CN102952327B - A kind of resin composite materials, preparation method and application thereof - Google Patents
A kind of resin composite materials, preparation method and application thereof Download PDFInfo
- Publication number
- CN102952327B CN102952327B CN201110244870.XA CN201110244870A CN102952327B CN 102952327 B CN102952327 B CN 102952327B CN 201110244870 A CN201110244870 A CN 201110244870A CN 102952327 B CN102952327 B CN 102952327B
- Authority
- CN
- China
- Prior art keywords
- composite materials
- resin composite
- natural fiber
- prepreg tape
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Reinforced Plastic Materials (AREA)
Abstract
The invention belongs to technical field of polymer materials, disclose a kind of resin composite materials, preparation method and application thereof.Resin composite materials of the present invention is made up of the component comprising following weight part: thermoplastic resin 70 ~ 100 parts, 0 ~ 5 part, oxidation inhibitor, fire retardant 0 ~ 5 part, expanding material 0 ~ 10 part, weather resisting agent 0 ~ 3 part, releasing agent 0 ~ 5 part, auxiliary agent 0 ~ 2 part.The preparation method of this resin composite materials comprises the following steps: the raw material of said ratio, in moderate-speed mixers, mix 3 ~ 7 minutes, fully joins forcing machine after mixing and extrudes pelletizing, obtain resin composite materials.The invention discloses the method for prepreg tape natural fiber/resin composite materials being prepared by above-mentioned resin composite materials, comprise the following steps: natural fiber is made cord fabrics, drawn, compression, heat drying dewater, at film forcing machine place, resin composite materials carries out preimpregnation, then impregnation cooling rolling, prepare the prepreg tape of natural fiber/resin composite materials, this prepreg tape porosity is low, mechanical strength is high.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of resin composite materials, preparation method and application thereof.
Background technology
Continuous fiber reinforced thermoplastic resin composite material presoaked belt has excellent mechanical property, as high tensile strength, flexural strength/modulus, high/low-temperature impact intensity etc., and there is the features such as relatively low density and recoverable, therefore development in recent years is rapid, and corresponding technology of preparing also achieves great breakthrough.In Chinese patent CN200610070280, Fang Kun adopts the method for hybrid yams to prepare the pellet of continuous glass fiber reinforced polypropylene PP, and the compound containing glass fibre is mixed yarn and mixes with PP resin and processing aid, heating and melting is blended, through forcing machine extruding pelletization.The product produced in this way of profit fully can regulate the content of fortifying fibre, but this method extruding pelletization, formation be short pelletizing material, can not be formed and strengthen prepreg tape continuously.Continuous print glass fibre is adopted in Chinese patent CN101474868A, organic fibres etc. are drawn from creel, the unidirectional fibre yarn of certain amplitude is made it sprawl into have through tension adjustment, contact with the extrusion die of two different positionss, the resin of melting floods then through three roller immersion systems, through cooling roller writing that surpasses all the others winding forming to continuous fibre.This method is utilized to prepare glass fibre, the thermoplastic resin prepreg tape such as Kafra fiber, but be not suitable for natural fiber, this is because the limited length of natural fiber, single fiber can not be formed continuous, have to pass through twisting and could form continuous print natural fiber line or rope, and after twisting, the dipping effect of resin is poor, occurs more dry yarn.Chen great Kai etc. prepare natural fiber reinforced composite, adopt atural staple fibre or natural macrofiber (comprising ramee, linen fiber, jute fibre etc.) to carry out melt blending with PLA to extrude, natural fiber/PLA matrix material (Chen great Kai, Li Jing, Ren Jie that preparation can be degradable; The progress of natural fiber enhanced polylactic acid acid matrix material, plastics, 2010 (6): 108).This kind of method prepares natural fiber reinforced composite, and obviously, its reinforced effects is not obvious, and with PLA blending extrusion process, natural fiber causes the viscosity of material to increase in natural fiber fracture, the wearing and tearing of aggravation machine.In Chinese patent CN200610037894.7, Dong Weiwei, by natural fiber and PLA and oxidation inhibitor, nucleator and mix lubricant, through melt extruding granulation, obtains product.The Fiber Aspect Ratio of natural fiber strongthener prepared by this method is less, and its reinforced effects is limited; And have comparatively galling to the screw rod of forcing machine.
Summary of the invention
For problems of the prior art, the object of this invention is to provide a kind of resin composite materials, this resin composite materials can long storage time.
Another object of the present invention is to provide a kind of preparation method of above-mentioned resin composite materials.
3rd object of the present invention is to provide a kind of method above-mentioned resin composite materials being prepared into the prepreg tape of natural fiber/resin composite materials.
Technical scheme of the present invention is as follows:
The invention provides a kind of resin composite materials, this resin composite materials is made up of the component comprising following weight part:
Thermoplastic resin 70 ~ 100 parts,
0 ~ 5 part, oxidation inhibitor,
Fire retardant 0 ~ 5 part,
Expanding material 0 ~ 10 part,
Weather resisting agent 0 ~ 3 part,
Releasing agent 0 ~ 5 part,
Auxiliary agent 0 ~ 2 part.
Described thermoplastic resin melting index is 10 ~ 100g/10min, is selected from one or more in polyolefine, thermoplastic polyester, polymeric amide or resins for universal use; Wherein: polyolefine be selected from homo-polypropylene, Co-polypropylene or polyethylene further one or more; Thermoplastic polyester be selected from polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate or poly(lactic acid) further one or more; Polymeric amide be selected from nylon 6, nylon66 fiber, nylon 12, nylon 1212 or nylon 612 further one or more; Resins for universal use is selected from polyvinyl chloride (PVC) and/or polycarbonate (PC) further.
Described oxidation inhibitor is selected from four { β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythritol ester, (3,5-di-tert-butyl-hydroxy phenyl) one or more in propionic acid octadecyl, Tyox B or phosphorous acid benzene two isodecyl ester, the object of oxidation inhibitor be in order to be reduced in prepare matrix material process in the degraded of thermoplastic resin and/or oxidation.
Described fire retardant be selected from magnesium hydroxide, aluminium hydroxide, ammonium polyphosphate, eight bromo ether, triphenylphosphate, hexabromocyclododecane, zinc borate, encapsulated red phosphorus, TDE, two (2, the 3-dibromopropyl) ether of tetrabromo-bisphenol or hexabromocyclododecane one or more; The effect adding fire retardant makes flammable polymkeric substance be difficult to burning.
Described expanding material be selected from polycaprolactone, polyhydroxyalkanoate or polyoxyethylene glycol one or more, the effect adding expanding material is the consistency improved between natural fiber and poly(lactic acid).
Described weather resisting agent is selected from two (2,2,6,6-tetramethyl--4-piperidyl) sebate, 2,4-dihydroxyl-benzophenone, one or more in 2-(2 '-hydroxyl-5 '-) benzotriazole or 2-(2 '-hydroxyl-3 '-the tertiary butyl-5 ' aminomethyl phenyl)-5-chlorinated benzotriazole.The object adding weather resisting agent suppresses or shielded from light redox or photoaging.
Described releasing agent be selected from silicone oil, polyoxyethylene glycol or low molecular weight polyethylene one or more, the effect of releasing agent makes in the process of natural fiber and resin impregnation, and resin can not cover on pressure roller.
Described auxiliary agent be selected from the different monooctyl ester of 3-thiohydracrylic acid, 4-phenylbenzene-4-methyl-1-pentene or 4,4-dimethyl-2,4-phenylbenzene-1-butylene one or more.
Present invention also offers a kind of preparation method of above-mentioned resin composite materials, the method comprises the following steps:
By 70 ~ 100 parts of thermoplastic resins, 0 ~ 5 part of oxidation inhibitor, 0 ~ 5 part of fire retardant, 0 ~ 10 part of expanding material, 0 ~ 3 part of weather resisting agent, 0 ~ 5 part of releasing agent and 0 ~ 2 part of auxiliary agent, 3 ~ 7 minutes are mixed in moderate-speed mixers, join forcing machine after abundant mixing and extrude pelletizing, obtain resin composite materials.
Described forcing machine is twin screw extruder, and screw speed is 10 ~ 250r/min, and extrusion temperature is 150 ~ 190 DEG C.
Present invention also offers a kind of method prepreg tape of natural fiber/resin composite materials being prepared by above-mentioned resin composite materials, the method comprises the following steps:
Natural fiber is made cord fabrics, and drawn, compression, heat drying dewater, and at film forcing machine place, resin composite materials carries out preimpregnation, and then impregnation cooling rolling, prepares the prepreg tape of natural fiber/resin composite materials.
The yarn number of axle needed for described cord fabrics is 1 ~ 500 volume, preferably 50 ~ 200 volumes, is more preferably 80 ~ 150 volumes.
Described cord fabrics thickness is 0.1 ~ 2mm, and its warp is the thermoplastic fibres such as polypropylene fibre, nylon fiber or acid fiber by polylactic.
Described draft temperature is room temperature, and draw speed is rolling speed.
Described compression temperature is room temperature, and pressure is 4 ~ 10MPa.
Described heat drying temperature is 101 ~ 110 DEG C, after drying moisture content < 1%.
Described preimpregnation temperature is 190 ~ 220 DEG C, and resin extruded speed is 1 ~ 5kg/min, floods width with cord fabrics with wide or wider than cord fabrics 10 ~ 100mm.
Described is cooled to cool to room temperature.
The speed of described rolling is 1 ~ 20m/min.
Described natural fiber is selected from hemp fibre, cotton fibre, bamboo fibers, ramee, flax fiber, jute fibre or silky fibre and/or their hybrid yams, natural fiber content of cellulose >=60%.
One or more process in plasma body, alkaline purification or coupling agent treatment of described natural fiber, carry out untwisting again after twisting, become the loose form expanded.
Prepreg tape of the present invention can be made into the product of the shaping complexity such as phone housing or computer casing as required.
Compared with the existing technology, tool has the following advantages and beneficial effect in the present invention:
1, in natural fiber/thermoplastic resin composite material presoaked belt of the present invention, wild phase natural fiber exists with external phase, because be adopt the form of cord fabrics to strengthen thermoplastic resin, the wild phase in prepreg tape is unidirectional, and during making product, mechanical property can design.
2, the matrix material longitudinal length prepared of the present invention is adjustable, and wide cut also can adjust, can meet the later stage produce in length requirement.
3, the present invention prepare matrix material can long storage time, and natural fiber is completely by resin impregnation, does not have exposed, and especially natural fiber is dry can to keep material, and natural fiber can not moldy metamorphism.
4, method of the present invention, can adjust the content of natural fiber, prepares the fortifying fibre prepreg tape of different natural fibres content.
5, the present invention adopts the mode of cord fabrics, can ensure that natural fiber does not disconnect when being subject to drawing, and strengthens natural fiber as external phase.
6, the present invention adopts cord fabrics to strengthen resin, can limit the fabric width of strongthener, will because of wide or narrow, and the position of natural fiber be changed.
7, method of the present invention can ensure resin thorough impregnation natural fiber, resin thorough impregnation natural fiber, can ensure that, in the process of preparing product, the defect of product is few, and mechanical strength is high.
8, to prepare the porosity of prepreg tape lower in the present invention, lower than 1%, time porosity is low, can ensure the stability of product performance.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of the prepreg tape of natural fiber/resin composite materials.
Wherein 1 is creel; 2 is yarn axle; 3 is natural fiber; 4 is cord fabrics loom; 5 is tenslator; 6,7 is natural fiber pressure roller; 8 is heat drying system; 9 is tenslator; 10 is impregnation refrigerating unit; 11 is film forcing machine; 12 is wrap-up.
Embodiment
Below in conjunction with accompanying drawing illustrated embodiment, the present invention is further illustrated.
In the present invention, unless otherwise stated, all percentage ratio, part and ratio etc. are all based on weight.
The invention describes suitable method and material, but be similar to or be equivalent to materials and methods of the present invention for implementing or inspection the present invention.
When enumerating numerical range in the present invention, unless otherwise noted, such scope is intended to comprise all integers and number in its end points and scope.
Term in the present invention " comprise " " containing " " have " or its arbitrarily other changes be all intended to contain and non-exclusive comprise scope.Such as, comprise the Material selec-tion of a series of mechanical means, listed by the particular location of device etc. are not only confined to herein.
Raw material herein, method and embodiment are only schematic, unless otherwise indicated, otherwise do not form restriction.
In the present invention, the natural fiber pressure roller shown in Fig. 1 comprises 6,7 and in order to improve product performance, and the pressure roller on continuing to add, namely pressure roller not only comprises two couple shown in figure, can have three to, four to, five to, as example.
Thermoplastic resin melting index used in the present invention is 10 ~ 100g/10min.
The natural fiber used in following examples is through alkaline purification, and its treatment process is as follows, is soaked in NaOH solution under normal temperature by natural fiber, concentration is 5% (massfraction), after 2h, is taken out by natural fiber, clear water washs 3 times, dry, takes out at 80 DEG C of temperature.
Embodiment 1
Get polylactic resin 87 parts, 2 part of four { β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythritol ester, 5 parts of polycaprolactones, 2 parts two (2,2,6,6-tetramethyl--4-piperidyl) sebate, 2 parts of polyoxyethylene glycol, 2 parts of TDE mix 4 minutes in moderate-speed mixers, join after mixing in twin screw extruder, extruding pelletization, screw speed is 75r/min, and extruder head temperature is 190 DEG C.
Fig. 1 is the preparation flow figure of the prepreg tape of natural fiber/resin composite materials.Natural fiber used herein refers to has comparatively long fiber length, after twisting, can present continuous regime, a branch of twisted fibers nominal count 0.2 ~ 1; Natural fiber content of cellulose >=60%; Carry out untwisting again after natural fiber twisting, become the loose form expanded.To learn from else's experience in the present embodiment jute fibre line 100 volume of alkaline purification, be placed on creel 1, the product commercially produced due to natural fiber passes through twisting, become continuous regime to exist, natural fiber is after twisting, resin is not easy dipping, if the product of excellent, and must to the natural fiber untwisting after twisting.Yarn axle on creel is herein all through untwisting; Natural fiber 3 on yarn axle 2 (jute fibre on yarn axle is now through untwisting), it is jute fibre herein, jute fibre is drawn to cord fabrics loom 4, cord fabrics loom energy production wide cut is the cord fabrics of 0.8 ~ 4.5m, its warp is acid fiber by polylactic, is made into the cord fabrics that fabric width is 1m; Tension force through tenslator 5 launches, and makes the tension force of natural fiber basically identical, impels it evenly to arrange; At natural fiber pressure roller 6,7 places are through pressure roller roll-in, pressure is 5MPa, after roll-in, the thickness of fiber is 0.8mm, the material of natural fiber pressure roller can be rubber, plastics etc. (this type of material, when being subject to larger pressure, deformation can occur, and natural fiber can not rupture because of extruding herein).In natural fiber cord fabrics, natural fiber is in bond, and resin is not easy to soak into fiber.The effect of pressure roller is herein exactly that the thicker natural fiber of script is pressed into very thin one deck, and the rotational line speed of pressure roller is consistent with the rotational line speed of wrap-up, through heat drying system 8, the moisture regain of natural fiber is about 12%, moisture a large amount of in natural fiber will affect the properties of material, such as excess moisture, carrying out in the process of flooding with resin, natural fiber discharges a large amount of water vapour, these water vapour can cause the porosity of prepreg tape to increase, a large amount of steam can reduce the weathering resistance of material, natural fiber can addle under the environment of a large amount of water vapour, affect the working life of material, now temperature is 103 DEG C, the moisture content of jute fibre is 0.9%, the traffic direction of jute fibre is changed through tenslator 9, enter film forcing machine 11 place's preimpregnation, now the temperature of film forcing machine is 205 DEG C, resin extruded speed is 2kg/min, dipping width and cord fabrics with wide jute fibre herein through preimpregnation, then impregnation refrigerating unit 10 is arrived, 3 rollers are herein all steelwork, the rotational line speed of impregnation refrigerating unit 10 is the same with wrap-up rotational line speed, through being cooled to room temperature roll-in, rolling is carried out at wrap-up 12, its rotational line speed is 5m/min, prepare jute/poly(lactic acid) prepreg tape, its the performance test results is in table 1.
Embodiment 2
Get homo-polypropylene resin 72 parts, 3 parts of Tyox Bs, 10 parts of polycaprolactones, 3 parts two (2,2,6,6-tetramethyl--4-piperidyl) sebate, 3 parts of low molecular weight polyethylenes, 5 parts of tetrabromo-bisphenols two (2,3-dibromopropyl) ether, 1 part of different monooctyl ester of 3-thiohydracrylic acid, mixes 4 minutes in moderate-speed mixers, join after mixing in twin screw extruder, extruding pelletization, screw speed is 75r/min, and extruder head temperature is 190 DEG C.
The natural fiber that the present embodiment uses refers to and has comparatively long fiber length, after the twisting, can present continuous regime, a branch of twisted fibers nominal count 0.2 ~ 1; Natural fiber content of cellulose >=60%; Carry out untwisting again after natural fiber twisting, become the loose form expanded.By jute fibre line 100 volume through alkaline purification, be drawn to cord fabrics loom, its warp is polypropylene fibre, is made into the cord fabrics that fabric width is 1m; Tension force through tenslator launches, at room temperature compress through natural fiber pressure roller pressure roller, pressure is 4MPa, the cord fabrics that thickness is 0.7mm is formed after roll-in, through heat drying system, Heating temperature is 103 DEG C, and drying dewaters, after drying moisture content 0.9%, add the place's preimpregnation of resin composite materials film forcing machine, temperature is 210 DEG C, and resin extruded speed is 2kg/min, dipping width 10mm wider than cord fabrics, then cool to room temperature, rolling, the speed of rolling is 10m/min, obtains jute/PP prepreg tape.The performance test results is in table 1.
Embodiment 3
Get homo-polypropylene resin 95 parts, 3 parts of two (2,3-dibromopropyl) ethers of tetrabromo-bisphenol, 2 parts of low molecular weight polyethylenes.In moderate-speed mixers, mix 4 minutes, join after mixing in twin screw extruder, extruding pelletization, screw speed is 75r/min, and extruder head temperature is 190 DEG C.
The natural fiber that the present embodiment uses refers to and has comparatively long fiber length, after the twisting, can present continuous regime, a branch of twisted fibers nominal count 0.2 ~ 1; Natural fiber content of cellulose >=60%; Carry out untwisting again after natural fiber twisting, become the loose form expanded.By jute fibre line 100 volume through alkaline purification, be drawn to cord fabrics loom, its warp is polypropylene fibre, is made into the cord fabrics that fabric width is 1m; Tension force through tenslator launches, at room temperature compress through natural fiber pressure roller pressure roller, pressure is 7MPa, the cord fabrics that thickness is 0.8mm is formed after roll-in, through heat drying system, Heating temperature is 103 DEG C, and drying dewaters, after drying moisture content 0.9%, add the place's preimpregnation of resin composite materials film forcing machine, temperature is 210 DEG C, and resin extruded speed is 2kg/min, and dipping width and cord fabrics are with wide, then cool to room temperature, rolling, the speed of rolling is 10m/min, obtains jute/PP prepreg tape.The performance test results is in table 1.
Embodiment 4
The natural fiber that the present embodiment uses refers to and has comparatively long fiber length, after the twisting, can present continuous regime, a branch of twisted fibers nominal count 0.2 ~ 1; Natural fiber content of cellulose >=60%; Carry out untwisting again after natural fiber twisting, become the loose form expanded.Get homopolymerisation polyethylene (PP) resin 100 parts and directly put into film forcing machine, by jute fibre line 100 volume through alkaline purification, be drawn to cord fabrics loom, its warp is polypropylene fibre, is made into the cord fabrics that fabric width is 1m; Tension force through tenslator launches, at room temperature compress through natural fiber pressure roller pressure roller, pressure is 8MPa, the cord fabrics that thickness is 0.6mm is formed after roll-in, through heat drying system, Heating temperature is 103 DEG C, and drying dewaters, after drying moisture content 0.9%, add the place's preimpregnation of resin composite materials film forcing machine, temperature is 210 DEG C, and resin extruded speed is 2kg/min, and dipping width and cord fabrics are with wide, then cool to room temperature, rolling, the speed of rolling is 10m/min, obtains jute/PP prepreg tape.The performance test results is in table 1.
Embodiment 5
Get homo-polypropylene resin 70 parts, 5 part of four { β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythritol ester, 10 parts of polycaprolactones, 3 parts two (2,2,6,6-tetramethyl--4-piperidyl) sebate, 5 parts of low molecular weight polyethylenes, 5 parts of two (2,3-dibromopropyl) ethers of tetrabromo-bisphenol, 2 parts of different monooctyl esters of 3-thiohydracrylic acid, in moderate-speed mixers, mix 4 minutes, join after mixing in twin screw extruder, extruding pelletization, screw speed is 75r/min, and extruder head temperature is 190 DEG C.
The natural fiber that the present embodiment uses refers to and has comparatively long fiber length, after the twisting, can present continuous regime, a branch of twisted fibers nominal count 0.2 ~ 1; Natural fiber content of cellulose >=60%; Carry out untwisting again after natural fiber twisting, become the loose form expanded.By jute fibre line 120 volume through alkaline purification, be drawn to cord fabrics loom, its warp is polypropylene fibre, is made into the cord fabrics that fabric width is 1.2m; Tension force through tenslator launches, at room temperature compress through natural fiber pressure roller pressure roller, pressure is 10MPa, the cord fabrics that thickness is 0.5mm is formed after roll-in, through heat drying system, Heating temperature is 104 DEG C, and drying dewaters, after drying moisture content 0.8%, add the place's preimpregnation of resin composite materials film forcing machine, temperature is 210 DEG C, and resin extruded speed is 3kg/min, and dipping width and cord fabrics are with wide, then cool to room temperature, rolling, the speed of rolling is 10m/min, obtains jute/PP prepreg tape.The performance test results is in table 1.
Embodiment 6
Get homo-polypropylene resin 75 parts, 5 part of four { β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythritol ester, 10 parts of polycaprolactones, 3 parts two (2,2,6,6-tetramethyl--4-piperidyl) sebate, 5 parts of low molecular weight polyethylenes, 2 parts of different monooctyl esters of 3-thiohydracrylic acid, in moderate-speed mixers, mix 4 minutes, join after mixing in twin screw extruder, extruding pelletization, screw speed is 75r/min, and extruder head temperature is 190 DEG C.
The natural fiber that the present embodiment uses refers to and has comparatively long fiber length, after the twisting, can present continuous regime, a branch of twisted fibers nominal count 0.2 ~ 1; Natural fiber content of cellulose >=60%; Carry out untwisting again after natural fiber twisting, become the loose form expanded.By jute fibre line 100 volume through alkaline purification, be drawn to cord fabrics loom, its warp is polypropylene fibre, is made into the cord fabrics that fabric width is 1m; Tension force through tenslator launches, and at room temperature compresses through natural fiber pressure roller pressure roller, and pressure is 5MPa, form the cord fabrics that thickness is 0.8mm after roll-in, through heat drying system, Heating temperature is 103 DEG C, drying dewaters, after drying moisture content 0.9%, adds the place's preimpregnation of resin composite materials film forcing machine, temperature is 205 DEG C, resin extruded speed is 2kg/min, then cool to room temperature, rolling, the speed of rolling is 10m/min, obtains jute/PP prepreg tape.The performance test results is in table 1.
Embodiment 7
Get homo-polypropylene resin 76 parts, 5 part of four { β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythritol ester, 10 parts of polycaprolactones, 3 parts two (2,2,6,6-tetramethyl--4-piperidyl) sebate, 5 parts of tetrabromo-bisphenols two (2,3-dibromopropyl) ether, 2 parts of different monooctyl esters of 3-thiohydracrylic acid, mix 8 minutes in moderate-speed mixers, join after mixing in twin screw extruder, extruding pelletization, screw speed is 75r/min, and extruder head temperature is 190 DEG C.
The natural fiber that the present embodiment uses refers to and has comparatively long fiber length, after the twisting, can present continuous regime, a branch of twisted fibers nominal count 0.2 ~ 1; Natural fiber content of cellulose >=60%; Carry out untwisting again after natural fiber twisting, become the loose form expanded.By jute fibre line 120 volume through alkaline purification, be drawn to cord fabrics loom, its warp is polypropylene fibre, is made into the cord fabrics that fabric width is 1.2m; Tension force through tenslator launches, at room temperature compress through natural fiber pressure roller pressure roller, pressure is 5MPa, the cord fabrics that thickness is 0.8mm is formed after roll-in, through heat drying system, Heating temperature is 103 DEG C, and drying dewaters, after drying moisture content 0.9%, add the place's preimpregnation of resin composite materials film forcing machine, temperature is 215 DEG C, and resin extruded speed is 2kg/min, dipping width 20mm wider than cord fabrics, then cool to room temperature, rolling, the speed of rolling is 20m/min, obtains jute/PP prepreg tape.The performance test results is in table 1.
Table 1
| Typical case's performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Jute content/% ① | 40 | 35 | 40 | 45 | 35 | 40 | 45 |
| Tensile strength/MPa | 106 | 92 | 101 | 115 | 90 | 98 | 98 |
| Flexural strength/MPa | 124 | 102 | 105 | 110 | 100 | 104 | 112 |
| Shock strength/J/m 2 | 45 | 43 | 50 | 56 | 40 | 46 | 46 |
| Oxygen index | 24 | 23 | 19 | 19 | 23 | 19 | 23 |
1.: jute content herein utilizes densimetry to test
Its testing method is as follows: utilize air-discharging method to test jute fibre density respectively for ρ
jute, resin density is ρ
resin, prepreg tape density is ρ
prepreg tape, utilize formula C=(ρ
resin-ρ
prepreg tape)/(ρ
resin-ρ
jute), calculate jute content.
Tensile strength testing standard in table 1 is GB/T3354-1999, and flexural strength testing standard is GB/T356-1999, and shock strength testing standard is GB/T1451-1983, and oxygen index testing standard is GB8924.
Can be found out by table 1, in natural fiber/resin prepreg band, natural fiber content is between 35 ~ 45%, but this scope is not fixing, can be regulated by the temperature of the extruded velocity and forcing machine that regulate film forcing machine; The tensile strength of prepreg tape is not only relevant with the content of natural fiber with flexural strength, and relevant with the content of thermoplastic resin in resin composite materials, and in prepreg tape, natural fiber content is higher, and the tensile strength of prepreg tape is higher; In resin composite materials, the content of thermoplastic resin is higher, and the tensile strength of prepreg tape is higher.Flexural strength is not only relevant with the content of the natural fiber in prepreg tape, and relevant with the content of thermoplastic resin in resin composite materials, and in resin composite materials, the content of thermoplastic resin is more, and the flexural strength value of prepreg tape is higher; In prepreg tape, natural fiber content is more, and the flexural strength value of prepreg tape is higher.The shock strength of prepreg tape is not only relevant with natural fiber content in prepreg tape, and relevant with the content of thermoplastic resin in resin composite materials, and the natural fiber content in prepreg tape is higher, and the shock strength of prepreg tape is larger; In resin composite materials, the content of thermoplastic resin is larger, and the shock strength of prepreg tape is larger.After adding fire retardant, the oxygen index resin of prepreg tape obviously increases, and the oxygen index not adding fire retardant prepreg tape is very low, about 19, belong to inflammable substance, and with the addition of the oxygen index of flame retardant materials 23, illustrate and with the addition of the combustionproperty that fire retardant can improve material.
Embodiment 8
By the prepreg tape material produced, cut into different shape, put into mould, through melting heating, pressurization, prepares phone housing.This kind of phone housing is shock-resistant, and after discarding, recovery of degrading, little to environmental influence.
The present invention is made up of aforesaid method, by the untwisting of natural fiber, roll-in is in blocks, it is made fully to launch, in impregnation refrigerating unit, by the natural fiber launched, resin impregnation is carried out to its two sides, to improve the dipping effect of natural fiber, resin is now the thermoplastic resin of molten state, obtains prepreg tape through overcooling, rolling.This kind of prepreg tape can produce the internals of such as vehicle, removable phone housing, can solve the recovery problem of other non-degradable resins.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and one principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (17)
1. resin composite materials prepares a method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: the method comprises the following steps:
Natural fiber is made cord fabrics, and drawn, compression, heat drying dewater, and at film forcing machine place, resin composite materials carries out preimpregnation, and then impregnation cooling rolling, prepares the prepreg tape of natural fiber/resin composite materials;
The warp of described cord fabrics is selected from polypropylene fibre, nylon fiber or acid fiber by polylactic;
Described resin composite materials is made up of the component comprising following weight part:
Described oxidation inhibitor is selected from four { β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid } one or more in pentaerythritol ester, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl, Tyox B or phosphorous acid benzene two isodecyl ester;
Described fire retardant be selected from magnesium hydroxide, aluminium hydroxide, ammonium polyphosphate, eight bromo ether, triphenylphosphate, hexabromocyclododecane, zinc borate, encapsulated red phosphorus, TDE, two (2, the 3-dibromopropyl) ether of tetrabromo-bisphenol or hexabromocyclododecane one or more;
Described expanding material be selected from polycaprolactone, polyhydroxyalkanoate or polyoxyethylene glycol one or more;
Described weather resisting agent is selected from two (2,2,6,6-tetramethyl--4-piperidyl) sebate, 2,4-dihydroxyl-benzophenone, one or more in 2-(2 '-hydroxyl-5 '-) benzotriazole or 2-(2 '-hydroxyl-3 '-the tertiary butyl-5 ' aminomethyl phenyl)-5-chlorinated benzotriazole;
Described releasing agent be selected from silicone oil, polyoxyethylene glycol or low molecular weight polyethylene one or more;
Described auxiliary agent be selected from the different monooctyl ester of 3-thiohydracrylic acid, 4-phenylbenzene-4-methyl-1-pentene or 4,4-dimethyl-2,4-phenylbenzene-1-butylene one or more;
Described natural fiber is selected from hemp fibre, cotton fibre, bamboo fibers, ramee, flax fiber, jute fibre or silky fibre and/or their hybrid yams, natural fiber content of cellulose >=60%;
One or more process in plasma body, alkaline purification or coupling agent treatment of described natural fiber, carry out untwisting after twisting again.
2. resin composite materials according to claim 1 prepares the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: described thermoplastic resin melting index is 10 ~ 100g/10min, be selected from one or more in polyolefine, thermoplastic polyester, polymeric amide or resins for universal use.
3. resin composite materials according to claim 2 prepares the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: described polyolefine be selected from homo-polypropylene, Co-polypropylene or polyethylene one or more.
4. resin composite materials according to claim 2 prepares the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: described thermoplastic polyester is selected from polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate or poly(lactic acid).
5. resin composite materials according to claim 2 prepares the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: described polymeric amide be selected from nylon 6, nylon66 fiber, nylon 12, nylon 1212 or nylon 612 one or more.
6. resin composite materials according to claim 2 prepares the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: described resins for universal use is selected from polyvinyl chloride and/or polycarbonate.
7. the arbitrary described resin composite materials of claim 1 to 6 prepares the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: the preparation method of described resin composite materials comprises the following steps:
By 70 ~ 100 parts of thermoplastic resins, 2 ~ 5 parts of oxidation inhibitor, 2 ~ 5 parts of fire retardants, 5 ~ 10 parts of expanding materials, 2 ~ 3 parts of weather resisting agent, 2 ~ 5 parts of releasing agents and 1 ~ 2 part of auxiliary agent, 3 ~ 7 minutes are mixed in moderate-speed mixers, join forcing machine after abundant mixing and extrude pelletizing, obtain resin composite materials.
8. resin composite materials according to claim 7 prepares the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: described forcing machine is twin screw extruder, and screw speed is 10 ~ 250r/min, and extrusion temperature is 150 ~ 190 DEG C.
9. resin composite materials according to claim 1 prepares the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: the yarn number of axle needed for described cord fabrics is 1 ~ 500 volume, and described cord fabrics thickness is 0.1 ~ 2mm.
10. resin composite materials according to claim 1 prepares the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: described draft temperature is room temperature, and draw speed is rolling speed.
11. resin composite materials according to claim 1 prepare the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: described compression temperature is room temperature, and pressure is 4 ~ 10MPa.
12. resin composite materials according to claim 9 prepare the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: the yarn number of axle needed for described cord fabrics is 50 ~ 200 volumes.
13. resin composite materials according to claim 9 prepare the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: the yarn number of axle needed for described cord fabrics is 80 ~ 150 volumes.
14. resin composite materials according to claim 1 prepare the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: described heat drying temperature is 101 ~ 110 DEG C, after drying moisture content < 1%.
15. resin composite materials according to claim 1 prepare the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: described preimpregnation temperature is 190 ~ 220 DEG C, resin extruded speed is 1 ~ 5kg/min, floods width with cord fabrics with wide or wider than cord fabrics 10 ~ 100mm.
16. resin composite materials according to claim 1 prepare the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: described is cooled to cool to room temperature.
17. resin composite materials according to claim 1 prepare the method for the prepreg tape of natural fiber/resin composite materials, it is characterized in that: the speed of described rolling is 1 ~ 20m/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110244870.XA CN102952327B (en) | 2011-08-25 | 2011-08-25 | A kind of resin composite materials, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110244870.XA CN102952327B (en) | 2011-08-25 | 2011-08-25 | A kind of resin composite materials, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102952327A CN102952327A (en) | 2013-03-06 |
| CN102952327B true CN102952327B (en) | 2016-01-06 |
Family
ID=47761752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110244870.XA Active CN102952327B (en) | 2011-08-25 | 2011-08-25 | A kind of resin composite materials, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102952327B (en) |
Families Citing this family (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467955A (en) * | 2013-08-23 | 2013-12-25 | 吴江市天源塑胶有限公司 | Flame-retardant PC plastic |
| CN103497495B (en) * | 2013-10-08 | 2015-11-18 | 福建农林大学 | A kind of plasma modification bamboo fiber strengthens unsaturated polyester composite |
| CN103589144A (en) * | 2013-10-29 | 2014-02-19 | 安徽安缆模具有限公司 | Lightproof infrared-ray transmitting nylon PA12 material for automobile connectors |
| CN103554787A (en) * | 2013-11-08 | 2014-02-05 | 苏州市双赢包装材料有限公司 | Formula of flame-retardant polyvinyl chloride (PVC) plastics |
| CN103603207A (en) * | 2013-11-12 | 2014-02-26 | 贵州龙里蓝图新材料有限公司 | Ultra-high molecular weight polyethylene fiber slope protective net and preparation method thereof |
| CN103802410B (en) * | 2014-01-16 | 2015-11-18 | 福建农林大学 | Give up fibre/bamboo fiber of PET strengthens unsaturated polyester composite and preparation method thereof |
| CN103834105B (en) * | 2014-03-04 | 2016-02-17 | 芜湖市艾德森自动化设备有限公司 | Capacitor metalized film of a kind of withstand voltage fire-retardant isotatic polypropylene and preparation method thereof |
| CN103849090A (en) * | 2014-03-10 | 2014-06-11 | 深圳市领亚电子有限公司 | High-performance polyvinyl chloride composite material for wires and cables and preparation method thereof |
| CN104312093B (en) * | 2014-10-15 | 2016-08-24 | 东莞市若茂环保建材有限公司 | A kind of fire retardant PBT with no halogen/PP base wood-plastic composite material and preparation method thereof |
| CN104987620A (en) * | 2015-07-13 | 2015-10-21 | 金宝丽科技（苏州）有限公司 | Fiber-reinforced composite PVC (polyvinyl chloride) material and preparation method thereof |
| CN105153572A (en) * | 2015-07-14 | 2015-12-16 | 苏州恒辉科技有限公司 | Composite nanometer polymer injection molded material for communication equipment, and preparation method thereof |
| CN104961990A (en) * | 2015-07-30 | 2015-10-07 | 苏州荣昌复合材料有限公司 | Punching-resistant modified plastic |
| CN104987579A (en) * | 2015-07-30 | 2015-10-21 | 苏州荣昌复合材料有限公司 | Environmentally friendly low friction modified plastic |
| CN105086244A (en) * | 2015-08-26 | 2015-11-25 | 无锡贺邦金属制品有限公司 | Method for manufacturing plastics for flat type clothes hangers |
| CN105255329B (en) * | 2015-11-07 | 2018-04-06 | 浙江华江科技发展有限公司 | A kind of modification bamboo fibre of UV-cured resin cladding and preparation method thereof |
| CN105860448A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Pbt material for automobile exterior part and preparing method thereof |
| CN105778439A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Phosphorized pbt material and preparation method thereof |
| CN105860454A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Anti-oxidant pbt material and preparation method thereof |
| CN105802148A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Pbt material and preparation method thereof |
| CN105778440A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Environment-friendly pbt material and preparing method thereof |
| CN105860451A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Antistatic pbt material and preparation method thereof |
| CN105860450A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Zinc oxide loaded pbt material and preparation method thereof |
| CN105778441A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Heat-preservation pbt material and preparing method thereof |
| CN105802149A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Fiber-containing flexible pbt material and preparation method thereof |
| CN105778438A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Stable type pbt material and preparation method thereof |
| CN105778437A (en) * | 2016-04-14 | 2016-07-20 | 滁州优胜高分子材料有限公司 | Composite silicon modified pbt material and preparing method thereof |
| CN105802150A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Hydrophobic anti-leakage pbt material and preparation method thereof |
| CN105860453A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Outdoor sunlight-resistant pbt material and preparation method thereof |
| CN105802147A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Flame-retardant pbt material and preparation method thereof |
| CN105802151A (en) * | 2016-04-14 | 2016-07-27 | 滁州优胜高分子材料有限公司 | Pbt material for roaster shell and preparation method of pbt mateiral |
| CN105838042A (en) * | 2016-04-14 | 2016-08-10 | 滁州优胜高分子材料有限公司 | Insulating pbt material used for electronic equipment and preparation method thereof |
| CN105838043A (en) * | 2016-04-14 | 2016-08-10 | 滁州优胜高分子材料有限公司 | Attapulgite-modified pbt material and preparation method thereof |
| CN105838041A (en) * | 2016-04-14 | 2016-08-10 | 滁州优胜高分子材料有限公司 | Composite calcareous pbt material and preparation method thereof |
| CN105860452A (en) * | 2016-04-14 | 2016-08-17 | 滁州优胜高分子材料有限公司 | Antimicrobial pbt material and preparation method thereof |
| CN105924907A (en) * | 2016-05-13 | 2016-09-07 | 金宝丽科技（苏州）有限公司 | Anti-corrosion inflaming retarding plastic floor and preparing method thereof |
| CN108066822A (en) * | 2016-11-14 | 2018-05-25 | 上海微创医疗器械（集团）有限公司 | The preparation method of orthopaedics implant, the material for being used to prepare implantation material and implantation material |
| CN106750952A (en) * | 2016-12-26 | 2017-05-31 | 浙江普利特新材料有限公司 | A kind of numb long fiber reinforced thermoplastic composite based on cable cladding process and preparation method thereof |
| EP3603918B1 (en) | 2017-03-28 | 2023-11-01 | Resonac Corporation | Method for producing an frp precursor for a printed wiring board |
| CN107353616A (en) * | 2017-06-26 | 2017-11-17 | 俞惠英 | A kind of transparent PC material fire-retardant master granule and its preparation method and application |
| JP7022302B2 (en) * | 2017-12-01 | 2022-02-18 | トヨタ紡織株式会社 | Fiber composite material and manufacturing method of fiber composite material |
| CN108250464B (en) * | 2018-01-11 | 2020-07-07 | 东北林业大学 | Method for preparing continuous prepreg tape by using biomass fiber reinforced thermoplastic polymer |
| CN109735075A (en) * | 2019-01-15 | 2019-05-10 | 南通大学 | A kind of antibacterial degradable founds the syringe of structure lactic acid composite material and its preparation |
| CN110551392A (en) * | 2019-09-23 | 2019-12-10 | 安徽旭升新材料有限公司 | Preparation method of carbon fiber PA66 thermoplastic composite material |
| CN110684280B (en) * | 2019-10-15 | 2022-06-03 | 国际竹藤中心 | Continuous extrusion thermoplastic plant fiber prepreg and preparation method thereof |
| CN112521689A (en) * | 2020-12-04 | 2021-03-19 | 惠州莹光塑胶颜料有限公司 | Transparent flame-retardant plastic master batch and preparation method thereof |
| CN114108017B (en) * | 2021-12-03 | 2022-11-08 | 中国科学院大连化学物理研究所 | Enhanced PEM water electrolysis proton exchange membrane and continuous preparation method thereof |
| CN114750056B (en) * | 2022-05-30 | 2022-12-23 | 广州傲群刷业科技有限公司 | A wear-resisting super bullet polish brush for getting rid of screen through-hole burr |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474868A (en) * | 2008-10-15 | 2009-07-08 | 上海杰事杰新材料股份有限公司 | Equipment for preparing continuous fiber reinforced thermoplastic resin composite material presoaked belt and use thereof |
| CN101619199A (en) * | 2008-07-03 | 2010-01-06 | 李俊辉 | Manufacture technique of easy tear tape |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053460A (en) * | 1990-01-15 | 1991-07-31 | 苏州丝绸科学研究所 | Manufacture method of real silk deformed filament yarn and products thereof |
| KR100956150B1 (en) * | 2001-05-03 | 2010-05-06 | 바데이 인코포레이티드 | Quasi-unidirectional fabric for ballistic applications |
| FR2839001A1 (en) * | 2002-04-25 | 2003-10-31 | Joel Patrick Jean Luc Breard | PROCESS FOR THE MANUFACTURE OF A NEW MATERIAL COMPRISING BEAMS OF NATURAL FIBERS PRE-IMPREGNATED WITH ORGANIC RESIN AND IN THE FORM OF YARN OR RIBBON |
| DK1892071T4 (en) * | 2003-03-06 | 2018-10-15 | Vestas Wind Sys As | Process for preparing a preform |
| WO2009084800A1 (en) * | 2007-12-28 | 2009-07-09 | Cheil Industries Inc. | Flameproof thermoplastic resin composition and method for preparing the same |
| CN102115594B (en) * | 2009-12-31 | 2014-06-25 | 合肥杰事杰新材料股份有限公司 | Ultrahigh-toughness high-intensity organic fiber reinforced thermoplastic composite material and preparation technology thereof |
-
2011
- 2011-08-25 CN CN201110244870.XA patent/CN102952327B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619199A (en) * | 2008-07-03 | 2010-01-06 | 李俊辉 | Manufacture technique of easy tear tape |
| CN101474868A (en) * | 2008-10-15 | 2009-07-08 | 上海杰事杰新材料股份有限公司 | Equipment for preparing continuous fiber reinforced thermoplastic resin composite material presoaked belt and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102952327A (en) | 2013-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102952327B (en) | A kind of resin composite materials, preparation method and application thereof | |
| CN103061162B (en) | A kind of degradable composite material prepreg cloth and preparation method thereof and device | |
| CN102585358B (en) | Natural fiber reinforced polypropylene composite material and preparation method thereof | |
| CN100463934C (en) | Continuous long fiber reinforced fire-retardant thermoplastic resin and its prepn | |
| CN103215686B (en) | Preparation method of halogen-free flame retardant recycled polyester fiber | |
| CN102352116B (en) | Wood-plastic composite material and preparation method thereof | |
| CN102234405B (en) | Water-resistant polyvinyl alcohol (PVA) film composition as well as fusion preparation method thereof | |
| CN104723582A (en) | Manufacture equipment for continuous fiber reinforced thermoplastic composite material and application thereof | |
| CN102295792A (en) | Continuous fiber enhanced thermoplastic antiflaming presoaking belt composite material and preparation method thereof | |
| CN104194126A (en) | Preparation method of plastic woven bag | |
| CN103849141A (en) | Long glassfiber reinforced nylon composite material and preparation method thereof | |
| CN103160080B (en) | A kind of halogen-free flame-retardant long fiber glass reinforced PBT composite and preparation method thereof | |
| CN104371291A (en) | High-performance halogen-free flame-retardant long fiber reinforced polylactic acid composite material and preparation method thereof | |
| CN103571038A (en) | Nature fiber reinforced thermoplastic resin unidirectional prepreg tape and preparation method thereof | |
| CN204604939U (en) | A kind of manufacturing equipment of continuous fiber reinforced thermoplastic composite material | |
| CN103305954A (en) | Method for preparing ultra-high molecular weight polyethylene fiber | |
| CN103435997A (en) | Continuous long-fiber enhanced halogen-free flame-retardant polycarbonate composite material and preparation method thereof | |
| CN101531787A (en) | Halogen-free flame-retardant long glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN108624032A (en) | A kind of long glass fiber reinforced thermoplastic material and preparation method thereof | |
| CN104448803A (en) | Halogen-free flame-retardant long-fiber-reinforced nylon 6 composite material and preparation method thereof | |
| CN102011897A (en) | Fiber reinforced pipe for mine and production method thereof | |
| CN104278349A (en) | Antistatic and flame retardant copolyester fiber and preparation method thereof | |
| CN108624016B (en) | Aramid fiber modified carbon fiber reinforced polylactic acid thermoplastic composite material and preparation method thereof | |
| CN103374177A (en) | Fiber-reinforced thermoplastic composite material and preparation method thereof | |
| CN104960143A (en) | Injection-molded flexible stab-resistant composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |