CN1033820A - Matrix material, preparation and its goods - Google Patents
Matrix material, preparation and its goods Download PDFInfo
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- CN1033820A CN1033820A CN 87105994 CN87105994A CN1033820A CN 1033820 A CN1033820 A CN 1033820A CN 87105994 CN87105994 CN 87105994 CN 87105994 A CN87105994 A CN 87105994A CN 1033820 A CN1033820 A CN 1033820A
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Abstract
The matrix material of high strength, light weight, comprise the disperse reinforcing of wrapping up by the matrix that contains the polymkeric substance microplate, expansible, complete hole hydrophobic, the thermoplastic polymer that this microplate of the essentially no production of above-mentioned polymkeric substance microplate is used, this matrix material adopts the composition of hot pressed paper shape to produce by paper-making technique.
Description
The present invention relates to matrix material, their preparation method and the used water dispersion of this method and the sheet material or the coiled material (web) of paper shape, the article that also relate to composite structure and make with these matrix materials.
" matrix material " used herein speech is meant the material that two or more material combined of sheet material or web form, and it comprises a kind of successive matrix phase, and this matrix phase is wrapped in by dispersive and is enhanced to the wild phase that branch is formed.Matrix material can be used for making various article, the wing and airframe structure, helicopter blade, shell and the sports equipment that comprise automobile reed, brake pads, chemical process equipment, aircraft are as golf club (handle), bat, ski and games racket frame.These structures are referred to as successive fiber process method by employing and produce; this working method must and vacuumize by pressurization matrix material is carefully reinforced; reducing porosity and to guarantee that matrix phase is coalescent fully, thereby avoid the finished product heterogeneity to occur.These working methods usually need special equipment, and this equipment has increased initial cost and the tooling cost of making these structures.
In recent years, allegedly adopt conventional paper making equipment and method, made matrix material by aqueous methods by solid polymer, strongthener and latex binder.For example United States Patent (USP) 4,426,470, this patent has described in detail to be used high density polyethylene(HDPE) to make solid polymer, glass fibre to make strongthener with various or have a method that latex binder that negatively charged ion is connected electric charge or has a water-fast organic polymer basically of positively charged ion connection electric charge prepares composite sheet.It is said that producing the used water-based oar material of matrix material with paper-making technique must carefully process to obtain satisfied product.The powdery polymer that must pay special attention to avoid loose or pitch are on the surface of the paper shape coiled material of preparation matrix material.For example because pulverous polymkeric substance can deposit and be bonded in papermaking operating period and the coiled material that wets or the heating surface of the contacted drying plant of sheet material, the surface aggregation of loose powdery polyolefin can disturb the normal effect of paper making equipment.
Someone advises adopting special flocculation agent and dispersing auxiliary to alleviate by the caused problem of the surface aggregation of polymer powder or resin.But use this class additive can increase the production cost of matrix material.In addition, according to the component of the used concrete combination of matrix material, some dispersing auxiliary can damage physical integrity or the required characteristic of the finished product is had a negative impact.For example, when using the vitriol oil to do to produce the dispersing auxiliary of the matrix material that contains glass fibre, final coiled material is very easily crisp; When using neutral auxiliary agent (as Lubrizol
TMOr Katapol
TM) time, matrix material is made laminate product, each of this product layer tends to peel away.
Another undesirable characteristic of the matrix material produced of the paper-making technique of Cai Yonging is that " edge seepage " take place so far, and this shows that resin flow crosses the edge of strongthener net in the matrix material.The wet layer preparation method of the feasible matrix material that proposes so far of these shortcomings and the matrix material of gained lack the magnetism of commercial exploitation.
Have found that,, adopt paper-making technique, by producing matrix material effectively to preparing the polymkeric substance microplate that adds in used heating eutectic sheet material of matrix material or the coiled material according to the present invention.This polymkeric substance microplate has suppressed polymer powder basically or resin is assembled on sheet material or coiled material and keep all components in the matrix material to be dispersed in the whole the finished product.The use of polymkeric substance microplate has also suppressed the generation of edge seepage effectively.
One aspect of the present invention provides the matrix material that exists with sheet material or web form, it comprises a kind of successive matrix phase, this matrix phase parcel is enhanced to the wild phase that branch is formed by dispersive, this successive matrix phase comprises the hot-melt polymer microplate, this microplate is made by a kind of expansible, hydrophobic, thermoplastic polymer, the polymkeric substance of this swelling state is difficult for crisp, and the polymkeric substance microplate is not produced the expansion of this microplate or the complete hole of foamable polymer basically.These matrix materials have various application, comprise bearing and shell, shellproof guard shield and the various sports equipment of (but being not limited thereto) furniture-plates, buff wheel, low friction.
The present invention provides a kind of composition that exists with uniform water dispersion form on the other hand, it comprises foregoing polymkeric substance microplate and the used enhancing ingredients of one or more matrix materials, adopt conventional paper making equipment and method, with the batching of said composition as the preparation matrix material.The water-dispersion physical efficiency that contains the polymkeric substance microplate forms hot melt sheet material or coiled material quite uniformly, and these materials can be processed into final matrix material easily.
Formed hot melt sheet material of intermediate steps or the coiled material that provides on the one hand again at the production matrix material of the present invention.
A further aspect of the present invention provides the method for producing above-mentioned matrix material, this method comprises that the disperse phase that makes above-mentioned water dispersion forms a kind of wet sheet material or continuous coiled material, dry this sheet material or coiled material, heating sheet material or coiled material are enough to that the polymkeric substance microplate is changed into and are wrapped in the continuous matrix phase of enhancing ingredients, obtain matrix material thus.
Other aspects and advantages of the present invention are conspicuous to reading the following those skilled in the art that describe part in detail.
The concrete composition of implementing each used component of the present invention has obtained the to have many desired properties matrix material of (comprising hot formability, quite light weight, high strength, dimensional stabilizing and anti-deformation).These characteristics still can keep when temperature and humidity changes broad.Matrix material of the present invention also has fabulous water absorption resistance.
Main component in the matrix material is polymkeric substance microplate and pulverizing, enhancing ingredients hydrophobic and thermoplastic resin (these compositions form matrix phase) and at least a formation wild phase.Other component such as binding agent also can be used for producing matrix material, and be as described below.
A. matrix phase
Matrix phase accounts for 10% to 70%(weight of final matrix material usually).The polymkeric substance microplate component of matrix phase is by any expansible, hydrophobic and thermoplastic polymer production, and this polymkeric substance exists with non-shattering expanded form.A key property of polymkeric substance microplate is the complete hole of the inflated polymer raw material of their essentially no production polymkeric substance microplates.That the used raw material of polymkeric substance microplate preferentially is selected from is non-shattering, expansible, hydrophobic and multipolymer or blends thermoplastic styrene polymkeric substance, lower polyolefins or these polymkeric substance.Lower polyolefins can be that 2 to 6 ethylenically unsaturated hydrocarbons monomer makes by any carbonatoms, for example polyethylene, polypropylene, polybutene or polymethylpentene." being difficult for crisp " used herein speech is meant that polymer raw material is quite soft, and the density that has usually is 5 pounds/cubic feet or lower.Density is the production that 1 to 2 pound/cubic feet styrene polymer is particularly useful for microplate.
Expansible, hydrophobic and microplate thermoplastic styrene polymkeric substance or lower polyolefins with and preparation method thereof done more complete description at my United States Patent (USP) 4,207, No. 378 (on April 29th, 1980 issued).The whole open text of this patent is incorporated the application as a reference into.Microplate can be pulverized polymer raw material with the form of expansible polymer sheet and obtain in fact by using the described machine of confused broken machine such as my aforesaid U.S. Patent (the 4th hurdle 22 walks to the 5th hurdle 35 row).The microplate that obtains is except the complete hole of the expanded polymer of essentially no this microplate of production, generally also have following properties: (a) the microplate size is about 40 to 325 microns long, 20 to 320 microns wide and 0.5 micron thickness, (b) essentially no in shape unified profile, (c) density be about the concrete not expanded polymer of producing the inflated polymer raw material density 85% or higher.The surface-area of polymkeric substance microplate is about 6 meters squared per gram.When with scanning electronic microscope physical size being amplified 1000 times of observations, microplate has distortion paper slip, tangible random wavy profile and has many wrinkles, folding line and folding.As if SEM check and also demonstrate the deformable contour that is trailed and break profile that above-mentioned profile is the regular geometric cross section of the hole of expansion honeycomb arrangement before pulverizing.
Because the physical features of their uniquenesses, polymkeric substance microplate have promoted to make the preparation of the used water dispersion of matrix material.This microplate helps homodisperse solid ingredient and the stability that keeps water dispersion in whole matrix material as dispersing auxiliary.The low powdery resin (as polyolefine and polycarbonate) of proportion uses this microplate, even also can be disperseed and remain in the suspension equably.The polymkeric substance microplate also can make the solid ingredient of making sheet material or coiled material remain in the paper shape sheet material or coiled material of thermally melting.About 20% to 100%(weight in the matrix phase) component can be the polymkeric substance microplate.This microplate preferably accounts for 20% to 60%(weight of matrix phase).
Have now found that the matrix material with special required physical properties can obtain by using the polystyrene microplate.The application of polystyrene in matrix material of this discovery and consideration traditionally antithesis.It has been generally acknowledged that polystyrene is quite easily crisp material, this material especially is not suitable for use in the component of matrix material.For example, it has been generally acknowledged that the polyethylene and/or the polycarbonate that are usually used in compound composition are incompatible with polystyrene, this is because the important physicals of the molten mixture of these polymkeric substance is relatively poor, comprises tensile strength, shock strength and bending strength and thermotolerance.Adulterated enhancing ingredients tends to further these performances be produced adverse influence in this resin compound.Therefore, in fact the polystyrene that the form with microplate with above-mentioned physical property of mixing in matrix material of the present invention exists has improved the shown physicals of the finished product, and this discovery is beat all fully.
Matrix phase also can contain hot-melt resin various pulverizing, hydrophobic.These resins comprise polycarbonate, comprise the polyolefine of lower molecular weight and High molecular weight polyethylene and polypropylene and its multipolymer, polyester, nylon, polyacetal, the chlorine-containing polymer that comprises ethylene chloride and polyvinyl chloride, the fluoropolymer that comprises tetrafluoroethylene, acrylic resin, acrylonitrile-butadiene-styrene (ABS) (A.B.S) polymkeric substance etc.If desired, also can use the blend or the molten alloy of aforementioned multipolymer.These resins are ground into the powder that particle diameter is 1 to 425 little length.The consumption of these thermoplastic hot molten resin's powder can account for 70% of matrix phase weight at the most.The amount ranges of toner component preferably is about 40% to 70% in the matrix phase.Usually need 10%(weight at least) polymkeric substance microplate (gross weight with matrix is a benchmark) to obtain high toner loading level (60% weight or higher).
B. wild phase
Wild phase accounts for 30% to 90% of final matrix material weight usually.The enhancing composition that constitutes wild phase can be fibrous or granular.Fibrous enhancing ingredients can be selected from glass fibre, carbonizedfibres, polymkeric substance (natural and synthetic) fiber, inorganic fibre and steel fiber.Preferred fibrous enhancing ingredients is a cellulosic fibre material, as hardwood wood pulp cellulose or fibrous wood pulp mixture, can be produced by the defective work in the papermaking processing.These wood pulps have 350 or lower freeness (freeness) usually.Other available cellulosic fibre comprises those fibers that obtained by semi-refined plant material (for example finished cereal grass is as straw).Therefore, the actual applied various fibers of the present invention can not have the raw material of practical use to obtain by other.Because these fibrous enhancing ingredients energy matrix materials that the quality of production is light, intensity is high and cost is quite low, so they are preferred.With regard to gaining in strength, should comprise glass microfiber at matrix material.The synthetic polymeric fibers enhancing ingredients can give final matrix material required quality, but it is much more expensive than above-mentioned wood pulp cellulose.Satisfied matrix material is by using Kevlar and/or polytetrafluoroethylene (PTFE) fiber to obtain.Have found that and contain for example Kevlare
The matrix material of fiber has special physicals, comprises very high intensity and thermotolerance.Use Nomex
Fiber has also obtained to have the matrix material of better physical performance and high heat resistance, above-mentioned Nomex
Fiber by-multipolymer of phenylenediamine and isophthalyl chloride forms.The suitable length of nylon fiber is about 0.5 centimetre to 1.5 centimetres.
When preparation matrix material of the present invention, should utilize the tight blend of making by above-mentioned polymkeric substance microplate and cellulosic fibre or the material (cobeat) of pulling an oar altogether.Cellulosic fibre can be the cellulosic fibre (as the wood pulp that is obtained by cork and hardwood) in cotton fibre (as velveteen) or other source.Why be referred to as " altogether making beating material " be because in the papermaking pulping engine with behind the cellulose fiber peacekeeping polymer formation homogeneous dispersion, also need to add this dispersion in hollander and making beating until its freeness in 400 to 450 scopes.Those skilled in the art it has been generally acknowledged that freeness is that a kind of of speed that water flows through slurry measures, and can also be referred to as the Canadian standard freeness according to Tappi standard T227-m-58() measure.The freeness value is high more, and water is just high more by the flow velocity of slurry.Can add one or more noncontractile thread-forming polyesters of relatively small amount in pulling an oar altogether, preferably the polyterephthalate fiber is (as Trevira
101) to strengthen the wet tearing strength of making the used paper shape composition of matrix material.The best polymkeric substance microplate and about 50% by about 35% to 50% weight of making beating material is formed to the cellulosic fibre of about 65% weight altogether, if use polyester, its total amount is about 7% of cellulose fiber peacekeeping microplate gross weight at the most.
Making beating material dispersion can in statu quo be used altogether, maybe can adopt conventional papermaking process and equipment to be processed into the successive coiled material, latter Geng Jia.After suitable drying, the coiled material of pulling an oar altogether becomes the product that can store, and when needs were made matrix material, this product was fit to.If desired, can when the preparation batching, add cellulose fiber peacekeeping trevira respectively.The preparation altogether step of making beating material has been done detailed description in the embodiment 1 of my No. 4,293,378, United States Patent (USP), the open text of the entire chapter of this patent is incorporated this specification sheets as a reference into.
One of advantage of using the material of pulling an oar altogether in making matrix material is its water dispersion that helps to form identical uniform plural components.The making beating material also can improve the confining force of grain fraction in coiled material or the sheet material altogether.
The particulate state enhancing ingredients can be selected from the low clay of diatomite, urethane microplate, aluminum oxide, wood chip, sawdust, carbon dust (graphite that comprises pulverizing), silicon-dioxide, lime carbonate, mica and various cost etc.
It is that its median size is 18 microns by the product of the commodity " Hi-Flow Supercel " by name of Manville company supply that the used preferred merchant of the present invention sells diatomite, and mean pore size is 7 microns, and softening temperature is 982 ℃.Diatomite is except as the lower-cost filler, it is believed that the generation that also helps in batching homodisperse toner and suppress the edge seepage during the sheet material of heat fused matrix material.
Urethane microplate and its preparation is described in my No. 4,200,679, United States Patent (USP), and the open text of the entire chapter of this patent is incorporated this specification sheets as a reference into.
Certainly, the selection of any concrete enhancing ingredients is mainly decided by the contemplated end-use of final matrix material.
C. other composition
Thereby can contain in the matrix material according to the present invention preparation and variously can make it have some character to help the generation of wet coil or sheet material or can make the finished product have other composition of some character (or both have concurrently).If the fiber of fibrillation (as glass fibre) not is incorporated in this matrix material, then should be in batching the compatible binding agent of adding relatively small amount so that coiled material or sheet material have desired physical integrity to a certain degree in the course of processing.The consumption of compatible binding agent is enough to make effectively the point of contact of fiber composition in the matrix material bonding.This binding agent should be insoluble to cold water, and is dissolved in hot water, and keeps its adhesive property when cooling.A kind of suitable organic binder bond that satisfies these requirements is polyvinyl alcohol (PVA).Adopt a kind of hydrolysis prods of the fibrous or pulverous polyvinyl acetate (PVA) available from E.I.Du Pont Company to obtain very gratifying result.Be purpose of the present invention, should adopt the PVA fiber to form the homogeneous dispersion of these compositions in the batching that is used for preparing matrix material.PVA is insoluble to cold water substantially, but tends to water-solublely rapidly when temperature is higher than 140 °F, can utilize this character when producing matrix material.Wet coil is separated from after the porous carrier, and it is passed through under the high-temperature infrared hot-plate, and this hot-plate is heated coiled material, thereby makes PVA fiber softening, swelling and be dissolved in the water contained in the coiled material.Lysed polyvinyl alcohol will flow to the point of contact between the fiber, and assemble on point of contact, and when the same material complete drying of this class paper, solid PVA bonds together the fiber of sheet material like this.Have now found that the add-on of PVA fiber is at most the 7%(weight of other solid composition in the matrix material) can cause required bond effect.If the consumption of PVA surpasses 7%, then the matrix material that is obtained is too tough and tensile and have " as plank " feature.The PVA of other form as powder, also can use.
The another kind of composition that can optionally join in the matrix material is a melamine-formaldehyde resin, and its effect is as helping binding agent.It is very favourable that melamino-formaldehyde resin and the common making beating material of introducing are previously united use.Be applicable to that melamino-formaldehyde resin of the present invention is a United States Patent (USP) the 2nd, 345, No. 543 and 2,559, that resinoid of introducing in No. 220, this resinoid make melamine and formaldehyde condensation and make in the water acidic medium.This resinoid can be buied from the LOF plastics company limited of branch office of Pioneer Plastics, is 11% water dispersion for a kind of solid content.The consumption of melamino-formaldehyde resin in the incendivity sheet material generally is lower than the 3%(weight of other solid composition in the matrix material).
It is believed that the cellulosic fibre composition that melamino-formaldehyde resin is pulled an oar in expecting together reacts, form stable connection, this makes coiled material or sheet material have higher wet tenacity.Melamino-formaldehyde resin is a non-ionic type in pH value (about 7.5 to the about 8.5) scope of water dispersion.
The another kind of composition that can select to add is a kind of viscosity, elastic, gelationus latex, and its consumption should be enough to make the ability that keeps the particulate state composition in the process of wet coil or sheet material formation to improve and make final paper shape product have flexible effect.The solid content of this viscosity latex should be within about 35% to about 55%, and its median size is preferably about 0.2 micron.At pH value is 7.5 between 8.5 the time, and it should be a non-ionic type.
Implement a kind of solid content suitable viscosity used when of the present invention, that elastic, gluey latex is produced for B.F.Goodrich company and be 50% water dispersion, commodity are called " Hucar2671 ".Except making the scatter and disappear possibility of particulate state composition of water dispersion reduce and the final material that is similar to paper is had the toughness in the process that forms wet coil or sheet material, viscosity latex can also be offset the hardening effect that organic binder bond produces.
If required, also can contain a kind of siloxane polymer in the matrix material.The consumption of siloxane polymer should be enough to help keep the particulate state composition when forming wet coil or sheet material, and helps to make wet coil or sheet material from separate (wet web or sheet material form) on the porous support on porous support.Refer to have the linear chain structure of following general formula at this used " siloxane polymer " speech:
R in the formula
1Be low alkyl group, methyl preferably, R
2Be low alkyl group or hydroxyl, n is about 150 °." siloxane polymer " speech also comprises the derivative of this compounds that has various functional groups substituting groups (as aminoalkyl).It is about 30% that the solid content of siloxane polymer is preferably, and be non-ionic type at pH value at 7.5 to 8.5 o'clock.
Employing can obtain good result available from a kind of siloxane polymer (solid content is 30% aqueous phase emulsion, and commodity are called " Uscosoft AF ") of SUS chemical company.This product contains a kind of by quadrol deutero-amine functional groups, and one of them nitrogen-atoms is attached on the Siliciumatom of polymer chain of above-mentioned general formula.
Siloxane polymer helps to make wet coil to break away from porous support significantly, and the ability of maintenance particulate state composition in the forming process of wet coil is significantly improved.Another effect of siloxane polymer is to increase bond effect when using binding agent.
If desired, can also use various chemical additives, as oxidation inhibitor, pigment, oxygenant (as ammonium salt, sodium salt or sylvite and/or the Powdered aluminum oxide of perchloric acid), sterilant, electromagnetic radiation absorber, fire retardant etc.
The papermaking hollander of use standard or similar mixing device can prepare the water dispersion that is used to make matrix material of the present invention at an easy rate.If at first in mixing device, add a small amount of material of making beating altogether (add-on be disperse phase total amount about 2% to 6%), add the polymkeric substance microplate then, add other composition by order arbitrarily again, then can obtain best result.As previously described, be total to the even water dispersion that the making beating material helps generating compound composition.Mixing time should be enough to obtain uniform dispersion, generally needs about 1 to 20 minute, and this depends on the prescription of dispersion.
With common flat, oblique net formula or cylinder shape papermaking apparatus (as the device of modified form fourdrinier wire, cylinder mould or the association type device that existing modified form fourdrinier wire has cylinder mould again are housed) but can make water dispersion change into the sheet material or the coiled material of hot melt.This method generally comprises: make the abundant homogenizing of dispersion to guarantee homogeneity in tempering tank, the dispersion of homogenizing is coated on a kind of porous support (normally a kind of endless felt) to form coiled material or sheet material, coiled material or sheet material are separated on porous support, and make its drying.Certainly, in drying step, can on coiled material or sheet material, exert pressure therefrom to extrude moisture content.Batching should be coated on the profiled surface of paper machine, and applying speed is about 20 pounds to 150 pounds of per 1300 square feet of finished-product material, and this depends on drainability and drying power, and drainability and drying power depend on the composition of material.One sheet material can be used sheet die manufacturing commonly used.The finished product coiled material also passes through a hot gas tunnel so that its drying by a naked light formula high pressure, steam-heated roller usually.The required temperature of dry coiled material (or sheet material) is generally between about 275 °F to about 475 °F.If cellulose, it is about 3% that the final water content of coiled material or sheet material should be lower than, if cellulose not, final water content should be lower than about 1%.
Can be that about 4000 to 6000 pounds heating platen or heating rolling press makes sheet material or coiled material hot melt to make composite finished product with operating pressure.Heating sheet material or coiled material are enough to make polymkeric substance composition or the fusion of resin composition in coiled material or the sheet material about 15 to 30 seconds usually under about 430 temperature.Can adopt slightly higher temperature with the shortening time, for example 440 °F were heated for 10 to 15 seconds, and vice versa.Certainly, the top condition of hot melt depends on the thickness and the composition of concrete sheet material or coiled material, and can determine by experience.
Can be with the sheet material hot melt of a plurality of matrix materials, obtaining a complete blank, and adopt suitable moulding process to make blank change into composite structure.Can make solid and hollow middle layer plate at an easy rate according to the present invention.Fall to obtain cavity or space by the center or the interior location punching press in middle layer of matrix material that is used to make finished product some amount.The condition of hot melt is identical substantially with the top condition of introducing that is used for single sheet or sheet material.
If matrix material is carried out any forming process or machining (as cross cutting), then (being that material still is in heating status) implemented this course of processing immediately and can be made efficiency optimization after hot melt.The frictional coefficient of matrix material that contains the PTFE fiber is very low, thereby is particularly useful for the sealing member of axle as pump shaft, though this material is harder relatively.Exemplified the suitable material that is applicable to this purpose below.The frictional coefficient of material is low to help being cut into ring-type, it can be contained in a bit on, or be divided into two semi-circular in case be embedded in respectively axle around.
The following examples have been introduced the present invention in more detail, comprising mode and the method making and use, and have introduced the enforcement that the present inventor recommended optimum implementation of the present invention.Unless otherwise indicated, all percentage, umber or ratio all by weight, all temperature all are Fahrenheit temperature.
In addition, outside the person, used following material among the embodiment unless otherwise indicated:
Polyethylene microplate: by the microplate of the method preparation of in the embodiment 1 of No. the 4th, 207,378, the inventor's United States Patent (USP), introducing;
Polyethylene powders: Hostalen
GUR412
Polycarbonate resin powder: Lexan
(median size is 275 microns)
Making beating material altogether: by the polystyrene microplate of the method preparation of in the embodiment 1 of No. the 4th, 293,378, the inventor's United States Patent (USP), introducing and the blend of cellulosic fibre
Glass fibre: DE-636(Ovens-Corning Incorporated's product), 1/4 inch long, diameter 6-7 micron
Kevlar: Kevlar
29 Wet Lap Aramid, 4 millimeters, model 979
PTFE fiber: Teflon
, 1/2 to 1/4 inch long, 12 microns of diameters (approximately)
Diatomite: Hi-Flow Supercel
Silver plated nylon fibers: the product of Sousquoit Fibers company limited
Carbon fiber: the Panex(trade(brand)name) Massachusetts, United States Lowell city Stackpole Fibers company product
Stainless Steel Fibre: length is that 3/16 inch, diameter are 4 microns fiber (size is by the N.V.Bekaert S.A. of production firm design)
Polyvinyl alcohol adhesive: Kuralon 105-2(is fibrous), 4 millimeters long
Melamino-formaldehyde resin: Piomide, Maine State Auburn city Pioneer Plastics company product, 11% water dispersion
Viscosity latex: Hycar 2671, the water miscible liquid of mixing acrylic polymers, total solid content is 50%
Carbon granule: Electrodag 230, micropowder, density is 1.11 kilograms/liter 25% solid dispersion
Oxidation inhibitor: Heveamol C-100, the water dispersion of hindered phenol, 45% activity, Massachusetts, United States Fall River city Heveatex company produces
Siloxane polymer: Uscosoft AF, water miscible liquid, solid content 30%.
Embodiment 1
In 12 premium on currency of containing in 5 gallons of plastic containers, add following composition, prepare a kind of water dispersion or batching:
Composition add-on (kilogram, gram)
A. matrix phase
Polystyrene microplate 20
Polyethylene powders 60
B. wild phase
Cellulosic fibre
a40
Kevlar
Glass fibre 10
Diatomite 10
C. other composition
Polyvinyl alcohol adhesive 3
Oxidation inhibitor 3
A: freeness is 610 velveteen
Before sampling is with the preparation sheet material, stirred this water dispersion about 20 minutes with air actuation three leaf paddle agitators.
12 inches * 12 inches sheet die with standard are made sheet material by above-mentioned batching.When the preparation sheet material, in sheet die, 2500 ml water dispersion samples are joined in about 8 gallons waters.Prepare at least 5 uniform sheet materials thus, found no tear-away polymkeric substance or resin composition on its surface.Make a slice sheet material in edition drying machine of taking pictures under 240～260 ° temperature heat drying, and be cut into 6,5 inches of every lengths of a film, wide 4 inches.Sheet material a slice under two cuttings is stacked in to place flat extrusion machine on another sheet be that 430 °, pressure are to dispose about 30 seconds under 6000 pounds the condition in temperature.Then remaining cutting sheet material is down added to the front on the fused sheet material, constantly repeats above-mentioned hot melt circulation, like this, 6 all fusion together forms solid, a complete high-intensity blank, its composition is complete uniform.Do not see the matrix material of individual layer on the finished product, the polymkeric substance composition fully has been fused to together.
For determining of the influence of polymkeric substance microplate, prepare several samples of sheets with the essentially identical water dispersion of water dispersion that just introduced (but not containing the polymkeric substance microplate) with a kind of to the matrix material characteristic.The surface of the exposure of resulting sheet material has covered the loose polyethylene powders of one deck on (promptly not towards the surface of lay wire), and these powder are easy to split away off from the exsiccant sheet material.
Embodiment 2-11
Other several matrix materials of the present invention have been prepared with the batching of introducing in the following table I.The sheet material hot pressing that is similar to paper that will make by primary condition given below.
Stack with the matrix material of pressure sintering, form complete blank block or plate multilayer embodiment 2～7 and 10.Can make multiple useful composite structure by these blanks.Some examples have been enumerated in the table II by the blank of the present invention's preparation.
Though all contain powdery resin (except that the polymkeric substance microplate) in the above-described embodiments in the matrix material of Jie Shaoing, also can be made into useful material as unique composition of matrix phase with the polymkeric substance microplate.Introduced this class material in the following examples.
Embodiment 12
Prepare thermoformable glass/resin paper from following batching, wherein prepare burden and in 5 gallon container, mix mutually with 10 premium on currency.
Composition add-on (dry weight, gram)
A. matrix phase
Polystyrene microplate 81.6
a
B. wild phase
Cellulosic fibre
b3.0
Poly terephthalic acid diol ester fiber
b0.4
Glass fibre
d35
c
Nylon fiber
d30
C. other composition
Polyvinyl alcohol 5
Viscosity latex 5
A.-wherein 1.6 grams adds as the part of expecting of pulling an oar altogether
B.-is as the part adding of making beating material altogether
C.-contains 5 gram Evans 4100 glass fine-fibereds (U.S. Oregon Corvalis city Evans Products company product)
The d.-nylon 66(2 dawn)
Get the sample of 2000 milliliters of above-mentioned batchings, and in the hand sheet mould of a standard with in about 8 gallons waters of its impouring.The hand sheet that makes was heated 20～30 seconds under the pressure of 385 ° and 6000 pounds in the experiment trigger squeeze.The matrix material that hot pressing gets has goodish snappiness, but easily broken during wrinkle.
Again prepare above-mentioned batching by adding 100 gram low molecular weight polyethylene micro mists (Dow Chemical company product) and adding 30 gram DE glass fibre again.By same condition manufacturing and the hot pressing hand sheet just introduced.The matrix material that makes does not like this have broken sign when wrinkle.
The following example is introduced the preparation method of the quite low matrix material of cost.
Embodiment 13
Prepare a kind of water dispersion by the same basic technology of introducing in the foregoing description 1 with following composition, different is that this dispersion is mixed mutually with 14 premium on currency.
Composition add-on (dry weight, gram)
A. matrix phase
Polystyrene microplate 26
Polyethylene powders 20
Polycarbonate resin powder 10
B. wild phase
Cellulosic fibre 60.8
Glass fibre 20
Aromatic polyamide fibre 5
Diatomite 20
C. other composition
Polyvinyl alcohol 5
Oxidation inhibitor 3
Used cellulosic fibre is a paste-like in the present embodiment, by the refuse production of paper industry.This slurry is to take from the Crane in Massachusetts, United States Dalton city on October 25th, 1985; Co.The composition of the waste slurry of paper industry alters a great deal, and measures its very difficulty.The composition of concrete one day depends on the type of the paper that the machine of this day operation is produced.Mainly contain cellulosic fibre in the used slurry in this example, and contain a small amount of glass fibre and other additive commonly used in paper industry.Because its discharge rate is low, waste paper pulp can't reclaim economically, thereby is discharged usually.
Press the technology of the foregoing description 1, make sheet material with the sample of 3000 milliliters of this example batchings.The drainage performance of hygrometric state sheet material is good, has good wet tenacity.Press the composite block that heat pressing process manufacturing that embodiment 1 introduces is made up of 20 layers of prepared sheet material, processing conditions is 6000 pounds of pressure, 25 seconds, 435, and final dimension is 5 inches * 5 inches * 11/32 inch.Finished product block weight is 135 grams.
Embodiment 14
, high strength composite low-cost with the preparation of hardwood wood pulp.At first, by the basic technology of introducing previously 1400 gram hardwood Oxybrite Craft and 600 gram polystyrene microplates are heated together, to prepare a kind of material of making beating altogether.After approximately pulling an oar 1 hour 15 minutes, the freeness of making beating material drops to 600 by initial value 850 altogether.Beating solid content of slurry altogether is about 3%.
In 5 gallon container, 300 milliliters of common making beating material that make (about 9 grams of dry weight) are joined in 14 premium on currency, add following composition subsequently to prepare a kind of batching.
Composition add-on (dry weight, gram)
A. matrix phase
Polystyrene microplate 28
Polyethylene powders 20
Polycarbonate resin powder 10
B. wild phase
Hardwood wood pulp cellulose 42
Diatomite 20
Glass fibre 10
C. other composition
Polyvinyl alcohol 5
Oxidation inhibitor 3
Press the technology of the foregoing description 1, make sheet material with the sample of the batching of 3000 milliliters of these examples.This sheet material contains considerable moisture content, however, still can be translated into matrix material.Press the composite block of being made up of 20 layers of resulting sheet with the identical method manufacturing of embodiment 10 introductions, finished product is of a size of 5 inches * 5 inches * 1/4 inch.The production cost of this matrix material is estimated as about 80 cents every pound.
The following examples are introduced those need pass through special processing or processing, so that it can be scattered in the preparation method of the matrix material composition in the batching system.
Embodiment 15
Cereal grass (as straw used among the embodiment 5) must pass through defibrination at least, so that the fiber that is suitable for mixing in the matrix material to be provided.The composition of straw is about 20% silicon-dioxide, 30% lignin, 20% solubility hemicellulose and about 30% pair of fibrous cellulose that paper industry is useful.Found that the straw of processing (as introducing in this example) can obtain being applicable to the fiber of composite-material formula in hollander commonly used.
To capacity is to add straw (1 inch of mean length), 400 gram (dry weight) polystyrene microplate and 85 premium on currency that 2000 grams are cut into chunks in 5 pounds the hollander.At first (pivot arm) adds 5 pound weights on middle armshaft.In 1 hour beating time, added 5 pound weights at interval in 15 minutes in addition.Obtain the dispersion of fabulous rice-straw fibre.
The inventor finds to add microplate for obtaining useful rice-straw fibre to closing weight in hollander.Under the situation that does not add microplate, carrying out once similarly making beating operation make straw become a kind of that cut very carefully, dispersive, can't filtering product, this product can not be used to make matrix material fully.
Also can process straw easily with ball mill, wherein use microplate as grinding aid.
Embodiment 16
With used Stainless Steel Fibre in the matrix material of ball mill processing and implementation example 11, so that it has the necessary dispersibility of preparation batching.In being 1.7 liters standard laboratory ball mill, a capacity inserts the steel ball (diameter is 1 inch or 1/2 inch) of 10 gram (dry weight) polystyrene microplates, 40 gram Stainless Steel Fibres, 1.3 premium on currency, basic equivalent and ceramic cylinder (high 1/2 inch, girth 1/2 inch), to be filled into about 75% of ball mill capacity.Microplate is used as grinding aid.If without microplate, can produce the agglomerate of steel fiber.After ball milling carried out about one day, obtain the uniform water dispersion of Stainless Steel Fibre.This water dispersion can be directly used in makes the batching that contains the Stainless Steel Fibre matrix material.
Though top introduction and enumerated some and thought embodiment of the present invention preferably at present, this is not meant to limit the present invention in the scope of these embodiments, because under the situation of the spirit and scope of the invention that does not exceed claims and limited, it is done various changes can accomplish.
Claims (12)
1, the method for the matrix material that exists of the form with sheet material or coiled material of producing, above-mentioned matrix material comprises a kind of continuous matrix phase, and this matrix phase is wrapped in by dispersive and is enhanced to the wild phase that branch is formed, and this method comprises:
(a) provide a kind of uniform basically water dispersion, its disperse phase comprises (i) polymkeric substance microplate by expansible, hydrophobic, thermoplastic, the non-shattering polymer production of expanded state, this polymkeric substance is gone up the complete hole of not making the used expanded polymer of this microplate fully substantially, (ii) described enhancing ingredients;
(b) wet coil or the sheet material of the disperse phase of the described water dispersion of formation;
(c) dry described wet coil or sheet material;
(d) heating described wet coil or sheet material is enough to that the polymkeric substance microplate is melt into and is wrapped in the continuous matrix phase of described enhancing ingredients.
2, method according to claim 1, wherein expansible, hydrophobic, multipolymer or blend that thermoplastic polymer is selected from styrene polymer, lower polyolefins (carbonatoms is 2 to 6 the not luxuriant stable hydrocarbon polymer of monomers of olefinic) or these polymkeric substance.
3, the described method of claim 2, wherein said water dispersion comprise at least a pulverizing, hydrophobic, thermoplastic resin, this resin and the matrix phase of polymkeric substance microplate fusion when heating sheet material or coiled material with the formation matrix material.
4, the described method of claim 3, wherein said water dispersion comprises a kind of fibrous enhancing ingredients, and this fibrous enhancing ingredients is selected from glass fibre, carbonizedfibres, polymer fiber, inorganic fibre and steel fiber.
5, the described method of claim 4, wherein the polymkeric substance microplate component of a part of disperse phase and the tight blend of cellulosic fibre are to form common making beating material.
6, the described method of claim 5, the material package of wherein pulling an oar altogether contains trevira.
7, the described method of claim 4, wherein water dispersion comprises a certain amount of mutual appearance binding agent, the consumption of this binding agent is enough to make each component of the disperse phase that forms coiled material or sheet material to bond together effectively.
8, claim 3 or 4 described methods, wherein said water dispersion comprises a kind of particulate state enhancing ingredients, and this enhancing ingredients is selected from diatomite, urethane microplate, aluminum oxide, wood chip, sawdust, carbon dust, silicon-dioxide, lime carbonate, mica and clay.
9, a kind of matrix material that exists with sheet material or web form, this matrix material comprises a kind of continuous matrix phase, this matrix phase is wrapped in by dispersive and is enhanced to the wild phase that branch is formed, described continuous matrix phase comprises the hot-melt polymer microplate, it is by expansible, hydrophobic, thermoplastic polymer is produced, these polymkeric substance are selected from styrene polymer, lower polyolefins (carbonatoms is the polymkeric substance of 2 to 6 ethylenically unsaturated monomer) but or styrene monomer or carbonatoms be 2 to 6 the ethylenically unsaturated hydrocarbons monomer and the formed multipolymer of monomer of other copolymerization, or comprise the blend of described polymkeric substance or multipolymer, described polymkeric substance or multipolymer are non-shattering expanded form, and described polymkeric substance microplate is not produced the complete hole of used expanded polymer of this microplate or multipolymer basically fully.
10, matrix material according to claim 9, wherein continuously matrix phase comprises at least a pulverizing, hydrophobic, thermoplastic resin.
11, matrix material according to claim 10 wherein comprises a kind of fibrous enhancing ingredients.
12,, wherein comprise a kind of particulate state strongthener according to the described matrix material of claim 10 or 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87105994 CN1033820A (en) | 1987-12-29 | 1987-12-29 | Matrix material, preparation and its goods |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87105994 CN1033820A (en) | 1987-12-29 | 1987-12-29 | Matrix material, preparation and its goods |
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| CN1033820A true CN1033820A (en) | 1989-07-12 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102149533A (en) * | 2008-05-14 | 2011-08-10 | 纳幕尔杜邦公司 | Method to produce stab and ballistic resistant composite structures |
| CN102432893A (en) * | 2003-08-25 | 2012-05-02 | 陶氏环球技术有限责任公司 | Aqueous dispersion, its production method, and its use |
| CN105189618A (en) * | 2013-01-24 | 2015-12-23 | 阿肯马法国公司 | Halogenated polymer composite composition, its manufacturing process and its use |
-
1987
- 1987-12-29 CN CN 87105994 patent/CN1033820A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432893A (en) * | 2003-08-25 | 2012-05-02 | 陶氏环球技术有限责任公司 | Aqueous dispersion, its production method, and its use |
| CN102604124A (en) * | 2003-08-25 | 2012-07-25 | 陶氏环球技术有限责任公司 | Aqueous dispersion, its production method, and its use |
| CN102604124B (en) * | 2003-08-25 | 2015-07-29 | 陶氏环球技术有限责任公司 | Water dispersion, its production method and uses thereof |
| CN102432893B (en) * | 2003-08-25 | 2015-08-12 | 陶氏环球技术有限责任公司 | Water dispersion, its production method and uses thereof |
| CN102149533A (en) * | 2008-05-14 | 2011-08-10 | 纳幕尔杜邦公司 | Method to produce stab and ballistic resistant composite structures |
| CN102149533B (en) * | 2008-05-14 | 2013-12-04 | 纳幕尔杜邦公司 | Method to produce stab and ballistic resistant composite structures |
| CN105189618A (en) * | 2013-01-24 | 2015-12-23 | 阿肯马法国公司 | Halogenated polymer composite composition, its manufacturing process and its use |
| CN105189618B (en) * | 2013-01-24 | 2019-03-12 | 阿肯马法国公司 | Halogenated polymer composite, its manufacturing method and its purposes |
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