CN116200153A - Flame-retardant high-temperature-resistant adhesive and manufacturing process thereof - Google Patents
Flame-retardant high-temperature-resistant adhesive and manufacturing process thereof Download PDFInfo
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- CN116200153A CN116200153A CN202310363210.6A CN202310363210A CN116200153A CN 116200153 A CN116200153 A CN 116200153A CN 202310363210 A CN202310363210 A CN 202310363210A CN 116200153 A CN116200153 A CN 116200153A
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- Prior art keywords
- flame
- retardant
- temperature
- resistant adhesive
- modifier
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- 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 80
- 239000003063 flame retardant Substances 0.000 title claims abstract description 80
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 59
- 239000000853 adhesive Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000003607 modifier Substances 0.000 claims abstract description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000011256 inorganic filler Substances 0.000 claims abstract description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 16
- -1 polydimethylsiloxane Polymers 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- IUTPJBLLJJNPAJ-UHFFFAOYSA-N 3-(2,5-dioxopyrrol-1-yl)propanoic acid Chemical compound OC(=O)CCN1C(=O)C=CC1=O IUTPJBLLJJNPAJ-UHFFFAOYSA-N 0.000 claims description 10
- ZPDWRQORROQQLX-UHFFFAOYSA-N 4-[[2,4,4,6,6-pentakis(4-aminophenoxy)-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-trien-2-yl]oxy]aniline Chemical compound C1=CC(N)=CC=C1OP1(OC=2C=CC(N)=CC=2)=NP(OC=2C=CC(N)=CC=2)(OC=2C=CC(N)=CC=2)=NP(OC=2C=CC(N)=CC=2)(OC=2C=CC(N)=CC=2)=N1 ZPDWRQORROQQLX-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 6
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical group ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229920000459 Nitrile rubber Polymers 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000007792 addition Methods 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 abstract description 24
- 229920000647 polyepoxide Polymers 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 8
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical group C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000002313 adhesive film Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920006332 epoxy adhesive Polymers 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical compound [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives and discloses a flame-retardant high-temperature-resistant adhesive and a manufacturing process thereof, wherein the flame-retardant high-temperature-resistant adhesive is prepared by mutually combining liquid epoxy resin-based adhesives, branched flame-retardant modifiers, toughening modifiers, inorganic fillers, silane coupling agents and curing agents, and the high-temperature-resistant performance of the epoxy resin adhesives can be effectively enhanced by utilizing rigid structures such as triazine rings, maleimide rings and the like in the branched flame-retardant modifier structures and high-bond-energy silicon-oxygen bonds, and meanwhile, the flame-retardant performance of the epoxy resin adhesives can be effectively improved by utilizing the synergistic flame-retardant effect formed by nitrogen, phosphorus and silicon three elements in the branched flame-retardant modifier structures, so that the application field of the epoxy resin adhesives is further widened.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a flame-retardant high-temperature-resistant adhesive and a manufacturing process thereof.
Background
The epoxy resin has various advantages, such as excellent chemical stability, corrosion resistance, electrical insulation and the like, and is widely applied to various fields of coatings, composite materials, casting and filling materials, adhesives and the like, wherein the epoxy adhesive prepared by taking the epoxy resin as a base material has strong adhesive property, and can realize the adhesion of various materials, so that the epoxy resin plays an important role in the adhesive field. After the common epoxy resin adhesive is simply modified, the performance is excellent, the use requirement of the adhesive in daily life can be basically met, however, the high temperature resistance of the epoxy resin is poor, the strength is obviously reduced under the temperature environment of about 200 ℃, the epoxy resin adhesive cannot be used for a long time, meanwhile, the limiting oxygen index of the epoxy resin matrix is about 19.8, the epoxy resin adhesive belongs to inflammable materials, and the defects cause that the epoxy resin adhesive cannot be basically applied in the fields with high requirements on high temperature resistance and flame retardant performance, such as aerospace, so the epoxy resin adhesive is improved, and the application of the epoxy resin adhesive is further promoted to have great significance.
The Chinese patent application No. CN201310723847.8 discloses a high-temperature-resistant flame-retardant epoxy adhesive and a preparation method thereof, wherein the heat distortion temperature and thermal oxidation stability of the epoxy adhesive are greatly improved by using matrix epoxy resin containing heat-resistant rigid groups such as aromatic rings, alicyclic rings and heterocyclic rings on molecular chains, so that the heat resistance of a product is remarkably improved, meanwhile, flame-retardant auxiliary components are added to achieve the aim of improving the flame-retardant effect of the epoxy adhesive, the natural and combustible safety performance of the epoxy adhesive at high temperature is further improved, but a certain interfacial compatibility problem actually exists through a physically filled flame retardant, the phenomenon that flame-retardant components are separated out can occur in the long-term storage or use process, so that the long-term flame-retardant effect of the epoxy adhesive cannot be ensured, and the material selection of raw materials is limited only by selecting the epoxy matrix resin containing heat-resistant rigid groups such as aromatic rings, alicyclic rings and heterocyclic rings on molecular chains, so that the manufacturing of the epoxy adhesive is not facilitated.
Disclosure of Invention
The invention aims to provide a flame-retardant high-temperature-resistant adhesive and a manufacturing process thereof.
The aim of the invention can be achieved by the following technical scheme:
the flame-retardant high-temperature-resistant adhesive comprises the following raw materials in parts by weight: 50-80 parts of liquid epoxy resin base gum, 2-6 parts of branched flame retardant modifier, 1-5 parts of toughening modifier, 5-10 parts of inorganic filler, 1-2 parts of silane coupling agent and 10-20 parts of curing agent;
the branched flame retardant modifier is prepared by dehydrating and condensing 3-maleimidopropionic acid and hexa (p-aminophenoxy) cyclotriphosphazene to form an intermediate, and then performing hydrosilylation reaction with hydrogen-terminated polydimethylsiloxane.
Further, the toughening modifier is any one of nitrile rubber or styrene-butadiene rubber; the inorganic filler is any one of nano calcium carbonate, nano silicon dioxide or montmorillonite; the silane coupling agent is 3-glycidol ether oxygen propyl trimethoxy silane; the curing agent is dicyandiamide.
Further, the preparation of the branched flame retardant modifier specifically comprises the following steps:
i: mixing 3-maleimidopropionic acid, hexa (p-aminophenoxy) cyclotriphosphazene and tetrahydrofuran, stirring uniformly, adding a compound catalyst, stirring for 12-24 hours at room temperature, pouring the materials into acetone for precipitation, taking out the precipitate, washing, and vacuum drying to obtain an intermediate;
i I: mixing the intermediate, hydrogen-terminated polydimethylsiloxane and ethanol, introducing nitrogen, stirring for 10-20min, placing the system at 70-80 ℃, dropwise adding the catalyst, preserving heat for 6-12h, cooling the materials, and decompressing to remove low-boiling substances to obtain the branched flame retardant modifier.
Further, the molar ratio of the 3-maleimidopropionic acid to the hexa (p-aminophenoxy) cyclotriphosphazene is 2-4:1.
Further, the compound catalyst is N-hydroxysuccinimide and dicyclohexylcarbodiimide with the mass ratio of 1:6-10.
Further, the hydrogen-terminated polydimethylsiloxane has an average molecular weight of 2360.
Further, the catalyst is a platinum catalyst, and the addition amount of the platinum catalyst is 0.01-0.03% of the total mass of the intermediate and the hydrogen-terminated polydimethylsiloxane.
According to the technical scheme, under the catalysis of N-hydroxysuccinimide and dicyclohexylcarbodiimide, carboxyl in the 3-maleimidopropionic acid structure can be dehydrated and condensed with amino in the hexa (p-aminophenoxy) cyclotriphosphazene structure, an intermediate containing triazine ring, hydroxyl and maleimide groups in the structure can be prepared by controlling the molar ratio of reactants, and under the action of a platinum catalyst, alkenyl functional groups contained in the maleimide groups in the intermediate structure can undergo a hydrosilylation reaction with hydrogen-terminated polydimethylsiloxane, so that a polydimethylsiloxane molecular chain is introduced into the intermediate structure, and the nitrogen-phosphorus-silicon branched flame retardant modifier is prepared.
A process for manufacturing the flame-retardant and high-temperature-resistant adhesive according to claim 1, which comprises the following steps:
step one: adding liquid epoxy resin, a toughening modifier and a silane coupling agent into a stirring kettle, stirring for 1-2 hours at room temperature at the rotating speed of 500-800r/min, adding inorganic filler, and continuously stirring for 30-60min to obtain a premix;
step two: and mixing the branched flame retardant modifier, the curing agent and the premix, stirring for 1-2h, and vacuumizing under the vacuum pressure of-0.098 MPa to obtain the flame retardant high temperature resistant adhesive.
The invention has the beneficial effects that:
(1) According to the invention, the branched flame retardant modifier is prepared and mixed with auxiliaries such as liquid epoxy resin and the like to prepare the flame retardant high temperature resistant adhesive, the branched flame retardant modifier structure contains rigid structures such as triazine rings, maleimide rings and the like, and contains rich high bond energy silica bonds, so that the epoxy resin adhesive is favorable for bearing higher temperature and has higher heat distortion temperature, and simultaneously, hydroxyl in the branched flame retardant modifier structure can participate in the thermoplastic curing process of the epoxy resin adhesive, so that the interfacial compatibility of the branched flame retardant modifier and an epoxy resin matrix can be improved, the crosslinking density of epoxy resin molecular chains can be improved, and the movement of the epoxy resin molecular chains can be limited, thereby further enhancing the high temperature resistant performance of the epoxy resin adhesive.
(2) The branched flame retardant modifier prepared by the invention contains a plurality of flame retardant elements of nitrogen, phosphorus and silicon, wherein organic acid generated by burning phosphorus element can promote the carbon formation of epoxy resin until a compact carbon layer is formed on the surface of a matrix, incombustible gas such as nitrogen generated by burning nitrogen element can be wrapped by the carbon layer to form an expanded carbon layer, oxygen and heat generated by burning are effectively isolated, the further damage of the inside of the epoxy resin adhesive is prevented, meanwhile, silicon element is adhered and deposited in the carbon layer after burning, the strength of the carbon layer is enhanced, the nitrogen-phosphorus-silicon synergistic flame retardant effect of the carbon layer is avoided, and the epoxy resin adhesive is endowed with excellent flame retardant effect.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The flame-retardant high-temperature-resistant adhesive comprises the following raw materials in parts by weight: 50 parts of liquid epoxy resin-based gum, 2 parts of branched flame retardant modifier, 1 part of nitrile rubber, 5 parts of nano calcium carbonate, 1 part of 3-glycidyl ether oxypropyl trimethoxy silane and 10 parts of dicyandiamide;
the preparation process of the flame-retardant high-temperature-resistant adhesive specifically comprises the following steps:
step one: adding liquid epoxy resin, a toughening modifier and a silane coupling agent into a stirring kettle, stirring for 1h at room temperature at the rotating speed of 500 r/min, adding inorganic filler, and continuously stirring for 30 min to obtain a premix;
step two: and mixing the branched flame retardant modifier, the curing agent and the premix, stirring for 1h, and vacuumizing under the vacuum pressure of-0.098 MPa to obtain the flame retardant high temperature resistant adhesive.
Wherein the preparation of the branched flame retardant modifier specifically comprises the following steps:
i: mixing 4.3g of 3-maleimidopropionic acid, 10g of hexa (p-aminophenoxy) cyclotriphosphazene and tetrahydrofuran, stirring uniformly, adding 0.1g of N-hydroxysuccinimide and 0.6g of dicyclohexylcarbodiimide, stirring for 12 hours at room temperature, pouring the materials into acetone for precipitation, taking out the precipitate, washing, and drying in vacuum to obtain an intermediate;
i I: 5g of intermediate, 12.5g of hydrogen-terminated polydimethylsiloxane and ethanol are mixed, nitrogen is introduced and stirred for 10 min, the system is placed under the temperature condition of 70 ℃, 0.175g of platinum catalyst is dripped, the temperature is kept for 6h, the materials are cooled, and low-boiling substances are removed under reduced pressure, so that the branched flame retardant modifier is prepared, wherein the average molecular weight of the hydrogen-terminated polydimethylsiloxane is 2360.
Example 2
The flame-retardant high-temperature-resistant adhesive comprises the following raw materials in parts by weight: 60 parts of liquid epoxy resin-based glue, 4 parts of branched flame retardant modifier, 3 parts of styrene-butadiene rubber, 8 parts of nano silicon dioxide, 1.5 parts of 3-glycidyl ether oxypropyl trimethoxy silane and 15 parts of dicyandiamide;
the preparation process of the flame-retardant high-temperature-resistant adhesive specifically comprises the following steps:
step one: adding liquid epoxy resin, a toughening modifier and a silane coupling agent into a stirring kettle, stirring for 1h at room temperature at the rotating speed of 600 r/min, adding inorganic filler, and continuously stirring for 40 min to obtain a premix;
step two: and mixing the branched flame retardant modifier, the curing agent and the premix, stirring for 2 hours, and vacuumizing under the vacuum pressure of-0.098 MPa to obtain the flame retardant high temperature resistant adhesive.
Wherein the preparation of the branched flame retardant modifier specifically comprises the following steps:
i: mixing and stirring 6g of 3-maleimidopropionic acid, 10g of hexa (p-aminophenoxy) cyclotriphosphazene and tetrahydrofuran uniformly, adding 0.15g of N-hydroxysuccinimide and 1.2g of dicyclohexylcarbodiimide, stirring for 18 hours at room temperature, pouring the materials into acetone for precipitation, taking out the precipitate, washing and vacuum drying to obtain an intermediate;
i I: 5g of intermediate, 12.5g of hydrogen-terminated polydimethylsiloxane and ethanol are mixed, nitrogen is introduced and stirred for 15 min, the system is placed under the temperature condition of 80 ℃, 0.4g of platinum catalyst is dripped, the temperature is kept for 9h, the materials are cooled, and low-boiling substances are removed under reduced pressure, so that the branched flame retardant modifier is prepared, wherein the average molecular weight of the hydrogen-terminated polydimethylsiloxane is 2360.
Example 3
The flame-retardant high-temperature-resistant adhesive comprises the following raw materials in parts by weight: 80 parts of liquid epoxy resin-based gum, 6 parts of branched flame retardant modifier, 5 parts of nitrile rubber, 10 parts of montmorillonite, 2 parts of 3-glycidyl ether oxypropyl trimethoxy silane and 20 parts of dicyandiamide;
the preparation process of the flame-retardant high-temperature-resistant adhesive specifically comprises the following steps:
step one: adding liquid epoxy resin, a toughening modifier and a silane coupling agent into a stirring kettle, stirring for h at room temperature at the rotating speed of 800r/min, adding inorganic filler, and continuously stirring for 60min to obtain a premix;
step two: and mixing the branched flame retardant modifier, the curing agent and the premix, stirring for 2 hours, and vacuumizing under the vacuum pressure of-0.098 MPa to obtain the flame retardant high temperature resistant adhesive.
Wherein the preparation of the branched flame retardant modifier specifically comprises the following steps:
i: mixing 8.6g of 3-maleimidopropionic acid, 10g of hexa (p-aminophenoxy) cyclotriphosphazene and tetrahydrofuran, stirring uniformly, adding 0.2g of N-hydroxysuccinimide and 2g of dicyclohexylcarbodiimide, stirring for 24 hours at room temperature, pouring the materials into acetone for precipitation, taking out the precipitate, washing, and vacuum drying to obtain an intermediate;
i I: 5g of intermediate, 12.5g of hydrogen-terminated polydimethylsiloxane and ethanol are mixed, nitrogen is introduced and stirred for 20min, the system is placed under the temperature condition of 80 ℃, 0.525g of platinum catalyst is dripped, the temperature is kept for 12h, the materials are cooled, and low-boiling substances are removed under reduced pressure, so that the branched flame retardant modifier is prepared, wherein the average molecular weight of the hydrogen-terminated polydimethylsiloxane is 2360.
Comparative example 1
An adhesive comprises the following raw materials in parts by weight: 80 parts of liquid epoxy resin-based rubber, 5 parts of nitrile rubber, 10 parts of montmorillonite, 2 parts of 3-glycidoxypropyl trimethoxysilane and 20 parts of dicyandiamide;
the preparation process of the adhesive specifically comprises the following steps:
step one: adding liquid epoxy resin, a toughening modifier and a silane coupling agent into a stirring kettle, stirring for h at room temperature at the rotating speed of 800r/min, adding inorganic filler, and continuously stirring for 60min to obtain a premix;
step two: mixing the curing agent with the premix, stirring for 2 hours, and vacuumizing under the vacuum pressure of-0.098 MPa to obtain the flame-retardant high-temperature-resistant adhesive.
Performance detection
A. The adhesives prepared in examples 1 to 3 and comparative example 1 were poured into a mold and thermally cured to form a film, and UL-94 test was performed on the film using a ZRS-TC type horizontal vertical combustion tester at 25 ℃ and 50±5% humidity with reference to the national standard GB/T2408-2021, and the test results are shown in the following table:
| group of | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| UL-94 rating | V-0 | V-0 | V-0 | V-2 |
As can be seen from the above table, the adhesive films UL-94 formed by the adhesives prepared in the examples 1-3 of the invention reach V-0 level, and have good flame retardant effect, while the adhesive film UL-94 formed by the adhesive prepared in the comparative example 1 has lower level and poorer flame retardant effect, presumably because the branched flame retardant modifier is not added in the components, the flame retardant effect of the flame retardant cannot be utilized to endow the adhesive with good flame retardant performance.
B. Weighing 5g of adhesive film, placing in an oven at 180 ℃ for baking for 24 hours, taking out, weighing the adhesive film, calculating the thermal weight loss rate, observing the surface phenomenon of the adhesive film, evaluating the high temperature resistance of the adhesive, and testing the following table:
| group of | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Thermal weight loss ratio (%) | 0.6 | 0.3 | 0.5 | 6.4 |
| Phenomenon (1) | Cracking-free pulverization | Cracking-free pulverization | Cracking-free pulverization | Partial cracking |
As can be seen from the above table, the adhesive films formed by the adhesives prepared in examples 1-3 of the present invention have low thermal weight loss rate and no cracking and pulverization phenomenon on the surface after being baked in an oven at 180 ℃ for 24 hours, so that the adhesive film formed by the adhesive prepared in comparative example 1 has good high temperature resistance, the thermal weight loss rate of the adhesive film formed by the adhesive film prepared in comparative example 1 is as high as 6.4%, and the surface has partial cracking phenomenon, which is presumed that the adhesive film contains no branched flame retardant modifier, and the rigid triazine ring, maleimide group and high bond energy silicon-oxygen bond in the branched flame retardant modifier structure cannot be utilized, so that the high temperature resistance is poor.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (8)
1. The flame-retardant high-temperature-resistant adhesive is characterized by comprising the following raw materials in parts by weight: 50-80 parts of liquid epoxy resin base gum, 2-6 parts of branched flame retardant modifier, 1-5 parts of toughening modifier, 5-10 parts of inorganic filler, 1-2 parts of silane coupling agent and 10-20 parts of curing agent;
the branched flame retardant modifier is prepared by dehydrating and condensing 3-maleimidopropionic acid and hexa (p-aminophenoxy) cyclotriphosphazene to form an intermediate, and then performing hydrosilylation reaction with hydrogen-terminated polydimethylsiloxane.
2. The flame-retardant and high-temperature-resistant adhesive according to claim 1, wherein the toughening modifier is any one of nitrile rubber or styrene-butadiene rubber; the inorganic filler is any one of nano calcium carbonate, nano silicon dioxide or montmorillonite; the silane coupling agent is 3-glycidol ether oxygen propyl trimethoxy silane; the curing agent is dicyandiamide.
3. The flame-retardant and high-temperature-resistant adhesive according to claim 1, wherein the preparation of the branched flame-retardant modifier comprises the following steps:
i: mixing 3-maleimidopropionic acid, hexa (p-aminophenoxy) cyclotriphosphazene and tetrahydrofuran, stirring uniformly, adding a compound catalyst, stirring for 12-24 hours at room temperature, pouring the materials into acetone for precipitation, taking out the precipitate, washing, and vacuum drying to obtain an intermediate;
II: mixing the intermediate, hydrogen-terminated polydimethylsiloxane and ethanol, introducing nitrogen, stirring for 10-20min, placing the system at 70-80 ℃, dropwise adding the catalyst, preserving heat for 6-12h, cooling the materials, and removing low-boiling substances under reduced pressure to obtain the branched flame retardant modifier.
4. A flame retardant and high temperature resistant adhesive according to claim 3, wherein in step I, the molar ratio of 3-maleimidopropionic acid to hexa (p-aminophenoxy) cyclotriphosphazene is 2-4:1.
5. The flame-retardant and high-temperature-resistant adhesive according to claim 3, wherein in the step I, the compound catalyst is N-hydroxysuccinimide and dicyclohexylcarbodiimide with the mass ratio of 1:6-10.
6. A flame retardant, high temperature resistant adhesive according to claim 3 wherein in step II the hydrogen terminated polydimethylsiloxane has an average molecular weight of 2360.
7. The flame-retardant and high-temperature-resistant adhesive according to claim 3, wherein in the step II, the catalyst is a platinum catalyst, and the addition amount of the platinum catalyst is 0.01-0.03% of the total mass of the intermediate and the hydrogen-terminated polydimethylsiloxane.
8. A process for manufacturing the flame-retardant and high-temperature-resistant adhesive according to claim 1, which comprises the following steps:
step one: adding liquid epoxy resin, a toughening modifier and a silane coupling agent into a stirring kettle, stirring for 1-2 hours at room temperature at the rotating speed of 500-800r/min, adding inorganic filler, and continuously stirring for 30-60min to obtain premix;
step two: and mixing the branched flame retardant modifier, the curing agent and the premix, stirring for 1-2h, and vacuumizing under the vacuum pressure of-0.098 MPa to obtain the flame retardant high temperature resistant adhesive.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117511244A (en) * | 2023-11-27 | 2024-02-06 | 江苏大自然智能家居有限公司 | Fireproof composite wooden floor and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117511244A (en) * | 2023-11-27 | 2024-02-06 | 江苏大自然智能家居有限公司 | Fireproof composite wooden floor and preparation method thereof |
| CN117511244B (en) * | 2023-11-27 | 2024-05-28 | 江苏大自然智能家居有限公司 | Fireproof composite wooden floor and preparation method thereof |
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