CN107034529B - Fiber, unidirectional cloth, laminated board comprising unidirectional cloth, pipe and application of unidirectional cloth - Google Patents

Fiber, unidirectional cloth, laminated board comprising unidirectional cloth, pipe and application of unidirectional cloth Download PDF

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CN107034529B
CN107034529B CN201610079586.4A CN201610079586A CN107034529B CN 107034529 B CN107034529 B CN 107034529B CN 201610079586 A CN201610079586 A CN 201610079586A CN 107034529 B CN107034529 B CN 107034529B
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core
polymer
skin
sheath
unidirectional
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CN107034529A (en
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李化毅
陈鹏
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Institute of Chemistry CAS
Ningbo Institute of Material Technology and Engineering of CAS
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Institute of Chemistry CAS
Ningbo Institute of Material Technology and Engineering of CAS
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/08—Interconnection of layers by mechanical means
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D3/00—Woven fabrics characterised by their shape
    • D03D3/02—Tubular fabrics

Abstract

The invention relates to a fiber with a sheath-core structure, unidirectional cloth, a laminated board containing the unidirectional cloth, a pipe and application thereof, wherein the diameter of the fiber is between 0.5 and 150 mu m; the polymers of the core layer and the skin layer are the same or different and are independently selected from the following polymers: polyolefins, polyamides, polyurethanes, polyesters, polyoxymethylenes, and the like. Melting point T of the sheath polymerm1And melting point T of the core Polymerm2Satisfies the following relation: t ism2>Tm1(1). The laminated board has high tensile strength, high transparency, high rigidity and good toughness, is particularly suitable for the fields of trays, boxes, buildings, vehicles and the like, and is used as a stressed part or a decorative part. The pipe of the invention has high transparency, high toughness and excellent pressure resistance, and is suitable for the fields of buildings, vehicles and the like.

Description

Fiber, unidirectional cloth, laminated board comprising unidirectional cloth, pipe and application of unidirectional cloth
Technical Field
The invention relates to a fiber, unidirectional cloth, a laminated board and a pipe comprising the unidirectional cloth and application thereof, in particular to a laminated board and a pipe with high transparency, high strength and high toughness, belonging to the field of composite materials.
Background
The polymer fiber is a commonly used raw material, such as polypropylene fiber, polyester fiber, nylon fiber, polyurethane fiber, and the like. Polymer fibers are generally prepared by melt spinning or solution spinning, and the cross-sectional shape of the fiber can be controlled by controlling the die shape of a spinneret. In order to produce multifunctional fiber materials, the fibers of the sheath-core structure can be formed by multicomponent coextrusion, i.e. the fiber sheath material and the core material are different. The fiber can be woven into cloth, the process for preparing the cloth can be mechanical weaving, and the fiber can be bonded to form the unidirectional cloth by coating a certain adhesive on the surface of the fiber. The unidirectional fabric is cross-compounded to form a composite material with high strength.
Due to poor compatibility between the adhesive and the fiber, the performance of the prepared composite material is limited. In order to overcome the disadvantages of the prior art, a new technology is provided for preparing novel fibers and composites thereof.
Disclosure of Invention
The invention provides a fiber and a preparation method thereof to overcome the defects of the prior art.
The invention also aims to provide a unidirectional fabric prepared from the fiber and a preparation method thereof.
Another object of the present invention is to provide a laminated sheet comprising the above unidirectional fabric, which has high rigidity, high transparency, high strength, high toughness, etc., and a method for preparing the same.
It is still another object of the present invention to provide a pipe made of the above fiber, which has high transparency, high toughness, high pressure resistance, etc., and a method for preparing the same.
It is a further object of the present invention to provide the use of the unidirectional cloth, laminate and tube described above.
It is a further object of the present invention to provide an article comprising the unidirectional fabric, laminate or tube described above.
The invention provides a fiber with a sheath-core structure, the diameter of which is between 0.5 and 150 mu m; the polymers of the core layer and the skin layer are the same or different and are independently selected from the following polymers: polyolefins, polyamides, polyurethanes, polyesters, polyamidesAldehydes and the like; melting point T of the sheath polymerm1And melting point T of the core Polymerm2Satisfies the following relation:
Tm2>Tm1(1)。
further, the melting point T of the skin layer polymerm1And melting point T of the core Polymerm2Satisfies the following relation:
Tm2≥Tm1+10 (1’)。
further, the melting point T of the skin layer polymerm1And melting point T of the core Polymerm2Satisfies the following relation:
Tm2≥Tm1+20 (1”)。
further, the melting point T of the skin layer polymerm1And melting point T of the core Polymerm2Satisfies the following relation:
Tm2≥Tm1+30 (1”’)。
further, said Tm1In the range of 30-300 ℃; the T ism2In the range of 60-300 ℃.
Still further, the diameter of the fibers is between 1 μm and 100 μm, more preferably between 5 μm and 80 μm, still more preferably between 10 μm and 60 μm.
Further, the mass of the sheath layer accounts for 5-60 wt% of the total mass of the fiber. Preferably, 5 to 50 wt%.
Still further, the polyolefin is selected from C2-20α -homopolymers or copolymers of olefins selected in particular from polyethylene, polypropylene, polybutene-1, ethylene copolymers with one or more comonomers of propylene, butene, pentene, hexene or octene, propylene copolymers with one or more comonomers of ethylene, butene, pentene, hexene or octene or butene copolymers with one or more comonomers of ethylene, propylene, pentene, hexene or octene.
Further, the polyester is a condensate of a dibasic acid and a dihydric alcohol, or a ring-opened polymer of a lactone. The polyester is obtained by homopolymerization or copolymerization. For homopolyesters, only one diacid and one diol, or only one lactone; for copolyesters, at least two diacids or two diols, or two lactones are present. Preferably, the polyester is selected from polyethylene terephthalate, polybutylene terephthalate or blends thereof.
Still further, the polyamide is a condensate of a dibasic acid and a diamine, or a ring-opened polymer of lactam. The polyamide is obtained by homopolymerization or copolymerization. For homopolyamides, only one diacid and one diamine, or only one lactam; for copolyamides, at least two diacids or two diamines, or two lactams are present. Preferably, the Polyamide (PA) is selected from PA6, PA66, PA45, PA56, PA10, PA1010, PA11 or PA 12; or a copolycondensate of a plurality of diamines, diacids, such as adipic acid, dodecanedioic acid, hexamethylenediamine and dodecyldiamine.
Further, the polyoxymethylene is a homo-or co-polyoxymethylene, more preferably, a homopolymer of trioxane or a copolymer of trioxane, dioxolane and other epoxy compounds.
Still further, the polyurethane is selected from polycondensation products of diols and diisocyanates, such as polyester diols, polyether diols, polycarbonate diols, and the like, with diphenylmethane diisocyanate, hexamethylene diisocyanate, and the like.
Further, the core and sheath layers of the fiber are well compatible, most preferably of the same type of polymer.
The invention also provides unidirectional cloth prepared from the fiber or the fibers.
Further, the unidirectional fabric is prepared by the following method: arranging the fibers in a single direction, and forming the single-direction cloth under the action of hot pressing, wherein the hot pressing temperature is controlled to be lower than Tm2。
In the present invention, since the hot pressing temperature is lower than Tm2When hot-pressed, the fiber skin layer melts and the core layer also meltsAnd the fiber skins are mutually melted and bonded under the action of pressure without melting.
The invention also provides a laminated board which is prepared by laminating at least two layers of the unidirectional fabrics in sequence and then hot-pressing.
Further, the laminate is made by laminating 2 to 2000 (e.g. 2 to 100, or 5 to 50, or 10 to 20) unidirectional plies in sequence and then hot pressing.
Further, the angle α of the superposition of the two adjacent unidirectional fabrics satisfies the following formula: alpha is more than or equal to 0 and less than or equal to 90 degrees, and the angle alpha is an included angle between the longitude directions of the two unidirectional fabrics.
Further, the hot pressing temperature is lower than Tm2. In the present invention, since the hot pressing temperature is lower than Tm2And during hot pressing, the fiber skin layers are melted, the core layer is not melted yet, and the fiber skin layers between the unidirectional fabrics are mutually melted and bonded under the action of pressure. Preferably, said hot pressing temperature is about equal to said Tm1. The temperature is the initial melting temperature of the polymer of the skin layer, namely, the skin layers can be fused with each other under the condition of hot pressing pressure.
Further, the pressure of the hot pressing is 0.5MPa to 30 MPa.
Still further, the laminate has a thickness of between 100 μm and 200mm, preferably between 2mm and 50 mm.
The invention also provides a pipe which is prepared by continuously winding the fiber with the sheath-core structure on a cylindrical die and then carrying out hot pressing.
Further, the hot pressing temperature is lower than Tm2. In the present invention, since the hot pressing temperature is lower than Tm2And during hot pressing, the fiber skin layers melt, the core layer does not melt yet, and the fiber skin layers mutually melt and are bonded under the action of pressure. Preferably, said hot pressing temperature is about equal to said Tm1(ii) a The temperature is the initial melting temperature of the polymer of the skin layer, namely, the skin layers can be fused with each other under the condition of hot pressing pressure.
Further, the pressure of the hot pressing is 0.5MPa to 30 MPa.
Further, the pipe has a wall thickness of between 100 μm and 200mm, preferably between 2mm and 50 mm.
The invention also provides a preparation method of the fiber with the sheath-core structure, which comprises the following steps:
(1) the melting point is Tm1Sheath polymer of (b) and a melting point of Tm2Respectively injecting the core layer polymer into a single screw extruder with a heating device for melting and plasticizing, wherein the temperatures of corresponding screw plasticizing sections are respectively Tp1And Tp2Wherein: t ism1+30≤Tp1≤Tm1+50，Tm1+50≤Tp2≤Tm1+90；
(2) Spitting the melt formed in the step (1) into filaments through a bicomponent spinning component and a spinneret plate;
(3) spinning and heat setting to obtain the skin-core structure fiber.
Preferably, in the step (2), the melts formed in the step (1) are precisely metered through a gear pump respectively, the volume ratio of the sheath polymer to the core polymer is controlled to be 1/9-9/1, and the melts are discharged into filaments through a bicomponent spinning assembly and a spinneret plate.
Preferably, in the step (3), the filaments discharged in the step (2) are bundled and oiled, and then wound at a speed of 500-2500 m/min to obtain pre-oriented yarns, and then the pre-oriented yarns are drawn and heat-set to obtain the skin-core structure fibers, namely the skin-core composite fully oriented yarns with the monofilament linear density of 2-12 dtex. Preferably, the drawing temperature and the heat-setting temperature are respectively TdAnd TsWherein: (T)g1+Tm1)/2≤Td≤(Tg2+Tm2)/2，Td≤Ts≤(Tg2+Tm2)/2，Tg1And Tg2The glass transition temperatures of the skin and core polymers, respectively. More preferably, the drafting magnification is 1.5 to 4.5 times, and the heat setting magnification is 0.9 to 1.1 times; alternatively, the first and second electrodes may be,
bundling and oiling the filaments discharged in the step (2), spinning, heat setting and winding at the speed of 2500-4500 m/min to obtain the skin-core structure fiber which is a monofilamentThe sheath-core composite fully oriented yarn has a linear density of 2-12 dtex. Preferably, the heat-setting temperature is Ts，(Tg1+Tm1)/2≤Ts≤(Tg2+Tm2)/2，Tg1And Tg2The glass transition temperatures of the skin and core polymers, respectively. More preferably, the heat-setting magnification is 0.85 to 1.15 times.
The invention also provides a preparation method of the unidirectional fabric, which comprises the following steps: and arranging the fibers in a single direction, and forming the single-direction cloth under the action of hot pressing.
Preferably, the temperature of the hot pressing is controlled below Tm2。
According to the invention, the preparation method specifically comprises the following steps:
the fiber of the sheath-core structure is arranged in a single direction, the yarn is withdrawn on a creel, and the unidirectional fabric is formed under the action of hot pressing after sequentially passing through a godet roller, a tension roller, a yarn separator, a hot roller, a cooling area, a traction roller and a winding device, wherein the hot pressing temperature is controlled to be lower than Tm2。
Preferably, the godet roll, the tension roll and the traction roll are five rolls or seven rolls, and the hot roll is 1 pair or 2 pairs. Further, the roll surface temperature (i.e., hot-pressing temperature) of the heat roll is Tr，Tm1≤Tr<Tm2. Further, the cooling zone may take natural cooling or forced air cooling.
The invention also provides a preparation method of the laminated board, which comprises the following steps: preparing unidirectional cloth; and laminating at least two layers of unidirectional cloth in sequence and then carrying out hot pressing to obtain the laminated board.
Further, the laminate is produced by laminating 2 to 2000 layers (e.g., 2 to 100 layers, or 5 to 50 layers, or 10 to 20 layers) of the unidirectional fabric in sequence and then hot-pressing.
Further, the hot pressing temperature is lower than Tm2. In the present invention, since the hot pressing temperature is lower than Tm2And during hot pressing, the fiber skin layers are melted, the core layer is not melted yet, and the fiber skin layers between the unidirectional fabrics are mutually melted and bonded under the action of pressure. Superior foodOptionally, the hot pressing temperature is about equal to the Tm1. The temperature is the initial melting temperature of the polymer of the skin layer, namely, the skin layers can be fused with each other under the condition of hot pressing pressure. The hot pressing pressure is 0.5MPa to 30 MPa.
Further, the unidirectional fabric is prepared according to the method of the unidirectional fabric.
Further, the angle α of the superposition of the two adjacent unidirectional fabrics satisfies the following formula: alpha is more than or equal to 0 and less than or equal to 90 degrees, and the angle alpha is an included angle between the longitude directions of the two unidirectional fabrics.
The invention also provides a preparation method of the pipe, which comprises the following steps: the fiber with the skin-core structure is prepared by continuously winding the fiber on a cylindrical die and then hot-pressing.
Further, the hot pressing temperature is lower than Tm2. In the present invention, since the hot pressing temperature is lower than Tm2And during hot pressing, the fiber skin layers melt, the core layer does not melt yet, and the fiber skin layers mutually melt and are bonded under the action of pressure. Preferably, the hot pressing temperature is about equal to the Tm1. The temperature is the initial melting temperature of the polymer of the skin layer, namely, the skin layers can be fused with each other under the condition of hot pressing pressure. The hot pressing pressure is 0.5MPa to 30 MPa.
The invention also provides the application of the unidirectional cloth, the laminated board or the pipe, which is used in the fields of trays, boxes, buildings, vehicles and the like and is used as a stressed part or a decorative part.
The invention also provides an article prepared from the laminate of the invention. Specifically, the laminated board of the invention is further processed, such as a plastic uptake process, to prepare a container or other parts, such as a refrigerator panel, a container, an automobile bumper or automobile interior and exterior trim, and the like.
The invention has the beneficial effects that:
1. the fiber with the sheath-core structure, namely the sheath-core composite fully-oriented yarn, has the strength of 300-600 MPa and the elongation at break of 15-30%.
2. The laminated board has high tensile strength, high transparency, high rigidity and good toughness, is particularly suitable for the fields of trays, boxes, buildings, vehicles and the like, and is used as a stressed part or a decorative part (such as a refrigerator panel, a container, an automobile bumper or an automobile interior and exterior trimming part).
3. The pipe of the invention has high transparency, high toughness and excellent pressure resistance, and is suitable for the fields of buildings, vehicles and the like.
Description of the drawings:
FIG. 1 is a schematic structural view of a cross section of a fiber of the present invention
Fig. 2 schematic diagram of a 90 ° structure in a laminate of the present invention
FIG. 3 schematic of the structure 0< alpha <90 deg. in another laminate of the invention
FIG. 4 is a photograph of a cross-section of a fiber of the sheath-core structure of the present invention: (a) pre-oriented yarn (spinning speed: 500 m/min); (b) all-orientation yarn (draft ratio: 2.8 times)
1 fiber; 2, a skin layer; 3, a core layer.
Detailed Description
The temperature in the present invention is, unless otherwise specified, in degrees centigrade (. degree. C.).
[ Polymer ]
The polymers of the skin or core layers of the present invention are selected from: polyolefins, polyesters, polyamides, polyurethanes, polyoxymethylenes, and the like.
The polyolefin is selected from C2-20α -homopolymers or copolymers of olefins, in particular selected from polyethylene, polypropylene, polybutene-1, ethylene copolymers with one or more comonomers of propylene, butene, pentene, hexene or octene, propylene copolymers with one or more comonomers of ethylene, butene, pentene, hexene or octene, or butene copolymers with one or more comonomers of ethylene, propylene, pentene, hexene or octene.
Further, the polyester is a condensate of a dibasic acid and a dihydric alcohol, or a ring-opened polymer of a lactone. The polyester is obtained by homopolymerization or copolymerization. For homopolyesters, only one diacid and one diol, or only one lactone; for copolyesters, at least two diacids or two diols, or two lactones are present. Preferably, the polyester is selected from polyethylene terephthalate, polybutylene terephthalate or blends thereof.
Still further, the polyamide is a condensate of a dibasic acid and a diamine, or a ring-opened polymer of lactam. The polyamide is obtained by homopolymerization or copolymerization. For homopolyamides, only one diacid and one diamine, or only one lactam; for copolyamides, at least two diacids or two diamines, or two lactams are present. Preferably, the Polyamide (PA) is selected from PA6, PA66, PA45, PA56, PA10, PA1010, PA11 or PA 12; or a copolycondensate of a plurality of diamines, diacids, such as adipic acid, dodecanedioic acid, hexamethylenediamine and dodecyldiamine.
Further, the polyoxymethylene is homo-or copolyoxymethylene, preferably a homopolymer of trioxane or a copolymer of trioxane and dioxolane and other epoxy compounds.
Still further, the polyurethane is selected from polycondensation products of diols and diisocyanates, such as polyester diols, polyether diols, polycarbonate diols, and the like, with diphenylmethane diisocyanate, hexamethylene diisocyanate, and the like.
Furthermore, the core layer and the skin layer of the fiber have good compatibility, and preferably are the same kind of polymer.
The melt index of the above polymer is 0.5 to 10g/10min, preferably 1 to 8g/10 min.
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1 (preparation of fiber having sheath-core Structure)
The sheath polymer is a propylene copolymer containing ethylene and butylene and has a melt index of2.8g/10min, its melting point Tm1(DSC measurement) was 134 ℃.
The core layer polymer is propylene homopolymer with melt index of 2.8g/10min and melting point Tm2(DSC measurement) was 163 ℃.
(1) Respectively injecting the skin layer polymer and the core layer polymer into a single screw extruder with a heating device for melting and plasticizing, wherein the temperatures of corresponding screw plasticizing sections are respectively Tp1And Tp2Wherein: t ism1+30≤Tp1≤Tm1+50，Tm1+50≤Tp2≤Tm1+90；
(2) Accurately metering the melts formed in the step (1) through a gear pump, controlling the volume ratio of a skin layer polymer to a core layer polymer to be 1/9-9/1, and then spitting the melts into filaments through a bicomponent spinning component and a spinneret plate;
(3) bundling and oiling the filaments discharged in the step (2), winding at the speed of 500-2500 m/min to obtain pre-oriented yarns, and then drafting and heat setting to obtain the skin-core structure fibers, wherein the skin-core structure fibers are skin-core composite fully-oriented yarns with the monofilament linear density of 2-12 dtex; wherein the drafting temperature and the heat setting temperature are respectively TdAnd TsWherein: (T)g1+Tm1)/2≤Td≤(Tg2+Tm2)/2，Td≤Ts≤(Tg2+Tm2)/2，Tg1And Tg2Glass transition temperatures of the skin layer polymer and the core layer polymer, respectively; and secondly, the drafting multiplying factor is 1.5-4.5 times, and the heat setting multiplying factor is 0.9-1.1 times.
Example 2 (preparation of fiber having sheath-core Structure)
Steps (1) and (2) were the same as example 1, and step (3) was replaced with:
bundling and oiling the filaments discharged in the step (2), and then spinning, heat setting and winding at the speed of 2500-4500 m/min to obtain the skin-core structure fiber, namely the skin-core composite fully oriented yarn with the monofilament linear density of 2-12 dtex; wherein the heat setting temperature is Ts，(Tg1+Tm1)/2≤Ts≤(Tg2+Tm2)/2，Tg1And Tg2Glass transition temperatures of the skin layer polymer and the core layer polymer, respectively; and secondly, the heat setting multiplying power is 0.85-1.15 times.
Example 3 (preparation of fiber having sheath-core Structure)
The procedure is as in example 1 except that the skin polymer and the core polymer are replaced with:
skin layer polymer: polyamide with a melt index of 2.8g/10min and a melting point Tm1(DSC measurement) 130 ℃;
core layer polymer: polyamide with a melt index of 2.8g/10min and a melting point Tm2(DSC measurement) was 154 ℃.
Example 4 (preparation of fiber having sheath-core Structure)
The procedure is as in example 2 except that the skin polymer and the core polymer are replaced with:
skin layer polymer: polyamide with a melt index of 2.8g/10min and a melting point Tm1(DSC measurement) 130 ℃;
core layer polymer: polyamide with a melt index of 2.8g/10min and a melting point Tm2(DSC measurement) was 154 ℃.
The fibers prepared in examples 1 to 4 had a strength of 300 to 600MPa and an elongation at break of 15 to 30%.
Example 5 (preparation of unidirectional Fabric)
The fibers with the sheath-core structure prepared in the example 1 are arranged in a single direction, and are drawn off on a creel, and sequentially pass through a godet roller, a tension roller, a yarn separator, a hot roller, a cooling zone, a traction roller and a winding device to form the single-direction cloth under the action of hot pressing; the godet roller, the tension roller and the traction roller are five rollers or seven rollers, and the hot rollers are 1 pair or 2 pairs; the roll surface temperature (i.e., hot pressing temperature) of the heat roll is Tr，Tm1≤Tr<Tm2(ii) a The cooling zone may take natural cooling or forced air cooling.
Examples 6 to 8 (preparation of unidirectional cloth)
The procedure is as in example 5, except that the fibers of examples 2-4 are replaced respectively.
Example 9 (preparation of laminate)
Laminates were made by hot pressing using the unidirectional cloths of examples 5-8, with the fibers crossing at 90 ℃ between each two cloths, and the results are given in table 1.
Table 1 composition and processing of the laminate in example 9
Figure BDA0000922338080000081
Example 10 (preparation of tube)
The fibers of example 1 were continuously wound on a cylindrical die and a tube was prepared by hot pressing (10MPa, 130 c) and the maximum static pressure to which the prepared tube was subjected was 300 MPa.
Example 11 (preparation of tube)
The fibers of example 3 were continuously wound on a cylindrical die and a tube was prepared by hot pressing (10MPa, 130 c) with the maximum static pressure of 360 MPa.

Claims (48)

1. The unidirectional fabric is characterized in that the unidirectional fabric is prepared from fibers with a sheath-core structure; wherein the diameter of the fibers of the sheath-core structure is between 0.5 μm and 60 μm; the polymers of the core layer and the skin layer are the same or different and are independently selected from the following polymers: polyolefins, polyamides, polyurethanes, polyesters, polyoxymethylenes; melting Point T of the sheath Polymerm1And melting point T of the core Polymerm2Satisfies the following relation:
Tm2>Tm1(1)；
the fiber of the skin-core structure is a skin-core composite fully oriented yarn with monofilament linear density of 2-12 dtex;
the fiber with the sheath-core structure is prepared by adopting a method comprising the following steps:
(1) the melting point is Tm1Sheath polymer of (b) and a melting point of Tm2Respectively injecting the core layer polymer into a single-screw extruder with a heating device for melting and plasticizing, and correspondingly plasticizing the screwSegment temperatures are respectively Tp1And Tp2Wherein: t ism1+30≤Tp1≤Tm1+50，Tm1+50≤Tp2≤Tm1+90；
(2) Accurately metering the melts formed in the step (1) through a gear pump, controlling the volume ratio of a skin layer polymer to a core layer polymer to be 1/9-9/1, and then spitting the melts into filaments through a bicomponent spinning component and a spinneret plate;
(3a) bundling and oiling the filaments discharged in the step (2), winding at the speed of 500-2500 m/min to obtain pre-oriented yarns, and then drafting and heat setting to obtain the skin-core structure fibers, wherein the skin-core structure fibers are skin-core composite fully-oriented yarns with the monofilament linear density of 2-12 dtex; alternatively, the first and second electrodes may be,
(3b) bundling and oiling the filaments discharged in the step (2), and then spinning, heat setting and winding at the speed of 2500-4500 m/min to obtain the skin-core structure fiber, namely the skin-core composite fully oriented yarn with the monofilament linear density of 2-12 dtex;
in the step (3a), the drawing temperature and the heat-setting temperature are TdAnd TsWherein: (T)g1+Tm1)/2≤Td≤(Tg2+Tm2)/2，Td≤Ts≤(Tg2+Tm2)/2，Tg1And Tg2Glass transition temperatures of the skin layer polymer and the core layer polymer, respectively;
in the step (3b), the heat-setting temperature is Ts，(Tg1+Tm1)/2≤Ts≤(Tg2+Tm2)/2，Tg1And Tg2The glass transition temperatures of the skin and core polymers, respectively.
2. A unidirectional fabric as claimed in claim 1, wherein the sheath polymer has a melting point Tm1And melting point T of the core Polymerm2Satisfies the following relation:
Tm2≥Tm1+10(1’)。
3. the sheet of claim 2To the fabric, wherein the melting point T of the sheath polymerm1And melting point T of the core Polymerm2Satisfies the following relation:
Tm2≥Tm1+20(1”)。
4. a unidirectional fabric as claimed in claim 3, wherein the sheath polymer has a melting point Tm1And melting point T of the core Polymerm2Satisfies the following relation:
Tm2≥Tm1+30(1”’)。
5. a unidirectional cloth as claimed in any one of claims 1 to 4, wherein said T ism1In the range of 30-300 ℃; the T ism2In the range of 60-300 ℃.
6. A unidirectional fabric as claimed in any one of claims 1 to 4, wherein the fibres have a diameter of between 1 μm and 60 μm.
7. A unidirectional fabric as claimed in claim 6, wherein the fibres have a diameter of between 5 μm and 60 μm.
8. A unidirectional fabric as claimed in claim 7, wherein the fibres have a diameter of between 10 μm and 60 μm.
9. A unidirectional fabric as claimed in any one of claims 1 to 4, wherein the mass of the sheath layer is in the range of 5 to 60 wt% of the total mass of the fibre.
10. A unidirectional fabric as claimed in claim 9, wherein the mass of the sheath layer is 5 to 50 wt% of the total mass of the fibre.
11. A unidirectional fabric as claimed in any one of claims 1 to 4, wherein said polyolefin is selected from polyethylene; polypropylene; polybutene-1; the ethylene copolymer comprises one or more of propylene, butene, pentene, hexene or octene as a comonomer; the propylene copolymer comprises one or more of ethylene, butene, pentene, hexene or octene as a comonomer; or butene copolymer, the comonomer is one or more of ethylene, propylene, pentene, hexene or octene;
the polyester is a condensation compound of dibasic acid and dihydric alcohol or a ring-opening polymer of lactone;
the polyamide is a condensation compound of dibasic acid and diamine or a ring-opening polymer of lactam;
the polyformaldehyde is homo-polyformaldehyde or co-polyformaldehyde;
the polyurethane is selected from the polycondensation products of diols and diisocyanates.
12. A unidirectional fabric as claimed in claim 11, wherein the polyester is obtained by homo-or co-polymerisation; for homopolyesters, only one diacid and one diol, or only one lactone; for copolyesters, at least two diacids or two diols, or two lactones are present.
13. A unidirectional fabric as recited in claim 12, wherein the polyester is selected from polyethylene terephthalate, polybutylene terephthalate, or blends thereof.
14. A unidirectional fabric as claimed in claim 11, wherein said polyamide is obtained by homopolymerization or copolymerization; for homopolyamides, only one diacid and one diamine, or only one lactam; for copolyamides, at least two diacids or two diamines, or two lactams are present.
15. Unidirectional fabric as claimed in claim 14, wherein said Polyamide (PA) is selected from PA6, PA66, PA45, PA56, PA10, PA1010, PA11 or PA 12; or a copolycondensation polymer selected from adipic acid, dodecanedioic acid, hexamethylenediamine and dodecyldiamine.
16. A unidirectional fabric as recited in claim 11, wherein the polyoxymethylene is a homopolymer of trioxane or a copolymer of trioxane and dioxolane and other epoxy compounds.
17. A unidirectional fabric as recited in claim 11, wherein the polyurethane is selected from the group consisting of polycondensation products of at least one of polyester diol, polyether diol, polycarbonate diol, and at least one of diphenylmethane diisocyanate, hexamethylene diisocyanate.
18. A unidirectional fabric as claimed in any one of claims 1 to 4, wherein the core and sheath layers of the fibre are of the same polymer type.
19. A unidirectional fabric as claimed in claim 1, wherein the unidirectional fabric is prepared by a process comprising: arranging the fibers in a single direction, and forming the single-direction cloth under the action of hot pressing, wherein the hot pressing temperature is controlled to be lower than Tm2。
20. A laminate produced by laminating at least two unidirectional fabrics of any one of claims 1 to 19 in sequence and then hot-pressing; wherein, the angle alpha of superposition of two adjacent unidirectional fabrics satisfies the following formula: alpha is more than or equal to 0 and less than or equal to 90 degrees, and the angle alpha is an included angle between the longitude directions of the two unidirectional fabrics.
21. The laminate of claim 20, wherein the laminate is made by 2-2000 layers of unidirectional cloth in-line lamination followed by hot pressing.
22. The laminate of claim 21 wherein the laminate is made by 2-100 layers of unidirectional cloth in-line lamination followed by hot pressing.
23. The laminate of claim 22, wherein the laminate is manufactured by sequentially laminating 5 to 50 unidirectional fabrics and then hot-pressing.
24. The laminate of claim 23, wherein the laminate is manufactured by laminating 10-20 unidirectional fabrics in sequence and then hot-pressing.
25. The laminate of claim 20, wherein the hot pressing temperature is less than Tm2。
26. The laminate panel of claim 25, wherein the hot pressing temperature is equal to the Tm1。
27. The laminate of claim 20, wherein the pressure of the hot pressing is from 0.5MPa to 30 MPa.
28. The laminate of any one of claims 20-27, wherein the laminate has a thickness of between 100 μ ι η and 200 mm.
29. The laminate of claim 28, wherein the laminate has a thickness of between 2mm and 50 mm.
30. A tube produced by continuously winding the fiber of the sheath-core structure in the unidirectional fabric of any one of claims 1 to 18 on a cylindrical mold and then hot-pressing.
31. The tube of claim 30, wherein the hot pressing temperature is less than Tm2。
32. The tube of claim 31, wherein the hot pressing temperature is equal to the Tm1。
33. The tube of claim 30, wherein the hot pressing pressure is 0.5MPa to 30 MPa.
34. The tube according to any one of claims 30-33, wherein the tube has a wall thickness of between 100 μ ι η and 200 mm.
35. The tube of claim 34, wherein the tube has a wall thickness between 2mm and 50 mm.
36. A method of making a unidirectional fabric as claimed in any one of claims 1 to 19, comprising the steps of: preparing a fiber with a skin-core structure; arranging the fibers in a single direction, and forming the single-direction cloth under the action of hot pressing;
wherein, the preparation of the fiber with the sheath-core structure comprises the following steps:
(1) the melting point is Tm1Sheath polymer of (b) and a melting point of Tm2Respectively injecting the core layer polymer into a single screw extruder with a heating device for melting and plasticizing, wherein the temperatures of corresponding screw plasticizing sections are respectively Tp1And Tp2Wherein: t ism1+30≤Tp1≤Tm1+50，Tm1+50≤Tp2≤Tm1+90；
(2) Accurately metering the melts formed in the step (1) through a gear pump, controlling the volume ratio of a skin layer polymer to a core layer polymer to be 1/9-9/1, and then spitting the melts into filaments through a bicomponent spinning component and a spinneret plate;
(3a) bundling and oiling the filaments discharged in the step (2), winding at the speed of 500-2500 m/min to obtain pre-oriented yarns, and then drafting and heat setting to obtain the skin-core structure fibers, wherein the skin-core structure fibers are skin-core composite fully-oriented yarns with the monofilament linear density of 2-12 dtex; alternatively, the first and second electrodes may be,
(3b) bundling and oiling the filaments discharged in the step (2), and then spinning, heat setting and winding at the speed of 2500-4500 m/min to obtain the skin-core structure fiber, namely the skin-core composite fully oriented yarn with the monofilament linear density of 2-12 dtex;
in the step (3a), the drawing temperature and the heat-setting temperature are TdAnd TsWherein: (T)g1+Tm1)/2≤Td≤(Tg2+Tm2)/2，Td≤Ts≤(Tg2+Tm2)/2，Tg1And Tg2Glass transition temperatures of the skin layer polymer and the core layer polymer, respectively;
in the step (3b), the heat-setting temperature is Ts，(Tg1+Tm1)/2≤Ts≤(Tg2+Tm2)/2，Tg1And Tg2The glass transition temperatures of the skin and core polymers, respectively.
37. The process according to claim 36, wherein in the step (3a), the draw ratio is 1.5 to 4.5 times and the heat-setting ratio is 0.9 to 1.1 times.
38. The method according to claim 36, wherein in the step (3b), the heat-setting magnification is 0.85 to 1.15 times.
39. The production method according to claim 36, wherein the temperature of the heat press is controlled to be lower than T when the unidirectional fabric is formed under the heat press actionm2。
40. The preparation method according to claim 36, wherein the preparation method specifically comprises the steps of:
preparing said core-sheath structured fiber according to the method of claim 36;
the fiber of the sheath-core structure is arranged in a single direction, the yarn is withdrawn on a creel, and the unidirectional fabric is formed under the action of hot pressing after sequentially passing through a godet roller, a tension roller, a yarn separator, a hot roller, a cooling area, a traction roller and a winding device, wherein the hot pressing temperature is controlled to be lower than Tm2。
41. The production method as claimed in claim 40, wherein the godet roll, the tension roll and the drawing roll are five rolls or seven rolls, and the heat roll is 1 pair or 2 pairs.
42. A production method as set forth in claim 40, wherein a roll surface temperature of said heat roll, i.e., a hot pressing temperature, is Tr，Tm1≤Tr<Tm2。
43. The production method according to claim 40, wherein the cooling zone adopts natural cooling or forced air cooling.
44. A process for the preparation of the laminate of any one of claims 20 to 29, characterized in that it comprises the following steps: preparing a unidirectional fabric according to the method of any one of claims 36-43; and laminating at least two layers of unidirectional cloth in sequence and then carrying out hot pressing to obtain the laminated board.
45. A method of producing a pipe as claimed in any one of claims 30 to 35, wherein the method comprises the steps of: preparing a core-sheath fiber according to the method of preparing a core-sheath fiber according to any one of claims 36 to 43; and continuously winding the prepared fiber with the sheath-core structure on a cylindrical die and then carrying out hot pressing to obtain the fiber.
46. Use of the unidirectional fabric of any one of claims 1 to 19 in the tray, box, building, vehicle field, as a stressed component or as a decorative component.
47. Use of the laminate of any one of claims 20-29 in the tray, box, building, vehicle field, as a stressed or decorative component.
48. Use of the tube according to any one of claims 30-35 in the tray, box, building, vehicle field, as a stressed or decorative component.
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