CN115771322A - Bio-based polyamide composite board and preparation method and application thereof - Google Patents
Bio-based polyamide composite board and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a bio-based polyamide composite board, which comprises a first surface layer, a middle layer and a second surface layer; the first surface layer, the middle layer and the second surface layer are sequentially stacked; the first surface layer and the second surface layer are long carbon chain polyamide resin unidirectional prepreg tapes, and the middle layer is a composite material layer of bio-based polyamide 56 silk glass fiber blended cloth and fiber cloth. The composite board compression molding ensures the processing rate and the efficient molding of the board, improves the mechanical property and the thermal deformation temperature of the composite board, reduces the water absorption rate of the composite board, has light overall weight, and meets the requirement of lightweight boards.
Description
The application claims application date is 2021/9/6, which is named as a bio-based polyamide composite board and a preparation method thereof, and the priority of Chinese patent application 2021110369262 which is 2021/9/6, named as a bio-based polyamide composite board, and Chinese patent application 2021221405126 which is 2021/9/6. The present application refers to the above-mentioned chinese patent application in its entirety.
Technical Field
The invention relates to a bio-based polyamide composite board and a preparation method and application thereof.
Background
The composite material plays an important role in many fields and also replaces many traditional materials. The forming process of the composite material mainly comprises winding forming, laying forming, compression molding, autoclave forming, resin transfer molding forming and the like. The composite forming process generally comprises two stages, first of all deforming or flowing the raw material at a certain temperature and pressure, obtaining the desired shape, and then trying to maintain its shape. Different forming methods can be selected according to different raw materials. The compression molding method is relatively simple and efficient. The composite material compression molding process mainly comprises the following steps: the design of a forming die, the design of a laying layer, the forming of a composite material component, the characteristics of a compression molding process, factors influencing the quality of a molded product and the like. The plate prepared by the composite material through compression molding is applied to various fields.
The bio-based polyamide resin is a semi-crystalline thermoplastic polymer, part or all of synthetic monomers are derived from biomass, and the bio-based polyamide resin has the characteristics of sustainable raw material sources, green and environment-friendly preparation process, recyclable products and recyclability, can keep higher rigidity and strength at higher temperature, and is excellent fiber reinforced thermoplastic composite resin.
In the injection molding method, the structure of the glass fiber is easily damaged due to the secondary heating and the shearing action of the screw on the glass fiber, so that the final performance of the composite material is influenced. The PVC wood-plastic composite board is limited by the resin matrix, and has the advantages of low use temperature, small modulus, poor strength and high water absorption rate. The thermosetting composite material is influenced by the forming process, and has high processing cost and poor heat resistance. Therefore, in order to adapt the polyamide composite material to more complicated use occasions, widen the use temperature, reduce the water absorption influence and increase the light weight, it is necessary to design and develop a composite board with high strength, high heat deformation temperature and low water absorption and a preparation process thereof.
Disclosure of Invention
The invention provides a bio-based polyamide composite board and a preparation method and application thereof, aiming at improving the performance of the existing polyamide composite board and widening the use scene. The bio-based polyamide composite board disclosed by the invention is formed by compression molding the mixed woven fabric of the bio-based polyamide filaments and the glass fibers, the fiber fabric and the bio-based polyamide unidirectional prepreg tape, so that the processing rate and the efficient forming of the board are ensured, the mechanical property and the thermal deformation temperature of the composite board are improved, the water absorption rate of the composite board is reduced, the overall weight is light, and the requirement of a light-weight board is further met.
The relative viscosity of the present invention is measured by the Ubbelohde viscometer concentrated sulfuric acid method (96%). The biobased content is determined by carbon 14, for example by biobased content test standard method ASTM D6866.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the technical schemes is as follows: a bio-based polyamide composite board comprises a first surface layer, a middle layer and a second surface layer; the first surface layer, the middle layer and the second surface layer are sequentially stacked; the first surface layer and the second surface layer are long carbon chain polyamide resin unidirectional prepreg tapes, and the middle layer is a composite material layer of bio-based polyamide 56 silk-glass fiber blended cloth and fiber cloth.
Long carbon chain polyamide resin unidirectional prepreg tape:
in the present invention, the long carbon chain polyamide resin unidirectional prepreg tape may be a material known in the art.
In some specific embodiments, the long carbon chain polyamide resin unidirectional prepreg tape is a continuous long fiber reinforced long carbon chain polyamide resin unidirectional prepreg tape comprising a continuous long fiber and a biobased long carbon chain polyamide 5X resin; the mass percentage of the continuous long fibers is 40 to 80%, more preferably 60 to 70%, for example 32.8%, and the mass percentage is the mass of the continuous long fibers in the mass of the prepreg tape.
In some specific embodiments, the bio-based long carbon chain polyamide 5X resin is selected from one or more of PA510, PA511, PA512, PA513, PA514, PA515, PA516, PA517, and PA 518. Wherein the relative viscosity of the bio-based long carbon chain polyamide resin is 1.8-2.7, preferably 2.1-2.8; the content of terminal amino groups is 42-60mmol/kg; melting point 170-320 deg.C, preferably 180-230 deg.C; the content of biobased is 28% -100%.
In some specific embodiments, the bio-based long carbon chain polyamide 5X resin is PA510 with a viscosity of 2.51, a terminal amino group content of 54mmol/kg, and a melting point of 217 ℃.
In some specific embodiments, the bio-based long carbon chain polyamide 5X resin is PA512 with a viscosity of 2.32, a terminal amino group content of 56mmol/kg, and a melting point of 210 ℃.
In some specific embodiments, the continuous long fibers may be continuous long fibers conventionally available in the art and may be of the kind conventionally available in the art, such as carbon fibers, glass fibers, basalt fibers, or aramid fibers.
In some embodiments, the continuous long fibers are continuous long glass fibers, and the monofilament diameter may be 8 to 20 μm, preferably 8 to 15 μm or 15 to 20 μm, and more preferably 8 to 10 μm. The linear density of the continuous long glass fiber is 500-3600Tex, preferably 1200Tex and 2400Tex. The continuous long glass fiber is, for example, a 1200Tex continuous long glass fiber available from Owens Costing (OC) and a 2400Tex continuous long glass fiber available from boulders.
In some specific embodiments, the continuous long fibers are continuous long carbon fibers. The continuous long carbon fiber is preferably a polyacrylonitrile-based carbon fiber. The number of filaments of the continuous long carbon fiber may be 8000 to 50000, preferably 20000 to 30000, more preferably 8000, 12000 (12K), 24000 (24K), 45000. The continuous long carbon fibers may have a monofilament diameter of 5 to 10 μm, preferably 6 to 8 μm. The continuous long carbon fiber is, for example, dongli T700 with a specification of 24K, or Guangwei composite material continuous long carbon fiber 700S with a specification of 12K or 24K.
In some embodiments, the long carbon chain polyamide resin unidirectional prepreg tape is prepared by a melt impregnation method. Among them, the melt impregnation method may be a melt impregnation method that is conventional in the art.
In some specific embodiments, the melt impregnation method comprises the steps of:
s1, stirring and mixing a long-carbon-chain polyamide resin composition containing the long-carbon-chain polyamide 5X resin, extruding by a double-screw extruder (the length and diameter ratio is preferably 1; preferably, the double-screw extruder adopts an eight-zone heating mode, and the temperatures of the first zone to the eight zones (feeding to a machine head) are 195-260 ℃, 255-305 ℃, 255-325 ℃ and 255-325 ℃ in sequence.
S2, introducing the continuous long fiber into the impregnation die head, and impregnating the melt and the continuous long fiber; the temperature of the impregnation die head can be 240-335 ℃; the introduction preferably comprises the following processes: unwinding the continuous long fiber from a creel through a tension controller, passing through a yarn dividing frame, entering a yarn spreading system to fully spread each tow, then entering a yarn drying device for preheating, and then entering an impregnation die head to impregnate the continuous long fiber with the melt, wherein the temperature of the yarn drying device is preferably 70-400 ℃;
s3, shaping, cooling, drawing and winding the impregnated continuous long fiber to obtain the long carbon chain polyamide resin unidirectional prepreg tape;
in some specific embodiments, the shaping, cooling can be performed using a four roll machine as is conventional in the art; the four-roller machine mainly comprises a setting roller and a cooling roller, wherein the setting roller plays a role in secondary infiltration and cooling forming, the cooling roller plays a role in cooling forming, the temperature of internal circulation oil in the setting roller can be 30-250 ℃, and the four-roller machine comprises the following components in percentage by weight: 90 ℃, 120 ℃, 150 ℃ and 180 ℃; the temperature of the internally circulating water in the cooling roll may be 15 to 90 c, preferably 15 to 40 c, for example 20 c, or 60 to 90 c, for example 80 c. The drawing can be carried out using drawing devices conventional in the art, in which further cooling and trimming takes place. The speed of the traction can be 5-15m/min. The winding can be carried out using winding devices conventional in the art, preferably an automatic winder, and the winding speed can be from 5 to 15m/min.
In some specific embodiments, the long carbon chain polyamide resin composition comprises the following components in parts by weight: 90-95 parts of long carbon chain polyamide 5X resin, 0.4-0.6 part of antioxidant, 0.3-0.5 part of lubricant, 4-8 parts of compatilizer and 0.4-0.5 part of coupling agent. Wherein, the antioxidant is preferably selected from one or more of antioxidant 168, antioxidant 1098, antioxidant 1010 and antioxidant S9228. Wherein the lubricant comprises WAXC and WAXE. Wherein the compatilizer can be one or more selected from PP-g-MAH, POE-g-GMA or EPDM-g-MAH. Wherein the coupling agent can be selected from one or more of a coupling agent KH550, a coupling agent KH560 or a coupling agent KH 570.
In some specific embodiments, the long carbon chain polyamide resin unidirectional prepreg tape has a thickness of 0.15 to 0.5mm, preferably 0.21 to 0.33mm, e.g., 0.31mm,0.32mm,0.33mm.
In some specific embodiments, the long carbon chain polyamide resin unidirectional prepreg tape may be a polyamide glass fiber composite prepreg tape, a polyamide aramid fiber composite prepreg tape, a polyamide basalt fiber composite prepreg tape, a polyamide boron fiber composite prepreg tape, or a polyamide carbon fiber composite prepreg tape.
In some specific embodiments, the long carbon chain polyamide resin unidirectional prepreg tape may be a continuous long glass fiber reinforced long carbon chain polyamide thermoplastic unidirectional prepreg tape or a continuous long carbon fiber reinforced long carbon chain polyamide thermoplastic unidirectional prepreg tape, such as the continuous long fiber reinforced long carbon chain polyamide resin unidirectional prepreg tape disclosed in patent CN 113232384A.
The bio-based polyamide 56 silk glass fiber blended cloth comprises the following components:
in the present invention, the bio-based polyamide 56 silk glass fiber blended cloth may be a material known in the art.
According to the invention, the bio-based polyamide 56 silk glass fiber blended fabric is prepared by blending bio-based polyamide 56 silk/glass fiber mixed silk, the bio-based polyamide 56 silk/glass fiber mixed silk is prepared by mixing bio-based polyamide 56 silk and glass fiber, and the mass ratio of the bio-based polyamide 56 silk to the glass fiber is 1:0.15-4.
In some specific embodiments, in the mixed silk of bio-based polyamide 56 and glass fiber, the linear density ratio of the bio-based polyamide 56 silk to the glass fiber is 1:0.15 to 4, preferably 1:1.
in some specific embodiments, the bio-based polyamide 56 silk is prepared according to the method disclosed in chinese patent CN 110373736A.
In some specific embodiments, the bio-based polyamide 56 filaments have a breaking strength of 2.5 to 5.5cN/dtex, an elongation at break of 40 to 100%, and a dry heat shrinkage of 5 to 10%.
In some specific embodiments, the glass fibers are continuous long glass fibers.
In some specific embodiments, the glass fibers have a filament diameter of 5 to 20 μm.
In some specific embodiments, the glass fibers have a linear density of 1000 to 3600Tex, such as 1200Tex, 2400Tex.
In some specific embodiments, the glass fibers have a moisture content of 0.10% or less.
In some specific embodiments, the bio-based polyamide 56 filament/glass fiber mixed filament is obtained by twisting the bio-based polyamide 56 filament and glass fiber by a twisting machine.
In some specific embodiments, the warp yarn and the weft yarn of the bio-based polyamide 56 filament glass fiber blended cloth are both bio-based polyamide 56 filament/glass fiber blended filaments.
In some specific embodiments, the linear density ratio of the warp yarns and the weft yarns of the bio-based polyamide 56 silk glass fiber blended fabric is 1:0.5-3, preferably 1.
In some specific embodiments, the bio-based polyamide 56 filament glass fiber blended cloth has a tensile strength above 300Mpa, and/or a tensile modulus above 13Gpa, preferably above 16Gpa, and/or a tensile strain below 5%, and/or a water content below 1.5%.
In some specific embodiments, the bio-based polyamide 56 filament/glass fiber blended fabric is obtained by bidirectional blending of bio-based polyamide 56 filament/glass fiber blended yarn by a rapier loom (such as a flexible rapier loom of GA731B-210 type), specifically, the weaving process parameters are as follows: the vehicle speed is 300-310r/min; the height of the back beam is 1020-1050mm, the height of the warp stop frame is 60-70mm, and the front and the back are 130-140mm; the comprehensive leveling time is 300-320 s.
In some specific embodiments, the warp yarns and the weft yarns of the bio-based polyamide 56 silk glass fiber blended cloth are interwoven in a crisscross shape.
Fiber cloth:
in the present invention, the fiber cloth may be a material known in the art. In some specific embodiments, the fiber cloth includes any one or more of a woven cloth, a unidirectional prepreg cloth, a bidirectional prepreg cloth, or a multiaxial cloth made of carbon fiber, glass fiber, basalt fiber, or aramid fiber.
In some specific embodiments, the fiber cloth is a fiberglass cloth, such as a plain weave fiberglass cloth or a twill weave fiberglass cloth, such as commercially available under the designation EWR400 or EWR500T3, from gigantism corps, china.
In some specific embodiments, the fiber cloth has a thickness of 0.1 to 0.4mm, preferably 0.175 to 0.193mm. For example, three pieces of right twill glass fiber cloth with the thickness of 0.175mm and twill glass fiber cloth with the thickness of 0.185mm.
In some specific embodiments, the middle layer is an alternate ply of bio-based polyamide 56 glass fiber blended cloth and fiber cloth.
In some specific embodiments, the number of the first skin layer and the second skin layer is 1 or more, and may be 2, 3, 4 or more. For example, the first skin layer and the second skin layer are each laid up with 1 layer of long carbon chain polyamide resin unidirectional prepreg tape, or 2 layers of long carbon chain polyamide resin unidirectional prepreg tapes are respectively cross-laid.
In some specific embodiments, the number of layers of the intermediate layer is 3 or more, for example, 4, 5 or more layers. For example, when the middle layer is 3 layers, the bio-based polyamide 56 silk glass fiber blended cloth and the fiber cloth are alternately layered, and the middle layer is sequentially: PA56 silk glass fiber blended cloth-fiber cloth-PA 56 silk glass fiber blended cloth. For example, when the intermediate layer is 15 layers, PA56 yarn and fiber cloth are alternately layered, and the intermediate layer is sequentially: the blended fabric comprises PA56 silk glass fiber blended fabric, fiber cloth, PA56 silk glass fiber blended fabric, fiber cloth and PA56 silk glass fiber blended fabric.
In some specific embodiments, the total number of layers of the first skin layer, the intermediate layer, and the second skin layer is 5 or more, for example, the total number of layers is 5 to 200, such as 13, 17, 29, 33. Wherein, when the total number of layers is 5, the bio-based polyamide composite board sequentially comprises the following components from the first surface layer: the long carbon chain polyamide resin unidirectional prepreg tape comprises a long carbon chain polyamide resin unidirectional prepreg tape, PA56 silk glass fiber blended cloth, a fiber cloth, PA56 silk glass fiber blended cloth and a long carbon chain polyamide resin unidirectional prepreg tape.
The number of layers is an integer.
In some embodiments, the composite board may be molded with different total number of layers depending on the thickness of the composite board.
In some specific embodiments, the bio-based polyamide composite panel has a thickness of 0.5mm or more.
In some specific embodiments, the thickness of the bio-based polyamide composite board is 2-40mm, such as 2mm,4mm, 10mm.
The second technical proposal is as follows: a preparation method of the bio-based polyamide composite board comprises the steps of sequentially layering a first surface layer, a middle layer and a second surface layer, and then carrying out compression molding, wherein the compression molding temperature is 170-310 ℃, and the pressure is 0-5Mpa. In some specific embodiments, the bio-based polyamide 56 silk glass fiber blended cloth and the fiber cloth of the middle layer are alternately layered.
In some embodiments, the equipment used for molding may be equipment conventionally used in the art for molding, such as a molding press, which may be a double steel belt molding compound machine.
Preferably, the temperature for compression molding is preferably 250-310 ℃, for example 265 ℃.
In some embodiments, the compression molding may be a compression molding conventional in the art, such as continuous compression molding or direct compression molding.
When the compression molding mode is continuous compression molding, the continuous automatic layering step can be included according to the conventional method in the field, for example, the steps of preheating for 1-7min and maintaining the pressure for 1-30min are included. When the compression molding is direct compression molding, the steps of preheating, exhausting, holding pressure and cooling can be included according to the convention in the field.
In some embodiments, it is preferable to further include a step of drying the material of each layer before layering. Reducing the water content of the material by drying prevents excessive air bubbles from being generated during the molding process.
The drying operation may be a drying operation conventional in the art, such as vacuum drying. The temperature of the drying is preferably 85 to 120 c, for example 105 c. The drying time is preferably from 4 to 25h, further from 15 to 24h, for example 15h,20h,24h.
The third technical proposal: a molded article comprising the bio-based polyamide composite panel.
The fourth technical proposal is that: the application of the bio-based polyamide composite board in the aerospace field, the military field, the automobile material, the sports equipment, the building material or the electronic and electric appliance is provided.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention. The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1. the invention adopts bio-based polyamide as raw material: the monomer pentanediamine in the raw material is prepared by biological fermentation, the bio-based content is high, the concept of sustainable development of material sources is met, the bio-based content is high, and the use of fossil raw materials is effectively reduced, so that the carbon emission is reduced.
2. The bio-based polyamide composite board of the invention comprises the following components: the fiber content is high and can be higher than 60 percent; the paint has excellent mechanical properties and heat resistance, the water absorption is lower than 0.3 percent, and the paint can be applied to wider occasions; the fibers are uniformly distributed, no fiber is exposed, and the processing is easy; the thickness of the composite material can be set between 2mm and 40mm according to requirements, so that more design freedom can be provided for products; the final formed product containing the bio-based polyamide composite board can be recycled and reused, and the resource utilization rate is high.
3. The preparation method of the bio-based polyamide composite board is simple and feasible.
Drawings
Fig. 1 is a schematic view of a bio-based polyamide composite panel in example 1 of the present invention, in which: 1-first surface layer PA510 unidirectional prepreg tape; 2-middle layer PA56 silk glass fiber blended cloth; 3-three pieces of right twill glass fiber cloth in the middle layer.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples and comparative examples: the purchase sources of the raw materials are as follows: PA510 and PA512 were purchased from Kaiser (Jinxiang) biomaterials Co., ltd; antioxidants were purchased from basf group, germany; WAXE and WAXC were purchased from Clariant, germany; compatibilizers were purchased from Shanghai good easy polymer, inc.; the coupling agent is purchased from Hangzhou Jesseka chemical industry Co., ltd; the continuous long glass fiber is purchased from China megalite and has the specification of 1200Tex; three pieces of right twill fiberglass cloth (designation EWR 400) were purchased from china megalite. The molding press used for compression molding was a double steel belt molding compound machine (mold width 40 mm).
Wherein the characteristics of each polyamide resin are as follows:
the viscosity of the PA510 is 2.51, the content of terminal amino groups is 54mmol/kg, and the melting point is 217 ℃;
PA512 had a viscosity of 2.32, an amino end group content of 56mmol/kg and a melting point of 210 ℃.
Preparation example 1 PA510 unidirectional prepreg tape as shown in preparation example 3 of the description of the invention patent CN113232384A
Preparation example 2 preparation of PA512 unidirectional prepreg tape as shown in preparation example 3 of the specification of patent CN113232384A
Preparation example 3 preparation of bio-based PA56 silk glass fiber blended cloth
PA56 yarn (1200 dtex/1100 f) is prepared according to the embodiment seven of the specification of the Chinese invention patent CN 110373736A, the breaking strength is 4.7cN/dtex, the elongation at break is 59.1 percent, and the dry heat shrinkage is 8.2 percent. Twisting the PA56 yarns and continuous long glass fibers (1200 tex) into PA 56/glass fiber mixed yarns (2400 tex) by a twisting machine; then, the mixed yarn is subjected to bidirectional blending by a rapier loom, both warp yarns and weft yarns are PA 56/glass fiber mixed yarn (2400 tex), and the weaving technological parameters on the loom are as follows: the vehicle speed is 300r/min; the height of the back beam is 1050mm, the height of the warp stop frame is 70mm, and the front-back distance is 140mm; and the heald leveling time is 320s, the blended fabric unit is formed by interweaving PA 56/glass fiber mixed silk warp yarns and weft yarns in a crossed manner, the PA56 silk glass fiber blended fabric is obtained, the average tensile strength in the warp yarn and weft yarn directions is 340.3Mpa, the tensile modulus is 18.9GPa, the tensile strain is 2.5 percent, and the water content is 0.79 percent. The tensile strength, the tensile modulus and the tensile strain of the blended fabric are tested according to a reference standard GB/T7689.5-2013, and the water content is tested according to a reference standard GB/T-9914.1.
Comparative preparation example 1 preparation of PA6 silk glass fiber blended cloth
The commercially available PA6 yarn was used, and had a breaking strength of 7.5cN/dtex, an elongation at break of 21.4% and a boiling water shrinkage of 9.0%. Twisting the PA6 yarn and continuous long glass fiber (1200 tex) into PA 6/glass fiber mixed yarn (2400 tex) by a twisting machine; and then, carrying out bidirectional blending on the mixed yarn by a rapier loom, wherein warp yarns and weft yarns are PA 56/glass fiber mixed yarns (2400 tex), the weaving technological parameters on the loom are the same as those of the preparation example 3, and the blended cloth unit is formed by crisscross weaving of PA 6/glass fiber mixed yarn warp yarns and weft yarns to obtain PA6 yarn glass fiber blended cloth, wherein the average tensile strength of the warp yarns and the weft yarns in the direction is 318.9MPa, the tensile modulus is 16.3GPa, the tensile strain is 3.0%, and the water content is 1.01%. The tensile strength, the tensile modulus and the tensile strain of the blended fabric are tested according to a reference standard GB/T7689.5-2013, and the water content is tested according to a reference standard GB/T-9914.1.
Example 1 Bio-based polyamide composite sheet
A first skin layer: PA510 unidirectional prepreg tape (prepared as in preparation example 1), 0.31mm thick, 62.8wt% fiber content;
an intermediate layer: PA56 silk glass fiber blended fabric (preparation method is as in preparation example 3); three pieces of right twill glass fiber cloth with the thickness of 0.175mm;
a second surface layer: PA510 unidirectional prepreg tape (prepared as in preparation example 1) with a thickness of 0.31mm and a fibre content of 62.8 wt.%.
Cutting prepreg tape, blended fabric, glass fiber cloth into the mould size, placing one deck drawing of patterns cloth on the upper strata and the lower floor of template, placing the first top layer, intermediate level and the second top layer of the different numbers of piles in the centre, carrying out continuous compression molding on two steel band mould pressing compounding machines, specifically:
(1) 1 layer of the first surface layer is laid, namely a PA510 unidirectional prepreg tape;
(2) 15 layers of middle layers are paved, the upper and lower layers are the PA56 silk glass fiber blended cloth layers, the middle layers are the PA56 silk glass fiber blended cloth and three pieces of right twill glass fiber cloth which are alternately paved up and down, the PA56 silk glass fiber blended cloth is paved by 8 layers, the three pieces of right twill glass fiber cloth are paved by 7 layers, namely PA56 silk glass fiber blended cloth-glass fiber cloth-PA 56 silk glass fiber blended cloth-glass fiber cloth-PA 56 silk glass fiber blended cloth;
(3) Laying 1 layer of PA510 unidirectional prepreg tape on the second surface layer;
the temperature of the molding press is set to be 265 ℃, the pressure of the molding press is controlled to be 2MPa, and the bio-based polyamide composite board with the thickness of 2mm and 17 layers is prepared. A schematic diagram of the bio-based polyamide composite board prepared in this example is shown in fig. 1.
Example 2 Bio-based polyamide composite sheet
A first skin layer: PA512 unidirectional prepreg tape (prepared as in preparation example 2), 0.31mm thick, 61.8wt% fiber content;
an intermediate layer: PA56 silk glass fiber blended fabric (preparation method is as in preparation example 3); three pieces of right twill glass fiber cloth with the thickness of 0.175mm;
a second surface layer: PA512 unidirectional prepreg tape (prepared as in preparation example 2), 0.31mm thick, 61.8wt% fiber content;
cutting prepreg tape, blended fabric, glass fiber cloth into the mould size, placing one deck drawing of patterns cloth on the upper strata and the lower floor of template, placing the first top layer, intermediate level and the second top layer of the different numbers of piles in the centre, carrying out continuous compression molding on two steel band mould pressing compounding machines, specifically:
(1) 1 layer of the first surface layer is paved, namely a PA512 unidirectional prepreg tape;
(2) 15 layers of middle layers are paved, the upper and lower layers are paved with PA56 silk glass fiber blended cloth, the middle layers are paved with PA56 silk glass fiber blended cloth and three pieces of right twill glass fiber cloth alternately up and down, the PA56 silk glass fiber blended cloth is paved with 8 layers, the three pieces of right twill glass fiber cloth are paved with 7 layers, namely PA56 silk glass fiber blended cloth-glass fiber cloth-PA 56 silk glass fiber blended cloth-PA 56 silk glass fiber cloth-PA 56 silk glass fiber blended cloth;
(3) Laying 1 layer of PA512 unidirectional prepreg tape on the second surface layer;
the temperature of the molding press is set to be 265 ℃, the pressure of the molding press is controlled to be 2MPa, and the bio-based polyamide composite board with the thickness of 2mm and 17 layers is prepared.
Example 3 biobased polyamide composite sheet
The raw materials of the first surface layer, the second surface layer and the middle layer are the same as those of the embodiment 1, and the difference is that the first surface layer and the third surface layer are respectively formed by crossly layering two layers of prepreg tapes.
With prepreg area, blend cloth, fine cloth of glass cut into the mould size, place one deck drawing of patterns cloth on the upper strata and the lower floor of template, place the first top layer, intermediate level and the second top layer of the different numbers of piles in the centre, carry out continuous compression molding on two steel band mould pressing compounding machines, specifically:
(1) 2 layers of PA510 unidirectional prepreg tapes are crossly layered at 0 degree/90 degrees;
(2) 9 layers of middle layers are paved, the upper and lower layers are paved with PA56 silk glass fiber blended cloth, the middle layers are paved with PA56 silk glass fiber blended cloth and three pieces of right twill glass fiber cloth which are alternately paved up and down, 5 layers of PA56 silk are paved, and 4 layers of three pieces of right twill glass fiber cloth are paved, namely PA56 silk glass fiber blended cloth-glass fiber cloth-PA 56 silk glass fiber blended cloth;
(3) Laying 2 layers on the second surface layer, wherein the two layers of PA510 unidirectional prepreg tapes are crossly laid at an angle of 0 DEG/90 DEG;
the temperature of the molding press is set to be 265 ℃, the pressure of the molding press is controlled to be 2MPa, and the bio-based polyamide composite board with the thickness of 2mm and 13 layers is prepared.
Example 4 Bio-based polyamide composite sheet
The raw materials of the first surface layer, the second surface layer and the middle layer are the same as those of the example 2, except that the first surface layer and the third surface layer are respectively crossly paved by two layers of prepreg tapes.
With prepreg area, blend cloth, fine cloth of twill glass cut into the mould size, place one deck drawing of patterns cloth on the upper strata of template and lower floor, place the first top layer, intermediate level and the second top layer of the different numbers of piles in the centre, carry out continuous compression molding on two steel band mould pressing compounding machines, specifically:
(4) 2 layers of the first surface layer are paved, and two layers of PA512 unidirectional prepreg tapes are crossly paved at 0 degree/90 degrees;
(5) 9 layers of middle layers are paved, the upper and lower layers are paved with PA56 silk glass fiber blended cloth, the middle layers are paved with PA56 silk glass fiber blended cloth and three pieces of right twill glass fiber cloth which are alternately paved up and down, 5 layers of PA56 silk are paved, and 4 layers of three pieces of right twill glass fiber cloth are paved, namely PA56 silk glass fiber blended cloth-glass fiber cloth-PA 56 silk glass fiber blended cloth;
(6) 2 layers of the second surface layer are paved, and two layers of PA512 unidirectional prepreg tapes are crossly paved at an angle of 0 degree/90 degrees;
setting the temperature of a molding press to be 265 ℃, controlling the pressure of the molding press to be 2MPa, and preparing the bio-based polyamide composite board with the thickness of 2mm and 13 layers.
Example 5 Bio-based Polyamide composite sheet Material
The raw materials of the first surface layer, the second surface layer and the middle layer are the same as those of the embodiment 1, and the difference is that the paving modes are different: with prepreg area, blend cloth, fine cloth of glass cut into the mould size, place one deck drawing of patterns cloth on the upper strata and the lower floor of template, place the first top layer, intermediate level and the second top layer of the different numbers of piles in the centre, carry out continuous compression molding on two steel band mould pressing compounding machines, specifically:
(1) 1 layer of the first surface layer is laid, namely the PA510 unidirectional prepreg tape;
(2) The middle layer is paved with 31 layers, the upper surface layer and the lower surface layer of the middle layer are paved with PA56 silk glass fiber blended cloth layers, the middle layer is paved with PA56 silk glass fiber blended cloth and three pieces of right twill glass fiber cloth layers which are alternately paved up and down, the PA56 silk glass fiber blended cloth is paved with 16 layers, and the three pieces of right twill glass fiber cloth are paved with 15 layers;
(3) Laying 1 layer on the second surface layer to obtain a PA510 unidirectional prepreg tape;
the temperature of the molding press is set to 270 ℃, the pressure of the molding press is controlled to be 3MPa, and the bio-based polyamide composite board with the thickness of 4mm and the number of layers of 33 is prepared.
Example 6 Bio-based Polyamide composite sheet Material
The raw materials of the first surface layer, the second surface layer and the middle layer are the same as those of the embodiment 2, and the difference is that the layering modes are different: cutting prepreg tape, blended fabric, glass fiber cloth into the mould size, placing one deck drawing of patterns cloth on the upper strata and the lower floor of template, placing the first top layer, intermediate level and the second top layer of the different numbers of piles in the centre, carrying out continuous compression molding on two steel band mould pressing compounding machines, specifically:
(1) 1 layer of the first surface layer is laid, and each layer is a PA512 unidirectional prepreg tape;
(2) The middle layer is paved with 31 layers, the upper surface layer and the lower surface layer of the middle layer are paved with PA56 silk glass fiber blended cloth layers, the middle layer is paved with PA56 silk glass fiber blended cloth and three pieces of right twill glass fiber cloth layers which are alternately paved up and down, the PA56 silk glass fiber blended cloth is paved with 16 layers, and the three pieces of right twill glass fiber cloth are paved with 15 layers;
(3) Laying 1 layer on the second surface layer, wherein each layer is a PA512 unidirectional prepreg tape;
the temperature of a molding press is set to 270 ℃, the pressure of the molding press is controlled to be 3MPa, and the bio-based polyamide composite board with the thickness of 4mm and 33 layers is prepared.
Example 7 biobased polyamide composite sheet
The first surface layer, the second surface layer and the middle layer are made of the same raw materials as those in the embodiment 1, except that: cutting prepreg tape, blended fabric, glass fiber cloth into the mould size, placing one deck drawing of patterns cloth on the upper strata and the lower floor of template, placing the first top layer, intermediate level and the second top layer of the different numbers of piles in the centre, carrying out continuous compression molding on two steel band mould pressing compounding machines, specifically:
(1) 2 layers of the first surface layer are paved, and two layers of PA510 unidirectional prepreg tapes are crossly paved at 0 degree/90 degrees;
(2) 25 layers of middle layers are paved, the upper and lower layers are PA56 silk glass fiber blended cloth layers, the middle layers are PA56 silk glass fiber blended cloth and three pieces of right twill glass fiber cloth which are alternately paved up and down, 13 layers of PA56 silk glass fiber blended cloth are paved, and 12 layers of three pieces of right twill glass fiber cloth are paved;
(3) 2 layers of the second surface layer are paved, and two layers of PA510 unidirectional prepreg tapes are crossly paved at an angle of 0 degree/90 degrees;
the temperature of the molding press is set to 270 ℃, the pressure of the molding press is controlled to be 3MPa, and the bio-based polyamide composite board with the thickness of 4mm and 29 layers is prepared.
Example 8 Bio-based Polyamide composite sheet Material
The raw materials of the first surface layer, the second surface layer and the middle layer are the same as those of the embodiment 2, and the difference is that the layering modes are different: cutting prepreg tape, blended fabric, glass fiber cloth into the mould size, placing one deck drawing of patterns cloth on the upper strata and the lower floor of template, placing the first top layer, intermediate level and the second top layer of the different numbers of piles in the centre, carrying out continuous compression molding on two steel band mould pressing compounding machines, specifically:
(4) 2 layers of the first surface layer are paved, and two layers of PA512 unidirectional prepreg tapes are crossly paved at 0 degree/90 degrees;
(5) 25 layers of middle layers are paved, the upper and lower layers are PA56 silk glass fiber blended cloth layers, the middle layers are PA56 silk glass fiber blended cloth and three pieces of right twill glass fiber cloth which are alternately paved up and down, 13 layers of PA56 silk glass fiber blended cloth and 13 layers of three pieces of right twill glass fiber cloth are paved together;
(6) 2 layers of the second surface layer are paved, and two layers of PA512 unidirectional prepreg tapes are crossly paved at an angle of 0 degree/90 degrees;
the temperature of the molding press is set to 270 ℃, the pressure of the molding press is controlled to be 3MPa, and the bio-based polyamide composite board with the thickness of 4mm and 29 layers is prepared.
Comparative example 1 Polyamide 6 composite sheet
The raw materials of the first skin layer and the first skin layer were the same as in example 1 except that the intermediate layer: PA6 silk glass fiber blended fabric (preparation method as comparative preparation example 1); three pieces of right twill glass fiber cloth with the thickness of 0.175mm;
cutting prepreg tape, blended fabric, glass fiber cloth into the mould size, placing one deck drawing of patterns cloth on the upper strata and the lower floor of template, placing the first top layer, intermediate level and the second top layer of the different numbers of piles in the centre, carrying out continuous compression molding on two steel band mould pressing compounding machines, specifically:
(1) 1 layer of the first surface layer is laid, namely a PA510 unidirectional prepreg tape;
(2) 15 layers of middle layers are paved, the upper surface layer and the lower surface layer are PA6 silk layers, the middle layer is PA6 silk glass fiber blended cloth and three pieces of right twill glass fiber cloth which are alternately paved up and down, the PA6 silk glass fiber blended cloth is paved by 8 layers, the three pieces of right twill glass fiber cloth are paved by 7 layers, namely PA6 fiber glass fiber blended cloth-glass fiber cloth-PA 6 fiber glass blended cloth-glass fiber cloth-PA 6 silk glass fiber blended cloth-glass fiber cloth-PA 6 silk glass fiber blended cloth;
(3) Laying 1 layer of PA510 unidirectional prepreg tape on the second surface layer;
the temperature of the molding press is set to 240 ℃, the pressure of the molding press is controlled to 2MPa, and the polyamide 6 composite board with the thickness of 2mm and 17 layers is prepared.
Comparative example 2 polyamide 6 composite sheet
The raw materials of the first skin layer and the first skin layer were the same as in example 2, except that the intermediate layer: PA6 silk glass fiber blended fabric (preparation method as comparative preparation example 1); three pieces of right twill glass fiber cloth with the thickness of 0.175mm;
cutting prepreg tape, blended fabric, glass fiber cloth into the mould size, placing one deck drawing of patterns cloth on the upper strata and the lower floor of template, placing the first top layer, intermediate level and the second top layer of the different numbers of piles in the centre, carrying out continuous compression molding on two steel band mould pressing compounding machines, specifically:
(1) 1 layer of the first surface layer is paved, namely a PA512 unidirectional prepreg tape;
(2) 15 layers of middle layer are laid together, wherein the upper surface layer and the lower surface layer of the middle layer are PA6 silk layer, the middle layer is PA6 silk glass fiber blended cloth and three pieces of right twill glass fiber cloth which are alternately laid up and down, the PA6 silk glass fiber blended cloth is laid 8 layers together, and the three pieces of right twill glass fiber cloth are laid 7 layers together, namely PA6 silk glass fiber blended cloth-glass fiber cloth-PA 6 silk glass fiber blended cloth-glass fiber cloth-PA 6 silk glass fiber blended cloth;
(3) Laying 1 layer of PA512 unidirectional prepreg tape on the second surface layer;
the temperature of the molding press is set to 240 ℃, the pressure of the molding press is controlled to 2MPa, and the polyamide 6 composite board with the thickness of 2mm and 17 layers is prepared.
Comparative example 3 Polyamide 6 composite sheet
The raw materials of the first skin layer and the first skin layer were the same as in example 1 except that the intermediate layer: PA6 silk glass fiber blended fabric (preparation method as comparative preparation example 1); three pieces of right twill glass fiber cloth with the thickness of 0.175mm;
cutting prepreg tape, blended fabric, glass fiber cloth into the mould size, placing one deck drawing of patterns cloth on the upper strata and the lower floor of template, placing the first top layer, intermediate level and the second top layer of the different numbers of piles in the centre, carrying out continuous compression molding on two steel band mould pressing compounding machines, specifically:
(1) 1 layer of PA510 unidirectional prepreg tape is laid on the first surface layer;
(2) The middle layer is paved with 31 layers, the upper surface layer and the lower surface layer are paved with PA6 silk glass fiber blended cloth, the middle layer is paved with PA6 silk glass fiber blended cloth and three pieces of right twill glass fiber cloth which are alternately paved up and down, the PA6 silk is paved with 16 layers, and the three pieces of right twill glass fiber cloth are paved with 15 layers;
(3) Laying 1 layer of PA510 unidirectional prepreg tape on the second surface layer;
the temperature of the molding press is set to 240 ℃, the pressure of the molding press is controlled to 2MPa, and the polyamide 6 composite board with the thickness of 4mm and the number of layers of 33 is prepared.
Comparative example 4 Polyamide 6 composite sheet
The raw materials of the first skin layer and the first skin layer were the same as in example 1 except that the intermediate layer: PA6 silk glass fiber blended fabric (preparation method as comparative preparation example 1); three pieces of right twill glass fiber cloth with the thickness of 0.175mm;
with prepreg area, blend cloth, fine cloth of glass cut into the mould size, place one deck drawing of patterns cloth on the upper strata and the lower floor of template, place the first top layer, intermediate level and the second top layer of the different numbers of piles in the centre, carry out continuous compression molding on two steel band mould pressing compounding machines, specifically:
(1) 2 layers are laid on the first surface layer, namely two layers of PA510 unidirectional prepreg tapes are laid at 90 degrees;
(2) 25 layers of middle layers are paved, the upper and lower layers are PA6 silk glass fiber blended cloth layers, the middle layers are PA6 silk glass fiber blended cloth and three pieces of right twill glass fiber cloth which are alternately paved up and down, 13 layers of PA6 silk glass fiber blended cloth are paved, and 12 layers of three pieces of right twill glass fiber cloth are paved;
(3) 2 layers are laid on the second surface layer, namely two layers of PA510 unidirectional prepreg tapes are laid at 90 degrees;
the temperature of the molding press is set to 240 ℃, the pressure of the molding press is controlled to 2MPa, and the polyamide 6 composite board with the thickness of 4mm and 29 layers is prepared.
The composite boards obtained in the above examples and comparative examples were tested according to the following criteria:
1. flexural strength and flexural modulus: cutting the composite board sample into sample strips with the dimensions of 127mm long, 12.7mm wide and 2mm thick according to ASTM D790-2017 for testing;
2. heat Distortion Temperature (HDT) test: according to the national standard GB/T1634.2-2004, a sample strip with the sample size of 120mm long, 10mm wide and 4mm thick is prepared, and the applied bending stress is 1.8Mpa.
3. Water absorption test: a sample of 60mm length, 60mm width and 2mm thickness is first prepared according to the standard ASTM-D570-2005 and the test time is 24h according to the plastics method.
4. Testing the fiber content of the composite board: calcining at 700 deg.C for 2 hr according to GB/T9345.1-2008.
TABLE 1
As can be seen from Table 1: by comparing the examples with the comparative examples, it can be found that: the mechanical property strength and modulus of the bio-based polyamide composite board are obviously improved compared with the corresponding properties of a PA6 composite board, the heat resistance is also obviously superior to that of the PA6 composite board, and the water absorption is lower than that of the PA6 composite board.
Claims (10)
1. The bio-based polyamide composite board is characterized by comprising a first surface layer, a middle layer and a second surface layer; the first surface layer, the middle layer and the second surface layer are sequentially overlapped; the first surface layer and the second surface layer are long carbon chain polyamide resin unidirectional prepreg tapes, and the middle layer is a composite material layer of bio-based polyamide 56 silk-glass fiber blended cloth and fiber cloth.
2. The bio-based polyamide composite board according to claim 1, wherein the long carbon chain polyamide resin unidirectional prepreg tape is a continuous long fiber reinforced long carbon chain polyamide resin unidirectional prepreg tape comprising a continuous long fiber and a bio-based long carbon chain polyamide 5X resin;
preferably, the mass percent of the continuous long fiber is 40-80%, and more preferably 60-70%;
preferably, the bio-based long carbon chain polyamide 5X resin is selected from one or more of PA510, PA511, PA512, PA513, PA514, PA515, PA516, PA517 and PA 518;
preferably, the relative viscosity of the bio-based long carbon chain polyamide resin is 1.8-3.2, preferably 2.1-2.8; the content of terminal amino groups is 42-60mmol/kg; melting point 170-320 deg.C, preferably 180-230 deg.C; the content of the bio-based is 28-100 percent;
preferably, the continuous long fiber comprises carbon fiber, glass fiber, basalt fiber or aramid fiber;
preferably, the continuous long fiber is a continuous long glass fiber or a continuous long carbon fiber.
3. The bio-based polyamide composite board according to claim 1, wherein the long carbon chain polyamide resin unidirectional prepreg tape has a thickness of 0.15-0.5mm, preferably 0.21-0.33mm, such as 0.31mm,0.32mm or 0.33mm.
4. The bio-based polyamide composite board according to claim 1, wherein the bio-based polyamide 56 filament glass fiber blended fabric is prepared by blending bio-based polyamide 56 filament/glass fiber blended filaments; the bio-based polyamide 56 filament/glass fiber mixed filament is prepared by mixing bio-based polyamide 56 filaments and glass fibers, and the mass ratio of the bio-based polyamide 56 filaments to the glass fibers is 1:0.15-4;
preferably, the tensile strength of the bio-based polyamide 56 silk glass fiber blended fabric is more than 300Mpa, and/or the tensile modulus is more than 13Gpa, preferably more than 16Gpa, and/or the tensile strain is less than 5%, and/or the water content is less than 1.5%;
preferably, the warp and weft of the bio-based polyamide 56 silk and glass fiber blended fabric are bio-based polyamide 56 silk/glass fiber blended silk;
preferably, the warp yarns and the weft yarns of the bio-based polyamide 56 silk and glass fiber blended fabric are interwoven in a crisscross shape.
5. The bio-based polyamide composite panel according to claim 1, wherein the fiber cloth includes any one or more of woven cloth, unidirectional prepreg cloth, bidirectional prepreg cloth, or multi-axial cloth made of carbon fiber, glass fiber, basalt fiber, or aramid fiber;
preferably, the thickness of the fibre cloth is 0.1-0.4mm, more preferably 0.175-0.193mm, for example 0.185mm.
6. The bio-based polyamide composite board according to claim 1, wherein the bio-based polyamide 56 filament glass fiber blended cloth and the fiber cloth of the middle layer are alternately layered;
preferably, the number of the intermediate layers is more than 3.
7. The bio-based polyamide composite panel according to claim 1, wherein the thickness of the bio-based polyamide composite panel is 0.5mm or more, preferably 2 to 40mm;
preferably, the total number of the first surface layer, the intermediate layer and the second surface layer is 5 or more.
8. A method for preparing the bio-based polyamide composite board as claimed in any one of claims 1 to 7, wherein the first surface layer, the middle layer and the second surface layer are sequentially laminated and then compression molded, wherein the compression molding temperature is 170-310 ℃, and the compression molding pressure is 0-5MPa, such as 2MPa;
preferably, the compression molding is continuous compression molding or direct compression molding.
9. A molded article comprising the bio-based polyamide composite panel according to any one of claims 1 to 7.
10. Use of the bio-based polyamide composite sheet according to any one of claims 1 to 7 in the fields of aerospace, military, automotive, sports, construction or electrical and electronic applications.
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| CN2021110369262 | 2021-09-06 | ||
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| CN2021221405126 | 2021-09-06 |
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| CN115260753A (en) * | 2021-04-30 | 2022-11-01 | 上海凯赛生物技术股份有限公司 | Long carbon chain polyamide resin composition and continuous fiber reinforced long carbon chain polyamide composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115260753A (en) * | 2021-04-30 | 2022-11-01 | 上海凯赛生物技术股份有限公司 | Long carbon chain polyamide resin composition and continuous fiber reinforced long carbon chain polyamide composite material |
| CN115260753B (en) * | 2021-04-30 | 2024-02-09 | 上海凯赛生物技术股份有限公司 | Long carbon chain polyamide resin composition and continuous fiber reinforced long carbon chain polyamide composite material |
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