CN103289313B - A kind of preparation method improveing glass-reinforced plastic material - Google Patents
A kind of preparation method improveing glass-reinforced plastic material Download PDFInfo
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- CN103289313B CN103289313B CN201210044010.6A CN201210044010A CN103289313B CN 103289313 B CN103289313 B CN 103289313B CN 201210044010 A CN201210044010 A CN 201210044010A CN 103289313 B CN103289313 B CN 103289313B
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- reactive diluent
- reinforced plastic
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Abstract
The invention discloses a kind of method of modified form glass-reinforced plastic material.Its preparation method is for taking texturized glass yarn, epoxy resin, epoxide resin reactive diluent, tackifier, 1 ~ 2 part, softening agent, silane coupling agent, solidifying agent, the filler that length is 15 ~ 50mm; Epoxide resin reactive diluent is added in texturized glass yarn; Epoxy resin, surplus epoxide resin reactive diluent are mixed, enters softening agent, silane coupling agent is prepared into dipping glue; Described dipping glue is walked by putting into c through the article prepared by b step; Add softening agent, after stirring, add filler, solidifying agent stirs, airtight preservation.The inventive method technique is simple, and the matrix material provided has good interface performance, intensity is high, supporting capacity is large, impact resistance is good.
Description
Technical field
The present invention relates to the preparation method of fibre reinforced composites, specifically a kind of preparation method improveing glass-reinforced plastic material.
Background technology
Glass-reinforced plastic material embeds in the thermosetting resin solidified by glass fibre reinforcement or is wrapped to form the material of composite structure by it.Glass-reinforced plastic material many employings resin Sized glass cloth material of production and application comes shaping in the market.The method effect of impregnation is good, and prepared content of glass fiber is high.But due to the restriction by woven fiber glass volume and shape, make it be not suitable with product for such as tube stub, tee pipe fitting, bend pipe tools etc. not easily uniform-compression especially.In addition, its impact resistance of glass-reinforced plastic material prepared by the method is poor, and laminated face easily layering occurs.In order to solve the problem, Fiber Aspect Ratio is about 1000, length is 3 ~ 5mm glass fiber powder to have investigator to be cut into by glass fibre, then glass fiber powder is put in the mixed solution be made up of epoxy resin, softening agent, silane coupling agent, stir in ball mill again and add filler, solidifying agent, be prepared into thus a kind of not containing woven fiber glass laying glass-reinforced plastic material (refer to Zhang Juan etc. the preparation [J] of fiber glass epoxy and test. engineering, 2008, NO.13).Although the glass-reinforced plastic material that the method provides overcomes the defect that woven fiber glass itself causes, because glass fibre is cut into powdery, thus the specific physical property of its fiber itself is also weakened severely.Usually to fracture, fiber extraction, fibre breakage 3 kinds of modes by resin distortion and crack propagation as matrix material absorbs the mode of striking energy.Be not difficult to find out when the glass fibre in matrix material is that powdery embeds in the thermosetting resin solidified thus, when being subject to external impacts, mealiness fiber no longer has when fiber is extracted out and can endergonicly act on, the energy that can absorb when simultaneously also losing fibre breakage.Also the shock-resistance of investigator by adopting the optimum design of laminate layup of woven fiber glass to improve glass-reinforced plastic material is had.As the researchists such as Dong Weiwei devise respectively 4 kinds of ply sequences (be respectively 0 °/0 °/0 °/0 °/, 0 °/90 °/0 °/90 °/, 0 °/﹢, 45 °/﹢ 45 °/0 °/, ﹢ 45 °/0 °/-45 °/﹢ 90 ° /), adopt vacuum assisted resin injection moulding to carry out compound to glass fibre/unsaturated polyester resin laminated wood.And to its impact resistance carried out testing (refer to Dong Weiwei, etc. impact resistance research [J] Tianjin University of Technology journal of glass fibre/unsaturated polyester composite plate, 2008,27 (1) 24-25).Experimental result shows that employing 0 °/90 °/0 °/90 °/ply sequence can improve the intensity of matrix material, supporting capacity and energy absorption capability, but its non-deformability is more weak.Glass reinforced plastic in addition prepared by the method still will be subject to the restriction of woven fiber glass volume and shape when applying.Directly being mixed in thermosetting resin by the glass fibre of certain length and forming a kind of glass-reinforced plastic material not containing woven fiber glass laying is perhaps a kind of selection well.But fiberglass surfacing is smooth, fiber contacts is tight, therefore its dispersiveness is very poor.Therefore, when glass fibre is directly mixed into thermosetting resin, the non-constant of the wetting property of resin to it, so glass fibre is difficult to be formed firmly bonding with resin matrix.In order to improve the adhesive capacity of glass fibre and resin matrix, during research emphasis has been placed on and has processed the surface of glass fibre by many researchists.At present the method that fiberglass surfacing processes is mainly contained: heat treating process, namely utilize high temperature to make original sizing material oxygenolysis of fiberglass surfacing, remove the water that glass fibre adsorbs due to storage simultaneously.The method is simple, practical, but it is used alone less effective, thus usually all as the pretreatment process of fiberglass surfacing process; Soda acid etching processing method, namely carries out chemical reaction by soda acid at fiberglass surfacing and forms some depression or micropores.Treat that glass fibre and matrix carry out compound tense, the segment of some superpolymer enters into hole. and play similar anchorage effect, thereby increase the bonding force between glass fibre and polymer interface.But research shows that though soda acid etching processing method effectively can increase the surface-area of glass fibre, improves the wetting property of fiberglass surfacing, but glass fibre is being destroyed by soda acid etching rear surface layer, thus causes stress concentration, and self-strength declines to some extent.
Summary of the invention
Object of the present invention is exactly will provide a kind of to prepare not containing woven fiber glass laying and the method for the good modified form glass-reinforced plastic material of impact resistance.
The object of the invention is to be achieved by the following technical programs:
The method of preparation improvement glass-reinforced plastic material provided by the present invention, it comprises the following steps:
A () takes the raw material of following weight part ratio: length is the texturized glass yarn 15 ~ 25 parts of 15 ~ 50mm, epoxy resin 20 ~ 25 parts, epoxide resin reactive diluent 3-8 part, 1 ~ 2 part, tackifier 0.05 ~ 0.1 part of softening agent, silane coupling agent 1 ~ 2 part, 2 ~ 5 parts, solidifying agent, filler 10 ~ 20 parts;
B (), by texturized glass yarn, at 350 ~ 400 DEG C of temperature, thermal treatment 1-2h, removes the sizing material oxide compound that fiberglass surfacing is residual;
C the epoxide resin reactive diluent of 1/3 ~ 1/2 amount adds in described texturized glass yarn by (), after stirring, for subsequent use;
D epoxy resin, surplus epoxide resin reactive diluent mix by (), then add softening agent, silane coupling agent is prepared into dipping glue, for subsequent use;
E () walks described dipping glue by putting into d through the article prepared by c step, after stirring, and airtight dipping 4-12 hour;
F () adds tackifier, after stirring, add filler, solidifying agent stirs, airtight preservation.
Certain thickness sheet material or can be coated into, solidification, dry 12-24 hour when embody rule; Or be filled into and scribble in the mould of releasing agent, be prepared into the product of desired shape; Or sealing is preserved, and is poured in use in spray gun, described material spraying is carried out reinforcing in the surface being repaired product.
Epoxide resin reactive diluent of the present invention can select epoxy propane butyl ether, glycidyl allyl ether, butylglycidyl ether, phenyl glycidyl ether, cresylglycidylether, fragrant monoglycidyl ether, epoxy styrene, diepoxy propane ethyl ether, ethylene glycol diglycidylether
,one in polypropylene glycol diglycidyl ether.
Softening agent of the present invention can select phthalate, as: dioctyl phthalate (DOP); Dibutyl phthalate; DBP, DOP, DIDP.
Tackifier of the present invention can select epoxide modified pair of maleinamide, maleinamide (BMI) as two in 4,4 '-two amido ditane types.
Solidifying agent of the present invention can select the one in methylethyl ketone peroxide, 2-ethyl-4-methylimidazole, polyamide 6 50, T31 epoxy curing agent, contracting amine-105 epoxy curing agent, KJP-1002 epoxy curing agent.
Silane coupling agent of the present invention can select KH550, the one in KH560, KH570, KH792, DL602, DL171.
Filler of the present invention can select silica powder, also can select carbon silica flour.
Staple glass fibre in material of the present invention because of fiber be expanded type, therefore spatial area shared by it is large, loft is high, is easy to fully be soaked into by glue.Simultaneously also because spatial area shared by it is large, so the situation of intertwinding of fiber and fiber is good, match with matrix formulation of the present invention again, thus can a kind of heterozygosis net of self-assembling formation, and form and a kind of there is good interface performance and good Stress transmit effect, intensity is high, supporting capacity is large, impact resistance is good matrix material.
The more preferred scheme of the present invention is:
Texturized glass yarn 15 ~ 25 parts, epoxy resin 20 ~ 25 parts, epoxide resin reactive diluent 3-8 part, tackifier 0.05 ~ 0.1 part, 1 ~ 2 part, softening agent, silane coupling agent 1 ~ 2 part, 2 ~ 5 parts, solidifying agent, filler 10 ~ 20 parts, tackifier are wherein epoxide modified pair of maleinamide.
Texturized glass yarn in the present invention be by (nothing) alkali containing glass fibre yarn form through expanded machine is expanded, it also directly can buy from market.
Its preferred length of texturized glass yarn of the present invention is 15 ~ 30mm.The mobility that more effectively can increase fiber fluffy degree thus, improve itself and bond matrix effect, improve matrix.
The inventive method is simple, environmental protection, texturized glass yarn can more uniformly be scattered among matrix by its what is more important quickly and efficiently, texturized glass yarn can be made thus to connect better and to form good Stress transmit net, further increase the Resisting fractre of institute's prepared material, the performance such as shock-resistant.
Material of the present invention can be used for making the component of machine such as bumper and vehicle body, also can be used for carrying out reinforcing to damaged, corrosion building slab.
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment
Embodiment 1
A () takes the texturized glass yarn 25kg that length is 15 ~ 30mm, bisphenol A epoxide resin 25kg, diepoxy propane ethyl ether (epoxide resin reactive diluent) 8kg, epoxide modified couple of maleinamide (tackifier) 0.1kg dioctyl phthalate (DOP) (softening agent) 2kg, Silane coupling agent KH550 2kg, methylethyl ketone peroxide (solidifying agent) 5kg, silica powder (filler) 20kg;
Above-mentioned raw materials is all buied from market.Wherein texturized glass yarn is by the production and sales of glass fibre factory of Dongtai City.
B (), by texturized glass yarn, at 350 DEG C of temperature, toasts 1 hour, the sizing material oxide compound that removing fiberglass surfacing is residual;
C the epoxide resin reactive diluent of 1/2 amount adds in texturized glass yarn by (), after stirring, for subsequent use;
D epoxy resin, surplus epoxide resin reactive diluent mix by (), then add softening agent, silane coupling agent is prepared into dipping glue, for subsequent use;
E () walks described dipping glue by putting into d through the article prepared by c step, after stirring, and airtight dipping 12 hours;
F () adds tackifier, after stirring, add filler, solidifying agent stirs, and is then coated into the sheet material of 0.58 ~ 0.64 thickness, solidification, drying 12 hours;
Embodiment 2
A () takes the texturized glass yarn 15kg that length is 35mm, bisphenol A epoxide resin 20kg, polypropylene glycol diglycidyl ether (epoxide resin reactive diluent) 3kg, 4,4 '-two amido ditane type two maleinamide (tackifier) 0.05kg dibutyl phthalate (softening agent) 1kg, silane coupling agent DL6021kg, T31 epoxy resin (solidifying agent) 2kg, silica powder (filler) 10kg;
B (), by texturized glass yarn, at 400 DEG C of temperature, toasts 2 hours, the sizing material oxide compound that removing fiberglass surfacing is residual;
C the epoxide resin reactive diluent of 1/3 amount adds in texturized glass yarn by (), after stirring, for subsequent use;
D epoxy resin, surplus epoxide resin reactive diluent mix by (), then add softening agent, silane coupling agent is prepared into dipping glue, for subsequent use;
E () walks described dipping glue by putting into d through the article prepared by c step, after stirring, and airtight dipping 6 hours;
F () adds tackifier, after stirring, place 40 minutes, add filler, solidifying agent stirs, be then coated into the sheet material of 0.58 ~ 0.64 thickness, solidification, drying 24 hours;
Embodiment 3
Take the texturized glass yarn 20kg that length is 50mm, bisphenol A epoxide resin 25kg, polypropylene glycol diglycidyl ether (epoxide resin reactive diluent) 5kg, epoxide modified couple of maleinamide (tackifier) 0.08kg dibutyl phthalate (softening agent) 1.5kg, silane coupling agent KH5601kg, contracting amine-105 epoxy resin (solidifying agent) 4kg, carbon silica flour (filler) 15kg.
Concrete preparation method is with embodiment 1.
Embodiment 4
Take the texturized glass yarn 18kg that length is 15mm, bisphenol A epoxide resin 22kg, epoxy propane butyl ether (epoxide resin reactive diluent) 4kg, epoxide modified couple of maleinamide (tackifier) 0.05kg dibutyl phthalate (softening agent) 2kg, silane coupling agent KH7921.5kg, methylethyl ketone peroxide 3kg, silica powder (filler) 15kg.
Concrete preparation method is with embodiment 2.
Comparative example 1
Take following raw material:
Bisphenol A epoxide resin 24kg, polyamide 6 507kg, T312kg, glass fiber powder (length is 3 ~ 5mm) 24kg, epoxy propane butyl ether 10kg, dibutyl phthalate 2kg, silane coupling agent KH5602kg, silica powder 7kg, carbon silica flour 12kg.
Preparation method:
After epoxy resin is diluted, add softening agent, coupling agent, stir, add glass fiber powder, rotate in ball mill high speed, make glass fibre be dispersed in sample, add filler, solidifying agent, solidify 12 hours.Make the sheet material that thickness is 0.58 ~ 0.64.
Comparative example 2
Take following raw material:
Unsaturated polyester resin 100kg, cobalt naphthenate 1.25kg methyl ethyl ketone peroxide solution 1.05kg, be prepared into dipping glue;
By glasscloth according to 0 °/90 °/0 °/90 °/ply sequence carry out laying, adopt vacuum assisted resin injection molding technology to carry out compound to glass fibre/unsaturated polyester resin laminated wood.Namely discharge the gas in fibre reinforcement under vacuum conditions, to the dipping of fiber and fabric thereof, and at room temperature solidified by the flowing of resin, infiltration, realization.Make the sheet material that thickness is 0.58 ~ 0.64.
Embodiment 5 impact resistance is tested
Testing tool: U.S. Dynatup92 shaped material Apparatus for Impacting at low-temp, punch shape: bullet-shaped, sample dimensions: 95mm × 95mm; Be divided into 6 groups, the 1st group of sheet material, the 2nd group of sheet material, the 3rd group of sheet material, the 4th group of sheet material, the 5th group of sheet material, the 6th group of sheet material prepared by comparative example 2 prepared by comparative example 1 prepared by embodiment 4 prepared by embodiment 3 prepared by embodiment 2 prepared by embodiment 1; Each group adopts 5 test specimens, and testing data gets the mean value of 5 test specimens.Experimental result refers to table 1.
Table 1:
Data from table 1 compare, and the sheet material parameters value prepared by the present invention is all greater than the sheet material prepared by comparative example 1.It is compared with comparative example 2, and its elastic performance is relatively weak compared with comparative example 2, and all the other are every is all greater than comparative example 2.Test-results shows: the sheet material prepared by the present invention is to energy absorbing efficiency is good, intensity is high, non-deformability is good, supporting capacity is large.
Claims (4)
1. improve a preparation method for glass-reinforced plastic material, it is characterized in that it comprises the following steps:
A () takes the raw material of following weight part ratio: length is the texturized glass yarn 15 ~ 25 parts of 15 ~ 50mm, epoxy resin 20 ~ 25 parts, epoxide resin reactive diluent 3-20 part, tackifier 0.05 ~ 0.1 part, 1 ~ 2 part, softening agent, silane coupling agent 1 ~ 2 part, 2 ~ 5 parts, solidifying agent, filler 10 ~ 20 parts; Described solidifying agent is the one in methylethyl ketone peroxide, 2-ethyl-4-methylimidazole, polyamide 6 50, T31 epoxy curing agent, contracting amine-105 epoxy curing agent, KJP-1002 epoxy curing agent; Described epoxide resin reactive diluent is the one in epoxy propane butyl ether, glycidyl allyl ether, fragrant monoglycidyl ether, ethylene glycol diglycidylether, polypropylene glycol diglycidyl ether;
B (), by texturized glass yarn, at 350 ~ 400 DEG C of temperature, thermal treatment 1-2h, removes the sizing material oxide compound that fiberglass surfacing is residual;
C the epoxide resin reactive diluent of 1/3 ~ 1/2 amount adds in described texturized glass yarn by (), after stirring, for subsequent use;
D epoxy resin, surplus epoxide resin reactive diluent mix by (), then add softening agent, silane coupling agent is prepared into dipping glue, for subsequent use;
E () walks described dipping glue by putting into d through the article prepared by c step, after stirring, and airtight dipping 4-12 hour;
F () adds tackifier, after stirring, add filler, solidifying agent stirs, for subsequent use.
2. the preparation method of improvement glass-reinforced plastic material according to claim 1, is characterized in that its length of described texturized glass yarn is 15 ~ 30mm.
3. the preparation method of improvement glass-reinforced plastic material according to claim 1 and 2, is characterized in that described texturized glass yarn is 15 ~ 20 parts, and tackifier are epoxide modified pair of maleinamide.
4. the preparation method of improvement glass-reinforced plastic material according to claim 1, is characterized in that described epoxide resin reactive diluent is phenyl glycidyl ether or cresylglycidylether.
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| CN201210044010.6A CN103289313B (en) | 2012-02-27 | 2012-02-27 | A kind of preparation method improveing glass-reinforced plastic material |
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| CN116948377B (en) * | 2023-07-11 | 2024-03-19 | 南京科工煤炭科学技术研究有限公司 | Preparation method of glass fiber reinforced plastic tray nut |
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