CN102311585A - Long glass fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
Long glass fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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- CN102311585A CN102311585A CN201110269380A CN201110269380A CN102311585A CN 102311585 A CN102311585 A CN 102311585A CN 201110269380 A CN201110269380 A CN 201110269380A CN 201110269380 A CN201110269380 A CN 201110269380A CN 102311585 A CN102311585 A CN 102311585A
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Abstract
The invention discloses a long glass fiber reinforced polypropylene composite material, which comprises the following ingredients by weight percentage: 55-70% of polypropylene, 45-30% of long glass fiber, 0.3-1% of coupling agent,0-10% of MPP compatilizer, 0-15% of propylene copolymer, 0-5% of flexibilizer, 0.3-0.6% of anti-oxidant and 0-20% of filling materials. Simultaneously, the invention discloses a method for preparing the composite material. The invention uses a direct method for preparing the long glass fiber reinforced polypropylene composite material, which simplifies the technical links of cooling, solidifying heating and melting of prepreg, so that the long glass fiber reinforced polypropylene composite material saves the energy consumption, reduces the cost, and the production process is flexible.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of long glass fiber reinforced polypropylene composite sheet and preparation method thereof.
Background technology
Glass fiber reinforced polypropylene composite material is called for short LFT; Not only have intensity height, density little (be merely metal 1/5～1/7), superior corrosion resistance, good formability, operating procedure environment can regenerated using than cleaning, waste material and goods etc. advantage; Also have high specific strength and shock strength, good thermal property, insulating property and heat-insulation and heat-preservation effect, the characteristic that can in atmospheric environment, use for a long time; Be the green material of less energy-consumption, non-environmental-pollution, in automobile lightweight, environmental protectionization, play a significant role.Automobile industry and multi-field in; To weight, environmental protection, can be recycled, toughness is good etc. has under the situation of an urgent demand; The above characteristic of LFT sheet material is the growth requirement that very meets the whole world and China, has prospective a kind of advanced composite material.
Viscosity is very high during the thermoplastic polymer fusion, and how dipping difficulty forms good dipping, both are fully contacted between fiber and matrix, reduces the damage of fiber in preparation and the moulding process, the key issue that to be high-performance LFT preparation faced with moulding process.To this, carried out a large amount of research both at home and abroad, formed a series of dipping techniques, like in-situ polymerization dipping technique, powder impregnation technology and melt impregnation technology etc.But for various reasons, current technology capable of being industrialized mainly is powder impregnation technology and melt impregnation technology.
The powder impregnation method is that fibrous bundle gets into a fluidized-bed that is full of toner, and the fluidizing toner is adsorbed on the surface of fibrous bundle, and through heating, the resin fusion combines with fiber, and cooling, cutting obtain the LFT pellet.But after the moulding of long fiber reinforced thermoplastic composites particle, fibre-tendering is serious, and most fibers become staple fibre.
Melt impregnation is that the layer glass fibre felt is clipped between the three-layer polypropylene melt, and the cold semifinished material of getting into sheet material is solidified in hot rolling on the track type thermocompressor then.Melt impregnation also can adopt pultrusion technique; Promptly adopt a kind of pultrusion die head of special construction; Let the continuous tow of homodisperse, pre-tension through this when being full of the die head of pressurized melt; Repeated multiple times is born alternative and is changed, and impels the enforceable dipping of fiber and melt, reaches the ideal dipping effect.But current melt impregnation squeezes pull technology several important shortcomings are arranged:
1. structure design is undesirable.Current roving glass fiber strengthens the particle technology that adopt more and is mostly that dipping squeezes pull technology, and mostly mould structure is Wave-shaped structural or wheel train structure, and its core technology is a large-scale company monopolizing of domestic and international a few family, and security classification is very high.Finding shows that the dipping and the dispersion effect of the crowded pull technology of current dipping on the whole are also undesirable, depends merely on wave or wheel train structure and is difficult to realize dispersion of monofilament level and good dipping effect.
2. be not suitable for preparing full-bodied PP/LGF.At present, the viscosity of the used resin of each PP/LGF of system is lower on the market, the molten finger at 50-100g/10min.Because of material flowability better. flood more or less freelyly, reduced the G-LFT manufacture difficulty generally.Refer at 10-20g/10min or littler high viscosity resin that to molten current dipping technique is difficult to realize the dispersion of single seam level and good dipping effect.
3. be not suitable for preparing the LFT of thermo-sensitivity system.Thermo-sensitivity system, material are to temperature sensitive, and thermotolerance is not strong, and mould does not allow more base-material.But the current structure that impregnation mold adopted has more base-material in the mould, very easily cause the degraded of material, and therefore unsuitable preparation temperature-sensitive is the enhancing particle of system, like POM/LGF.In addition, the viscosity of POM is high, and current dipping technique also is difficult to the dipping and the dispersion of realizing ideal.So current dipping squeezes the drawing-die tool and has specificity, does not possess versatility.
In addition, finished-product material need be passed through post forming, and cost value is high, and process flexibility is not enough.
Summary of the invention
Goal of the invention: the object of the invention is the deficiency to prior art, and a kind of long glass fiber reinforced polypropylene composite sheet is provided.
Another object of the present invention is to provide the preparation method of above-mentioned composite sheet.
Technical scheme: in order to achieve the above object; The present invention specifically realizes like this: a kind of long glass fiber reinforced polypropylene composite sheet comprises following components in weight percentage: 50～70% Vestolen PP 7052,25～45% long glass fibres, 0.3～1% coupling agent, 0～10% maleic anhydride inoculated polypropylene, 0～15% COPP, 0～5% toughner, 0.3～0.6% oxidation inhibitor and 0～20% filler.
Wherein, said coupling agent is a silane coupling agent, and general formula is Y (CH
2)
nSiX, Y=vinyl, amino, epoxy group(ing), methacryloxy, sulfydryl or urea groups; N=0～3; X=chloro, methoxyl group, oxyethyl group, methoxy ethoxy or acetoxyl group.
Wherein, said toughner is a kind of in polyolefin elastomer, styrene block copolymer, polyethylene elastomer body or the ethylene-propylene rubber(EPR).
Wherein, said oxidation inhibitor is aromatic amine oxidation inhibitor, Hinered phenols antioxidant or auxiliary antioxidant.
Wherein, said filler is a kind of in talcum powder, lime carbonate, glass microballon or the maleic anhydride inoculated polypropylene waste material.
Prepare above-mentioned long glass fiber reinforced polypropylene composite sheet method, may further comprise the steps:
(1) measures Vestolen PP 7052, coupling agent, maleic anhydride inoculated polypropylene, COPP, toughner, oxidation inhibitor and filler by prescription, it is mixed;
(2) mixture is joined in twin screw extruder, processing temperature is at 180～240 ℃;
(3) mixed melt of twin screw extruder being extruded is injected No. two twin screw extruders, introduces the long glass fibres of preheating dispersive formula ratio simultaneously, and processing temperature is at 180～240 ℃;
(4) after heating finishes, the mixture in No. two twin screw extruders is extruded, by the four-wheel pressure roller it is pressed into the thick sheet material of 2～5mm, i.e. moulding again.
Wherein, the preheating temperature of said step (3) long glass fibres is 150～200 ℃.
Beneficial effect: the present invention compared with prior art has the following advantages:
Hang down 20～50% than glass mat strongthener (GMT) cost when (1) producing complex component, become the strong substitute technology of GMT;
(2) product strength, rigidity are improved, and overall performance is excellent;
(3) shaping cycle is short, and production efficiency is high, does not have leftover bits, and it is convenient to reclaim;
(4) performance of assurance long glass fiber reinforced plastic material products makes goods glass length distribution in about 10mm;
(5) cut down the consumption of energy, shorten the production cycle, save production cost;
(6) widen process window, material flexibility strengthens;
(7) be employed in the matrix Vestolen PP 7052 methods such as the functional poly propylene that adds grafted maleic anhydride, coupling agent, the interface of improving the glass fiber reinforced polyester compound system combines, and significantly improves the mechanical property of thermoplastic composite;
(8) in the plasticizing process, resin is difficult for degraded;
(9) glass fiber reinforced polypropylene material impelling strength is high.
Embodiment
Embodiment 1:
Get 50% Vestolen PP 7052 (unit is a weight percentage), 45% long glass fibres, 0.3% NH
2CH
2SiOCH
3, 1% maleic anhydride inoculated polypropylene, 1% COPP, 1% polyolefin elastomer, 0.7% pentanoic (aromatic amine oxidation inhibitor) and 1% talcum powder, long glass fibres is preheated to 150～200 ℃, other components are mixed; Mixture is joined in twin screw extruder, and processing temperature is at 180～240 ℃; The mixed melt that twin screw extruder is extruded is injected No. two twin screw extruders, introduce the long glass fibres of preheating dispersive simultaneously, processing temperature is at 180～240 ℃; After heating finishes, the mixture in No. two twin screw extruders is extruded, by the four-wheel pressure roller it is pressed into the thick sheet material of 2～5mm, i.e. moulding again.
Embodiment 2:
Get 55% Vestolen PP 7052 (unit is a weight percentage), 38% long glass fibres, 0.5% CH
2CH (CH) 2SiCl, 2% maleic anhydride inoculated polypropylene, 2% COPP, 0.5% styrene block copolymer and 2% the tertiary butyl are to biphenol (Hinered phenols antioxidant); Long glass fibres is preheated to 150～200 ℃, other components are mixed; Mixture is joined in twin screw extruder, and processing temperature is at 180～240 ℃; The mixed melt that twin screw extruder is extruded is injected No. two twin screw extruders, introduce the long glass fibres of preheating dispersive simultaneously, processing temperature is at 180～240 ℃; After heating finishes, the mixture in No. two twin screw extruders is extruded, by the four-wheel pressure roller it is pressed into the thick sheet material of 2～5mm, i.e. moulding again.
Embodiment 3:
Get 60% Vestolen PP 7052 (unit is a weight percentage), 32% long glass fibres, 1% H
2C (O) CHCH
2SiOC
2H
5, 1% maleic anhydride inoculated polypropylene, 2% COPP, 2% thio-2 acid dibasic acid esters (auxiliary antioxidant) and 2% lime carbonate, long glass fibres is preheated to 150～200 ℃, other components are mixed; Mixture is joined in twin screw extruder, and processing temperature is at 180～240 ℃; The mixed melt that twin screw extruder is extruded is injected No. two twin screw extruders, introduce the long glass fibres of preheating dispersive simultaneously, processing temperature is at 180～240 ℃; After heating finishes, the mixture in No. two twin screw extruders is extruded, by the four-wheel pressure roller it is pressed into the thick sheet material of 2～5mm, i.e. moulding again.
Embodiment 4:
Get 65% Vestolen PP 7052 (unit is a weight percentage), 28% long glass fibres, 0.5% HS (CH
2)
3SiOCH
3, 0.5% COPP, 1% polyethylene elastomer body, 3% Ursol D (aromatic amine oxidation inhibitor) and 2% glass microballon, long glass fibres is preheated to 150～200 ℃, other components are mixed; Mixture is joined in twin screw extruder, and processing temperature is at 180～240 ℃; The mixed melt that twin screw extruder is extruded is injected No. two twin screw extruders, introduce the long glass fibres of preheating dispersive simultaneously, processing temperature is at 180～240 ℃; After heating finishes, the mixture in No. two twin screw extruders is extruded, by the four-wheel pressure roller it is pressed into the thick sheet material of 2～5mm, i.e. moulding again.
Embodiment 5:
Get 70% Vestolen PP 7052 (unit is a weight percentage), 25% long glass fibres, 0.5% CH
2CHCH
2SiOC
2H
5, 1% maleic anhydride inoculated polypropylene, 2% ethylene-propylene rubber(EPR), 0.5% phosphorous acid ester (auxiliary antioxidant) and 1% talcum powder, long glass fibres is preheated to 150～200 ℃, other components are mixed; Mixture is joined in twin screw extruder, and processing temperature is at 180～240 ℃; The mixed melt that twin screw extruder is extruded is injected No. two twin screw extruders, introduce the long glass fibres of preheating dispersive simultaneously, processing temperature is at 180～240 ℃; After heating finishes, the mixture in No. two twin screw extruders is extruded, by the four-wheel pressure roller it is pressed into the thick sheet material of 2～5mm, i.e. moulding again.
Claims (7)
1. long glass fiber reinforced polypropylene composite sheet; It is characterized in that, comprise following components in weight percentage: 50～70% Vestolen PP 7052,25～45% long glass fibres, 0.3～1% coupling agent, 0～10% maleic anhydride inoculated polypropylene, 0～15% COPP, 0～5% toughner, 0.3～0.6% oxidation inhibitor and 0～20% filler.
2. long glass fiber reinforced polypropylene composite sheet according to claim 1 is characterized in that, said coupling agent is a silane coupling agent, and general formula is Y (CH
2)
nSiX, Y=vinyl, amino, epoxy group(ing), methacryloxy, sulfydryl or urea groups; N=0～3; X=chloro, methoxyl group, oxyethyl group, methoxy ethoxy or acetoxyl group.
3. long glass fiber reinforced polypropylene composite sheet according to claim 1 is characterized in that, said toughner is a kind of in polyolefin elastomer, styrene block copolymer, polyethylene elastomer body or the ethylene-propylene rubber(EPR).
4. long glass fiber reinforced polypropylene composite sheet according to claim 1 is characterized in that, said oxidation inhibitor is aromatic amine oxidation inhibitor, Hinered phenols antioxidant or auxiliary antioxidant.
5. long glass fiber reinforced polypropylene composite sheet according to claim 1 is characterized in that, said filler is a kind of in talcum powder, lime carbonate, glass microballon or the maleic anhydride inoculated polypropylene waste material.
6. the described long glass fiber reinforced polypropylene composite sheet of preparation claim 1 method is characterized in that, may further comprise the steps:
(1) measures Vestolen PP 7052, coupling agent, maleic anhydride inoculated polypropylene, COPP, toughner, oxidation inhibitor and filler by prescription, it is mixed;
(2) mixture is joined in twin screw extruder, processing temperature is at 180～240 ℃;
(3) mixed melt of twin screw extruder being extruded is injected No. two twin screw extruders, introduces the long glass fibres of preheating dispersive formula ratio simultaneously, and processing temperature is at 180～240 ℃;
(4) after heating finishes, the mixture in No. two twin screw extruders is extruded, by the four-wheel pressure roller it is pressed into the thick sheet material of 2～5mm, i.e. moulding again.
7. the method for preparing the long glass fiber reinforced polypropylene composite sheet according to claim 6 is characterized in that, the preheating temperature of said step (3) long glass fibres is 150～200 ℃.
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| CN201110269380A CN102311585A (en) | 2011-09-13 | 2011-09-13 | Long glass fiber reinforced polypropylene composite material and preparation method thereof |
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|---|---|---|---|
| CN201110269380A CN102311585A (en) | 2011-09-13 | 2011-09-13 | Long glass fiber reinforced polypropylene composite material and preparation method thereof |
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|---|---|
| CN102311585A true CN102311585A (en) | 2012-01-11 |
Family
ID=45425175
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|---|---|---|---|
| CN201110269380A Pending CN102311585A (en) | 2011-09-13 | 2011-09-13 | Long glass fiber reinforced polypropylene composite material and preparation method thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102581978A (en) * | 2012-01-13 | 2012-07-18 | 华南理工大学 | Method for preparing modified plastic granules by utilizing automobile waste glass fiber plastic interior trim part |
| CN103030891A (en) * | 2013-01-09 | 2013-04-10 | 华东理工大学 | Long glass fiber-reinforced polypropylene composite material and preparation method thereof |
| WO2013139264A1 (en) * | 2012-03-20 | 2013-09-26 | 深圳市科聚新材料有限公司 | Co-rotating twin screw extruder for processing lft-pp material |
| CN103341962A (en) * | 2013-07-15 | 2013-10-09 | 湘潭大学 | Scraped car upholstery recycling technique |
| CN103360677A (en) * | 2012-03-28 | 2013-10-23 | 辽宁辽杰科技有限公司 | Container top plate and preparation method thereof |
| CN103756125A (en) * | 2013-10-29 | 2014-04-30 | 奇瑞汽车股份有限公司 | Polypropylene composite material automobile water tank cross beam and preparation method thereof |
| CN105482242A (en) * | 2015-12-30 | 2016-04-13 | 上海普利特复合材料股份有限公司 | High-strength and high-toughness long glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN105542297A (en) * | 2016-03-16 | 2016-05-04 | 常州塑金高分子科技有限公司 | Regenerative composite for automobile parts and preparing technology of regenerative composite |
| CN105542310A (en) * | 2016-01-30 | 2016-05-04 | 珠海格力电器股份有限公司 | PP (Propene Polymer) resin composition, glass fiber reinforcement PP resin and preparation method of glass fiber reinforcement PP resin |
| CN106633584A (en) * | 2016-09-29 | 2017-05-10 | 中广核高新核材集团（东莞）祈富新材料有限公司 | High-rigidity glass fiber reinforced polypropylene material and preparation method of high-rigidity glass fiber reinforced polypropylene material |
| CN107892772A (en) * | 2017-11-23 | 2018-04-10 | 中钢集团马鞍山矿山研究院有限公司 | A kind of lightweight that resist warping continuous glass-fiber reinforced polypropylene compound material and preparation method |
| CN113337035A (en) * | 2020-10-31 | 2021-09-03 | 王永芳 | High-thermal-conductivity low-dielectric polypropylene continuous composite sheet composition and preparation method thereof |
| CN114806010A (en) * | 2022-04-12 | 2022-07-29 | 青岛中集创赢复合材料科技有限公司 | Composite sheet |
| CN115895116A (en) * | 2022-11-30 | 2023-04-04 | 珠海格力新材料有限公司 | Regenerated PP glass fiber material for enameled wire spool material and preparation method thereof |
| CN116728921A (en) * | 2023-08-14 | 2023-09-12 | 广州市华英防腐设备有限公司 | Thermoplastic composite board based on waste glass fiber product and application of thermoplastic composite board in aluminum profile oxidation |
| CN117089163A (en) * | 2023-08-30 | 2023-11-21 | 洛阳双瑞橡塑科技有限公司 | Light epoxy resin composite board, preparation process and preparation device |
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| CN101381492A (en) * | 2007-09-06 | 2009-03-11 | 比亚迪股份有限公司 | Polypropylene composite material and preparation method thereof |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102581978A (en) * | 2012-01-13 | 2012-07-18 | 华南理工大学 | Method for preparing modified plastic granules by utilizing automobile waste glass fiber plastic interior trim part |
| CN102581978B (en) * | 2012-01-13 | 2015-01-28 | 华南理工大学 | Method for preparing modified plastic granules by utilizing automobile waste glass fiber plastic interior trim part |
| WO2013139264A1 (en) * | 2012-03-20 | 2013-09-26 | 深圳市科聚新材料有限公司 | Co-rotating twin screw extruder for processing lft-pp material |
| CN103360677A (en) * | 2012-03-28 | 2013-10-23 | 辽宁辽杰科技有限公司 | Container top plate and preparation method thereof |
| CN103030891A (en) * | 2013-01-09 | 2013-04-10 | 华东理工大学 | Long glass fiber-reinforced polypropylene composite material and preparation method thereof |
| CN103341962A (en) * | 2013-07-15 | 2013-10-09 | 湘潭大学 | Scraped car upholstery recycling technique |
| CN103341962B (en) * | 2013-07-15 | 2016-01-06 | 湘潭大学 | A kind of technique of abandoned car inside gadget recycling |
| CN103756125A (en) * | 2013-10-29 | 2014-04-30 | 奇瑞汽车股份有限公司 | Polypropylene composite material automobile water tank cross beam and preparation method thereof |
| CN103756125B (en) * | 2013-10-29 | 2016-05-18 | 奇瑞汽车股份有限公司 | A kind of PP composite material cross beams of automobile water tank and preparation method |
| CN105482242A (en) * | 2015-12-30 | 2016-04-13 | 上海普利特复合材料股份有限公司 | High-strength and high-toughness long glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN105542310A (en) * | 2016-01-30 | 2016-05-04 | 珠海格力电器股份有限公司 | PP (Propene Polymer) resin composition, glass fiber reinforcement PP resin and preparation method of glass fiber reinforcement PP resin |
| CN105542297A (en) * | 2016-03-16 | 2016-05-04 | 常州塑金高分子科技有限公司 | Regenerative composite for automobile parts and preparing technology of regenerative composite |
| CN106633584A (en) * | 2016-09-29 | 2017-05-10 | 中广核高新核材集团（东莞）祈富新材料有限公司 | High-rigidity glass fiber reinforced polypropylene material and preparation method of high-rigidity glass fiber reinforced polypropylene material |
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| CN113337035A (en) * | 2020-10-31 | 2021-09-03 | 王永芳 | High-thermal-conductivity low-dielectric polypropylene continuous composite sheet composition and preparation method thereof |
| CN114806010A (en) * | 2022-04-12 | 2022-07-29 | 青岛中集创赢复合材料科技有限公司 | Composite sheet |
| CN114806010B (en) * | 2022-04-12 | 2023-08-29 | 青岛中集创赢复合材料科技有限公司 | Composite sheet |
| CN115895116A (en) * | 2022-11-30 | 2023-04-04 | 珠海格力新材料有限公司 | Regenerated PP glass fiber material for enameled wire spool material and preparation method thereof |
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| CN116728921A (en) * | 2023-08-14 | 2023-09-12 | 广州市华英防腐设备有限公司 | Thermoplastic composite board based on waste glass fiber product and application of thermoplastic composite board in aluminum profile oxidation |
| CN116728921B (en) * | 2023-08-14 | 2023-11-10 | 广州市华英防腐设备有限公司 | Thermoplastic composite board based on waste glass fiber product and application of thermoplastic composite board in aluminum profile oxidation |
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Application publication date: 20120111 |