CN102952327A - Resin composite material and its preparation method and use - Google Patents
Resin composite material and its preparation method and use Download PDFInfo
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- CN102952327A CN102952327A CN201110244870XA CN201110244870A CN102952327A CN 102952327 A CN102952327 A CN 102952327A CN 201110244870X A CN201110244870X A CN 201110244870XA CN 201110244870 A CN201110244870 A CN 201110244870A CN 102952327 A CN102952327 A CN 102952327A
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- 238000000034 method Methods 0.000 claims abstract description 30
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- 238000005470 impregnation Methods 0.000 claims abstract description 13
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- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
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- 239000012964 benzotriazole Substances 0.000 claims description 3
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- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
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- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims 1
- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical class C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 claims 1
- ZHUWXKIPGGZNJW-UHFFFAOYSA-N 6-methylheptyl 3-sulfanylpropanoate Chemical compound CC(C)CCCCCOC(=O)CCS ZHUWXKIPGGZNJW-UHFFFAOYSA-N 0.000 claims 1
- 240000008564 Boehmeria nivea Species 0.000 claims 1
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- 239000002202 Polyethylene glycol Substances 0.000 claims 1
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- 239000003513 alkali Substances 0.000 claims 1
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 claims 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical group C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 claims 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明属于高分子材料技术领域，公开了一种树脂复合材料、制备方法及其应用。本发明的树脂复合材料由包括以下重量份的组分制成：热塑性树脂70～100份，抗氧剂0～5份，阻燃剂0～5份，增容剂0～10份，耐候剂0～3份，脱模剂0～5份，助剂0～2份。该树脂复合材料的制备方法包括以下步骤：上述配比的原料，在中速混合器中混合3～7分钟，充分混合后加入到挤出机挤出切粒，得到树脂复合材料。本发明公开了将上述树脂复合材料制备天然纤维/树脂复合材料的预浸带的方法，包括以下步骤：将天然纤维制成帘子布，经拉伸、压紧、加热干燥除水，在淋膜挤出机处树脂复合材料进行预浸渍，然后浸胶冷却收卷，制备得到天然纤维/树脂复合材料的预浸带，该预浸带孔隙率低、力学强度高。The invention belongs to the technical field of polymer materials, and discloses a resin composite material, a preparation method and an application thereof. The resin composite material of the present invention is made of the following components by weight: 70-100 parts of thermoplastic resin, 0-5 parts of antioxidant, 0-5 parts of flame retardant, 0-10 parts of compatibilizer, and weather-resistant agent 0-3 parts, 0-5 parts of release agent, 0-2 parts of auxiliary agent. The preparation method of the resin composite material comprises the following steps: the raw materials in the above ratio are mixed in a medium-speed mixer for 3-7 minutes, fully mixed and then added to an extruder to extrude and pelletize to obtain the resin composite material. The invention discloses a method for preparing a prepreg tape of a natural fiber/resin composite material from the above-mentioned resin composite material. The resin composite material at the extruder is pre-impregnated, and then the impregnation is cooled and rolled up to prepare a pre-preg tape of the natural fiber/resin composite material. The pre-preg tape has low porosity and high mechanical strength.
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, such as high tensile strength, flexural strength/modulus, high/low-temperature impact intensity etc., and have characteristics such as relatively low density and recoverable, therefore development in recent years is rapid, and corresponding technology of preparing has also obtained great breakthrough.Among the 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 mixed yarn that will contain glass fibre mixes with PP resin and processing aid, and the heating and melting blend is through the forcing machine extruding pelletization.The product that utilizes this method to produce can fully be regulated the content of fortifying fibre, but this method extruding pelletization, formation be chopped pellet, can not form continuous enhancing prepreg tape.Adopt continuous glass fibre among the Chinese patent CN101474868A, organic fibres etc. are drawn from creel, make it sprawl into the unidirectional fibre yarn with certain amplitude 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 continuous fibre.Utilize this method can prepare glass fibre, the thermoplastic resin prepreg tapes such as Kafra fiber, but be not suitable for natural fiber, this is because the limited length of natural fiber, it is continuous to form single fiber, must could form continuous natural fiber line or rope through twisting, and through after the twisting, the dipping effect of resin is relatively poor, more dried yarn occurs.The preparation such as Chen Dakai natural fiber reinforced composite, adopt atural staple fibre or natural macrofiber (comprising ramee, linen fiber, jute fibre etc.) and PLA to carry out melt blending and extrude, the natural fiber that preparation can be degradable/PLA matrix material (Chen Dakai, Li Jing, an outstanding person; The progress of natural fiber enhanced polylactic acid acid matrix material, plastics, 2010 (6): 108).This kind method prepares the natural fiber reinforced composite, natural fiber fracture obviously, its reinforced effects is not obvious, and with PLA blending extrusion process in, natural fiber causes the viscosity of material to increase, the wearing and tearing of aggravation machine.Among the Chinese patent CN200610037894.7, Dong Weiwei through melt extruding granulation, obtains product with natural fiber and PLA and oxidation inhibitor, nucleator and mix lubricant.The Fiber Aspect Ratio of the natural fiber strongthener of this method preparation is less, and its reinforced effects is limited; And the screw rod of forcing machine had than galling.
Summary of the invention
For problems of the prior art, the purpose 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 provides a kind of preparation method of above-mentioned resin composite materials.
The 3rd purpose of the present invention provides a kind of method that above-mentioned resin composite materials is 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 by the component that comprises following weight part:
70～100 parts of thermoplastic resins,
0～5 part in 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,
0～2 part of auxiliary agent.
Described thermoplastic resin melting index is 10～100g/10min, is selected from polyolefine, thermoplastic polyester, polymeric amide or the resins for universal use one or more; Wherein: polyolefine further is selected from one or more in homo-polypropylene, Co-polypropylene or the polyethylene; Thermoplastic polyester further is selected from one or more in polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate or the poly(lactic acid); Polymeric amide further is selected from one or more in nylon 6, nylon 66, nylon 12, nylon 1212 or the nylon 612; Resins for universal use further is selected from polyvinyl chloride (PVC) and/or polycarbonate (PC).
Described oxidation inhibitor is selected from four { β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid } pentaerythritol ester, (3, the 5-di-tert-butyl-hydroxy phenyl) one or more in propionic acid stearyl alcohol ester, Tyox B or the phosphorous acid benzene two isodecyl esters, the purpose of oxidation inhibitor are degraded and/or the oxidations for thermoplastic resin in the process that is reduced in the preparation matrix material.
Described fire retardant is selected from one or more in magnesium hydroxide, aluminium hydroxide, ammonium polyphosphate, eight bromo ether, triphenylphosphate, hexabromocyclododecane, zinc borate, encapsulated red phosphorus, TDE, two (2, the 3-dibromopropyl) ethers of tetrabromo-bisphenol or the hexabromocyclododecane; The effect that adds fire retardant is to make flammable polymkeric substance be difficult to burning.
Described expanding material is selected from one or more in polycaprolactone, polyhydroxyalkanoate or the polyoxyethylene glycol, and the effect that adds expanding material is the consistency of improving between natural fiber and the poly(lactic acid).
Described weather resisting agent is selected from two (2,2,6,6-tetramethyl--4-piperidyl) sebate, 2, one or more in 4-dihydroxyl-benzophenone, 2-(2 '-hydroxyl-5 '-) benzotriazole or 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 ' aminomethyl phenyl)-5-chlorinated benzotriazole.The purpose that adds weather resisting agent is inhibition or shielded from light redox or photoaging.
Described releasing agent is selected from one or more in silicone oil, polyoxyethylene glycol or the low molecular weight polyethylene, and the effect of releasing agent is to make in the process of natural fiber and resin impregnation, and resin can not cover on pressure roller.
Described auxiliary agent is selected from the different monooctyl ester of 3-thiohydracrylic acid, 4-phenylbenzene-4-methyl-1-pentene or 4,4-dimethyl-2, one or more in 4-phenylbenzene-1-butylene.
The present invention also provides a kind of preparation method of above-mentioned resin composite materials, and the method may further comprise the steps:
With 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, in moderate-speed mixers, mixed 3～7 minutes, join forcing machine after fully 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 ℃.
The present invention also provides a kind of above-mentioned resin composite materials has been prepared the method for the prepreg tape of natural fiber/resin composite materials, and the method may further comprise the steps:
Natural fiber is made cord fabrics, and drawn, compression, heat drying dewater, and resin composite materials carries out preimpregnation at film forcing machine place, and then impregnation cools off rolling, prepare the prepreg tape of natural fiber/resin composite materials.
The required yarn number of axle of described cord fabrics is 1～500 volume, and preferred 50～200 volumes are 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 ℃, after drying moisture content＜1%.
Described preimpregnation temperature is 190～220 ℃, and resin extruded speed is 1～5kg/min, and dipping width and cord fabrics are with wide or than the wide 10～100mm of cord fabrics.
The described cool to room temperature that is cooled to.
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%.
Described natural fiber carries out untwisting through one or more processing in plasma body, alkaline purification or the coupling agent treatment after the twisting again, becomes the loose form that expands.
Prepreg tape of the present invention can be made into the product of the moulding complexity such as phone housing or computer casing as required.
The present invention compares with prior art, has following advantage and beneficial effect:
1, in natural fiber/thermoplastic resin composite material presoaked belt of the present invention, the wild phase natural fiber exists with external phase, because be to adopt the form of cord fabrics to strengthen thermoplastic resin, the wild phase in the prepreg tape is unidirectional, and mechanical property can design when making product.
2, the matrix material longitudinal length of the present invention preparation is adjustable, and wide cut also can adjust, and can satisfy the length requirement of later stage in producing.
3, the present invention prepare matrix material can long storage time, and natural fiber is fully by resin impregnation, do not have exposedly, especially natural fiber is dry can to keep material, natural fiber can moldy metamorphism.
4, method of the present invention can be adjusted 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 guarantee 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, can be because of not wide or narrow, and so that the position of natural fiber change.
7, method of the present invention can guarantee resin thorough impregnation natural fiber, and resin thorough impregnation natural fiber can guarantee that in the process of preparing product, the defective of product is few, and mechanical strength is high.
8, to prepare the porosity of prepreg tape lower in the present invention, is lower than 1%, when porosity is low, can guarantee the stability of product performance.
Description of drawings
Fig. 1 is the preparation flow figure of the prepreg tape of natural fiber/resin composite materials.
Wherein 1 is creel; 2 is the yarn axle; 3 is natural fiber; 4 is the cord fabrics loom; 5 is tenslator; 6,7 is the natural fiber pressure roller; 8 is the heat drying system; 9 is tenslator; 10 is the impregnation refrigerating unit; 11 is the film forcing machine; 12 is wrap-up.
Embodiment
The present invention is further illustrated below in conjunction with the accompanying drawing illustrated embodiment.
Among the present invention, except as otherwise noted, otherwise all percentage ratios, part and ratio etc. are all based on weight.
The invention describes suitable method and material, be used for implementing or checking the present invention but be similar to or be equivalent to materials and methods of the present invention.
When enumerating numerical range among the present invention, unless otherwise noted, such scope is intended to comprise all integers and umber in its end points and the scope.
Term among the present invention " comprises " that " containing " " has " or its any other variations all are intended to contain the non-exclusive scope that comprises.For example, the material that comprises a series of mechanical means is selected, the particular location of device etc. be not only be confined to listed herein.
The raw material of this paper, method and embodiment only are schematically, unless otherwise indicated, otherwise do not consist of restriction.
Among the present invention, natural fiber pressure roller shown in Figure 1 comprises 6,7 and in order to improve product performance, and the pressure roller on continuing to add, and namely pressure roller not only comprises two couple shown in the figure, can have three pairs, four pairs, five pairs, as example.
Used thermoplastic resin melting index is 10～100g/10min among the present invention.
The natural fiber of using in following examples is through alkaline purification, and its treatment process is as follows, under the normal temperature natural fiber is soaked in the NaOH solution, concentration is 5% (massfraction), behind the 2h, natural fiber is taken out, clear water washing 3 times, drying is taken out under 80 ℃ of temperature.
Embodiment 1
Get 87 parts of polylactic resin, 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 were mixed in moderate-speed mixers 4 minutes, join in the twin screw extruder after the mixing, extruding pelletization, screw speed are 75r/min, and the extruder head temperature is 190 ℃.
Fig. 1 is the preparation flow figure of the prepreg tape of natural fiber/resin composite materials.Natural fiber used herein refers to has than 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 again untwisting after the natural fiber twisting, become the loose form that expands.Learnt from else's experience in the present embodiment jute fibre line 100 volumes of alkaline purification, be placed on the creel 1, because the product that natural fiber is commercially produced is by twisting, making it become continuous regime exists, natural fiber is through after the twisting, resin is not easy dipping, if the product of excellent, must be to the natural fiber untwisting after the twisting.Yarn axle on the creel herein all passes through untwisting; Natural fiber 3 on the yarn axle 2 (jute fibre on the yarn axle of this moment is through untwisting), it is jute fibre herein, jute fibre is drawn to cord fabrics loom 4, the cord fabrics loom can the production wide cut be 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 the pressure roller roll-in, pressure is 5MPa, the thickness of fiber is 0.8mm after the roll-in, the material of natural fiber pressure roller can be rubber, plastics etc. (materials when being subject to larger pressure deformation can occur, and natural fiber can not rupture because of extruding herein).Natural fiber is in bond in the natural fiber cord fabrics, and resin is not easy to soak into fiber.The effect of pressure roller herein is 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%, a large amount of moisture will affect the properties of material in the natural fiber, such as excess moisture, 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, this moment, temperature was 103 ℃, the moisture content of jute fibre is 0.9%, change the traffic direction of jute fibre through tenslator 9, enter the 11 places preimpregnation of film forcing machine, this moment, the temperature of film forcing machine was 205 ℃, resin extruded speed is 2kg/min, dipping width and cord fabrics through preimpregnation, then arrive impregnation refrigerating unit 10 with wide herein jute fibre, and 3 rollers herein are all steelwork, the rotational line speed of impregnation refrigerating unit 10 is the same with wrap-up rotational line speed, through being cooled to the room temperature roll-in, carry out rolling at wrap-up 12, its rotational line speed is 5m/min, prepare jute/poly(lactic acid) prepreg tape, its performance test results sees Table 1.
Embodiment 2
Get 72 parts of homo-polypropylene resins, 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, the 3-dibromopropyl) ether, 1 part of different monooctyl ester of 3-thiohydracrylic acid mixed 4 minutes in moderate-speed mixers, join in the twin screw extruder after the mixing, extruding pelletization, screw speed are 75r/min, and the extruder head temperature is 190 ℃.
The natural fiber that present embodiment uses refers to has than 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 again untwisting after the natural fiber twisting, become the loose form that expands.To be drawn to the cord fabrics loom through jute fibre line 100 volumes of alkaline purification, 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, form the cord fabrics that thickness is 0.7mm after the roll-in, through the heat drying system, Heating temperature is 103 ℃, and drying dewaters, and moisture content 0.9% after drying, add the place's preimpregnation of resin composite materials film forcing machine, temperature is 210 ℃, and resin extruded speed is 2kg/min, the wide 10mm of dipping Width cord fabrics, then cool to room temperature, rolling, the speed of rolling is 10m/min, obtains jute/PP prepreg tape.The performance test results sees Table 1.
Get 95 parts of homo-polypropylene resins, 3 parts of two (2,3-dibromopropyl) ethers of tetrabromo-bisphenol, 2 parts of low molecular weight polyethylenes.Mixed 4 minutes in moderate-speed mixers, join after the mixing in the twin screw extruder, extruding pelletization, screw speed are 75r/min, and the extruder head temperature is 190 ℃.
The natural fiber that present embodiment uses refers to has than 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 again untwisting after the natural fiber twisting, become the loose form that expands.To be drawn to the cord fabrics loom through jute fibre line 100 volumes of alkaline purification, 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, form the cord fabrics that thickness is 0.8mm after the roll-in, through the heat drying system, Heating temperature is 103 ℃, and drying dewaters, and moisture content 0.9% after drying, add the place's preimpregnation of resin composite materials film forcing machine, temperature is 210 ℃, 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 sees Table 1.
Embodiment 4
The natural fiber that present embodiment uses refers to has than 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 again untwisting after the natural fiber twisting, become the loose form that expands.Get 100 parts of homopolymerisation polyethylene (PP) resins and directly put into the film forcing machine, will be drawn to the cord fabrics loom through jute fibre line 100 volumes of alkaline purification, 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, form the cord fabrics that thickness is 0.6mm after the roll-in, through the heat drying system, Heating temperature is 103 ℃, and drying dewaters, and moisture content 0.9% after drying, add the place's preimpregnation of resin composite materials film forcing machine, temperature is 210 ℃, 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 sees Table 1.
Embodiment 5
Get 70 parts of homo-polypropylene resins, 5 part of four { β-(3, the 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, mixed 4 minutes, join in the twin screw extruder extruding pelletization after the mixing, screw speed is 75r/min, and the extruder head temperature is 190 ℃.
The natural fiber that present embodiment uses refers to has than 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 again untwisting after the natural fiber twisting, become the loose form that expands.To be drawn to the cord fabrics loom through jute fibre line 120 volumes of alkaline purification, 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, form the cord fabrics that thickness is 0.5mm after the roll-in, through the heat drying system, Heating temperature is 104 ℃, and drying dewaters, and moisture content 0.8% after drying, add the place's preimpregnation of resin composite materials film forcing machine, temperature is 210 ℃, 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 sees Table 1.
Embodiment 6
Get 75 parts of homo-polypropylene resins, 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, mixed 4 minutes, join in the twin screw extruder extruding pelletization after the mixing, screw speed is 75r/min, and the extruder head temperature is 190 ℃.
The natural fiber that present embodiment uses refers to has than 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 again untwisting after the natural fiber twisting, become the loose form that expands.To be drawn to the cord fabrics loom through jute fibre line 100 volumes of alkaline purification, 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 the roll-in, through the heat drying system, Heating temperature is 103 ℃, drying dewaters, and moisture content 0.9% after drying, adds the place's preimpregnation of resin composite materials film forcing machine, temperature is 205 ℃, resin extruded speed is 2kg/min, cool to room temperature then, rolling, the speed of rolling is 10m/min, obtains jute/PP prepreg tape.The performance test results sees Table 1.
Embodiment 7
Get 76 parts of homo-polypropylene resins, 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, the 3-dibromopropyl) ether, 2 parts of different monooctyl esters of 3-thiohydracrylic acid mixed 8 minutes in moderate-speed mixers, join in the twin screw extruder after the mixing, extruding pelletization, screw speed are 75r/min, and the extruder head temperature is 190 ℃.
The natural fiber that present embodiment uses refers to has than 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 again untwisting after the natural fiber twisting, become the loose form that expands.To be drawn to the cord fabrics loom through jute fibre line 120 volumes of alkaline purification, 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, form the cord fabrics that thickness is 0.8mm after the roll-in, through the heat drying system, Heating temperature is 103 ℃, and drying dewaters, and moisture content 0.9% after drying, add the place's preimpregnation of resin composite materials film forcing machine, temperature is 215 ℃, and resin extruded speed is 2kg/min, the wide 20mm of dipping Width cord fabrics, then cool to room temperature, rolling, the speed of rolling is 20m/min, obtains jute/PP prepreg tape.The performance test results sees Table 1.
Table 1
| Typical case's performance | Embodiment 1 | Embodiment 2 | |
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 the air-discharging method to test respectively jute fibre density and be 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 the table 1 is GB/T3354-1999, and the flexural strength testing standard is GB/T 356-1999, and the shock strength testing standard is GB/T1451-1983, and the oxygen index testing standard is GB8924.
Can find out by table 1, in natural fiber/resin prepreg band natural fiber content between 35～45%, but this scope do not fix, extruded velocity that can be by regulating the film forcing machine and the temperature of forcing machine be regulated; 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 the resin composite materials, and natural fiber content is higher in the prepreg tape, and the tensile strength of prepreg tape is higher; The content of thermoplastic resin is higher in the resin composite materials, and the tensile strength of prepreg tape is higher.Flexural strength is not only relevant with the content of natural fiber in the prepreg tape, and relevant with the content of thermoplastic resin in the resin composite materials, and the content of thermoplastic resin is more in the resin composite materials, and the flexural strength value of prepreg tape is higher; Natural fiber content is more in the prepreg tape, 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 the prepreg tape, and relevant with the content of thermoplastic resin in the resin composite materials, and the natural fiber content in the prepreg tape is higher, and the shock strength of prepreg tape is larger; The content of thermoplastic resin is larger in the resin composite materials, and the shock strength of prepreg tape is larger.Add after the fire retardant, the oxygen index resin of prepreg tape obviously increases, and the oxygen index that does not add the fire retardant prepreg tape is very low, about 19, belong to inflammable substance, and the oxygen index that has added flame retardant materials is 23, illustrates and added the combustionproperty that fire retardant can improve material.
Embodiment 8
Prepreg tape material with producing cuts into different shape, puts into mould, and through the melting heating, phone housing is prepared in pressurization.This kind phone housing is shock-resistant, and after discarded, the recovery of degrading, little to environmental influence.
The present invention is made of aforesaid method, untwisting by natural fiber, roll-in is in blocks, it is fully launched, in the impregnation refrigerating unit, with the natural fiber that launches, resin impregnation is carried out on its two sides, to improve the dipping effect of natural fiber, the resin of this moment is the thermoplastic resin of molten state, obtains prepreg tape through overcooling, rolling.This kind prepreg tape can be produced the internals such as vehicle, and removable phone housing can solve the recovery problem of other non-degradable resins.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and at one application of principle of this explanation in other embodiment and needn't pass through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
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