CN100346960C - Method for mfg. moulding plastic and its products by offcut of glassfibre cloth - Google Patents
Method for mfg. moulding plastic and its products by offcut of glassfibre cloth Download PDFInfo
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- CN100346960C CN100346960C CNB2005100507093A CN200510050709A CN100346960C CN 100346960 C CN100346960 C CN 100346960C CN B2005100507093 A CNB2005100507093 A CN B2005100507093A CN 200510050709 A CN200510050709 A CN 200510050709A CN 100346960 C CN100346960 C CN 100346960C
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Abstract
The present invention discloses a method for manufacturing moulding plastic and products thereof by leftover materials of glass fiber cloth. The present invention uses a kneading machine as shearing and dispersing equipment and thermoset liquid resin as adhesive for preparing moulding plastic and products thereof and as lubricants during kneading and dispersion at the same time. Under the squeezing, pulling, tearing, shearing and kneading action of the kneading machine, the leftover materials of glass fiber cloth are dispersed into cellosilk in the moulding plastic and a fiber bundle containing adhesive. Because the present invention is used for manufacturing the moulding plastic and the products thereof by using the leftover materials of the glass fiber cloth, the leftover materials of the glass fiber cloth can be effectively reused, a waste resource is effectively used, phenolic resin and coupling agents sticking to the leftover materials can be effectively utilized, and the pollution to environment is avoided. The present invention has the characteristics of convenient processing and low manufacturing cost.
Description
Technical field
The present invention relates to a kind of glass fabric leftover pieces and make the method for moulding compound and moulding article.
Background technology
Glass fabric is tailored or strikes out certain shape, as the reinforcing material of some composites or pressing at the heat of immersion thermosetting resin and through after the suitable drying.Above-mentioned thermosetting resin is mainly kinds such as uncured phenolic resins, epoxy resin, amino resins, furane resins, acrylic resin, to the glass fabric leftover pieces of handling through this resinoid, still there is not effective recoverying and utilizing method at present, can only handle as solid waste, not only waste resource but also polluted environment.For this glass fabric leftover pieces, two kinds of processing methods are generally arranged now: a kind of method is to adopt buried processing, but because the thermosetting resin on the leftover pieces is uncured resin, the leftover pieces resin content that has is up to 20～25%, contain higher free phenol, free aldehyde or other organic monomer, thereby can produce lasting pollution the groundwater quality in buried place.Another kind method is to adopt burning to handle, but the awkward combustion of thermosetting resin resin can produce a large amount of black smokes during burning.Therefore, the glass fabric leftover pieces that contain the heat of immersion thermosetting resin are a kind of unmanageable solid waste.The patent No. is that 01114921.3 Chinese invention patent discloses a kind of method of utilizing glass fabric leftover pieces processing short glass fiber, it adopts alkaline aqueous solution to soak the glass fabric leftover pieces, wash with clear water, to wash with cutter then and the leftover pieces of draining cut off and become cutting back, utilize at last getting rid of of blower fan beat and the leftover pieces of centrifugal action after with short cutting to be processed into length be 2～3 centimetres short glass fiber in bulk.The employed alkaline aqueous solution of this method is the NaOH or the potassium hydroxide aqueous solution of concentration 3～5%, and soak time is 3～5 hours.Mainly there is following some deficiency in this method: contain a certain amount of thermosetting resin on (1) leftover pieces, the leftover pieces resin content that has is up to 20～25%, the leftover pieces that have in addition contain silane coupler, and above-mentioned washing methods all is wasted resin and the coupling agent on the leftover pieces; (2) because the glass fibre alkali resistance is bad, soak in strong alkali solution, can make the intensity of glass fibre produce very big damage, this glass fibre that is damaged can only be done low-grade material; (3) washing can produce a large amount of organic wastewater, or even the unmanageable organic wastewater of high concentration COD; (4) profile of glass fabric leftover pieces is mixed and disorderly, and the hardness of fiber is higher, adopts cutter with its short very difficulty of cutting, and that is to say that the short cost of cutting can be too high.So this patented method is difficult to adopt in industrial practice.Some glass fabric leftover pieces does not contain impregnating resin, according to above-mentioned patent, can handle with alkaline aqueous solution, directly the glass fabric leftover pieces are cut off and become cutting back with cutter, beat and centrifugal action with getting rid of of blower fan again, the leftover pieces after short the cutting are processed into the short glass fibre of cutting.Though this method is feasible, it is too high that the processing cost of beating is cut and got rid of to weak point.It is carried out buried processing,, handle, wasted valuable glass fibre resource as solid waste though can not produce lasting pollution to the groundwater quality in buried place.
Summary of the invention
Technical problem to be solved by this invention is to propose a kind of glass fabric leftover pieces that utilize easy to process, low cost of manufacture and makes the method for moulding compound and moulding article, it can make the glass fabric leftover pieces obtain effective reuse, for containing a certain amount of uncured phenolic resins, silane coupler or other uncured thermoset resin on the leftover pieces, it is effectively utilized simultaneously.
For solving the problems of the technologies described above, the method that the present invention adopts the glass fabric leftover pieces to make moulding compound comprises the steps: 1, with kneader as shearing and dispersing apparatus, with the adhesive of liquid thermoset resin as the preparation moulding compound, lubricant when also disperseing simultaneously as kneading, draw kneader crowded, under tearing, shearing and the kneading action, the glass fabric leftover pieces are disperseed to become the filament that contains in glue fiber bundle or the moulding compound, and then form moulding compound.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, and described liquid thermoset resin is the one or more combination of the cashew nut shell oil resin that contains an amount of solvent, phenolic resins, epoxy resin, amino resins.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, and the viscosity during 25 ℃ of described liquid thermoset resins is 500～10,000mPas.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, and the viscosity during 25 ℃ of described liquid thermoset resins is 1,000～3,000mPa s.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, described cashew nut shell oil resin refers to cashew nut shell oil autohemagglutination resin, boron modification cashew nut shell oil autohemagglutination resin, organic-silicon-modified cashew nut shell oil autohemagglutination resin, acrylonitrile butadiene rubber modified cashew nut shell oil autohemagglutination resin, cashew nut shell oil formaldehyde condensation polymer resin, cashew nut shell oil acetaldehyde condensation resin or cashew nut shell oil furfural condensation resin, the technical indicator of described cashew nut shell oil resin is: solid content 75～80%, viscosity (25 ℃ time) 500～10,000mPas.In the manufacture process, in the cashew nut shell oil resin, need to add the hexamethylenetetramine that accounts for weight resin 5～8%, can when using resin, add, also can when the preparation resin, hexamethylenetetramine directly be added in the above-mentioned cashew nut shell oil resin.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, described phenolic resins refers to unmodified phenolic resins and phenol-formaldehyde resin modified, and described phenol-formaldehyde resin modified is urea modified phenolic resin, cyanurotriamide modified phenolic resins, the cyanurotriamide modified phenolic resins of cashew nut shell oil, furan modified phenolic resins or dimethylbenzene phenol-formaldehyde resin modified; Described unmodified and resin modified phenol resin can be the liquid resin of base catalysis, also can be acid catalyzed solid or powdered resin; The technical indicator of described base catalysis resin is: solid content 65～75%, viscosity (25 ℃ time) 500～10,000mPas, polymerization speed (150 ℃ time) 60～150 seconds; The technical indicator of described acid-catalyzed resin is: polymerization speed (150 ℃ time) 40～120 seconds, and free phenol≤2.0%, methenamine content 9～11% adopts solvent will resin moderatedly arrive viscosity (25 ℃ time) 500～10,000mPas.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, and the solvent that is adopted in the described liquid thermoset resin is the one or more combination in methyl alcohol, ethanol, ethyl acetate, gasoline, solvent naphtha, toluene, the dimethylbenzene.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, add a certain amount of flexibilizer in manufacture process, and described flexibilizer consumption is 5～50% of a described liquid thermoset weight resin.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, described flexibilizer is LNBR, liquid styrene butadiene rubber, liquid isoprene rubber or liquid polybutadiene rubber, need add corresponding vulcanizing agent, promoter and age resistor simultaneously when adding described flexibilizer.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, and described flexibilizer is polyvinyl butyral resin.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, described moulding compound adopts the direct method preparation, its raw material also comprises filler, flexibilizer and other fortifying fibre, be about to described liquid thermoset resin, glass fabric leftover pieces, filler, flexibilizer and other fortifying fibre and in kneader, carry out batch mixing and kneading simultaneously, directly prepare moulding compound.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, each raw material weight content of described moulding compound is respectively: liquid thermoset resin 10～40%, glass fabric leftover pieces 5～70%, other fortifying fibre 1～40%, filler 5～60%, flexibilizer 0～20%.Described leftover pieces are progressively added in the described kneader in batches, other raw materials in sequence is added in the described kneader.When described kneader was worked, material temperature was controlled in 60～100 ℃ of scopes in the kneader, and the vacuum in the kneader is 40～80KPa, and the time that kneader is mediated is 1～6 hour.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, adopt blade type high speed rotating disintegrator that described moulding compound is carried out dispersion treatment, and filament or fibre bundle length are controlled at certain length range.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, described moulding compound adopts the indirect method preparation, promptly earlier described liquid thermoset resin and glass fabric leftover pieces are mediated in kneader, preparation become 3～25mm long contain the glue fiber bundle, adopt blade type high speed rotating disintegrator to disperse to containing glue fiber Shu Jinhang, and will contain glue fiber Shu Changdu and be controlled at certain length, will contain the moulding compound that the glue fiber bundle is prepared into various uses again.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, and described each raw material weight content that contains the glue fiber bundle is respectively: liquid thermoset resin 10～30%, 70～90% of glass fabric leftover pieces.Described leftover pieces are progressively added in the described kneader in batches, the liquid thermoset resin is once added in the described kneader.When described kneader was worked, material temperature was controlled in 60～90 ℃ of scopes in the kneader, and the vacuum in the kneader is 20～60KPa, and the time that kneader is mediated is 0.5～3 hour.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, adopt blade type high speed rotating disintegrator to contain glue fiber Shu Jinhang dispersion treatment to described, and fibre bundle length is controlled at certain length range.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding compound, each raw material weight content of described moulding compound is respectively: powdered phenol-formaldehyde resin 7～25% contains glue fiber bundle 5～40%, other fortifying fibre 1～40%, filler 5～60%, powder rubber 0～20%.Described raw material is added in high speed mixer or the plough type batch mixer, and the dry method batch mixing through 3～20 minutes promptly becomes moulding compound.
Adopt the glass fabric leftover pieces to make the method for moulding article, it is the moulding compound that above-mentioned employing glass fabric leftover pieces are formed or contains the glue fiber bundle and make moulding article.
Above-mentioned employing glass fabric leftover pieces are made the method for moulding article, and described moulding compound is made moulding article through die press technology for forming or injection molding technique.The technological parameter of compression molding is: molding pressure 5～50MPa, 120～180 ℃ of press temperatures, molding time 30～90s/mm.Injection molding technological parameter is: injection pressure 80～200MPa, 160～190 ℃ of mold temperatures, molding time 20～40s/mm.
The present invention directly uses the glass fabric leftover pieces owing to adopted said method as raw material, have easy to process and characteristics low cost of manufacture.It not only can make the glass fabric leftover pieces become fortifying fibre in moulding compound and the moulding article, and the uncured resin that adheres on the leftover pieces can both effectively be utilized.In addition, all contain a certain amount of coupling agent in most of glass fabric leftover pieces, these coupling agents can both play a role effectively, improve the adhesion of fiber with resin.Thereby effectively utilized waste and old resource, avoided pollution to environment.The viscosity of liquid thermoset resin (25 ℃ time) is controlled at 500～10,000mPas, leftover pieces will have good dispersion effect.If viscosity (25 ℃ time) is controlled in 1,000～3,000mPas, leftover pieces will have better dispersion effect.Cashew nut shell oil resin, phenolic resins are used separately or the two is used in combination, can make molding product have better cost performance.Add flexibilizer in the manufacture process, can make the material of preparation have good toughness, perhaps make dispersed fiber have good pliability, in preparation process subsequently, be not damaged or less damage.
The specific embodiment
Below in conjunction with embodiment the present invention is described in further details.
Embodiment 1 direct method prepares brake friction material moulding compound and goods thereof.Its processing step comprises: the preparation of bonding agent and preparation, moulding compound preparation and friction material moulding.Used each proportion of raw materials such as following table:
| Composition | Weight content (%) | Composition | Weight content (%) |
| The BY120 liquid resin | 12 | 5184 liquid resins | 9 |
| Organic fiber | 6 | LNBR | 5 |
| Mineral wool | 12 | Barite | 8 |
| Sepiolite | 15 | Troilite powder | 8 |
| The glass fabric leftover pieces | 20 | Micro crystal graphite | 3.7 |
| Chromite powder (325 order) | 7 |
Wherein the BY120 liquid resin is a boron modification cashew nut shell oil autohemagglutination resin, and 5184 liquid resins are the cyanurotriamide modified liquid phenolic resin of cashew nut shell oil, and the glass fabric leftover pieces are the leftover pieces that contain impregnated phenolic resin.The technical indicator of BY120 resin is: solid content 75%, viscosity (25 ℃) 2,000mPas, methenamine content 5～6%; The technical indicator of 5184 resins is: solid content 70%, viscosity (25 ℃) 1,500mPas.Organic fiber can be Kevlar fiber, vinal, polyacrylonitrile fibre, polyester fiber, cellulose fibre.Except the glass fabric leftover pieces, in the disposable whole adding kneaders of above-mentioned raw material, in the kneader chuck, feed steam, start kneader, progressively add the glass fabric leftover pieces then.When temperature of charge in the kneader reaches 60 ℃ of left and right sides, stop to add steam, the waste heat of chuck can make the kneading built-in temperature slowly rise.When temperature reaches 75 ℃, start vavuum pump, make the interior vacuum of kneader at 40～80KPa, material was mediated 30～90 minutes under the condition of above-mentioned vacuum and 80～85 ℃ of temperature, promptly can discharging.With blade type high speed rotating disintegrator compound is disperseed, promptly become the shape moulding compound that looses.
Adopt above-mentioned moulding compound to prepare the technological parameter of brake friction material: 130～165 ℃ of mold temperatures, mold pressing 10～30MPa, 10～25 minutes dwell times in mould.The material hot treatment condition is as follows: directly be warmed up to 110 ℃ from room temperature, kept 1 hour, be warmed up to 120 ℃, kept 2 hours, from 130 ℃, per hour heat up 10 ℃, kept 6 hours for 180 ℃ in maximum temperature.The moulding compound of present embodiment is particularly suitable for preparing the drum brake friction material, and mould adopts the cartridge type progressive die, and the number of plies of cartridge type mould is 6～8 layers.
Embodiment 2 indirect methods prepare brake friction material moulding compound and pressing thereof.Be that 8: 2 glass fabric leftover pieces and BY120 resins contains glue short fiber bundle earlier with weight ratio.The glass fabric leftover pieces are the leftover pieces that contain impregnated phenolic resin, and the technical indicator of BY120 resin is: solid content 75%, viscosity (25 ℃ time) 2,000mPas, methenamine content 5～6%./ 4th to 1/5th of all resins and a total addition of leftover pieces added in the kneader, in the kneader chuck, feed steam, start kneader, will remain leftover pieces and progressively add.When temperature of charge in the kneader reaches 60 ℃ of left and right sides, stop to add steam, the waste heat of chuck can make the kneading built-in temperature slowly rise, when temperature reaches 75 ℃, start vavuum pump, make the interior vacuum of kneader at 20～60KPa, material was mediated 15～60 minutes under the condition of above-mentioned vacuum and 80～85 ℃ of temperature, promptly can discharging.With blade type high speed rotating disintegrator compound is disperseed, promptly become and contain glue short fiber bundle.
Adopt the above-mentioned glue short fiber bundle that contains to prepare brake friction material, each raw material and weight content thereof are as follows:
| Composition | Weight content (%) |
| Contain glue short fiber bundle 25 | 5160 resin-oatmeals 11 |
| Acrylonitrile-butadiene rubber powder 3 | Tyre talc 3 |
| Mineral wool 25 | Barite 4 |
| Friction powder 4 | Vermiculite 7 |
| Chromite (325 order) 5 | Troilite (325 order) 5 |
| Petroleum coke 4 | Micro crystal graphite 4 |
Wherein, 5160 resin-oatmeals are the cyanurotriamide modified phenolic resins of cashew nut shell oil.The raw material of above-mentioned prescription are all added high speed mixer, and batch mixing 5 minutes can be sent to compacting.The pressing process parameter is as follows: 130～165 ℃ of mold temperatures, mold pressing 10～30MPa, 10～25 minutes dwell times in mould.The material hot treatment condition is as follows: directly be warmed up to 110 ℃ from room temperature, per hour heat up 10 ℃, kept 6 hours down for 180 ℃ in maximum temperature.The moulding compound of present embodiment is particularly suitable for preparing the drum brake friction material, and mould adopts the cartridge type progressive die, and the number of plies of cartridge type mould is 6～8 layers.
Embodiment 3 direct methods prepare short fiber reinforced composite piston moulding compound and goods thereof.The prescription of short fiber reinforced composite piston moulding compound is as shown in the table:
| Composition | Weight content (%) | Composition | Weight content (%) |
| The BY150 resin | 10 | 5124 liquid resins | 18 |
| The glass fabric leftover pieces | 48 | Vinal | 6 |
| Carbon black | 3 | Micro crystal graphite | 5 |
| Calcium carbonate | 9 | Barite | 8.9 |
Wherein, the BY150 resin is acrylonitrile butadiene rubber modified cashew nut shell oil autohemagglutination resin, and 5124 liquid resins are the liquid phenolic formaldehyde resin, and the glass fabric leftover pieces are the leftover pieces that contain impregnated phenolic resin.The technical indicator of BY150 resin is: solid content 75%, viscosity (25 ℃) 3,000mPas, methenamine content 5～6%; The technical indicator of 5124 resins is: solid content 70%, viscosity (25 ℃) 1,200mPas.Except the glass fabric leftover pieces, above-mentioned raw material are all added in the kneader, in the kneader chuck, feed steam, start kneader, leftover pieces are progressively added.When temperature of charge in the kneader reaches 60 ℃ of left and right sides, stop to add steam, the waste heat of chuck can make the kneading built-in temperature slowly rise, when temperature reaches 75 ℃, start vavuum pump, make the interior vacuum of kneader at 40～80KPa, material was mediated 15～45 minutes under the condition of above-mentioned vacuum and 80～85 ℃ of temperature, glass fibre length is controlled at 5～12mm, and reaching requirement promptly can discharging, becomes BMC.
Adopt above-mentioned moulding compound to prepare the technological parameter of piston: 135～165 ℃ of mold temperatures, mold pressing 10～30MPa, dwell time 80s/mm in mould.The material hot treatment condition is as follows: directly be warmed up to 110 ℃ from room temperature, per hour heat up 10 ℃, kept 8 hours for 160 ℃ in maximum temperature.Above-mentioned moulding compound piston can be used as the piston of automobile brake oil cylinder, the piston of hydraulic system oil cylinder.
Embodiment 4 indirect methods prepare rubber tire moulding compound and goods thereof.With weight ratio earlier 8: 2 glass fabric leftover pieces and BY150 resins rubber alloy short fiber bundle.The glass fabric leftover pieces are the leftover pieces that contain impregnated phenolic resin, and the technical indicator of BY150 resin is: solid content 75%, viscosity (25 ℃) 3,000mPas, methenamine content 5～6%./ 4th to 1/5th of all resins and a total addition of leftover pieces added in the kneader, in the kneader chuck, feed steam, start kneader, will remain leftover pieces and progressively add.When temperature of charge in the kneader reaches 60 ℃ of left and right sides, stop to add steam, the waste heat of chuck can make the kneading built-in temperature slowly rise, when temperature reaches 75 ℃, start vavuum pump, make the interior vacuum of kneader at 20～60KPa, material was mediated 10～30 minutes under above-mentioned vacuum and 80～85 ℃ of temperature conditions, promptly can discharging.With the high speed rotating disintegrator compound is disperseed, promptly become and contain glue short fiber bundle.
Adopt and above-mentionedly contain glue short fiber bundle to prepare the raw material and the weight content of rubber tire moulding compound as follows:
| Raw material | Weight content (%) | Raw material | Weight content (%) |
| Contain glue short fiber bundle | 50 | 5120 resins | 10 |
| Blanc fixe | 18 | Tyre talc | 7 |
| Feldspar powder | 15 |
Wherein, 5120 powder resins are powdered phenol-formaldehyde resin.The raw material of above-mentioned prescription are all added high speed mixer, and batch mixing can be sent to compacting in 3～5 minutes.The pressing process parameter is as follows: 135～165 ℃ of mold temperatures, mold pressing 10～30MPa, dwell time 80s/mm in mould.The material hot treatment condition is as follows: directly be warmed up to 120 ℃ from room temperature, per hour heat up 10 ℃, kept 2 hours down for 150 ℃ in maximum temperature.
Embodiment 5 direct methods prepare the fiberglass pump housing and valve body.Raw materials used and weight content is as shown in the table:
| Composition | Weight content (%) | Composition | Weight content (%) |
| 5124 liquid resins | 38 | The glass fabric leftover pieces | 56 |
| Iron oxide red | 2 | Polyvinyl butyral resin | 4 |
5124 liquid resins are the liquid phenolic formaldehyde resin, and the technical indicator of 5124 resins is: solid content 70%, and viscosity (25 ℃) 1,200mPas, the glass fabric leftover pieces do not contain the resin of dipping.It is 50～60% liquid that polyvinyl butyral resin is prepared into solid content with industrial alcohol.Except leftover pieces, above-mentioned raw material are all added in the kneader, in the kneader chuck, feed steam, start kneader, leftover pieces are progressively added, leftover pieces added in 5～30 minutes.When temperature of charge in the kneader reaches 60 ℃ of left and right sides, stop to add steam, the waste heat of chuck can make the kneading built-in temperature slowly rise, when temperature reaches 75 ℃, start vavuum pump, make the interior vacuum of kneader at 40～80KPa, material was mediated 15～45 minutes under the condition of above-mentioned vacuum and 80～85 ℃ of temperature, promptly can discharging, promptly become the bulk molding compound.Can adopt tablet press machine that the bulk molding compound is prepared into the bar shaped sheet.
The hot pressing parameters of above-mentioned molding compound: 140～155 ℃ of mold temperatures, mold pressing 10～30MPa, dwell time 80s/mm in mould.The material hot treatment condition is as follows: directly be warmed up to 120 ℃ from room temperature, per hour heat up 10 ℃, kept 2 hours for 160 ℃ in maximum temperature.
Embodiment 6 direct methods prepare composite gear die plastics and goods thereof.Raw materials used and weight content is as shown in the table:
| Composition | Weight content (%) | Composition | Weight content (%) |
| The BY110 resin | 5 | 5124 liquid resins | 12 |
| 5020 powdered resins | 16 | Epoxy resin E51 | 5 |
| Polyvinyl butyral resin | 4 | The glass fabric leftover pieces | 50 |
| Calcium carbonate | 7 | Pigment | 1 |
Wherein, the BY110 resin is a cashew nut shell oil autohemagglutination resin, and 5124 liquid resins are the liquid phenolic formaldehyde resin, and 5020 resins are high reaction activity phenolic aldehyde formaldehyde resin, and the glass fabric leftover pieces do not contain the resin of dipping.The technical indicator of BY110 resin is: solid content 75%, viscosity (25 ℃) 2,000mPas, methenamine content 5～6%; The technical indicator of 5124 resins is: solid content 70%, viscosity (25 ℃) 1,200mPas; The technical indicator of 5020 resins is: polymerization speed (150 ℃) 40～50 seconds, and free phenol≤2.0%, methenamine content 9～11% adopts solvent with resin moderated viscosity (25 ℃) 2,000～3, the 000mPas of arriving.It is 50～60% liquid that polyvinyl butyral resin is prepared into solid content with industrial alcohol.Except leftover pieces, above-mentioned raw material are all added in the kneader, in the kneader chuck, feed steam, start kneader, leftover pieces are progressively added.When temperature of charge in the kneader reaches 60 ℃ of left and right sides, stop to add steam, the waste heat of chuck can make the kneading built-in temperature slowly rise, when temperature reaches 75 ℃, start vavuum pump, make the interior vacuum of kneader at 40～80KPa, material was mediated 30～90 minutes under the condition of above-mentioned vacuum and 80～85 ℃ of temperature, glass fibre length is controlled at 2～3mm, and reaching requirement promptly can discharging, becomes the powder or granule moulding compound.
Adopt injection moulding above-mentioned moulding compound to be prepared into the technological parameter of composite gear: injection pressure 120MPa, 170～175 ℃ of mold temperatures, molding time 30s/mm.The material hot treatment condition is as follows: directly be warmed up to 110 ℃ from room temperature, per hour heat up 10 ℃, kept 8 hours for 160 ℃ in maximum temperature.
The alleged moulding compound of the present invention refers to sheet, the bulk that is suitable for compression molding and injection mo(u)lding, loose shape or powdery moulding compound, and moulding article refers to brake friction material, short fiber strengthens clutch friction material, fiberglass pump and valve, GRP pipe and pipe fitting, fiberglass blast pipe, short fiber reinforced composite piston, short fiber reinforced composite castor, short fiber reinforced composite gear, short fiber reinforced composite belt pulley.
Claims (21)
1, adopt the glass fabric leftover pieces to make the method for moulding compound, it is characterized in that, it comprises the steps: with kneader as shearing and dispersing apparatus, with the adhesive of liquid thermoset resin as the preparation moulding compound, lubricant when also disperseing simultaneously as kneading, draw kneader crowded, under tearing, shearing and the kneading action, the glass fabric leftover pieces disperseed to become the filament in the moulding compound or contain the glue fiber bundle, and then form moulding compound.
2, employing glass fabric leftover pieces as claimed in claim 1 are made the method for moulding compound, it is characterized in that, employing blade type high speed rotating disintegrator is to described moulding compound or contain glue fiber Shu Jinhang dispersion treatment, and the length of fiber is controlled at certain scope.
3, employing glass fabric leftover pieces as claimed in claim 1 are made the method for moulding compound, it is characterized in that described liquid thermoset resin is the one or more combination of the cashew nut shell oil resin that contains an amount of solvent, phenolic resins, epoxy resin, amino resins.
4, make the method for moulding compounds as claim 1 or 3 described employing glass fabric leftover pieces, it is characterized in that, the viscosity during 25 ℃ of described liquid thermoset resins is 500～10,000mPas.
5, make the method for moulding compounds as claim 1 or 3 described employing glass fabric leftover pieces, it is characterized in that, the viscosity during 25 ℃ of described liquid thermoset resins is 1,000～3,000mPas.
6, employing glass fabric leftover pieces as claimed in claim 3 are made the method for moulding compound, it is characterized in that, described cashew nut shell oil resin refers to cashew nut shell oil autohemagglutination resin, boron modification cashew nut shell oil autohemagglutination resin, organic-silicon-modified cashew nut shell oil autohemagglutination resin, acrylonitrile butadiene rubber modified cashew nut shell oil autohemagglutination resin, cashew nut shell oil formaldehyde condensation polymer resin, cashew nut shell oil acetaldehyde condensation resin or cashew nut shell oil furfural condensation resin, the technical indicator of described cashew nut shell oil resin is: solid content 75～80%, viscosity 500～10 in the time of 25 ℃, 000mPas; In the manufacture process, in the cashew nut shell oil resin, need to add the hexamethylenetetramine that accounts for its weight 5～8%, can when using resin, add, also can when the preparation resin, hexamethylenetetramine directly be added in the above-mentioned cashew nut shell oil resin.
7, employing glass fabric leftover pieces as claimed in claim 3 are made the method for moulding compound, it is characterized in that, described phenolic resins refers to unmodified phenolic resins and phenol-formaldehyde resin modified, and described phenol-formaldehyde resin modified is urea modified phenolic resin, cyanurotriamide modified phenolic resins, the cyanurotriamide modified phenolic resins of cashew nut shell oil, furan modified phenolic resins or dimethylbenzene phenol-formaldehyde resin modified; Described unmodified resin and modified resin can be the liquid resins of base catalysis, also can be acid catalyzed solid or powdered resin; The technical indicator of described base catalysis resin is: solid content 65～75%, and viscosity 500～10 in the time of 25 ℃, 000mPas, polymerization speed is 60～150 seconds in the time of 150 ℃; The technical indicator of described acid-catalyzed resin is: polymerization speed is 40～120 seconds in the time of 150 ℃, free phenol≤2.0%, methenamine content 9～11%, adopt solvent with resin moderated during to 25 ℃ viscosity be 500～10,000mPas.
8, employing glass fabric leftover pieces as claimed in claim 3 are made the method for moulding compound, it is characterized in that the solvent that is adopted in the described liquid thermoset resin is the one or more combination in methyl alcohol, ethanol, ethyl acetate, gasoline, solvent naphtha, toluene, the dimethylbenzene.
As the method for claim 1 or 3 described employing glass fabric leftover pieces manufacturing moulding compounds, it is characterized in that 9, add a certain amount of flexibilizer in manufacture process, described flexibilizer consumption is 5～50% of a described liquid thermoset weight resin.
10, employing glass fabric leftover pieces as claimed in claim 9 are made the method for moulding compound, it is characterized in that, described flexibilizer is LNBR, liquid styrene butadiene rubber, liquid isoprene rubber or liquid polybutadiene rubber, need add corresponding vulcanizing agent, promoter and age resistor simultaneously when adding described flexibilizer.
11, employing glass fabric leftover pieces as claimed in claim 9 are made the method for moulding compound, it is characterized in that described flexibilizer is polyvinyl butyral resin.
12, make the method for moulding compounds as claim 1 or 3 described employing glass fabric leftover pieces, it is characterized in that, described moulding compound adopts the direct method preparation, its raw material also comprises filler, flexibilizer and other fortifying fibre, be about to described liquid thermoset resin, glass fabric leftover pieces, filler, flexibilizer and other fortifying fibre and in kneader, carry out batch mixing and kneading simultaneously, directly prepare moulding compound.
13, employing glass fabric leftover pieces as claimed in claim 12 are made the method for moulding compound, it is characterized in that, each raw material weight content of described moulding compound is respectively: liquid thermoset resin 10～40%, glass fabric leftover pieces 5～70%, other fortifying fibre 1～40%, filler 5～60%, flexibilizer 0～20%; Described leftover pieces are progressively added in the described kneader in batches, other raw materials in sequence is added in the described kneader; When described kneader was worked, material temperature was controlled in 60～100 ℃ of scopes in the kneader, and the vacuum in the kneader is 40～80KPa, and the time that kneader is mediated is 1～6 hour.
14, make the method for moulding compounds as claim 1 or 3 described employing glass fabric leftover pieces, it is characterized in that, described moulding compound adopts the indirect method preparation, promptly earlier described liquid thermoset resin and glass fabric leftover pieces are mediated in kneader, preparation become 3～25mm long contain the glue fiber bundle, will contain the moulding compound that the glue fiber bundle is prepared into various uses again.
15, employing glass fabric leftover pieces as claimed in claim 14 are made the method for moulding compound, it is characterized in that described each raw material weight content that contains the glue fiber bundle is respectively: liquid thermoset resin 10～30%, glass fabric leftover pieces 70～90%; Described leftover pieces are progressively added in the described kneader in batches, the liquid thermoset resin is once added in the described kneader; When described kneader was worked, material temperature was controlled in 60～90 ℃ of scopes in the kneader, and the vacuum in the kneader is 20～60KPa, and the time that kneader is mediated is 0.5～3 hour.
16, employing glass fabric leftover pieces as claimed in claim 14 are made the method for moulding compound, each raw material weight content of described moulding compound is respectively: powdered phenol-formaldehyde resin 7～25%, contain glue fiber bundle 5～40%, other fortifying fibre 1～40%, filler 5～60%, powder rubber 0～20%; Described raw material is added in high speed mixer or the plough type batch mixer, through 3～20 minutes batch mixing.
As the method for claim 1 or 3 described employing glass fabric leftover pieces manufacturing moulding compounds, it is characterized in that 17, described moulding compound refers to sheet, bulk, diffusing shape or the powdery moulding compound that is suitable for compression molding and injection mo(u)lding.
18, employing glass fabric leftover pieces as claimed in claim 1 are made the method for moulding compound, it is characterized in that, described glass fabric leftover pieces refer to leftover pieces that contain uncured thermoset resin and the leftover pieces that do not contain resin, and described uncured thermoset resin refers to uncured phenolic resins, epoxy resin, amino resins, furane resins or acrylic resin.
19, adopt the glass fabric leftover pieces to make the method for moulding article, it is characterized in that, it is the moulding compound that will form in above-mentioned every claim or contains the glue fiber bundle and make moulding article.
20, employing glass fabric leftover pieces as claimed in claim 19 are made the method for moulding article, it is characterized in that, described moulding compound is made moulding article through die press technology for forming or injection molding technique, and the technological parameter of compression molding is: molding pressure 5～50MPa, 120～180 ℃ of press temperatures, molding time 30～90s/mm; Injection molding technological parameter is: injection pressure 80～200MPa, 160～190 ℃ of mold temperatures, molding time 20～40s/mm.
21, make the method for moulding articles as claim 19 or 20 described employing glass fabric leftover pieces, it is characterized in that described moulding article refers to brake friction material, short fiber strengthens clutch friction material, fiberglass pump and valve, GRP pipe and pipe fitting, fiberglass blast pipe, short fiber reinforced composite piston, short fiber reinforced composite castor, short fiber reinforced composite gear or short fiber reinforced composite belt pulley.
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| CNB2005100507093A CN100346960C (en) | 2005-07-14 | 2005-07-14 | Method for mfg. moulding plastic and its products by offcut of glassfibre cloth |
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| CN1911600A (en) * | 2006-09-01 | 2007-02-14 | 东莞市天盛玻璃纤维有限公司 | Method for producing glass fiber net cover using glass fiber net sheet waste material and net cover |
| CN102922833B (en) * | 2011-08-12 | 2015-06-17 | 明安国际企业股份有限公司 | Fiber reinforced shell manufacturing method |
| CN103797171B (en) * | 2011-12-20 | 2016-02-17 | 日本电气硝子株式会社 | The manufacture method of fiberglas chopped strand mat and the manufacture method of motor vehicle molded ceiling material |
| CN102585768B (en) * | 2012-01-09 | 2014-05-14 | 丁庆军 | Braided fiber-based friction material and preparation method thereof |
| CN103351574B (en) * | 2013-06-03 | 2017-04-26 | 海盐华强树脂有限公司 | Method for preparing short fiber reinforced friction material through adopting long fibers |
| CN103740062B (en) * | 2013-12-19 | 2015-11-18 | 国家电网公司 | Electric power cabinet special glass Steel Facing material |
| CN103939446A (en) * | 2014-05-15 | 2014-07-23 | 湖北金力工程复合材料有限公司 | Toughening FRP spiral connecting piece and manufacturing method thereof |
| CN106928456B (en) * | 2017-02-17 | 2019-12-10 | 上海长风石棉五金厂有限公司 | self-curing phenol-free cashew nut shell oil resin and preparation method thereof |
| CN107355640A (en) * | 2017-07-19 | 2017-11-17 | 四川迈科隆真空新材料有限公司 | The method and vacuum heat-insulating plate of core material of vacuum heat insulation plate are prepared using glass fibre aggregation leftover pieces |
| CN107325481A (en) * | 2017-08-16 | 2017-11-07 | 常州信息职业技术学院 | A kind of phenoplasts inspection shaft well lid and preparation method thereof |
| CN109624357A (en) * | 2018-12-10 | 2019-04-16 | 闫凯 | A kind of compound glass fibre mesh matrix and preparation method thereof |
| CN110048036B (en) * | 2019-04-19 | 2024-05-17 | 桑顿新能源科技有限公司 | Reinforcing rib sheet and preparation method thereof, battery cell and preparation method thereof, and soft package battery |
| CN116005359A (en) * | 2022-12-30 | 2023-04-25 | 安徽弘徽科技有限公司 | Low-density high-elasticity glass fiber felt and preparation method thereof |
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