CN115260702A - A kind of preparation method of phenolic resin composition and modified phenolic resin composite material - Google Patents
A kind of preparation method of phenolic resin composition and modified phenolic resin composite material Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 71
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 39
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012745 toughening agent Substances 0.000 claims abstract description 16
- 239000003365 glass fiber Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 4
- 239000013530 defoamer Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000003085 diluting agent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- -1 Sericite Chemical compound 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011208 reinforced composite material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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Abstract
Description
技术领域technical field
本发明涉及有机高分子化合物制备技术领域，尤其涉及一种酚醛树脂组合物制备方法及改性酚醛树脂复合材料。The invention relates to the technical field of preparation of organic polymer compounds, in particular to a method for preparing a phenolic resin composition and a modified phenolic resin composite material.
背景技术Background technique
酚醛树脂是指以酚和醛为主要原料，在碱性或酸性条件下通过缩聚反应生成的有机高分子聚合物，其具有优异的耐高温性，即使在非常高的环境温度下，也能通过高残碳率维持结构的稳定性和整体性。现有技术针对酚醛树脂特性给出具体制备方案形成具有特定功能的树脂产品，例如，申请号201910387321.4的发明专利申请公开了一种改性酚醛组合物的制备方法，以水性酚醛树脂、水玻璃、绢云母、铜粉、固化剂、润湿剂、糠醇为主要组分，制备了储存时间较长、有优良的阻燃性和韧性的改性酚醛组合物；申请号201710174840.3的发明专利申请公开了一种改性酚醛树脂混合物材料，该酚醛树脂混合物主要包括：热熔型酚醛树脂、绝缘子硅橡胶微粉、发泡剂、固化剂、改性蒙脱土、六次甲基四胺和偶联剂，能够提供良好的绝缘性和耐热性。Phenolic resin refers to the organic high molecular polymer produced by polycondensation reaction with phenol and aldehyde as the main raw materials under alkaline or acidic conditions. It has excellent high temperature resistance and can pass through the The high carbon residue rate maintains the stability and integrity of the structure. The existing technology provides specific preparation schemes for the characteristics of phenolic resins to form resin products with specific functions. For example, the invention patent application with application number 201910387321.4 discloses a preparation method of a modified phenolic composition, which uses water-based phenolic resin, water glass, Sericite, copper powder, curing agent, wetting agent, and furfuryl alcohol are the main components, and a modified phenolic composition with long storage time, excellent flame retardancy and toughness has been prepared; the invention patent application with application number 201710174840.3 has been published A modified phenolic resin mixture material, the phenolic resin mixture mainly includes: hot-melt phenolic resin, silicon rubber powder for insulators, foaming agent, curing agent, modified montmorillonite, hexamethylenetetramine and coupling agent , can provide good insulation and heat resistance.
但是，由于酚醛树脂原料中使用的各类酚中都含有苯环，酚和醛缩聚反应后，与亚甲基相连的刚性芳环紧密堆砌，会导致固化后的酚醛树脂的韧性较差，耐冲击性能不佳。虽然通过在酚醛树脂中增加特定无机填料能够在一定程度上改善其性能，但会明显影响酚醛树脂固化后的透明性，只能用于不考虑固化后材料透明性的应用环境，适用范围非常有限。However, since all kinds of phenols used in phenolic resin raw materials contain benzene rings, after the polycondensation reaction between phenols and aldehydes, the rigid aromatic rings linked to methylene groups are closely packed, which will lead to poor toughness of the cured phenolic resin Impact performance is poor. Although the performance of phenolic resin can be improved to a certain extent by adding specific inorganic fillers, it will obviously affect the transparency of the cured phenolic resin. It can only be used in application environments where the transparency of the cured material is not considered, and the scope of application is very limited. .
发明内容Contents of the invention
为解决现有技术的不足，本发明提出一种酚醛树脂组合物制备方法及改性酚醛树脂复合材料，通过增加增韧剂，使得固化后的树脂体系有一定的韧性和耐冲击性能，制备得到高韧性、透明性好、实用性高改性酚醛树脂组合物，特别适用于与玻璃纤维浸渍后作为保护层缠绕在复合气瓶上，提高复合气瓶的耐火烧性能、耐冲击性能等。In order to solve the deficiencies in the prior art, the present invention proposes a preparation method of a phenolic resin composition and a modified phenolic resin composite material. By adding a toughening agent, the cured resin system has certain toughness and impact resistance, and the prepared The modified phenolic resin composition with high toughness, good transparency and high practicability is especially suitable for wrapping the composite gas cylinder as a protective layer after impregnated with glass fiber, so as to improve the fire resistance and impact resistance of the composite gas cylinder.
为实现以上目的，本发明所采用的技术方案包括：For realizing the above object, the technical scheme adopted in the present invention comprises:
一种酚醛树脂组合物制备方法，其特征在于，包括以质量份执行下列步骤：A kind of preparation method of phenolic resin composition, is characterized in that, comprises carrying out following steps with mass parts:
S1、混合6至8份纳米增韧剂、2至3份消泡剂A和2至3份消泡剂B，使用气动搅拌器搅拌均匀得到第一混合物；所述纳米增韧剂的粘度为4500至8000cps且环氧当量为0；所述消泡剂A为不含有有机硅的破泡聚合物溶液，所述消泡剂B为聚醚改性甲基烷基聚硅氧烷共聚体溶液；S1, mixing 6 to 8 parts of nano toughening agent, 2 to 3 parts of defoamer A and 2 to 3 parts of defoaming agent B, using a pneumatic agitator to stir evenly to obtain the first mixture; the viscosity of the nano toughening agent is 4500 to 8000cps and the epoxy equivalent is 0; the defoamer A is a foam-breaking polymer solution that does not contain organic silicon, and the defoamer B is a polyether-modified methylalkylpolysiloxane interpolymer solution ;
S2、混合3至4份稀释剂和96至97份溶剂型酚醛树脂，加热至预设温度恒温搅拌均匀得到第二混合物；S2, mixing 3 to 4 parts of diluent and 96 to 97 parts of solvent-based phenolic resin, heating to a preset temperature and stirring at a constant temperature to obtain a second mixture;
S3、混合10份第一混合物、85份第二混合物和5至7份固化剂，使用气动搅拌器搅拌均匀得到液态的改性酚醛树脂组合物。S3. Mix 10 parts of the first mixture, 85 parts of the second mixture and 5 to 7 parts of curing agent, and stir evenly with an air agitator to obtain a liquid modified phenolic resin composition.
进一步地，所述稀释剂为乙二醇稀释剂，所述固化剂为聚醚胺类固化剂。Further, the diluent is ethylene glycol diluent, and the curing agent is polyetheramine curing agent.
进一步地，所述步骤S1包括：Further, the step S1 includes:
混合6份纳米增韧剂、2份消泡剂A和2份消泡剂B，使用气动搅拌器搅拌3分钟及以上至均匀得到第一混合物。Mix 6 parts of nano-toughener, 2 parts of defoamer A and 2 parts of defoamer B, and stir with an air mixer for 3 minutes or more until the first mixture is obtained uniformly.
进一步地，所述步骤S2包括：Further, the step S2 includes:
混合3份稀释剂和97份溶剂型酚醛树脂，加热至95至105℃恒温搅拌10分钟及以上至均匀得到第二混合物。Mix 3 parts of diluent and 97 parts of solvent-based phenolic resin, heat to 95 to 105° C. and stir at constant temperature for 10 minutes or more to obtain a second mixture uniformly.
进一步地，所述步骤S3包括：Further, the step S3 includes:
混合10份第一混合物、85份第二混合物和5份固化剂，使用气动搅拌器搅拌6分钟及以上至均匀得到液态的改性酚醛树脂组合物。Mix 10 parts of the first mixture, 85 parts of the second mixture and 5 parts of curing agent, and stir for 6 minutes or more with an air agitator until a liquid modified phenolic resin composition is obtained uniformly.
本发明还涉及一种改性酚醛树脂复合材料，其特征在于，使用如上的酚醛树脂组合物制备。The present invention also relates to a modified phenolic resin composite material, which is characterized in that it is prepared using the above phenolic resin composition.
进一步地，所述的复合材料，其特征在于，通过如下步骤制备：Further, the composite material is characterized in that it is prepared through the following steps:
A1、将玻璃纤维浸渍在如上的酚醛树脂组合物中得到待固化材料；A1, glass fibers are impregnated in the above phenolic resin composition to obtain the material to be cured;
A2、将待固化材料置于预热至115至125℃的炉中恒温加热2.5至3.5小时，得到第一固化材料；A2. Place the material to be cured in a furnace preheated to 115 to 125° C. and heat it at a constant temperature for 2.5 to 3.5 hours to obtain the first cured material;
A3、将第一固化材料随炉空冷到达85至95℃，得到改性酚醛树脂复合材料。A3. Air-cool the first cured material with the furnace to 85 to 95° C. to obtain a modified phenolic resin composite material.
本发明的有益效果为：The beneficial effects of the present invention are:
采用本发明所述酚醛树脂组合物制备方法及改性酚醛树脂复合材料，通过增加增韧剂，在酚醛树脂固化体系中形成纳米级的均匀相份，使固化后的酚醛树脂有更强、更一致可靠的韧性，使得固化后的树脂体系有一定的韧性和耐冲击性能，且同样保持高透明度，制备得到高韧性、透明性好、实用性高改性酚醛树脂组合物，同时对酚醛树脂固化体系的玻璃化转变温度几乎不影响，特别适用于与玻璃纤维浸渍后作为保护层缠绕在复合气瓶上，提高复合气瓶的耐火烧性能、耐冲击性能等。By adopting the preparation method of the phenolic resin composition and the modified phenolic resin composite material of the present invention, by adding a toughening agent, a nano-scale uniform phase is formed in the phenolic resin curing system, so that the cured phenolic resin has stronger and more Consistent and reliable toughness, so that the cured resin system has a certain toughness and impact resistance, and also maintains high transparency, and prepares a modified phenolic resin composition with high toughness, good transparency, and high practicability. The glass transition temperature of the system is hardly affected, and it is especially suitable for wrapping the composite gas cylinder as a protective layer after impregnated with glass fiber, so as to improve the fire resistance and impact resistance of the composite gas cylinder.
具体实施方式Detailed ways
为了更清楚的理解本发明的内容，将结合实施例详细说明。In order to understand the content of the present invention more clearly, it will be described in detail in conjunction with the embodiments.
本发明第一方面涉及一种高韧性、透明性好、实用性高的改性酚醛树脂组合物制备方法，包括以物料重量份计算执行的下列步骤：The first aspect of the present invention relates to a method for preparing a modified phenolic resin composition with high toughness, good transparency and high practicability, comprising the following steps calculated in parts by weight of materials:
步骤一：优选的，将6份的纳米增韧剂FORTEGRA202、2份的消泡剂A和2份的消泡剂B混合，用气动搅拌器搅拌3分钟以上形成第一混合物。Step 1: Preferably, mix 6 parts of nano toughening agent FORTEGRA202, 2 parts of defoamer A and 2 parts of defoamer B, and stir with an air mixer for more than 3 minutes to form the first mixture.
其中，纳米增韧剂的粘度为4500至8000cps且环氧当量为0，可以优选采用FORTEGRA202型纳米增韧剂；消泡剂A为不含有有机硅的破泡聚合物溶液，可以优选为BYK-A500型消泡剂；消泡剂B为聚醚改性甲基烷基聚硅氧烷共聚体溶液，可以优选为BYK-A525型消泡剂。通过以定量方式组合使用消泡剂A与消泡剂B，能够提高与酚醛树脂相容性较好，特别适用于透明体系。Wherein, the viscosity of nano toughening agent is 4500 to 8000cps and epoxy equivalent is 0, can preferably adopt FORTEGRA202 type nano toughening agent; A500 type defoamer; defoamer B is polyether modified methyl alkyl polysiloxane copolymer solution, preferably BYK-A525 type defoamer. Combining defoamer A and defoamer B in a quantitative manner can improve compatibility with phenolic resins, and is especially suitable for transparent systems.
增韧剂的添加量通常会降低体系其它性能，如玻璃化转变温度等，故根据实际应用环境与需要，所述纳米增韧剂重量份可为6-8份，消泡剂A可为2-3份，消泡剂B可为2-3份。The amount of toughening agent added usually reduces other properties of the system, such as glass transition temperature, etc., so according to the actual application environment and needs, the nano toughening agent can be 6-8 parts by weight, and the defoamer A can be 2 parts by weight. -3 parts, defoamer B can be 2-3 parts.
步骤二：优选的，将3份稀释剂添加到97份溶剂型酚醛树脂中，在100±5℃恒温下加热搅拌十分钟以形成均匀的第二混合物。Step 2: Preferably, add 3 parts of diluent to 97 parts of solvent-based phenolic resin, heat and stir at a constant temperature of 100±5° C. for ten minutes to form a uniform second mixture.
其中，稀释剂优选为乙二醇稀释剂。Among them, the diluent is preferably ethylene glycol diluent.
为了调整组合物体系粘度，所述稀释剂重量份可为3-4份，以便达到所需要的体系粘度，但过量增加会导致稀释剂难以挥发，并增加固化所需时间。In order to adjust the viscosity of the composition system, the weight part of the diluent can be 3-4 parts, so as to achieve the required system viscosity, but excessive increase will make the diluent difficult to volatilize and increase the time required for curing.
步骤三：优选的，将步骤一中的混合物量取10份、步骤二中的混合物量取85份和聚醚胺类固化剂5份混合，用气动搅拌器搅拌6分钟以上形成改性酚醛树脂组合物液体。Step 3: preferably, mix 10 parts of the mixture in step 1, 85 parts of the mixture in step 2 with 5 parts of polyether amine curing agent, and stir with a pneumatic mixer for more than 6 minutes to form a modified phenolic resin Composition liquid.
其中，聚醚胺类固化剂可以优选为T-403型聚醚胺固化剂。Among them, the polyetheramine curing agent can preferably be T-403 type polyetheramine curing agent.
所述的固化剂重量份可为5-7份，以便有足够的操作时间，而又不增加固化所需时间。The weight part of the curing agent can be 5-7 parts, so as to have enough operation time without increasing the time required for curing.
通过上述方法制备得到的液态改性酚醛树脂组合物可以用于制作所需的酚醛树脂产品，例如复合气瓶的外部保护层材料。具体的，本发明还涉及一种改性酚醛树脂复合材料，包括如下步骤：The liquid modified phenolic resin composition prepared by the above method can be used to make desired phenolic resin products, such as external protective layer materials for composite gas cylinders. Specifically, the present invention also relates to a modified phenolic resin composite material, comprising the steps of:
A1、将玻璃纤维浸渍在如上的酚醛树脂组合物中得到待固化材料，用于后续的复合材料成型工艺。A1. The glass fiber is impregnated in the above phenolic resin composition to obtain the material to be cured, which is used in the subsequent composite material forming process.
A2、将待固化材料置于预热至115至125℃的炉中恒温加热2.5至3.5小时，得到第一固化材料。A2. Put the material to be cured in a furnace preheated to 115 to 125° C. and heat it at a constant temperature for 2.5 to 3.5 hours to obtain the first cured material.
优选的，可以选择在预热至115至125℃的炉中恒温加热3小时，充分完成固化。Preferably, it may be chosen to heat at a constant temperature in an oven preheated to 115 to 125° C. for 3 hours to fully complete the curing.
A3、将第一固化材料随炉空冷到达85至95℃，得到改性酚醛树脂复合材料。即通过一定速率的降温过程充分释放第一固化材料内应力，即可完成固化过程。A3. Air-cool the first cured material with the furnace to 85 to 95° C. to obtain a modified phenolic resin composite material. That is, the internal stress of the first cured material can be fully released through a cooling process at a certain rate, and the curing process can be completed.
通过上述方法制备得到的改性酚醛树脂复合材料具有较高的透明度，且有更强、更一致可靠的韧性，特别是能够很好的应对复合气瓶的抗冲击试验。The modified phenolic resin composite material prepared by the above method has high transparency, and stronger, more consistent and reliable toughness, and can especially cope well with the impact resistance test of the composite gas cylinder.
以下通过一用于复合气瓶的具体实施例进一步说明本发明制备方法所得复合材料技术效果。The technical effect of the composite material obtained by the preparation method of the present invention is further illustrated below through a specific example for a composite gas cylinder.
酚醛树脂组合物及复合材料制备过程如上述所示，将300g的纳米增韧剂FORTEGRA202，100g消泡剂A和100g的消泡剂B进行预混，用气动搅拌器搅拌3分钟以上形成混合物A；将60g的稀释剂1940g的溶剂型酚醛树脂混合，在100℃恒温下加热搅拌十分钟以形成均匀的混合物B。将混合物A量取200g、混合物B量取1700g、聚醚胺类固化剂量取100g后进行混合，使用气动搅拌器搅拌6分钟以上形成改性酚醛树脂组合物液体。将玻璃纤维浸渍到改性酚醛树脂组合物液体中10秒，使玻璃纤维充分吸收改性酚醛树脂组合物液体，拿出后控干液体，使液体不再滴落，擦去玻璃纤维边上多余的改性酚醛树脂组合物液体。所形成的的浸渍酚醛树脂的玻璃纤维在120℃的温度下恒温加热3h就可形成玻璃纤维基酚醛树脂增强复合材料。The preparation process of the phenolic resin composition and composite material is as shown above. Premix 300g of nano-toughener FORTEGRA202, 100g of defoamer A and 100g of defoamer B, and stir with a pneumatic stirrer for more than 3 minutes to form mixture A ; Mix 60g of diluent and 1940g of solvent-based phenolic resin, heat and stir at a constant temperature of 100°C for ten minutes to form a uniform mixture B. Mix 200g of mixture A, 1700g of mixture B, and 100g of polyetheramine curing agent, and mix them with a pneumatic stirrer for more than 6 minutes to form a liquid modified phenolic resin composition. Immerse the glass fiber into the modified phenolic resin composition liquid for 10 seconds, so that the glass fiber can fully absorb the modified phenolic resin composition liquid, take it out and control the dry liquid so that the liquid no longer drips, and wipe off the excess on the edge of the glass fiber A liquid modified phenolic resin composition. The formed glass fiber impregnated with phenolic resin is heated at a constant temperature of 120° C. for 3 hours to form a glass fiber-based phenolic resin reinforced composite material.
将所得复合材料缠绕在复合气瓶上，所得缠绕气瓶在经过52.5MPa的水压高压试验后，缠绕层为浸渍改性酚醛树脂的玻璃纤维层未发生开裂现象。The obtained composite material is wound on the composite gas cylinder, and after the obtained wound gas cylinder passes through the hydraulic pressure test of 52.5 MPa, the winding layer is a glass fiber layer impregnated with modified phenolic resin and no cracking occurs.
按照《ASTM D2794有机涂层对快速变形(冲击)影响的标准测试方法》进行抗冲击试验，表面酚醛树脂层只发生压痕而未开裂。其韧性得到明显改善。According to "ASTM D2794 Standard Test Method for the Effect of Organic Coatings on Rapid Deformation (Impact)", the impact resistance test was carried out, and the surface phenolic resin layer only had indentations but no cracks. Its toughness has been significantly improved.
火烧试验对玻璃纤维基酚醛树脂增强复合材料进行1000℃温度下局部火烧15min试验。火烧过程中酚醛树脂燃烧碳化后涂层起到阻燃作用。Fire test The glass fiber-based phenolic resin reinforced composite was subjected to a local fire test at 1000°C for 15 minutes. During the burning process, the phenolic resin is burned and carbonized, and the coating plays a role of flame retardancy.
由上述实施例可知，采用本发明所述方法制备所得复合材料能够有效提高复合气瓶的耐火性能、耐冲击性能等且表面未产生气泡。同时，本发明所得玻璃纤维基酚醛树脂增强复合材料固化后透明性良好，改性酚醛树脂层下可以清晰看到玻璃纤维层，以方便在改性酚醛树脂层下植入标签信息，实用性较高。It can be seen from the above examples that the composite material prepared by the method of the present invention can effectively improve the fire resistance and impact resistance of the composite gas cylinder, and no air bubbles are generated on the surface. At the same time, the glass fiber-based phenolic resin reinforced composite material obtained in the present invention has good transparency after curing, and the glass fiber layer can be clearly seen under the modified phenolic resin layer, so as to facilitate the implantation of label information under the modified phenolic resin layer, which is more practical. high.
以上所述仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换等都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求书的保护范围为准。The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention etc. should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.
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