CN109532159A - A kind of thermoplastic polymer articles and preparation method thereof - Google Patents

A kind of thermoplastic polymer articles and preparation method thereof Download PDF

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Publication number
CN109532159A
CN109532159A CN201910011073.3A CN201910011073A CN109532159A CN 109532159 A CN109532159 A CN 109532159A CN 201910011073 A CN201910011073 A CN 201910011073A CN 109532159 A CN109532159 A CN 109532159A
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China
Prior art keywords
layer
base layer
polymer
thermoplastic polymer
enhancement layer
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Chinese (zh)
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杨鲜锋
张建民
郑天成
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Shanghai Zhonghua Technology Co Ltd
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Shanghai Zhonghua Technology Co Ltd
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Priority to CN201910011073.3A priority Critical patent/CN109532159A/en
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    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B37/04—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the partial melting of at least one layer
    • 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
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness

Abstract

The purpose of the specific embodiment of the invention is to provide a kind of product and preparation method thereof of thermoplastic polymer, and the product is made of enhancement layer and base layer；The enhancement layer is reinforcement made from the orientation band or fiber of polymer one；The base layer is made of polymeric layer two；The base layer is easy to melt or soften than the enhancement layer；The polymer one is made of by polyamide (PA), polycarbonate (PC), polystyrene (PS), acrylonitrile-butadiene-styrene terpolymer (ABS) or one or more of at least two copolymers formed in four kinds of polymer；The polymer two is made of one or more of at least two copolymers formed in polyamide, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene terpolymer or four kinds of polymer.The product is formed by the applications as laminates of enhancement layer and base layer through hot pressing, has excellent mechanical performance, especially good toughness and shock resistance.

Description

A kind of thermoplastic polymer articles and preparation method thereof
Technical field
The invention belongs to polymer product fields, and in particular to a kind of thermoplastic polymer articles and preparation method thereof.
Background technique
Polymer material has many advantages, such as lightweight, high-strength, corrosion-resistant, in addition its efficient and convenient production and processing skill The quite high cost of raw material of art, cost performance, so that it is just more and more widely used from being born certainly.And conventional plastic The research of product new application technology is never interrupted from beginning to end.
In recent years, the technology that polymer chemical fibre is used to enhance homogeneity polymer product is realized into industrial application, such as GB2253420A discloses a kind of hot-forming high performance plastics obtained of utilization aggregate as made from melt-spun polyethylene fiber Plate, WO2006136323 disclose a kind of including at least the novel of a polyolefin textile layer and polyolefin polymer panel Wound packet technology of preparing, thermoplastic polymer of the same race used realize self-reinforcing, and product mechanical strength greatly improves, The method that CN182213B, JP2012228883 disclose a kind of similar polyolefin or the manufacture of polyester polymer product.
Prior art reinforcement mostly uses non-woven felt material or fabric, and structure type is single, product mechanical property obtained Can be poor, it is not able to satisfy customization, Diversified Products demand.The present invention designability excellent from structure enhanced article, The preparation of such material is optimized.Such as by increasing fabric construction enhancing in non-woven felt material, it is remarkably improved system The structural strength of product；And increase the non-woven felt material of different densities in fabric construction, it can not only reduce technology difficulty and system This is caused, and product can be realized in the variable density of thickness direction, intensity adjustable and performance designability.
In addition, the compatibility and interface bond strength of enhancement layer and base layer are also an important factor for influencing material property. Such as the toughness of PC is poor, ABS is added in PC, the intensity and toughness for being remarkably improved material is blended.PA fiber-reinforced layer and PC The interfacial combined function of base layer is poor, can effectively improve interface bond strength, the mechanical property of product by the way that PA is blended in PC It can be substantially improved.
Currently, polymer product involved in such technology is mainly with polyolefin such as polyethylene (PE), polypropylene (PP) Or based on polyester such as polyethylene terephthalate (PET), poly- comparison benzene dicarboxylic acid butanediol ester (PBT) etc., do not have also Application in terms of other materials.
Summary of the invention
The purpose of the specific embodiment of the invention is to provide a kind of polyamide with high-strength and high ductility, polycarbonate, polyphenyl Ethylene or the product of acrylonitrile-butadiene-styrene terpolymer thermoplastic polymer and preparation method thereof, concrete scheme is such as Under:
A kind of thermoplastic polymer articles, the product are made of enhancement layer and base layer；The enhancement layer is polymer Reinforcement made from one orientation band, fiber；The base layer is made of polymer two；The base layer is than the enhancement layer It is easy to melt or soften；The polymer one is by polyamide, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene (ABS) three At least two in membered copolymer or four kinds of polymer copolymer, one or more of the blend compositions formed；It is described Polymer two is by polyamide, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene terpolymer or this four kinds polymerizations One or more of at least two copolymers formed in object composition.
Optionally, the thermoplastic polymer articles are formed by one layer of fabric or more of composite yarn through hot pressing.
Optionally, the thermoplastic polymer articles are formed by the applications as laminates of enhancement layer and base layer through hot pressing.
Optionally, the polymer one be polyamide, the polymer two be polyamide, polycarbonate or polycarbonate with The blend of acrylonitrile-butadiene-styrene terpolymer；
Or the polymer one is polycarbonate, the polymer two is polyamide or polycarbonate；
Or the polymer one is the blend of polyamide and polycarbonate, the polymer two is polycarbonate and propylene Nitrile-butadiene-styrene terpolymer blend.
Optionally, the strip width or fibre diameter are 0.05~10mm, and the fiber is selected from profiled filament, differential Fiber, long filament, multifilament, strand, broadening one of yarn and covering yarn, slub or a variety of.
Optionally, the fiber is twist yarn, and the twist is 1000 twirls/m or less.
Optionally, the reinforcement is in non-woven felt material, sheet molding compound, tubular molding compound, web material or fabric It is one or more.
Optionally, the textile reinforcement structure includes woven fabric, knitted fabric, braided fabric, the structure type of the woven fabric Selected from plain weave, twill-weave, satin weave, three-dimensional orthogonal structure or 2.5D braiding structure.
Optionally, at least there is a base layer between two neighboring enhancement layer.
Optionally, at least one superficial layer of the thermoplastic article is base layer.
Optionally, the superficial layer of the thermoplastic article is enhancement layer, is the double-deck base layer with the adjacent layer of superficial layer.
Optionally, not identical between the enhancement layer.
Optionally, the base layer be film, sheet material, silk, band, felt or fabric, thickness in monolayer be 0.05~ 200mm, preferably 0.15~7mm.
Optionally, in hot pressing forming process, enhancement layer total volume shared by the volume of enhancement layer melting or softening part Proportional region is 0%~50%, preferably 0%~30%；Base layer shared by the volume of base layer melting or softening part is overall Long-pending proportional region is 30%~100%, preferably 70%~100%.
A kind of preparation method of the thermoplastic polymer articles, by one layer of fabric or more hot pressing of the composite yarn Molding, control hot pressing temperature makes the wrap yarn of the composite yarn partly or entirely melt or soften to form base layer, described The heart yarn of composite yarn do not melt or soften or partial melting or softening form enhancement layer.
The enhancement layer and base layer are pressed Lay up design by a kind of preparation method of thermoplastic polymer articles described above Laying overlapping is carried out, hot pressing synthesis type is then carried out, control hot pressing temperature makes base layer partly or entirely melt or soften, enhances Layer does not melt or softens or partial melting or softening.
A specific embodiment of the invention provides a kind of novel polyamide, polycarbonate, polystyrene or acrylonitrile- The product and preparation method thereof of butadiene-styrene thermoplastic polymer, the product have the characteristics that intensity height, good toughness.
Further, in reinforcement, tissue layer is reasonably added by Lay up design, product obtained has higher power Learn performance, especially impact property；Further, the fiber be twist yarn, the twist be 1000 twirls/m hereinafter, assign enhancing compared with Strong cohesive force can be improved the structural strength of reinforcement, and then improve the mechanical property of product；Further, the fiber is Yarn is broadened, the structural strength of reinforcement can be improved, and then improve the mechanical property of product；Further, the product is by wrapping Heart yarn fabric directly presses, and mechanical property is better than injection-molded item, and does not need overlapping base layer；Further, two enhancement layers Between at least have a base layer, alternatively, at least one superficial layer of the thermoplastic article be base layer, product can be improved Appearance aesthetics；Further, the polymer one is by being added with acrylonitrile-butadiene-styrene terpolymer Polycarbonate constitute, be conducive to improve product tensile strength, the polymer two by be added with polycarbonate polyamide It constitutes, the bond strength of enhancement layer and base layer is remarkably improved, to improve the mechanical property of product；Further, the increasing The proportional region of enhancement layer total volume shared by the volume of strong layer melting or softening part is 0~30%；The base layer melting or The proportional region for softening base layer total volume shared by the volume of part is 70%~100%, and base layer puddle is high, in conjunction with few Partial enhancement layer melting, the matrix one polymer for being conducive to liquid infiltrate the enhancing body portion not melted, it is strong to promote interface cohesion Degree, so as to improve the mechanical property of product.
Specific embodiment
A specific embodiment of the invention provides a kind of thermoplastic polymer articles, and the product is by enhancement layer and base layer It constitutes；The enhancement layer is the orientation band of polymer one, reinforcement made from fiber；The base layer is by two structure of polymer At；The base layer is easy to melt or soften than the enhancement layer；The polymer one is by polyamide, polycarbonate, polyphenyl second One at least two copolymers formed in alkene, acrylonitrile-butadiene-styrene terpolymer or four kinds of polymer Kind or several compositions；The polymer two is by polyamide, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene (ABS) ternary One or more of at least two copolymers formed in copolymer or four kinds of polymer composition.
In a specific embodiment of the invention, the base layer is easy to melt or soften, i.e., the described base than the enhancement layer Body layer and the enhancement layer meet following relationship: T1<T2, T1’<T2'；Wherein, T1、T1' be respectively matrix one polymer two glass The upper limit value and lower limit value of glass transformetion range or melt temperature scope, when base layer is amorphous polymer, the T1、T1’ The respectively upper limit value and lower limit value of the glass transition temperature range of described matrix one polymer two, when base layer is crystallinity Or when semi-crystalline polymer, the T1、T1' be respectively described matrix one polymer two melt temperature scope upper limit value and under Limit value；T2For enhance one polymer one glass transformation temperature or melting temperature, when the enhancing one polymer one be amorphous When state, the T2、T2' be respectively it is described enhancing one polymer one glass transition temperature range upper limit value and lower limit value, when When enhancing one polymer one is crystallinity state, the T2、T2' respectively the melt temperature scope of enhancing one polymer one is upper Limit value and lower limit value.
In a specific embodiment of the invention, the product can by the applications as laminates of enhancement layer and base layer through hot pressing and At, it can also be formed by one layer of fabric or more of composite yarn through hot pressing, the product is directly pressed by composite yarn fabric, After hot pressing, heart yarn line forms enhancement layer, and wrap yarn forms base layer, so that self-reinforcing product be made, mechanical property is excellent In injection-molded item, and overlapping base layer is not needed.
The polymer one or polymer two in a specific embodiment of the invention, in the thermoplastic polymer articles By polyamide (PA), polycarbonate (PC), polystyrene (PS), acrylonitrile-butadiene-styrene terpolymer (ABS) or At least two in four kinds of polymer copolymer, one or more of the blend compositions formed, refer to the polymer One or polymer two in, polyamide (PA), polycarbonate (PC), polystyrene (PS), acrylonitrile-butadiene-styrene (ABS) ternary At least two in copolymer (ABS) or four kinds of polymer copolymer, the blends formed account for major part, and accounting exists 50wt% or more, preferably 80wt% or more, further preferably 90wt% or more are still more preferably 100%.
Specifically for example, the polymer one is polyamide, the polymer two is polyamide, polycarbonate or polycarbonate With the blend of acrylonitrile-butadiene-styrene terpolymer；Or the polymer one is polycarbonate, the polymer Two be polyamide or polycarbonate；Or the polymer one is the blend of polyamide and polycarbonate, the polymer two is Polycarbonate and the blend of acrylonitrile-butadiene-styrene terpolymer etc. can be selected according to product properties demand Different types of material plays the effect of a variety of materials, function, structure, manufacture integrated molding is realized, for example, when using poly- When the blend of carbonic ester and polystyrene is as base layer, product has good transparency, and the twill texture of enhancement layer is clear When high to rigidity requirement, polycarbonate is can be selected in clear beauty, and polycarbonate material is harder, has higher rigidity, when needing When suitable morphotropism, polystyrene may be selected, the material is soft for polystyrene.In another example acrylonitrile-butadiene-styrene (ABS) three The blend of membered copolymer and polycarbonate, may be due to being added acrylonitrile-butadiene-styrene (ABS) as enhancing one polymer one Terpolymer blending modified and melt spinning improves the degree of orientation of polymer, thus assign enhancement layer excellent mechanical property, It is remarkably improved the intensity and toughness of product, the blend of polycarbonate and polyamide, can be significant as matrix one polymer two The bond strength for improving enhancement layer and base layer, promotes the mechanical property of product.
In a specific embodiment of the invention, the polymer one or polymer two include that various usual auxiliaries and function help Agent.The usual auxiliaries for example have heat stabilizer, filler, colorant, antioxidant, ultraviolet absorber or age resister etc.. The function additive can be various functional aids, mainly include fire retardant and inorganic nano-filler, the fire retardant master Will include halogen flame, phosphate flame retardant, nitrogenated flame retardant and expansion type flame retardant, additive amount can according to need into Row addition, usually 5~40wt%, preferably 10~25wt%, the inorganic nano-filler mainly include nano silica, Nanometer covers and opens up soil, galapectite, sepiolite, carbon nanotube and graphene etc., and additive amount, which can according to need, to be added, and leads to Often less than 10wt%, preferably additive amount are less than 5wt%, more preferably less than 2wt%.
In a specific embodiment of the invention, the enhancement layer is the orientation band of polymer one, enhances made from fiber Body, the reinforcement are selected from one of non-woven felt material, sheet molding compound, tubular molding compound, web material or fabric or a variety of, The web material includes unidirectional or polyaxial web material, and the fabric includes the (plain weave, tiltedly of woven fabric made from continuous fiber or band Line, satin weave, orthogonal, 2.5D), knitted fabric (warp knit, weft knitting), the construction fabrics such as braided fabric.Different fabric constructions are all made of continuously Fiber weaving forms, and has good structural integrity and designability, assigns product excellent structural strength.The reinforcement In, at least one layer is tissue layer, reasonably adds tissue layer by Lay up design in the enhancement layer, is increased compared to non-woven felt material Product made from strong body has higher mechanical property, especially shock resistance, this has benefited from continuous fiber in fabric construction Have higher structural integrity and structural strength, it can be according to processing deformation quantity, fiber volume fraction, product in actual production The suitably one or more fabric construction forms of selections such as energy demand.The enhancement layer thickness in monolayer is 0.05~100mm, comprehensive Consider that enhancement layer sufficiently infiltrates under fabrication process condition and the intensity of product, preferably 0.1~10mm, surface density can pass through adjusting Textile technology parameter is designed according to the actual situation, the fibrofelt, such as subject to the mixed and disorderly felt mechanical property performance of staple fiber Isotropism, under the same terms, intensity is lower than continuous fiber reinforcement structure, can be used for adjusting the isotropism of product, described Unidirectional or polyaxial long silk screen medium-length fibre is arranged along single direction, is shown as along fiber axial direction intensity highest, perpendicular to Machine direction intensity is minimum, can orient reinforcement according to product demand, the fabric property shows as the two-way same sex of nearly orthogonal, edge Warp thread is almost the same with the mechanical property of weft yarn axial direction, so as to improve the thermoplastic polymer articles on the whole Intensity and toughness.
In a specific embodiment of the invention, the width of the band or the diameter of fiber are 0.05~10mm, for reality The orientation enhancing of different polymer two in existing reinforcement, according to product and design requirement, the fiber can take profiled filament, The modes such as fibre in differentiation, long filament, multifilament, mixed yarn, broadening yarn, covering yarn, strand or slub.For example, the fiber To broaden yarn, the width of the broadening yarn broadens yarn and fused solution substrate contact in 1mm or more, preferably 3mm or more Specific surface area is larger, is conducive to promote effect of impregnation, while broadening realizes the thin layer of product, and reinforcing fiber volume can be improved Content is conducive to the raising of article construction intensity.In order to realize the orientation enhancing of different polymer two in reinforcement, the fiber The modes such as mixed yarn, covering yarn, strand, slub can be taken.
In a specific embodiment of the invention, the yarn is twist yarn, and the twist is 1000 twirls/m hereinafter, yarn is appropriate Twisting the mechanical property of product can be improved, reason may be because Yarn twisting imparts the stronger obvolvent of fiber assembly Power improves the structural strength of reinforcement, but when the twist is excessive, and the bond strength of the liquid matrix after fiber and melting reduces, The mechanical property of product reduces instead.
In a specific embodiment of the invention, the base layer is polymeric layer, and the polymeric layer can be by gathering It closes object and film or sheet material is made by techniques such as blown film, curtain coating, biaxial tensiones, can also be silk, band, felt, fabric etc., structure type It is unlimited, thickness in monolayer be 0.05~200mm, preferably 0.1~10mm, further preferably 0.15~7mm, specifically can basis The polymeric layer of the performance requirements such as product thickness selection different size.
Not identical between the enhancement layer in a specific embodiment of the invention, enhancement layer can have multilayer, can between layer With different materials, different structure form.In the Lay up design, enhance the structure type of laminated base layer, number of plies ratio can root According to Combination Design is needed, the diversity of the product parameters such as structural strength, density, appearance is realized.
In a specific embodiment of the invention, the material property of enhancement layer single layer, laying quantity and ratio in the product Example, hybrid mode, technical parameter and use environment etc. can be designed according to demand；The enhancement layer is one layer or more, in order to Polymer product has better intensity and toughness on the whole, and at least one layer is fabric.In general, between two enhancement layers at least With a base layer,
In order to improve product flatness, the superficial layer of the preferably described thermoplastic article is enhancement layer, with superficial layer adjoining Layer is the double-deck base layer；In order to improve the apparent brightness of the thermoplastic article, in the preferably described thermoplastic polymer articles At least one surface layer be base layer, it is contemplated that base layer too high levels, then enhancement layer content is too low, and structure enhancement effect subtracts Weak, the base layer is no more than 80%, preferably no more than 60% in the accounting of total number of plies.
In a specific embodiment of the invention, during applications as laminates is through hot pressing, can by control hot pressing parameters, The melting or softening ratio of enhancement layer and base layer is adjusted in especially press temperature and time.The enhancement layer of proper proportion is molten It is merged into each other after melting with base layer molten polymer, improves the interface binding power of solid-liquid two-phase, improve the mechanical property of product Can, especially shock resistance significantly improves, and reason may be that base layer puddle improves, the melting of small part enhancement layer, The matrix one polymer for being conducive to liquid infiltrates the enhancing body portion not melted, interface bond strength is promoted, so as to improve product Mechanical property.Enhancement layer partial melting and in conjunction with the base layer of melting, improves two-phase bond strength, to a certain extent It can be improved the mechanical property of product, but when enhancement layer melting is excessive cannot give full play to its structural re-enforcement, and work as matrix When layer melting is very few, also will affect bonding, the effect for infiltrating enhancement layer, therefore preferably during hot pressing, enhancement layer melting or The proportional region for softening enhancement layer total volume shared by the volume of part is the volume institute of 0-50%, base layer melting or softening part The proportional region for accounting for base layer total volume is 30%~100%；Further, the volume of the enhancement layer melting or softening part The proportional region of shared enhancement layer total volume is 0~30%, base layer shared by the volume of the base layer melting or softening part The proportional region of total volume is 70%~100%, and base layer shared by the volume of best the base layer melting or softening part is total The ratio 100% of volume, i.e. all meltings.
The present invention provides a kind of preparation method of above-mentioned thermoplastic polymer articles, by one layer of fabric of the composite yarn The above hot pressing synthesis type, control hot pressing temperature make the wrap yarn of the composite yarn partly or entirely melt or soften to form base Body layer, the heart yarn of the composite yarn do not melt or soften or partial melting or softening form enhancement layer.The present invention also provides The enhancement layer and base layer are overlapped design by laying and spread by the preparation method of another above-mentioned thermoplastic polymer articles Stacking close, then carry out it is hot-forming, control hot pressing temperature so that base layer is partly or entirely melted or is softened, enhancement layer does not melt Or softening or partial melting or softening.In process, control hot pressing temperature so that enhancement layer is not melted or is softened or Partial melting or softening have excellent so that the molecule segment in thermoplastic polymer band or fiber keeps height-oriented property Mechanical property.Meanwhile base layer partial melting or all meltings in processing, to connect adjacent enhancement layer structure, into one Step improves the globality of product.Polymeric articles made from the above method have the characteristics that intensity is high, good toughness, in use Shock resistance is greatly improved.
Embodiment
Test specification:
DSC test: with the heating rate of 2 DEG C/min, test obtains the fiber assembly of matrix one polymer or enhancement layer Peak melting temperature or glass transition temperature, to crystallinity or semi-crystalline material, with the starting of the melting peak of DSC curve Temperature and end temperature are as its melt temperature scope, for non-crystalline material, with the initial temperature of the glass transition of DSC curve With end temperature as its softening range.
Melting or softening part account for the ratio characterizing method of material total volume: preparation is in plate forming processing temperature to be tested The thermoplastic sheet development test part under pressing process parameter is set, the section (vertical profile that plate through-thickness is made is processed Face).Because through-thickness conducts heat in plate hot pressing, it may be assumed that melted on each vertical section or softening volume ratio is equal. Vertical section (area S is observed under the microscope0), the melting of enhancement layer and base layer or softening part (area S1) be orientated or crystallize Form disappears, and shows as unformed state, with non-puddle there are apparent split-phase interface, calculates vertical under microscopic S in sectional view0、S1Numerical value, then melt or soften part volume ratio k=S of the total volume1/S0。
Extension test: it is tested by GB/T 1,447 2005
Low-temperature impact test: under the conditions of -40 DEG C, the punching of plastics simply supported beam is completed referring to national standard GB/T 1043.1-2008 The measurement of performance is hit, the impact strength of material under prescribed conditions is obtained.
Limit oxygen index test: reference standard GB/T 8924-2005 fibre reinforced plastics combustibility test method-oxygen Index method measures the combustion characteristics of different materials, obtains limit oxygen index experimental data.
Embodiment 1-1
Enhancement layer: the plain cloth (thickness in monolayer 0.4mm, abbreviation P) of PA fiber preparation, long fibre is selected unidirectionally to enhance fibre Net (thickness in monolayer 0.2mm, abbreviation U), staple fiber batt (thickness in monolayer 0.2mm, abbreviation S)；Fiber linear density used is 2500D, Cross section is flat belt-like, and the PA melt temperature scope is 170-200 DEG C；
Base layer: thin layer is made in the PA polymer that melt temperature scope is 150-180 DEG C on inflation film manufacturing machine, and (thickness in monolayer is 0.2mm, abbreviation L)；
Lay up design: 3 layers of plain cloth are used altogether, unidirectional 2 layers of fibre web of enhancing, 2 layers of staple fiber batt, enhancement layer is 7 layers total； 8 layers of base layer thin layer；Its ply stacking-sequence is [P/L/L/S/L/U/L/P/L/U/L/S/L/L/P]；
Hot pressing synthesis type: applications as laminates is hot-forming, and hot compaction temperature is 175 DEG C, hot pressing time 75S, and pressure maintaining cooling is cold But it is formed.So that the ratio that the volume of base layer puddle accounts for base layer total volume is 70%, the body of enhancement layer puddle The ratio that product accounts for enhancement layer total volume is 10%.
Product is it is observed that the flatness that surface has had.
Embodiment 1-2
Other than hot pressing condition of molding is following, remaining condition is consistent with embodiment 1-1.
Hot pressing synthesis type: applications as laminates is hot-forming, and hot compaction temperature is 180 DEG C, hot pressing time 5min, and pressure maintaining cooling is cold But it is formed, so that the ratio that the volume of base layer puddle accounts for base layer total volume is 100%, the body of enhancement layer puddle The ratio that product accounts for enhancement layer total volume is 30%.
Embodiment 1-3
With PA staple fiber batt reinforcement, single layer felts face density is 160g/cm3；Base layer and embodiment 1-1,1-2 phase Together；Lay up design is [S/L/L/S/L/S/L/S/L/S/L/S/L/L/S], and enhancement layer and the total number of plies of base layer are respectively 7,8, with Embodiment 1-1,1-2 is equal；The melting of enhancement layer and base layer or softening volume ratio, working process parameter and 1 phase of embodiment Together.
Comparative example 1
Using above-mentioned PA as raw material, use traditional injection moulding technique preparation PA board product for check experiment.
The tensile property and low temperature of testing example 1-1,1 product of embodiment 1-2, embodiment 1-3 and comparative example respectively Impact property, result such as the following table 1.
The performance test table of table 1 embodiment 1-1,1-2,1-3 and 1 product of comparative example
Show from the test result of upper table 1 compared to comparative example 1, prepare 1 times of products machinery strength enhancing of embodiment 1 More than, especially low-temperature impact resistance be conventional plastic plate 2 times or more.
The result shows that: embodiment 1-1 and embodiment 1-3 is knitted it is found that reasonably being added by Lay up design in the enhancement layer Nitride layer has higher mechanical property, especially shock resistance compared to composite material made from non-woven felt material reinforcement Promote 26%, this have benefited from fabric construction continuous fiber compared to the staple fiber in felt material have higher structural integrity and Structural strength.
Furthermore it measuring in embodiment 1-1, the tensile strength for being parallel to machine direction in the unidirectional fibre web of long fibre is 227MPa, And 172MPa is the tensile strength perpendicular to machine direction in the unidirectional fibre web of long fibre, is shown by Reinforcement structure designs Long fibre orientation fibre web, which is added, can realize the orientation reinforcement of composite material, and mechanical property has excellent designability.
It is found that when base layer melting ratio is improved by 70% to 100%, enhancement layer melts embodiment 1-1 and embodiment 1-2 When partial volume accounts for the ratio 30% of enhancement layer total volume, the mechanical property of composite material, especially shock resistance are significant It improves, tracing it to its cause may be that base layer puddle improves, and the matrix one polymer for being conducive to liquid infiltrates the increasing not melted Strong body portion promotes interface bond strength, so as to improve the mechanical property of composite material.
It is noted, however, that enhancement layer partial melting and in conjunction with the base layer of melting, improve two combine it is strong Degree, can be improved the mechanical property of composite material to a certain extent, but when enhancement layer melting is excessive cannot give full play to its knot Structure humidification, and when base layer melting is very few, it also will affect bonding, the effect for infiltrating enhancement layer, it is therefore preferable that enhancing Layer melting ratio is 0-50%；Preferred base layer melting ratio is 30%-100%.
Embodiment 2-1
Enhancement layer: the plain cloth (thickness in monolayer 0.2mm) of PC fiber preparation is selected, fiber used is by adding 8% Halogen The modified PC polymer melt spinning of fire retardant is made, fiber linear density 3000D, and cross section is circle, glass transition temperature Spending range is 210-230 DEG C；
Base layer: curtain coating thin layer is made in the PC polymer that glass transition temperature range is 180-200 DEG C, and thickness in monolayer is 0.15mm；
Laying overlapping design: replace the structure type of laying, ply stacking-sequence with base layer using enhancement layer plain cloth It is represented by [the 1st layer of base layer/1st layer enhancement layer/n-th layer base layer/n-th layer enhancement layer]；
Hot pressing synthesis type: by laminates in 220 DEG C of hot compaction 2min, the sizing of pressure maintaining cooling down.The wherein PC of base layer Casting films all melt, by control bonding processes in temperature and heating time, the volume of the puddle of enhancement layer account for increasing The ratio of strong body total volume is controlled 20% or so.
Product is it is observed that surface, the apparent brightness that surface where the 1st layer of base layer has had.
Embodiment 2-2
Other than hot pressing condition of molding is following, remaining condition is consistent with embodiment 1-1.
Hot pressing synthesis type: by applications as laminates heat in 200 DEG C of hot compaction 5min, the sizing of pressure maintaining cooling down.So that base layer is complete Portion's melting, enhancement layer do not melt.
Comparative example 2
Using PC as raw material, use traditional injection moulding technique preparation PC plate material product for check experiment.
The tensile property and limit oxygen index of testing example 2-1,2 product of embodiment 2-2 and comparative example respectively, knot Fruit such as the following table 2.
The performance test table of table 2 embodiment 2-1,2-2 and 2 product of comparative example
Show that the performance of product can be significantly improved by adding modifying agent from the test result of upper table 2, it is excellent fire-retardant to assign its Equal functional characteristics.Compared to comparative example 2, embodiment 2-1 and 2-2 realize the self-reinforcing of PC plastic product, and tensile strength mentions The 2 times or more of a height of original Injection moulded part.Comparative example 2-1 and embodiment 2-2 pass through control in product pressing process The melting ratio of enhancement layer and base layer is adjusted in hot pressing parameters, especially press temperature and time.The increasing of proper proportion It is merged into each other after strong layer melting with base layer molten polymer, improves the interface binding power of solid-liquid two-phase, improve product Mechanical property.
Embodiment 3-1
Enhancement layer: selecting the twills (thickness in monolayer 0.4mm, abbreviation M) of surface density 300g/m2 made from PA fiber, Melt temperature scope is 240-260 DEG C；
Base layer: modified PC polymer plate (thickness in monolayer 7mm, abbreviation L), glass transition temperature range are selected 200-220℃；
Lay up design: design laying scheme is [M/L/M/L/M/L/M/L/M]；
Hot pressing synthesis type: applications as laminates is hot-forming, 220 DEG C of hot pressing temperature；Time 3min；Pressing pressure 10MPa, pressure maintaining Cooling down sizing.Enhancement layer does not melt, and base layer puddle institute ratio of the total volume is 100%.
Embodiment 3-2
Base layer PC polymer plate thickness 2mm is identical as embodiment 3-1 in condition.
Embodiment 3-3
Base layer is the PS plate (melt temperature scope is 200-220 DEG C) of thickness in monolayer 7mm thickness, remaining condition and implementation Example 3-1 is identical.
Test implementation 3-1, embodiment 3-2 and embodiment 3-3 tensile property are listed in the table below in 3.
Table 3 implements 3-1,3-2,3-3 product properties and tests table
Show embodiment 3-2 from the test result of upper table 3 it is found that base layer all melting, enhancement layer sufficiently infiltrate with And in the identical situation of other processing conditions, the volume content of enhancement layer increases, and the intensity of resulting product improves, by embodiment 3- 1 and 3-3 is it is found that when using PC and PS as base layer, and product all has good transparency, and the twill texture of enhancement layer is clear Clear beauty；PC material is harder, has higher rigidity, and the material is soft by PS, has suitable morphotropism.
It follows that the type product in selection, has excellent designability.It can be selected according to product performance demands Different types of material is selected, the complex effect of a variety of materials is played, realizes function, structure, manufacture integrated molding.
Material system of the present invention includes PA, PS, ABS, PC and its copolymer, and is not limited only to previous materials, In this analog thermoplastic plastics preparation process, broader material system, such as PP, PE, PET, PMMA can be introduced, is played different The performance advantage of material, to realize the diversification of properties of product and kind.For example on the surface layer of PA self-reinforcing product, 1 layer is added PET can significantly improve the appearance of material, improve the intensity and resisting breakage ability on its surface layer.
Embodiment 4-1
Enhancement layer: selecting fiber made from modified PC/ABS alloy to prepare plain cloth (thickness in monolayer 0.4mm, abbreviation P), Manufacture fiber used or yarn material are made by being modified PC/ABS polymer melting spinning, for the obdurability for improving fiber, institute It states and adds 3% graphene in PC/ABS alloy, fiber linear density 3000D, cross section is circle, glass transition temperature range 180-200℃；
Base layer: the PA polymer that melt temperature scope is 130-150 DEG C, addition 20%PC is blended, using this blend It is made thin layer (thickness in monolayer 0.2mm, abbreviation A)；
Lay up design: 3 layers of enhancement layer plain cloth are used；4 layers of base layer polymer blend thin slice；Its ply stacking-sequence is [P/A/A/P/A/A/P]；Primary layer is bilayer, and centre is plain cloth.
Hot pressing synthesis type: laminates are hot-forming, and hot compaction temperature is 160 DEG C, hot pressing time 70S, and pressure maintaining cooling is cold But it is formed.
Product is it is observed that the flatness that surface has had.
Embodiment 4-2
Enhancement layer is that material is that PC/ABS replaces with corresponding PC, and matrix layer material is replaced with by PA with PC blending corresponding PA, remaining condition are identical as embodiment 4-1.
Embodiment 4-3
Matrix layer material replaces with corresponding PA with PC blending by PA, remaining condition is identical as embodiment 4-1.
Test implementation 4-1, embodiment 4-2 and embodiment 4-3 tensile property are listed in the table below in 4.
Table 4 implements 4-1,4-2,4-3 product properties and tests table
Show that the component of polymer having in enhancement layer is blended in base layer thin layer PA from the test result of upper table 4 PC is remarkably improved the bond strength of enhancement layer and base layer, promotes the mechanical property of product.Blended ABS can be significant in PC The intensity and toughness for improving material are embodied in reinforcement using the tensile strength phase of product made from PC/ABS alloy Compared with product tensile strength made from pure PC reinforcement improve 50% or more, trace it to its cause may be added ABS blending and modifying and Melt spinning improves the degree of orientation of polymer, assigns material excellent mechanical property.
Embodiment 5-1
Enhancement layer: being made twist yarn, line density 1400dtex using modified PA fiber spinning, the twist be 950 twirls/ m；Warp knit grid cloth is weaved on tricot machine using this yarn, mesh size is 60 mesh, and surface density is about 100g/m2.It is melted Temperature range is 230-260 DEG C.
Base layer: using low melting point PA material system blown film, and the thin layer of 0.2mm thickness is made.Its softening point is 125 DEG C, is melted Melting temperature range is 210-230 DEG C.
Lay up design: [base layer/enhancement layer/base layer] n, n=5.
Hot pressing synthesis type: using hot press compacting applications as laminates and Slow cooling molding, press temperature is 220 DEG C, compacting pressure Power 20MPa, pressing time 5min.
Embodiment 5-2
Use non-twist boundling yarn weaving surface density made from the similar PA fiber in embodiment 5-1 for 100g/m2It is oblique Pattern fabric, remaining condition are identical as 5-1 is implemented.
Embodiment 5-3
It using yarn is broadened made from the similar PA fiber in embodiment 5-1, i.e., is 1400dtex's by original line density Untwisted yarn broadening is flat, boundling cotton yarn tape, width 5mm；Remaining condition is identical as 5-1 is implemented.
Embodiment 5-4
Using the non-twist line density in embodiment 5-1 for the yarn of 1400dtex is heart yarn, with embodiment 5-1 base layer Yarn made from the low melting point PA spinning of same material is wrap yarn, and the volume ratio for designing heart yarn and wrap yarn is 1:1.It adopts With this cored weaving yarns plain cloth, it is set as 90/10cm through close, filling density, warp and weft is smooth, arrangement is close, without obvious net Hole, the woven plain cloth lamination of this composite yarn of hot pressing, makes fasciated yarn bond vitrified, and product, hot pressing is made in cooling and shaping It is identical as embodiment 5-1 to close technique.Experiments have shown that replacing the woven fabric of covering yarn obtained through hot press molding using slub Plate has similar effect, and junction parts matrix content is big in slub, and by force and other parts, this characteristic can for caking property Assign the special trait of product bulked fabric and hardened plastics.
Embodiment 5-5
Using the similar PA material in embodiment 5-1, biaxial tension BOPA sheet material is made by curtain coating extrusion process, with a thickness of 0.125mm；The band that width is 2mm is made in chopping；2/2 twills, surface density are weaved on rapier loom using this band For 100g/m2It is identical as fabric made from Untwisted yarn in embodiment 5-2.Remaining condition is identical as 5-1 is implemented.
Comparative example 5
Plate is made using low melting point PA system injection molding described in embodiment 5-1 base layer.
Test the mechanical property of above-described embodiment 5-1, embodiment 5-2,5 product of embodiment 5-3, embodiment 5-4 and comparative example Can, as a result such as the following table 5.
Table 5 embodiment 5-1,5-2,5-3,5-4,5-5 and 5 product properties of comparative example test table
Show from the test result of upper table 5 using embodiment 5-1, embodiment 5-2, embodiment 5-3, embodiment 5-4, reality PA self-reinforcing product made from a 5-5 is applied, compared to 5 traditional injection moulding product of comparative example, mechanical property is substantially improved.By embodiment It is found that the mechanical property of product can be improved in the twisting of yarn appropriateness, tracing it to its cause may be because Yarn twisting assigns by 5-1,5-2 Fiber assembly stronger cohesive force, improves the structural strength of reinforcement.Liquid but when the twist is excessive, after fiber and melting The bond strength of state matrix reduces, and the mechanical property of composite material reduces instead.
By embodiment 5-3 it is found that the collection of filaments in yarn is broadened, the mechanical property of product can be improved, reason can Can be broaden yarn and fused solution substrate contact specific surface area it is larger, be conducive to promoted effect of impregnation, while broaden realize Composite material it is thin layer, reinforcing fiber volume content can be improved, be conducive to the raising of composite structure strength.
When embodiment 5-4 makees enhancement layer using the type fabric, heart yarn is reinforced phase fasciated yarn is fusible and serves as matrix Phase, product have good interface adhesion, excellent in mechanical performance.Core-spun single woven fabric directly presses, and the base layer number of plies can at this time It is 0, base layer can also be added in fabric interlayer, self-reinforcing product can be made, mechanical property is better than injection-molded item, and does not need Overlap base layer.Composite material is obtained likewise, the weavings such as mixed yarn, strand, slub reinforcement can be used and overlap hot pressing, The excellent designability and the adaptation of product of such polymer product manufacturing technology that the present invention designs are presented again.
Embodiment 5-5 is enhanced using band fabric, and article construction intensity and excellent shock resistance, tracing it to its cause may be The defects of band is approximately homogeneous reinforced phase, and there is no the problem of infiltrating that is difficult to of fabric, stomata in product is less, and And processing method, thickness, width, draft ratio, the degree of orientation and the crystallinity for enhancing band all have extensive designability, it can Meet product diversification demand.
Although present disclosure is as above, present invention is not limited to this.Anyone skilled in the art are not departing from this It in the spirit and scope of invention, can make various changes or modifications, therefore protection scope of the present invention should be with claim institute Subject to the range of restriction.

Claims (16)

1. a kind of thermoplastic polymer articles, which is characterized in that the product is made of enhancement layer and base layer；The enhancement layer Reinforcement made from orientation band or fiber for polymer one；The base layer is made of polymer two；The base layer ratio The enhancement layer is easy to melt or soften；The polymer one is by polyamide, polycarbonate, polystyrene, acrylic nitrile-butadiene two One or more of at least two copolymers formed in alkene-styrene copolymer or four kinds of polymer composition； The polymer two is by polyamide, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene terpolymer or this four kinds One or more of at least two copolymers formed in polymer composition.
2. thermoplastic polymer articles according to claim 1, which is characterized in that the product by composite yarn fabric One layer or more forms through hot pressing.
3. thermoplastic polymer articles according to claim 1, which is characterized in that the thermoplastic polymer articles are by increasing The applications as laminates of strong layer and base layer is formed through hot pressing.
4. thermoplastic polymer articles according to claim 1, which is characterized in that the polymer one is polyamide, institute Stating polymer two is being blended for polyamide, polycarbonate or polycarbonate and acrylonitrile-butadiene-styrene terpolymer Object；
Or the polymer one is polycarbonate, the polymer two is polyamide or polycarbonate；
Or the polymer one is the blend of polyamide and polycarbonate, the polymer two is polycarbonate and acrylonitrile- The blend of butadiene-styrene terpolymer.
5. thermoplastic polymer articles according to claim 1, which is characterized in that the strip width or fibre diameter are 0.05~10mm, the fiber are selected from twist yarn, profiled filament, fibre in differentiation, long filament, multifilament, strand, broadening yarn, packet One of heart yarn or slub are a variety of.
6. thermoplastic polymer articles according to claim 5, which is characterized in that the fiber is twist yarn, the twist For 1000 twirls/m or less.
7. thermoplastic polymer articles according to claim 1, which is characterized in that the reinforcement is selected from non-woven felt One of material, sheet molding compound, tubular molding compound, web material or fabric are a variety of.
8. thermoplastic polymer articles according to claim 7, which is characterized in that the fabric is woven fabric, knitted fabric Or braided fabric, the structure type of the woven fabric be selected from plain weave, twill-weave, satin weave, three-dimensional orthogonal structure or 2.5D braiding structure.
9. thermoplastic polymer articles according to claim 1, which is characterized in that at least have between two neighboring enhancement layer There is a base layer.
10. thermoplastic polymer articles according to claim 1, which is characterized in that at least the one of the thermoplastic article A superficial layer is base layer.
11. thermoplastic polymer articles according to claim 1, the superficial layer of the thermoplastic article is enhancement layer, with The adjacent layer of superficial layer is the double-deck base layer.
12. thermoplastic polymer articles according to claim 4, which is characterized in that not identical between the enhancement layer.
13. thermoplastic polymer articles according to claim 1, which is characterized in that the base layer be film, sheet material, Silk, band, felt or fabric, thickness in monolayer are 0.05~200mm, preferably 0.15~7mm.
14. thermoplastic polymer articles according to claim 2 or 3, which is characterized in that in hot pressing forming process, increase The proportional region of enhancement layer total volume shared by the volume of strong layer melting or softening part is 0%~50%, preferably 0%~ 30%；The proportional region of base layer total volume shared by the volume of base layer melting or softening part is 30%~100%, preferably 70%~100%.
15. a kind of preparation method of thermoplastic polymer articles as claimed in claim 2, which is characterized in that by the covering yarn One layer of fabric or more hot pressing synthesis type of line, control hot pressing temperature melt the wrap yarn of the composite yarn partly or entirely Or softening forms base layer, the heart yarn of the composite yarn does not melt or softens or partial melting or softening form enhancement layer.
16. a kind of preparation method of the thermoplastic polymer articles as described in claim 3-14 any one, which is characterized in that will The enhancement layer and base layer are by Lay up design progress laying overlapping, and then hot pressing synthesis type, control hot pressing temperature make base layer Partly or entirely melting or softening, enhancement layer do not melt or soften or partial melting or softening.
CN201910011073.3A 2019-01-04 2019-01-04 A kind of thermoplastic polymer articles and preparation method thereof Pending CN109532159A (en)

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