CN115772731A - Bio-based polyamide/glass fiber mixed filament, mixed woven cloth and preparation method thereof - Google Patents
Bio-based polyamide/glass fiber mixed filament, mixed woven cloth and preparation method thereof Download PDFInfo
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- CN115772731A CN115772731A CN202111036859.4A CN202111036859A CN115772731A CN 115772731 A CN115772731 A CN 115772731A CN 202111036859 A CN202111036859 A CN 202111036859A CN 115772731 A CN115772731 A CN 115772731A
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Abstract
The invention provides a bio-based polyamide/glass fiber mixed filament and a preparation method thereof. Also provides a bio-based polyamide/glass fiber mixed woven fabric and a preparation method thereof. The mixed silk and the mixed woven cloth improve the performance of the existing mixed fiber material and broaden the use scene.
Description
Technical Field
The invention relates to a bio-based polyamide/fiber composite filament, a mixed woven fabric and a preparation method thereof.
Background
Polyamide fiber is one of the synthetic fibers that was first put into industrial production in the world, and the production amount is the second place among synthetic fibers. It is made up by using polyamide as raw material through the process of melt spinning, and can be extensively used in the fields of medicine, household and industrial application. The fiber has the advantages of low density, high breaking strength, large extension, excellent rebound resilience and fatigue resistance, small bending modulus and relative bending rigidity, relatively soft fiber, moisture absorption which is second to that of vinylon in synthetic fiber, and good dyeability in synthetic fiber.
The glass fiber is an inorganic non-metallic material, has excellent performances of high strength, high temperature resistance, heat insulation, corrosion resistance and the like, is widely applied to a plurality of fields of transportation, electronic information, aerospace, infrastructure, medical sanitation, environmental protection energy and the like, and is widely and rapidly developed in the world.
The mixed fiber material generally refers to a material composed of two or more kinds of fibers, and the fibers mixed with the glass fibers may be thermoplastic fibers, metal fibers, carbon-fiber aramid fibers, or the like. Glass fibers, while excellent in function and important in many specific applications, have the disadvantage of being brittle and having poor abrasion resistance. After other fibers are mixed, the advantages of all components can be combined, the performance is complementary, the overall performance of the product is improved, and good conditions are created for further reinforcing the composite material. With the advancement of global low-carbon economic development, energy conservation, environmental protection and sustainable development become the focus of world attention, the demand of various industries and fields on high-performance composite materials is more urgent, and higher and more complex requirements are put forward on the performance of the composite materials, so that various reinforcing materials are developed while the manufacturing process and equipment technology are continuously improved, and the mixed fiber materials are produced at the same time.
Therefore, in order to adapt the mixed fiber 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 mixed fiber product with high strength and low water content.
Disclosure of Invention
The invention provides a bio-based polyamide/glass fiber mixed filament, a mixed woven fabric and a preparation method thereof, aiming at improving the performance of the existing mixed fiber material and widening the use scene.
According to the invention, the bio-based polyamide and the glass fiber are co-spun into filaments and then are mixed and woven into the cloth, so that the defects of the performance of the glass fiber can be made up, and the problem of difficulty in impregnation of the thermoplastic resin is solved; the blended fabric can also be used as a raw material for preparing more diversified composite materials, and the application range of the composite materials is widened. The composite molding material has higher glass fiber content, obvious mechanical property and uniform glass fiber distribution.
The relative viscosity of the invention is measured by a Ubbelohde viscometer concentrated sulfuric acid (96%) method. 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:
the technical scheme is as follows: a bio-based polyamide/glass fiber mixed filament is prepared by mixing a bio-based polyamide filament and a glass fiber, wherein the mass ratio of the bio-based polyamide filament to the glass fiber is 1:0.15-4.
In some specific embodiments, the linear density ratio of the bio-based polyamide filaments to the glass fibers is 1:0.15-4.
In some specific embodiments, the linear density ratio of the bio-based polyamide filaments to the glass fibers is 1:1.
in some specific embodiments, the bio-based polyamide filaments are obtained by spinning a bio-based polyamide resin selected from one or more of PA56, PA510, PA511, PA512, PA513, PA514, PA515 and PA 516.
In some specific embodiments, the bio-based polyamide resin has a relative viscosity of 1.8 to 3.2, preferably 2.1 to 2.8, and/or a terminal amino group content of 42 to 60mmol/kg, and/or a melting point of 170 ℃ to 320 ℃, and/or a bio-based content of 43% to 100%, and/or a water content of 400 to 600ppm.
In some specific embodiments, the bio-based polyamide resin PA56 has a relative viscosity of 2.3 to 2.8, and/or a terminal amino group content of 42 to 60mmol/kg, and/or a melting point of 253 to 256 ℃, and/or a bio-based content of 45%, and/or a water content of 400 to 600ppm.
In some specific embodiments, the bio-based polyamide resin PA510 has a relative viscosity of 2.3 to 2.8, and/or a terminal amino group content of 42 to 60mmol/kg, and/or a melting point of 215 ℃ to 219 ℃, and/or a bio-based content of 100%, and/or a water content of 400 to 600ppm.
In some specific embodiments, the bio-based polyamide filament has a breaking strength of 3.0cN/dtex or more, preferably 4.5cN/dtex or more, more preferably 6.5cN/dtex or more, and/or an elongation at break of 72.9% or less, preferably 33% or less, more preferably 22% or less, and/or a boiling water shrinkage of 15.0% or less, preferably 8.0% or less, more preferably 4.0% or less, and/or a linear density of 5 to 35000dtex.
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 4800Tex, e.g., 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/glass fiber mixed filament has a tensile strength at break of 60cN/Tex or more, and/or an elongation at break of 8% or less, and/or a boiling water shrinkage of 11% or less, and/or a water content of 1.5% or less, and further 1.3% or less.
In some specific embodiments, the preparation method of the bio-based polyamide/glass fiber mixed filament comprises the following steps: and spinning the bio-based polyamide melt to obtain bio-based polyamide filaments, and twisting the bio-based polyamide filaments and the glass fibers to obtain the mixed filaments.
In some embodiments, the bio-based polyamide melt may be obtained from a bio-based polyamide resin chip by heating to a molten state, or the bio-based polyamide melt obtained by using a continuous polymerization apparatus may be directly spun.
In some specific embodiments, the bio-based polyamide melt is transported to a spinning beam through a booster pump for direct spinning; or preparing the bio-based polyamide resin, heating to a molten state to form a bio-based polyamide melt, and spinning; the spinning is to spray a bio-based polyamide melt through a spinneret plate of a spinning box body to form primary yarns; and then drawing, oiling, winding and forming the primary yarn, and drawing and shaping to obtain the bio-based polyamide yarn.
In some specific embodiments, the temperature of heating to the molten state is at least 10 ℃, e.g., 20 ℃, 30 ℃ higher than the melting point of the bio-based polyamide resin.
In some specific embodiments, the temperature of heating to the molten state is from 200 ℃ to 320 ℃.
In the present invention, the apparatus used for spinning may be an apparatus conventionally used for spinning in the art, such as a melt spinning machine.
In some specific embodiments, the method for preparing the bio-based polyamide/glass fiber mixed filament comprises the following steps: putting the bio-based polyamide resin into a spinning cylinder, wherein the temperature of a screw is 200-320 ℃, the temperature of a machine head is 210-330 ℃, the rotating speed of the screw is 20-30rpm, and then uniformly discharging filaments from a spinneret plate to be wound into a silk cylinder; then twisting the glass fiber on a twisting machine, and stranding to prepare the mixed silk.
In some specific embodiments, the preparation method of the bio-based polyamide PA 56/glass fiber mixed filament comprises the following steps: melting polyamide 56 resin by a screw at 250-290 ℃, spraying the molten polyamide 56 resin by a spinneret plate of a spinning box body, and winding the molten polyamide 56 resin into a silk tube; then twisting the glass fiber on a twisting machine, and stranding to prepare the mixed silk.
In some specific embodiments, the preparation method of the bio-based polyamide PA 510/glass fiber mixed filament comprises the following steps: melting the polyamide 510 resin by a screw at 210-260 ℃, spraying out by a spinneret plate of a spinning box body, and winding into a spinning tube; then twisting the glass fiber on a twisting machine, and stranding to prepare the mixed silk.
The second technical proposal is that: the mixed knitted fabric is prepared by blending any one or two of a bio-based polyamide filament, a glass fiber and a bio-based polyamide/glass fiber mixed filament.
In some specific embodiments, the hybrid woven cloth is any one of bio-based polyamide filaments, glass fibers and bio-based polyamide/glass fiber hybrid filaments in the warp direction; the weft direction is any one of bio-based polyamide yarns, glass fibers and bio-based polyamide/glass fiber mixed yarns.
In some specific embodiments, the hybrid fabric is bio-based polyamide filaments in the warp direction and glass fibers in the weft direction; the warp direction is bio-based polyamide silk, and the weft direction is mixed silk; both the warp direction and the weft direction are mixed yarns; the warp direction is mixed silk, and the weft direction is glass fiber.
In some specific embodiments, the warp and weft directions of the hybrid woven fabric are not both 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 filaments include one or more of PA56 filaments, PA510 filaments, PA511 filaments, PA512 filaments, PA513 filaments, PA514 filaments, PA515 filaments, and PA516 filaments.
In some specific embodiments, the bio-based polyamide filament has a breaking strength of 3.0cN/dtex or more, preferably 4.5cN/dtex or more, more preferably 6.5cN/dtex or more, and/or an elongation at break of 72.9% or less, preferably 33% or less, more preferably 22% or less, and/or a boiling water shrinkage of 15.0% or less, preferably 8.0% or less, more preferably 7.0% or less, and/or a linear density of 5 to 35000dtex.
In some specific embodiments, the linear density ratio of the warp direction to the weft direction of the hybrid woven fabric is 1:0.5-3, preferably 1.
In the present invention, the warp and weft directions are also referred to as warp and weft.
In the invention, the blended fabric can be prepared by blending different or same types of fibers in two directions by a rapier loom in a blending mode commonly used in the field.
In some specific embodiments, the equipment used for said blending may be equipment conventionally used in the art for blending, such as flexible rapier looms of the GA747 type.
In some specific embodiments, the warp and weft of the blended fabric are any one of bio-based polyamide, glass fiber or bio-based polyamide/glass fiber mixed filament, and the weaving parameters on the machine 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 leveling time is 300-320 degrees.
In some specific embodiments, the hybrid fabric warp and weft are interwoven in a crisscross pattern.
In some specific embodiments, the bio-based polyamide/glass fiber hybrid braid has a 0 ° tensile strength above 300MPa, and/or a 0 ° tensile modulus above 16GPa, and/or a 0 ° tensile strain below 1.7%, and/or a 90 ° tensile strength above 70MPa, and/or a 90 ° tensile modulus above 2500MPa, and/or a 90 ° tensile strain below 5.0%, and/or a water content below 1.2%.
The prepared bio-based polyamide/glass fiber mixed filament and mixed fabric can be applied to the technical fields of aerospace, military, automobile materials, sports equipment, building materials, electronic and electric appliances and the like.
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, and the carbon neutralization development trend is adapted.
2. The invention relates to a bio-based polyamide/glass fiber mixed filament and a mixed woven fabric, which are prepared by the following steps:
(1) The mechanical properties of the bio-based polyamide/glass fiber mixed filament and the mixed fabric are excellent;
(2) The water content is low and is all lower than 1.5 percent.
(3) The glass fiber content of the mixed woven cloth is high, and the mixed woven cloth can be designed within the range of 25-75% according to needs.
3. The preparation method of the bio-based polyamide/glass fiber mixed filament is simple and feasible.
Drawings
Fig. 1 is a schematic structural diagram of a bio-based polyamide PA56 and glass fiber mixed woven fabric in example 3 of the present invention, wherein 1: warp-PA 56 yarn; 2: weft-glass fibers.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
In the following examples and comparative examples: the purchase sources of the raw materials are as follows: the bio-based polyamide resins PA56, PA510, PA56 wires and PA510 wires are purchased from Kaiser (Jinxiang) biomaterials Co., ltd; the glass fiber is purchased from megalite; the blending equipment is GA747 type flexible rapier loom.
Wherein the characteristics of the raw materials are as follows:
PA56 resin: the viscosity is 2.29, the content of terminal amino groups is 55mmol/kg, the melting point is 253 ℃, the content of bio-based groups is 45 percent, and the water content is less than or equal to 2000ppm;
PA510 resin: the viscosity is 2.51, the content of terminal amino groups is 54mmol/kg, the melting point is 217 ℃, the content of bio-based groups is 100 percent, and the water content is less than or equal to 2000ppm;
PA6 resin: the viscosity is 2.46, the content of terminal amino groups is 54mmol/kg, the melting point is 223 ℃, the content of bio-based is 0, and the water content is less than or equal to 2000ppm.
Glass fiber (1200 Tex): the water content is less than or equal to 0.10 percent and the diameter is 17 mu m.
Glass fiber (2400 Tex): the water content is less than or equal to 0.10 percent and the diameter is 24 mu m.
PA56 silk: the breaking strength is 5.8cN/dtex, the elongation at break is 21.5%, and the boiling water shrinkage is 7.0%.
PA510 filament: the breaking strength is 5.4cN/dtex, the elongation at break is 20.2%, and the boiling water shrinkage is 4.3%.
PA6 silk: the breaking strength is 4.8cN/dtex, the elongation at break is 21.4%, and the boiling water shrinkage is 9.0%.
EXAMPLE 1 Bio-based Polyamide PA 56/glass fibre Mixed yarn
Mixing silk: the yarn comprises PA56 yarns and glass fibers (both having a linear density of 1200 tex) in a mass ratio of 1.
The preparation method comprises the following steps: putting the bio-based PA56 resin into a spinning material cylinder, controlling the temperature of a single screw rod to be 285 ℃, the temperature of a machine head to be 285 ℃, the rotating speed of the screw rod to be 30rpm, and uniformly discharging filaments from a spinneret plate to form multifilaments when the temperature is stable; winding into a monofilament tube, twisting with glass fiber on a twisting machine, and stranding to obtain the final product.
Example 2 Bio-based polyamide PA 510/glass fibre blend yarn
Mixing silk: the composite material comprises PA510 filaments and glass fibers (both having a linear density of 1200 tex) in a mass ratio of 1.
The preparation method comprises the following steps: putting the bio-based PA510 resin into a spinning material cylinder, controlling the temperature of a single screw to be 255 ℃, the temperature of a machine head to be 260 ℃ and the rotating speed of the screw to be 30rpm, and uniformly discharging filaments from a spinneret plate to form multifilaments when the temperature is stable; winding into a monofilament tube, twisting with glass fiber on a twisting machine, and stranding to obtain the final product.
Example 3 biobased polyamide PA56 and glass fiber hybrid woven cloth
Raw materials: PA56 filament (1200 tex) and glass fibre (1200 tex)
The preparation method comprises the following steps: warp is PA56 silk, weft is glass fiber, and the weaving parameters on the machine 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; the heald leveling time is 310 degrees, and the mixed weaving unit is formed by interweaving PA56 silk warp yarns and glass fiber weft yarns in a cross shape.
Example 4 Bio-based Polyamide PA56 and PA 56/glass fibre Mixed yarn Mixed plaited Fabric
Raw materials: PA56 yarn (2400 tex), PA 56/glass fibre mixed yarn (2400 tex) made in example 1
The preparation method comprises the following steps: warp yarns are PA56 yarns, weft yarns are PA 56/glass fiber mixed yarns, and the weaving 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 310s, and the mixed woven cloth unit is formed by interweaving PA56 silk warp yarns and PA 56/glass fiber mixed silk weft yarns in a cross shape.
Example 5 glass fiber and PA 56/glass fiber Mixed yarn Mixed Fabric
Raw materials: glass fibre (2400 tex), PA 56/glass fibre hybrid yarn from example 1 (2400 tex)
The preparation method comprises the following steps: the warp is glass fiber, the weft is PA 56/glass fiber mixed yarn, and the weaving parameters on the machine 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; the heald leveling time is 310 degrees, and the mixed weaving unit is formed by interweaving PA56 silk warp yarns and PA 56/glass fiber mixed silk weft yarns in a cross shape.
Example 6PA 56/glass fibre Mixed yarn Fabric
Raw materials: PA 56/glass fibre hybrid yarn (2400 tex) prepared in example 1
The preparation method comprises the following steps: warp yarns and weft yarns are PA 56/glass fiber mixed yarns, and the weaving parameters on the machine 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; the heald leveling time is 310 degrees, and the mixed weaving unit is formed by interweaving PA 56/glass fiber mixed silk warp yarns and weft yarns in a cross shape.
Example 7 biobased polyamide PA510 and glass fiber hybrid woven cloth
Raw materials: PA510 filaments (1200 tex) and glass fibres (1200 tex)
The preparation method comprises the following steps: warp is PA510 silk, weft is glass fiber, and the weaving parameters on the machine 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; the heald leveling time is 310 degrees, and the mixed weaving unit is formed by interweaving PA510 silk warp yarns and glass fiber weft yarns in a cross shape.
Example 8 bio-based polyamide PA510 and PA510 glass fiber hybrid yarn hybrid cloth raw material: PA510 yarn (2400 tex), PA 510/glass fibre mixed yarn (2400 tex) from example 2
The preparation method comprises the following steps: warp yarns are PA510 yarns, weft yarns are PA 510/glass fiber mixed yarns, and the weaving 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 in the heald leveling time of 310s, the mixed woven cloth unit is formed by interweaving PA510 wire warp yarns and PA 510/glass fiber mixed wire weft yarns in a cross shape.
Example 9 woven Fabric of glass fiber and PA 510/glass fiber Mixed yarn
Raw materials: glass fibre (2400 tex), PA 510/glass fibre hybrid yarn (2400 tex) from example 2
The preparation method comprises the following steps: the warp is glass fiber, the weft is PA 510/glass fiber mixed yarn, and the weaving parameters on the machine 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; the heald leveling time is 310 degrees, and the mixed weaving unit is formed by interweaving PA510 wire warp yarns and PA 510/glass fiber mixed wire weft yarns in a cross shape.
Example 10PA 510/glass fiber Mixed yarn Mixed Fabric
Raw materials: PA 510/glass fibre hybrid yarn (2400 tex) prepared in example 2
The preparation method comprises the following steps: warp yarns and weft yarns are PA 510/glass fiber mixed yarns, and the weaving 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; the heald leveling time is 310 degrees, and the mixed weaving unit is formed by interweaving PA 510/glass fiber mixed silk warp yarns and weft yarns in a cross shape.
Comparative example 1: PA 6/glass fiber mixed filament
Mixing silk: the composite material comprises PA6 filaments and glass fibers (both having a linear density of 1200 tex) in a mass ratio of 1.
The preparation method comprises the following steps: putting the PA6 resin into a spinning material cylinder, controlling the temperature of a single screw to be 225 ℃, the temperature of a machine head to be 230 ℃, the rotating speed of the screw to be 30rpm, and uniformly discharging filaments from a spinneret plate to form multifilaments when the temperature is stable; winding into a monofilament tube, twisting with glass fiber on a twisting machine, and stranding to obtain PA 6/glass fiber mixed filament.
Comparative example 2: PA6 and glass fiber mixed woven fabric
The preparation method is the same as that of the embodiment 3, except that the mixed woven cloth comprises the following raw materials: the warp yarns are PA6 filaments (1200 tex) and the weft yarns are glass fibers (1200 tex).
Comparative example 3: PA6 and PA 6/glass fiber mixed silk mixed woven fabric
The preparation method is the same as that of the embodiment 4, except that the mixed woven cloth comprises the following raw materials: the warp yarn was PA6 yarn (2400 tex) and the weft yarn was the PA 6/glass fiber hybrid yarn (2400 tex) prepared in comparative example 1.
Comparative example 4: glass fiber and PA 6/glass fiber mixed silk mixed woven fabric
The preparation method is the same as that of the embodiment 5, except that the mixed weaving cloth raw material comprises the following steps: the warp yarn was glass fiber (2400 tex), and the weft yarn was PA 6/glass fiber mixed yarn (2400 tex) prepared in comparative example 1.
Comparative example 5: PA 6/glass fiber mixed silk mixed woven fabric
The preparation method is the same as that of the embodiment 6, except that the mixed weaving cloth raw material comprises the following steps: both the warp and weft yarns were PA 6/glass fibre hybrid yarns (2400 tex) as prepared in comparative example 1.
The mixed yarns prepared in the above examples and comparative examples were tested with reference to the following standards, and the test results are shown in table 1:
1. tensile strength at break and elongation at break: according to the standard GB/T3916-2013, an YG021DL type electronic single-yarn strength machine is adopted, each sample is tested for 20 times under the conditions of the gauge length of 250.00mm, the moving speed of a clamp holder of 250mm/min and the pre-tension of 5.00cN, and the results are averaged;
2. shrinkage in boiling water: reference is made to the standard GB/T6506-1986.
3. Testing the water content: reference is made to the standard GB/T21655.1-2008.
TABLE 1
As can be seen from table 1, in examples 1 and 2, compared to comparative example 1, the bio-based polyamide fiber and glass fiber mixed yarn has higher tensile strength at break and elongation at break, higher strength than the corresponding PA 6/glass fiber mixed yarn, and lower water absorption and boiling water shrinkage.
The hybrid mats obtained in the above examples and comparative examples were tested with reference to the following standards, and the test results are shown in table 2:
1. tensile strength, tensile modulus, tensile strain: reference is made to the standard GB/T7689.5-2013, wherein the warp direction is 0 degrees and the weft direction is 90 degrees;
2. testing the water content: reference is made to the standard GB/T-9914.1.
TABLE 2
As can be seen from Table 2, the bio-based polyamide/glass fiber hybrid fabrics of examples 3-10 have higher tensile strength and modulus than those of comparative examples 2-5, and have better performance than the corresponding PA6 glass fiber hybrid fabrics, and also have better water absorption and tensile strain. The glass fiber content of the mixed woven cloth is high, and the mixed woven cloth can be designed within the range of 25-75% according to needs.
According to the invention, the bio-based polyamide and the glass fiber are co-spun into filaments and then are mixed and woven into the cloth, so that the defects of the performance of the glass fiber can be made up, and the problem of difficulty in impregnation of the thermoplastic resin is solved; the blended fabric can also be used as a raw material for preparing more diversified composite materials, and the application range of the composite materials is widened. The composite molding material has higher glass fiber content, obvious mechanical property and uniform glass fiber distribution.
Claims (10)
1. The mixed yarn of the bio-based polyamide and the glass fiber is characterized in that the mixed yarn is prepared by mixing the bio-based polyamide yarn and the glass fiber, and the mass ratio of the bio-based polyamide yarn to the glass fiber is 1:0.15-4.
2. The bio-based polyamide/glass fiber hybrid yarn according to claim 1, wherein the bio-based polyamide yarn is obtained by spinning a bio-based polyamide resin selected from one or more of PA56, PA510, PA511, PA512, PA513, PA514, PA515 and PA 516;
preferably, the relative viscosity of the bio-based polyamide resin is 1.8-3.2, preferably 2.1-2.8, and/or the content of terminal amino groups is 42-60mmol/kg, and/or the melting point is 170-320 ℃, and/or the bio-based content is 43-100%, and/or the water content is 400-600ppm;
preferably, the relative viscosity of the bio-based polyamide resin PA56 is 2.3-2.8, and/or the content of terminal amino groups is 42-60mmol/kg, and/or the melting point is 253-256 ℃, and/or the bio-based content is 45%, and/or the water content is 400-600ppm;
preferably, the relative viscosity of the bio-based polyamide resin PA510 is 2.3-2.8, and/or the content of terminal amino groups is 42-60mmol/kg, and/or the melting point is 215-219 ℃, and/or the content of bio-based groups is 100%, and/or the water content is 400-600ppm.
3. The bio-based polyamide/glass fiber hybrid yarn according to claim 1, wherein said glass fiber has a monofilament diameter of 5 to 20 μm;
preferably, the glass fibers have a linear density of 1000 to 4800Tex;
preferably, the water content of the glass fiber is less than or equal to 0.10 percent.
4. The mixed bio-based polyamide/glass fiber yarn according to claim 1, wherein the mixed bio-based polyamide/glass fiber yarn has a tensile strength at break of 60cN/Tex or more, and/or an elongation at break of 8% or less, and/or a boiling water shrinkage of 11% or less, and/or a water content of 1.5% or less.
5. The bio-based polyamide/glass fiber hybrid yarn according to claim 1, wherein the preparation method comprises: providing a bio-based polyamide melt, spinning to obtain bio-based polyamide filaments, and twisting the bio-based polyamide filaments and glass fibers to obtain mixed filaments;
preferably, the bio-based polyamide melt can be obtained by heating bio-based polyamide resin slices to a molten state, or directly spinning the bio-based polyamide melt obtained by adopting a continuous polymerization device;
preferably, the temperature of heating to the molten state is 200-320 ℃;
preferably, the bio-based polyamide resin is put into a spinning cylinder, the temperature of a screw is 200-320 ℃, the temperature of a machine head is 210-330 ℃, the rotation speed of the screw is 20-30rpm, and then a spinneret plate uniformly discharges filaments and the filaments are wound into a spinning cylinder; then twisting the glass fiber on a twisting machine, and stranding to prepare the mixed silk.
6. A bio-based polyamide/glass fiber blended fabric, which is characterized in that the blended fabric is prepared by blending any one or two of bio-based polyamide yarns, glass fibers and the bio-based polyamide/glass fiber blended yarns according to any one of claims 1 to 5;
preferably, the warp direction of the mixed woven cloth is any one of bio-based polyamide yarns, glass fibers and bio-based polyamide/glass fiber mixed yarns; the weft direction is any one of bio-based polyamide yarns, glass fibers and bio-based polyamide/glass fiber mixed yarns;
preferably, the linear density ratio of the warp direction to the weft direction of the mixed woven fabric is 1:0.5-3, preferably 1.
7. The bio-based polyamide/glass fiber hybrid plaited fabric according to claim 6, wherein the bio-based polyamide filaments include one or more of PA56 filaments, PA510 filaments, PA511 filaments, PA512 filaments, PA513 filaments, PA514 filaments, PA515 filaments, and PA516 filaments;
preferably, the bio-based polyamide filament has a breaking strength of above 3.0cN/dtex, preferably above 4.5cN/dtex, more preferably above 6.5cN/dtex, and/or an elongation at break of below 72.9%, preferably below 33%, more preferably below 22%, and/or a boiling water shrinkage of below 15.0%, preferably below 8.0%, more preferably below 4.0%, and/or a linear density of 5-35000dtex.
8. The bio-based polyamide/glass fiber hybrid fabric according to claim 6, wherein the glass fiber has a filament diameter of 5-20 μm;
preferably, the linear density of the glass fibers is 1000 to 3600Tex;
preferably, the water content of the glass fiber is less than or equal to 0.10 percent.
9. The bio-based polyamide/glass fiber blended fabric according to claim 6, wherein the warp and weft of the bio-based polyamide/glass fiber blended fabric are any one of bio-based polyamide, glass fiber or bio-based polyamide/glass fiber blended yarn, and the weaving parameters on the loom 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 leveling time is 300-320 degrees.
10. The bio-based polyamide/glass fiber blended fabric according to claim 6, wherein warp yarns and weft yarns of the blended fabric are woven in a crisscross manner;
preferably, the bio-based polyamide/glass fiber blended fabric has a 0 ° tensile strength of 300MPa or more, and/or a 0 ° tensile modulus of 16GPa or more, and/or a 0 ° tensile strain of 1.7% or less, and/or a 90 ° tensile strength of 70MPa or more, and/or a 90 ° tensile modulus of 2500MPa or more, and/or a 90 ° tensile strain of 5.0% or less, and/or a water content of 1.2% or less.
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| CN103437020A (en) * | 2012-12-31 | 2013-12-11 | 安徽科聚新材料有限公司 | Nylon fiber-glass fiber composite fiber fabric and preparation method and application thereof |
| CN105008603A (en) * | 2013-03-06 | 2015-10-28 | 三菱瓦斯化学株式会社 | Combined filamanet yarn, woven and knitted fabric, composite material, and process for manufacturing composite material |
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