CN102936466A - 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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- 239000011347 resin Substances 0.000 title claims abstract description 96
- 229920005989 resin Polymers 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003292 glue Substances 0.000 title 1
- 239000002313 adhesive film Substances 0.000 claims abstract description 36
- 239000000945 filler Substances 0.000 claims abstract description 17
- 239000012745 toughening agent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000003490 calendering Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 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 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000004693 Polybenzimidazole Substances 0.000 claims description 7
- 229920002480 polybenzimidazole Polymers 0.000 claims description 7
- LSEBTZWHCPGKEF-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C=C1 LSEBTZWHCPGKEF-UHFFFAOYSA-N 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 229920002312 polyamide-imide Polymers 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004962 Polyamide-imide Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000010425 asbestos Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- -1 ether ether ketone Chemical class 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229910052895 riebeckite Inorganic materials 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 238000002679 ablation Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
Abstract
一种改性双邻苯二甲腈树脂结构胶膜及其制备方法，它涉及一种胶膜及其制备方法。本发明是要解决现有耐高温胶膜固化温度高，以及现有方法制备的耐高温胶膜在固化过程中工艺性能较差的问题，本发明的胶膜是由主体树脂、增韧剂、成膜改性树脂和填料制成，制备方法为：一、称取主体树脂、增韧剂、成膜改性树脂和填料；二、将成膜改性树脂与增韧剂在反应釜中进行加热共混；三、将反应釜降温；四、将主体树脂加入到反应釜中混匀；五、将填料加入到反应釜中搅拌均匀后倒出，得到胶料；六、将胶料在烘箱中预热，然后热压延成膜。本发明胶膜较同类胶膜固化温度低、固化时间短；本方法制备的胶膜在固化过程中工艺性能好。本发明应用于高分子材料技术领域。A modified bisphthalonitrile resin structural adhesive film and a preparation method thereof, which relate to an adhesive film and a preparation method thereof. The present invention aims to solve the problems that the existing high-temperature-resistant adhesive film has a high curing temperature, and the high-temperature-resistant adhesive film prepared by the existing method has poor process performance during the curing process. The adhesive film of the present invention is composed of a main resin, a toughening agent, It is made of film-forming modified resin and filler. The preparation method is as follows: 1. Weigh the main resin, toughener, film-forming modified resin and filler; Heating and blending; 3. Cool down the reaction kettle; 4. Add the main resin into the reaction kettle and mix; 5. Add the filler to the reaction kettle and pour it out to obtain the rubber compound; Preheating in medium, and then hot calendering to form a film. The adhesive film of the invention has lower curing temperature and shorter curing time than similar adhesive films; the adhesive film prepared by the method has good technical performance in the curing process. The invention is applied in the technical field of polymer materials.
Description
技术领域technical field
本发明涉及一种胶黏剂及其制备方法。The invention relates to an adhesive and a preparation method thereof.
背景技术Background technique
目前用于航空航天领域的耐高温结构胶粘剂主要有环氧类型、双马树脂类型、氰酸酯类型和聚酰亚胺类型等。其中聚酰亚胺类型胶黏剂的耐温性最高，长期使用温度可以达到300℃以上，但其固化温度较高，后处理温度高达316℃或更高，且其固化过程中产生挥发份(胶黏剂本身含有溶剂)和小分子化合物，导致固化工艺过程控制较难，限制了其在耐高温领域的应用。因此，研制比聚酰亚胺类型胶黏剂固化温度低、固化工艺性能好且耐温性与之相当(300℃)的胶黏剂具有重要的意义，以满足航空航天领域对耐高温胶黏剂的要求。At present, the high temperature resistant structural adhesives used in the aerospace field mainly include epoxy type, double horse resin type, cyanate ester type and polyimide type. Among them, the polyimide type adhesive has the highest temperature resistance, and the long-term use temperature can reach above 300°C, but its curing temperature is relatively high, and the post-treatment temperature is as high as 316°C or higher, and volatile matter ( The adhesive itself contains solvents) and small molecular compounds, which makes it difficult to control the curing process and limits its application in the field of high temperature resistance. Therefore, it is of great significance to develop adhesives with lower curing temperature than polyimide adhesives, better curing process performance and equivalent temperature resistance (300 ° C), so as to meet the requirements of high temperature resistant adhesives in the aerospace field. agent requirements.
发明内容Contents of the invention
本发明是要解决现有耐高温胶膜固化温度高，以及现有方法制备的耐高温胶膜在固化过程中工艺性能较差的问题，提供了一种改性双邻苯二甲腈树脂结构胶膜及其制备方法。The present invention aims to solve the problem of high curing temperature of the existing high-temperature-resistant adhesive film and the poor process performance of the high-temperature-resistant adhesive film prepared by the existing method in the curing process, and provides a modified bis-phthalonitrile resin structure Adhesive film and its preparation method.
本发明的一种改性双邻苯二甲腈树脂结构胶膜，按照质量份数是由70～100份的主体树脂、10～40份的增韧剂、20～50份的成膜改性树脂和2～15份的填料制成；其中主体树脂由双酚A型双邻苯二甲腈树脂、联苯型双邻苯二甲腈树脂或酚羟基改性双邻苯二甲腈树脂中的一种或几种按任意比组成的混合物。A modified bisphthalonitrile resin structural adhesive film of the present invention is composed of 70-100 parts by mass of main resin, 10-40 parts of toughening agent, and 20-50 parts of film-forming modified resin and 2 to 15 parts of filler; the main resin is made of bisphenol A type bisphthalonitrile resin, biphenyl type bisphthalonitrile resin or phenolic hydroxyl modified bisphthalonitrile resin One or several mixtures in any ratio.
本发明一种改性双邻苯二甲腈树脂结构胶膜的制备方法按照以下步骤进行：一、按照质量份数称取70～100份的主体树脂、10～40份的增韧剂、20～50份的成膜改性树脂和2～15份的填料；二、将步骤一中称取的成膜改性树脂与增韧剂在200℃反应釜中进行树脂共混20min～40min；三、将步骤二中的反应釜降温至150℃；四、将步骤一中称取的主体树脂加入到降温后的反应釜中混匀；五、将步骤一中称取的填料加入到反应釜中搅拌均匀后倒出，得到胶料；六、将步骤五中的胶料在50℃～80℃的烘箱中预热20min～40min，然后在辊温为60℃～80℃的胶膜压延机上用载体热压延成膜，即得到改性双邻苯二甲腈树脂结构胶膜。A preparation method of a modified bisphthalonitrile resin structural film of the present invention is carried out according to the following steps: 1. Take 70 to 100 parts of main resin, 10 to 40 parts of toughening agent, 20 parts by mass ～50 parts of film-forming modified resin and 2～15 parts of filler; 2. Blend the film-forming modified resin and toughening agent in a 200°C reactor for 20min～40min; 3. 1. Cool down the reaction kettle in step 2 to 150°C; 4. Add the main resin weighed in step 1 into the cooled reaction kettle and mix well; 5. Add the filler weighed in step 1 into the reaction kettle Stir evenly and pour it out to obtain the rubber material; 6. Preheat the rubber material in step 5 in an oven at 50°C to 80°C for 20min to 40min, and then use it on a film calender with a roll temperature of 60°C to 80°C The carrier is thermally calendered to form a film, and the modified bisphthalonitrile resin structural adhesive film is obtained.
本发明的改性双邻苯二甲腈树脂结构胶膜与同样耐热等级的胶膜产品相比，具有更低的固化温度，固化温度为260℃；更短的固化时间，固化时间为2h。本发明的方法制备的改性双邻苯二甲腈树脂结构胶膜具有良好的耐热性、耐烧蚀性，600℃时残炭率大于60％，10％的热失重率达到了500℃以上；具有较高的剪切强度和耐高温强度，常温剪切强度能达到15.0MPa以上，350℃的剪切强度能达到10.0MPa以上，400℃的剪切强度能达到7.0MPa以上，滚筒剥离强度能达到20.0Nmm/mm以上，平面拉伸强度能达到3.0N/mm2以上。Compared with the adhesive film products of the same heat-resistant grade, the modified bisphthalonitrile resin structural adhesive film of the present invention has a lower curing temperature, the curing temperature is 260 ° C; shorter curing time, the curing time is 2h . The modified bisphthalonitrile resin structural adhesive film prepared by the method of the present invention has good heat resistance and ablation resistance, the carbon residue rate is greater than 60% at 600°C, and the thermal weight loss rate of 10% reaches 500°C Above; it has high shear strength and high temperature resistance strength, the shear strength at room temperature can reach above 15.0MPa, the shear strength at 350°C can reach above 10.0MPa, the shear strength at 400°C can reach above 7.0MPa, and the roller peeling The strength can reach more than 20.0Nmm/mm, and the plane tensile strength can reach more than 3.0N/mm2.
具体实施方式Detailed ways
具体实施方式一：本实施方式的一种改性双邻苯二甲腈树脂结构胶膜，按照质量份数是由70～100份的主体树脂、10～40份的增韧剂、20～50份的成膜改性树脂和2～15份的填料制成；其中主体树脂由双酚A型双邻苯二甲腈树脂、联苯型双邻苯二甲腈树脂或酚羟基改性双邻苯二甲腈树脂中的一种或几种按任意比组成的混合物。Specific embodiment 1: A modified bisphthalonitrile resin structural film according to the present embodiment is composed of 70-100 parts by mass of main resin, 10-40 parts of toughening agent, 20-50 parts The main resin is made of bisphenol A type bisphthalonitrile resin, biphenyl type bisphthalonitrile resin or phenolic hydroxyl modified bisphthalonitrile resin. A mixture of one or several kinds of phthalonitrile resins in any ratio.
本实施方式的的改性双邻苯二甲腈树脂结构胶膜与同样耐热等级的胶膜产品相比，具有更低的固化温度，固化温度为260℃；更短的固化时间，固化时间为2h。Compared with the adhesive film products of the same heat-resistant grade, the modified bisphthalonitrile resin structural adhesive film of this embodiment has a lower curing temperature, the curing temperature is 260 ° C; shorter curing time, curing time for 2h.
具体实施方式二：本实施方式与具体实施方式一不同的是改性双邻苯二甲腈树脂胶膜按照质量份数是由80～95份的主体树脂、15～25份的增韧剂、25～40份的成膜改性树脂和5～12份的填料制成。其它步骤及参数与具体实施方式一相同。Specific embodiment two: the difference between this embodiment and specific embodiment one is that the modified bisphthalonitrile resin film is composed of 80-95 parts of main resin, 15-25 parts of toughening agent, It is prepared by 25-40 parts of film-forming modified resin and 5-12 parts of filler. Other steps and parameters are the same as those in Embodiment 1.
具体实施方式三：本实施方式与具体实施方式一或二不同的是改性双邻苯二甲腈树脂胶膜按照质量份数是由90份的主体树脂、20份的增韧剂、35份的成膜改性树脂和10份的填料制成。其它步骤及参数与具体实施方式一或二相同。Specific embodiment three: the difference between this embodiment and specific embodiment one or two is that the modified bisphthalonitrile resin film is composed of 90 parts of main resin, 20 parts of toughening agent, 35 parts of Made of film-forming modified resin and 10 parts of filler. Other steps and parameters are the same as those in Embodiment 1 or Embodiment 2.
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是增韧剂为聚酰胺酰亚胺(PAI)、聚醚酰亚胺(PEI)、聚苯并咪唑(PBI)、聚醚醚酮(PEEK)、酚酞基聚芳醚砜(PES-C)或酚酞基聚醚酮(PEK-C)中的一种或几种按任意比组成的混合物。。其它步骤及参数与具体实施方式一至三之一相同。Embodiment 4: This embodiment differs from Embodiment 1 to Embodiment 3 in that the toughening agent is polyamideimide (PAI), polyetherimide (PEI), polybenzimidazole (PBI), poly A mixture of one or more of ether ether ketone (PEEK), phenolphthalein-based polyarylether sulfone (PES-C) or phenolphthalein-based polyether ketone (PEK-C) in any ratio. . Other steps and parameters are the same as those in Embodiments 1 to 3.
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是成膜改性树脂由酚醛型氰酸酯、烯丙基双酚A、烯丙基酚醛、烯丙基双酚A改性双马树脂或烯丙基酚醛改性双马树脂中的一种或几种按任意比组成的混合物。其它步骤及参数与具体实施方式一至四之一相同。Embodiment 5: This embodiment is different from Embodiment 1 to Embodiment 4 in that the film-forming modified resin is modified from phenolic cyanate, allyl bisphenol A, allyl phenolic, and allyl bisphenol A. A mixture of one or several kinds of permanent double horse resin or allyl phenolic modified double horse resin in any ratio. Other steps and parameters are the same as in one of the specific embodiments 1 to 4.
具体实施方式六：本实施方式与具体实施方式一至五之一不同的是填料由白炭黑、纳米级钛白粉、纳米级云母粉、石棉粉或碳纳米管中的一种或几种按任意比组成的混合物。其它步骤及参数与具体实施方式一至五之一相同。Specific embodiment six: This embodiment is different from one of the specific embodiments one to five in that the filler is made of one or more of white carbon black, nano-scale titanium dioxide, nano-scale mica powder, asbestos powder or carbon nanotubes. than the composition of the mixture. Other steps and parameters are the same as one of the specific embodiments 1 to 5.
具体实施方式七：本实施方式的一种改性双邻苯二甲腈树脂结构胶膜的制备方法按照以下步骤进行：一、按照质量份数称取70～100份的主体树脂、10～40份的增韧剂、20～50份的成膜改性树脂和2～15份的填料；二、将步骤一中称取的成膜改性树脂与增韧剂在200℃反应釜中进行树脂共混20～40min；三、将步骤二中的反应釜降温至150℃；四、将步骤一中称取的主体树脂加入到降温后的反应釜中混匀；五、将步骤一中称取的填料加入到反应釜中搅拌均匀后倒出，得到胶料；六、将步骤五中的胶料在50℃～80℃的烘箱中预热20～40min，然后在辊温为60℃～80℃的胶膜压延机上用载体热压延成膜，即得到改性双邻苯二甲腈树脂结构胶膜。Specific Embodiment Seven: The preparation method of a modified bisphthalonitrile resin structural adhesive film in this embodiment is carried out according to the following steps: 1. Weigh 70 to 100 parts of the main resin, 10 to 40 parts according to the parts by mass Toughening agent of 20-50 parts, film-forming modified resin of 20～50 parts and filler of 2～15 parts; 2, the film-forming modified resin and toughening agent weighed in the step 1 are carried out resin in 200 ℃ reaction kettle Blending for 20-40 minutes; 3. Cool down the reaction kettle in step 2 to 150°C; 4. Add the main resin weighed in step 1 into the cooled reaction kettle and mix well; 5. Weigh the main resin in step 1 Add the filler into the reaction kettle and pour it out after stirring evenly to obtain the rubber material; 6. Preheat the rubber material in step 5 in an oven at 50°C to 80°C for 20 to 40 minutes, and then roll it at a temperature of 60°C to 80°C. ℃ on the adhesive film calendering machine, the film is formed by thermal calendering with the carrier, and the modified bisphthalonitrile resin structural adhesive film is obtained.
本实施方式的的方法制备的改性双邻苯二甲腈树脂结构胶膜具有良好的耐热性、耐烧蚀性，600℃时残炭率大于60％，10％的热失重率达到了500℃以上；具有较高的剪切强度和耐高温强度，常温剪切强度能达到15.0MPa以上，350℃的剪切强度能达到10.0MPa以上，400℃的剪切强度能达到7.0MPa以上，滚筒剥离强度能达到20.0Nmm/mm以上，平面拉伸强度能达到3.0N/mm2以上。The modified bisphthalonitrile resin structural adhesive film prepared by the method of this embodiment has good heat resistance and ablation resistance, the carbon residue rate is greater than 60% at 600°C, and the thermal weight loss rate of 10% reaches Above 500°C; with high shear strength and high temperature resistance strength, the shear strength at room temperature can reach above 15.0MPa, the shear strength at 350°C can reach above 10.0MPa, and the shear strength at 400°C can reach above 7.0MPa. The roller peel strength can reach more than 20.0Nmm/mm, and the plane tensile strength can reach more than 3.0N/mm2.
具体实施方式八：本实施方式与具体实施方式七不同的是步骤六中胶料在60℃～70℃之间的烘箱中预热30min。其它步骤及参数与具体实施方式一至七之一相同。Embodiment 8: The difference between this embodiment and Embodiment 7 is that in step 6, the rubber material is preheated in an oven between 60° C. and 70° C. for 30 minutes. Other steps and parameters are the same as one of the specific embodiments 1 to 7.
具体实施方式九：本实施方式与具体实施方式七或八不同的是步骤五中胶膜压延机的辊温为65℃～70℃。其它步骤及参数与具体实施方式一至八之一相同。Embodiment 9: The difference between this embodiment and Embodiment 7 or 8 is that the roll temperature of the film calender in step 5 is 65°C-70°C. Other steps and parameters are the same as those in Embodiments 1 to 8.
具体实施方式十：本实施方式与具体实施方式七至九之一不同的是步骤六中的载体为玻璃丝布或碳纤维布。其它步骤及参数与具体实施方式七至九之一相同。Embodiment 10: This embodiment is different from Embodiment 7 to Embodiment 9 in that the carrier in step 6 is glass cloth or carbon fiber cloth. Other steps and parameters are the same as one of the seventh to ninth specific embodiments.
通过以下试验验证本发明的有益效果：Prove the beneficial effect of the present invention by following test:
本试验的一种改性双邻苯二甲腈树脂结构胶膜及其制备方法制作方法按照以下步骤进行：一、按照质量分数比称取60份的双酚A型双邻苯二甲腈树脂、30份酚羟基改性双邻苯二甲腈树脂、10份的PAI、10份的PBI、20份的酚醛型氰酸酯、15份的烯丙基双酚A、4份的白炭黑、2份的纳米级钛白粉、2份的纳米级云母粉；二、将步骤一中称取的10份的PAI、10份的PBI、20份的酚醛型氰酸酯和15份的烯丙基双酚A在200℃反应釜中进行树脂共混30min；三、将步骤二中的反应釜降温至150℃；四、将步骤一中称取的60份的双酚A型双邻苯二甲腈树脂和30份酚羟基改性双邻苯二甲腈树脂加入到降温后的反应釜中混匀；五、将步骤一中称取的4份的白炭黑、2份的纳米级钛白粉和2份的纳米级云母粉加入到反应釜中搅拌均匀后倒出；六、将步骤五中的胶料在60℃到70℃的烘箱中预热30min，然后在辊温为65℃～70℃的胶膜压延机上用玻璃丝布热压延成膜，即得到改性双邻苯二甲腈树脂结构胶膜产品。A kind of modified bis-phthalonitrile resin structural adhesive film of this test and its preparation method The production method is carried out according to the following steps: one, take by weighing 60 parts of bisphenol A type bis-phthalonitrile resin according to the mass fraction ratio , 30 parts of phenolic hydroxyl modified bisphthalonitrile resin, 10 parts of PAI, 10 parts of PBI, 20 parts of phenolic cyanate, 15 parts of allyl bisphenol A, 4 parts of white carbon black , 2 parts of nano-scale titanium dioxide, 2 parts of nano-scale mica powder; 2, 10 parts of PAI, 10 parts of PBI, 20 parts of phenolic cyanate and 15 parts of allyl Base bisphenol A in a 200°C reactor for resin blending for 30min; 3. Cool down the reactor in step 2 to 150°C; Formaldehyde resin and 30 parts of phenolic hydroxyl modified bis-phthalonitrile resins are added to the reaction kettle after cooling and mixed; 5. 4 parts of white carbon black and 2 parts of nano-scale titanium Add the white powder and 2 parts of nano-sized mica powder into the reaction kettle, stir evenly and pour it out; 6. Preheat the rubber material in step 5 in an oven at 60°C to 70°C for 30 minutes, and then roll it at a temperature of 65°C~ The film is formed by thermal calendering with glass cloth on a film calender at 70°C, and the modified bisphthalonitrile resin structural film product is obtained.
本试验中的双酚A型双邻苯二甲腈树脂购买于中科院化学所；酚羟基改性双邻苯二甲腈树脂购买于中科院化学所；聚酰胺酰亚胺PAI购买于美国苏威；聚苯并咪唑PBI购买于美国杜邦；酚醛型氰酸酯购买于江都吴桥树脂厂；烯丙基双酚A购买于莱州市莱玉化工有限公司；白炭黑购买于沈阳化工股份有限公司；纳米级钛白粉购买于上海振江化工有限公司；纳米级云母粉购买于河北灵寿县北方矿业加工厂；玻璃丝布载体购买于杭州高科复合材料有限公司。The bisphenol A bis-phthalonitrile resin in this test was purchased from the Institute of Chemistry, Chinese Academy of Sciences; the phenolic hydroxyl modified bis-phthalonitrile resin was purchased from the Institute of Chemistry, Chinese Academy of Sciences; the polyamide-imide PAI was purchased from Solvay, USA; Polybenzimidazole PBI was purchased from DuPont in the United States; phenolic cyanate was purchased from Jiangdu Wuqiao Resin Factory; allyl bisphenol A was purchased from Laizhou Laiyu Chemical Co., Ltd.; white carbon black was purchased from Shenyang Chemical Co., Ltd.; The high-grade titanium dioxide was purchased from Shanghai Zhenjiang Chemical Co., Ltd.; the nano-scale mica powder was purchased from the North Mining Processing Plant in Lingshou County, Hebei; the glass cloth carrier was purchased from Hangzhou Gaoke Composite Materials Co., Ltd.
本试验的改性双邻苯二甲腈树脂结构胶膜与同样耐热等级的胶膜产品相比，具有更低的固化温度，固化温度为260℃；更短的固化时间，固化时间为2h。Compared with the film products of the same heat-resistant grade, the modified bisphthalonitrile resin structural adhesive film in this test has a lower curing temperature, the curing temperature is 260°C; a shorter curing time, the curing time is 2h .
本试验制备的的改性双邻苯二甲腈树脂结构胶膜具有良好的耐热性、耐烧蚀性。600℃时残炭率大于60％，在升温速率为10℃/min、空气氛，气流量为50mL/min的热失重条件下，10％的热失重率达到了500℃以上。在胶膜的厚度为0.15～0.20mm时，按照GB7124-2008(常温剪切强度标准)及GJB444-88(高温剪切强度标准)对胶膜粘接性能的剪切强度进行测试，剪切试片为高强度钢，表面进行喷砂处理。结果如表1所示，由表1可以看出本试验制备的改性双邻苯二甲腈树脂结构胶膜的剪切强度高、耐高温强度好。在胶膜厚度为0.35mm～0.40mm的条件下对本试验制备的改性双邻苯二甲腈树脂结构胶膜进行剥离强度进行测试得知，按照GBT1457-2005测试滚筒剥离强度能达到20.0Nmm/mm以上，按照GJB130.4-1986测试平面拉伸强度能达到3.0N/mm2以上。The modified bisphthalonitrile resin structural adhesive film prepared in this experiment has good heat resistance and ablation resistance. At 600°C, the carbon residue rate is greater than 60%. Under the conditions of thermal weight loss at a heating rate of 10°C/min, an air atmosphere, and an air flow rate of 50mL/min, the 10% thermal weight loss rate reaches above 500°C. When the thickness of the film is 0.15 ~ 0.20mm, according to GB7124-2008 (normal temperature shear strength standard) and GJB444-88 (high temperature shear strength standard) to test the shear strength of the adhesive performance of the film, the shear test The sheet is made of high-strength steel, and the surface is sandblasted. The results are shown in Table 1. It can be seen from Table 1 that the modified bisphthalonitrile resin structural adhesive film prepared in this test has high shear strength and good high temperature resistance strength. Under the condition that the thickness of the film is 0.35mm-0.40mm, the peel strength of the modified bisphthalonitrile resin structural film prepared in this test is tested. According to GBT1457-2005, the test roller peel strength can reach 20.0Nmm/ More than mm, according to GJB130.4-1986 test plane tensile strength can reach more than 3.0N/mm2.
对耐热老化性能进行测试得知，320℃/100h后剪切强度保持率在90％以上；湿热老化1000h后剪切强度保持率在90％以上。The heat aging resistance test shows that the shear strength retention rate is above 90% after 320°C/100h; the shear strength retention rate is above 90% after humid heat aging for 1000h.
表1改性双邻苯二甲腈树脂结构胶膜的剪切强度Table 1 The shear strength of modified bisphthalonitrile resin structural adhesive film
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980850A (en) * | 2014-06-09 | 2014-08-13 | 黑龙江省科学院石油化学研究院 | Phthalonitrile-modified phenol-formaldehyde resin adhesive and preparation method thereof |
| CN104845349A (en) * | 2015-05-25 | 2015-08-19 | 吉林大学 | PES (polyether sulfone) toughened bisphthalonitrile resin material and preparation method thereof |
| CN108659530A (en) * | 2018-04-28 | 2018-10-16 | 哈尔滨玻璃钢研究院有限公司 | A kind of the POSS modification bi-phthalonitriles and cyanate blending resin system of heatproof flame-retardant |
| CN109071808A (en) * | 2016-03-31 | 2018-12-21 | 3M创新有限公司 | Bis-phenol M bi-phthalonitrile ether resin blend and product comprising filler |
| 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 |
| CN113201302A (en) * | 2021-05-06 | 2021-08-03 | 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 |
| CN115466390A (en) * | 2022-09-13 | 2022-12-13 | 中国人民解放军国防科技大学 | A kind of low-temperature fast-curing imidazole-containing structure cyanate ester resin and preparation method thereof |
Citations (2)
| 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 bisphthalonitrile resin containing aryl ether nitrile segment, 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 |
-
2012
- 2012-11-28 CN CN 201210494916 patent/CN102936466B/en not_active Expired - Fee Related
Patent Citations (2)
| 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 bisphthalonitrile resin containing aryl ether nitrile segment, 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 |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103980850A (en) * | 2014-06-09 | 2014-08-13 | 黑龙江省科学院石油化学研究院 | Phthalonitrile-modified phenol-formaldehyde resin adhesive and preparation method thereof |
| 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 |
| CN104845349A (en) * | 2015-05-25 | 2015-08-19 | 吉林大学 | PES (polyether sulfone) toughened bisphthalonitrile resin material and preparation method thereof |
| US11401364B2 (en) | 2016-03-31 | 2022-08-02 | 3M Innovative Properties Company | Bisphenol M diphthalonitrile ether resin, bisphenol P diphthalonitrile ether resin, methods of making same, resin blends, and two component systems |
| CN109071808A (en) * | 2016-03-31 | 2018-12-21 | 3M创新有限公司 | Bis-phenol M bi-phthalonitrile ether resin blend and product comprising filler |
| US10899865B2 (en) | 2016-03-31 | 2021-01-26 | 3M Innovative Properties Company | Bisphenol M diphthalonitrile ether resin blends including a filler, and articles |
| CN108659530A (en) * | 2018-04-28 | 2018-10-16 | 哈尔滨玻璃钢研究院有限公司 | A kind of the POSS modification bi-phthalonitriles and cyanate blending resin system of heatproof flame-retardant |
| 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 |
| CN113201302A (en) * | 2021-05-06 | 2021-08-03 | 黑龙江省科学院石油化学研究院 | Diamino bisphthalonitrile modified epoxy resin adhesive and preparation method thereof |
| CN113201302B (en) * | 2021-05-06 | 2023-03-03 | 黑龙江省科学院石油化学研究院 | A kind of bisaminobisphthalonitrile 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 |
| CN115466390A (en) * | 2022-09-13 | 2022-12-13 | 中国人民解放军国防科技大学 | A kind of low-temperature fast-curing imidazole-containing structure cyanate ester resin and preparation method thereof |
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