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CN1115772A - Open-loop polymerized phenolic resin and relevant composite fibre-reinforced material - Google Patents

Open-loop polymerized phenolic resin and relevant composite fibre-reinforced material Download PDF

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CN1115772A
CN1115772A CN 94111852 CN94111852A CN1115772A CN 1115772 A CN1115772 A CN 1115772A CN 94111852 CN94111852 CN 94111852 CN 94111852 A CN94111852 A CN 94111852A CN 1115772 A CN1115772 A CN 1115772A
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composite material
resin
benzoxazine
ring
phenolic resin
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CN1058738C (en
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顾宜
鲁在君
谢美丽
蔡兴贤
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Sichuan University
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Abstract

一种开环聚合酚醛树脂与纤维增强复合材料，它是由自制Benzoxazine与环氧树脂和/或酚醛树脂共混，经过调节溶剂、催化剂或固化剂种类及用量、浸渍或涂敷纤维、织物来实现复合材料的增强作用。该产品具有较高的热稳定性、电气、物理和机械性能优良，尤其是高温机械强度突出，适用作150-180℃长期使用的耐高温的结构材料和电绝缘材料。成本低，易于推广应用，有显著的经济效益和社会效益。A ring-opening polymerized phenolic resin and fiber reinforced composite material, which is blended with self-made Benzoxazine and epoxy resin and/or phenolic resin, through adjusting the type and amount of solvent, catalyst or curing agent, impregnating or coating fibers and fabrics. Realize the reinforcement of composite materials. The product has high thermal stability, excellent electrical, physical and mechanical properties, especially high-temperature mechanical strength, and is suitable for high-temperature-resistant structural materials and electrical insulation materials for long-term use at 150-180 °C. The cost is low, easy to popularize and apply, and has significant economic and social benefits.

Description

Ring-opening polymerization resol and fibre reinforced composites
The present invention relates to a kind of ring-opening polymerization resol and fibre reinforced composites and manufacture method thereof, this resin contains benzoxazine (1-Evil-3-azoles tetraline) ring texture compound (containing a ring texture in each molecule at least), Resins, epoxy and/or resol and solidifying agent and/or catalyst component.Fibre reinforced composites can make the high-temperature-resistant structure material and electrically insulating material uses.
The forties, abroad the building-up reactions of phenolic compound, aminated compounds and formaldehyde has been carried out than systematic research, synthesized the compound that contains benzoxazine (Benzoxazine) ring texture, reaction formula is as follows:
R=hydrogen, halogen atom in the formula, alkyl, alkoxyl group etc.
R 1=aliphatics or aromatic group
Compare with the condensation reaction of other relevant phenolic aldehyde, outstanding characteristics of this reaction are that phenolic hydroxyl group has been participated in ring-closure reaction.
1973, fritz H.Schreiber reported the ring-opening polymerization of Benzoxazine compound in German Patent 2255504 and 2323936, and made novel phenoplast by the copolymerization of Benzoxazine compound and Resins, epoxy or resol.The thermotolerance of this ring-opening polymerization Bakeland is lower, though through 200 ℃ of processing 21 hours, Martin heat resistance still is lower than 100 ℃.Schreiber has carried out many-sided trial, can only reach 120～130 ℃ but Martin heat resistance is the highest, adopt alicyclic Resins, epoxy and the copolymerization of Benzo-xazine compound just to obtain the plastics of second-order transition temperature＞200 ℃ at last, and obtain United States Patent (USP) Re.32745 authorization date: on September 6th, 1988.Because the cost of cycloaliphatic epoxy resin is higher, is difficult to realize the production and the application of industrially scalable.Meanwhile, American Higginbottom also is mixed with ability cathode electrophoresis coating acquisition United States Patent (USP) 4557979 with regard to Benzoxazine compound and aminated compounds.
The objective of the invention is provides a kind of ring-opening polymerization resol and fibre reinforced composites at the deficiencies in the prior art.It is by self-control Benzoxazine and Resins, epoxy and/or resol blend, kind through overregulating solvent, catalyzer or solidifying agent and consumption, and dipping or coated fiber, fabric are realized the enhancement of matrix material.This product has higher thermostability, and is electric, physical and mechanical property is good, is suitable for high-temperature-resistant structure material and the electrically insulating material of making 150～180 ℃ of life-time service.
The recipe ingredient (by weight) of ring-opening polymerization resol provided by the invention and fibre reinforced composites is:
30-90 parts of Benzoxazine
Resins, epoxy (available two senses, trifunctional or the universal or high-performance epoxy resin of four senses)
10-50 parts
20-70 parts in resol (lacquer resinss that the useful molecules amount is different)
Solidifying agent or catalyzer (available mineral acid, organic acid, primary amine, secondary amine, tertiary amine, acid anhydrides
Or hexamethylenetetramine) 0.1-8 part
80-120 parts of solvents (available toluene, dimethylbenzene, ethanol, acetone or tetrahydrofuran (THF))
By the weighing respectively of above-mentioned prescription, ring-opening polymerization resol (Benzoxazine, Resins, epoxy or resol) is mixed with solution, this resin solution viscosity (is coated with 4 #The cup 25 ℃) in 10～20 seconds, gelation time (150 ℃ of dull and stereotyped pocket knife methods) between 30 seconds to 6 minutes, solid content 40-60%.Use this resin solution dipping or coated fiber or fabric then, fiber useable glass fiber, woven fiber glass, carbon fiber and carbon cloth, in order to remove solvent fully, and the level of response that suitably improves prepolymer is to satisfy the requirement of matrix material pressing process, according to differential thermal analysis (DTA) with turn round and distinguish result of study and the measurement result of resin gel time of analysis (TBA) to resin curing process, the condition of curing of determining the impregnation material is: stoving temperature is 50-140 ℃, and the time of curing is 5～15 minutes.Volatile content in the prepreg that obtains thus＜2%, soluble resin content＞90%, glue content are 35-45%, the final compression moulding temperature of matrix material is 160-200 ℃.2～3 hours press times, obtain various composite products.
The synthetic of Benzoxazine is to make by phenolic compound, aminated compounds and formaldehyde reaction, and the recipe ingredient of its starting raw material (by weight) is:
Phenolic compound (available phenol, p-cresol, p-tert-butylphenol, meta-cresol, para-chlorophenol, p-NP, p-aminophenol, 4-hydroxybenzonitrile or lower molecular weight lacquer resins)
30～70 parts
Aminated compounds (available methylamine, aniline, ammonia, diphenylmethane diamine, phenyl ether diamines, two
Benzene sulfone diamines, Ursol D, mphenylenediamine, hexanediamine or quadrol)
30～70 parts
25～35 parts of formaldehyde or Paraformaldehyde 96s
Solvent (available toluene, dimethylbenzene, dioxane, ethanol, ethylene dichloride, Virahol or
Tetrahydrofuran (THF)) 120～250 part
The reaction formula of Benzoxazine is
Figure A9411185200061
R is hydrogen, halogen atom, alkyl, alkoxyl group; R 1Be aliphatics or aromatic group.
The synthetic of Benzoxazine ring texture carries out in two steps, and the first step is in the presence of solvent, and in 0-20 ℃, aminated compounds and formaldehyde or polyformaldehyde reaction generate N-dihydroxymethyl compound, (add KOH, NaOH, Mg (OH) by control 2, trolamine, triethylamine, pyridine, imidazoles) pH value between 8-10, make the N-dihydroxymethyl stable in solution, thereby avoid dewatering etherificate or intramolecular dehydration generate western Buddhist alkali; After second step added phenolic compound, N-dihydroxymethyl compound was at first in the reaction of phenolic hydroxyl group ortho position, and dehydration closed-loop generates Benzoxazine ring texture compound subsequently and between the phenolic hydroxyl group, and becoming the ring rate is 60-95%.
The synthetic aminated compounds that also can add under comparatively high temps (40-60 ℃) of Benzoxazine ring texture adds phenolic compound reaction generation Benzoxa-zine ring compound rapidly in formaldehyde solution.
Table 1 compares (comprising modification diphenyl ether, organosilicon epoxy resin and bimaleimide resin glass cloth laminated board) with regard to the performance test value of ring-opening polymerization resol glass cloth laminated board of the present invention (MDAPF1-EGF) and the performance number of domestic main several H level electrical insulation glass cloth laminated boards.Except Martens temperature be 222 ℃ slightly on the low side, all other mechanical propertys of ring-opening polymerization resol glass cloth laminated board and electric property value all meet or exceed the index of above-mentioned various veneer sheets, especially 180 ℃ flexural strength is 262MPa, conservation rate＞50%.Ring-opening polymerization phenolic resin fibre reinforced composite is applicable to the 150 ℃～high temperature resistant machine parts of 180 ℃ of life-time service, structural part, Vacuum pump rotary vane, and makes high-temperature insulation members such as slot wedge, insulating pad, cushion block, wiring board in the equipment such as F, H level motor, transformer.
The performance of several H level of table 1 glass cloth laminated sheet relatively
Index name Desired value
Last 3255 phenyl ether glass cloth laminated sheets 9334 bismaleimides glass cloth laminated sheets 3250 organosilicon laminated epoxy glass-cloth boards MDAPF1-EGF glass cloth laminated sheet of the present invention
Density, g/cm 3The temperature classification Martens temperature, ℃ flexural strength, MPa, 180 ℃ of tensile strengths of normality, MPa, impact of collision intensity, KJ/m 2Vertical bond strength, the N surface resistivity, M Ω, immersion back volume specific resistance during normality, M Ω .m, the back 180 ℃ of dielectric dissipation factors of soaking during normality ??????H ????≥250 ????≥343 ????≥294 ????≥147 ????≥5688 ????≥10 5????≥10 3????≥10 5????≥10 3????≥10 2 ???≥1.70 ??????H ???≥280 ???≥343 ???≥176 ???≥147 ???≥4900 ???≥10 6???≥10 4???≥10 5???≥10 3???≥10 2???≤0.05 ????H ??≥250 ??≥196 ??≥167 ??≥78.4 ??≥1960 ??≥10 7??≥10 5??≥10 5??≥10 8??≥10 2??≤0.04 ????1.73 ?????H ????222 ????443 ????262 ????327 ????176 ????7068 ??4.3×10 7??4.6×10 5??1.7×10 7??1.2?×10 5??1.4×10 4????0.012
The present invention has following advantage:
1. ring-opening polymerization resol is a class new type resin system, and no small molecules is emitted in the solidification process, and to have overcome traditional phenolic resin curing be condensation reaction, discharge micromolecular disadvantage, and the goods porosity is low.The forming process of fibre reinforced composites is good, and Device-General is easy to realize suitability for industrialized production.
2. ring-opening polymerization resol has higher thermostability, electric, the physics and the mechanical property of fibre reinforced composites are good, especially high-temperature machinery intensity is outstanding, is suitable for fire-resistant high-performance structured material and the electrically insulating material of making 150 ℃～180 ℃ of life-time service.
3. the synthesis technique of Benzoxazine compound of the present invention is simple, and is easy to operate, Device-General, cyclisation rate height.
4. the cost of ring-opening polymerization resol is significantly less than bimaleimide resin, diphenyl ether and silicone resin, has high P/C ratio, remarkable in economical benefits.
Embodiment:
1. in the three-necked bottle that is equipped with agitator, reflux exchanger and thermometer, add by 200 parts of example 5 synthetic Benzoxazine compound toluene solutions (solid content 40%), 20 parts of 6101 Resins, epoxy, N, 1 part of N-dimethyl benzylamine, mixed 30 minutes at 50 ℃, obtain the ring-opening polymerization phenol resin solution of solid content 43%, viscosity (is coated with 4 #Cup, 25 ℃) be 12.5 seconds, gelation time (the dull and stereotyped little skill in using a kitchen knife in cookery, 150 ℃) is 4 minutes.Resin solution floods the alkali-free glass cloth that KH-550 handles, and cures through 100～120 ℃ and gets prepreg in 12 minutes.Prepreg added template after 21 stacking adding and puts into press, heats up, and looks the gummosis situation and progressively pressurizes, and executes full pressure for 150～160 ℃, 170～180 ℃ of hot-press solidifyings 2 hours.Through 170 ℃ of aftertreatments 3 hours, obtain the glass cloth laminated board of reddish-brown again.TGA analyzes, and cured resin weightlessness 5%, 15% and 50% temperature are respectively 336 ℃, 468 ℃ and 609 ℃.Rerum natura detects, and the water-absorbent of glass cloth laminated board (distilled water immersion 48 hours) is 0.7%, cohesive strength 6.7KN, and flexural strength, the volume specific resistance of normality and 180 ℃ are respectively 517MPa and 267MPa, 4.1 * 10 11Ω .m and 5.2 * 10 8Ω .m, the specific inductivity of normality and dielectric loss angle tangent are 4.75 and 0.03.
2. press example 4 250 parts of synthetic Benzoxazine compound solutions (solid content 32%), 20 parts of 6101 Resins, epoxy, N, 1 part of N-dimethyl benzylamine mixed 30 minutes at 50 ℃, obtained orange-yellow ring-opening polymerization phenol resin solution, viscosity (4 #Cup, 25 ℃) 11.5 seconds, gelation time (the dull and stereotyped little skill in using a kitchen knife in cookery, 150 ℃) 5 minutes and 40 seconds.The alkali-free glass cloth that resin solution dipping KH-550 handles according to the moulding process of example 1, obtains pale red brown glass cloth laminated board.The flexural strength 650MPa of veneer sheet normality, volume specific resistance 4.2 * 10 12Ω .m, 180 ℃ flexural strength 223MPa.
3. by example 5 synthetic Benzoxazine compound solutions, remove through underpressure distillation and to desolvate.Components such as 50 parts of Benzoxazine solids, 50 parts of linear phenolic resins, 6 parts of hexamethylenetetramines are dissolved in 100 parts of acetone, and 30 ℃ were stirred 30 minutes, obtained reddish-brown ring-opening polymerization phenol resin solution, and viscosity (is coated with 4 #Cup, 25 ℃) 14 seconds, gelation time (the dull and stereotyped little skill in using a kitchen knife in cookery, 150 ℃) 37 seconds.The alkali-free glass cloth that resin solution dipping KH-550 handles, cured 10 minutes at 60 ℃, prepreg 22 stacking closing add template, go into press for 90 ℃, heat up, look the gummosis situation and exert pressure gradually, execute full pressure for 130 ℃, 170 ℃ of hot-press solidifyings 2 hours, again in 170 ℃ of aftertreatments 3 hours, the yellowish brown glass cloth laminated board.Cured resin weightlessness (TGA) 5%, 15% and 50% temperature are respectively 295 ℃, 435 ℃ and 530 ℃.Veneer sheet normality flexural strength, volume specific resistance and specific inductivity are respectively 576MPa, 4.1 * 10 12The flexural strength of Ω .m and 4.65,155 ℃ is 318MPa.
4. in the three-necked bottle that is equipped with agitator, condenser and thermometer, add Paraformaldehyde 96 12g (0.4mol), ethanol 20ml, NaOH 0.2g, react 1 hour to solution transparent (PH＞8) at 40 ℃, ice bath is cooled to 5 ℃, add aniline 18.8g (0.2mol), dioxane 60ml, after 1 hour, add dihydroxyphenyl propane 22.8g (0.1mol), dioxane 40ml 5 ℃ of stirrings, be warming up to 80 ℃ of backflows cooling after 5 hours, generate faint yellow Benzo-xazine compound clear solution. 1H-NMR is detected as ring rate＞80%.
5. Paraformaldehyde 96 6g (0.2mol), ethanol 20ml, NaOH 0.1g, 40 ℃ the reaction 1 hour transparent to solution, be cooled to 14 ℃ and add toluene 20ml, diphenylmethane diamine 9.98g (0.05mol), after 1 hour, add toluene 20ml, phenol 9.4g (0.1mol) 15 ℃ of reactions, be warming up to 80 ℃ refluxed 5 hours after cooling, standing demix, separate upper water liquid, obtain flaxen Benzoxazine compound toluene solution.Become ring rate＞70%.
6.36% formalin 7.6ml (0.1mol), triethylamine 0.18g, stirring is warming up to 50 ℃, add diphenylmethane diamine 4.95g (0.025mol), add meta-cresol 5.4g (0.05mol), toluene 30ml behind two amine solvents, be warming up to 80 ℃ and refluxed 4 hours, cooling separates out Benzoxazine compound white meal.Become ring rate＞95%.

Claims (6)

1.一种开环聚合酚醛树脂与纤维增强复合材料，其特征在于该复合材料的配方组分(按重量分计)为：1. a kind of ring-opening polymerization phenolic resin and fiber reinforced composite material, it is characterized in that the formula component (by weight) of this composite material is: Benzoxazine                       30—90份Benzoxazine 30—90 servings 环氧树脂(可用二官能、三官能或四官能通用型或高性能环氧树脂)Epoxy resin (two-functional, three-functional or four-functional general-purpose or high-performance epoxy resin can be used)                                   10—50份                                                                                    酚醛树脂(可用分子量不同的线型酚醛树脂) 20—70份Phenolic resin (novolac resin with different molecular weight can be used) 20-70 parts 固化剂或催化剂(可用无机酸、有机酸、酸酐、伯胺、仲胺、叔胺Curing agent or catalyst (available inorganic acid, organic acid, acid anhydride, primary amine, secondary amine, tertiary amine                或六次甲基四胺)    0.1—8份or hexamethylenetetramine) 0.1-8 parts 溶剂(可用甲苯、二甲苯、乙醇、丙酮或四氢呋喃) 80-120份Solvent (available toluene, xylene, ethanol, acetone or tetrahydrofuran) 80-120 parts 按上述配方分别称量，将开环聚合酚醛树脂(Benzoxazine、环氧树脂或酚醛树脂)配制成溶液，该树脂溶液粘度(涂4#杯25℃)在10～20秒内，凝胶化时间(平板小刀法150℃)在30秒至6分钟之间，固含量为40—60％，然后用该树脂溶液浸渍或涂敷纤维或纤维织物，浸胶料的烘焙温度为50—140℃，烘焙时间5—15分钟，预浸料中挥发物含量＜2％，可溶性树脂含量＞90％，胶含量为35-45％，复合材料的压制成型温度为160-200℃，压制时间为2～3小时，Weigh separately according to the above formula, and prepare ring-opening polymerized phenolic resin (Benzoxazine, epoxy resin or phenolic resin) into a solution. (Plate knife method 150°C) Between 30 seconds and 6 minutes, the solid content is 40-60%, then impregnate or coat the fiber or fiber fabric with the resin solution, the baking temperature of the dipping material is 50-140°C, The baking time is 5-15 minutes, the volatile matter content in the prepreg is <2%, the soluble resin content is >90%, the glue content is 35-45%, the compression molding temperature of the composite material is 160-200°C, and the compression time is 2～ 3 hours, 2.按照权利要求1所述开环聚合酚醛树脂与纤维增强复合材料，其特征在于该复合材料的Benzoxazine制备用原料配方组分(按重量计)为：2. according to the described ring-opening polymerization phenolic resin of claim 1 and fiber-reinforced composite material, it is characterized in that the Benzoxazine preparation of this composite material is with raw material formula component (by weight):     酚类化合物                 30-70份Phenolic compounds 30-70 parts     胺类化合物                 30-70份Amine compounds 30-70 parts     甲醛或多聚甲醛             25-35份  Formaldehyde or paraformaldehyde           25-35 parts     溶剂                       120-250份Solvent 120-250 parts Benzoxazine的合成分两步进行，第一步是在溶剂下，于0～20℃(或在40-60℃下加入胺类化合物于甲醛溶液中后，迅速加入酚类化合物)胺类化合物与甲醛或多聚甲醛反应生成N-二羟甲基化合物，通过控制(加入KOH、NaOH、Mg(OH)2、三乙醇胺、三乙胺、吡啶、咪唑)PH值在8—10之间，使N-二羟甲基在溶液中稳定。第二步加入酚类化合物后，使N-二羟甲基化合物首先在酚羟基邻位反应，随后与酚羟基之间脱水闭环生成Benzoxazine环状结构化合物，成环率为60～95％。The synthesis of Benzoxazine is carried out in two steps. The first step is to add the phenolic compound quickly after adding the amine compound to the formaldehyde solution at 0-20°C (or add the amine compound to the formaldehyde solution at 40-60°C) under the solvent) and formaldehyde. Or paraformaldehyde reacts to generate N-dimethylol compound, by controlling (adding KOH, NaOH, Mg(OH) 2 , triethanolamine, triethylamine, pyridine, imidazole) the pH value is between 8-10, so that N - Dimethylol is stable in solution. After the phenolic compound is added in the second step, the N-dimethylol compound is first reacted at the ortho position of the phenolic hydroxyl group, and then dehydrated and ring-closed with the phenolic hydroxyl group to form a Benzoxazine ring structure compound, and the ring-forming rate is 60-95%. 3、按照权利要求1或2所述开环聚合酚醛树脂与纤维增强复合材料，其特征在于该复合材料的Benzoxazine制备的酚类化合物为苯酚、对甲酚、对叔丁基苯酚、间甲酚、对氯苯酚、对硝基苯酚、对氰基苯酚、双酚A、双酚S、二羟基二苯醚、对苯二酚或低分子量线型酚醛树脂。3. According to claim 1 or 2, the ring-opening polymerized phenolic resin and fiber-reinforced composite material is characterized in that the phenolic compound prepared by the Benzoxazine of the composite material is phenol, p-cresol, p-tert-butylphenol, m-cresol , p-chlorophenol, p-nitrophenol, p-cyanophenol, bisphenol A, bisphenol S, dihydroxydiphenyl ether, hydroquinone or low molecular weight novolac resin. 4.按照权利要求1或2所述开环聚合酚醛树脂与纤维增强复合材料，其特征在于该复合材料的Benzoxazine制备的胺类化合物为甲胺、苯胺、氨、对苯二胺、间苯二胺、己二胺、乙二胺、二苯甲烷二胺、二苯醚二胺或二苯砜二胺。4. According to the described ring-opening polymerization phenolic resin and fiber-reinforced composite material of claim 1 or 2, it is characterized in that the amine compound prepared by the Benzoxazine of this composite material is methylamine, aniline, ammonia, p-phenylenediamine, m-phenylenediamine Amine, hexamethylenediamine, ethylenediamine, diphenylmethanediamine, diphenyletherdiamine or diphenylsulfonediamine. 5.按照权利要求1或2所述开环聚合酚醛树脂与纤维增强复合材料，其特征在于该复合材料的Benzoxazine制备的溶剂为甲苯、二甲苯、二氧六环、乙醇、二氯乙烷、异丙醇或四氢呋喃。5. according to the described ring-opening polymerization phenolic resin of claim 1 and 2 and fiber-reinforced composite material, it is characterized in that the solvent that the Benzoxazine of this composite material prepares is toluene, dimethylbenzene, dioxane, ethanol, ethylene dichloride, isopropanol or tetrahydrofuran. 6.按照权利要求1所述开环聚合酚醛树脂与纤维增强复合材料，其特征在于该树脂体系的固化剂或催化剂为无机酸、有机酸、伯胺、仲胺、叔胺、酸酐或六次甲基四胺。6. According to the described ring-opening polymerization phenolic resin and fiber reinforced composite material of claim 1, it is characterized in that the curing agent or catalyst of the resin system is inorganic acid, organic acid, primary amine, secondary amine, tertiary amine, acid anhydride or six times Methyltetramine.
CN94111852A 1994-07-29 1994-07-29 Open-loop polymerized phenolic resin and relevant composite fibre-reinforced material Expired - Fee Related CN1058738C (en)

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US7087467B2 (en) 2000-12-27 2006-08-08 Matsushita Electric Industrial Co., Ltd. Lead frame and production process thereof and production process of thermally conductive substrate
WO2008051373A3 (en) * 2006-10-19 2008-06-19 Dow Global Technologies Inc Curable epoxy resin composition having improved adhesion to metal substrates and process for making coated and fiber-reinforced composite article
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