CN102198730B - Pultrusion process and pultrusion device of phenolic resin composite - Google Patents
Pultrusion process and pultrusion device of phenolic resin composite Download PDFInfo
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- CN102198730B CN102198730B CN 201110100751 CN201110100751A CN102198730B CN 102198730 B CN102198730 B CN 102198730B CN 201110100751 CN201110100751 CN 201110100751 CN 201110100751 A CN201110100751 A CN 201110100751A CN 102198730 B CN102198730 B CN 102198730B
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Abstract
The invention discloses a pultrusion process and a pultrusion device of phenolic resin composite. The device is sequentially provided with a yarn releasing device, an impregnating vessel, a felt releasing device, a pre-pultrusion template, a mold, a traction device and a cutting device from front to back, and is characterized in that double driven rollers and a drying device are additionally arranged between the impregnating vessel and the pre-pultrusion device; the pultrusion process which is implemented by using the above devices comprises an impregnating step, a pre-pultrusion template guiding step and a mold solidifying step, wherein a double driven rollers extruding step and a drying step are added between the impregnating step and the pre-pultrusion template guiding step; the impregnated yarn and the felt released by the felt releasing device are extruded in the double driven rollers, the glue solution on the yarn is redistributed, and the felt is impregnated; the yarn and the felt are discharged by the double driven rollers, the discharged yarn and felt are delivered into the drying device for being dried, and finally the dried yarn and felt are delivered into the mould for being solidified. The process is simple, the content and the homogeneity of phenolic resin can be effectively controlled, volatile matters can be removed, the performances are improved, and popularization and application of the composite are favored.
Description
Technical field
The present invention relates to a kind of composite material pultrusion technique and shaped device thereof, particularly a kind of phenolic resin composite pultrusion molding process and shaped device thereof.
Background technology
Pultrusion molding process is a kind of composite material process planning, its basic craft course is, fibre reinforced materials (woven glass roving fabric, glass fibre continuous felt and fiberglass surfacing mat etc.), under the traction of external force, solidify through impregnation, preformed template guiding, hot-die, obtain shape product, and be cut into the process of certain-length by instructions for use.
In pultrusion molding process, use maximum resin matrixes and generally include epoxy resin, vinylite, unsaturated polyester (UP), phenolic resins etc.In numerous resin matrixes, phenolic resins receives publicity with characteristics such as fire-retardant, the low cigarette of its uniqueness, low toxicities, is widely used on the airport, the various fire protection flame retarding occasions such as the public building facility such as railway station, school, hospital and interior of aircraft ornament materials.But use the defective of phenolic resins to be, its processing characteristics is relatively poor, and is especially outstanding in pultrusion molding process.As in pultrusion molding process, normally with the dipping of fibre reinforced materials through the phenolic resins glue, then through after preformed template guiding, directly enter the mold heated curing molding; Because of phenolic resins in adding thermal response, can emit the little molecule volatile materials such as part moisture content, free phenol, free aldehyde, these volatile materials are not removed, and can cause that product section bar after moulding is loose, intensity is low, of poor quality, phenolic resin content and uniformity can't be effectively controlled.How effectively to remove the little molecule volatile materials that reacts the ill-effect that produces in the phenolic resins pultrusion, effectively control content and the uniformity of phenolic resins in shaped article, improve pultrusion product surface and mechanical property, become those skilled in the art's difficult problem anxious to be resolved.
In recent years, open for controlling the existing research of the resin content that infiltrates fiber in pultrude process; As: the patent No. is that the Chinese patent of ZL200820178349.4 has been announced the gumming device in a kind of pultrude process, formed by a lowering or hoisting gear that is arranged on resin storage tank both sides with the cylindrical roller of bearing and, continuously change the roller bearing height by lowering or hoisting gear and come continuous control to infiltrate the resin content of fiber.The method makes the resin content that infiltrates fibre reinforced materials obtain certain control by improving gumming device, but gum dipping process is more complicated, and when the inhomogeneities of fibre reinforced materials impregnation and use phenolic resin curing, the elimination problem of little molecule volatile materials still is not resolved.
Up to the present, also do not see the relevant phenolic resins that solves in pultrusion molding process, its content and uniformity can be effectively controlled, and in course of reaction, volatile materials such as can effectively remove at the successful report of problem.
Summary of the invention
In order to solve the defective that exists in above-mentioned prior art, the purpose of this invention is to provide the pultrusion device that a kind ofly can control phenolic resin content in pultrusion molding process, guarantee that phenolic resins is evenly distributed and can effectively remove the pultrusion molding process of volatile materials and realize this technique.
To achieve these goals, the present invention adopts following technical scheme: a kind of phenolic resin composite pultrusion device, comprise set gradually from front to back put yarn feeding device, steeping vat, put the felt device, preformed template, mould, draw-gear and cutter sweep; Its characteristics are: also be equipped with passive pair of roller and drying unit between steeping vat and preformed template; Wherein, the installation site of the passive pair of roller and drying unit with put yarn feeding device, preformed template, mould, draw-gear and cutter sweep for being horizontally disposed with.
Above-mentioned put the top that the felt device is positioned at this passive pair of roller; By sequentially passing through passive pair of roller, drying unit, preformed template, mould after the fibre reinforced materials termination impregnation of putting that yarn feeding device emits and by the Surface of profile felt termination of putting that the felt device emits, by the draw-gear traction until cutter sweep cutting aftershaping is phenolic resin composite of the present invention; Wherein, draw-gear is by motor-driven; Fibre reinforced materials and Surface of profile felt drive passive pair of roller and rotate under the draw of draw-gear.
Another object of the present invention, be a kind of phenolic resin composite pultrusion molding process that utilizes above-mentioned pultrusion device to realize, it comprises putting the yarn step, carrying out the step of impregnation, the guiding step of preformed template, the curing schedule of mould, dragline step and the excision forming step of draw-gear with the phenolic resins glue of fibre reinforced materials; Its characteristics are: between impregnation step and preformed template guiding step, be provided with step and the baking step of extruding glue; Described extruding glue step and baking step are realized by the passive pair of roller and the drying unit that are set in sequence between steeping vat and preformed template respectively.
The concrete operations of above-mentioned extruding glue step are as follows: be provided with one and put the felt device above passive pair of roller; Fibre reinforced materials after impregnation and together entering in passive pair of roller by putting the Surface of profile felt that the felt device emits; By the extruding of this passive pair of roller, impel glue evenly to distribute on this fibre reinforced materials; Simultaneously, the described Surface of profile felt that enters in passive pair of roller is implemented impregnation;
The concrete operations of above-mentioned baking step are as follows: latex bonded fibre reinforcing material and Surface of profile felt drive passive pair of roller and rotate under the dragline effect of draw-gear, the latex bonded fibre reinforcing material that squeezes out through passive pair of roller and the composition of impregnation Surface of profile felt are sent in drying unit, under the bake out temperature of 60 ℃～120 ℃, dried the volatilization of phenolic resins glue small molecular 6～10 minutes; To be dried to doing of fibre reinforced materials and Surface of profile felt wet consistent after, then be shaped to phenolic resin composite through lead step, mold cured step, traction and excision forming step of preformed template.
Drying unit used is the case structure of both ends open, opening with respect to passive pair of roller one end is the entrance of latex bonded fibre reinforcing material and impregnation Surface of profile felt, is the outlet of latex bonded fibre reinforcing material and impregnation Surface of profile felt with respect to the opening of preformed template one end; Cabinet wall is evenly distributed with heater block; The temperature control unit that is connected with this heater block is housed outside casing; Bake out temperature is controlled and is regulated by temperature control unit.
Above-mentioned temperature control unit can be selected in transformer, programmable logic controller (PLC) or thyristor regulating depressor any.Above-mentioned heater block optional with in electric hot plate, electrothermal tube, quartz heating-pipe or infrared heating pipe any.
The bake out temperature of above-mentioned drying unit is 60 ℃～120 ℃, and temperature control precision is ± 5 ℃, and drying time is 6～10 minutes.
The dragline speed of above-mentioned draw-gear dragline step is 0.1～0.6m/min.
Owing to having adopted technique scheme, beneficial effect of the present invention is as follows: the 1) setting of passive pair of roller, make the glue redistribution on the fibre reinforced materials after impregnation, completed simultaneously the dipping to the Surface of profile felt, glue be fully used and effectively controlled content and the uniformity of phenolic resins, having overcome the content of resin adhesive liquid and the defective that uniformity can't be controlled in the prior art; Wherein, the gelatin viscosity of phenolic resins can be regulated as diluent with alcohol according to the forming requirements of product.2) setting of drying unit, bake out temperature can be regulated, and makes the fibre reinforced materials that adheres to the phenolic resins glue and Surface of profile felt after oven dry, and this is consistent for dried wet basis.Effectively removed little molecule volatile matter before entering mould, solved and effectively to have removed the problem that reactive modified phenolic resin small molecular volatile matter discharges in the prior art; 3) compare with traditional method, owing to introducing passive pair of roller and drying unit, greatly improved impregnation uniformity between fibre reinforced materials, completed simultaneously the impregnation of felt, realized phenolic resin content and inhomogeneity controllability; Simultaneously, guaranteed effectively that also product dense materials, the intensity of pultrusion is high.4) technique of the present invention is simple, easy to operate, shaping efficiency is high, product properties is excellent; Can be used for the moulding of the various cross sections section bars such as I-steel, crossbeam, side bar, diagonal brace and bar; Be suitable for promotion and application in the fire protection flame retarding engineering of the civil areas such as communications and transportation, building, the energy.
Description of drawings
Fig. 1 is installation site and the process flow diagram of pultrusion device of the present invention.
The specific embodiment
As shown in Figure 1, a kind of phenolic resin composite pultrusion device of the present invention comprises horizontally disposed frame and extruder from front to back, is provided with in frame the place ahead and puts creel, is equipped with on it and puts yarn feeding device 1; Passive pair of roller 3, drying unit 5, preformed template 6 are installed on frame from front to back successively; Steeping vat 2 is placed on the frame front end; Be provided with a support that is fixedly connected with its frame both sides above passive pair of roller 3, be equipped with one and put felt device 4 on support; Mould 7 is arranged on extruder, and the equipment that draw-gear 8 carries for extruder is by motor-driven draw-gear 8; In the extruder rear end, cutter sweep 9 is housed;
Put felt device 4 and be positioned at the top of passive pair of roller 3; Together order is through passive pair of roller 3, drying unit 5, preformed template 6, mould 7 in after putting the phenolic resins glue impregnation of fibre reinforced materials termination in steeping vat 2 that yarn feeding device 1 emits and the Surface of profile felt termination of putting that felt device 4 emits, and draw-gear 8 is to cutter sweep 9 outlets; The pultrusion of whole section bar product is to draw by the draw-gear 8 that extruder carries to form, draw-gear 8 is by motor-driven, fibre reinforced materials and Surface of profile felt are under the draw of draw-gear 8, driving passive pair of roller 3 rotates, latex bonded fibre reinforcing material and the Surface of profile felt that passes through pushed, realize the phenolic resins glue again and be evenly distributed on fibre reinforced materials and Surface of profile felt.
The concrete technology flow process comprises that step is as follows:
1) fibre reinforced materials puts the yarn step; 2) impregnation step; 3) step of extruding glue; 4) put the felt step; 5) baking step; 6) preformed template guiding step; 7) mold cured forming step; 8) the dragline step of draw-gear; 9) excision forming step.
Concrete operations are as follows:
According to product requirement formulated phenolic resin glue, after being mixed in proportion, phenolic resins and alcohol puts into steeping vat; Emit the not fibre reinforced materials of impregnation with putting yarn feeding device 1, fibre reinforced materials enters the interior impregnation of steeping vat 2; The fibre reinforced materials that soaked glue is by passive pair of roller 3 time, puts felt device 4 and emits the Surface of profile felt and also together enter passive pair of roller 3, completed the dipping to its Surface of profile felt when the phenolic resins glue is redistributed on this fibre reinforced materials; By the yarn after 3 extruding of passive pair of roller and the composition of Surface of profile felt; Enter drying unit 5 after drying 6～10 minutes at the temperature of 60 ℃～120 ℃, make the dried wet basis of fibre reinforced materials and Surface of profile felt originally consistent, to satisfy the performance requirement into the mould product; And then the fibre reinforced materials after drying and Surface of profile felt by preformed template 6 guiding after, enter that in mould 7, heating cure is shaped to the section bar product; Section bar product after curing molding is completed after its product being cut with cutter sweep 9 according to user's request under the traction of draw-gear 8.
Due to the fibre reinforced materials that enters mould 7 and extruding and drying unit 5 oven dry of passive pair of roller 3 of process of Surface of profile felt, phenolic resins glue on fibre reinforced materials and Surface of profile felt distributes more even, phenolic resins adds the volatile matters such as bad little molecule that produce in thermal response effectively to be removed, and has guaranteed that phenolic resin composite product dense materials, the intensity of pultrude process moulding is high.
The temperature of steeping vat 2 used is room temperature; The phenolic resins glue is optional with conventional phenolic resins, and the viscosity of phenolic resins can require according to the resin content of section bar to regulate with diluent, and diluent adopts alcohol usually;
Drying unit 5 used is the case structure of both ends open, opening with respect to passive pair of roller 3 one ends is the entrance of latex bonded fibre reinforcing material and impregnation Surface of profile felt, is the outlet of latex bonded fibre reinforcing material and impregnation Surface of profile felt with respect to the opening of preformed template 6 one ends; Cabinet wall is evenly distributed with heater block; The temperature control unit that is connected with this heater block is housed outside casing; Bake out temperature is controlled and is regulated by temperature control unit.
Above-mentioned temperature control unit can be selected in transformer, programmable logic controller (PLC) or thyristor regulating depressor any.Above-mentioned heater block optional with in electric hot plate, electrothermal tube, quartz heating-pipe or infrared heating pipe any.
Adopt the two-part mode of heating of drying unit 5 and mould 7, can satisfy the performance indications requirement of fibre reinforced materials and Surface of profile felt curing molding.
Compare with traditional method, owing to introducing passive pair of roller 3 and drying unit 5, greatly improved impregnation uniformity between fiber, completed simultaneously the impregnation of felt, can effectively control resin content and uniformity, and can effectively remove the volatile matter such as bad little molecule before entering mould, make that section bar is fine and close, intensity is high.Have that technique is simple, easy to operate, shaping efficiency is high, the excellent characteristics of section quality.
Below moulding example by specific product technical scheme of the present invention is elaborated.Except as otherwise noted, following examples various raw materials used all can obtain by commercial sources.
Adopting phenolic resin system and glass fibre pultrusion is composite material section bar.
I-steel:Fibre reinforced materials is put yarn by putting yarn feeding device, and its fibre reinforced materials is selected the medium-alkali glass fibre of the nominal line density 9600tex of long wind glass fibre factory of Handan Mining Group Co., Ltd; The phenolic resins glue that is mixed by the NR9450 of Changshu Southeast Plastic Co., Ltd. model phenolic resins and alcohol is housed in steeping vat; Wherein, phenolic resins and alcohol mix with the 1:0.3 mass ratio.Put yarn feeding device and emit medium-alkali glass fibre, immerse in the glue groove that the phenolic resins glue is housed and flood; The medium-alkali glass fibre that is impregnated with phenolic resins by the glue groove out after, and put the together extruding by passive pair of roller of Surface of profile felt that the felt device emits; Phenolic resins on the medium-alkali glass fibre of extruding is redistributed, and is evenly covering on the medium-alkali glass fibre surface; Simultaneously, the unnecessary phenolic resins that is squeezed out, the synchronous dipping of Surface of profile felt enforcement that puts down putting the felt device.
Composition by the medium-alkali glass fibre after passive pair of roller and Surface of profile felt, send into temperature and be in the drying unit of 60 ℃ oven dry after 10 minutes, medium-alkali glass fibre after oven dry and Surface of profile felt enter in mould after leading through the preformed template, are heating and curing 2 minutes in 170 ℃ of-190 ℃ of moulds; Drying unit used adopts the electric hot plate heating of transformer temperature control.
From putting medium-alkali glass fibre, impregnation that yarn feeding device emits, putting Surface of profile felt and the medium-alkali glass fibre after impregnation that the felt device emits and together enter passive pair of roller, through extruding, oven dry, draw by entering after preformed template guiding in mould by the draw-gear that is arranged on the mould back again, then complete after the cutter sweep cutting.Wherein, the dragline speed of draw-gear is 0.1m/min.
The I-steel performance: resin content is 20% of phenolic composite quality, resin content deviation ± 1%.Bending strength 454 MPa, bending modulus 29.8 GPa, compressive strength 127 MPa, modulus of compressibility 15.2 GPa.
Its performance indications are to adopt: the standards such as GB/T 2577-2005 Test method for resin content of glass fiber reinforced plastics, GB/T 1449-2005 fibre reinforced plastics bending property test method, GB/T 1448-2005 fibre reinforced plastics compression performance test method are tested and are obtained.
Handrail:Fibre reinforced materials is put yarn by putting yarn feeding device, and its fibre reinforced materials is selected the medium-alkali glass fibre of the nominal line density 9600tex of long wind glass fibre factory of Handan Mining Group Co., Ltd; Being equipped with in steeping vat by Changshu Southeast Plastic Co., Ltd.'s model is phenolic resins and the mixed phenolic resins glue of alcohol of NR9450, and wherein, phenolic resins and alcohol mix with the 1:0.1 mass ratio.Put yarn feeding device and emit medium-alkali glass fibre, immerse in the glue groove that the phenolic resins glue is housed and flood; The medium-alkali glass fibre that is impregnated with phenolic resins by the glue groove out after, and put the Surface of profile felt that the felt device emits and together enter passive pair of roller extruding; On the one hand the phenolic resins on the medium-alkali glass fibre of extruding is redistributed, and is evenly covering on the medium-alkali glass fibre surface; On the other hand, the unnecessary phenolic resins that is squeezed out; The synchronous dipping of Surface of profile felt enforcement that puts down putting the felt device.
By the medium-alkali glass fibre after the extruding of the passive pair of roller and the composition of Surface of profile felt, sent into temperature and be in the drying unit of 120 ℃ oven dry 6 minutes, then by entering in mould after preformed template guiding, be heating and curing 2 minutes in 180 ℃ of-200 ℃ of moulds; Drying unit used adopts the electrothermal tube heating of transformer temperature control.
From putting medium-alkali glass fibre, impregnation that yarn feeding device emits, putting Surface of profile felt and the medium-alkali glass fibre after impregnation that the felt device emits and together enter passive pair of roller, through extruding, oven dry, by entering after preformed template guiding in mould by the draw-gear traction that is arranged on the mould back, then complete after the cutter sweep cutting.Wherein, the dragline speed of draw-gear is 0.6m/min.
The handrail performance:, resin content is 25% of phenolic composite quality, resin content deviation ± 1%.Bending strength 465MPa, bending modulus 30.4GPa, compressive strength 130MPa, modulus of compressibility 17.1GPa.
Its performance indications are to adopt: the standards such as GB/T 2577-2005 Test method for resin content of glass fiber reinforced plastics, GB/T 1449-2005 fibre reinforced plastics bending property test method, GB/T 1448-2005 fibre reinforced plastics compression performance test method are tested and are obtained.
Except the said goods, method of the present invention also is applicable to produce the composite material section bar of various section configurations, as rod, pipe, solid profile (as flute profile, square section bar) and hollow section etc.; In baking step wherein, the heater block in drying unit used also can be selected quartz heating-pipe or infrared heating pipe except adopting electric hot plate or electrothermal tube; Temperature control unit also can adopt programmable logic controller (PLC) or thyristor regulating depressor except adopting transformer; Resulting shaped article performance is identical.
Claims (9)
1. phenolic resin composite pultrusion device, comprise set gradually from front to back put yarn feeding device, steeping vat, put the felt device, preformed template, mould, draw-gear and cutter sweep; It is characterized in that: also be equipped with passive pair of roller and drying unit between described steeping vat and described preformed template; Wherein, the passive pair of roller and drying unit and described yarn feeding device, described preformed template, described mould, described draw-gear and the described cutter sweep put are for being horizontally disposed with.
2. phenolic resin composite pultrusion device as claimed in claim 1 is characterized in that: describedly put the top that the felt device is positioned at described passive pair of roller; Described passive pair of roller, described drying unit, described preformed template, described mould are sequentially passed through in after the described fibre reinforced materials termination impregnation of putting that yarn feeding device emits and described Surface of profile felt termination of putting that the felt device emits, by described draw-gear traction until described cutter sweep cutting aftershaping is described phenolic resin composite; Described draw-gear is by motor-driven; Described fibre reinforced materials and Surface of profile felt drive described passive pair of roller and rotate under the draw of draw-gear.
3. pultrusion molding process that utilizes claim 1 or the described shaped device of 2 any one to prepare phenolic resin composite comprises putting the yarn step, carrying out the step of impregnation, the guiding step of preformed template, the curing schedule of mould, dragline step and the excision forming step of draw-gear with the phenolic resins glue of fibre reinforced materials; It is characterized in that: between described impregnation step and preformed template guiding step, be provided with step and the baking step of extruding glue; Described extruding glue step and baking step are realized by the passive pair of roller and the drying unit that are set in sequence between steeping vat and preformed template respectively.
4. phenolic resin composite pultrusion molding process as claimed in claim 3, it is characterized in that: the concrete operations of described extruding glue step are: arrange one and put the felt device above described passive pair of roller; Described fibre reinforced materials after impregnation and put the Surface of profile felt that the felt device emits and together enter in described passive pair of roller by described; By the extruding of this passive pair of roller, impel glue evenly to distribute on this fibre reinforced materials; Simultaneously, the described Surface of profile felt that enters in passive pair of roller is implemented impregnation.
5. pultrusion molding process as claimed in claim 4 is characterized in that: described baking step operation is as follows: the latex bonded fibre reinforcing material that squeezes out through described passive pair of roller and the composition of impregnation Surface of profile felt are sent in described drying unit oven dry to doing of described fibre reinforced materials and Surface of profile felt and are wet consistent; Be shaped to described phenolic resin composite through described preformed template guiding step, mold cured step, traction and excision forming step again.
6. pultrusion molding process as claimed in claim 5, it is characterized in that: described drying unit is the case structure of both ends open, opening with respect to passive pair of roller one end is the entrance of latex bonded fibre reinforcing material and impregnation Surface of profile felt, is the outlet of latex bonded fibre reinforcing material and impregnation Surface of profile felt with respect to the opening of preformed template one end; Cabinet wall is evenly distributed with heater block; The temperature control unit that is connected with this heater block is housed outside casing; Bake out temperature is controlled and is regulated by temperature control unit.
7. pultrusion molding process as claimed in claim 6 is characterized in that: described temperature control unit be in transformer, programmable logic controller (PLC) or thyristor regulating depressor any; Described heater block be in electric hot plate, electrothermal tube, quartz heating-pipe or infrared heating pipe any.
8. pultrusion molding process as claimed in claim 7, it is characterized in that: described bake out temperature is 60 ℃～120 ℃, and temperature control precision is ± 5 ℃, and drying time is 6～10 minutes.
9. pultrusion molding process as described in claim 3～8 any one, it is characterized in that: the dragline speed of described draw-gear is 0.1～0.6m/min.
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| CN102490378A (en) * | 2011-12-19 | 2012-06-13 | 中格复合材料（南通）有限公司 | Production method of the phenolic glassfiber reinforced plastic sectional material |
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| CN109251332B (en) * | 2018-08-20 | 2021-07-20 | 浙江亚太机电股份有限公司 | Chopped carbon fiber reinforced phenolic resin matrix composite material and preparation method thereof |
| CN111907093A (en) * | 2020-06-24 | 2020-11-10 | 杭州卡涞复合材料科技有限公司 | Method for quickly forming frame of automobile composite material battery box |
| CN113414900A (en) * | 2021-05-25 | 2021-09-21 | 广东粤港澳大湾区黄埔材料研究院 | Wire rod dipping glue solidification device |
| CN114193798A (en) * | 2021-08-29 | 2022-03-18 | 北京工业大学 | Continuous preparation method and anchoring method of FRP pultrusion profile |
| CN115284487B (en) * | 2022-09-28 | 2023-02-17 | 北京玻钢院复合材料有限公司 | Preparation system and preparation method of premix for quartz fiber reinforced phenolic mould pressing part |
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| EP0403607A1 (en) * | 1988-10-13 | 1990-12-27 | Weyerhaeuser Company | Pultrusion system for condensation resin injection |
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