CN101014731A - Loaded polymer fibre, method for the production thereof, use of the same, and composition comprising such fibres - Google Patents

Loaded polymer fibre, method for the production thereof, use of the same, and composition comprising such fibres Download PDF

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Publication number
CN101014731A
CN101014731A CNA2005800251653A CN200580025165A CN101014731A CN 101014731 A CN101014731 A CN 101014731A CN A2005800251653 A CNA2005800251653 A CN A2005800251653A CN 200580025165 A CN200580025165 A CN 200580025165A CN 101014731 A CN101014731 A CN 101014731A
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fiber
filled polymer
polymer fiber
aforesaid right
product
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G·卡多雷特
R·莫拉特
C·比安奇
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Saint Gobain Materiaux de Construction SAS
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Saint Gobain Materiaux de Construction SAS
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/04—Macromolecular compounds
    • C04B16/06—Macromolecular compounds fibrous
    • C04B16/0616—Macromolecular compounds fibrous from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B16/0625—Polyalkenes, e.g. polyethylene
    • C04B16/0633—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
    • E04C5/07—Reinforcing elements of material other than metal, e.g. of glass, of plastics, or not exclusively made of metal
    • E04C5/073—Discrete reinforcing elements, e.g. fibres
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Architecture (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Civil Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Artificial Filaments (AREA)
  • Nonwoven Fabrics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Reinforced Plastic Materials (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Paper (AREA)

Abstract

The invention relates to a loaded polymer fibre comprising a mass of additives and having a Young's modulus which is higher than that of a non-charged polymer fibre, said additives comprising mineral additives having at least one submicronic dimension.

Description

Filled polymer fiber and production method thereof, purposes and contain the composition of such some fibre
The present invention relates to fiber art, relate more specifically to a kind of filled polymer fiber.
These polymer fibers are applied to many fields.That for example can mention M.Jambrich and P.Hodul is entitled as " textile applications of polypropylene fibre " literary composition, this article enrolls in " polypropylene: A-Z reference " (Polypropyl é ne an A Z reference) book, and this book is that J.Karger-Kocsis edits, Kluwer Academic publishing house in 1999 publishes.
These polymer fibers are because its intrinsic characteristic and using separately, or they merge use with other material, other fiber of adding in the various base materials (inorganic matter, polymer etc.), mainly are in order to strengthen function.
In addition, these fibers are used to produce various forms of products: yarn, fabric, pad, one-way product etc.
And, also need to have the polymer fiber of good mechanical properties.
File US6331265 has disclosed a kind of by the 3% filled polypropylene fiber that is added to the CNT in the polypropylene body.These CNTs are about 1 μ m, diameter 1-50nm.The number of this filled polypropylene fiber is 1 dtex, high tenacity, and Young's modulus is higher than non-filled polypropylene fiber.The reinforcing material of this fiber as mortar, concrete or cement mortar proposed.
In fact be difficult to obtain highly purified CNT.In fact, some relict catalysts may constitute the big or small impurity of micron that last fibre property is reduced.In addition, be difficult to produce a large amount of CNTs, this is reflected in the cost of fiber.
In addition, under laboratory condition, produced this filled polymer fiber, do not considered industrial constraints, particularly aspect reliability and output.Therefore, the production method of proposition is impracticable for industrial production.
The present invention proposes a kind of polymer fiber, and it has good mechanical properties, and particularly high Young's modulus also is easy to realize industrial-scale production simultaneously.
For this reason, first purpose of the present invention is the filled polymer fiber that body contains additive, and the Young's modulus of this filled polymer fiber is higher than non-filled polymer fiber, and these additives contain some inorganic additives with at least one submicron-scale.
A kind of polymer and the inorganic additive combination with at least one submicron-scale of the present invention can access a kind of fiber, and its Young's modulus increases with respect to the non-fiberfill fibers that with the same polymer is base.
In addition, in fact inorganic additive of the present invention is easy to obtain or be easy to synthesize, and also is easy to purifying if necessary.These additives also have not too expensive advantage.
The production of fiber of the present invention is consistent with industrial requirement.
In this application, submicron-scale of the present invention (dimension submicronique) should be appreciated that it is the submicron-scale that inorganic additive is averaged.For example submicron-scale is corresponding to diameter or thickness.
In this application, the term fiber is a generalized definition.When not adding other adjective or describing in detail, non-drawn fiber of term fibring (canned paragraph) and drawn fiber (one or many).This fibring yarn or slender silk are also represented the many filaments set (fabric fibre class) that are same to each other or different to each other.This fiber can be continuous or cut off, and is that lack or long.
Advantageously, the submicron-scale of inorganic additive can be less than 500nm, preferably less than 100nm.
Inorganic additive can be the structure of ball, shaft-like or stratiform class.
Certainly, it is contemplated that the combination of additive with different structure.
Preferably, the form factor of these inorganic additives (facteur de forme) greater than 5, is preferably more than 50.
Can mention, this form factor is defined as the ratio of full-size and minimum dimension.
High form factor has been guaranteed high tenacity, and is especially true when the large scale of additive of the present invention and the substantially parallel axes of this fiber.
Inorganic additive can be metal oxide or clay.
In these metal oxides, can enumerate aluminium oxide, barium monoxide, titanium oxide, zirconia, manganese oxide, talcum, magnesia and calcium carbonate.
These clays can be stratiforms, i.e. sheet or fibrous.
These inorganic additives can comprise peelable stratiform clay, it preferably is selected from synthetic or natural phyllosilicate, smectite clay (argiles smectites), for example montmorillonite, nontronite, beidellite, hectorite, saponite, sauconite, vermiculite and equivalent, and magadiite, kenyaite, stevensite, galapectite, aluminate oxide, hydrotalcite and equivalent.
Preferably, the surface negative charge of these clays is that the described additive of per 100 grams is at least 20 milliequivalents, preferably at least 50 milliequivalents, more preferably 50-150 milliequivalent.
Therefore, can use in mineral, for example absorbent organic molecule carries out modification to these clays between the clay thin layer, can they peel off like this.Though clay may have any cation exchange capacity, yet preferably clay is rationally peeled off.
Preferably, these inorganic additives can be selected from montmorillonite and boehmite.
Boehmite is an alumina monohydrate Al-O-OH base.For example boehmite is bar-shaped.
Montmorillonite has the thin layer that can peel off, and can be uniformly distributed in the filled polymer fiber of the present invention.
Montmorillonite and boehmite also have extra high Young's modulus, are higher than 100GPa.
Can use at least a following reagent to make these inorganic additive surface modifications: cationic surfactant, amphiprotic agents, aliphatic series, aromatics or aryl aliphatic amine derivative, phosphine and sulfide, preferably ammonium,  or sulfonium salt.
These reagent are as the swelling agent of laminated clay.
In addition, these reagent also help the dispersion of inorganic additive of the present invention.
Can also use adhesion promoter that these inorganic additives are carried out modification, this adhesion promoter is organic silane compound preferably, more preferably is silane, amino silane, vinyl silanes and composition thereof.
In total weight of fiber, the weight content of inorganic additive is preferably lower than 10%, more preferably is lower than 5%.
This filled polymer fiber can be a polymer-matrix, and this polymer for example is selected from polyolefin, polyamide, polyester, polyacrylonitrile and polyvinyl alcohol and copolymer thereof.
Advantageously, this filled polymer fiber can be a kind of filled polyolefin fiber, and for example polyethylene or polypropylene more preferably are filled polypropylenes.
This fiber can also contain polyolefin and the polyolefinic mixture of polar functional group is arranged, this polyolefin is maleic anhydride, glycidyl methacrylate, vinyl pyrrolidone, styrene-methacrylate, acrylate or acetic acid esters graft polyolefin preferably, in the filled polymer total weight of fiber, polyolefin weight content with polar functional group is preferably lower than 10%, more preferably is lower than 5%.
Polyolefin with polar functional group can carry out grafting before and after synthetic.Be grafted with after synthetic to be beneficial to and wait to spin mixture dispersion and fiber elongation.In order to improve Young's modulus, can limit polyolefinic percentage biglyyer with polar functional group.
The fiber number of this filled polymer fiber (titre) is 0.5-10 dtex (dtex), more preferably is the 0.5-2 dtex.
Use the fiber (monofilament) of relative small bore can reach particularly advantageous enhancing effect in composite.
It is circular that the cross section of filled polymer fiber of the present invention needs not to be, and can have irregular shape or mutliblade shape.
The toughness of filled polymer fiber of the present invention equals at least 80% of non-fiberfill fibers toughness.
In a particularly advantageous specific embodiment, this filled polymer fiber has the high tenacity of 4cN/ dtex at least, 5cN/ dtex at least preferably, most preferably 7cN/ dtex, 8-9cN/ dtex especially at least.
Can reach this toughness scope by regulating spinning and drafting method in a suitable manner.As an example, can select to have the basic polyolefine material of suitable molecular weight distribution especially.
This filled polymer fiber preferably contains a kind of sizing material in its surface, and this sizing material contains the compound of amine or polyamine, phosphorus or poly-phosphorus, more preferably the phosphate of aliphatic chain-Ji.
Use sizing material that this fiber exposed surface is carried out simple modification, can effectively and enduringly improve the interaction between fiber and the hydraulicity material.
Use one or more to provide the jelly that is coated with that helps the spinning function, the surface nature of this polymer fiber is improved.
Help the spinning function to be to help at least one spinning section, to form polymer fiber: to relate to lubricated these fibers (is monofilament in this stage) especially, to improve the transporting equipment operation in the different phase of producing, the electrostatic charge that fiber is carried drops to minimum.
For example, can select following product: Schill﹠amp; Seilacher with trade name SILASTOLCut 5A and Cut 5B, Dr Boehme with trade name SYNTHESIN 7292, Cognis with trade name KB 144/2, Cognis with trade name STANTEX S6077 and Cognis with trade name STANTEX S6087/4 product sold.
Sizing material amount on this fiber is with fiber dry weight basis 0.05-5 weight % dry.
For the application of hydraulicity matrix, this sizing material also provides the wettable function of hydraulic binder based composition and use thereof in packaging, promotes to give the further function of improving mechanical performance with the function of hydraulicity matrix adhesion with to fiber-cement composite.
The wettable function of hydraulic binder based composition and use thereof in packaging is to help the dispersion of polymer fiber in this matrix, and this is because fibrous material good dispersion in the initial binder/water mixture of producing this product.It is hydrophilic that this function mainly utilizes the polarity on fibrous material surface that it is become.
The function of promotion and the adhesion of hydraulicity matrix is to strengthen the interaction between fabric reinforcement and hardening product matrix.The function in back is also utilized the polar functional group that exists at fiber surface.
Be selected from one or more following agent these functions can be provided: lubricant, antistatic additive, surfactant, have the aliphatic chain compound and the polymer of polar functional group, wherein lubricant can be the aliphatic chain compound, similarly surfactant also can be the aliphatic chain compound, and perhaps antistatic medium can be the polymer with polar functional group.
Drawn fiber can be that cut-out is thread, the about 2-20mm of length, 5-12mm especially.
Another object of the present invention be as described previously the filled polymer fiber in fiber based products as the purposes of fortifying fibre.
Another object of the present invention be a kind of with the fiber be the base product, it is characterized in that it contain just like as previously defined filled polymer fiber.
Advantageously, product is fabric, yarn (voile), long fiber pad, cut staple pad, one-way (unidirectionnel) product, nonwoven products, rope, net (filet), belt, flat wealthy belt, ribbon form, or be the form of the mixture of described fiber and heterogeneity fiber, preferably be the blended fiber form.
The blended fiber example is the fiber that Saint-Gobain sells with trade name TWINTEX, and it contains polypropylene filament and glass yarn.
Filled polymer fiber of the present invention has a plurality of Application Areass: carpet, hygiene applications, belt, rope and cord, textile industry (clothes, yarn), household textiles (decorate with nonwoven products, wall with fabric etc.), geotextile, geotextile, pack, medical textile, bioactive fiber, multicomponent fibre, high-performance yarn or high strength monofilament (safety belt, safety net or fishing net etc.).
Naturally, filled polymer fiber of the present invention can be solid or solid substantially, and promptly for example it has hollow along fiber axis.
Naturally, can apply the present invention's (gluing or not gluing) filled polymer fiber.
This fiber can be added in product from oil, the asphaltic products with various forms, for example is added in the asphaltic base product with the mat form, for example roof element.
Various forms of fibers can also be thermoformings.
In first favourable embodiment of the present invention, this product comprises inorganic matrix, hydraulicity material (masse à prise hydraulique) preferably, and this product preferably is selected from adhesive, mortar, concrete, mortar and asbestos cement.
Hydraulicity material is made of hydraulic binder, mainly is selected from existing various cement, and these cement have randomly added inertia or active filler.
In filler and additive, can enumerate rheology modifier (dispersant, plasticizer, superplasticizer, flocculating agent), inorganic filler (silica, flying dust, slag, volcanic ash, carbonate), and the support or the fibrous skeleton (natural fabric of filtration or dewatering use, particularly cellulose fibre, or synthetic fiber).
During bend test, this known series products generally believes and tends to damage when being the compression strength level of epimere when reaching.
The applicant is definite, and this situation is that too big " morphotropism " by the fiber that absorbs hypomere tension force causes, so this crack elongate fiber of developing more is just long more.
And, use high Young's modulus fiberfill fibers of the present invention to reach and reduce the percentage elongation of fiber at the tension face.
Therefore, the Young's modulus of raising fiberfill fibers can limit the distortion of this hypomere.This has just limited the neutral axis displacement, has therefore limited the increase of epimere compression stress.
So these hydraulicity products have extra high fracture load.
Fiber of the present invention is effective especially as the reinforcing material as asbestos cement, and their ratio is in the about 0.2-5 weight of beginning mixture gross dry weight %.
In the original stock gross dry weight, fiber of the present invention is effective especially as the reinforcing material of mortar, and for " anti-fracture ", their ratio is in the about 0.01-0.2 weight of beginning mixture gross dry weight % fiber, for the structuring effect, their ratio is 0.2-5%.
In this first mode, these fibers can be the fibers that cuts off, its length 2-20mm, more particularly 5-12mm.
This product can have multiple shape (hollow, tubulose), preferably flat board or corrugated plating shape.
Adopt the aqueous suspension filtering technique to make and be processed into tabular hydraulic binder based article, this aqueous suspension contains hydraulic binder, fortifying fibre and filler randomly.
Usually the method that adopts based on this technology is with the known method of title Hatschek method: guarantee in outfit in the jar of component equally distributed member in tank volume very rare aqueous suspension to be housed; Filter drum partly is immersed in the jar, and its rotation causes material to deposit skim (fiber and hydration adhesive) on the jar surface; This thin layer takes on the glue spreader by felt, wraps up in continuously on this roller; When this thin layer reaches expectation thickness, cut this layer, so that take off the single piece of water hard material from roller.At this moment this sheet is made formed product, solidifies by adhesive to obtain final characteristic again.Stacked the sheet of right quantity, exerting pressure guarantees to be bonded to integral body again, can obtain thicker product.
Some sheet materials are as roof or facade member like this.
In second embodiment of the present invention, this product can contain polymer substrate, and it preferably is selected from polyethylene, polypropylene, polyamide, polyester, epoxy resin and phenol matrix.
Composite, for example the main application fields of polypropylene-base composite is: transportation (part under the automotive hood, parcel shelf etc.), electric application, family expenses and consumer goods, building and public work and industrial product.
Another object of the present invention is to produce as the method for previously defined filled polymer fiber, and this method comprises the spinning step of polymer composition, and said composition contains and has the inorganic additive of submicron-scale at least.
Additive of the present invention is easy to disperse, and can obviously not change the rheological property (viscosity etc.) of the polymer composition of waiting to spin.
Can adopt to extrude and obtain this polymer composition.Extrusion temperature is adjusted according to polymer and described additive.As an example, for filled polypropylene, the spinning temperature can be 250-300 ℃.
This spinning step can comprise cooling, preferably for good heat-exchange capacity, uses the cooling of suitably cooling and wet air and (radial) cooling down operation radially.
One preferred embodiment in, this method be included in after the spinning immediately or then carry out in drawing-off (é tirage) step that is lower than under the fusion temperature.
Preferably, this method can be included in the filament contraction step of carrying out in the continuous drafting equipment.
Use has the roller of different temperatures and friction speed, uses baking oven can implement this step.
One preferred embodiment in, this method comprises described preparation of compositions step, this packing comprises at least one filter operation.
Therefore, for example use filter, before spinning, remove possible aggregation and impurity in the extruding machine outlet.
In addition, in order to realize control (at aspects such as concentrated, dispersion, compatibilities) better, described preparation of compositions step can comprise the enforcement premixed, makes particle then, with the polymer dilution, and randomly uses polymer-modified dilution.The graininess masterbatch that will contain inorganic additive of the present invention, preferably noncommodity graininess masterbatch is diluted in this polymer, can obtain this pre-composition.In its preparation process, this masterbatch can filter.
Can add the gluing step in the spinning step.
The gluing step can be carried out after drawing-off, then a drying steps that uses one or more baking oven.
This gluing can be coated with gum stock, or is coated with solution, dispersion or emulsion moisture or other suitable liquid-carrier base.
Another object of the present invention be with as previously defined fiberfill fibers and hydraulicity material be the product processes of base.
According to this method, preparation with as previously defined hydraulic binder, water and fiber be the starting mixt of base, on fixing or mobile supporter, filter these fibers, form wet basic (é l é mentaire) thin slice, randomly stacked a plurality of basic thin slice, make wet intermediate product, dry then this thin slice or wet intermediate product.
Another object of the present invention is a kind of composition of hydraulic material, and said composition contains just like previously defined hydraulic binder and fiber.When can being dewatering, make these compositions the cement products of suspension, or the cement products of mortar during other manufacturing process.
Last purpose of the present invention is to contain the composition of polymer substrate and fiber as described previously.
Some matrix optimization ground are thermoplastic matrix, heat-curable matrix like this, preferably polyethylene, polypropylene, polyamide, polyester, epoxy resin or phenol matrix.
The present invention is described now in the following embodiments without limitation.
Embodiment 1 (contrast)
The reference fiber is the non-fiberfill fibers of a kind of high tenacity, minor diameter (1 dtex), be not use inorganic additive of the present invention and use the HF445FB acrylic resin of Borealis company to obtain, it is 18g/10min that the melt flow index of HF445FB acrylic resin (so-called MFI) records under 230 ℃ and 2.16kg.
Export-have the about 0.35mm of diameter hole-dimension at spinning head, promptly all monofilament cool off after coagulation fast at the cooling air that uses control temperature and speed.
During spinning, the sizing material of the standard SYNTHESIN 7292 that Dr Boehme company sells is deposited on the polypropylene fibre of spinning head outlet, and its amount is 0.45 weight % polypropylene fibre dry extracts.
Fiber is on bobbin then, uncoiling and at drawing-off migration continuous drafting then, and this drawing-off zone comprises not warm-up mill on the same group, these rollers are with more and more higher rotational speed.Do not injecting hot-air or steam oven between on the same group the roller.Fiber cools off at drawing-off zone end.Then this fiber is cut into the section of 30mm, tests.
Embodiment 2
Use following polymer composition to produce the filled polypropylene fiber, its amount is to represent in total weight of fiber weight %.
The NANOMER C44PA product that-5.5%Nanocor company produces, it contains have an appointment 45% montmorillonite and polypropylene (PP);
The PP of-94.5%Borealis HF445FB.
Montmorillonite is a kind of clay, and its clay thin layer has nanoscale average thickness and hundreds of nanometer average length, and its form factor is greater than 50.
Use single multiple screw extruder to produce polymer composition down for about 250 ℃, and deliver in the spinning head in hole with diameter 0.35mm in temperature.The viscosity of said composition is suitable with the viscosity of using polymer.
During spinning, the sizing material of the standard SYNTHESIN 7292 that Dr Boehme company sells is deposited on the filled polypropylene fiber of spinning head outlet, and its amount is 0.45 weight % of filled polypropylene fiber dry extracts.
Embodiment 3
Use following polymer composition to produce the filled polypropylene fiber, its amount is that the material weight % in total weight of fiber represents.
-40% dense pre-composition, it contains 5% graininess montmorillonite, and this pre-composition is to use the 87.5%PP Bor é alis HF445FB that sold by Polyone company and 12.5%NANOBLEND 1001 to obtain, and they contain have an appointment 40% montmorillonite and PP;
-60％PP Borealis HF445FB。
This clay thin layer has nanoscale average thickness and hundreds of nanometer average length, and its form factor is greater than 50.
Use two-screw rod to rotate extruding machine in the same way and produce this pre-composition down for 220 ℃,, deliver to then in the spinning head in hole, produce particle with diameter 3mm by having the filter in the about 40 μ m holes of diameter in temperature.
Use list-multiple screw extruder to produce this polymer composition down for about 250 ℃, send in the spinning head in hole with 0.35mm diameter in temperature.The viscosity of said composition and the polymer phase of use are worked as.
During spinning, the sizing material of the standard SYNTHESIN 7292 that Dr Boehme company sells is deposited on the filled polypropylene fiber of spinning head outlet, and its amount is 0.45 weight % of polypropylene fibre dry extracts.
Embodiment 4
Use following polymer composition to produce the filled polypropylene fiber, its amount is that the material weight % in total weight of fiber represents.
-40% dense pre-composition, it contains 5% graininess montmorillonite, and this pre-composition is to use 87.5%PP Borealis HF445FB and 12.5%NANOBLEND 1001 to obtain;
-58%PP Borealis HF445FB; With
2% polypropylene of-grafting 1% maleic anhydride, so-called PPgMA is the product of the standard P OLYBOND3200 of Crompton company sale.
This clay thin layer has nanoscale average thickness and hundreds of nanometer average length, and its form factor is greater than 50.
Under condition similar to Example 3, produce this fiber.
Embodiment 5
Use following polymer composition to produce the filled polypropylene fiber, its amount is that the material weight % in total weight of fiber represents.
-60% dense pre-composition, it contains 5% graininess montmorillonite, and this pre-composition is to use 87.5% PP Borealis HF445FB and 12.5%NANOBLEND 1001 to obtain;
-37%PP Borealis HF445FB; With
-3%PPgMA is the product of the standard P OLYBOND3200 of Crompton company sale.
This clay thin layer has nanoscale average thickness and hundreds of nanometer average length, and its form factor is greater than 50.
Under condition similar to Example 3, produce this fiber.
Embodiment 6
Use following polymer composition to produce the filled polypropylene fiber, its amount is that the material weight % in total weight of fiber represents.
-60% dense pre-composition, it contains 5% graininess montmorillonite, and this pre-composition is to use the 87.5%PP Borealis HF445FB that sold by Polyone and 12.5%NANOBLEND1012 to obtain, and it contains have an appointment 40% montmorillonite and PP;
-37%PP Borealis HF445FB; With
The PPgMA of the standard P OLYBOND3200 of-3%Crompton company.
These clay thin layers have nanoscale average thickness and hundreds of nanometer average length, and its form factor is greater than 50.
Under condition similar to Example 3, produce this fiber.
Embodiment 7
Use following polymer composition to produce the filled polypropylene fiber, its amount is that the material weight % in total weight of fiber represents.
-20% dense pre-composition, it contains 5% graininess montmorillonite, and this pre-composition uses the 84.5%PP Borealis HF445FB that sold by Multibase company and 15.5%PL19315 product to obtain, and it contains have an appointment 32% montmorillonite and PP;
-79.5%PP Borealis HF445FB; With
The PPgMA of the standard P OLYBOND3200 of-0.5%Crompton company.
This clay thin layer has nanoscale average thickness and hundreds of nanometer average length, and its form factor is greater than 50.
Under condition similar to Example 3, produce this fiber.
Embodiment 8
Use following polymer composition to produce the filled polypropylene fiber, its amount is that the material weight % in total weight of fiber represents.
-60% dense pre-composition, it contains 5% modified montmorillonite used, graininess, this pre-composition is to use 90%PP, 5%PPgMA and 5% modified montmorillonite used obtaining, and it contains have an appointment 62% montmorillonite and alkylammonium;
-40％PP Borealis HF445FB。
This clay thin layer has nanoscale average thickness and hundreds of nanometer average length, and its form factor is greater than 50.
Use is rotated two-multiple screw extruder in the same way and is produced this pre-composition down for about 180 ℃ in temperature, and this pre-composition is delivered in the spinning head with diameter 0.35mm hole then by having the filter in the about 40 μ m holes of diameter, produces particle.This pre-composition is the lean mixture of 80%PP Borealis HF445FB and 20% noncommodity graininess masterbatch mixture, they contain the PPgMA of the standard P OLYBOND3200 that 50%PPBorealis HF445FB, 25% sells by Crompton company and 25% Powdered modified montmorillonite used, and it is the product of the standard C loisite C20A that sells of Southern Clay Products company.Use is rotated two-multiple screw extruder in the same way and is produced this masterbatch mixture down for 180 ℃ in temperature, and it is delivered in the spinning head with diameter 3mm hole then by having the filter in the about 40 μ m holes of diameter, makes the graininess masterbatch.
Use single multiple screw extruder under about 250 ℃ of temperature, to produce this polymer composition, it is delivered in the spinning head with diameter 0.35mm hole.The viscosity of said composition is suitable with the viscosity of using polymer.
During spinning, the sizing material of the standard SYNTHESIN 7292 that Dr Boehme company sells is deposited on the filled polypropylene fiber of spinning head outlet, and its amount is 0.45 weight % of filled polypropylene fiber dry extracts.
Embodiment 9
Use following polymer composition to produce the filled polypropylene fiber, its amount is that the material weight % in total weight of fiber represents.
-70% is concentrated to 3% and be granular modification boehmite base pre-composition, this pre-composition is to use the PPgMA of 94%PP Borealis HF445FB, 3% standard P OLYBOND3200 and 3% boehmite of being sold with trade name CAM9010 by SAINT-GOBAIN company to obtain, and with 0.5% (gamma-amino propyl group) triethoxysilane of selling with trade name A1100 by Aldrich company carry out surface modification and
-30％PP Borealis HF445FB。
This boehmite is bar-shaped, the about 20nm of average diameter, and average length 100-200nm, so form factor is greater than 5.
Under condition similar to Example 3, produce this fiber.
Test
Following table 1 has write down No. 1 reference fiber and 2-8 fiberfill fibers in the preceding result of drawing-off (cold drawn continuously).
Following table 2 has write down No. 1 reference fiber and the result of 2-8 fiberfill fibers after drawing-off (cold drawn continuously).
Young's modulus is defined as secant modulus, equals the ratio of stress and distortion, and they are respectively 1,5 or 10%.
The Fafegraph that uses Textechno company to sell, the toughness-extension curve that is obtained by filament calculates Young's modulus.The Vibromat that uses Textechno company to sell has measured these diameters.Determine these measuring conditions according to the ISO5079 standard.These fibers distance between chuck before drawing-off is 10mm, fixing reaches the maximum drafting ratio with continuous drafting, avoids simultaneously on (at continuous yarn of this stage) after the fibrous fracture, and its distance is 20mm.
Table 1
Fiber embodiment before the cold drawing-off The weight content of inorganic additive (%) Spinning fiber number (dtex) Elongation at break (%) Toughness (cN/ dtex) In 1% (GPa) modulus Increase 1% o'clock modulus
1 (reference) 0 4.9 470 1.5 1.08 -
2 2.5 4.8 520 1.4 1.45 34％
3 2 4.8 510 1.4 1.61 49％
4 2 5.1 500 1.4 1.54 42％
5 3 5.1 460 1.4 1.56 44％
6 3 4.6 490 1.3 1.59 47％
7 1 5 470 1.4 1.41 31％
8 3 4.7 530 1.3 1.55 43％
9 2 5.1 500 1.2 1.39 29％
Table 2
Cold drawn fiber embodiment The weight content of inorganic additive (%) Fiber number (dtex) Elongation at break (%) Toughness (cN/ dtex) At 5% modulus (GPa) Increase in 5% modulus At 10% modulus (GPa) Increase in 10% modulus
1 (reference) 0 1 23 9.3 6 5.4 -
2 2.5 0.9 18 9.1 7.5 25％ 6.4 19％
3 2 0.9 19 9.0 6.9 15％ 5.9 9％
4 2 0.9 19 9.0 6.8 13％ 6.1 13％
5 3 0.9 18 9.4 7.8 30％ 6.7 24％
6 3 0.9 18 9.7 7.5 25％ 6.5 20％
7 1 1.1 20 8.9 6.6 10％ 5.8 8％
8 3 0.9 19 8.5 7.2 20％ 6.0 12％
9 2 0.8 16 8.5 7 17％ 6.1 13％
The Young's modulus of 2-9 number non-drawn fiber and drawn fiber is apparently higher than No. 1 non-drawing-off and drawing-off reference fiber separately.In addition, the 2-9 drawn fiber has kept high tenacity.
Following embodiment illustrates the application of the different filled polypropylene fibers of the present invention in producing cement products.
Embodiment 10
Adopt laboratory method to adopt and filter the production cement products, this method is reproduced the key property of commercial run (for example Hatschek technology) product that obtains quite faithfully.
With the following cement matrix of making suspension with excessive water greatly is two kinds of cement compositions of base preparation.
Component Quality (in g)
CPA cement (95% clinker) 79.2
Calcium carbonate 15.5
Pinus Radiada cellulose 3.5
Non-filled polypropylene fiber or filled polypropylene fiber 1.8
Cotton-shaped dose of BASF AE70 400ppm
Total amount 100
Use so first kind of reference cement composition of preparation of the filled polypropylene fiber identical with embodiment 1 reference fiber.These fibers also are to produce in the mode that is similar to embodiment 1, but an additional back-gluing step of carrying out after drawing-off is arranged, and its amount is 0.4 weight % of filled polypropylene fiber dry extracts.
Use so second kind of cement composition of preparation of the filled polypropylene fiber identical with embodiment 5 fibers.These fibers also are to produce in the mode that is similar to embodiment 5, but an additional back-gluing step of carrying out after drawing-off is arranged, and its amount is 0.4 weight % of filled polypropylene fiber dry extracts.
It is long that these fibers are cut into 10mm.
For every kind of composition, allow said composition filter by wire netting, form the individual layer of the about 1mm of thickness.Make six individual layers stacked, carry out circulation laminated into type, obtain before solidifying, containing material in the about 50 weight % water of cement weight, the about 6mm of thickness.
This laboratory material solidified 6 days down at 40 ℃ in sealing bag, cut into the above sample of wide 20mm, long 260mm then.These samples placed cold water 24 hours, mechanically applied pulling force.
These samples are placed between the chuck of pull test instrument and carry out tension test, the distance between the chuck is 180mm.This tension test is carried out with the 1.2mm/min interval velocity.
These samples 10a is corresponding to reference sample (non-fiberfill fibers).These samples 10b is corresponding to sample of the present invention (fiberfill fibers).
Draw out force-displacement curve, this curve has the representative configuration that adopts the Hatschek technology to obtain the observed result of product.
When displacement began, this power increased sharply, and observed steady section then, and at this moment this power slowly changes, and repeatedly chapped corresponding to sample, and up to large fracture occurring, after this this power reduces because of phorogenesis when large fracture ftractures.
The length of steady section of repeatedly chapping has reflected that plate is with whole fibre-reinforced effect.
Observe especially, destructive power is defined as the specimen width that this power is listed divided by table 3, and the destructive power of each sample 10b is extra high, also is higher than the destructive power of reference sample 10a.
Table 3
Sample Destructive power (N/mm) Destructive power increases (%) The steady section length that repeatedly chaps (mm) The steady section length that repeatedly chaps increases (%)
10a (reference) 24 - 9 -
10b 28 17 12 33
In a specific embodiments, calcium carbonate percentage increases to 60%, even 80%, on the contrary, cement percentage reduces greatly.
The sample that can also contain the fiber identical with similar approach production with embodiment 2-4 or 6-9 fiber.
Embodiment 11
These embodiment 11 explanations are adopted the Hatschek method to use fiberfill fibers of the present invention and are produced cement products.
Preparation with the matrix phase that embodiment 10 fiberfill fibers are arranged with matrix be the aqueous suspension of base.Every kind of suspension is added in the groove of Hatschek machine and forms thin slice, and form the hydrated cementitious material sheet of the about 1mm of thickness in the glue spreader surrounding.After the cutting, the hydrated material thin plate is stacked on the framework, forms flat board or the corrugated blank of thickness 6mm.
These plates at room temperature solidify after 28 days and carry out mechanical test.
Have with the sample of embodiment 10 same sizes and under identical condition, carry out pull test.Its force-displacement curve has similar form with the plate that repeatedly chaps, and is breaking the back reduction.
It is extra high observing each sample destruction power.
The sample that can also contain the fiber identical with similar approach production with embodiment 2-4 or 6-9 fiber.
Other purposes of filled polymer fiber
Filled polymer fiber of the present invention, for example with filled polypropylene fiber like the embodiment 2-9 fiber-like, or the filled polymer fiber with higher fiber number, can be used as technical yarn or high strength monofilament as production safety band, packing, protecting wire net, fishing net etc.
So, method according to following article description, filled polymer fiber of the present invention can be used to produce the one-way fabric or the pad kind fabric of hot pressing: these title of article are " hot pressing behavior I. mechanical performances of woven orientation PP fiber and band ", people such as author P.J.Hine, be published in " polymer " (Polymer) on, 44,2003,1117-1131 page or leaf, and " hot pressing of high-modulus melt-spun polyethylene fiber ", people such as author P.J.Hine, be published on " material science magazine " (Journal of Materials Science), 28,1993, the 316-324 page or leaf.
Method according to following article description, filled polypropylene fiber of the present invention also can be used for producing geotextile and geotextile: these title of article are " geotextile and geomembranes ", author K.Chan, be published in " polypropylene: A-Z reference " book, edit by J.Karger-Kocsis, Kluwer Academic Publisher publishes, and 1999.
Filled polypropylene fiber of the present invention also can be used for producing any polypropylene (PP) thermoforming composite, PP yarn long filament around volume, complete-the PP laminated plate, and they are by forming at the PP on surface fabric or mat and at the PP of core honeycomb line or PP foamed plastics.Can also be referring to being entitled as " recycling composite " article, author T.Pejis is published in " material of today " (MaterialsToday), 2003, the 30-35 pages or leaves.A kind of like this composite has complete recycling advantage.
Filled polypropylene fiber of the present invention also can be used for producing:
-dipping yarn bundle, they are to produce according to the method for describing in " dipping technique of bundle or fibre bundle ", its author is people such as A.Lutz, be published in " polypropylene: A-Z reference " book, J.Karger-Kocsis edits, and Kluwer Academic Publisher publishes, and 1999.
-composite plate of PP fabric, one-way material or pad arranged, they flood with thermosetting resin: according to the method for describing in " the polyolefinic melting behaviour of gel spinning/drawing-off ", people such as author C.W.M.Bastiaansen., be published in " Makromol.Chem., Macromol.Sym. ", 28,1989, the 73-84 page or leaf.
The mixture of-PP fiber and glass fibre, it is for example to produce according to the Twintex method of Saint-Gobain.
In addition, filled polymer fiber of the present invention also can be the fiber that adopts a step continuous drafting method (not having subsequent operation) to obtain.
In addition, filled polymer fiber of the present invention also can be not have premixed in advance but the fiber that adopts the polymer composition spinning to obtain.
Filled polymer fiber of the present invention also can be the fiber that adopts the solvent method spinning to obtain, and this solvent method spinning is used the polymer of making solution or used polymer precursor.Can be with reference to being entitled as " the gel spinning research of ultra-high molecular weight polyethylene " literary composition, author Y.Zhang, C.Xiao, J.Guangxia, A.Shulin, " journal of applied " (Journal of AppliedPolymer Science), 1999, the 4th phase, the 3rd phase, 670-675 page or leaf.
Filled polymer fiber of the present invention can also be to use fills the fiber that fibrillation (fibrill é) band obtains.

Claims (29)

1. body contains the filled polymer fiber of additive, and the Young's modulus of this filled polymer fiber is higher than non-filled polymer fiber, it is characterized in that these additives contain the inorganic additive with at least one submicron-scale.
2. filled polymer fiber according to claim 1, the submicron-scale that it is characterized in that inorganic additive are less than 500nm, preferably less than 100nm.
3. the described filled polymer fiber of each claim in requiring according to aforesaid right is characterized in that these inorganic additives have the structure of sphere, shaft-like or stratiform class.
4. the described filled polymer fiber of each claim in requiring according to aforesaid right, the form factor that it is characterized in that these inorganic additives is preferably more than 50 greater than 5.
5. the described filled polymer fiber of each claim in requiring according to aforesaid right is characterized in that these inorganic additives are selected from metal oxide, clay and their mixture.
6. the described filled polymer fiber of each claim in requiring according to aforesaid right, it is characterized in that these inorganic additives contain peelable stratiform clay, it preferably is selected from synthetic and natural phyllosilicate, smectite clay, hydroxyl wheat silicon sodium stone, kenyaite, stevensite, galapectite, aluminate oxide, hydrotalcite and equivalent.
7. the described filled polymer fiber of each claim in requiring according to aforesaid right is characterized in that these inorganic additives are selected from montmorillonite and boehmite.
8. the described filled polymer fiber of each claim in requiring according to aforesaid right, it is characterized in that these inorganic additives are to use at least a following reagent to carry out surface modification: derivative, phosphine, the sulfide of cationic surfactant, amphiprotic agents, aliphatic series, aromatics or aryl aliphatic amine, preferably ammonium, sulfonium or  salt.
9. the described filled polymer fiber of each claim in requiring according to aforesaid right is characterized in that these inorganic additives are to use adhesion promoter to carry out modification, and it is organic silane compound preferably.
10. the described filled polymer fiber of each claim in requiring according to aforesaid right, the weight content that it is characterized in that inorganic additive is to be lower than 10% in total weight of fiber, is preferably lower than 5%.
11., it is characterized in that it is the filled polyolefin fiber, preferably the filled polypropylene fiber according to the described filled polymer fiber of each claim in the aforesaid right requirement.
12. require described filled polymer fiber according to aforesaid right, it is characterized in that this fiber contains polyolefin and the polyolefinic mixture with polar functional group, it is the polyolefin of grafted maleic anhydride, glycidyl methacrylate, vinyl pyrrolidone, styrene-methacrylate, acrylate or acetic acid esters preferably, and the polyolefin weight content with polar functional group preferably is lower than 10% in the filled polymer total weight of fiber.
13. according to the described filled polymer fiber of each claim in the aforesaid right requirement, the fiber number that it is characterized in that this polymer fiber is the 0.5-10 dtex, preferably the 0.5-2 dtex.
14. the described filled polymer fiber of each claim in requiring according to aforesaid right, the toughness that it is characterized in that it are 4cN/ dtexs at least, preferably 7cN/ dtex at least.
15. the described filled polymer fiber of each claim in requiring according to aforesaid right is characterized in that it contains sizing material in its surface, this sizing material contains the compound of amine or polyamine, phosphorous or poly-phosphorus, preferably based on the phosphate of aliphatic chain.
16. the described filled polymer fiber of each claim is as the purposes of fortifying fibre in the product in requiring according to aforesaid right.
17. with the fiber is the product of base, it is characterized in that it contains the described filled polymer fiber of each claim among the with good grounds claim 1-15.
18. requiring described according to aforesaid right is the product of base with the fiber, it is characterized in that it is fabric, yarn, cut staple pad, long fiber pad, nonwoven products, one-way product, rope, net, belt, flat wealthy belt, ribbon form, or be the form of the mixture of described fiber and heterogeneity fiber, preferably be the blended fiber form.
19. described according to each claim in claim 17 or 18 is the product of base with the fiber, it is characterized in that it comprises inorganic matrix, hydraulicity material preferably, and this product more preferably is selected from adhesive, mortar, concrete, grout and asbestos cement.
20. according to claim 19 is the product of base with the fiber, it is characterized in that this product is an asbestos cement, it contains the described fiber in starting mixt gross dry weight 0.2-5 weight %.
21. described according to each claim in claim 19 or 20 is the product of base with the fiber, it is characterized in that it has the shape of flat or corrugated plating.
22. described according to each claim in claim 17 or 18 is the product of base with the fiber, it is characterized in that it contains polymer substrate, it preferably is selected from the matrix of polyethylene, polypropylene, polyamide, polyester, epoxy resin or phenol.
23. according to the production method of the described filled polymer fiber of arbitrary claim among the claim 1-15, it is characterized in that it comprises the polymer composition spinning step that contains inorganic additive, these inorganic additives have at least one submicron-scale.
24. the production method of polymer fiber according to claim 23 is characterized in that it is included in the drafting step that is lower than under the fusion temperature.
25. according to the production method of the described polymer fiber of arbitrary claim in claim 23 or 24, it is characterized in that it comprises the step for preparing described composition, this step comprises at least one filter operation.
26. with fiber and hydraulicity material is the production method of the product of base, it is characterized in that:
-preparation is the starting mixt of base with hydraulic binder, water with according to the filled polymer fiber that arbitrary claim was limited among the claim 1-15;
-on fixing or mobile supporter, filter these fibers, form wet basic thin slice;
The stacked formation of-a plurality of basic thin slices intermediate product that wets, its feature also be dry should wet intermediate product.
27. the composition of hydraulic material, it contains hydraulic binder and according to the described filled polymer fiber of arbitrary claim among the claim 1-15.
28. contain polymer substrate and according to the composition of the described filled polymer fiber of arbitrary claim among the claim 1-15.
29. require described composition according to aforesaid right, it is characterized in that this matrix is the matrix of polyethylene, polypropylene, polyamide, polyester, epoxy resin or phenol.
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