CN105131827A - Modified cyanate ester resin surface film and preparation method thereof - Google Patents
Modified cyanate ester resin surface film and preparation method thereof Download PDFInfo
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- CN105131827A CN105131827A CN201510599888.XA CN201510599888A CN105131827A CN 105131827 A CN105131827 A CN 105131827A CN 201510599888 A CN201510599888 A CN 201510599888A CN 105131827 A CN105131827 A CN 105131827A
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Abstract
The invention provides a modified cyanate ester resin surface film and a preparation method thereof, relates to a resin surface film and a preparation method thereof, and solves the problems that an existing epoxy composite surface film and cyanate ester resin prepreg are not matched well, as a result, the curing temperature is inconsistent, the long-term working service temperature is low, the dielectric property of a workpiece cannot meet the standard and the like. The cyanate ester resin surface film comprises cyanate ester resin, a polymerization process modifier, a toughening modifier, a curing accelerator, a coupling agent, inorganic filler, UV (ultraviolet) stabilizer and a carrier. The preparation method of the cyanate ester resin surface film comprises steps as follows: cyanate ester resin and the modifier are kneaded, and copolymerized and modified cyanate ester resin is obtained; the toughening modifier, the coupling agent, the inorganic filler and the UV stabilizer are added and mixed, and a modified cyanate ester resin surface film adhesive is obtained; a three-roller rotating coating film making machine is adopted for film forming. The modified cyanate ester resin surface film is used for improving the surface quality of a cyanate ester resin composite structural member.
Description
Technical field
The present invention relates to a kind of modified cyanic acid ester resin surface film and preparation method thereof.
Background technology
Cyanate ester resin composite material relies on the excellent advantage such as thermotolerance, mechanical property, dimensional stability, humidity resistance, low-dielectric energy to be widely used in aerospace field, as the manufacture of aircraft stealth structure, advanced capabilities radar cover structure etc.
For giving full play to the loss of weight advantage of matrix material on aerospace structure, easily produce the problem of surface quality for composite element, countries in the world all adopt at multiple material component surface laid surface film to improve surface quality problems.As FM99, SUPERMASTER905 of Cytec company of the U.S., EA9845, EA9895, EA9837.1 of Henkel company of Germany, the J-266 surface film material of Institute of Petrochemistry, HLJ Academy of Science, this kind of surface film has the features such as good fillibility, mobility, surface hardness, anti-tiny crack characteristic and weather resistance.Composite material surface film can also be resisted due to complex environment factors such as temperature, humidity, wind and rain and surrounding mediums in addition, prevents composite element from occurring weathering, the problem such as aging.But existing surface film kind is all for the development of epoxy group(ing) prepreg, and its matrix resin is epoxy resin, bad with cyanate ester resin prepreg matching, the problems such as cause solidification value inconsistent, life-time service temperature is low, and product dielectric properties are not up to standard.For fully playing the advantage of cyanate ester resin prepreg, this patent proposes a kind of modified cyanic acid ester resin surface film and preparation method thereof, improve the compactness on cyanate ester resin composite material surface, improve its surface quality, reduce the operation of one drop priming Puttying, a cyanate ester resin composite material article surface that can supply spraying is provided.
With epoxy type surface film method for toughening unlike, the traditional method for toughening of epoxy type surface film is that under epoxy resin and thermoplastic engineering plastic high temperature, (about 200 DEG C) hot melt is blended, but this method for toughening controls reaction cyanate ester resin is difficult and affects storage period of cyanate ester resin surface film.In addition, it is comparatively large that common rubber toughened method causes resin system second-order transition temperature to decline, and effects on surface film hardness also has certain influence.This patent adopts the block copolymer-toughened cyanate ester resin of response type, it is one end graft reaction group at segmented copolymer, the curing reaction of cyanate ester resin can be participated in, increase the bonding force of cyanate ester resin and segmented copolymer, transmit rupture stress to greatest extent, fully by Stress transmit to toughness reinforcing inside particles, plastic deformation effectively can be there is to consume failure energy.The second-order transition temperature impact of this method for toughening his-and-hers watches facial mask is less in addition.
Summary of the invention
The present invention be in order to solve existing epoxy type composite material surface film and cyanate ester resin prepreg matching bad, the problems such as cause solidification value inconsistent, life-time service temperature is low, and product dielectric properties are not up to standard.A kind of modified cyanic acid ester resin surface film and preparation method thereof is provided.
A kind of modified cyanic acid ester resin surface film of the present invention, it is made up of the cyanate ester resin of 75 ~ 100 parts, 25 ~ 40 parts of copolymerization technology properties-correcting agent, the plasticized modifier of 10 ~ 25 parts, 2 ~ 4 parts of curing catalysts, 1 ~ 3 part of coupling agent, the mineral filler of 1 ~ 4 part, 1 ~ 5 part of UV stablizer and carriers according to parts by weight.
The preparation method of a kind of modified cyanic acid ester resin surface film of the present invention carries out according to following steps:
One, the cyanate ester resin of 75 ~ 100 parts, the copolymerization technology properties-correcting agent of 25 ~ 50 parts, 10 ~ 25 parts of plasticized modifiers, 2 ~ 4 parts of curing catalysts, the mineral filler of 1 ~ 3 part of coupling agent 1 ~ 4 part and 1 ~ 5 part of UV stablizer is taken by mass fraction;
Two, cyanate ester resin step one taken and properties-correcting agent join in kneader and under kneading state, are heated to 90 ~ 150 DEG C and are incubated 20 ~ 30min, obtain copolymerization modified cyanic acid ester resin;
Three, the toughner taken in step one is added in kneader, together after the mixing of polymeric modification cyanate ester resin, keep kneader temperature to be 90 ~ 150 DEG C, carry out kneading 10 ~ 30min, obtain hybrid resin;
Four, hybrid resin is cooled to 60 ~ 80 DEG C, then curing catalyst that step one takes, coupling agent, mineral filler and UV stablizer is added, blended 10 ~ 30min in kneader, then vacuumize kneading 10 ~ 30min, obtain modified cyanic acid ester resin surface film sizing;
Five, above-mentioned sizing material is turned film forming on painting film-making machine at auxiliary lower employing three roller of carrier, surface film thicknesses is 0.10mm ~ 0.18mm, and film-forming temperature is 60 ~ 80 DEG C.
A kind of modified cyanic acid ester resin surface film advantage of the present invention is as follows:
1, present invention employs three kinds of cyanate resin alicyclic monomers is matrix resin, wherein bisphenol A cyanate ester, Novolac Cyanate Eater Resin, bisphenol-f type cyanate, makes the second-order transition temperature of modified cyanic acid ester resin surface film reach more than 260 DEG C; Frequency is under 10Ghz, and specific inductivity is less than 3.1, and tangent of the dielectric loss angle value is less than 0.012.
2, the present invention adopts and carries out toughness reinforcing with reactive segmented copolymer his-and-hers watches facial mask, increase interface cohesion and the cohesive strength of segmented copolymer and interlaminar resin, realize the chemical bonding of particle and matrix resin, effectively can increase resin toughness and opposing micro-crack extension ability.
3, after a kind of modified cyanic acid ester resin surface film solidification of the present invention, pencil hardness is greater than 6H, has uv-resistant radiation, solvent resistance, the features such as cold-hot circulation.
Accompanying drawing explanation
Fig. 1 is cyanate surface film and prepreg co-curing frock schematic diagram; Wherein, 1. vacuum bag; 2. gas permeable material; 3. equal pressing plate; 4. release materials; 5. the stacked version of cyanate prepreg or prepreg covering honeycomb sandwich panel; 6. cyanate surface film; 7. demoulding material; 8. mould; 9. joint strip;
Fig. 2 is second-order transition temperature figure after the solidification of test 1 ~ 3 sample;
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: a kind of modified cyanic acid ester resin surface film of present embodiment, it is made up of the cyanate ester resin of 75 ~ 100 parts, 25 ~ 40 parts of copolymerization technology properties-correcting agent, the plasticized modifier of 10 ~ 25 parts, 2 ~ 4 parts of curing catalysts, 1 ~ 3 part of coupling agent, the mineral filler of 1 ~ 4 part, 1 ~ 5 part of UV stablizer and carriers according to parts by weight.
Embodiment two: present embodiment and embodiment one unlike: cyanate ester resin by bisphenol A cyanate ester resin, Novolac Cyanate Ester Resins and bisphenol-f type cyanate ester resin in mass ratio for the ratio of 5:3:1 forms.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: copolymerization technology properties-correcting agent by diallyl bisphenol S modified bismaleimide resin and diallyl bisphenol modified bismaleimide resin in mass ratio for 2:1 ratio forms.Other is identical with embodiment one or two.
Embodiment four: present embodiment and embodiment one to three unlike: plasticized modifier is segmented copolymer; Described segmented copolymer adopts glycidyl methacrylate (GMA), Rocryl 410 (HPMA) or methacrylic acid diamine ethyl ester (DMA) to activate; Other is identical with embodiment one to three.
The segmented copolymer of present embodiment is MBS, polystyrene-poly methyl methacrylate, butyl polyacrylate to be main chain-polymethylmethacrylate be in the segmented copolymer of side chain one or more by arbitrarily than forming.
Embodiment five: one of present embodiment and embodiment one to four are by arbitrarily than forming by one or more in 2-ethyl-4-methylimidazole, 1,1-dimethyl-3-phenylurea, diallyl bisphenol, 2-chavicol unlike: curing catalyst.Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: coupling agent by one or more in γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane, methyl tri-tert peroxy-silane by arbitrarily than forming.Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: mineral filler by one or more in ceramic microspheres, hollow glass micropearl, fumed silica, talcum powder, boron powder, boron nitride powder by arbitrarily than forming.Other is identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: UV stablizer by one or more in rutile type nano titanium dioxide, nano zine oxide, ESCALOL 567, Octabenzone by arbitrarily than forming.Other is identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: carrier is polyester non-woven fabric, glass fiber woven cloth or silica fibrage cloth.Other is identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: modified cyanic acid ester surface film is made up of the cyanate ester resin of 80 ~ 100 parts, 30 ~ 40 parts of properties-correcting agent, the plasticized modifier of 15 ~ 25 parts, 2 ~ 4 parts of curing catalysts, 1 ~ 3 part of coupling agent, the mineral filler of 1 ~ 4 part, 1 ~ 5 part of UV stablizer and carriers according to parts by weight.Other is identical with one of embodiment one to nine.
Embodiment 11: one of present embodiment and embodiment one to ten unlike: modified cyanic acid ester surface film is made up of the cyanate ester resin of 80 ~ 90 parts, 30 ~ 35 parts of properties-correcting agent, the plasticized modifier of 15 ~ 20 parts, 2 ~ 3 parts of curing catalysts, 1 ~ 2 part of coupling agent, the mineral filler of 1 ~ 3 part, 1 ~ 4 part of UV stablizer and carriers according to parts by weight.Other is identical with one of embodiment one to ten.
Embodiment 12: one of present embodiment and embodiment one to ten one unlike: modified cyanic acid ester surface film is made up of the cyanate ester resin of 80 ~ 85 parts, 30 ~ 32 parts of properties-correcting agent, the plasticized modifier of 15 ~ 18 parts, 2 ~ 3 parts of curing catalysts, 1 ~ 2 part of coupling agent, the mineral filler of 1 ~ 3 part, 1 ~ 3 part of UV stablizer and carriers according to parts by weight.Other is identical with one of embodiment one to ten one.
Embodiment 12: one of present embodiment and embodiment one to ten one unlike: modified cyanic acid ester surface film is made up of the cyanate ester resin of 82 parts, 30 parts of properties-correcting agent, the plasticized modifier of 16 parts, 3 parts of curing catalysts, 2 parts of coupling agents, the mineral filler of 3 parts, 2 parts of UV stablizers and carriers according to parts by weight.Other is identical with one of embodiment one to ten one.
Embodiment 13: one of present embodiment and embodiment one to ten two unlike: modified cyanic acid ester surface film is made up of the cyanate ester resin of 80 parts, 30 parts of properties-correcting agent, the plasticized modifier of 15 parts, 3 parts of curing catalysts, 2 parts of coupling agents, the mineral filler of 3 parts, 2 parts of UV stablizers and carriers according to parts by weight.Other is identical with one of embodiment one to ten two.
Embodiment 14: one of present embodiment and embodiment one to ten three unlike: modified cyanic acid ester surface film is made up of the cyanate ester resin of 90 parts, 30 parts of properties-correcting agent, the plasticized modifier of 20 parts, 3 parts of curing catalysts, 2 parts of coupling agents, the mineral filler of 4 parts, 3 parts of UV stablizers and carriers according to parts by weight.Other is identical with one of embodiment one to ten three.
Embodiment 15: one of present embodiment and embodiment one to ten four unlike: modified cyanic acid ester surface film is made up of the cyanate ester resin of 100 parts, 30 parts of properties-correcting agent, the plasticized modifier of 25 parts, 3.5 parts of curing catalysts, 2 parts of coupling agents, the mineral filler of 4 parts, 3 parts of UV stablizers and carriers according to parts by weight.Other is identical with one of embodiment one to ten four.
Embodiment 16: the preparation method of a kind of modified cyanic acid ester resin surface film of present embodiment, is characterized in that a kind of modified cyanic acid ester resin surface film preparation method carries out according to following steps:
One, the cyanate ester resin of 75 ~ 100 parts, the copolymerization technology properties-correcting agent of 25 ~ 50 parts, 10 ~ 25 parts of plasticized modifiers, 2 ~ 4 parts of curing catalysts, the mineral filler of 1 ~ 3 part of coupling agent 1 ~ 4 part and 1 ~ 5 part of UV stablizer is taken by mass fraction;
Two, cyanate ester resin step one taken and properties-correcting agent join in kneader and under kneading state, are heated to 90 ~ 150 DEG C and are incubated 20 ~ 30min, obtain copolymerization modified cyanic acid ester resin;
Three, the toughner taken in step one is added in kneader, together after the mixing of polymeric modification cyanate ester resin, keep kneader temperature to be 90 ~ 150 DEG C, carry out kneading 10 ~ 30min, obtain hybrid resin;
Four, hybrid resin is cooled to 60 ~ 80 DEG C, then curing catalyst that step one takes, coupling agent, mineral filler and UV stablizer is added, blended 10 ~ 30min in kneader, then vacuumize kneading 10 ~ 30min, obtain modified cyanic acid ester resin surface film sizing;
Five, above-mentioned sizing material is turned film forming on painting film-making machine at auxiliary lower employing three roller of carrier, surface film thicknesses is 0.10mm ~ 0.18mm, and film-forming temperature is 60 ~ 80 DEG C.
Vacuum kneader vacuum tightness described in present embodiment is not less than-0.092MPa.
Embodiment 17: present embodiment and embodiment 16 unlike: cyanate ester resin by bisphenol A cyanate ester resin, Novolac Cyanate Ester Resins and bisphenol-f type cyanate ester resin in mass ratio for the ratio of 5:3:1 forms.Other is identical with embodiment 16.
Embodiment 18: present embodiment and embodiment 16 or 17 unlike: copolymerization technology properties-correcting agent by diallyl bisphenol S modified bismaleimide resin and diallyl bisphenol modified bismaleimide resin in mass ratio for 2:1 ratio forms.Other is identical with embodiment 16 or 17.
Embodiment 19: one of present embodiment and embodiment ten six to ten eight unlike: plasticized modifier is segmented copolymer; Described segmented copolymer adopts glycidyl methacrylate (GMA), Rocryl 410 (HPMA) or methacrylic acid diamine ethyl ester (DMA) to activate.Other is identical with one of embodiment ten six to ten eight.
The segmented copolymer of present embodiment is MBS, polystyrene-poly methyl methacrylate, butyl polyacrylate to be main chain-polymethylmethacrylate be in the segmented copolymer of side chain one or more by arbitrarily than forming.
Embodiment 20: one of present embodiment and embodiment ten six to two ten unlike: curing catalyst be by one or more in 2-ethyl-4-methylimidazole, 1,1-dimethyl-3-phenylurea, diallyl bisphenol, 2-chavicol by arbitrarily than forming.Other is identical with one of embodiment ten six to two ten.
Embodiment 22: one of present embodiment and embodiment ten six to two 11 unlike: coupling agent by one or more in γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane, methyl tri-tert peroxy-silane by arbitrarily than forming.Other is one of ten six to two ten one identical with embodiment.
Embodiment 23: one of present embodiment and embodiment ten six to two 12 unlike: mineral filler by one or more in ceramic microspheres, hollow glass micropearl, fumed silica, talcum powder, boron powder, boron nitride powder by arbitrarily than forming.Other is one of ten six to two ten two identical with embodiment.
Embodiment 24: one of present embodiment and embodiment ten six to two 13 unlike: UV stablizer by one or more in rutile type nano titanium dioxide, nano zine oxide, ESCALOL 567, Octabenzone by arbitrarily than forming.Other is one of ten six to two ten three identical with embodiment.
Embodiment 25: one of present embodiment and embodiment ten six to two 14 unlike: carrier is polyester non-woven fabric, glass fiber woven cloth or silica fibrage cloth.Other is one of ten six to two ten four identical with embodiment.
Embodiment 26: one of present embodiment and embodiment ten six to two 15 unlike: take the cyanate ester resin of 80 ~ 100 parts, 30 ~ 40 parts of properties-correcting agent, the plasticized modifier of 15 ~ 25 parts, 2 ~ 4 parts of curing catalysts, 1 ~ 3 part of coupling agent, the mineral filler of 1 ~ 4 part and 1 ~ 5 part of UV stablizer by mass fraction.Other is one of ten six to two ten five identical with embodiment.
Embodiment 27: one of present embodiment and embodiment ten six to two 16 unlike: take the cyanate ester resin of 80 ~ 90 parts, 30 ~ 35 parts of properties-correcting agent, the plasticized modifier of 15 ~ 20 parts, 2 ~ 3 parts of curing catalysts, 1 ~ 2 part of coupling agent, the mineral filler of 1 ~ 3 part and 1 ~ 4 part of UV stablizer by mass fraction.Other is one of ten six to two ten six identical with embodiment.
Embodiment 28: one of present embodiment and embodiment ten six to two 17 unlike: take the cyanate ester resin of 80 ~ 85 parts, 30 ~ 32 parts of properties-correcting agent, the plasticized modifier of 15 ~ 18 parts, 2 ~ 3 parts of curing catalysts, 1 ~ 2 part of coupling agent, the mineral filler of 1 ~ 3 part and 1 ~ 3 part of UV stablizer by mass fraction.Other is one of ten six to two ten seven identical with embodiment.
Embodiment 29: one of present embodiment and embodiment ten six to two 18 unlike: take the cyanate ester resin of 82 parts, 30 parts of properties-correcting agent, the plasticized modifier of 16 parts, 3 parts of curing catalysts, 2 parts of coupling agents, the mineral filler of 3 parts and 2 parts of UV stablizers by mass fraction.Other is one of ten six to two ten eight identical with embodiment.
Embodiment 30: one of present embodiment and embodiment ten six to two 19 unlike: take the cyanate ester resin of 80 parts, 30 parts of properties-correcting agent, the plasticized modifier of 15 parts, 3 parts of curing catalysts, 2 parts of coupling agents, the mineral filler of 3 parts and 2 parts of UV stablizers by mass fraction.Other is one of ten six to two ten nine identical with embodiment.
Embodiment 31: one of present embodiment and embodiment ten six to three ten unlike: take the cyanate ester resin of 90 parts, 30 parts of properties-correcting agent, the plasticized modifier of 20 parts, 3 parts of curing catalysts, 2 parts of coupling agents, the mineral filler of 4 parts and 3 parts of UV stablizers by mass fraction.Other is identical with one of embodiment ten six to three ten.
Embodiment 32: one of present embodiment and embodiment ten six to three 11 unlike: take the cyanate ester resin of 100 parts, 30 parts of properties-correcting agent, the plasticized modifier of 25 parts, 3.5 parts of curing catalysts, 2 parts of coupling agents, the mineral filler of 4 parts and 3 parts of UV stablizers by mass fraction.Other is one of ten six to three ten one identical with embodiment.
Embodiment 33: one of present embodiment and embodiment ten six to three 12 unlike: in step 4, hybrid resin is cooled to 60 ~ 65 DEG C, then curing catalyst that step one takes, coupling agent, mineral filler and UV stablizer is added, blended 20min in kneader, vacuumize again and mediate 15min, obtain modified cyanic acid ester surface film sizing.Other is one of ten six to three ten one identical with embodiment.
Embodiment 34: one of present embodiment and embodiment ten six to three 12 unlike: cyanate ester resin and copolymerization properties-correcting agent join in kneader and under kneading state, are heated to 110 ~ 120 DEG C and obtain copolymerization modified cyanic acid ester resin after being incubated 25 ~ 30 minutes.Other is one of ten six to three ten two identical with embodiment.
By following verification experimental verification beneficial effect of the present invention:
Test 1, this preparation method testing a kind of modified cyanic acid ester resin surface film carry out according to the following steps:
One, the cyanate ester resin of 80 parts, the copolymerization technology properties-correcting agent of 30 parts, 15 parts of plasticized modifiers, 3 parts of curing catalysts, 2 parts of coupling agents, the mineral filler of 3 parts and 2 parts of UV stablizers are taken by mass parts;
Two, cyanate ester resin step one taken and properties-correcting agent join in kneader and under kneading state, are heated to 120 DEG C and are incubated 25min, obtain copolymerization modified cyanic acid ester resin;
Three, the toughner taken in step one is added in kneader, together after the mixing of polymeric modification cyanate ester resin, keep kneader temperature to be 110 DEG C, carry out kneading 30min, obtain hybrid resin;
Four, hybrid resin is cooled to 70 DEG C, then adds curing catalyst that step one takes, coupling agent, mineral filler and UV stablizer, blended 20min in kneader, then vacuumize and mediate 20min, obtain modified cyanic acid ester resin surface film sizing;
Five, above-mentioned sizing material is turned painting film-making machine at auxiliary lower employing three roller of carrier, be film forming under the condition of 65 DEG C at film-forming temperature, make the modified cyanic acid ester resin surface film that thickness is 0.15mm ± 0.02mm.
The cyanate ester resin of this test is made up of bisphenol A cyanate ester resin, Novolac Cyanate Ester Resins, bisphenol-f type cyanate ester resin, and the consumption of three is the ratio composition of 5:3:1 in mass ratio;
Copolymerization technology properties-correcting agent by diallyl bisphenol S modified quartz sand, diallyl bisphenol modified quartz sand in mass ratio for 2:1 ratio forms;
Plasticized modifier is MBS segmented copolymer, it adopts glycidyl methacrylate (GMA) to activate block polymer, effective bonding is produced between the block polymer of Shi Dai response type functional group and matrix resin, effectively can resist the transmission of stress, give full play to the toughening effect of segmented copolymer;
Curing catalyst is 2-ethyl-4-methylimidazole;
Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane;
The ratio that mineral filler is 10:1 by hollow glass micro-ball (soda lime borosilicate glass), fumed silica in mass ratio forms;
UV stablizer is rutile type nano titanium dioxide;
Vacuum kneader vacuum tightness is not less than-0.092MPa;
Carrier is polyester non-woven fabric.
Test 2, this preparation method testing a kind of modified cyanic acid ester resin surface film carry out according to the following steps:
One, the cyanate ester resin of 90 parts, the copolymerization technology properties-correcting agent of 30 parts, 20 parts of plasticized modifiers, 3 parts of curing catalysts, 2 parts of coupling agents, the mineral filler of 4 parts and 3 parts of UV stablizers are taken by mass parts;
Two, cyanate ester resin step one taken and properties-correcting agent join in kneader and under kneading state, are heated to 120 DEG C and are incubated 25min, obtain copolymerization modified cyanic acid ester resin;
Three, the toughner taken in step one is added in kneader, together after the mixing of polymeric modification cyanate ester resin, keep kneader temperature to be 110 DEG C, carry out kneading 30min, obtain hybrid resin;
Four, hybrid resin is cooled to 70 DEG C, then adds curing catalyst that step one takes, coupling agent, mineral filler and UV stablizer, blended 20min in kneader, then vacuumize and mediate 20min, obtain modified cyanic acid ester resin surface film sizing;
Five, above-mentioned sizing material is turned painting film-making machine at auxiliary lower employing three roller of carrier, be film forming under the condition of 65 DEG C at film-forming temperature, make the modified cyanic acid ester resin surface film that thickness is 0.15mm ± 0.02mm.
The cyanate ester resin of this test is made up of bisphenol A cyanate ester resin, Novolac Cyanate Ester Resins, bisphenol-f type cyanate ester resin, and the consumption of three is the ratio composition of 5:3:1 in mass ratio;
Copolymerization technology properties-correcting agent by diallyl bisphenol S modified quartz sand, diallyl bisphenol modified quartz sand in mass ratio for 2:1 ratio forms;
The segmented copolymer of plasticized modifier is butyl polyacrylate to be main chain-polymethylmethacrylate be side chain, it adopts glycidyl methacrylate (GMA) to activate block polymer, effective bonding is produced between the block polymer of Shi Dai response type functional group and matrix resin, effectively can resist the transmission of stress, give full play to the toughening effect of segmented copolymer;
Curing catalyst is 1,1-dimethyl-3-phenylurea; Coupling agent is gamma-amino propyl trimethoxy silicane;
Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane;
The ratio that mineral filler is 10:1 by hollow glass micro-ball (soda lime borosilicate glass), fumed silica in mass ratio forms;
UV stablizer is rutile type nano titanium dioxide;
Vacuum kneader vacuum tightness is not less than-0.092MPa;
Carrier is polyester non-woven fabric.
Test 3, this preparation method testing a kind of modified cyanic acid ester resin surface film carry out according to the following steps:
One, the cyanate ester resin of 100 parts, the copolymerization technology properties-correcting agent of 30 parts, 25 parts of plasticized modifiers, 3.5 parts of curing catalysts, 2 parts of coupling agents, the mineral filler of 4 parts and 3 parts of UV stablizers are taken by mass parts;
Two, cyanate ester resin step one taken and properties-correcting agent join in kneader and under kneading state, are heated to 120 DEG C and are incubated 25min, obtain copolymerization modified cyanic acid ester resin;
Three, the toughner taken in step one is added in kneader, together after the mixing of polymeric modification cyanate ester resin, keep kneader temperature to be 110 DEG C, carry out kneading 30min, obtain hybrid resin;
Four, hybrid resin is cooled to 70 DEG C, then adds curing catalyst that step one takes, coupling agent, mineral filler and UV stablizer, blended 20min in kneader, then vacuumize and mediate 20min, obtain modified cyanic acid ester resin surface film sizing;
Five, above-mentioned sizing material is turned painting film-making machine at auxiliary lower employing three roller of carrier, be film forming under the condition of 65 DEG C at film-forming temperature, make the modified cyanic acid ester resin surface film that thickness is 0.15mm ± 0.02mm.
The cyanate ester resin of this test is made up of bisphenol A cyanate ester resin, Novolac Cyanate Ester Resins, bisphenol-f type cyanate ester resin, and the consumption of three is the ratio composition of 5:3:1 in mass ratio;
Copolymerization technology properties-correcting agent by diallyl bisphenol S modified quartz sand, diallyl bisphenol modified quartz sand in mass ratio for 2:1 ratio forms;
The segmented copolymer of plasticized modifier is butyl polyacrylate to be main chain-polymethylmethacrylate be side chain, it adopts glycidyl methacrylate (GMA) to activate block polymer, effective bonding is produced between the block polymer of Shi Dai response type functional group and matrix resin, effectively can resist the transmission of stress, give full play to the toughening effect of segmented copolymer;
Curing catalyst is that 2-ethyl-4-methylimidazole and 1,1-dimethyl-3-phenylurea form according to the ratio that mass ratio is 1:1;
Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane;
Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane;
The ratio that mineral filler is 10:1 by hollow glass micro-ball (soda lime borosilicate glass), fumed silica in mass ratio forms;
UV stablizer is that rutile type nano titanium dioxide and ESCALOL 567 (UV-9) form according to the ratio that mass ratio is 2:1;
Vacuum kneader vacuum tightness is not less than-0.092MPa;
Carrier is polyester non-woven fabric.
Test 1 ~ test 3 prepares modified cyanic acid ester surface film fundamental property as following table 1:
Table 1 modified cyanic acid ester surface film fundamental property
Cyanate ester resin surface film fluidity testing method is as follows: test sample is of a size of the circular surface film test piece of 3.81cm.By being placed in processed good template with the cyanate surface film of barrier film up and down, under 0.2 ~ 0.3MPa pressure, with the ramp to 195 of 2 ~ 8 DEG C/min DEG C ~ 200 DEG C, insulation 25 ~ 35min, and then be cooled to room temperature with the speed of 2 ~ 8 DEG C/min; Take out the surface film after solidification, use area measurement instrument survey area.Percent flow rate is calculated according to following manner.
In formula
A
f: the area of sample after solidification;
A
0: the original area before sample solidification.
Cyanate ester resin surface film mobility of the present invention is moderate, the space can filled up the pin hole after solidifying with cyanate ester resin prepreg or stay because of starved, poor glue etc., and has certain thixotropy, ensures the planeness of bondline thickness and product.
Test 1 ~ test 3 is prepared the product that modified cyanic acid ester surface film carries out test board in accordance with the following methods.
6 layers of smooth 300mm × 300mm unidirectional fibre strengthen cyanate ester based prepreg by 0 °/90 ° direction order pavings, or 3 layers of 300mm × 300mm fabric fibre strengthen the smooth paving of cyanate ester based prepreg.Again by the paving of modified cyanic acid ester surface film on fibre-reinforced prepregs plate.Carry out frock according to accompanying drawing 1, enter solidification of hot-press tank.Condition of cure is: vacuumize (vacuum tightness is not less than 0.092MPa) under room temperature and start to be warming up to 180 DEG C ± 5 DEG C after pressurization, being incubated 100min ~ 120min at this temperature; Be warming up to 200 DEG C ± 5 DEG C, be incubated 60min ~ 80min at this temperature waiting pressure to continue; Average heating rate: 0.5 DEG C/min ~ 2.0 DEG C/min; Release condition is after solidification process terminates, and sample can should take off to less than 60 DEG C at Temperature fall under pressurize (rate of temperature fall≤1.5 DEG C/min) in release.
Get the modified cyanic acid ester surface film test board be cured to carry out as tested in table 2, experimental result is as follows:
Performance after the solidification of table 2 modified cyanic acid ester surface film
Claims (10)
1. a modified cyanic acid ester resin surface film, is characterized in that modified cyanic acid ester resin surface film is made up of the cyanate ester resin of 75 ~ 100 parts, 25 ~ 40 parts of copolymerization technology properties-correcting agent, the plasticized modifier of 10 ~ 25 parts, 2 ~ 4 parts of curing catalysts, 1 ~ 3 part of coupling agent, the mineral filler of 1 ~ 4 part, 1 ~ 5 part of UV stablizer and carriers according to parts by weight.
2., according to a kind of modified cyanic acid ester resin surface film described in claim 1, it is characterized in that cyanate ester resin by bisphenol A cyanate ester resin, Novolac Cyanate Ester Resins and bisphenol-f type cyanate ester resin in mass ratio for the ratio of 5:3:1 forms.
3., according to a kind of modified cyanic acid ester resin surface film described in claim 1, it is characterized in that copolymerization technology properties-correcting agent by diallyl bisphenol S modified bismaleimide resin and diallyl bisphenol modified bismaleimide resin in mass ratio for 2:1 ratio forms.
4., according to a kind of modified cyanic acid ester resin surface film described in claim 1, it is characterized in that plasticized modifier is segmented copolymer; Described segmented copolymer adopts the glycidyl methacrylate of band response type functional group, Rocryl 410 or methacrylic acid diamine ethyl ester to activate; Segmented copolymer is MBS, polystyrene-poly methyl methacrylate, butyl polyacrylate to be main chain-polymethylmethacrylate be in the segmented copolymer of side chain one or more by arbitrarily than forming.
5. according to a kind of modified cyanic acid ester resin surface film described in claim 1, it is characterized in that curing catalyst is pressed arbitrarily than composition by one or more in 2-ethyl-4-methylimidazole, 1,1-dimethyl-3-phenylurea, diallyl bisphenol, 2-chavicol.
6., according to a kind of modified cyanic acid ester resin surface film described in claims 1, it is characterized in that coupling agent by one or more in γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane, methyl tri-tert peroxy-silane by arbitrarily than forming.
7., according to a kind of modified cyanic acid ester resin surface film described in claim 1, it is characterized in that mineral filler by one or more in ceramic microspheres, hollow glass micropearl, fumed silica, talcum powder, boron powder, boron nitride powder by arbitrarily than forming.
8., according to a kind of modified cyanic acid ester resin surface film described in claim 1, it is characterized in that UV stablizer by one or more in rutile type nano titanium dioxide, nano zine oxide, ESCALOL 567, Octabenzone by arbitrarily than forming.
9., according to a kind of modified cyanic acid ester resin surface film described in claim 1, it is characterized in that carrier is polyester non-woven fabric, glass fiber woven cloth or silica fibrage cloth.
10. prepare the method for a kind of modified cyanic acid ester resin surface film according to claim 1, it is characterized in that modified cyanic acid ester resin surface film preparation method carries out according to following steps:
One, the cyanate ester resin of 75 ~ 100 parts, the copolymerization technology properties-correcting agent of 25 ~ 50 parts, 10 ~ 25 parts of plasticized modifiers, 2 ~ 4 parts of curing catalysts, the mineral filler of 1 ~ 3 part of coupling agent 1 ~ 4 part and 1 ~ 5 part of UV stablizer is taken by mass fraction;
Two, cyanate ester resin step one taken and properties-correcting agent join in kneader and under kneading state, are heated to 90 ~ 150 DEG C and are incubated 20 ~ 30min, obtain copolymerization modified cyanic acid ester resin;
Three, the toughner taken in step one is added in kneader, together after the mixing of polymeric modification cyanate ester resin, keep kneader temperature to be 90 ~ 150 DEG C, carry out kneading 10 ~ 30min, obtain hybrid resin;
Four, hybrid resin is cooled to 60 ~ 80 DEG C, then curing catalyst that step one takes, coupling agent, mineral filler and UV stablizer is added, blended 10 ~ 30min in kneader, then vacuumize kneading 10 ~ 30min, obtain modified cyanic acid ester resin surface film sizing;
Five, above-mentioned sizing material is turned painting film-making machine at auxiliary lower employing three roller of carrier, be film forming under the condition of 60 ~ 80 DEG C at film-forming temperature, make the modified cyanic acid ester resin surface film that thickness is 0.10mm ~ 0.18mm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106189225A (en) * | 2016-08-22 | 2016-12-07 | 威海光威复合材料股份有限公司 | Nano-ceramic powder modified cyanic acid ester resin prepares the method for composite |
| CN106700877A (en) * | 2016-12-27 | 2017-05-24 | 常州百佳薄膜科技有限公司 | Aqueous adhesive, anti-scratching wearing-resistant PVC (Polyvinyl Chloride) weather-resistant membrane and preparation method thereof |
| CN108559263A (en) * | 2018-05-25 | 2018-09-21 | 黑龙江省科学院石油化学研究院 | A kind of high temperature resistant bismaleimide resin composite material skin covering of the surface and preparation method thereof |
| CN109398910A (en) * | 2018-09-27 | 2019-03-01 | 广州品赫生物科技有限公司 | Facial mask bag material, production technology and mask packaging bag |
| CN109486186A (en) * | 2018-12-24 | 2019-03-19 | 苏州大学 | Epoxy-modified cyanate pre-polymerization material |
| CN113681934A (en) * | 2021-07-30 | 2021-11-23 | 江西昌河航空工业有限公司 | Forming method of composite honeycomb sandwich part with U-shaped part at 90-degree edge |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2398790A (en) * | 2002-12-24 | 2004-09-01 | Bosch Gmbh Robert | Polymer composition |
| CN101993670A (en) * | 2010-10-29 | 2011-03-30 | 黑龙江省科学院石油化学研究院 | Active group containing polyacrylate flexibilizer, preparation method thereof and epoxy resin adhesive modified by same |
| CN102676112A (en) * | 2012-06-08 | 2012-09-19 | 黑龙江省科学院石油化学研究院 | Low-temperature curing cyanate ester adhesive and preparation method thereof |
| CN103074026A (en) * | 2013-01-11 | 2013-05-01 | 西北工业大学 | Bismaleimide/cyanate ester resin adhesive resisting to temperature as high as 220 DEG C and preparation method |
| CN103131346A (en) * | 2013-03-25 | 2013-06-05 | 黑龙江省科学院石油化学研究院 | High temperature-resistant carrier adhesive film and preparation method thereof |
-
2015
- 2015-09-18 CN CN201510599888.XA patent/CN105131827B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2398790A (en) * | 2002-12-24 | 2004-09-01 | Bosch Gmbh Robert | Polymer composition |
| CN101993670A (en) * | 2010-10-29 | 2011-03-30 | 黑龙江省科学院石油化学研究院 | Active group containing polyacrylate flexibilizer, preparation method thereof and epoxy resin adhesive modified by same |
| CN102676112A (en) * | 2012-06-08 | 2012-09-19 | 黑龙江省科学院石油化学研究院 | Low-temperature curing cyanate ester adhesive and preparation method thereof |
| CN103074026A (en) * | 2013-01-11 | 2013-05-01 | 西北工业大学 | Bismaleimide/cyanate ester resin adhesive resisting to temperature as high as 220 DEG C and preparation method |
| CN103131346A (en) * | 2013-03-25 | 2013-06-05 | 黑龙江省科学院石油化学研究院 | High temperature-resistant carrier adhesive film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘丽等: "《天线罩用透波材料》", 30 June 2008 * |
| 马之庚等: "《工程塑料手册.材料卷》", 31 October 2004 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106189225A (en) * | 2016-08-22 | 2016-12-07 | 威海光威复合材料股份有限公司 | Nano-ceramic powder modified cyanic acid ester resin prepares the method for composite |
| CN106700877A (en) * | 2016-12-27 | 2017-05-24 | 常州百佳薄膜科技有限公司 | Aqueous adhesive, anti-scratching wearing-resistant PVC (Polyvinyl Chloride) weather-resistant membrane and preparation method thereof |
| CN106700877B (en) * | 2016-12-27 | 2019-08-30 | 常州百佳年代薄膜科技股份有限公司 | Water-based glue, scratch resistance are wear-resistant PVC Weather-proof film and preparation method |
| CN108559263A (en) * | 2018-05-25 | 2018-09-21 | 黑龙江省科学院石油化学研究院 | A kind of high temperature resistant bismaleimide resin composite material skin covering of the surface and preparation method thereof |
| CN108559263B (en) * | 2018-05-25 | 2020-11-10 | 黑龙江省科学院石油化学研究院 | High-temperature-resistant bismaleimide resin composite material surface film and preparation method thereof |
| CN109398910A (en) * | 2018-09-27 | 2019-03-01 | 广州品赫生物科技有限公司 | Facial mask bag material, production technology and mask packaging bag |
| CN109486186A (en) * | 2018-12-24 | 2019-03-19 | 苏州大学 | Epoxy-modified cyanate pre-polymerization material |
| CN109486186B (en) * | 2018-12-24 | 2021-02-26 | 苏州大学 | Epoxy modified cyanate ester prepolymer |
| CN113681934A (en) * | 2021-07-30 | 2021-11-23 | 江西昌河航空工业有限公司 | Forming method of composite honeycomb sandwich part with U-shaped part at 90-degree edge |
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