the material to meet the requirements of special environment work, the continuous improvement of the special performance of the material is the trend of the current material development. In the practical application process, the fire-resistant flame-retardant performance of the phenolic resin cannot meet the high-performance requirement of special environment work, and meanwhile, the mechanical property of the phenolic resin can be damaged to a certain extent due to the addition of the conventional flame retardant. Therefore, it is urgently needed to provide a high-performance fire-retardant phenolic resin to solve the problems that the fire-retardant performance of the existing phenolic resin is not strong and the mechanical properties are seriously damaged, so that the fire-retardant performance of the phenolic resin is improved on the premise of having good mechanical properties, and the phenolic resin further better meets the high-performance requirement in a special environment.
Disclosure of Invention
In order to solve the problems that the existing phenolic resin is not strong in fire resistance and flame retardant property and seriously damaged in mechanical property, the application provides the fire-resistant flame-retardant phenolic resin.
The application provides a fire-resistant flame-retardant phenolic resin, which adopts the following technical scheme:
the fire-resistant flame-retardant phenolic resin comprises the following raw materials in parts by weight: 60-80 parts of resorcinol, 30-40 parts of paraformaldehyde, 2-5 parts of cashew nut shell oil, 1-2 parts of succinic acid, 11-15 parts of a flame retardant and 8-10 parts of a toughening agent;
the flame retardant consists of a first flame retardant and a second flame retardant; the toughening agent consists of zinc oxide whiskers and modified basalt fibers.
By adopting the technical scheme, the phenolic resin is prepared by taking the resorcinol, the paraformaldehyde, the cashew nut shell oil and the succinic acid as raw materials, the resorcinol and the paraformaldehyde react to generate the thermoplastic phenolic resin under the catalytic action of the succinic acid, and the cashew nut shell oil is added and dispersed in the phenolic resin, so that the phenolic resin is modified, and the mechanical property of the phenolic resin can be improved; according to the phenolic resin, the flame retardant and the toughening agent are added, the flame retardant consists of the first flame retardant and the second flame retardant, the toughening agent consists of zinc oxide whiskers and modified basalt fibers, and the content of each component is controlled at the same time, so that the problems that the fire resistance and the flame retardance of the phenolic resin are not strong and the mechanical property is seriously damaged are effectively solved, the fire resistance and the flame retardance of the phenolic resin are improved on the premise of having good mechanical property, and the high-performance requirement under the special environment can be better met.
Preferably, the first flame retardant comprises the following raw materials in parts by weight: 10-20 parts of attapulgite, 1-3 parts of triethanolamine, 31-35 parts of dopamine, 9-10 parts of 10-12wt% aluminum nitrate solution and 30-60 parts of 5-8wt% sodium hydroxide solution.
Preferably, the first flame retardant is prepared by the following method:
firstly, adding attapulgite into triethanolamine, grinding for 10-15min, then adding dopamine, and carrying out ultrasonic reaction for 45-60min at the temperature of 30-40 ℃; adding an aluminum nitrate solution, continuing to perform ultrasonic reaction for 10-20min, and adding a sodium hydroxide solution; and finally, standing the reaction system at 60-80 ℃ under 10-15MPa for reaction, standing for 2-3h, filtering and drying to obtain the first flame retardant.
By adopting the technical scheme, the first flame retardant is prepared by taking the attapulgite, triethanolamine, dopamine, an aluminum nitrate solution and a sodium hydroxide solution as raw materials, firstly, the attapulgite is pretreated, and the triethanolamine is added in the grinding process, so that the grinding aid effect is achieved, the combination of the dopamine and the attapulgite can be promoted, and the dopamine is subjected to polymerization reaction on the surface of the attapulgite to form a poly-dopamine film layer; then, the formed polydopamine film layer has good adsorbability and can adsorb subsequently generated aluminum hydroxide particles, and finally an aluminum hydroxide-attapulgite compound is formed, namely a first flame retardant, and the obtained first flame retardant has good flame retardant property and high temperature resistance; in addition, the aluminum hydroxide particles of the first flame retardant are beneficial to uniformly dispersing the attapulgite in the phenolic resin, so that the problem that the mechanical property of the phenolic resin is seriously damaged is avoided.
Preferably, the second flame retardant comprises the following raw materials in parts by weight: 10-30 parts of tetradecyloxy silane, 15-28 parts of tributoxyethyl phosphate and 10-25 parts of guanidine sulfamate.
Preferably, the second flame retardant is prepared by the following method:
fully mixing tetradecylalkoxysilane, tris (butoxyethyl) phosphate and guanidine sulfamate, condensing and refluxing under the protection of nitrogen, wherein the reaction temperature is 80-180 ℃, and reacting for 3-5 hours until no distillate is generated; adding the obtained product into a dialysis bag with a molecular weight of 2100-2500, and dialyzing for 24-48h by using ethanol as a dialysis medium; and finally, carrying out supercritical drying to obtain a second flame retardant. According to the technical scheme, tetradecyloxy silane, tris (butoxyethyl) phosphate and guanidine sulfamate are good organic flame retardants, tetradecyloxy silane, tris (butoxyethyl) phosphate and guanidine sulfamate are prepared into gel with flame retardant performance under the conditions of no solvent and no catalyst and serve as a second flame retardant, the obtained second flame retardant is a phosphorus-silicon-nitrogen ternary synergistic efficient flame retardant, the surface of the second flame retardant contains active functional groups such as phosphate groups and amino groups and can be combined with a phenolic resin matrix, the flame retardant performance of the phenolic resin is improved, and the impact toughness of the phenolic resin is enhanced.
Preferably, the flame retardant is prepared by mixing a first flame retardant and a second flame retardant according to a mass ratio of 8 (7-11).
By adopting the technical scheme, the first flame retardant is an aluminum hydroxide-attapulgite composite, so that the flame retardant has remarkable flame retardant property and can contribute to improving the mechanical property of the phenolic resin; the second flame retardant is a phosphorus-silicon-nitrogen ternary synergistic efficient flame retardant, and can improve the impact toughness of the phenolic resin matrix on the basis of obviously enhancing the flame retardant property of the phenolic resin matrix; the fire retardant is obtained by mixing a first fire retardant and a second fire retardant, the mass ratio of the first fire retardant to the second fire retardant is controlled, the two fire retardants interact with each other, the first fire retardant is used as a node and connected with the second fire retardant, and a network-shaped fire retardant is formed in a phenolic resin matrix, so that the phenolic resin obtains excellent fire-resistant and fire-retardant performance, and meanwhile, the mechanical property is remarkably enhanced.
Preferably, the modified basalt fiber comprises the following raw materials in parts by weight: 40-50 parts of basalt short fiber, 100-150 parts of ethanol, 50-60 parts of 20-30wt% silane coupling agent KH550, 15-19 parts of cardanol and 8-9 parts of dodecyl diethanolamine.
Preferably, the modified basalt fiber is prepared by the following method:
s1, selecting basalt short fiber with the diameter of 6-10 microns, adding the basalt short fiber into ethanol, dispersing for 20-30min under ultrasound, then adjusting the pH to 4.8-5.2, then adding a silane coupling agent KH550, reacting for 60-90min at the temperature of 40-50 ℃ at the rotating speed of 2000-2500r/min, and drying to obtain pretreated basalt fiber;
s2, adding cardanol into dodecyl diethanolamine, stirring at the temperature of 50-60 ℃ at the rotating speed of 2000-2500r/min for 30-40min, adding pretreated basalt fiber, continuously stirring for 1-2h, filtering, and drying to obtain the modified basalt fiber.
By adopting the technical scheme, the method adopts cardanol to modify the basalt fiber, pretreats the basalt fiber, and controls the technological parameters, so that the cardanol can be better combined with the basalt fiber; the surface of the cardanol contains phenolic hydroxyl, and the cardanol modified basalt fiber can be well blended and compatible with a phenolic resin matrix, so that the modified basalt fiber can enhance and toughen the phenolic resin matrix, and meanwhile, the modified basalt fiber can also improve the fire-resistant and flame-retardant properties of the phenolic resin.
Preferably, the toughening agent is prepared by compounding zinc oxide whiskers and modified basalt fibers in a mass ratio of (3-8) to (1-6).
By adopting the technical scheme, the zinc oxide whiskers have ultrahigh strength and isotropy, are easy to be uniformly distributed in the matrix material, and can promote the isotropy of the phenolic resin; the modified basalt fiber has good reinforcing and toughening properties and excellent flame retardant property; according to the application, the mixture of the zinc oxide whiskers and the modified basalt fibers is selected as the toughening agent, the zinc oxide whiskers and the modified basalt fibers have different spatial structures, and the zinc oxide whiskers and the modified basalt fibers can be synergized in the phenolic resin, so that the mechanical property of the phenolic resin can be enhanced, the fire resistance and the flame retardance of the phenolic resin can be improved, and the overall performance of the phenolic resin is optimized.
Preferably, the preparation method of the fire-resistant and flame-retardant phenolic resin comprises the following steps:
step one, weighing m-diphenol, cashew nut shell oil, succinic acid, paraformaldehyde, a flame retardant and a toughening agent in parts by weight for later use;
step two, mixing the m-diphenol, the cashew nut shell oil and the succinic acid, heating to 90-95 ℃, and keeping the temperature for 60-90min; adding paraformaldehyde solution, heating to 100-105 deg.C, and maintaining for 90-120min to obtain initial product;
and step three, adding a flame retardant and a toughening agent into the primary product obtained in the step two, reacting at the temperature of 110-120 ℃ at the rotating speed of 1600-1800r/min for 30-40min, and then cooling to obtain the fire-resistant flame-retardant phenolic resin.
By adopting the technical scheme, the method comprises the steps of firstly taking m-diphenol, paraformaldehyde, cashew shell oil and succinic acid as raw materials to obtain an initial product, then adding a flame retardant and a toughening agent, and controlling process parameters, so that the flame retardance of the phenolic resin is greatly improved, and the phenolic resin can meet the fire resistance requirement in a special environment; the preparation method of the fire-resistant flame-retardant phenolic resin is simple in steps, low in cost and suitable for industrial production.
In summary, the present application has the following beneficial effects:
1. the phenolic resin is prepared from m-diphenol, paraformaldehyde, cashew nut shell oil and succinic acid, and the mechanical property of the phenolic resin can be improved by the cashew nut shell oil; meanwhile, a flame retardant and a toughening agent are added, the flame retardant consists of a first flame retardant and a second flame retardant, and the toughening agent consists of zinc oxide whiskers and modified basalt fibers, so that the problems of weak fire resistance and flame retardance and severe damage to mechanical properties of the phenolic resin are effectively solved.
2. The preparation method is simple, the preparation cost is low, the method is suitable for industrial production, and the obtained phenolic resin has excellent fire-resistant and flame-retardant properties and remarkable mechanical properties, and can better meet the high-performance requirements in special environments.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation examples 1-5, comparative preparation examples 1, 2 provide a first flame retardant and a method for preparing the same.
Preparation example 1
The first flame retardant comprises the following raw materials: 10kg of attapulgite, 1kg of triethanolamine, 31kg of dopamine, 9kg of 10wt% aluminum nitrate solution and 30kg of 5wt% sodium hydroxide solution.
A first flame retardant prepared by the following method:
firstly, adding attapulgite into triethanolamine, grinding for 10min, then adding dopamine, and carrying out ultrasonic reaction for 45min at the temperature of 30 ℃; adding an aluminum nitrate solution, continuing to perform ultrasonic reaction for 10min, and adding a sodium hydroxide solution; and finally, standing the reaction system at 60 ℃ and 10MPa for reaction, standing for 2h, filtering and drying to obtain the first flame retardant.
Preparation example 2
The first flame retardant comprises the following raw materials: 13kg of attapulgite, 1.5kg of triethanolamine, 32kg of dopamine, 9.2kg of 10wt% aluminum nitrate solution and 37kg of 6wt% sodium hydroxide solution.
A first flame retardant prepared by the following method:
firstly, adding attapulgite into triethanolamine, grinding for 11min, then adding dopamine, and carrying out ultrasonic reaction for 50min at the temperature of 33 ℃; adding an aluminum nitrate solution, continuing to perform ultrasonic reaction for 12min, and adding a sodium hydroxide solution; and finally, standing the reaction system at 65 ℃ and 11MPa for reaction, standing for 2.2h, filtering and drying to obtain the first flame retardant.
Preparation example 3
The first flame retardant comprises the following raw materials: 15kg of attapulgite, 2kg of triethanolamine, 33kg of dopamine, 9.5kg of 11wt% aluminum nitrate solution and 45kg of 7wt% sodium hydroxide solution.
A first flame retardant prepared by the following method:
firstly, adding attapulgite into triethanolamine, grinding for 13min, then adding dopamine, and carrying out ultrasonic reaction for 53min at the temperature of 35 ℃; adding an aluminum nitrate solution, continuing to perform ultrasonic reaction for 15min, and adding a sodium hydroxide solution; and finally, standing the reaction system at 70 ℃ and 13MPa for reaction, standing for 2.5h, filtering and drying to obtain the first flame retardant.
Preparation example 4
The first flame retardant comprises the following raw materials: 18kg of attapulgite, 2.5kg of triethanolamine, 34kg of dopamine, 9.8kg of a 11wt% aluminum nitrate solution and 54kg of a 7wt% sodium hydroxide solution.
A first flame retardant prepared by the following method:
firstly, adding attapulgite into triethanolamine, grinding for 14min, then adding dopamine, and carrying out ultrasonic reaction for 57min at the temperature of 38 ℃; adding an aluminum nitrate solution, continuing to perform ultrasonic reaction for 18min, and adding a sodium hydroxide solution; and finally, standing the reaction system at 75 ℃ and 14MPa for reaction, standing for 2.8h, filtering and drying to obtain the first flame retardant.
Preparation example 5
The first flame retardant comprises the following raw materials: 20kg of attapulgite, 3kg of triethanolamine, 35kg of dopamine, 10kg of 12wt% aluminum nitrate solution, and 60kg of 8wt% sodium hydroxide solution.
A first flame retardant prepared by the following method:
firstly, adding attapulgite into triethanolamine, grinding for 15min, then adding dopamine, and carrying out ultrasonic reaction for 60min at the temperature of 40 ℃; adding an aluminum nitrate solution, continuing to perform ultrasonic reaction for 20min, and adding a sodium hydroxide solution; and finally, standing the reaction system at 80 ℃ and 15MPa for reaction, standing for 3h, filtering and drying to obtain the first flame retardant.
Comparative preparation example 1
Comparative preparation 1, identical to preparation 1, differs only in that: no triethanolamine was added.
Comparative preparation example 2
Comparative preparation 2, identical to preparation 1, differs only in that: no dopamine was added.
Preparation examples 6-10, comparative preparation examples 3-5 provide second flame retardants and methods for their preparation.
Preparation example 6
The second flame retardant comprises the following raw materials: 10kg of tetradecyloxy silane, 15kg of tributoxyethyl phosphate and 10kg of guanidine sulfamate.
A second flame retardant prepared by the following method:
fully mixing tetradecyloxy silane, tris (butoxyethyl) phosphate and guanidine sulfamate, condensing and refluxing under the protection of nitrogen, wherein the reaction temperature is 180 ℃, and reacting for 3 hours until no distillate is generated; adding the obtained product into a 2100 molecular weight dialysis bag, and dialyzing for 24h by using ethanol as a dialysis medium; and finally, carrying out supercritical drying to obtain a second flame retardant.
Preparation example 7
The second flame retardant comprises the following raw materials: 15kg of tetradecyloxy silane, 18kg of tributoxyethyl phosphate and 13kg of guanidine sulfamate.
A second flame retardant prepared by the following method:
fully mixing tetradecyloxy silane, tris (butoxyethyl) phosphate and guanidine sulfamate, condensing and refluxing under the protection of nitrogen, wherein the reaction temperature is 150 ℃, and reacting for 3.5 hours until no distillate is generated; adding the obtained product into a dialysis bag with a molecular weight of 22500, and dialyzing with ethanol as dialysis medium for 30h; and finally, performing supercritical drying to obtain a second flame retardant.
Preparation example 8
The second flame retardant comprises the following raw materials: 20kg of tetradecyloxy silane, 22kg of tributoxyethyl phosphate and 18kg of guanidine sulfamate.
A second flame retardant prepared by the following method:
fully mixing tetradecyloxy silane, tris (butoxyethyl) phosphate and guanidine sulfamate, condensing and refluxing under the protection of nitrogen, wherein the reaction temperature is 130 ℃, and reacting for 4 hours until no distillate is generated; adding the obtained product into a dialysis bag with the molecular weight of 2300, and dialyzing for 35 hours by using ethanol as a dialysis medium; and finally, carrying out supercritical drying to obtain a second flame retardant.
Preparation example 9
The second flame retardant comprises the following raw materials: 25kg of tetradecyloxy silane, 25kg of tris (butoxyethyl) phosphate, 22kg of guanidine sulfamate.
A second flame retardant prepared by the following method:
fully mixing tetradecylalkoxysilane, tris (butoxyethyl) phosphate and guanidine sulfamate, condensing and refluxing under the protection of nitrogen, wherein the reaction temperature is 100 ℃, and reacting for 4.5 hours until no distillate is generated; adding the obtained product into a dialysis bag with the molecular weight of 2400, and dialyzing for 42 hours by using ethanol as a dialysis medium; and finally, performing supercritical drying to obtain a second flame retardant.
Preparation example 10
The second flame retardant comprises the following raw materials: 30kg of tetradecyloxy silane, 28kg of tributoxyethyl phosphate and 25kg of guanidine sulfamate.
A second flame retardant prepared by the following method:
fully mixing tetradecyloxy silane, tris (butoxyethyl) phosphate and guanidine sulfamate, condensing and refluxing under the protection of nitrogen, wherein the reaction temperature is 80 ℃, and reacting for 5 hours until no distillate is generated; adding the obtained product into a dialysis bag with molecular weight of 2500, and dialyzing for 48h by using ethanol as a dialysis medium; and finally, carrying out supercritical drying to obtain a second flame retardant.
Comparative preparation example 3
Comparative preparation 3, like preparation 6, differs only in that: tetradecyloxy silane was not added.
Comparative preparation example 4
Comparative preparation 4, like preparation 6, differs only in that: tri (butoxyethyl) phosphate was not added.
Comparative preparation example 5
Comparative preparation 5, like preparation 6, differs only in that: guanidine sulfamate was not added.
Preparation examples 11 to 15, comparative preparation 6 to 8 provide modified basalt fibers and a preparation method thereof.
Preparation example 11
The modified basalt fiber comprises the following raw materials in parts by weight: 40kg of basalt staple fiber, 100kg of ethanol, 50kg of 20wt% silane coupling agent KH550, 15kg of cardanol and 8kg of dodecyl diethanolamine.
The modified basalt fiber is prepared by the following method:
s1, selecting basalt short fibers with the diameter of 6 microns, adding the basalt short fibers into ethanol, dispersing for 20min under ultrasound, adjusting the pH value to be 5.2 by using acid, adding a silane coupling agent KH550, reacting for 60min at the temperature of 40 ℃ at the rotating speed of 2500r/min, and drying to obtain pretreated basalt fibers;
s2, adding cardanol into dodecyl diethanol amine, stirring at the temperature of 50 ℃ and the rotation speed of 2500r/min for 30min, adding pretreated basalt fiber, continuing stirring for 1h, filtering, and drying to obtain the modified basalt fiber.
Preparation example 12
The modified basalt fiber comprises the following raw materials in parts by weight: 42kg of basalt staple fiber, 120kg of ethanol, 52kg of 22wt% of silane coupling agent KH550, 16kg of cardanol and 8.3kg of dodecyl diethanolamine.
The modified basalt fiber is prepared by the following method:
s1, selecting basalt short fiber with the diameter of 7 microns, adding the basalt short fiber into ethanol, dispersing for 22min under ultrasound, adjusting the pH to 5.1 by using acid, adding a silane coupling agent KH550, reacting for 65min at the temperature of 42 ℃ and the rotating speed of 2400r/min, and drying to obtain pretreated basalt fiber;
s2, firstly adding cardanol into dodecyl diethanolamine, stirring at 52 ℃ at the rotating speed of 2400r/min for 32min, then adding pretreated basalt fiber, continuing stirring for 1.2h, filtering, and drying to obtain the modified basalt fiber.
Preparation example 13
The modified basalt fiber comprises the following raw materials in parts by weight: 45kg of basalt short fiber, 125kg of ethanol, 55kg of 25wt% silane coupling agent KH550, 17kg of cardanol and 8.5kg of dodecyl diethanolamine.
The modified basalt fiber is prepared by the following method:
s1, selecting basalt short fiber with the diameter of 8 microns, adding the basalt short fiber into ethanol, dispersing for 25min under ultrasound, adjusting the pH to 5.0 by using acid, adding a silane coupling agent KH550, reacting for 72min at the temperature of 45 ℃ and the rotating speed of 2200r/min, and drying to obtain pretreated basalt fiber;
s2, firstly adding cardanol into dodecyl diethanol amine, stirring for 35min at the temperature of 55 ℃ at the rotating speed of 2200r/min, then adding pretreated basalt fiber, continuing stirring for 1.5h, filtering, and drying to obtain the modified basalt fiber.
Preparation example 14
The modified basalt fiber comprises the following raw materials in parts by weight: 48kg of basalt short fiber, 140kg of ethanol, 58kg of 28wt% silane coupling agent KH550, 18kg of cardanol and 8.8kg of dodecyl diethanolamine.
The modified basalt fiber is prepared by the following method:
s1, selecting basalt short fiber with the diameter of 9 microns, adding the basalt short fiber into ethanol, dispersing for 28min under ultrasound, adjusting the pH to 4.9 by using acid, adding a silane coupling agent KH550, reacting for 85min at the temperature of 48 ℃ and the rotating speed of 2100r/min, and drying to obtain pretreated basalt fiber;
s2, firstly adding cardanol into dodecyl diethanol amine, stirring for 32min at the temperature of 58 ℃ at the rotating speed of 2100r/min, then adding the pretreated basalt fiber, continuing stirring for 1.8h, filtering, and drying to obtain the modified basalt fiber.
Preparation example 15
The modified basalt fiber comprises the following raw materials in parts by weight: 50kg of basalt short fiber, 150kg of ethanol, 60kg of 30wt% silane coupling agent KH550, 19kg of cardanol and 9kg of dodecyl diethanolamine.
The modified basalt fiber is prepared by the following method:
s1, selecting basalt short fiber with the diameter of 10 microns, adding the basalt short fiber into ethanol, dispersing for 30min under ultrasound, adjusting the pH to 4.8 by using acid, adding a silane coupling agent KH550, reacting for 90min at the temperature of 50 ℃ at the rotating speed of 2000r/min, and drying to obtain pretreated basalt fiber;
s2, firstly adding cardanol into dodecyl diethanol amine, stirring for 30min at the temperature of 60 ℃ at the rotating speed of 2000r/min, then adding pretreated basalt fiber, continuing stirring for 2h, filtering and drying to obtain the modified basalt fiber.
Comparative preparation example 6
Comparative preparation 6, identical to preparation 11, differs only in that: the basalt fiber is not subjected to the pretreatment of step S1.
Comparative preparation example 7
Comparative preparation 7, identical to preparation 11, differs only in that: cardanol is not added.
Comparative preparation example 8
Comparative preparation 8, like preparation 11, differs only in that: dodecyl diethanolamine was not added.
Examples 1-5 provide a fire resistant fire retardant phenolic resin and a method of making the same.
Example 1
A fire-resistant flame-retardant phenolic resin comprises the following raw materials: 60kg of resorcinol, 30kg of paraformaldehyde, 2kg of cashew nut shell oil, 1kg of succinic acid, 11kg of flame retardant and 8kg of toughening agent;
wherein the flame retardant is prepared by mixing a first flame retardant (preparation example 1) and a second flame retardant (preparation example 6) according to the mass ratio of 8:7; the toughening agent is prepared by compounding zinc oxide whiskers and modified basalt fibers (preparation example 11) in a mass ratio of 3:1.
The fire-resistant flame-retardant phenolic resin specifically comprises the following preparation steps:
weighing m-diphenol, cashew shell oil, succinic acid, paraformaldehyde, a flame retardant and a toughening agent for later use;
mixing the m-diphenol, the cashew nut shell oil and the succinic acid, heating to 90 ℃, and keeping the temperature for 60min; adding paraformaldehyde solution, heating to 100 deg.C, and maintaining for 90min to obtain primary product;
and step three, adding a flame retardant and a toughening agent into the primary product obtained in the step two, reacting for 30min at the temperature of 120 ℃ at the rotating speed of 1600r/min, and then cooling to obtain the fire-resistant flame-retardant phenolic resin.
Example 2
A fire-resistant flame-retardant phenolic resin comprises the following raw materials: 65kg of m-diphenol, 32kg of paraformaldehyde, 3kg of cashew nut shell oil, 1.2kg of succinic acid, 12kg of flame retardant and 8.5kg of toughening agent;
wherein the flame retardant is prepared by mixing a first flame retardant (preparation example 2) and a second flame retardant (preparation example 7) according to the mass ratio of 1:1; the toughening agent is prepared by compounding zinc oxide whiskers with the mass ratio of 2:1 and modified basalt fibers (preparation example 12).
The fire-resistant flame-retardant phenolic resin specifically comprises the following preparation steps:
weighing m-diphenol, cashew shell oil, succinic acid, paraformaldehyde, a flame retardant and a toughening agent for later use;
mixing the m-diphenol, the cashew nut shell oil and the succinic acid, heating to 92 ℃, and keeping the temperature for 65min; adding paraformaldehyde solution, heating to 102 deg.C, and keeping the temperature for 100min to obtain primary product;
and step three, adding a flame retardant and a toughening agent into the primary product obtained in the step two, reacting at the temperature of 118 ℃ at a rotating speed of 1650r/min for 32min, and then cooling to obtain the fire-resistant and flame-retardant phenolic resin.
Example 3
A fire-resistant flame-retardant phenolic resin comprises the following raw materials: 70kg of resorcinol, 35kg of paraformaldehyde, 3.5kg of cashew nut shell oil, 1.5kg of succinic acid, 13kg of flame retardant and 9kg of toughening agent;
wherein the flame retardant is prepared by mixing a first flame retardant (preparation example 3) and a second flame retardant (preparation example 8) according to the mass ratio of 8:9; the toughening agent is prepared by compounding zinc oxide whiskers and modified basalt fibers (preparation example 13) in a mass ratio of 5:3.
The fire-resistant flame-retardant phenolic resin specifically comprises the following preparation steps:
weighing m-diphenol, cashew shell oil, succinic acid, paraformaldehyde, a flame retardant and a toughening agent for later use;
mixing the resorcinol, the cashew nut shell oil and the succinic acid, heating to 93 ℃, and keeping the temperature for 75min; adding paraformaldehyde solution, heating to 103 deg.C, and keeping the temperature for 110min to obtain primary product;
and step three, adding a flame retardant and a flexibilizer into the primary product obtained in the step two, reacting at the temperature of 115 ℃ at the rotating speed of 1700r/min for 35min, and then cooling to obtain the fire-resistant flame-retardant phenolic resin.
Example 4
A fire-resistant flame-retardant phenolic resin comprises the following raw materials: 75kg of m-diphenol, 38kg of paraformaldehyde, 4.4kg of cashew nut shell oil, 1.8kg of succinic acid, 14kg of flame retardant and 9.5kg of toughening agent;
wherein the flame retardant is prepared by mixing a first flame retardant (preparation example 4) and a second flame retardant (preparation example 9) according to the mass ratio of 4:5; the toughening agent is prepared by compounding zinc oxide whiskers and modified basalt fibers (preparation example 14) in a mass ratio of 7:5.
The fire-resistant flame-retardant phenolic resin specifically comprises the following preparation steps:
weighing m-diphenol, cashew shell oil, succinic acid, paraformaldehyde, a flame retardant and a toughening agent for later use;
mixing the m-diphenol, the cashew nut shell oil and the succinic acid, heating to 94 ℃, and keeping the temperature for 85min; adding paraformaldehyde solution, heating to 104 deg.C, and keeping the temperature for 115min to obtain primary product;
and step three, adding a flame retardant and a toughening agent into the primary product obtained in the step two, reacting for 38min at the temperature of 113 ℃ at the rotating speed of 1750r/min, and then cooling to obtain the fire-resistant flame-retardant phenolic resin.
Example 5
A fire-resistant flame-retardant phenolic resin comprises the following raw materials: 80kg of resorcinol, 40kg of paraformaldehyde, 5kg of cashew nut shell oil, 2kg of succinic acid, 15kg of flame retardant and 10kg of toughening agent;
wherein the flame retardant is prepared by mixing a first flame retardant (preparation example 5) and a second flame retardant (preparation example 10) according to a mass ratio of 8; the toughening agent is prepared by compounding zinc oxide whiskers and modified basalt fibers (preparation example 15) in a mass ratio of 4:3.
The fire-resistant flame-retardant phenolic resin specifically comprises the following preparation steps:
weighing m-diphenol, cashew shell oil, succinic acid, paraformaldehyde, a flame retardant and a toughening agent for later use;
mixing the m-diphenol, the cashew nut shell oil and the succinic acid, heating to 95 ℃, and keeping the temperature for 90min; adding paraformaldehyde solution, heating to 105 deg.C, and maintaining for 120min to obtain primary product;
and step three, adding a flame retardant and a toughening agent into the primary product obtained in the step two, reacting at the temperature of 110 ℃ at the rotating speed of 1800r/min for 40min, and then cooling to obtain the fire-resistant flame-retardant phenolic resin.
To verify the performance of the fire resistant fire retardant phenolic resin provided herein, applicants set up comparative examples 1-18, wherein:
comparative example 1
Comparative example 1, like example 1, differs only in that: the first flame retardant in comparative example 1 was comparative preparation 1.
Comparative example 2
Comparative example 2, like example 1, differs only in that: the first flame retardant in comparative example 2 was comparative preparation 2.
Comparative example 3
Comparative example 3, like example 1, differs only in that: the first flame retardant in comparative example 3 was attapulgite.
Comparative example 4
Comparative example 4, like example 1, differs only in that: the first flame retardant in comparative example 4 was aluminum hydroxide.
Comparative example 5
Comparative example 5, like example 1, differs only in that: the second flame retardant in comparative example 5 was comparative preparation 3.
Comparative example 6
Comparative example 6, like example 1, differs only in that: the second flame retardant in comparative example 6 was comparative preparation 4.
Comparative example 7
Comparative example 7, like example 1, differs only in that: the second flame retardant in comparative example 7 was comparative preparation example 5.
Comparative example 8
Comparative example 8, like example 1, differs only in that: the flame retardant in comparative example 8 was only the first flame retardant (preparation example 1).
Comparative example 9
Comparative example 9, like example 1, differs only in that: the flame retardant in comparative example 9 was only the second flame retardant (preparation example 6).
Comparative example 10
Comparative example 10, like example 1, differs only in that: comparative example 10 did not contain a flame retardant.
Comparative example 11
Comparative example 11, like example 1, differs only in that: the modified basalt fiber in comparative example 11 is comparative preparation example 6.
Comparative example 12
Comparative example 12, like example 1, differs only in that: the modified basalt fiber in comparative example 12 is comparative preparation example 7.
Comparative example 13
Comparative example 13, like example 1, differs only in that: the modified basalt fiber in comparative example 13 is comparative preparation example 8.
Comparative example 14
Comparative example 14, like example 1, differs only in that: the basalt fiber in comparative example 14 was not modified.
Comparative example 15
Comparative example 15, like example 1, differs only in that: the toughening agent in comparative example 15 was only modified basalt fiber (preparation example 11).
Comparative example 16
Comparative example 16, like example 1, differs only in that: the toughening agent in comparative example 16 was only zinc oxide whiskers.
Comparative example 17
Comparative example 17, like example 1, differs only in that: comparative example 17 does not have a toughening agent added.
Comparative example 18
Comparative example 18, like example 1, differs only in that: comparative example 17 did not have cashew nut shell oil added.
The main properties of the fire-resistant and flame-retardant phenolic resins of examples 1 to 5 and comparative examples 1 to 18 were respectively compared to the following result parameters, which are shown in Table 1:
testing the limit oxygen index of the fire-resistant flame-retardant phenolic resin by referring to GB/T2046.2-2009;
testing the flame retardant performance grade of the fire-resistant flame-retardant phenolic resin by referring to GB-T2408-2008;
testing the cantilever beam notch impact strength of the fire-resistant flame-retardant phenolic resin by referring to GB/T1843-2008;
the bending strength of the fire-resistant flame-retardant phenolic resin is tested by referring to GB/T1696-2001;
table 1:
as can be seen from the data shown in table 1 above: the fire-resistant and flame-retardant phenolic resin prepared in the embodiments 1-5 is far better than the fire-resistant phenolic resin prepared in the comparative examples 1-18 in comprehensive performance, the limited oxygen index is higher, the vertical combustion grades are all V-0, the impact strength and the bending strength are higher, and the fire-resistant and flame-retardant phenolic resin prepared in the embodiments 1-5 has obvious flame retardant performance and excellent mechanical property.
From example 1 and comparative examples 1 to 4, it can be seen that: the first flame retardant of example 1 is an aluminum hydroxide-attapulgite composite, and compared with comparative examples 1-4, the flame retardant performance and the mechanical property of the fire-resistant flame-retardant phenolic resin obtained in example 1 are superior to those of comparative examples 1-4.
From example 1 and comparative examples 5 to 7, it can be seen that: the second flame retardant of the example 1 is a phosphorus-silicon-nitrogen ternary synergistic efficient flame retardant, compared with comparative examples 5 to 7, the limit oxygen index of the fire-resistant flame-retardant phenolic resin obtained in the example 1 is obviously improved, and the vertical burning grade is V-0.
It can be seen from example 1 and comparative examples 8 and 9 that the fire retardant in example 1 is obtained by mixing a first fire retardant and a second fire retardant, and compared with comparative examples 8 and 9, the fire-resistant fire-retardant phenolic resin obtained in example 1 has excellent fire-retardant performance, and the impact strength and the bending strength of the phenolic resin are both remarkably improved.
As can be seen from the example 1 and the comparative examples 11 to 14, the mechanical properties of the fire-resistant and flame-retardant phenolic resin obtained in the example 1 are remarkably enhanced compared with the comparative examples 11 to 14 because the basalt fiber in the example 1 is modified by cardanol.
As can be seen from the example 1 and the comparative examples 15 and 16, the toughening agent in the example 1 is obtained by compounding the modified basalt fiber and the zinc oxide whisker, and compared with the comparative examples 15 and 16, the fire-resistant and flame-retardant phenolic resin obtained in the example 1 has excellent mechanical properties and remarkable fire-resistant and flame-retardant properties.
As can be seen from example 1 and comparative examples 10, 17, and 18, the raw materials in example 1 include cardanol, a flame retardant, and a toughening agent, and the fire-resistant and flame-retardant phenolic resin obtained in example 1 has more excellent overall properties than those in comparative examples 10, 17, and 18.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The fire-resistant flame-retardant phenolic resin is characterized by comprising the following raw materials in parts by weight: 60-80 parts of resorcinol, 30-40 parts of paraformaldehyde, 2-5 parts of cashew nut shell oil, 1-2 parts of succinic acid, 11-15 parts of a flame retardant and 8-10 parts of a toughening agent;
the flame retardant consists of a first flame retardant and a second flame retardant; the toughening agent consists of zinc oxide whiskers and modified basalt fibers.
2. The fire-resistant and flame-retardant phenolic resin as claimed in claim 1, wherein the first flame retardant comprises the following raw materials in parts by weight: 10-20 parts of attapulgite, 1-3 parts of triethanolamine, 31-35 parts of dopamine, 9-10 parts of 10-12wt% aluminum nitrate solution and 30-60 parts of 5-8wt% sodium hydroxide solution.
3. The fire-resistant and flame-retardant phenolic resin according to claim 2, wherein the first flame retardant is prepared by the following method:
firstly, adding attapulgite into triethanolamine, grinding for 10-15min, then adding dopamine, and carrying out ultrasonic reaction for 45-60min at the temperature of 30-40 ℃; adding an aluminum nitrate solution, continuing to perform ultrasonic reaction for 10-20min, and adding a sodium hydroxide solution; and finally, standing the reaction system at 60-80 ℃ under 10-15MPa for reaction, standing for 2-3h, filtering and drying to obtain the first flame retardant.
4. The fire-resistant and flame-retardant phenolic resin as claimed in claim 1, wherein the second flame retardant comprises the following raw materials in parts by weight: 10-30 parts of tetradecyloxy silane, 15-28 parts of tributoxyethyl phosphate and 10-25 parts of guanidine sulfamate.
5. The fire-resistant and flame-retardant phenolic resin according to claim 4, wherein the second flame retardant is prepared by the following method:
fully mixing tetradecyloxy silane, tris (butoxyethyl) phosphate and guanidine sulfamate, condensing and refluxing under the protection of nitrogen, wherein the reaction temperature is 80-180 ℃, and reacting for 3-5 hours until no distillate is generated; adding the obtained product into a dialysis bag with a molecular weight of 2100-2500, and dialyzing for 24-48h by using ethanol as a dialysis medium; and finally, carrying out supercritical drying to obtain a second flame retardant.
6. The fire-resistant and flame-retardant phenolic resin as claimed in claim 1, wherein the fire retardant is prepared by mixing a first fire retardant and a second fire retardant according to a mass ratio of 8 (7-11).
7. The fire-resistant flame-retardant phenolic resin according to claim 1, wherein the modified basalt fiber comprises the following raw materials in parts by weight: 40-50 parts of basalt short fiber, 100-150 parts of ethanol, 50-60 parts of 20-30wt% silane coupling agent KH550, 15-19 parts of cardanol and 8-9 parts of dodecyl diethanolamine.
8. The fire-resistant and flame-retardant phenolic resin as claimed in claim 7, wherein the modified basalt fiber is prepared by the following method:
s1, selecting basalt short fiber with the diameter of 6-10 microns, adding the basalt short fiber into ethanol, dispersing for 20-30min under ultrasound, then adjusting the pH to 4.8-5.2, then adding a silane coupling agent KH550, reacting for 60-90min at the temperature of 40-50 ℃ at the rotating speed of 2000-2500r/min, and drying to obtain pretreated basalt fiber;
s2, firstly adding cardanol into dodecyl diethanolamine, stirring at the temperature of 50-60 ℃ and the rotation speed of 2000-2500r/min for 30-40min, then adding pretreated basalt fiber, continuing stirring for 1-2h, filtering and drying to obtain the modified basalt fiber.
9. The fire-resistant flame-retardant phenolic resin as claimed in claim 1, wherein the toughening agent is prepared by compounding zinc oxide whiskers and modified basalt fibers in a mass ratio of (3-8) to (1-6).
10. The fire-resistant and flame-retardant phenolic resin according to claim 1, wherein the fire-resistant and flame-retardant phenolic resin is prepared by the following method:
weighing m-diphenol, cashew shell oil, succinic acid, paraformaldehyde, a flame retardant and a toughening agent in parts by weight for later use;
mixing the resorcinol, the cashew nut shell oil and the succinic acid, heating to 90-95 ℃, and keeping the temperature for 60-90min; adding paraformaldehyde solution, heating to 100-105 deg.C, and maintaining for 90-120min to obtain initial product;
and step three, adding a flame retardant and a toughening agent into the primary product obtained in the step two, reacting at the temperature of 110-120 ℃ at the rotating speed of 1600-1800r/min for 30-40min, and then cooling to obtain the fire-resistant flame-retardant phenolic resin.
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Application publication date: 20221028 |