CN116874988B - High-flame-retardance medium-temperature curing epoxy resin premix and preparation method and application thereof - Google Patents
High-flame-retardance medium-temperature curing epoxy resin premix and preparation method and application thereof Download PDFInfo
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- CN116874988B CN116874988B CN202310965637.3A CN202310965637A CN116874988B CN 116874988 B CN116874988 B CN 116874988B CN 202310965637 A CN202310965637 A CN 202310965637A CN 116874988 B CN116874988 B CN 116874988B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 95
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 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 claims abstract description 72
- 239000003063 flame retardant Substances 0.000 claims abstract description 72
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 39
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007787 solid Substances 0.000 claims abstract description 38
- 239000007822 coupling agent Substances 0.000 claims abstract description 31
- 239000012745 toughening agent Substances 0.000 claims abstract description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 14
- 239000000853 adhesive Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 239000002313 adhesive film Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- -1 urea compound Chemical class 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229920006287 phenoxy resin Polymers 0.000 claims description 2
- 239000013034 phenoxy resin Substances 0.000 claims description 2
- HLPKYOCVWVMBMR-UHFFFAOYSA-N azane benzylbenzene Chemical compound N.N.C=1C=CC=CC=1CC1=CC=CC=C1 HLPKYOCVWVMBMR-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 239000002994 raw material Substances 0.000 description 10
- 229910052787 antimony Inorganic materials 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012796 inorganic flame retardant Substances 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- 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
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- 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
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a high-flame-retardance medium-temperature curing epoxy resin premix, a preparation method and application thereof, wherein the high-flame-retardance medium-temperature curing epoxy resin premix comprises the following components in parts by weight: 40-85 parts of epoxy resin, 5-10 parts of toughening agent, 18-35 parts of flame retardant, 0.5-2 parts of coupling agent, 5-10 parts of curing agent and 2-5 parts of accelerator, wherein the viscosity range of the epoxy resin is 20000-100000cps, the epoxy resin comprises epoxy resin, liquid bisphenol A epoxy resin, solid phenolic epoxy resin and solid brominated epoxy resin, and the flame retardant comprises the following components in percentage by mass: 3-5 of antimonous oxide and oligomeric phosphate liquid flame retardant, wherein the coupling agent is BYK-C8001 of Pick chemical Germany. The epoxy resin premix prepared by the invention has better flame retardant property and tensile shear strength.
Description
Technical Field
The invention relates to an epoxy resin formula system, in particular to a high-flame-retardance medium-temperature curing epoxy resin premix, and a preparation method and application thereof.
Background
The epoxy resin adhesive contains various polar groups and epoxy groups with high activity, so that the epoxy resin adhesive has high adhesive force with various polar materials such as metal, glass, cement, wood, plastic and the like, especially materials with high surface activity, and meanwhile, the cohesive strength of an epoxy cured product is also high, so that the adhesive strength is high, and the application is very wide. Epoxy resin has very low oxygen index, belongs to inflammables, has flame retardant requirements on adhesive materials in many environments at present, has very severe requirements in some environments, needs higher flame retardance, removes flame incombustibility after being in flame for a long time, and often needs more inorganic incombustible materials to be added to meet a high-requirement flame retardant resin system, even more than 50%, and has poor compatibility with epoxy resin, sedimentation is easy to occur in the storage and transportation process, the bonding effect of the adhesive is reduced, and the uniformity of the flame retardant adhesive cannot be ensured.
Chinese patent publication No. CN201610371422.9 discloses a flame retardant and heat resistant epoxy resin for self-adhesive prepregs. The resin for the prepreg consists of an epoxy resin mixture A component and a curing agent mixture B component. The epoxy resin mixture A accounts for 50-80 parts by weight of the resin, and the curing agent mixture B accounts for 10-40 parts by weight of the resin. Preparing prepreg by adopting the hot melt adhesive impregnated reinforcing material of the composition; the composite material is molded using a prepreg. The prepreg has moderate viscosity and good manufacturability; the preservation time at normal temperature is 3 months. The prepreg was able to be fully cured at 135 ℃ for 2 hours. The glass transition temperature of the cured composite material is 180-210 ℃. The antimony trioxide is only added as a flame retardant auxiliary agent, the addition amount is small, the flame retardant effect of the prepreg is to be improved, and the antimony trioxide is only suitable for preparing the prepreg and cannot be used for preparing the adhesive.
Disclosure of Invention
The invention aims to provide a high-flame-retardance medium-temperature curing epoxy resin premix, a preparation method and application thereof, and the prepared epoxy resin premix has better flame retardance and tensile shear strength.
The invention also provides application of the high-flame-retardance medium-temperature curing epoxy resin premix in preparation of functional resin adhesive film materials and adhesives.
The invention is realized by the following technical scheme:
the high-flame-retardance medium-temperature curing epoxy resin premix comprises the following components in parts by weight: 40-85 parts of epoxy resin, 5-10 parts of toughening agent, 18-35 parts of flame retardant, 0.5-2 parts of coupling agent, 5-10 parts of curing agent and 2-5 parts of accelerator, wherein the viscosity range of the epoxy resin is 20000-100000cps, the epoxy resin comprises epoxy resin, liquid bisphenol A epoxy resin, solid phenolic epoxy resin and solid brominated epoxy resin, and the flame retardant comprises the following components in percentage by mass: 3-5 of antimonous oxide and oligomeric phosphate liquid flame retardant, wherein the coupling agent is BYK-C8001 of Pick chemical Germany.
The inorganic powder and the liquid flame retardant have higher flame retardant effect, wherein the flame retardant mechanism of the antimony trioxide belongs to a gas-phase flame retardant mechanism, and when in combustion, the antimony trioxide reacts with a halogen-containing compound (such as brominated epoxy resin used in the patent) on the surface layer of the combustible to generate volatile antimony halide and antimony oxyhalide, the volatilization of the volatile antimony halide and the antimony oxyhalide can absorb heat, and the generated gas can isolate oxygen and dilute the combustible; the low-polymer phosphate flame retardant generates phosphoric acid during combustion, metaphosphoric acid is generated at a higher temperature, phosphoric acid and metaphosphoric acid are both dehydrating agents, so that the polymer is directly dehydrated and carbonized, the generation of combustible gas is avoided, and meanwhile, a coke layer is formed on the surface of a burning fabric, which can block the contact between the combustible gas and the flame front on one hand and separate air and heat from the surface of a burner on the other hand.
The mass ratio of the antimony trioxide to the oligomeric phosphate liquid flame retardant is 6:3 to 5. The proportion is favorable for the mutual synergistic effect of the two materials, if the proportion of the antimony trioxide is too high, agglomeration phenomenon can occur, so that the components which are actually compatible with the liquid flame retardant are lower, when the proportion of the antimony trioxide in a part of places where combustion occurs actually is lower, the generated antimony halide and antimony oxyhalide are lower, enough heat cannot be absorbed, and the flame retardant effect is poor; if the proportion of the oligomeric phosphate is higher, the charring degree of the combustible resin is too high, and the antimony trioxide cannot react to generate enough antimony halide and antimony oxyhalide, so that solids are enriched and drop, the heat absorption is affected, and the carbon can still be burnt at a higher temperature, so that the flame retardant effect is affected. Further preferably, the mass ratio of the antimony trioxide to the oligomeric phosphate liquid flame retardant is 3:2.
the antimony trioxide is inorganic metal oxide and has poor compatibility with organic resin, so that the antimony trioxide can be uniformly dispersed in the resin without layering or sedimentation through the action of the coupling agent (the coupling agent can react with the antimony trioxide and can react with epoxy groups on the surface of the resin, and the selected coupling agent can act with the resin and the flame retardant at normal temperature to uniformly combine the flame retardant with the resin), thereby being beneficial to uniform distribution of the flame retardant in the resin premix. The coupling agent is of a long-chain molecular structure, one end of the coupling agent is a group active on an epoxy group, the other end of the coupling agent is a group active on an inorganic oxygen-containing flame retardant, and the middle section of the coupling agent is a group compatible with resin, so that the flame retardant can be combined with the resin and dissolved in the resin, and the flame retardant property of the premix is improved.
The liquid bisphenol A type epoxy resin is used for adjusting the viscosity of a system, reducing the viscosity of the system which is promoted by the toughening agent and the solid resin, and is suitable for producing the required viscosity of the adhesive film by a hot melting method; the phenolic epoxy resin has higher oxygen index, can reduce the use amount of flame retardant, can react with a curing agent to form a denser reticular crosslinking structure, improves the crosslinking density of the whole system, improves the heat resistance, the strength, the modulus and the corrosion resistance, and has higher Tg (DSC method), wherein the Tg is more than 150 ℃; the brominated epoxy resin has a certain flame retardant effect, participates in the curing reaction of the system, forms a crosslinked reticular structure, and reduces the consumption of inorganic flame retardant.
Further preferably, in a preferred embodiment of the present invention, the mass part of the flame retardant is 20 to 30 parts.
In a preferred embodiment of the present invention, the liquid bisphenol a epoxy resin is 20 to 40 parts by mass, the solid novolac epoxy resin is 10 to 30 parts by mass, and the solid novolac epoxy resin is 10 to 15 parts by mass of the solid brominated epoxy resin. The premix prepared by the ratio of the solid-liquid epoxy resin has moderate viscosity, is favorable for manufacturing adhesive films, and meanwhile, the solid brominated epoxy resin is halogen-containing flame-retardant epoxy resin which is easy to generate more smog under open fire, and the ratio is compressed in the range, so that the flame-retardant effect can be achieved, too much smog can not be generated, and the flame-retardant epoxy resin is favorable for the effect in actual use.
In a preferred embodiment of the present invention, the toughening agent is one or more of high polymerization degree phenoxy resin PKHH, nylon powder, and hydroxyl-terminated nitrile rubber.
In the invention, the toughening agents have good compatibility with epoxy resin, and can fully exert the toughening effect, so that the cured product has stronger impact resistance. The thermoplastic toughening agents have good toughening effect and do not influence the flame retardant effect.
In a preferred embodiment of the present invention, the curing agent is one or both of dicyandiamide or diaminodiphenylmethane.
The curing agent itself needs to be fully reacted with the epoxy resin for curing for about 2 hours at 160 ℃, and the accelerator can reduce the curing temperature of the whole system and can be cured for about 2 hours at 120 ℃.
In a preferred embodiment of the present invention, the accelerator is one or more of organic urea compounds.
The invention also discloses a preparation method of the high-flame-retardance medium-temperature curing epoxy resin premix, which comprises the following steps:
s1, weighing the components in the claim 1 according to parts by weight;
s2, adding a coupling agent into the epoxy resin, heating to 70-90 ℃ for heat preservation, heating to 140-160 ℃, adding a toughening agent, and then preserving heat;
s3, cooling the mixture prepared in the step S2 to 65-70 ℃, sequentially adding the flame retardant, the coupling agent, the curing agent and the accelerator, uniformly stirring, and discharging.
The invention also discloses application of the high-flame-retardance medium-temperature curing epoxy resin premix in preparing a functional resin adhesive film material.
The invention also discloses application of the high-flame-retardance medium-temperature curing epoxy resin premix in preparation of an adhesive.
According to the invention, through selecting the epoxy resin and the coupling agent with proper types and proportions, the adding proportion of the flame retardant is less and is not more than 35%, so that the tensile shear strength is not affected on the premise of ensuring the flame retardant property.
Preferably, the liquid bisphenol A epoxy resin is selected from the group consisting of Nanying NPEL-127, NPEL-128, etc., the solid novolac epoxy resin is selected from the group consisting of Nanying NPCN-702, NPCN-703, etc., and the solid brominated epoxy resin is selected from the group consisting of Nanying NPEB-400, nanying star 153-B, etc.
Preferably, the organic urea compound comprises an azure UR200 and an azure UR300.
Specifically, the preparation method of the invention comprises the following steps:
(1) Weighing: weighing 20-40 parts of liquid bisphenol A epoxy resin, 10-20 parts of solid phenolic epoxy resin, 10-15 parts of solid brominated epoxy resin, 5-10 parts of toughening agent, 20-30 parts of flame retardant, 0.5-2 parts of coupling agent, 5-10 parts of curing agent and 2-5 parts of accelerator according to parts by weight;
(2) Preparing a resin mixture: the liquid bisphenol A epoxy resin weighed in the step (1) is divided into 2 parts by mass equally, wherein the first part is pure liquid bisphenol A epoxy resin, and the second part is mixed with a curing agent and an accelerator by adopting a high-speed dispersing machine and a three-roller mill to form curing agent paste;
(3) Mixing the resin components: adding the pure liquid bisphenol A epoxy resin component into a reaction kettle, raising the temperature to 80 ℃, sequentially adding the solid phenolic epoxy resin, the solid brominated epoxy resin and the coupling agent, fully preserving heat and mixing for 50-60 min at 80 ℃, raising the temperature to 150 ℃, adding the toughening agent, and preserving heat for 50-60 min;
(4) Blending and discharging: and (3) reducing the temperature of the components in the step (3) to 65-70 ℃, sequentially adding the flame retardant and the curing agent paste in the step (2), stirring for 30min until the system is uniform, and discharging.
Compared with the Chinese patent with the publication number of CN201610371422.9, the antimony trioxide is used as a main flame retardant and combines the interaction of the oligomeric phosphate, so that a higher flame retardant effect is achieved, the technical problem of preparing the adhesive film by the resin premix is considered, and the mass stable production is facilitated.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the epoxy resin and the coupling agent with proper types and proportions are selected, so that the adding proportion of the flame retardant is less and is not more than 35%, the flame retardance of the casting body can reach self-extinguishment after leaving fire on the premise of ensuring the flame retardance, the effect of the coupling agent enables the flame retardant and the epoxy resin to have a small influence on the tensile shear strength, and the tensile shear strength is more than 23Mpa. The premix can be coated on release paper at about 60 ℃ to form an adhesive film with uniform gram weight, and can be stored at 20-30 ℃ for 60 days and at 0 ℃ for 1 year.
Drawings
FIG. 1 is a film made from an epoxy resin premix in example 1 of the present application.
FIG. 2 is a photograph of a single lap test specimen made of epoxy resin premix in example 1 of the present application.
FIG. 3 is a photograph of a single lap test specimen made of epoxy resin premix in example 1 of the present application.
Detailed Description
The invention is further illustrated below with reference to specific examples.
Example 1
The raw material compositions of the high flame retardant medium temperature cured epoxy resin premix are shown in Table 1.
The bisphenol A epoxy resin is divided into 2 parts by mass equally, wherein the first part is pure liquid bisphenol A epoxy resin, and the second part is mixed with a curing agent and an accelerator by adopting a high-speed dispersing machine and a three-roller mill to form curing agent paste; adding the pure liquid bisphenol A epoxy resin component into a reaction kettle, raising the temperature to 80 ℃, sequentially adding the solid phenolic epoxy resin, the solid brominated epoxy resin and the coupling agent, fully preserving heat and mixing for 50min at 80 ℃, raising the temperature to 150 ℃, adding the toughening agent, preserving heat for 50min, reducing the kettle temperature to 65-70 ℃, adding the curing agent paste, stirring for 30min, and discharging.
Example 2
The raw material compositions of the high flame retardant medium temperature cured epoxy resin premix are shown in Table 1.
The bisphenol A epoxy resin is divided into 2 parts by mass equally, wherein the first part is pure liquid bisphenol A epoxy resin, and the second part is mixed with a curing agent and an accelerator by adopting a high-speed dispersing machine and a three-roller mill to form curing agent paste; adding the pure liquid bisphenol A epoxy resin component into a reaction kettle, raising the temperature to 80 ℃, sequentially adding the solid phenolic epoxy resin, the solid brominated epoxy resin and the coupling agent, fully preserving heat and mixing for 50min at 80 ℃, raising the temperature to 150 ℃, adding the toughening agent, preserving heat for 50min, reducing the kettle temperature to 65-70 ℃, adding the curing agent paste, stirring for 30min, and discharging.
Example 3
The raw material compositions of the high flame retardant medium temperature cured epoxy resin premix are shown in Table 1.
The bisphenol A epoxy resin is divided into 2 parts by mass equally, wherein the first part is pure liquid bisphenol A epoxy resin, and the second part is mixed with a curing agent and an accelerator by adopting a high-speed dispersing machine and a three-roller mill to form curing agent paste; adding the pure liquid bisphenol A epoxy resin component into a reaction kettle, raising the temperature to 80 ℃, sequentially adding the solid phenolic epoxy resin, the solid brominated epoxy resin and the coupling agent, fully preserving heat and mixing for 50min at 80 ℃, raising the temperature to 150 ℃, adding the toughening agent, preserving heat for 50min, reducing the kettle temperature to 65-70 ℃, adding the curing agent paste, stirring for 30min, and discharging.
Comparative example one
The raw material compositions of the high flame retardant medium temperature cured epoxy resin premix are shown in Table 1.
The bisphenol A epoxy resin is divided into 2 parts by mass equally, wherein the first part is pure liquid bisphenol A epoxy resin, and the second part is mixed with a curing agent and an accelerator by adopting a high-speed dispersing machine and a three-roller mill to form curing agent paste; adding the pure liquid bisphenol A epoxy resin component into a reaction kettle, raising the temperature to 80 ℃, sequentially adding the solid phenolic epoxy resin, the solid brominated epoxy resin and the coupling agent, fully preserving heat and mixing for 50min at 80 ℃, raising the temperature to 150 ℃, adding the toughening agent, preserving heat for 50min, reducing the kettle temperature to 65-70 ℃, adding the curing agent paste, stirring for 30min, and discharging.
Comparative example two
The raw material compositions of the high flame retardant medium temperature cured epoxy resin premix are shown in Table 1.
The bisphenol A epoxy resin is divided into 2 parts by mass equally, wherein the first part is pure liquid bisphenol A epoxy resin, and the second part is mixed with a curing agent and an accelerator by adopting a high-speed dispersing machine and a three-roller mill to form curing agent paste; adding the pure liquid bisphenol A epoxy resin component into a reaction kettle, raising the temperature to 80 ℃, sequentially adding the solid phenolic epoxy resin, the solid brominated epoxy resin and the coupling agent, fully preserving heat and mixing for 50min at 80 ℃, raising the temperature to 150 ℃, adding the toughening agent, preserving heat for 50min, reducing the kettle temperature to 65-70 ℃, adding the curing agent paste, stirring for 30min, and discharging.
Comparative example three
The raw material compositions of the high flame retardant medium temperature cured epoxy resin premix are shown in Table 1.
The bisphenol A epoxy resin is divided into 2 parts by mass equally, wherein the first part is pure liquid bisphenol A epoxy resin, and the second part is mixed with a curing agent and an accelerator by adopting a high-speed dispersing machine and a three-roller mill to form curing agent paste; adding the pure liquid bisphenol A epoxy resin component into a reaction kettle, raising the temperature to 80 ℃, sequentially adding the solid phenolic epoxy resin, the solid brominated epoxy resin and the coupling agent, fully preserving heat and mixing for 50min at 80 ℃, raising the temperature to 150 ℃, adding the toughening agent, preserving heat for 50min, reducing the kettle temperature to 65-70 ℃, adding the curing agent paste, stirring for 30min, and discharging.
Comparative example four
The raw material compositions of the high flame retardant medium temperature cured epoxy resin premix are shown in Table 1.
The bisphenol A epoxy resin is divided into 2 parts by mass equally, wherein the first part is pure liquid bisphenol A epoxy resin, and the second part is mixed with a curing agent and an accelerator by adopting a high-speed dispersing machine and a three-roller mill to form curing agent paste; adding the pure liquid bisphenol A epoxy resin component into a reaction kettle, increasing the temperature to 80 ℃, sequentially adding the solid phenolic epoxy resin and the solid brominated epoxy resin, fully preserving heat and mixing for 50min at 80 ℃, then increasing the temperature to 150 ℃, adding the toughening agent, preserving heat for 50min, reducing the kettle temperature to 65-70 ℃, adding the curing agent paste, stirring for 30min, and discharging.
Comparative example five
The raw material compositions of the high flame retardant medium temperature cured epoxy resin premix are shown in Table 1.
The bisphenol A epoxy resin is divided into 2 parts by mass equally, wherein the first part is pure liquid bisphenol A epoxy resin, and the second part is mixed with a curing agent and an accelerator by adopting a high-speed dispersing machine and a three-roller mill to form curing agent paste; adding the pure liquid bisphenol A epoxy resin component into a reaction kettle, raising the temperature to 80 ℃, sequentially adding the solid phenolic epoxy resin, the solid brominated epoxy resin and the coupling agent, fully preserving heat and mixing for 50min at 80 ℃, raising the temperature to 150 ℃, adding the toughening agent, preserving heat for 50min, reducing the kettle temperature to 65-70 ℃, adding the curing agent paste, stirring for 30min, and discharging.
Comparative example six
The raw material compositions of the high flame retardant medium temperature cured epoxy resin premix are shown in Table 1.
The bisphenol A epoxy resin is divided into 2 parts by mass equally, wherein the first part is pure liquid bisphenol A epoxy resin, and the second part is mixed with a curing agent and an accelerator by adopting a high-speed dispersing machine and a three-roller mill to form curing agent paste; adding the pure liquid bisphenol A epoxy resin component into a reaction kettle, raising the temperature to 80 ℃, sequentially adding the solid phenolic epoxy resin, the solid brominated epoxy resin and the coupling agent, fully preserving heat and mixing for 50min at 80 ℃, raising the temperature to 150 ℃, adding the toughening agent, preserving heat for 50min, reducing the kettle temperature to 65-70 ℃, adding the curing agent paste, stirring for 30min, and discharging.
Table 1 raw material compositions in examples one to three, comparative examples one to six
The main properties of the resin systems prepared in examples one to three and comparative examples one to six are shown in Table 2.
TABLE 2 Primary Performance test of resin premixes prepared in examples one to three, comparative examples one to six
In the first comparative example, the quality of the antimony trioxide and the oligomeric phosphate liquid flame retardant is relatively high, and the flame retardant effect of the resin system is also not ideal. The quality of the antimony trioxide and the oligomeric phosphate liquid flame retardant in the second comparative example is lower, and the flame retardant effect of the resin premix is poorer. In the fourth comparative example, no coupling agent in the resin causes delamination or sedimentation of the inorganic flame retardant, so that the flame retardant in the casting body is uneven, and the flame retardant performance of the resin system is affected. In the fifth comparative example, the premixing effect of the resin of other common coupling agents (Jiangxi Chen Guang KH-550) is similar to that of the fourth comparative example, and the inorganic flame retardant has layering or sedimentation phenomenon, so that the flame retardant property is affected. In the sixth comparative example, the ratio of antimony trioxide to the liquid flame retardant of the oligomeric phosphate is changed (the oligomeric phosphate is changed to a higher ratio), and the flame retardant effect is not ideal.
The resin premixes prepared in examples one to three and comparative examples one to six were prepared into resin adhesive films, and single lap test pieces were prepared and oven-cured at 120℃for 2 hours, and the properties after curing of the sample plates are shown in Table 3.
TABLE 3 Properties of samples made from the resin premixes prepared in examples one to three and comparative examples one to six
In the third comparative example, the flame retardant increases the quality of the flame retardant, the powder feel is strong when the single lap joint part is used for sample preparation, the increase of the flame retardant obviously influences the strength after curing, and the tensile shear strength is obviously reduced.
As shown in figure 1, the epoxy resin premix of the invention can be used for preparing a glue film, can be uniformly and thinly paved on a use object surface, has a flame retardant effect without affecting the tensile shear strength of a conventional epoxy adhesive, has higher flame retardant property, and can be automatically extinguished after being vertically combusted for 30 seconds at 800 ℃.
Claims (7)
1. A method for preparing a medium temperature cured epoxy resin premix, comprising the steps of:
(1) Weighing: weighing 20-40 parts of liquid bisphenol A epoxy resin, 10-20 parts of solid phenolic epoxy resin, 10-15 parts of solid brominated epoxy resin, 5-10 parts of toughening agent, 20-30 parts of flame retardant, 0.5-2 parts of coupling agent, 5-10 parts of curing agent and 2-5 parts of accelerator according to parts by weight;
(2) Preparing a resin mixture: the liquid bisphenol A epoxy resin weighed in the step (1) is divided into 2 parts by mass equally, wherein the first part is pure liquid bisphenol A epoxy resin, and the second part is mixed with a curing agent and an accelerator by adopting a high-speed dispersing machine and a three-roller mill to form curing agent paste;
(3) Mixing the resin components: adding pure liquid bisphenol A epoxy resin into a reaction kettle, raising the temperature to 80 ℃, sequentially adding solid phenolic epoxy resin, solid brominated epoxy resin and coupling agent, fully preserving heat and mixing for 50-60 min at 80 ℃, raising the temperature to 150 ℃, adding a toughening agent, and preserving heat for 50-60 min;
(4) Blending and discharging: reducing the components in the step (3) to 65-70 ℃, sequentially adding the flame retardant and the curing agent paste in the step (2), stirring for 30min until the system is uniform, and discharging;
the flame retardant comprises the following components in percentage by mass: 3-5 of antimony trioxide and oligomeric phosphate liquid flame retardant, wherein the coupling agent is BYK-C8001 of Pick chemical Germany.
2. A method of preparing a medium temperature cure epoxy resin premix as in claim 1, wherein: the toughening agent is one or more of high-polymerization-degree phenoxy resin PKHH, nylon powder and hydroxyl-terminated nitrile rubber.
3. A method of preparing a medium temperature cure epoxy resin premix as in claim 1, wherein: the curing agent is one or two of dicyandiamide and diamine diphenyl methane.
4. A method of preparing a medium temperature cure epoxy resin premix as in claim 1, wherein: the accelerator is an organic urea compound.
5. A medium temperature cured epoxy resin premix obtainable by the process for preparing a medium temperature cured epoxy resin premix according to any of claims 1-3.
6. Use of the medium temperature cured epoxy resin premix of claim 5 for the preparation of a functional resin adhesive film material.
7. Use of the medium temperature cured epoxy resin premix of claim 5 for the preparation of adhesives.
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