CN102936466B - Modified bisphthalonitrile resin structure glue film and preparation method thereof - Google Patents
Modified bisphthalonitrile resin structure glue film and preparation method thereof Download PDFInfo
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- CN102936466B CN102936466B CN 201210494916 CN201210494916A CN102936466B CN 102936466 B CN102936466 B CN 102936466B CN 201210494916 CN201210494916 CN 201210494916 CN 201210494916 A CN201210494916 A CN 201210494916A CN 102936466 B CN102936466 B CN 102936466B
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Abstract
The invention discloses a modified bisphthalonitrile resin structure glue film and a preparation method thereof, and relates to a glue film and a preparation method thereof. The glue film and the preparation method thereof are mainly used for solving the problems that the conventional high temperature resisting glue films are high in curing temperature and the high temperature resisting glue films prepared by the conventional methods are relatively poor in processing property in the curing process. The glue film provided by the invention is made by a matrix resin, a toughening agent, a film-forming modified resin and a filler. The preparation method comprises the steps of: (1) weighing the matrix resin, the toughening agent, the film-forming modified resin and the filler, (2) heating and blending the film-forming modified resin and the toughening agent in a reaction kettle, (3) cooling the reaction kettle, (4) adding the matrix resin into the reaction kettle and mixing evenly, (5) adding the filler into the reaction kettle, stirring evenly and pouring out to obtain a sizing material, and (6) preheating the sizing material in a drying oven and carrying out hot rolling to form the film. Compared with the similar glue films, the glue film is low in curing temperature and short in curing time; and the glue film prepared by the method is good in processing property in the curing process. The glue film and the preparation method are applied to the technical field of high polymer materials.
Description
Technical field
The present invention relates to a kind of sizing agent and preparation method thereof.
Background technology
High-temperature-resistant structure tackiness agent for aerospace field mainly contains epoxy type, bismaleimide resin type, cyanate type and polyimide type etc. at present.Wherein the temperature tolerance of polyimide type sizing agent is the highest, the life-time service temperature can reach more than 300 ℃, but its solidification value is higher, post-processing temperature is up to 316 ℃ or higher, and produce fugitive constituent (itself contains solvent sizing agent) and micromolecular compound in its solidification process, cause curing process to be controlled more difficult, limited its application in high temperature resistant field.Therefore, develop lower than polyimide type sizing agent solidification value, the curing process performance is good and temperature tolerance with it quite the sizing agent of (300 ℃) have great importance, to meet the requirement of aerospace field to high-temperature Resistance Adhesives.
Summary of the invention
The present invention is that will to solve existing high temperature resistant glued membrane solidification value high, and the poor problem of high temperature resistant glued membrane processing performance in solidification process for preparing of existing method, and a kind of modification bi-phthalonitrile resin structural film adhesive and preparation method thereof is provided.
A kind of modification bi-phthalonitrile resin structural film adhesive of the present invention is to be made by the matrix resin of 70～100 parts, the toughner of 10～40 parts, the film forming modified resin of 20～50 parts and the filler of 2～15 parts according to mass fraction; Wherein one or more in bisphenol A-type bi-phthalonitrile resin, biphenyl type bi-phthalonitrile resin or phenolic hydroxyl group modification bi-phthalonitrile resin of matrix resin are pressed arbitrarily than the mixture formed.
The preparation method of a kind of modification bi-phthalonitrile resin of the present invention structural film adhesive carries out according to following steps: one, according to mass fraction, take the matrix resin of 70～100 parts, the toughner of 10～40 parts, the film forming modified resin of 20～50 parts and the filler of 2～15 parts; Two, the film forming modified resin and the toughner that take in step 1 are carried out to resin alloy 20min～40min in 200 ℃ of reactors; Three, the reactor in step 2 is cooled to 150 ℃; Four, the matrix resin taken in step 1 is joined in the reactor after cooling and mix; Five, the filler taken in step 1 is joined in reactor after stirring and pour out, obtain sizing material; Six,, by the preheating 20min～40min in the baking oven of 50 ℃～80 ℃ of the sizing material in step 5, on the glued membrane rolling press that is then 60 ℃～80 ℃ in the roller temperature, by carrier hot calender film forming, obtain modification bi-phthalonitrile resin structural film adhesive.
Modification bi-phthalonitrile resin structural film adhesive of the present invention is compared with the laminate product of same temperature classification, has lower solidification value, and solidification value is 260 ℃; Shorter set time, be 2h set time.Modification bi-phthalonitrile resin structural film adhesive prepared by method of the present invention has good thermotolerance, ablation resistance, and in the time of 600 ℃, carbon yield is greater than 60%, 10% thermal weight loss rate and has reached more than 500 ℃; There is higher shearing resistance and high temperature strength, more than the normal temperature shearing resistance can reach 15.0MPa, more than the shearing resistance of 350 ℃ can reach 10.0MPa, more than the shearing resistance of 400 ℃ can reach 7.0MPa, more than climbing drum peel strength can reach 20.0Nmm/mm, planar stretch intensity can reach 3.0N/mm
2above.
Embodiment
Embodiment one: a kind of modification bi-phthalonitrile resin structural film adhesive of present embodiment is to be made by the matrix resin of 70～100 parts, the toughner of 10～40 parts, the film forming modified resin of 20～50 parts and the filler of 2～15 parts according to mass fraction; Wherein one or more in bisphenol A-type bi-phthalonitrile resin, biphenyl type bi-phthalonitrile resin or phenolic hydroxyl group modification bi-phthalonitrile resin of matrix resin are pressed arbitrarily than the mixture formed.
Present embodiment modification bi-phthalonitrile resin structural film adhesive with the laminate product of same temperature classification, compare, there is lower solidification value, solidification value is 260 ℃; Shorter set time, be 2h set time.
Embodiment two: what present embodiment was different from embodiment one is that modification bi-phthalonitrile resin glued membrane is to be made by the matrix resin of 80～95 parts, the toughner of 15～25 parts, the film forming modified resin of 25～40 parts and the filler of 5～12 parts according to mass fraction.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment was different from embodiment one or two is that modification bi-phthalonitrile resin glued membrane is to be made by the matrix resin of 90 parts, the toughner of 20 parts, the film forming modified resin of 35 parts and the filler of 10 parts according to mass fraction.Other step and parameter are identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three is that toughner is that one or more in polyamidoimide (PAI), polyetherimide (PEI), polybenzimidazole (PBI), polyether-ether-ketone (PEEK), polyethersulfone with cardo (PES-C) or phenolphthalein base polyetherketone (PEK-C) are by arbitrarily than the mixture of composition.。Other step and parameter are identical with one of embodiment one to three.
Embodiment five: what present embodiment was different from one of embodiment one to four is that one or more in Novolac Cyanate Eater Resin, allyl group dihydroxyphenyl propane, allyl group phenolic aldehyde, the bisphenol A modified bismaleimide resin of allyl group or allyl group phenolic aldehyde modification bismaleimide resin of film forming modified resin are by any mixture than forming.Other step and parameter are identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is that one or more in white carbon black, nano grade titanium white powder, nano level mica powder, asbestos powder or carbon nanotube of filler are by any mixture than forming.Other step and parameter are identical with one of embodiment one to five.
Embodiment seven: the preparation method of a kind of modification bi-phthalonitrile resin structural film adhesive of present embodiment carries out according to following steps: one, according to mass fraction, take the matrix resin of 70～100 parts, the toughner of 10～40 parts, the film forming modified resin of 20～50 parts and the filler of 2～15 parts; Two, the film forming modified resin and the toughner that take in step 1 are carried out to resin alloy 20～40min in 200 ℃ of reactors; Three, the reactor in step 2 is cooled to 150 ℃; Four, the matrix resin taken in step 1 is joined in the reactor after cooling and mix; Five, the filler taken in step 1 is joined in reactor after stirring and pour out, obtain sizing material; Six,, by the preheating 20～40min in the baking oven of 50 ℃～80 ℃ of the sizing material in step 5, on the glued membrane rolling press that is then 60 ℃～80 ℃ in the roller temperature, by carrier hot calender film forming, obtain modification bi-phthalonitrile resin structural film adhesive.
Present embodiment the modification bi-phthalonitrile resin structural film adhesive for preparing of method there is good thermotolerance, ablation resistance, in the time of 600 ℃, carbon yield is greater than 60%, 10% thermal weight loss rate and has reached more than 500 ℃; There is higher shearing resistance and high temperature strength, more than the normal temperature shearing resistance can reach 15.0MPa, more than the shearing resistance of 350 ℃ can reach 10.0MPa, more than the shearing resistance of 400 ℃ can reach 7.0MPa, more than climbing drum peel strength can reach 20.0Nmm/mm, planar stretch intensity can reach 3.0N/mm
2above.
Embodiment eight: present embodiment is different from embodiment seven is preheating 30min in the baking oven of sizing material between 60 ℃～70 ℃ in step 6.Other step and parameter are identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from embodiment seven or eight is that the roller temperature of glued membrane rolling press in step 5 is 65 ℃～70 ℃.Other step and parameter are identical with one of embodiment one to eight.
Embodiment ten: present embodiment is different from one of embodiment seven to nine is that carrier in step 6 is glass wool cloth or carbon cloth.Other step and parameter are identical with one of embodiment seven to nine.
By following verification experimental verification beneficial effect of the present invention:
A kind of modification bi-phthalonitrile resin structural film adhesive of this test and preparation method thereof making method is carried out according to following steps: one, according to massfraction than taking the bisphenol A-type bi-phthalonitrile resin of 60 parts, 30 parts of phenolic hydroxyl group modification bi-phthalonitrile resins, the PAI of 10 parts, the PBI of 10 parts, the Novolac Cyanate Eater Resin of 20 parts, the allyl group dihydroxyphenyl propane of 15 parts, the white carbon black of 4 parts, the nano grade titanium white powder of 2 parts, the nano level mica powder of 2 parts; Two, the PAI of 10 parts taken in step 1, the PBI of 10 parts, the Novolac Cyanate Eater Resin of 20 parts and the allyl group dihydroxyphenyl propane of 15 parts are carried out to resin alloy 30min in 200 ℃ of reactors; Three, the reactor in step 2 is cooled to 150 ℃; Four, the bisphenol A-type bi-phthalonitrile resin of 60 parts that takes in step 1 and 30 parts of phenolic hydroxyl group modification bi-phthalonitrile resins are joined in the reactor after cooling and mix; Five, the nano level mica powder of the white carbon black of 4 parts that takes in step 1, the nano grade titanium white powder of 2 parts and 2 parts is joined in reactor after stirring and pour out; Six,, by the preheating 30min in the baking oven of 60 ℃ to 70 ℃ of the sizing material in step 5, on the glued membrane rolling press that is then 65 ℃～70 ℃ in the roller temperature, by glass wool cloth hot calender film forming, obtain modification bi-phthalonitrile resin structural film adhesive product.
Bisphenol A-type bi-phthalonitrile resin in this test is bought the chemistry institute in the Chinese Academy of Sciences; Phenolic hydroxyl group modification bi-phthalonitrile resin is bought the chemistry institute in the Chinese Academy of Sciences; Polyamidoimide PAI buys the Su Wei in the U.S.; Polybenzimidazole PBI buys in Dupont; Novolac Cyanate Eater Resin is bought in Wuqiao, Jiangdu resin processing plant; The allyl group dihydroxyphenyl propane is bought in the beautiful chemical industry of Laizhou City's Lay company limited; White carbon black is bought in Shenyang Chemical Co., Ltd.; The nano grade titanium white powder is bought the river chemical industry company limited of shaking in Shanghai; The nano level mica powder is bought in the north, Lingshou County, Hebei mining industry source mill; The glass wool cloth carrier is bought in Hangzhou high-tech matrix material company limited.
The modification bi-phthalonitrile resin structural film adhesive of this test is compared with the laminate product of same temperature classification, has lower solidification value, and solidification value is 260 ℃; Shorter set time, be 2h set time.
This test preparation modification bi-phthalonitrile resin structural film adhesive there is good thermotolerance, ablation resistance.In the time of 600 ℃, carbon yield is greater than 60%, at temperature rise rate, is 10 ℃/min, air atmosphere, and under the thermal weight loss condition that airshed is 50mL/min, 10% thermal weight loss rate has reached more than 500 ℃.When the thickness of glued membrane is 0.15～0.20mm, according to GB7124-2008 (normal temperature shearing resistance standard) and GJB444-88 (shear at high temperature strength criterion), the shearing resistance of glued membrane adhesiveproperties is tested, the shearing test piece is high-strength steel, and sandblasting is carried out on surface.Result is as shown in table 1, and the shearing resistance of the modification bi-phthalonitrile resin structural film adhesive of this test preparation is high as can be seen from Table 1, high temperature strength good.Under the condition that is 0.35mm～0.40mm at film thickness, the modification bi-phthalonitrile resin structural film adhesive of this test preparation being carried out to stripping strength tests and learns, more than 20.0Nmm/mm can being reached according to GBT1457-2005 test climbing drum peel strength, according to GJB130.4-1986 test planar stretch intensity, can reach 3.0N/mm
2above.
Heat aging property is tested and learnt, after 320 ℃/100h, the shearing resistance conservation rate is more than 90%; After hydrothermal aging 1000h, the shearing resistance conservation rate is more than 90%.
The shearing resistance of table 1 modification bi-phthalonitrile resin structural film adhesive
Claims (9)
1. a modification bi-phthalonitrile resin structural film adhesive, is characterized in that modification bi-phthalonitrile resin structural film adhesive is to be made by the matrix resin of 70～100 parts, the toughner of 10～40 parts, the film forming modified resin of 35 parts and the filler of 2～15 parts according to mass fraction; Wherein one or more in bisphenol A-type bi-phthalonitrile resin, biphenyl type bi-phthalonitrile resin or phenolic hydroxyl group modification bi-phthalonitrile resin of matrix resin are pressed arbitrarily than the mixture formed; Wherein film forming modified resin is comprised of the Novolac Cyanate Eater Resin of 20 parts and the allyl group dihydroxyphenyl propane of 15 parts.
2. a kind of modification bi-phthalonitrile resin structural film adhesive according to claim 1, is characterized in that modification bi-phthalonitrile resin glued membrane is to be made by the matrix resin of 80～95 parts, the toughner of 15～25 parts, the film forming modified resin of 35 parts and the filler of 5～12 parts according to mass fraction.
3. a kind of modification bi-phthalonitrile resin structural film adhesive according to claim 1, is characterized in that modification bi-phthalonitrile resin glued membrane is to be made by the matrix resin of 90 parts, the toughner of 20 parts, the film forming modified resin of 35 parts and the filler of 10 parts according to mass fraction.
4. according to a kind of modification bi-phthalonitrile resin structural film adhesive described in claim 1, it is characterized in that one or more in polyamidoimide, polyetherimide, polybenzimidazole, polyether-ether-ketone, polyethersulfone with cardo or phenolphthalein base polyetherketone of toughner are by any mixture than forming.
5. a kind of modification bi-phthalonitrile resin structural film adhesive according to claim 1, is characterized in that one or more in white carbon black, nano grade titanium white powder, nano level mica powder, asbestos powder or carbon nanotube of filler are by any mixture than forming.
6. the preparation method of a kind of modification bi-phthalonitrile resin structural film adhesive as claimed in claim 1, is characterized in that modification bi-phthalonitrile resin glue film manufacturing process carries out according to following steps: one, according to mass fraction, take the matrix resin of 70～100 parts, the toughner of 10～40 parts, the film forming modified resin of 35 parts and the filler of 2～15 parts; Two, the film forming modified resin and the toughner that take in step 1 are carried out to resin alloy 20min～40min in 200 ℃ of reactors; Three, the reactor in step 2 is cooled to 150 ℃; Four, the matrix resin taken in step 1 is joined in the reactor after cooling and mix; Five, the filler taken in step 1 is joined in reactor after stirring and pour out, obtain sizing material; Six,, by the preheating 20min～40min in the baking oven of 50 ℃～80 ℃ of the sizing material in step 5, on the glued membrane rolling press that is then 60 ℃～80 ℃ in the roller temperature, by carrier hot calender film forming, obtain modification bi-phthalonitrile resin structural film adhesive.
7. the preparation method of a kind of modification bi-phthalonitrile resin structural film adhesive according to claim 6, is characterized in that in step 6 preheating 30min in the baking oven of sizing material between 60 ℃～70 ℃.
8. the preparation method of a kind of modification bi-phthalonitrile resin structural film adhesive described in claim 6 or 7, the roller temperature that it is characterized in that glued membrane rolling press in step 6 is 65 ℃～70 ℃.
9. the preparation method of a kind of modification bi-phthalonitrile resin structural film adhesive described in claim 8, is characterized in that the carrier in step 6 is glass wool cloth or carbon cloth.
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| CN 201210494916 CN102936466B (en) | 2012-11-28 | 2012-11-28 | Modified bisphthalonitrile resin structure glue film and preparation method thereof |
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| CN 201210494916 CN102936466B (en) | 2012-11-28 | 2012-11-28 | Modified bisphthalonitrile resin structure glue film and preparation method thereof |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103980850B (en) * | 2014-06-09 | 2016-02-17 | 黑龙江省科学院石油化学研究院 | The preparation method of phthalonitrile modified phenolic resin adhesive |
| CN104845349B (en) * | 2015-05-25 | 2017-03-08 | 吉林大学 | Toughness reinforcing bi-phthalonitrile resin material of polyether sulfone and preparation method thereof |
| CN108884023B (en) | 2016-03-31 | 2022-02-25 | 3M创新有限公司 | Bisphenol M bisphthalonitrile ether resin, bisphenol P bisphthalonitrile ether resin, preparation methods thereof, resin blend and two-component system |
| CN108659530B (en) * | 2018-04-28 | 2021-07-13 | 哈尔滨玻璃钢研究院有限公司 | Temperature-resistant flame-retardant POSS (polyhedral oligomeric silsesquioxane) modified bisphthalonitrile and cyanate ester blending resin system |
| CN111004505A (en) * | 2019-12-23 | 2020-04-14 | 哈尔滨工业大学 | Preparation method of modified cyanate ester resin with low volatility |
| CN113201302B (en) * | 2021-05-06 | 2023-03-03 | 黑龙江省科学院石油化学研究院 | Diamino bisphthalonitrile modified epoxy resin adhesive and preparation method thereof |
| CN114774054A (en) * | 2022-04-28 | 2022-07-22 | 广东汇齐新材料有限公司 | Environment-friendly TPU (thermoplastic polyurethane) hot melt adhesive film for insoles and preparation method thereof |
| CN115466390B (en) * | 2022-09-13 | 2023-07-25 | 中国人民解放军国防科技大学 | Low-temperature rapid-curing cyanate resin containing imidazole structure and preparation method thereof |
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| CN101914038A (en) * | 2010-07-15 | 2010-12-15 | 电子科技大学 | Bisphenol A type bis-phthalonitrile resin with aryl ether nitrile segments, cured product and preparation method thereof |
| CN102492140A (en) * | 2011-11-18 | 2012-06-13 | 电子科技大学 | Bi-phthalonitrile prepolymer as well as preparation method and application thereof, bi-phthalonitrile prepolymer/epoxy resin copolymer and preparation method thereof as well as bi-phthalonitrile prepolymer/epoxy resin cured material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914038A (en) * | 2010-07-15 | 2010-12-15 | 电子科技大学 | Bisphenol A type bis-phthalonitrile resin with aryl ether nitrile segments, cured product and preparation method thereof |
| CN102492140A (en) * | 2011-11-18 | 2012-06-13 | 电子科技大学 | Bi-phthalonitrile prepolymer as well as preparation method and application thereof, bi-phthalonitrile prepolymer/epoxy resin copolymer and preparation method thereof as well as bi-phthalonitrile prepolymer/epoxy resin cured material |
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