CN103112224A - Self-reinforced polypropylene composite material and preparation method thereof - Google Patents
Self-reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a self-reinforced polypropylene composite material and a preparation method thereof. The preparation method comprises the following steps: preparing a sheet composed of high-melting-point polypropylene and low-melting-point polypropylene by screw coextrusion, separating the sheet into strips which are 5-20mm wide, carrying out hot stretching, and coiling into cylinders; weaving the cylindrical strips into a fabric; and finally, carrying out hot pressing on a plurality of layers of fabrics to obtain the composite material. Compared with the prior art, the invention widens the hot pressing temperature window of the self-reinforced polypropylene composite material sheet, and the prepared product has favorable properties.
Description
Technical field
The invention belongs to the composite preparation field, especially relate to a kind of self-reinforcing PP composite material and preparation method thereof.
Background technology
Be to improve intensity and the hardness of bulk polymer, fibre reinforcement is used for structural enhancing polymer widely.But be generally the material of two kinds of different components due to fortifying fibre and matrix, as glass fiber reinforced polypropylene, this makes the recycling of material very difficult; Simultaneously due to comprise between reinforcement and matrix the surface can physics, the difference of chemical property, make directly to form good interface between both to be used for effectively transmitting stress also comparatively difficult.So researchers attempt to develop the composite that matrix and reinforcement have identical chemical composition and physical arrangement.
The researcher of the Leeds university of Britain has proposed single polymers composite (single polymer composites for the first time take the high density polyethylene (HDPE) system as the basis in 1975, SPC) concept---matrix and reinforcement are that the different shape by similar polymers is consisted of, the domestic self-reinforcing polymer that is referred to as.
The people such as Abo El Maaty attempt utilizing pressure sintering to prepare self-reinforcing PP composite first.
The people such as Hine utilize hot pressing to prepare self-reinforcing PP composite to the PP fabric and are studied, research finds that PP fabric hot pressing optimum temperature is 182 ℃, degree of crystallinity increases by 20% at this temperature, its good mechanical performance is the crystallizing layer that forms due between PP band and PP matrix, and points out that the molecular weight of PP matrix and geometry and the weaving mode of degree of crystallinity and enhancing PP fabric all will affect the mechanical performance of final composite.
The people such as Loos are studied the form of the isotactic PP enhancing isotactic PP matrix of high elongation, point out that again between matrix and fortifying fibre, being formed with of crystallizing layer is beneficial to the mechanical performance that improves composite.
The people such as Houshyar are studied mechanical property and the thermal property that PP strengthens random PPE composite reinforced fiber content, and the increase along with fiber content is pointed out in research, and stretching, elasticity and storage modulus also can increase.
The main manufacture methods of self-reinforced composite material has pellicular cascade method, melting (solution or powder) infusion process and pressure sintering at present.
The pellicular cascade method be with the polymer fiber uniform winding on a metal frame, repave into the matrix film, metallic plate is exerted pressure in addition up and down, fiber and matrix both the suitable temperature between melt temperature make polymeric matrix generation melting and impregnated polymer fiber, matrix crystallization and the fiber that disperses is bonded together and forms high performance composite in cooling procedure subsequently.The shortcoming of the method is that the high viscosity under the matrix molten condition is difficult to form perfect the infiltration to fiber, and the bubble in system can't be discharged fully, affects to a certain extent the overall performance of composite;
Melting (solution or powder) infusion process is similar to glass and strengthens PP composite melting (solution or powder) infusion process used, also to utilize full-bodied thermoplastic resin-impregnated fibers reinforcement, consider production cost, generally use low-molecular-weight resin impregnation of fibers reinforcement.The method production process is slower, and cost is higher, and fibre reinforcement may make its mechanical performance reduce because of local dissolution or melting;
Pressure sintering is that polymer fiber or band are under the restriction of certain pressure, be under the temperature action of its fusion range, the space that fiber or bar interband are filled up in optionally appropriate melting occurs in fiber or strip face, and the most of high orientation of fiber or band is kept simultaneously.The technological temperature scope of the method extremely narrow (1-2 ℃) has limited it in technologic application, the work complex process.
Summary of the invention
Purpose of the present invention is exactly the preparation method that the height-oriented self-reinforcing PP composite material of a kind of wide hot pressing temperature window, polypropylene is provided in order to overcome the defective that above-mentioned prior art exists.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of self-reinforcing PP composite material, the material of the layer structure that obtains through hot pressing for the sheet material of 2-8 layer, plain weave, twill, satin weave or the three-dimensional fabric of the sheet material of each layer for obtaining through the braiding of cylinder band.
Described sheet material is three-decker, and the intermediate layer of sheet material is the high isotactic polypropylene of fusing point, and the upper and lower surface in intermediate layer is the superficial layer that low-melting atactic copolymerized polypropene consists of.
A kind of preparation method of self-reinforcing PP composite material comprises the following steps:
(1) utilize screw rod coextrusion preparation by the sheet material that high-melting-point polypropylene and low melting point polypropylene form, then sheet material is divided into the wide band of 5-20mm, coil into cylinder through after hot-stretch;
(2) will become the cylinder band to be woven into fabric;
(3) multiply cloth is hot pressed into composite, namely obtains the self-reinforcing PP composite material.
High-melting-point polypropylene described in step (1) is isotactic polypropylene.
Low melting point polypropylene described in step (1) is atactic copolymerized polypropene.
Sheet material described in step (1) is three-decker, and the high-melting-point polypropylene constitutes the intermediate layer, and the low melting point polypropylene consists of two superficial layers in up and down, and the mass percent of superficial layer is 5%～10%.
Hot-stretch described in step (1) is a step or two step hot-stretch, and draft temperature is 120 ℃-140 ℃, and draw ratio is 5-30.
Fabric described in step (2) is plain weave, twill, satin weave or three-dimensional fabric.
Hot pressing described in step (3) is two roller hot pressing or dull and stereotyped hot pressing, and hot pressing temperature is 160-190 ℃, and the time is 10-60s.
Multiply cloth described in step (3) is the fabric of 2-8 layer.
Compared with prior art, the present invention has following characteristics and advantage:
1. the hot pressing temperature scope is 30 ℃, has increased its process application scope;
2. the height-oriented of high-melting-point polypropylene strap can most of keep, compared large increase available from the hot strength of reinforced polypropylene compound material with the plain polypropylene material, its hot strength reaches 160MPa;
3. all there is the low melting point polypropylene surface layer that serves as cohesive action evenly to distribute due to layer and interlayer, make the speed of cohering between the high-melting-point polypropylene strap and cohere efficient and greatly improve, and improve shock resistance and the compressive strength of its composite, its notched Izod impact strength reaches 4300J/m, and compressive strength is greater than 260MPa;
4. production technology is simple, and equipment energy consumption is low.
Description of drawings
Fig. 1 is the structural representation of sheet material;
Fig. 2 is screw rod coextrusion processes flow chart;
Fig. 3 is the weaving flow chart;
Fig. 4 is the heat pressing process flow chart.
The specific embodiment
The present invention is further described below in conjunction with the drawings and specific embodiments.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
referring to Fig. 2, high-melting-point isotactic polypropylene and low melting point atactic copolymerized polypropene are added respectively two spiral shell coextrusion machines 1 (or single screw rod coextrusion machine), obtain to have " sandwich " the crystalline p p sheet of structure (as shown in Figure 1) by coextrusion, the isotactic polypropylene that wherein fusing point is high is positioned at the intermediate layer of sheet material, low-melting atactic copolymerized polypropene is positioned at two superficial layers, the mass percent of superficial layer is 5%～10%, then be divided into the wide band of 5-20mm with rounding knife 2, through coiling into bobbin 4 after baking oven 3 hot-stretch, its oven temperature is 120 ℃-140 ℃, draw ratio is 10-30.
Referring to Fig. 3, above-mentioned technological process is obtained band bobbin 4 be placed on bobbin cradle 5, obtain required fabric 6 by weaving.
Referring to Fig. 4, obtaining fabric 6 is placed on conveying roller 7, then make multilayer self-reinforcing PP composite material through flat-bed press 8, its number of plies is the 2-8 layer, and hot pressing temperature is 160-190 ℃, and the time is 10-60s.Because the height-oriented of high-melting-point polypropylene strap can most ofly keep, the hot strength of the composite that obtains has had large increase; Layer all has the low melting point polypropylene surface layer that serves as cohesive action evenly to distribute with interlayer in addition, makes the speed of cohering between the high-melting-point polypropylene strap and coheres efficient and greatly improve, and improving shock resistance and the compressive strength of its composite.
Embodiment 1
A kind of preparation method of self-reinforcing PP composite material:
(1) the standby height-oriented polypropylene strap of twin-screw co-extrusion:
High-melting-point isotactic polypropylene and low melting point atactic copolymerized polypropene are added respectively two single-screw machines, regulate pump and make the extrusion capacity of high-melting-point isotactic polypropylene and low melting point atactic copolymerized polypropene be controlled to be 9: 1 for amount, obtain the crystalline p p sheet of " sandwich " structure by co-extrusion die; Utilize rounding knife that obtaining sheet material is divided into the wide band of 10mm; The band that to cut apart through the infrared heating ovens of 135 ℃ stretches 24 times, wherein is stretched as two step hot-stretch, and the ribbon curling after stretching is become cylinder.
(2) woven polypropylene bar narrow fabrics:
Above-mentioned technological process is obtained the band bobbin be placed on bobbin cradle, obtain plain cloth by weaving.
(3) pressure sintering prepares the self-reinforcing PP composite material:
4 volume plains cloth are placed on conveying roller, pass through flat-bed press at 170 ℃ of hot pressing 30s, at last the self-reinforcing PP composite material with 4 layers of structure of system.
Following table is self-reinforcing PP composite material and the plain polypropylene performance comparison that example is made:
| Typical case's performance | The self-reinforcing polypropylene | HOPP |
| Notched Izod impact strength (J/m)+20 ℃ | 4300 | 200 |
| Hot strength (MPa) | 160 | 25 |
| Compressive strength (MPa) | ＞260 | 46 |
Embodiment 2
A kind of self-reinforcing PP composite material, the material of the layer structure that this composite is obtained through hot pressing by the sheet material of 2 layers, the plain cloth of the sheet material of each layer for obtaining through the braiding of cylinder band, sheet material is three-decker, the intermediate layer of sheet material is the high isotactic polypropylene of fusing point, and the upper and lower surface in intermediate layer is the superficial layer that low-melting atactic copolymerized polypropene consists of.The preparation method of self-reinforcing PP composite material comprises the following steps:
(1) sheet material that utilizes screw rod coextrusion preparation to be formed by dystectic isotactic polypropylene and low melting point atactic copolymerized polypropene, the high-melting-point polypropylene constitutes the intermediate layer, the low melting point polypropylene consists of two superficial layers in up and down, the mass percent of superficial layer is 5%, then sheet material is divided into the wide band of 5mm, the restrained stretching temperature is 120 ℃, and draw ratio is 5 times, through coiling into cylinder after a step hot-stretch;
(2) will become the cylinder band to be woven into plain cloth;
(3) controlling hot pressing temperature is 160 ℃, and the time is 10s, and 2 layers of fabric are obtained composite by dull and stereotyped hot pressing, is self-reinforcing PP composite material product.
A kind of self-reinforcing PP composite material, the material of the layer structure that this composite is obtained through hot pressing by the sheet material of 5 layers, the twills of the sheet material of each layer for obtaining through the braiding of cylinder band, sheet material is three-decker, the intermediate layer of sheet material is the high isotactic polypropylene of fusing point, and the upper and lower surface in intermediate layer is the superficial layer that low-melting atactic copolymerized polypropene consists of.The preparation method of self-reinforcing PP composite material comprises the following steps:
(1) sheet material that utilizes screw rod coextrusion preparation to be formed by dystectic isotactic polypropylene and low melting point atactic copolymerized polypropene, the high-melting-point polypropylene constitutes the intermediate layer, the low melting point polypropylene consists of two superficial layers in up and down, the mass percent of superficial layer is 7%, then sheet material is divided into the wide band of 10mm, the restrained stretching temperature is 130 ℃, and draw ratio is 10 times, through coiling into cylinder after a step hot-stretch;
(2) will become the cylinder band to be woven into twills;
(3) controlling hot pressing temperature is 170 ℃, and the time is 30s, and 5 layers of fabric are obtained composite by dull and stereotyped hot pressing, is self-reinforcing PP composite material product.
A kind of self-reinforcing PP composite material, the material of the layer structure that this composite is obtained through hot pressing by the sheet material of 6 layers, the satin fabric of the sheet material of each layer for obtaining through the braiding of cylinder band, sheet material is three-decker, the intermediate layer of sheet material is the high isotactic polypropylene of fusing point, and the upper and lower surface in intermediate layer is the superficial layer that low-melting atactic copolymerized polypropene consists of.The preparation method of self-reinforcing PP composite material comprises the following steps:
(1) sheet material that utilizes screw rod coextrusion preparation to be formed by dystectic isotactic polypropylene and low melting point atactic copolymerized polypropene, the high-melting-point polypropylene constitutes the intermediate layer, the low melting point polypropylene consists of two superficial layers in up and down, the mass percent of superficial layer is 8%, then sheet material is divided into the wide band of 10mm, the restrained stretching temperature is 130 ℃, and draw ratio is 20 times, through coiling into cylinder after two step hot-stretch;
(2) will become the cylinder band to be woven into satin fabric;
(3) controlling hot pressing temperature is 180 ℃, and the time is 40s, and 6 layers of fabric are obtained composite by two roller hot pressing, is self-reinforcing PP composite material product.
Embodiment 5
A kind of self-reinforcing PP composite material, the material of the layer structure that this composite is obtained through hot pressing by the sheet material of 8 layers, the three-dimensional braid of the sheet material of each layer for obtaining through the braiding of cylinder band, sheet material is three-decker, the intermediate layer of sheet material is the high isotactic polypropylene of fusing point, and the upper and lower surface in intermediate layer is the superficial layer that low-melting atactic copolymerized polypropene consists of.The preparation method of self-reinforcing PP composite material comprises the following steps:
(1) sheet material that utilizes screw rod coextrusion preparation to be formed by dystectic isotactic polypropylene and low melting point atactic copolymerized polypropene, the high-melting-point polypropylene constitutes the intermediate layer, the low melting point polypropylene consists of two superficial layers in up and down, the mass percent of superficial layer is 10%, then sheet material is divided into the wide band of 20mm, the restrained stretching temperature is 140 ℃, and draw ratio is 30 times, through coiling into cylinder after two step hot-stretch;
(2) will become the cylinder band to be woven into three-dimensional braid;
(3) controlling hot pressing temperature is 190 ℃, and the time is 60s, and 8 layers of fabric are obtained composite by two roller hot pressing, is self-reinforcing PP composite material product.
Claims (10)
1. a self-reinforcing PP composite material, is characterized in that, this composite is the material of the layer structure that obtains through hot pressing of the sheet material of 2-8 layer, plain weave, twill, satin weave or the three-dimensional fabric of the sheet material of each layer for obtaining through the braiding of cylinder band.
2. a kind of self-reinforcing PP composite material according to claim 1, it is characterized in that, described sheet material is three-decker, and the intermediate layer of sheet material is the high isotactic polypropylene of fusing point, and the upper and lower surface in intermediate layer is the superficial layer that low-melting atactic copolymerized polypropene consists of.
3. the preparation method of a self-reinforcing PP composite material, is characterized in that, the method comprises the following steps:
(1) utilize screw rod coextrusion preparation by the sheet material that high-melting-point polypropylene and low melting point polypropylene form, then sheet material is divided into the wide band of 5-20mm, coil into cylinder through after hot-stretch;
(2) will become the cylinder band to be woven into fabric;
(3) multiply cloth is hot pressed into composite, namely obtains the self-reinforcing PP composite material.
4. the preparation method of a kind of self-reinforcing PP composite material according to claim 3, is characterized in that, the high-melting-point polypropylene described in step (1) is isotactic polypropylene.
5. the preparation method of a kind of self-reinforcing PP composite material according to claim 3, is characterized in that, the low melting point polypropylene described in step (1) is atactic copolymerized polypropene.
6. the preparation method of a kind of self-reinforcing PP composite material according to claim 3, it is characterized in that, sheet material described in step (1) is three-decker, the high-melting-point polypropylene constitutes the intermediate layer, the low melting point polypropylene consists of two superficial layers in up and down, and the mass percent of superficial layer is 5%～10%.
7. the preparation method of a kind of self-reinforcing PP composite material according to claim 3, is characterized in that, the hot-stretch described in step (1) is a step or two step hot-stretch, and draft temperature is 120 ℃-140 ℃, and draw ratio is 5-30.
8. the preparation method of a kind of self-reinforcing PP composite material according to claim 3, is characterized in that, the fabric described in step (2) is plain weave, twill, satin weave or three-dimensional fabric.
9. the preparation method of a kind of self-reinforcing PP composite material according to claim 3, is characterized in that, the hot pressing described in step (3) is two roller hot pressing or dull and stereotyped hot pressing, and hot pressing temperature is 160-190 ℃, and the time is 10-60s.
10. the preparation method of a kind of self-reinforcing PP composite material according to claim 3, is characterized in that, the multiply cloth described in step (3) is the fabric of 2-8 layer.
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| CN103707583A (en) * | 2013-12-25 | 2014-04-09 | 北京工商大学 | Reinforced polypropylene composite board and production method thereof |
| CN105172277A (en) * | 2015-10-30 | 2015-12-23 | 成都同明新材料技术有限公司 | Self-reinforcing polypropylene composite panel |
| CN105566744A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Polypropylene self-reinforced composite and preparation method thereof |
| CN105563976A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Polypropylene self-reinforced composite and preparation method thereof |
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| CN106739207A (en) * | 2015-11-21 | 2017-05-31 | 华东理工大学 | A kind of method using continuously polypropylene self-reinforced composite material is prepared to roll squeezer pressurization |
| CN106739387A (en) * | 2015-11-21 | 2017-05-31 | 华东理工大学 | A kind of continuous method for preparing polypropylene self-reinforced composite material of use double-steel belt pressing machine pressurization |
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| WO2021056247A1 (en) * | 2019-09-25 | 2021-04-01 | 佐福（天津）科技有限公司 | Non-woven fabric and processing device for non-woven fabric |
| US11330877B2 (en) | 2017-04-27 | 2022-05-17 | Paua Trading Limited | Protective case or cover |
| US11576473B2 (en) | 2015-10-21 | 2023-02-14 | Paua Trading Limited | Case or cover for hobby equipment |
| WO2023078441A1 (en) * | 2021-11-08 | 2023-05-11 | 中国石油化工股份有限公司 | Polypropylene composite material having melting point gradient structure, preparation method therefor and system and use thereof |
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| CN103707583A (en) * | 2013-12-25 | 2014-04-09 | 北京工商大学 | Reinforced polypropylene composite board and production method thereof |
| CN105566744A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Polypropylene self-reinforced composite and preparation method thereof |
| CN105563976A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Polypropylene self-reinforced composite and preparation method thereof |
| CN105563976B (en) * | 2014-10-15 | 2018-03-02 | 中国石油化工股份有限公司 | A kind of polypropylene self-reinforced composite material and preparation method thereof |
| CN105566744B (en) * | 2014-10-15 | 2018-03-02 | 中国石油化工股份有限公司 | A kind of polypropylene self-reinforced composite material and preparation method thereof |
| US11576473B2 (en) | 2015-10-21 | 2023-02-14 | Paua Trading Limited | Case or cover for hobby equipment |
| US11931645B2 (en) | 2015-10-21 | 2024-03-19 | Paua Trading Limited | Case or cover for hobby equipment |
| CN105172277A (en) * | 2015-10-30 | 2015-12-23 | 成都同明新材料技术有限公司 | Self-reinforcing polypropylene composite panel |
| CN106739207A (en) * | 2015-11-21 | 2017-05-31 | 华东理工大学 | A kind of method using continuously polypropylene self-reinforced composite material is prepared to roll squeezer pressurization |
| CN106739387A (en) * | 2015-11-21 | 2017-05-31 | 华东理工大学 | A kind of continuous method for preparing polypropylene self-reinforced composite material of use double-steel belt pressing machine pressurization |
| CN106273527A (en) * | 2016-09-06 | 2017-01-04 | 安徽开润股份有限公司 | A kind of production method of the high intensity hot-forming composite of film woven cloth |
| CN106994799A (en) * | 2017-03-15 | 2017-08-01 | 浙江正基塑业有限公司 | A kind of resistance to fracture plate and preparation method thereof |
| US11330877B2 (en) | 2017-04-27 | 2022-05-17 | Paua Trading Limited | Protective case or cover |
| US11350715B2 (en) | 2017-04-27 | 2022-06-07 | Paua Trading Limited | Protective case or cover |
| US11627787B2 (en) | 2017-04-27 | 2023-04-18 | Paua Trading Limited | Protective case or cover |
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| CN112318985A (en) * | 2020-11-10 | 2021-02-05 | 烟台正海合泰科技股份有限公司 | Non-woven fabric with glue-blocking film and production method thereof |
| WO2023078441A1 (en) * | 2021-11-08 | 2023-05-11 | 中国石油化工股份有限公司 | Polypropylene composite material having melting point gradient structure, preparation method therefor and system and use thereof |
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Application publication date: 20130522 |