WO2023070727A1 - Method for producing thermosetting phenolic resin-based composite material - Google Patents
Method for producing thermosetting phenolic resin-based composite material Download PDFInfo
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- WO2023070727A1 WO2023070727A1 PCT/CN2021/128898 CN2021128898W WO2023070727A1 WO 2023070727 A1 WO2023070727 A1 WO 2023070727A1 CN 2021128898 W CN2021128898 W CN 2021128898W WO 2023070727 A1 WO2023070727 A1 WO 2023070727A1
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- resin
- phenolic resin
- composite material
- thermosetting phenolic
- based composite
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- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 61
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 60
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims description 14
- 239000003365 glass fiber Substances 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052580 B4C Inorganic materials 0.000 claims description 2
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 abstract description 5
- 238000009755 vacuum infusion Methods 0.000 abstract description 2
- 238000001802 infusion Methods 0.000 abstract 2
- 238000001723 curing Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 230000002787 reinforcement Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000012779 reinforcing material Substances 0.000 description 6
- IWXAZSAGYJHXPX-BCEWYCLDSA-N Bisbentiamine Chemical compound C=1C=CC=CC=1C(=O)OCC/C(SS\C(CCOC(=O)C=1C=CC=CC=1)=C(/C)N(CC=1C(=NC(C)=NC=1)N)C=O)=C(/C)N(C=O)CC1=CN=C(C)N=C1N IWXAZSAGYJHXPX-BCEWYCLDSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000009745 resin transfer moulding Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000002679 ablation Methods 0.000 description 2
- 239000003733 fiber-reinforced composite Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
- B29C70/342—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation using isostatic pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
Definitions
- the invention belongs to the technical field of production of phenolic resin-based composite materials, and relates to a method for producing thermosetting phenolic resin-based composite materials.
- Phenolic resin is the first artificially synthesized high molecular polymer invented in the world. From 1905 to 1909, L.H. Baekeland conducted systematic research on phenolic resin and its molding process. In 1910, he established a general-purpose phenolic resin company in the Ruegers factory in Berlin and realized industrial production. Phenolic resin-based composite materials also have a long history and are widely used in fields such as fire prevention, flame retardancy, insulation, and ablation resistance.
- thermosetting phenolic resins are divided into two categories: thermosetting and thermoplastic. Among them, thermosetting phenolic resins are mainly used for continuous fiber reinforced composite materials. There are two main curing methods for thermosetting phenolic resins. One is direct heating and curing, and the other is curing at a lower temperature after adding an acid curing agent.
- Thermosetting phenolic resin itself has a relatively high molecular weight and is in a solid or semi-solid state at room temperature.
- solvents such as ethanol, acetone, and isopropanol are used to dilute the phenolic resin to become a liquid.
- phenolic resins are used to prepare composite materials through the RTM process.
- Chinese patent CN101417516 discloses a method of using two sets of RTM injection systems to simultaneously inject epoxy resin and phenolic resin to produce aerospace structural parts.
- Chinese patent CN101080313 discloses a method for preparing a low-porosity phenolic resin-based composite material using a resin transfer molding process, which is essentially a deformation of the autoclave process, and its product size is limited by the size of the pressurized tank; the molding pressure Also relatively high, 1.0-2.5MPa.
- Chinese patent CN108407336 discloses a method for preparing three-dimensional fabric-reinforced phenolic resin-based composite materials for high-speed aircraft and spacecraft using RTM technology. The main feature is to use an open exhaust method to discharge water generated when the phenolic resin is solidified.
- Chinese patent CN104760303 discloses a method for preparing the adiabatic diffusion section of a solid rocket motor using an improved VARTM process, the main feature of which is the use of an expandable silicone soft mold.
- the resin used is RTM barium phenolic resin produced by Beijing Glass Steel Institute Composite Materials Co., Ltd., which has a high solid content (90.92%) and a viscosity of 255mPa.s at 80°C.
- the vacuum introduction process is a commonly used molding process for continuous fiber reinforced composite materials.
- the vacuum is used to pump the resin into the space between the mold and the vacuum bag, infiltrate the fibers, and obtain a composite material after curing.
- the vacuum introduction process generally uses unsaturated polyester resin, vinyl ester resin and epoxy resin, and there is no report on the use of phenolic resin in the vacuum introduction process.
- the present invention provides a method for producing a thermosetting phenolic resin-based composite material, which has a simple production process, less investment, low cost, wide application range, and low porosity of the prepared composite material.
- thermosetting phenolic resin-based composite material A method for producing a thermosetting phenolic resin-based composite material, using a vacuum introduction process, using a thermosetting phenolic resin as a resin matrix, the thermosetting phenolic resin contains no more than 25% by weight of an organic solvent, and the viscosity at the introduction temperature is less than 300mPa.s; When the resin is cured, no acidic curing agent is added and the temperature is heated and cured in steps. The introduction temperature is 50-70°C, and the highest curing temperature is 100-130°C.
- Acidic curing agent refers to the acidic substance added to the phenolic resin, which can reduce the curing temperature of the phenolic resin.
- thermosetting phenolic resin is catalyzed and synthesized by a basic catalyst, the phenolic molar ratio is 1:1.2-1:1.6, it can gel at 80-100°C, and it can be cross-linked and cured at 100-130°C.
- a spare suction pipe is added on the basis of the conventional vacuum introduction process.
- the suction pipe is blocked by resin, it is switched to a spare suction pipe in turn so that the vacuum can continue.
- one resin pipe, one air extraction pipe and at least one spare air extraction pipe are respectively laid on both sides of the reinforcing material, the air extraction pipe is connected to a vacuum pump, and the resin pipe and the spare air extraction pipe are tied tightly to make it airtight , turn on the vacuum pump, and draw a vacuum through the exhaust pipe.
- the gradient temperature heating and curing refers to: after the introduction of the resin, the introduction temperature is gradually and slowly increased to 120-130° C. by heating in a drying room, an oven or a mold, and the heating time is not less than 2 hours.
- the composite material includes fiber-reinforced phenolic resins such as glass fiber (including quartz fiber and high silica fiber), carbon fiber, ceramic fiber, basalt fiber, boron fiber, boron carbide fiber, silicon carbide fiber, and aramid fiber.
- fiber-reinforced phenolic resins such as glass fiber (including quartz fiber and high silica fiber), carbon fiber, ceramic fiber, basalt fiber, boron fiber, boron carbide fiber, silicon carbide fiber, and aramid fiber.
- thermosetting phenolic resin-based composite materials using a vacuum introduction process, which changes the traditional cognition that phenolic resins are not suitable for vacuum introduction processes in the field.
- the production process is simple, with less investment, low cost, and a wide range of applications.
- the composite material has low porosity and excellent performance.
- the vacuum introduction molding process is a new molding process developed in the industry in the past 20 years.
- the basic method is to first spread the reinforcing material on the mold, and then spread the vacuum bag film, and vacuum through the vacuum pump to make the mold and the vacuum bag A vacuum is created between the membranes. Finally, under the action of vacuum, the resin matrix is sucked between the mold and the vacuum bag to impregnate the reinforcing material, and then the resin is cured at room temperature or under heating conditions, and finally demoulded to form a composite material, mainly using unsaturated polyester resin, vinyl Ester resins and epoxy resins.
- phenolic resin is not suitable for vacuum introduction process.
- the inventors of the present application have found in research practice that as long as the reaction temperature, speed, degree and process control parameters of the phenolic resin are matched well, the reaction speed of the resin is relatively slow when the early exhaust is made, and the solvent and water when the resin begins to gel Without boiling, phenolic resin-based composites can be produced using a vacuum infusion process.
- thermosetting phenolic resin used in the present invention contains an organic solvent not higher than 25% by weight, and has a viscosity of less than 300mPa.s at 50°C; it can be synthesized using an alkaline catalyst, and the phenolic molar ratio is 1:1.2 to 1: 1.6, phenolic resin that can be gelled at 80-100°C, and can be cross-linked and cured at 100-130°C.
- the above thermosetting phenolic resin has the characteristics of less solvent content, low viscosity, fast reaction speed and low curing temperature.
- PF series phenolic resins publicly available from Beston Composite Materials (Wuhan) Co., Ltd. were used.
- a resin pipe, a suction pipe and a spare suction pipe are respectively laid on both sides of the reinforcement material, and the suction pipe and the spare suction pipe are connected to the vacuum pump through the buffer tank. Tighten the resin tube and spare exhaust tube to make it airtight, turn on the vacuum pump, and draw a vacuum through the exhaust tube.
- Preheat BST-PF21 phenolic resin (provided by Beston Composite Materials (Wuhan) Co., Ltd., containing 25% ethanol, viscosity 200-300cP at 50°C) to 60 ⁇ 5°C, immerse the resin tube in the resin, release Ties to allow resin to be drawn in through the resin tube. When the resin has completely saturated the reinforcement, re-tighten the resin tube so that there is no air leakage.
- a resin pipe, a suction pipe and a spare suction pipe are respectively laid on both sides of the reinforcing material, and the suction pipe and the spare suction pipe are connected to the vacuum pump through the buffer tank. Tighten the resin tube and spare exhaust tube to make it airtight, turn on the vacuum pump, and draw a vacuum through the exhaust tube.
- Preheat BST-PF21 phenolic resin (provided by Beston Composite Materials (Wuhan) Co., Ltd., containing 25% ethanol, viscosity 200-300cP at 50°C) to 55 ⁇ 5°C, immerse the resin tube in the resin, release Ties to allow resin to be drawn in through the resin tube. When the resin has completely saturated the reinforcement, re-tighten the resin tube so that there is no air leakage.
- a resin pipe, a suction pipe and a spare suction pipe are respectively laid on both sides of the reinforcement material, and the suction pipe and the spare suction pipe are connected to the vacuum pump through the buffer tank. Tighten the resin tube and spare exhaust tube to make it airtight, turn on the vacuum pump, and draw a vacuum through the exhaust tube.
- Preheat BST-PF22 phenolic resin (provided by Beston Composite Materials (Wuhan) Co., Ltd., containing 15% ethanol, viscosity 200-300cP at 50°C) to 60 ⁇ 5°C, immerse the resin tube in the resin, release Ties to allow resin to be drawn in through the resin tube. When the resin has completely saturated the reinforcement, re-tighten the resin tube so that there is no air leakage.
- a resin pipe, a suction pipe and a spare suction pipe are respectively laid on both sides of the reinforcement material, and the suction pipe and the spare suction pipe are connected to the vacuum pump through the buffer tank. Tighten the resin tube and spare exhaust tube to make it airtight, turn on the vacuum pump, and draw a vacuum through the exhaust tube.
- Preheat BST-PF23 phenolic resin (provided by Beston Composite Materials (Wuhan) Co., Ltd., no organic solvent added, viscosity 200-300cP at 60°C) to 65 ⁇ 5°C, immerse the resin tube in the resin, release the tie belt to allow resin to be drawn in through the resin tube. When the resin has completely saturated the reinforcement, re-tighten the resin tube so that there is no air leakage.
- Example 1 Example 2
- Example 3 Example 4 Bending strength (MPa) 352 294 378 419 Fiber weight (g) 318 372 318 318 Sample thickness (mm) 3.7 3.7 3.7 3.7 3.7 Sample weight (g) 502 486 511 522 Apparent density (g/cm ⁇ 3) 1.51 1.46 1.53 1.57 Porosity(%) 14.4 18.5 12 9.1
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- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Provided is a method for producing a thermosetting phenolic resin-based composite material. A vacuum infusion process is used, a thermosetting phenolic resin is used as a resin matrix, the thermosetting phenolic resin contains not more than 25% by weight of an organic solvent, and the viscosity under the infusion temperature is less than 300 mPa.s; when the resin is cured, an acidic curing agent is not added, gradient temperature heating curing is adopted, the infusion temperature is 50-70℃, and the highest-stage curing temperature is 100-130℃. The production process is simple, the investment is low, the cost is low, the application range is wide, and the prepared composite material is low in porosity and excellent in performance.
Description
本发明属于酚醛树脂基复合材料生产技术领域，涉及生产热固性酚醛树脂基复合材料的方法。The invention belongs to the technical field of production of phenolic resin-based composite materials, and relates to a method for producing thermosetting phenolic resin-based composite materials.
酚醛树脂是世界上最早发明的人工合成高分子聚合物。1905～1909年L.H.贝克兰对酚醛树脂及其成型工艺进行了系统的研究，1910年在柏林吕格斯工厂建立通用酚醛树脂公司，实现了工业生产。酚醛树脂基复合材料也具有悠久的历史，广泛应用于防火、阻燃、绝缘、耐烧蚀等领域。Phenolic resin is the first artificially synthesized high molecular polymer invented in the world. From 1905 to 1909, L.H. Baekeland conducted systematic research on phenolic resin and its molding process. In 1910, he established a general-purpose phenolic resin company in the Ruegers factory in Berlin and realized industrial production. Phenolic resin-based composite materials also have a long history and are widely used in fields such as fire prevention, flame retardancy, insulation, and ablation resistance.
酚醛树脂分为热固性和热塑性两大类，其中用于连续纤维增强复合材料的，主要是热固性酚醛树脂。热固性酚醛树脂，主要有两种固化方式。一种是直接加热固化，另外一种是加入酸性固化剂后，在较低温度下固化。Phenolic resins are divided into two categories: thermosetting and thermoplastic. Among them, thermosetting phenolic resins are mainly used for continuous fiber reinforced composite materials. There are two main curing methods for thermosetting phenolic resins. One is direct heating and curing, and the other is curing at a lower temperature after adding an acid curing agent.
热固性酚醛树脂本身具有较高的分子量，常温下为固体或半固体状态。通常，为了施工方便，会使用乙醇、丙酮、异丙醇等溶剂对酚醛树脂进行稀释，成为液体。制备复合材料时，一般可以采用以下两种方法：Thermosetting phenolic resin itself has a relatively high molecular weight and is in a solid or semi-solid state at room temperature. Usually, for the convenience of construction, solvents such as ethanol, acetone, and isopropanol are used to dilute the phenolic resin to become a liquid. When preparing composite materials, the following two methods can generally be used:
1.先用含有溶剂的酚醛树脂液体，浸渍玻璃纤维、碳纤维等增强材料，然后自然晾干或烘干制成预浸料。第二步再将预浸料铺覆到模具中，使用热压罐或模压成型工艺，在较高温度下(一般大于150℃)使树脂固化，制成复合材料。这种方法制成的复合材料几乎不含有溶剂，含水量也很低，具有孔隙率低，力学性能好，耐烧蚀，残碳率高的特点。但是，这种方法工艺过程复杂，设备和模具投入较大，限制了其使用场景。特别是超过了液压机和热压罐尺寸限制的大型复合材料制品，无法使用这种方法制造。1. First impregnate reinforcing materials such as glass fiber and carbon fiber with solvent-containing phenolic resin liquid, and then dry naturally or dry to make prepreg. In the second step, the prepreg is applied to the mold, and the resin is cured at a higher temperature (generally greater than 150°C) by using an autoclave or compression molding process to make a composite material. The composite material produced by this method contains almost no solvent, low water content, low porosity, good mechanical properties, ablation resistance, and high carbon residual rate. However, the process of this method is complicated, and the investment in equipment and molds is large, which limits its application scenarios. In particular, large composite articles that exceed the dimensional limitations of hydraulic presses and autoclaves cannot be manufactured using this method.
2.在含有溶剂的酚醛树脂液体中，加入酸性固化剂，然后浸渍玻璃纤维、碳纤维等增强材料，铺覆到模具上，使其在较低温度下固化(100℃以内)。使用这种方法制备的复合材料，含有大量未挥发的溶剂和水，孔隙率高、力学性能也较差。2. Add acidic curing agent to the phenolic resin liquid containing solvent, then impregnate glass fiber, carbon fiber and other reinforcing materials, spread it on the mold, and let it cure at a lower temperature (within 100°C). Composite materials prepared by this method contain a large amount of non-volatile solvent and water, have high porosity and poor mechanical properties.
另外，在某些不计成本的领域，还有一些使用特殊的酚醛树脂，通过RTM 工艺制备复合材料。例如，中国专利CN101417516就公开了一种使用两套RTM注射系统同时注射环氧树脂和酚醛树脂生产航空航天结构件的方法。中国专利CN101080313公开了一种使用树脂传递模塑工艺制备低孔隙率酚醛树脂基复合材料的方法，其实质为热压罐工艺的一种变形，其产品尺寸受加压罐大小的限制；成型压力也较高，为1.0～2.5MPa。中国专利CN108407336公开了一种使用RTM工艺制备用于高速飞行器、航天器的立体织物增强酚醛树脂基复合材料的方法，主要特征是采用敞口排气的方法，排出酚醛树脂固化时产生的水。中国专利CN104760303公开了一种使用改进的VARTM工艺制备固体火箭发动机绝热扩散段的方法，主要特征是使用了可膨胀硅胶软模。其使用的树脂为北京玻钢院复合材料有限公司生产的RTM钡酚醛树脂，具有高固含(90.92％)的特点，80℃下粘度为255mPa.s。In addition, in some fields regardless of cost, some special phenolic resins are used to prepare composite materials through the RTM process. For example, Chinese patent CN101417516 discloses a method of using two sets of RTM injection systems to simultaneously inject epoxy resin and phenolic resin to produce aerospace structural parts. Chinese patent CN101080313 discloses a method for preparing a low-porosity phenolic resin-based composite material using a resin transfer molding process, which is essentially a deformation of the autoclave process, and its product size is limited by the size of the pressurized tank; the molding pressure Also relatively high, 1.0-2.5MPa. Chinese patent CN108407336 discloses a method for preparing three-dimensional fabric-reinforced phenolic resin-based composite materials for high-speed aircraft and spacecraft using RTM technology. The main feature is to use an open exhaust method to discharge water generated when the phenolic resin is solidified. Chinese patent CN104760303 discloses a method for preparing the adiabatic diffusion section of a solid rocket motor using an improved VARTM process, the main feature of which is the use of an expandable silicone soft mold. The resin used is RTM barium phenolic resin produced by Beijing Glass Steel Institute Composite Materials Co., Ltd., which has a high solid content (90.92%) and a viscosity of 255mPa.s at 80°C.
真空导入工艺是连续纤维增强复合材料常用的一种成型工艺，采用真空将树脂抽进模具和真空袋之间的空间，对纤维浸润，固化后得到复合材料。真空导入工艺一般使用不饱和聚酯树脂、乙烯基酯树脂和环氧树脂，将酚醛树脂用于真空导入工艺未见报道。The vacuum introduction process is a commonly used molding process for continuous fiber reinforced composite materials. The vacuum is used to pump the resin into the space between the mold and the vacuum bag, infiltrate the fibers, and obtain a composite material after curing. The vacuum introduction process generally uses unsaturated polyester resin, vinyl ester resin and epoxy resin, and there is no report on the use of phenolic resin in the vacuum introduction process.
发明内容Contents of the invention
针对上述技术问题，本发明提供了生产热固性酚醛树脂基复合材料的方法，生产工艺简单，投入少，成本低，适用范围广泛，制备的复合材料孔隙率低。Aiming at the above technical problems, the present invention provides a method for producing a thermosetting phenolic resin-based composite material, which has a simple production process, less investment, low cost, wide application range, and low porosity of the prepared composite material.
为了实现上述技术目的，本发明采用的技术方案为：In order to realize above-mentioned technical purpose, the technical scheme that the present invention adopts is:
生产热固性酚醛树脂基复合材料的方法，使用真空导入工艺，采用热固性酚醛树脂作为树脂基体，所述热固性酚醛树脂含有不高于重量比25％的有机溶剂，且导入温度下粘度小于300mPa.s；树脂固化时不添加酸性固化剂且采用梯次温度加热固化，导入温度为50～70℃，最高段固化温度为100～130℃。A method for producing a thermosetting phenolic resin-based composite material, using a vacuum introduction process, using a thermosetting phenolic resin as a resin matrix, the thermosetting phenolic resin contains no more than 25% by weight of an organic solvent, and the viscosity at the introduction temperature is less than 300mPa.s; When the resin is cured, no acidic curing agent is added and the temperature is heated and cured in steps. The introduction temperature is 50-70°C, and the highest curing temperature is 100-130°C.
酸性固化剂是指加入到酚醛树脂中，可以降低酚醛树脂固化温度的酸性物质。Acidic curing agent refers to the acidic substance added to the phenolic resin, which can reduce the curing temperature of the phenolic resin.
优选地，所述热固性酚醛树脂是使用碱性催化剂催化合成、酚醛摩尔比为1:1.2～1:1.6、80～100℃可以凝胶、100～130℃可以交联固化的酚醛树脂。Preferably, the thermosetting phenolic resin is catalyzed and synthesized by a basic catalyst, the phenolic molar ratio is 1:1.2-1:1.6, it can gel at 80-100°C, and it can be cross-linked and cured at 100-130°C.
优选地，在常规真空导入工艺基础上增加备用抽气管，当抽气管被树脂堵 塞后，依次切换成备用抽气管，使真空能够持续。Preferably, a spare suction pipe is added on the basis of the conventional vacuum introduction process. When the suction pipe is blocked by resin, it is switched to a spare suction pipe in turn so that the vacuum can continue.
更优选地，分别在增强材料的两侧铺设1根树脂管、1根抽气管和至少1根备用抽气管，抽气管连接到真空泵，扎紧树脂管和备用抽气管，使其密封不漏气，开启真空泵，通过抽气管抽真空。More preferably, one resin pipe, one air extraction pipe and at least one spare air extraction pipe are respectively laid on both sides of the reinforcing material, the air extraction pipe is connected to a vacuum pump, and the resin pipe and the spare air extraction pipe are tied tightly to make it airtight , turn on the vacuum pump, and draw a vacuum through the exhaust pipe.
优选地，所述梯次温度加热固化是指：树脂导入完成后，通过烘房、烘箱或模具加热的方式，从导入温度逐渐缓慢升高到120～130℃，升温时间不小于2小时。Preferably, the gradient temperature heating and curing refers to: after the introduction of the resin, the introduction temperature is gradually and slowly increased to 120-130° C. by heating in a drying room, an oven or a mold, and the heating time is not less than 2 hours.
优选地，所述复合材料的孔隙率<＝20％。Preferably, the porosity of the composite material is <=20%.
优选地，所述复合材料包括玻璃纤维(含石英纤维、高硅氧纤维)、碳纤维、陶瓷纤维、玄武岩纤维、硼纤维、碳化硼纤维、碳化硅纤维、芳纶纤维等纤维增强的酚醛树脂。Preferably, the composite material includes fiber-reinforced phenolic resins such as glass fiber (including quartz fiber and high silica fiber), carbon fiber, ceramic fiber, basalt fiber, boron fiber, boron carbide fiber, silicon carbide fiber, and aramid fiber.
本发明的有益效果为：The beneficial effects of the present invention are:
提供了使用真空导入工艺生产热固性酚醛树脂基复合材料的方法，改变了领域内酚醛树脂不适合用于真空导入工艺的传统认知，生产工艺简单，投入少，成本低，适用范围广泛，制备的复合材料孔隙率低，性能优异。Provides a method for producing thermosetting phenolic resin-based composite materials using a vacuum introduction process, which changes the traditional cognition that phenolic resins are not suitable for vacuum introduction processes in the field. The production process is simple, with less investment, low cost, and a wide range of applications. The composite material has low porosity and excellent performance.
为了更清楚地说明本发明，下面结合实施例对本发明作进一步详细说明。本领域技术人员应当理解，下面所具体描述的内容是说明性的而非限制性的，不应以此限制本发明的保护范围。In order to illustrate the present invention more clearly, the present invention will be further described in detail below in conjunction with the examples. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not limit the protection scope of the present invention.
真空导入成型工艺是本行业近20年内发展起来的一种新的成型工艺，其基本方法是先在模具上铺贴增强材料，然后铺贴真空袋膜，通过真空泵抽真空，使模具和真空袋膜之间形成真空。最后在真空的作用下，将树脂基体吸入模具和真空袋之间浸渍增强材料后，在常温下或加热条件下使树脂固化，最后脱模形成复合材料，主要使用不饱和聚酯树脂、乙烯基酯树脂和环氧树脂。The vacuum introduction molding process is a new molding process developed in the industry in the past 20 years. The basic method is to first spread the reinforcing material on the mold, and then spread the vacuum bag film, and vacuum through the vacuum pump to make the mold and the vacuum bag A vacuum is created between the membranes. Finally, under the action of vacuum, the resin matrix is sucked between the mold and the vacuum bag to impregnate the reinforcing material, and then the resin is cured at room temperature or under heating conditions, and finally demoulded to form a composite material, mainly using unsaturated polyester resin, vinyl Ester resins and epoxy resins.
本专业一般认为酚醛树脂不适合用于真空导入工艺。本申请发明人在研究实践中发现，只要将酚醛树脂的反应温度、速度、程度和工艺控制参数良好的匹配，使早期排气时树脂的反应速度较慢，而树脂开始凝胶时溶剂和水不沸腾，可以使用真空导入工艺生产酚醛树脂基复合材料。The profession generally believes that phenolic resin is not suitable for vacuum introduction process. The inventors of the present application have found in research practice that as long as the reaction temperature, speed, degree and process control parameters of the phenolic resin are matched well, the reaction speed of the resin is relatively slow when the early exhaust is made, and the solvent and water when the resin begins to gel Without boiling, phenolic resin-based composites can be produced using a vacuum infusion process.
本发明中采用的热固性酚醛树脂，含有不高于重量比25％的有机溶剂，且50℃下粘度小于300mPa.s；可以是使用碱性催化剂催化合成、酚醛摩尔比为1:1.2～1:1.6、80～100℃可以凝胶、100～130℃可以交联固化的酚醛树脂。以上热固性酚醛树脂具有溶剂含量少，粘度低，反应速度快，固化温度低的特点。实施例1-4中采用百思通复合材料(武汉)有限公司公开发售的PF系列酚醛树脂。The thermosetting phenolic resin used in the present invention contains an organic solvent not higher than 25% by weight, and has a viscosity of less than 300mPa.s at 50°C; it can be synthesized using an alkaline catalyst, and the phenolic molar ratio is 1:1.2 to 1: 1.6, phenolic resin that can be gelled at 80-100°C, and can be cross-linked and cured at 100-130°C. The above thermosetting phenolic resin has the characteristics of less solvent content, low viscosity, fast reaction speed and low curing temperature. In Examples 1-4, PF series phenolic resins publicly available from Beston Composite Materials (Wuhan) Co., Ltd. were used.
实施例1Example 1
先将模具清洁并涂覆脱模剂，然后在模具上铺贴27层300*300mm的018玻璃纤维方格布(重量为318g)；然后铺上1层脱模布，最后铺上真空袋膜并用密封胶条密封。分别在增强材料的两侧铺设1根树脂管、1根抽气管和1根备用抽气管，抽气管和备用抽气管通过缓冲罐连接到真空泵。扎紧树脂管和备用抽气管，使其密封不漏气，开启真空泵，通过抽气管抽真空。Clean the mold first and apply a release agent, then spread 27 layers of 300*300mm 018 glass fiber grid cloth (weight 318g) on the mold; then spread a layer of release cloth, and finally lay a vacuum bag film And seal with sealing tape. A resin pipe, a suction pipe and a spare suction pipe are respectively laid on both sides of the reinforcement material, and the suction pipe and the spare suction pipe are connected to the vacuum pump through the buffer tank. Tighten the resin tube and spare exhaust tube to make it airtight, turn on the vacuum pump, and draw a vacuum through the exhaust tube.
将BST-PF21酚醛树脂(百思通复合材料(武汉)有限公司提供，含有25％的乙醇，50℃下粘度200-300cP)预热到60±5℃，将树脂管浸入树脂中，放开扎带，使树脂通过树脂管抽入。当树脂完全浸透增强材料后，将树脂管重新扎紧，不漏气。Preheat BST-PF21 phenolic resin (provided by Beston Composite Materials (Wuhan) Co., Ltd., containing 25% ethanol, viscosity 200-300cP at 50°C) to 60±5°C, immerse the resin tube in the resin, release Ties to allow resin to be drawn in through the resin tube. When the resin has completely saturated the reinforcement, re-tighten the resin tube so that there is no air leakage.
持续开启真空，将模具放入烘箱内，经过4小时将烘箱温度从60℃逐渐升高到130℃，待树脂完全固化后，从烘箱取出，脱模，获得玻璃纤维增强酚醛树脂基复合材料板一块。Continue to turn on the vacuum, put the mold into the oven, and gradually increase the oven temperature from 60°C to 130°C after 4 hours. After the resin is completely cured, take it out of the oven and demould to obtain a glass fiber reinforced phenolic resin matrix composite material board piece.
上述过程中，当抽气管被抽出的树脂堵塞后，打开备用抽气管，使真空持续。During the above process, when the exhaust pipe is blocked by the extracted resin, open the spare exhaust pipe to keep the vacuum.
测试上述复合材料板的弯曲强度、表观密度和孔隙率。The flexural strength, apparent density and porosity of the above-mentioned composite panels were tested.
实施例2Example 2
先将模具清洁并涂覆脱模剂，然后在模具上铺贴6层300*300mm的600g/m
2玻璃纤维双轴向布(重量为372g)；然后铺上1层脱模布，最后铺上真空袋膜并用密封胶条密封。分别在增强材料的两侧铺设1根树脂管、1根抽气管和1根备用抽气管，抽气管和备用抽气管通过缓冲罐连接到真空泵。扎紧树脂管和备用抽气管，使其密封不漏气，开启真空泵，通过抽气管抽真空。
First clean the mold and apply a release agent, then spread 6 layers of 300*300mm 600g/ m2 glass fiber biaxial cloth (weight is 372g) on the mold; then spread a layer of release cloth, and finally lay Vacuum bag and seal with sealing tape. A resin pipe, a suction pipe and a spare suction pipe are respectively laid on both sides of the reinforcing material, and the suction pipe and the spare suction pipe are connected to the vacuum pump through the buffer tank. Tighten the resin tube and spare exhaust tube to make it airtight, turn on the vacuum pump, and draw a vacuum through the exhaust tube.
将BST-PF21酚醛树脂(百思通复合材料(武汉)有限公司提供，含有25％ 的乙醇，50℃下粘度200-300cP)预热到55±5℃，将树脂管浸入树脂中，放开扎带，使树脂通过树脂管抽入。当树脂完全浸透增强材料后，将树脂管重新扎紧，不漏气。Preheat BST-PF21 phenolic resin (provided by Beston Composite Materials (Wuhan) Co., Ltd., containing 25% ethanol, viscosity 200-300cP at 50°C) to 55±5°C, immerse the resin tube in the resin, release Ties to allow resin to be drawn in through the resin tube. When the resin has completely saturated the reinforcement, re-tighten the resin tube so that there is no air leakage.
持续开启真空，将模具放入烘箱内，经过4小时将烘箱温度从55℃逐渐升高到130℃，待树脂完全固化后，从烘箱取出，脱模，获得玻璃纤维增强酚醛树脂基复合材料板一块。Continue to turn on the vacuum, put the mold into the oven, and gradually increase the oven temperature from 55°C to 130°C after 4 hours. After the resin is completely cured, take it out of the oven and demould to obtain a glass fiber reinforced phenolic resin matrix composite material board piece.
上述过程中，当抽气管被抽出的树脂堵塞后，打开备用抽气管，使真空持续。During the above process, when the exhaust pipe is blocked by the extracted resin, open the spare exhaust pipe to keep the vacuum.
测试上述复合材料板的弯曲强度、表观密度和孔隙率。The flexural strength, apparent density and porosity of the above-mentioned composite panels were tested.
实施例3Example 3
先将模具清洁并涂覆脱模剂，然后在模具上铺贴27层300*300mm的018玻璃纤维方格布(重量为318g)；然后铺上1层脱模布，最后铺上真空袋膜并用密封胶条密封。分别在增强材料的两侧铺设1根树脂管、1根抽气管和1根备用抽气管，抽气管和备用抽气管通过缓冲罐连接到真空泵。扎紧树脂管和备用抽气管，使其密封不漏气，开启真空泵，通过抽气管抽真空。Clean the mold first and apply a release agent, then spread 27 layers of 300*300mm 018 glass fiber grid cloth (weight 318g) on the mold; then spread a layer of release cloth, and finally lay a vacuum bag film And seal with sealing tape. A resin pipe, a suction pipe and a spare suction pipe are respectively laid on both sides of the reinforcement material, and the suction pipe and the spare suction pipe are connected to the vacuum pump through the buffer tank. Tighten the resin tube and spare exhaust tube to make it airtight, turn on the vacuum pump, and draw a vacuum through the exhaust tube.
将BST-PF22酚醛树脂(百思通复合材料(武汉)有限公司提供，含有15％的乙醇，50℃下粘度200-300cP)预热到60±5℃，将树脂管浸入树脂中，放开扎带，使树脂通过树脂管抽入。当树脂完全浸透增强材料后，将树脂管重新扎紧，不漏气。Preheat BST-PF22 phenolic resin (provided by Beston Composite Materials (Wuhan) Co., Ltd., containing 15% ethanol, viscosity 200-300cP at 50°C) to 60±5°C, immerse the resin tube in the resin, release Ties to allow resin to be drawn in through the resin tube. When the resin has completely saturated the reinforcement, re-tighten the resin tube so that there is no air leakage.
持续开启真空，将模具放入烘箱内，经过5小时将烘箱温度从60℃逐渐升高到130℃，待树脂完全固化后，从烘箱取出，脱模，获得玻璃纤维增强酚醛树脂基复合材料板一块。Continue to turn on the vacuum, put the mold into the oven, and gradually increase the oven temperature from 60°C to 130°C after 5 hours. After the resin is completely cured, take it out of the oven and demould to obtain a glass fiber reinforced phenolic resin matrix composite material board piece.
上述过程中，当抽气管被抽出的树脂堵塞后，打开备用抽气管，使真空持续。During the above process, when the exhaust pipe is blocked by the extracted resin, open the spare exhaust pipe to keep the vacuum.
测试上述复合材料板的弯曲强度、表观密度和孔隙率。The flexural strength, apparent density and porosity of the above-mentioned composite panels were tested.
实施例4Example 4
先将模具清洁并涂覆脱模剂，然后在模具上铺贴27层300*300mm的018 玻璃纤维方格布(重量为318g)；然后铺上1层脱模布，最后铺上真空袋膜并用密封胶条密封。分别在增强材料的两侧铺设1根树脂管、1根抽气管和1根备用抽气管，抽气管和备用抽气管通过缓冲罐连接到真空泵。扎紧树脂管和备用抽气管，使其密封不漏气，开启真空泵，通过抽气管抽真空。Clean the mold first and apply a release agent, then spread 27 layers of 300*300mm 018 glass fiber grid cloth (weight 318g) on the mold; then spread a layer of release cloth, and finally lay a vacuum bag film And seal with sealing tape. A resin pipe, a suction pipe and a spare suction pipe are respectively laid on both sides of the reinforcement material, and the suction pipe and the spare suction pipe are connected to the vacuum pump through the buffer tank. Tighten the resin tube and spare exhaust tube to make it airtight, turn on the vacuum pump, and draw a vacuum through the exhaust tube.
将BST-PF23酚醛树脂(百思通复合材料(武汉)有限公司提供，未添加有机溶剂，60℃下粘度200-300cP)预热到65±5℃，将树脂管浸入树脂中，放开扎带，使树脂通过树脂管抽入。当树脂完全浸透增强材料后，将树脂管重新扎紧，不漏气。Preheat BST-PF23 phenolic resin (provided by Beston Composite Materials (Wuhan) Co., Ltd., no organic solvent added, viscosity 200-300cP at 60°C) to 65±5°C, immerse the resin tube in the resin, release the tie belt to allow resin to be drawn in through the resin tube. When the resin has completely saturated the reinforcement, re-tighten the resin tube so that there is no air leakage.
持续开启真空，将模具放入烘箱内，经过4小时将烘箱温度从65℃逐渐升高到120℃，并在120℃下保温2小时，待树脂完全固化后，从烘箱取出，脱模，获得玻璃纤维增强酚醛树脂基复合材料板一块。Continue to turn on the vacuum, put the mold into the oven, gradually increase the temperature of the oven from 65°C to 120°C after 4 hours, and keep it at 120°C for 2 hours. After the resin is completely cured, take it out of the oven, demould, and obtain One piece of glass fiber reinforced phenolic resin matrix composite material.
上述过程中，当抽气管被抽出的树脂堵塞后，打开备用抽气管，使真空持续。During the above process, when the exhaust pipe is blocked by the extracted resin, open the spare exhaust pipe to keep the vacuum.
测试上述复合材料板的弯曲强度、表观密度和孔隙率。The flexural strength, apparent density and porosity of the above-mentioned composite panels were tested.
实施例1-4的测试结果见表1。The test results of Examples 1-4 are shown in Table 1.
表1.实施例1-4的测试结果Table 1. Test results of Examples 1-4
| 项目project | 实施例1Example 1 | 实施例2Example 2 | 实施例3Example 3 | 实施例4Example 4 |
| 弯曲强度(MPa)Bending strength (MPa) | 352352 | 294294 | 378378 | 419419 |
| 纤维重量(g)Fiber weight (g) | 318318 | 372372 | 318318 | 318318 |
| 样板厚度(mm)Sample thickness (mm) | 3.73.7 | 3.73.7 | 3.73.7 | 3.73.7 |
| 样板重量(g)Sample weight (g) | 502502 | 486486 | 511511 | 522522 |
| 表观密度(g/cm^3)Apparent density (g/cm^3) | 1.511.51 | 1.461.46 | 1.531.53 | 1.571.57 |
| 孔隙率(％)Porosity(%) | 14.414.4 | 18.518.5 | 1212 | 9.19.1 |
显然，本发明的上述实施例仅仅是为更清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定，对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其他不同形式的变化或变动，这里无法对所有的实施方法予以穷举，凡是属于本发明的技术方案所引申出的显而易见的变化或变动仍处于本发明的保护范围之列。Apparently, the above-mentioned embodiments of the present invention are only examples for illustrating the present invention more clearly, and are not intended to limit the implementation of the present invention. For those of ordinary skill in the art, they can also Changes or changes in other different forms cannot be exhaustively listed here, and all obvious changes or changes derived from the technical solutions of the present invention are still within the scope of protection of the present invention.
Claims (7)
- 生产热固性酚醛树脂基复合材料的方法，其特征在于，使用真空导入工艺，采用热固性酚醛树脂作为树脂基体，所述热固性酚醛树脂含有不高于重量比25％的有机溶剂，且导入温度下粘度小于300mPa.s；树脂固化时不添加酸性固化剂且采用梯次温度加热固化，导入温度为50～70℃，最高段固化温度为100～130℃。The method for producing a thermosetting phenolic resin-based composite material is characterized in that a vacuum introduction process is used, and a thermosetting phenolic resin is used as a resin matrix, the thermosetting phenolic resin contains no more than 25% by weight of an organic solvent, and the viscosity at the introduction temperature is less than 300mPa.s; when the resin is cured, no acid curing agent is added and the resin is cured by heating and curing in stages. The introduction temperature is 50-70°C, and the highest curing temperature is 100-130°C.
- 根据权利要求1所述的生产热固性酚醛树脂基复合材料的方法，其特征在于，所述热固性酚醛树脂是使用碱性催化剂催化合成、酚醛摩尔比为1:1.2～1:1.6、80～100℃可以凝胶、100～130℃可以交联固化的酚醛树脂。The method for producing a thermosetting phenolic resin-based composite material according to claim 1, wherein the thermosetting phenolic resin is synthesized by catalytic synthesis using an alkaline catalyst, and the phenolic molar ratio is 1:1.2～1:1.6, 80～100°C It is a phenolic resin that can gel, and can be cross-linked and cured at 100-130°C.
- 根据权利要求1所述的生产热固性酚醛树脂基复合材料的方法，其特征在于，在常规真空导入工艺基础上增加备用抽气管，当抽气管被树脂堵塞后，依次切换备用抽气管抽真空，使真空能够持续。The method for producing a thermosetting phenolic resin-based composite material according to claim 1, characterized in that, on the basis of the conventional vacuum introduction process, a spare air extraction pipe is added, and when the air extraction pipe is blocked by resin, the standby air extraction pipe is switched successively to evacuate, so that The vacuum can last.
- 根据权利要求1所述的生产热固性酚醛树脂基复合材料的方法，其特征在于，所述梯次温度加热固化是指：树脂导入完成后，通过烘房、烘箱或模具加热的方式，从导入温度逐渐缓慢升高到120～130℃，升温时间不小于2小时。The method for producing a thermosetting phenolic resin-based composite material according to claim 1, wherein the stepwise temperature heating and curing refers to: after the introduction of the resin is completed, it is gradually heated from the introduction temperature by means of a drying room, an oven or a mold. Slowly increase to 120-130°C, and the heating time is not less than 2 hours.
- 根据权利要求1所述的生产热固性酚醛树脂基复合材料的方法，其特征在于，所述复合材料的孔隙率<＝20％。The method for producing a thermosetting phenolic resin-based composite material according to claim 1, wherein the porosity of the composite material is <=20%.
- 根据权利要求1或5所述的生产热固性酚醛树脂基复合材料的方法，其特征在于，所述复合材料包括玻璃纤维、碳纤维、陶瓷纤维、玄武岩纤维、硼纤维、碳化硼纤维、碳化硅纤维、芳纶纤维增强的酚醛树脂。The method for producing a thermosetting phenolic resin-based composite material according to claim 1 or 5, wherein said composite material comprises glass fiber, carbon fiber, ceramic fiber, basalt fiber, boron fiber, boron carbide fiber, silicon carbide fiber, Aramid fiber reinforced phenolic resin.
- 根据权利要求6所述的生产热固性酚醛树脂基复合材料的方法，其特征在于，所述玻璃纤维包含石英纤维和高硅氧纤维。The method for producing a thermosetting phenolic resin-based composite material according to claim 6, wherein the glass fibers comprise quartz fibers and high silica fibers.
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