CN103341985B - Vacuum-assisted resin diffusion molding method for fiber-reinforced PBT composite material - Google Patents
Vacuum-assisted resin diffusion molding method for fiber-reinforced PBT composite material Download PDFInfo
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- CN103341985B CN103341985B CN201310187953.9A CN201310187953A CN103341985B CN 103341985 B CN103341985 B CN 103341985B CN 201310187953 A CN201310187953 A CN 201310187953A CN 103341985 B CN103341985 B CN 103341985B
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Abstract
The invention provides a vacuum-assisted resin diffusion molding method for a fiber-reinforced PBT composite material. The method comprises: attaching a catalyst onto fiber cloth; putting fiber-reinforced materials into a mold pasted with high-temperature demolding cloth and embedded with a high-temperature sealing strip; heating the mold to 180-220 DEG C, heating a resin injecting pipe to 180-220 DEG C by using a polytetrafluoroethylene heating pipe and heating CBT resin to 180-220 DEG C through oil bath; immersing a nozzle of the resin injecting pipe into melted CBT resin, with the CBT resin being injected into the mold under the effect of the vacuum; insulating the mold at 180-220 DEG C for 30-60 minutes so that the CBT resin can fully immerse the fiber-reinforced materials and meanwhile the CBT resin is subjected to ring-opening polymerization and crystallization into high-molecular-weight PBT; annealing and demolding to obtain the fiber-reinforced PBT composite material. The invention provides a high-performance and low-cost technology which can be used for preparation of thin-wall products and production of large-size composite material components.
Description
Technical field
What the present invention relates to is a kind of forming method of fiber-resin composite, is applicable to the large-scale thermoplastic composite component producing high microsteping content.
Background technology
In recent years, the research of continuous fiber reinforced thermoplastic resin based composites receives aerospace industry, the great attention of auto manufacturing.Compared with thermosetting resin matrix composite, thermoplastic composite has number of important advantages, and such as have good toughness and shock resistance, molding cycle is short, low cost of manufacture, and waste material can be recycled.But thermoplastic composite is due to molecular structure, under room temperature, thermoplastic is solid-state; Under heating and melting state, resin melt viscosity large (> 1000Pa.s), melt flows difficulty, makes resin be difficult to complete wetting fiber.Because thermoplastic resin viscosity is higher, its melting viscosity is from far away higher than the viscosity of thermosetting resin, and therefore thermoplastic composite preparation is main adopts the moulding process such as Wrapping formed, roll-forming, pultrusion, hot-forming, vacuum compression molding.These moulding process forming temperatures and briquetting pressure higher, energy consumption is comparatively large, and harsher to the requirement of die apparatus, therefore production cost is higher, is especially restricted in the scale manufacture of large-scale component.
Ring-type mutual-phenenyl two acid bromide two alcohol ester (CBT) functional polymer has large ring oligomerization ester structure, be the mixture of different low molecular weight cyclic oligomer, its melt viscosity is extremely low, about 190 DEG C, just become as the liquid (under the same terms, the viscosity of PBT is approximately its 5000 times) water.Under the effect of tin class or titanium class catalyst, can there is ring-opening polymerization in CBT, obtain thermoplastic engineering plastic polycyclic shape mutual-phenenyl two acid bromide two alcohol ester (PBT).Without air release in CBT process, environmental protection, and finished product can be made to obtain well surface.The superiority of PBT performance makes fiber reinforcement PBT composite have higher intensity, impact resistance and recoverable, has great application potential in thermoplastic composite field.
Summary of the invention
The object of the present invention is to provide the vacuum assisted resin diffusion forming method of the fiber reinforcement PBT composite that a kind of technique is simple, with low cost, safety and environmental protection, energy consumption are low, efficiency is high.
The object of the present invention is achieved like this:
1) catalyst is attached in fiber cloth;
2) with the certain thickness fiber cloth with catalyst for fibre reinforced materials, fibre reinforced materials is placed in and posts High temperature release cloth, be embedded with in the mould of elevated-temperature seal bar; The valvular resin injection pipeline of connecting band and vacuum-pumping pipeline on described mould;
3) with Resistant heating, make mould be warming up to 180 ~ 220 DEG C, with polytetrafluoroethylene (PTFE) heating tube to resin injection pipeline heating to 180 ~ 220 DEG C, the oil bath of CBT resin is heated to 180 ~ 220 DEG C;
4) submerged by the resin injection pipe mouth of pipe in the CBT resin after melting, open filling line valve, CBT resin sucks in mould under vacuum, when having resin to flow out in vacuum-pumping pipeline, closes filling line valve;
5) mould is incubated 30min ~ 1h at 180 ~ 220 DEG C, CBT resin is fully infiltrated fibre reinforced materials, the crystallization of CBT resin ring-opening polymerisation is simultaneously the PBT of HMW, and after carrying out annealing in process, the demoulding obtains fiber reinforcement PBT composite.
The present invention can also comprise:
1, the described concrete operations be attached to by catalyst in fiber cloth are: poured into by catalyst in aqueous isopropanol, magnetic stirring apparatus is utilized to stir 10min at 80 DEG C, catalyst is dissolved completely, the catalyst solution brush of dissolution homogeneity is taken out in fiber cloth or in catalyst solution fiber cloth being immersed in dissolution homogeneity again, at 130 DEG C of temperature, dry 30min, midway is fiber cloth turn-over.
2, described fiber cloth is a kind of in glass fabric, basalt fiber cloth or carbon cloth or the wherein compound of at least two kinds.
3, described catalyst is tin class catalyst, is dihydroxy dibutyl tin oxide.
The structural formula of 4, described CBT resin is:
Described CBT resin first dries more than 10h before use at 105 DEG C of temperature.
5, the concrete operations of described annealing in process are: be heated to 230 ~ 250 DEG C, stop heating, naturally cool to room temperature after constant temperature 30min.
Utilize the fiber reinforcement PBT composite that forming method of the present invention obtains, through verification test, wherein, fiber volume fraction can reach more than 70%.
By adopting technique scheme, tool of the present invention has the following advantages: 1) compared with prior art, the present invention spreads the vacuum assisted resin being only applicable to same with thermosetting compound material to shaping process application in the production of thermoplastic composite, avoid higher forming temperature and briquetting pressure, effectively reduce cost, reduce energy consumption.2) be attached in fiber cloth in advance by catalyst, instead of directly add in CBT resin, catalyst and CBT resin are spatially isolated, and there is in-situ polymerization in CBT resin in fiber cloth.This just greatly reduces the injection viscosity of resin, enhances the infiltration of resin to fiber.3) this forming method technique is simple, and easily operate, with low cost, safety and environmental protection, production efficiency is high.Because resin viscosity is very low, the method can be used for fiber reinforced thermolplastic composite material thin-gage goods and large-size fiber strengthens the shaping of thermoplastic composite component, is conducive to applying.4) the fiber reinforcement PBT composite product fiber volume fraction produced of this moulding process is high, and product mechanical property is good.
There is for CBT the feature of low-viscosity, the present invention proposes a kind of novel preparation process of fiber reinforcement PBT composite, namely, under negative pressure of vacuum condition, utilize the flowing of resin and the dipping of infiltration realization to the fabric reinforcing material in airtight die cavity, then polymerizable crystallizable is shaping.Compared with traditional thermoplastic composite moulding process, this is the technique of a kind of high-performance, low cost, and may be used for the manufacture of thin-gage goods and the production of large-sized composite material component.
Accompanying drawing explanation
Accompanying drawing is flow chart of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing citing, the present invention is described in more detail.
The technological process of the vacuum assisted resin diffusion forming method of fiber reinforcement PBT composite of the present invention is given, wherein: 1 be CBT resin, 2 is oil bath heaters, 3 is that heating Tetrafluoroethylene manages, 4 are ball valves, 5 are moulds, 6 are resistance wires, 7 are resin traps, 8 is vavuum pumps in accompanying drawing.
Specific embodiments one:
Catalyst used is the model that Guangzhou Yuan Su Chemical Co., Ltd. produces is the dihydroxy dibutyl tin oxide of PC-4101; Fibre reinforced materials used is the surface density that Yixing recovery glass fibre Co., Ltd produces is 300g/m
2glass fibre unidirectional cloth; CBT resin used is the model that Cyclics company of the U.S. produces is the resin of CBT100, dries 10h before using in 105 DEG C of baking ovens.
Step 1), catalyst is attached on glass fibre unidirectional cloth, concrete operations are: be that appropriate aqueous isopropanol poured into by the catalyst injecting CBT resin quality 0.6% by quality, magnetic stirring apparatus is utilized to stir 10min at 80 DEG C, catalyst is dissolved completely, the brush of dissolution homogeneity on glass-fiber-fabric, puts into 130 DEG C of baking ovens, dry 30min, midway is glass-fiber-fabric turn-over.
Step 2), select die cavity thickness to be the flat plate mold of 2mm, paste High temperature release cloth, imbed elevated-temperature seal bar in die cavity, paving covers 12 layers of glass fibre unidirectional cloth successively, and laying angle is 0 degree, matched moulds, tightens fastening diebolt.The valvular resin injection pipeline of connecting band and vacuum-pumping pipeline on mould.The resin injection mouth of mould and vacuum orifice are located at both mold ends respectively, and resin injection mouth place has resin guide groove.
Step 3), with Resistant heating, makes mould be warming up to 190 DEG C, and with polytetrafluoroethylene (PTFE) heating tube to resin injection pipeline heating to 190 DEG C, the oil bath of CBT resin is heated to 190 DEG C.In the CBT resin submerged by the resin injection pipe mouth of pipe after melting, open filling line valve, CBT resin sucks in mould under vacuum, when having resin to flow out in vacuum-pumping pipeline, closes filling line valve.By mould at 190 DEG C of insulation 30min, CBT resin is infiltrated to fiber glass reinforcement, the crystallization of CBT resin ring-opening polymerisation is simultaneously the PBT of HMW.
Step 4), 240 DEG C (on fusing points of PBT) are heated to prepared glass fiber reinforcement PBT composite and carry out annealing in process, stop heating after constant temperature 30min, naturally cool to room temperature, the demoulding obtains the fiber glass reinforced PBT composite laminated plate that thickness is 1.86mm.
This scheme selection makes CBT carry out ring-opening polymerisation lower than the temperature of PBT fusing point, and the crystallization process of polymerisation and PBT carries out simultaneously, easy and simple to handle, reduces energy consumption.After CBT polymerizable crystallizable, carry out annealing in process on the fusing point prepared glass fiber reinforcement PBT composite being heated to PBT, make the crystallization of PBT more complete, strength and modulus all increases, and the mechanical property of composite strengthens.Obtained glass fiber reinforcement PBT composite laminate, fiber volume fraction is 75%, and this laminate resin is good to the wellability of fiber, and without lamination, the mass defects such as inner tight, dry spot, laminate presentation quality is good.
Specific embodiments two:
Catalyst used is the model that Guangzhou Yuan Su Chemical Co., Ltd. produces is the dihydroxy dibutyl tin oxide of PC-4101; Fibre reinforced materials used is the surface density that Sichuan Tuo Xin research institute produces is 424g/m
2basalt fibre woven cloth; CBT resin used is the model that Cyclics company of the U.S. produces is the resin of CBT100, dries 10h before using in 105 DEG C of baking ovens.
Step 1), catalyst is attached in basalt fibre woven cloth, concrete operations are: be that appropriate aqueous isopropanol poured into by the catalyst injecting CBT resin quality 0.6% by quality, magnetic stirring apparatus is utilized to stir 10min at 80 DEG C, catalyst is dissolved completely, the brush of dissolution homogeneity in fiber cloth, puts into 130 DEG C of baking ovens, dry 30min, midway is fibre knitting cloth turn-over.
Step 2), select die cavity thickness to be the flat plate mold of 4mm, paste High temperature release cloth, imbed elevated-temperature seal bar in die cavity, paving covers 20 layers of basalt fibre woven cloth, matched moulds successively, tightens fastening diebolt.The valvular resin injection pipeline of connecting band and vacuum-pumping pipeline on mould.The resin injection mouth of mould and vacuum orifice are located at both mold ends respectively, and resin injection mouth place has resin guide groove.
Step 3), with Resistant heating, makes mould be warming up to 190 DEG C, and with polytetrafluoroethylene (PTFE) heating tube to resin injection pipeline heating to 190 DEG C, the oil bath of CBT resin is heated to 190 DEG C.In the CBT resin submerged by the resin injection pipe mouth of pipe after melting, open filling line valve, CBT resin sucks in mould under vacuum, when having resin to flow out in vacuum-pumping pipeline, closes filling line valve.By mould at 190 DEG C of insulation 30min, CBT resin is infiltrated to basalt fibre reinforcing material, the crystallization of CBT resin ring-opening polymerisation is simultaneously the PBT of HMW.
Step 4), 240 DEG C (on fusing points of PBT) are heated to prepared basalt fibre enhancing PBT composite and carry out annealing in process, stop heating after constant temperature 30min, naturally cool to room temperature, the demoulding obtains the braiding basalt fibre enhancing PBT composite that thickness is 3.86mm.
This scheme selection makes CBT carry out ring-opening polymerisation lower than the temperature of PBT fusing point, and the crystallization process of polymerisation and PBT carries out simultaneously, easy and simple to handle, reduces energy consumption.After CBT polymerizable crystallizable, carry out annealing in process on the fusing point prepared fiber reinforcement PBT composite being heated to PBT, make the crystallization of PBT more complete, strength and modulus all increases, and the mechanical property of composite strengthens.Obtained fiber reinforcement PBT composite laminate, fiber volume fraction is 70%, and this laminate resin is good to the wellability of fiber, and without lamination, the mass defects such as inner tight, dry spot, laminate presentation quality is good.
Claims (6)
1. a vacuum assisted resin diffusion forming method for fiber reinforcement PBT composite, is characterized in that comprising the steps:
1) catalyst is attached in fiber cloth;
2) with the certain thickness fiber cloth with catalyst for fibre reinforced materials, fibre reinforced materials is placed in and posts High temperature release cloth, be embedded with in the mould of elevated-temperature seal bar; The valvular resin injection pipeline of connecting band and vacuum-pumping pipeline on described mould;
3) with Resistant heating, make mould be warming up to 180 ~ 220 DEG C, with polytetrafluoroethylene (PTFE) heating tube to resin injection pipeline heating to 180 ~ 220 DEG C, the oil bath of CBT resin is heated to 180 ~ 220 DEG C;
4) submerged by the resin injection pipe mouth of pipe in the CBT resin after melting, open filling line valve, CBT resin sucks in mould under vacuum, when having resin to flow out in vacuum-pumping pipeline, closes filling line valve;
5) mould is incubated 30min ~ 1h at 180 ~ 220 DEG C, CBT resin is fully infiltrated fibre reinforced materials, the crystallization of CBT resin ring-opening polymerisation is simultaneously the PBT of HMW, and after carrying out annealing in process, the demoulding obtains fiber reinforcement PBT composite.
2. the vacuum assisted resin diffusion forming method of fiber reinforcement PBT composite according to claim 1, it is characterized in that: the described concrete operations be attached to by catalyst in fiber cloth are: poured into by catalyst in aqueous isopropanol, magnetic stirring apparatus is utilized to stir 10min at 80 DEG C, catalyst is dissolved completely, the catalyst solution brush of dissolution homogeneity is taken out in fiber cloth or in catalyst solution fiber cloth being immersed in dissolution homogeneity again, at 130 DEG C of temperature, dry 30min, midway is fiber cloth turn-over.
3. the vacuum assisted resin diffusion forming method of fiber reinforcement PBT composite according to claim 1, is characterized in that: described fiber cloth is a kind of in glass fabric, basalt fiber cloth or carbon cloth or the wherein compound of at least two kinds.
4. the vacuum assisted resin diffusion forming method of fiber reinforcement PBT composite according to claim 1, is characterized in that: described catalyst is dihydroxy dibutyl tin oxide.
5. the vacuum assisted resin diffusion forming method of fiber reinforcement PBT composite according to claim 1, is characterized in that: the structural formula of described CBT resin is:
Described CBT resin first dries more than 10h before use at 105 DEG C of temperature.
6. the vacuum assisted resin diffusion forming method of fiber reinforcement PBT composite according to claim 1, is characterized in that: the concrete operations of described annealing in process are: be heated to 230 ~ 250 DEG C, stops heating, naturally cool to room temperature after constant temperature 30min.
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| CN201310187953.9A CN103341985B (en) | 2013-05-21 | 2013-05-21 | Vacuum-assisted resin diffusion molding method for fiber-reinforced PBT composite material |
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| CN201310187953.9A CN103341985B (en) | 2013-05-21 | 2013-05-21 | Vacuum-assisted resin diffusion molding method for fiber-reinforced PBT composite material |
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| CN103341985B true CN103341985B (en) | 2015-04-08 |
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| CN104262593B (en) * | 2014-03-14 | 2016-08-31 | 深圳航天科技创新研究院 | A kind of cyclic oligomer composite material and in-situ preparation method thereof |
| CN105922608B (en) * | 2016-06-14 | 2019-01-01 | 四川德源石油天然气工程有限公司 | A kind of composite material preparation facilities and preparation method for field pipes enhancing |
| CN106493972B (en) * | 2016-10-26 | 2018-10-19 | 沈阳航空航天大学 | A kind of preparation method of fiber reinforcement PBT composite melting jointing |
| CN106751583A (en) * | 2016-12-27 | 2017-05-31 | 铜陵市铜峰光电科技有限公司 | A kind of LED fire-retardant plastics of high heat conduction of the adjustable iridescent of cellulose CdTe and preparation method thereof |
| CN106985415A (en) * | 2017-05-04 | 2017-07-28 | 华东交通大学 | Fiber reinforcement PBT composite moulding process based on heating and mould pressing |
| CN109294268A (en) * | 2018-09-30 | 2019-02-01 | 吉林省华阳新材料研发有限公司 | A kind of basalt composite material and its preparation method and application |
| CN116100832A (en) * | 2023-02-10 | 2023-05-12 | 株洲时代新材料科技股份有限公司 | Continuous pouring device and pouring method for polyurethane material |
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| EP1570976A1 (en) * | 2004-03-04 | 2005-09-07 | Alcan Technology & Management Ltd. | Processes for converting cyclic oligomers into thermoplastic PBT products |
| CN101759965B (en) * | 2008-12-26 | 2012-10-17 | 上海杰事杰新材料(集团)股份有限公司 | PBT/montmorillonite nanocomposite material with high crystallization temperature and preparation method thereof |
| CN101987912B (en) * | 2009-08-07 | 2013-01-09 | 骏马化纤股份有限公司 | Modification method and spinning process for polyethylene naphthalate |
| CN102101936B (en) * | 2009-12-21 | 2013-02-27 | 上海杰事杰新材料(集团)股份有限公司 | Polybutylene terephthalate nano composite material and preparation method thereof |
| CN102555234B (en) * | 2012-02-01 | 2014-06-11 | 中材科技风电叶片股份有限公司 | Resin membrane melt impregnation forming method of fiber reinforced PBT composite material |
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