CA1189213A - Method for treating discontinuous cellulose fibers, fibers thus treated and composites made from the treated fibers - Google Patents
Method for treating discontinuous cellulose fibers, fibers thus treated and composites made from the treated fibersInfo
- Publication number
- CA1189213A CA1189213A CA000400652A CA400652A CA1189213A CA 1189213 A CA1189213 A CA 1189213A CA 000400652 A CA000400652 A CA 000400652A CA 400652 A CA400652 A CA 400652A CA 1189213 A CA1189213 A CA 1189213A
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- Prior art keywords
- fibers
- polymer
- treated
- mixture
- parts
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Classifications
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- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
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- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- 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
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/253—Cellulosic [e.g., wood, paper, cork, rayon, etc.]
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- 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
- Y10T428/2904—Staple length fiber
- Y10T428/2907—Staple length fiber with coating or impregnation
Abstract
ABSTRACT OF THE DISCLOSURE
Discontinuous cellulose fibers are treated to improve their dispersability into a matrix comprising plasticized vinyl chloride polymer. The treatment includes contacting the fibers with a mixture of an aqueous dispersion of a vinyl chloride polymer and a plasticizer so as to coat the fibers, and drying the fibers. The non-aqueous portion of the mixture is usually present in an amount of at least 25 parts per 100 parts of fibers by weight, and the weight ratio of plasticizer to vinyl chloride polymer in the mixture is from 2:1 to 25:1. The discontinuous fibers thus treated can be dispersed into a matrix comprising plasticized vinyl chloride polymer with a minimum of mixing, and the improved composites thus produced con-tain a minimum of clumps of undispersed fibers.
Discontinuous cellulose fibers are treated to improve their dispersability into a matrix comprising plasticized vinyl chloride polymer. The treatment includes contacting the fibers with a mixture of an aqueous dispersion of a vinyl chloride polymer and a plasticizer so as to coat the fibers, and drying the fibers. The non-aqueous portion of the mixture is usually present in an amount of at least 25 parts per 100 parts of fibers by weight, and the weight ratio of plasticizer to vinyl chloride polymer in the mixture is from 2:1 to 25:1. The discontinuous fibers thus treated can be dispersed into a matrix comprising plasticized vinyl chloride polymer with a minimum of mixing, and the improved composites thus produced con-tain a minimum of clumps of undispersed fibers.
Description
_ 1 -METHOD FOR TREATING DISCONTINUOUS
CELLULOSE FIBERS, THE FIXERS THUS TREATFD AND
COMPOSITE-S MADE FROM THE TREATED FIBRS
BACKGROUND OF THE INVENTION
S Th;s invention relates to a method of treat;ng cellulose f;bers to ;mprove the;r d;spersab;l;ty ;nto an organic polymer matrix, to the fibers thus treated, and to composites of organ;c polymers and the f;bers.
It ;s well known to ;ncorporate d;scont;nuous f;bers ;nto an organ;c polymer matrix to form composite materials hav;ng ;mproved propert;es. For example aoustany et al UO S. Patent 3,6~7,364 describes composites o-f this type ;n which the contained fibers are or;ented so as to g;ve considerable strength and st;ffness to the compos;tes ;n the d,rection of f;ber or;entat;on.
CELLULOSE FIBERS, THE FIXERS THUS TREATFD AND
COMPOSITE-S MADE FROM THE TREATED FIBRS
BACKGROUND OF THE INVENTION
S Th;s invention relates to a method of treat;ng cellulose f;bers to ;mprove the;r d;spersab;l;ty ;nto an organic polymer matrix, to the fibers thus treated, and to composites of organ;c polymers and the f;bers.
It ;s well known to ;ncorporate d;scont;nuous f;bers ;nto an organ;c polymer matrix to form composite materials hav;ng ;mproved propert;es. For example aoustany et al UO S. Patent 3,6~7,364 describes composites o-f this type ;n which the contained fibers are or;ented so as to g;ve considerable strength and st;ffness to the compos;tes ;n the d,rection of f;ber or;entat;on.
2~3 _z_ It is also known that the dispersion of discontinuous cellulose fibers into a polymeric matrix can be greatly facilitated by pretreatment of the fibers w;th a plast;c polymer and a lubricant. U. S. Patent 3,9~3,079 to Hamed describes such a pretreatment.
SUMMARY OF THE INVENTION
It has now been found that for incorporating discon-- t;nuous cellulose fibers into a matr;x comprising plast;c;zed v;nyl chloride polymer, certain critical ratios of polymer and lubricant to f;ber are essent;al in the pretreatment step.
According to the present invention, discontinuous cellulose fibers are contacted w;th a mixture of an aqueous suspension of a vinyl chlor;de polymer and a plastic;zer so as to cause the polymer and plasticizer to depos;t on the f;bers. The f;bers are then dried so as to produce treated fibers of improved ~ispersability ;nto a matr;x compr;s;ng plast;c;zed v;nyl chlor;de polymer. The vinyl chlor;de polymer in the treatment m;xture need not be the same as that ;n the matrix but should be compat;ble therew;th. Likew;se, the plast;cizer ;n the treatment mixture need not be the same as that in the matr;x, but should be compat;ble w;th the matr;x.
In the treatment of the ;nvent;on, the non-aqueous port;on of the m;xture ;s present in an amount of at 392~3
SUMMARY OF THE INVENTION
It has now been found that for incorporating discon-- t;nuous cellulose fibers into a matr;x comprising plast;c;zed v;nyl chloride polymer, certain critical ratios of polymer and lubricant to f;ber are essent;al in the pretreatment step.
According to the present invention, discontinuous cellulose fibers are contacted w;th a mixture of an aqueous suspension of a vinyl chlor;de polymer and a plastic;zer so as to cause the polymer and plasticizer to depos;t on the f;bers. The f;bers are then dried so as to produce treated fibers of improved ~ispersability ;nto a matr;x compr;s;ng plast;c;zed v;nyl chlor;de polymer. The vinyl chlor;de polymer in the treatment m;xture need not be the same as that ;n the matrix but should be compat;ble therew;th. Likew;se, the plast;cizer ;n the treatment mixture need not be the same as that in the matr;x, but should be compat;ble w;th the matr;x.
In the treatment of the ;nvent;on, the non-aqueous port;on of the m;xture ;s present in an amount of at 392~3
-3-least 25 parts, preferably at least 30 parts and more preferably at least 40 parts, per 100 parts of fibers by weight, and the we;ght ratio of plasticizer to polymer in the m;xture ;s from 2:1 to 25:1, preferably from 2.5:1 to 15:1, and more preferably from 2.8:1 Po 1 0 : 1 .
The invention also includes the treated f;bers produced by the descr;bed method and ;ncludes treated fiber compr;s;ng d;scont;nuous cellulose f;ber of aspect rat;o greater than 20, vinyl chloride polymer and a plast;c;zer for sa;d polymer wherein the polymer and plasticizer together are present in an amount of at least 25 parts by we;ght per 100 parts of cellulose fiber by weight and the we;ght rat;o of plast;c;zer to polymer ;s from 2:1 to 25:1. The invent;on also includes a compos;te of the treated fibers of the invention dispersed in a matrix compr;sing plastic;zed vinyl chlor;de polymer.
BRIEF DESCRIPTION OF THE DRAWING
za The drawing ;s a graphic representation of the effect of the relative quantities of fiber and fiber treatment mixture and of the ratio of plasticizer to polymer in the mixture on fiber dispersabil;ty.
, Cellulose is a carbohydrate polymer of glucose res;due units. It can be either regenerated or unregen-erated (natural) cellulose. Rayon is regenerated cellulose. Examples of natural cellulose fibers include seed fibers such as cotton, woody fibers represented by coniferous and deciduous woods, bast fibers represented by flax, leaf f;bers such as sisal, and fru;t f;bers such as coconut. However, wood f;bers, either hardwood or softwood, are preferred. Especially preferred is hardwood kraft, made by the sulfite process. The fibers have an aspect ratio length divided by average diameter) greater than 20.
Preferably, the fibers compr;se those hav;ng aspect rat;os w;thin the range of 20-350, with a more preferred range of 50-350, and an even more preferred range of 75-2ûO. In some instances, ;t is des;rable to use m;xtures of f;bers hav;ng w;dely d;ffer;ng aspect rat;os.
The ;mproved d;spersabil;ty of the f;bers of the invent;on ;s ;mportant in that excess;ve m;x;ng, wh;ch tends to ;ncrease f;ber breakage, can be avo;ded. The f;nal aspect rat;o of the f;bers strongly affects the modulus atta;ned ;n the compos;tes. Further, reduced m;x;ng times are favorable to process economy. In some ;nstances~
untreated f;bers w;ll never g;ve good d;spers;ons, regardless of the m;xing t;me.
The polymer contained in the treatment mixture is descr;bed as being "vinyl chloride polymer" and includes both vinyl chloride homopolymer and copolymer of a major proportion of vinyl chloride with a minor proportion of other copolymer;zable monomers such as v;nyl acetate or ~inylidene chlor;de. The polymer ;s employed ;n aqueous d;spers;on, preferably ;n the form of a latex, although a s1urry or d;spersion of small part;cle s;ze polymer in water can be employed. Particles of vinyl chlor;de polymer are preferably less than 10 em ;n diameter, more préferably less than 5 em in d;ameter, and even more preferably less than 2 em in d;ameter on the average The order of add;t;on of aqueous poliymer suspens;on and plastic;zer to the gibers is not critical--e;ther can be added f;rst, or both at once. Opt;onally,the polymer can be accompan;ed by a plast;cizer int;mately m;xed therew;th~ as ;n a latex of a pre-plast;c;zed polymer.
The plast;c;zer used ;n the treatment m;xture should be one wh;ch is compat;ble with the v;nyl chlor;de polymer matr;x as descr;bed. An ;ncompat;ble plast;c;zer can be used ;f the compos;te conta;ns enough of a pr;mary or compatibilizing plast;cizer. For a discussion of plast;cizers, see Enc_cloped;a of Polymer Science and Technology, Vol. 10, p. 128 _ seq. ~J. R. Darby, author) John W;ley Sons, Inc., New York, 1969. Examples of effect;ve plast;cizers include ad;pates, such as di-2-ethylhexyl adipate and diisodecyl adipate; azelates, such as d;-2-ethylhexyl azelate; benzoates, such as d;propylene glycol d;benzoate; phosphates, such as . I, tr;cresyl phosphate, cresyl d;phenyl phosphate, Z-ethylhexyl diphenyl phosphate, d;-n-octyl phenyl phos-phate, and tr;-n-hexyl phosphate; phthalates, such as diethyl phthalate, butyl benzyl phthalate, d;-2-ethylhexyl phthalate, and di;sodecyl phthalate; sebacates, such as d;-2-ethylhexyl sebacate and terephthalates, such as di-2-ethylhexyl terephthalate. A compatible blend of two or more plasticizers can be used. In use, the plasticizer has the effect no only of softening and modifying the polymer, but also of lubricating the fiber surfaces, promoting dispersion and m;n;m;z;ng f;ber breakage The f;bers are described as "discontinuous", to dist;ngu;sh from the well known ;ncorporat;on of cont;nuous cord re;nforcem nt ;nto rubber art;cles. The "matrix"
is the material form;ng a continuous phase which surrounds the fibers. A "composite" is the combination of discontinous fibers in a matrix wherein the contained fibers may be randomly oriented, or, to a greater or lesser degree, aligned in a particular direct;on.
Composites ;n wh;ch the f;bers are h;ghly aligned, as taught ;n U. S. Patent 3,697,364, mentioned above, are part;cularly useful, ;n calendered or extruded objects.
In the step of contact;ng the fibers w;th the treat-ment m;xture, the fibers can be slurried ;n water andm;xed w;th the polymer and plast;c;zer. Th;s step prov;des for separat;on of the fiber bundles to allow max;mum contact with the treatment mixture, and ;t also softens the fibers, making them more flexible during the contact;ng step. As compared ~;th the process of treat;ng f;bers accord;ng to the d;sclosure of Hamed U. S. Patent 3,943,079, the instant process is as . .
43-51~6361 effect;ve; yet, it does not require the heavy, powerful mix;ng equ;pment used by Hamed and it does not cause f;ber degradat;on.
Dur;ng the contacting step, which can be performed with d;ffer;ng degrees of ag;tat;on, the v;nyl chlor;de polymer and plast;c;zer are depos;ted onto the surfaces of the lens to form a relt;vely homogeneous coat;ng.
If necessary, h;gh shear ag;tat;on can be usedg and heat or a coagulant can be employed, ;n order to ;nsure coagulat;on of the polymer and plast;c;zer onto the f;bers. The f;bers are then de-watered by f11trat;on or other means, and dr;ed. Since cellulose ~;bers are somewhat hygroscopic, the drying step is usually not carried to a complete removal of water, although for some purposes the amount of contained water w;11 be minimized.
If desired, rather than slurrying them7 the f;bers can be treated wh;le they are in an agglomerated state, as in a sheet form. In treat;ng a sheet of f;bers, ;t can be saturated w;th a m;xture of plast;c;zer and an aqueous d;spersion of polymer and then dr;ed to produce a treated sheet. A continuous f;ber sheet can be d;pped, for example, ;nto the treatment mixture, and then fed ;nto dry;ng apparatus such as heated rolls or a hot a;r oven to remove the water. Such a treated sheet can then be later ;ncorporated into add;t;onal vinyl chloride polymer and plastic;zer or add;t;onal v;nyl chloride polymer and plast;c;zer can be applied to the sheet. for example a cont;nuous str;p of treated fiber can be fed ;nto an extruder along w;th the plast;ci~er and polymer, to form a cont;nuous extruded composite wh;ch is subjec-ted 9~13 to further shaping operat;ons, wh;ch a1;gn the f;bers as des;red.
When dry;ng f;bers wh;ch have been slurr;ed, treated, and then de-watered by filtration, any of a S var;ety of dry;ng methods can be used. The de-watered fibers w;ll usually form a fr;able cake, wh;ch can be mechanically broken up ;nto clumps of f;bers wh;ch are air dr;ed. Alternatively, the cake can be f;rst a;r-dr;ed, then broken up ;nto crumbs or clumps. If des;red, the cake can be pressed to compact ;t Rand expel add;t;onal water), then dr;ed ;n its pressed form.
As stated above, the treatment mixture, conta;n;ng v;nyl chlor;de polymer and plast;c;zer, ;s employed during the treatment of the fixers in an amount of at least 25 parts preferably at least 30 parts, and more preferably at least 40 parts or more of non-aqueous mixture per 100 parts of f;bers by weight. This treat-ment level ;s relat;vely h;gh compared to prior art ratios, and has been found to be a significant factor ;n enhanc;ng dispersion of the treated f;bers into a matrix. Although a maximum level of treatment mixture ;s not stated, it is clear that th;s level w;ll be ult;mately lim;ted by the amount of matr;x mater;al ;n the f;nal compositeO
For example, ;f the f;bers are to be used ;n a f;n;shed composite in an amount of fifteen we;gh~ percent of the total compos;te we;ght, then the treatmen-t level on the fibers cannot exceed e;ghty-f;ve parts per fifteen parts of f;ber, or stated another way, 5O7 parts per 100 parts of f;bers by we;ght. In th;s example, g;ven as an extreme, all of the matr;x (or non-f;ber) port;on of the compos;te ;s cons;dered to be treatment, and thus the compos;te ;s produced ;n a s;ngle step, .
~9--rather than by the ;nit;al step of pretreat;ng the f;bers followed by a final step of ;ncorporat;ng the treated f;bers ;nto a polymer;c matr;x to form a composite. If a lower f;ber level were des;red ;n the final compos;te, say 3 percent fiber based on the total composite weight, a s;milar calculat;on w;ll show that the treatment level, - expressed as parts by we;ght per 100 parts of fiber could be as h;gh as 3233 parts. Obviously, then the upper limit of the treatment level ;s d;ctated solely by the final composite composition and convenience of handl;ng. Frequently, ;t is desired to have the treated fibers in particulate form, rather than in a mass, so that a level of treatment would be selected to produce particulate or crumb product form This treatment level would usually be less than about 300-400 parts of coating per 100 parts of f;ber.
As indicated above, the weight ratio of plasticizer to v;nyl chlor;de polymer ;n the treatment mixture accord;ng to the method of the ;nvent;on ;s from 2:1 up to 25:1, preferably from 2.5:1 up to 15:1, and more preferably, from 2.~:1 up to 10:1. M;xtures w;th;n these ranges are found to produce treated f;bers having superior d;spersab;l;ty ;nto a matr;x to form a composite. In addition to plast;c;zer and v;nyl chlor;de polymer, the treatment m;xture can also conta;n carbon black; tiler such as clay; alumina; talc and the like, as we11 as other ingredients used ;n the polymer art, including stab;l;zers, ant;degradants, p;gments, colors, and the like.
The treated f;bers of the invention can be further combined with the matrix material ;n a su;table mixer, such as an internal mixer (e.g~, 9anbury) or roll mill.
The erabender m;xer is particularly effect;ve for th;s S purpose in the laboratory. Additional ;ngredients, such as fillers, colorants, stabilizers and additional plasticizer can also be added at this po;nt~ If desired, the f;bers can then be oriented ;n the final composite, by pass;ng a sheet of the composite through a hot roll m;ll. Several passages are often used in order -Jo opt;m;ze orientation of the f;bers in the direction of passage through the rolls. Th;s is followed by compres-s;on mold;ng of the sheet to produce a des;red article.
Alternat;vely, the compos;te can be extruded to al;gn the f;bers ax;ally. If a hose or tube shaped product is des;red, ax;al or;entat;on of f;bers can be produced therein, or, by us;ng the techn;ques set forth ;n U. S. Patents 4,056,591 and 4,057,610, in a direction other than ax;al.
EXAMPLE I
To ;llustrate a preferred method of fiber treatment twenty grams of "Pinnacle" wood pulp (produced by Westvaco) is charged to the bowl of a Waring 91ender~
The pulp is hygroscop;c and, as equ;librated w;th labora-tory a;r, contains about 8% mo;sture. To the pulp ;sadded about 700 ml. o-f water and the agitation is started Polyv;nylchloride latex (Geon 575 x 43, 56~ sol;ds, plast;c;zed w;th 25 phr of a phosphate plasticizer) di1uted with an equal volume of water is added at varying levels. Butyl benzyl phthalate plasticizer in the ~9 l 3 43-5l-6361 desired amount is then added, followed by a coagulant (0.3 to 1.3 grams alum dissolved in 50 ml. water).
M;xing ;s continued for about thirty seconds, and the fibers are then collected by filtration; washed w;th S water tw;ce, and dried, e;ther at room temperature or ;n an oven at 120C. The low turbidity of the effluent water ;nd;cates nearly quant;tat;ve depos;t;on of the ingred;ents onto the fibers.
EXAMPLE II
To show ;ncorporat;on of the treated f;bers ;nto a matrix of a p1as~;c;zed viny1 chlor;de polymer, the f;bers of Example I are m;xed w;th a typ;cal green garden hose compound. The compound, conta;n;ng approxi-mately 50 parts of plast;c;zer and 6 parts of other add;t;ves per lO0 parts polyv;nylchlor;de ~PVC) res;n, ;s charged to the chamber of a Brabender m;xer equ;pped ~;th cam type rotors, and fluxed, together w;th add;t;onal PVC, at a temperature of 150C, w;th a rotor speed of lOa rp~. The treated f;ber ;s added and m;xed for one minu~e3 then a bonding agent ;s added. The charge ;s then m;xed for additional t;me~ ~otal;ng e;ther 3 or 5 m;nutes aster the f;ber add;t;on.
The composites thus pr-oduced are removed from the m;xer and passed repeatedly through the n;p of a roll m;ll three to f;ve times, w;th doubl;ng each time) to orient the fibers in a s;ngle direction. The aligned sheet ;s then compress;on molded ;n a frame mold at 165C
under a pressure of 1.38 MPa to produce a void-free sheet.
In order to evaluate the d;spers;on of the fibers in the matrix, the density of undispersed clumps is . ., 43-Sl-6361 measured over a cut surface. Several slices are made in a sheet, to expose at least 8 cmr2 of cut surface Those white undispersed clumps wh;ch could be ident;f;ed without magnification were counted.
EXAMPLE III
In the course of our work, ;t has been determined that the amount of treatment mixture deposited on the fibers and the ratio of plasticizer to polymer ;n the mixture considerably affect the ease of dispersion of the treated fibers into the matrix In order to invest;-gate the nature of the causes and effects, an exper;ment was designed in which a logarithmic factorial array was employed for the composition var;at;ons.
my us;ng the procedure set worth in Example I, above, seventeen samples of treated f;ber were prepared the samples hav;ng varying ratios of plasticizer to vinyl chloride polymer and varying amounts of fiber treating materials deposited on the fibers. Composites were then prepared according to the procedures set forth in Example II~ above, in which all composite samples contained 15.0% by weight of cellulose fiber, 0.8% by weight bonding agent ~Vulcabond VP, a 25% solution of an isocyanurate polymer of toluene diisocyanate, ;n d;butyl phthalate, manufactured by Vulnax Interna-tional, lid the rema;nder being vinyl chloride polymer and plastici-zers. The dens;ty of und;spersed clumps was measured on each sample as in Example II, and the results were summar;zed as shown ;n the accompanying draw;ng, which shows, numer;cally, the density of und;spersed clumps ;n clumps per square meter, on logarithmic coordinates ~L~lB~2~
of f;ber treatment level and piasticizer to vinyl chloride polymer ~e;ght rat;o. The f;ber treatment level is expressed in parts by weight of coating material per 100 parts by we;ght of f;ber. L;mits of each variable are indicated by sol;d l;nes, the preferred l;mits by a line of long dashes, and the most preferred limits by a l;ne of short dashes. The letter "K" ;nd;cates one thousand thus 3K, for example, should be read as three thousand.
It can be seen that w;th;n the claimed lim;ts the clump dens;ty ;s at a m;n;mum level, but outs;de the claimed l;m;ts the clump density is considerably higher.
The transition between the m;nimum and the area of poor dispersion due to too low plasticizer concentrat;on tin the coat;ng) is especially abrupt9 indeed7 In summary; the method of the ;nvention offers a simple, low-energy process for producing treated cellulose fibers. The f;bers of the invention are particularly suited for rapid and efficient dispersion into plastic;zed polymers of vinyl chlor;de. The composites of the invent;on are useful in the form of articles having superior strength and stiffness without the use of continu-ous cord for reinforcement in a braided, knit or other conf;gurat;on. Add;tionally, the composites of the invention can take the form of floor t;le compos;t;ons, contain;ng a relat;vely h;gh proport;on of inert f;ller, such as calc;um carbonate.
Although the foregoing ;nvention has been described ;n some deta;l by Jay of illustrat;on and example for purposes of clar;ty of understand;ng, ;t w;ll be obv;ous that certa;n changes and modif;cations may be practiced w;th;n the scope of the appended cla;ms.
The invention also includes the treated f;bers produced by the descr;bed method and ;ncludes treated fiber compr;s;ng d;scont;nuous cellulose f;ber of aspect rat;o greater than 20, vinyl chloride polymer and a plast;c;zer for sa;d polymer wherein the polymer and plasticizer together are present in an amount of at least 25 parts by we;ght per 100 parts of cellulose fiber by weight and the we;ght rat;o of plast;c;zer to polymer ;s from 2:1 to 25:1. The invent;on also includes a compos;te of the treated fibers of the invention dispersed in a matrix compr;sing plastic;zed vinyl chlor;de polymer.
BRIEF DESCRIPTION OF THE DRAWING
za The drawing ;s a graphic representation of the effect of the relative quantities of fiber and fiber treatment mixture and of the ratio of plasticizer to polymer in the mixture on fiber dispersabil;ty.
, Cellulose is a carbohydrate polymer of glucose res;due units. It can be either regenerated or unregen-erated (natural) cellulose. Rayon is regenerated cellulose. Examples of natural cellulose fibers include seed fibers such as cotton, woody fibers represented by coniferous and deciduous woods, bast fibers represented by flax, leaf f;bers such as sisal, and fru;t f;bers such as coconut. However, wood f;bers, either hardwood or softwood, are preferred. Especially preferred is hardwood kraft, made by the sulfite process. The fibers have an aspect ratio length divided by average diameter) greater than 20.
Preferably, the fibers compr;se those hav;ng aspect rat;os w;thin the range of 20-350, with a more preferred range of 50-350, and an even more preferred range of 75-2ûO. In some instances, ;t is des;rable to use m;xtures of f;bers hav;ng w;dely d;ffer;ng aspect rat;os.
The ;mproved d;spersabil;ty of the f;bers of the invent;on ;s ;mportant in that excess;ve m;x;ng, wh;ch tends to ;ncrease f;ber breakage, can be avo;ded. The f;nal aspect rat;o of the f;bers strongly affects the modulus atta;ned ;n the compos;tes. Further, reduced m;x;ng times are favorable to process economy. In some ;nstances~
untreated f;bers w;ll never g;ve good d;spers;ons, regardless of the m;xing t;me.
The polymer contained in the treatment mixture is descr;bed as being "vinyl chloride polymer" and includes both vinyl chloride homopolymer and copolymer of a major proportion of vinyl chloride with a minor proportion of other copolymer;zable monomers such as v;nyl acetate or ~inylidene chlor;de. The polymer ;s employed ;n aqueous d;spers;on, preferably ;n the form of a latex, although a s1urry or d;spersion of small part;cle s;ze polymer in water can be employed. Particles of vinyl chlor;de polymer are preferably less than 10 em ;n diameter, more préferably less than 5 em in d;ameter, and even more preferably less than 2 em in d;ameter on the average The order of add;t;on of aqueous poliymer suspens;on and plastic;zer to the gibers is not critical--e;ther can be added f;rst, or both at once. Opt;onally,the polymer can be accompan;ed by a plast;cizer int;mately m;xed therew;th~ as ;n a latex of a pre-plast;c;zed polymer.
The plast;c;zer used ;n the treatment m;xture should be one wh;ch is compat;ble with the v;nyl chlor;de polymer matr;x as descr;bed. An ;ncompat;ble plast;c;zer can be used ;f the compos;te conta;ns enough of a pr;mary or compatibilizing plast;cizer. For a discussion of plast;cizers, see Enc_cloped;a of Polymer Science and Technology, Vol. 10, p. 128 _ seq. ~J. R. Darby, author) John W;ley Sons, Inc., New York, 1969. Examples of effect;ve plast;cizers include ad;pates, such as di-2-ethylhexyl adipate and diisodecyl adipate; azelates, such as d;-2-ethylhexyl azelate; benzoates, such as d;propylene glycol d;benzoate; phosphates, such as . I, tr;cresyl phosphate, cresyl d;phenyl phosphate, Z-ethylhexyl diphenyl phosphate, d;-n-octyl phenyl phos-phate, and tr;-n-hexyl phosphate; phthalates, such as diethyl phthalate, butyl benzyl phthalate, d;-2-ethylhexyl phthalate, and di;sodecyl phthalate; sebacates, such as d;-2-ethylhexyl sebacate and terephthalates, such as di-2-ethylhexyl terephthalate. A compatible blend of two or more plasticizers can be used. In use, the plasticizer has the effect no only of softening and modifying the polymer, but also of lubricating the fiber surfaces, promoting dispersion and m;n;m;z;ng f;ber breakage The f;bers are described as "discontinuous", to dist;ngu;sh from the well known ;ncorporat;on of cont;nuous cord re;nforcem nt ;nto rubber art;cles. The "matrix"
is the material form;ng a continuous phase which surrounds the fibers. A "composite" is the combination of discontinous fibers in a matrix wherein the contained fibers may be randomly oriented, or, to a greater or lesser degree, aligned in a particular direct;on.
Composites ;n wh;ch the f;bers are h;ghly aligned, as taught ;n U. S. Patent 3,697,364, mentioned above, are part;cularly useful, ;n calendered or extruded objects.
In the step of contact;ng the fibers w;th the treat-ment m;xture, the fibers can be slurried ;n water andm;xed w;th the polymer and plast;c;zer. Th;s step prov;des for separat;on of the fiber bundles to allow max;mum contact with the treatment mixture, and ;t also softens the fibers, making them more flexible during the contact;ng step. As compared ~;th the process of treat;ng f;bers accord;ng to the d;sclosure of Hamed U. S. Patent 3,943,079, the instant process is as . .
43-51~6361 effect;ve; yet, it does not require the heavy, powerful mix;ng equ;pment used by Hamed and it does not cause f;ber degradat;on.
Dur;ng the contacting step, which can be performed with d;ffer;ng degrees of ag;tat;on, the v;nyl chlor;de polymer and plast;c;zer are depos;ted onto the surfaces of the lens to form a relt;vely homogeneous coat;ng.
If necessary, h;gh shear ag;tat;on can be usedg and heat or a coagulant can be employed, ;n order to ;nsure coagulat;on of the polymer and plast;c;zer onto the f;bers. The f;bers are then de-watered by f11trat;on or other means, and dr;ed. Since cellulose ~;bers are somewhat hygroscopic, the drying step is usually not carried to a complete removal of water, although for some purposes the amount of contained water w;11 be minimized.
If desired, rather than slurrying them7 the f;bers can be treated wh;le they are in an agglomerated state, as in a sheet form. In treat;ng a sheet of f;bers, ;t can be saturated w;th a m;xture of plast;c;zer and an aqueous d;spersion of polymer and then dr;ed to produce a treated sheet. A continuous f;ber sheet can be d;pped, for example, ;nto the treatment mixture, and then fed ;nto dry;ng apparatus such as heated rolls or a hot a;r oven to remove the water. Such a treated sheet can then be later ;ncorporated into add;t;onal vinyl chloride polymer and plastic;zer or add;t;onal v;nyl chloride polymer and plast;c;zer can be applied to the sheet. for example a cont;nuous str;p of treated fiber can be fed ;nto an extruder along w;th the plast;ci~er and polymer, to form a cont;nuous extruded composite wh;ch is subjec-ted 9~13 to further shaping operat;ons, wh;ch a1;gn the f;bers as des;red.
When dry;ng f;bers wh;ch have been slurr;ed, treated, and then de-watered by filtration, any of a S var;ety of dry;ng methods can be used. The de-watered fibers w;ll usually form a fr;able cake, wh;ch can be mechanically broken up ;nto clumps of f;bers wh;ch are air dr;ed. Alternatively, the cake can be f;rst a;r-dr;ed, then broken up ;nto crumbs or clumps. If des;red, the cake can be pressed to compact ;t Rand expel add;t;onal water), then dr;ed ;n its pressed form.
As stated above, the treatment mixture, conta;n;ng v;nyl chlor;de polymer and plast;c;zer, ;s employed during the treatment of the fixers in an amount of at least 25 parts preferably at least 30 parts, and more preferably at least 40 parts or more of non-aqueous mixture per 100 parts of f;bers by weight. This treat-ment level ;s relat;vely h;gh compared to prior art ratios, and has been found to be a significant factor ;n enhanc;ng dispersion of the treated f;bers into a matrix. Although a maximum level of treatment mixture ;s not stated, it is clear that th;s level w;ll be ult;mately lim;ted by the amount of matr;x mater;al ;n the f;nal compositeO
For example, ;f the f;bers are to be used ;n a f;n;shed composite in an amount of fifteen we;gh~ percent of the total compos;te we;ght, then the treatmen-t level on the fibers cannot exceed e;ghty-f;ve parts per fifteen parts of f;ber, or stated another way, 5O7 parts per 100 parts of f;bers by we;ght. In th;s example, g;ven as an extreme, all of the matr;x (or non-f;ber) port;on of the compos;te ;s cons;dered to be treatment, and thus the compos;te ;s produced ;n a s;ngle step, .
~9--rather than by the ;nit;al step of pretreat;ng the f;bers followed by a final step of ;ncorporat;ng the treated f;bers ;nto a polymer;c matr;x to form a composite. If a lower f;ber level were des;red ;n the final compos;te, say 3 percent fiber based on the total composite weight, a s;milar calculat;on w;ll show that the treatment level, - expressed as parts by we;ght per 100 parts of fiber could be as h;gh as 3233 parts. Obviously, then the upper limit of the treatment level ;s d;ctated solely by the final composite composition and convenience of handl;ng. Frequently, ;t is desired to have the treated fibers in particulate form, rather than in a mass, so that a level of treatment would be selected to produce particulate or crumb product form This treatment level would usually be less than about 300-400 parts of coating per 100 parts of f;ber.
As indicated above, the weight ratio of plasticizer to v;nyl chlor;de polymer ;n the treatment mixture accord;ng to the method of the ;nvent;on ;s from 2:1 up to 25:1, preferably from 2.5:1 up to 15:1, and more preferably, from 2.~:1 up to 10:1. M;xtures w;th;n these ranges are found to produce treated f;bers having superior d;spersab;l;ty ;nto a matr;x to form a composite. In addition to plast;c;zer and v;nyl chlor;de polymer, the treatment m;xture can also conta;n carbon black; tiler such as clay; alumina; talc and the like, as we11 as other ingredients used ;n the polymer art, including stab;l;zers, ant;degradants, p;gments, colors, and the like.
The treated f;bers of the invention can be further combined with the matrix material ;n a su;table mixer, such as an internal mixer (e.g~, 9anbury) or roll mill.
The erabender m;xer is particularly effect;ve for th;s S purpose in the laboratory. Additional ;ngredients, such as fillers, colorants, stabilizers and additional plasticizer can also be added at this po;nt~ If desired, the f;bers can then be oriented ;n the final composite, by pass;ng a sheet of the composite through a hot roll m;ll. Several passages are often used in order -Jo opt;m;ze orientation of the f;bers in the direction of passage through the rolls. Th;s is followed by compres-s;on mold;ng of the sheet to produce a des;red article.
Alternat;vely, the compos;te can be extruded to al;gn the f;bers ax;ally. If a hose or tube shaped product is des;red, ax;al or;entat;on of f;bers can be produced therein, or, by us;ng the techn;ques set forth ;n U. S. Patents 4,056,591 and 4,057,610, in a direction other than ax;al.
EXAMPLE I
To ;llustrate a preferred method of fiber treatment twenty grams of "Pinnacle" wood pulp (produced by Westvaco) is charged to the bowl of a Waring 91ender~
The pulp is hygroscop;c and, as equ;librated w;th labora-tory a;r, contains about 8% mo;sture. To the pulp ;sadded about 700 ml. o-f water and the agitation is started Polyv;nylchloride latex (Geon 575 x 43, 56~ sol;ds, plast;c;zed w;th 25 phr of a phosphate plasticizer) di1uted with an equal volume of water is added at varying levels. Butyl benzyl phthalate plasticizer in the ~9 l 3 43-5l-6361 desired amount is then added, followed by a coagulant (0.3 to 1.3 grams alum dissolved in 50 ml. water).
M;xing ;s continued for about thirty seconds, and the fibers are then collected by filtration; washed w;th S water tw;ce, and dried, e;ther at room temperature or ;n an oven at 120C. The low turbidity of the effluent water ;nd;cates nearly quant;tat;ve depos;t;on of the ingred;ents onto the fibers.
EXAMPLE II
To show ;ncorporat;on of the treated f;bers ;nto a matrix of a p1as~;c;zed viny1 chlor;de polymer, the f;bers of Example I are m;xed w;th a typ;cal green garden hose compound. The compound, conta;n;ng approxi-mately 50 parts of plast;c;zer and 6 parts of other add;t;ves per lO0 parts polyv;nylchlor;de ~PVC) res;n, ;s charged to the chamber of a Brabender m;xer equ;pped ~;th cam type rotors, and fluxed, together w;th add;t;onal PVC, at a temperature of 150C, w;th a rotor speed of lOa rp~. The treated f;ber ;s added and m;xed for one minu~e3 then a bonding agent ;s added. The charge ;s then m;xed for additional t;me~ ~otal;ng e;ther 3 or 5 m;nutes aster the f;ber add;t;on.
The composites thus pr-oduced are removed from the m;xer and passed repeatedly through the n;p of a roll m;ll three to f;ve times, w;th doubl;ng each time) to orient the fibers in a s;ngle direction. The aligned sheet ;s then compress;on molded ;n a frame mold at 165C
under a pressure of 1.38 MPa to produce a void-free sheet.
In order to evaluate the d;spers;on of the fibers in the matrix, the density of undispersed clumps is . ., 43-Sl-6361 measured over a cut surface. Several slices are made in a sheet, to expose at least 8 cmr2 of cut surface Those white undispersed clumps wh;ch could be ident;f;ed without magnification were counted.
EXAMPLE III
In the course of our work, ;t has been determined that the amount of treatment mixture deposited on the fibers and the ratio of plasticizer to polymer ;n the mixture considerably affect the ease of dispersion of the treated fibers into the matrix In order to invest;-gate the nature of the causes and effects, an exper;ment was designed in which a logarithmic factorial array was employed for the composition var;at;ons.
my us;ng the procedure set worth in Example I, above, seventeen samples of treated f;ber were prepared the samples hav;ng varying ratios of plasticizer to vinyl chloride polymer and varying amounts of fiber treating materials deposited on the fibers. Composites were then prepared according to the procedures set forth in Example II~ above, in which all composite samples contained 15.0% by weight of cellulose fiber, 0.8% by weight bonding agent ~Vulcabond VP, a 25% solution of an isocyanurate polymer of toluene diisocyanate, ;n d;butyl phthalate, manufactured by Vulnax Interna-tional, lid the rema;nder being vinyl chloride polymer and plastici-zers. The dens;ty of und;spersed clumps was measured on each sample as in Example II, and the results were summar;zed as shown ;n the accompanying draw;ng, which shows, numer;cally, the density of und;spersed clumps ;n clumps per square meter, on logarithmic coordinates ~L~lB~2~
of f;ber treatment level and piasticizer to vinyl chloride polymer ~e;ght rat;o. The f;ber treatment level is expressed in parts by weight of coating material per 100 parts by we;ght of f;ber. L;mits of each variable are indicated by sol;d l;nes, the preferred l;mits by a line of long dashes, and the most preferred limits by a l;ne of short dashes. The letter "K" ;nd;cates one thousand thus 3K, for example, should be read as three thousand.
It can be seen that w;th;n the claimed lim;ts the clump dens;ty ;s at a m;n;mum level, but outs;de the claimed l;m;ts the clump density is considerably higher.
The transition between the m;nimum and the area of poor dispersion due to too low plasticizer concentrat;on tin the coat;ng) is especially abrupt9 indeed7 In summary; the method of the ;nvention offers a simple, low-energy process for producing treated cellulose fibers. The f;bers of the invention are particularly suited for rapid and efficient dispersion into plastic;zed polymers of vinyl chlor;de. The composites of the invent;on are useful in the form of articles having superior strength and stiffness without the use of continu-ous cord for reinforcement in a braided, knit or other conf;gurat;on. Add;tionally, the composites of the invention can take the form of floor t;le compos;t;ons, contain;ng a relat;vely h;gh proport;on of inert f;ller, such as calc;um carbonate.
Although the foregoing ;nvention has been described ;n some deta;l by Jay of illustrat;on and example for purposes of clar;ty of understand;ng, ;t w;ll be obv;ous that certa;n changes and modif;cations may be practiced w;th;n the scope of the appended cla;ms.
Claims (23)
1. The process of treating discontinuous cellulose fibers by contacting said fibers with a mixture of (a) an aqueous suspension of a vinyl chloride polymer and (b) a plasticizer for said polymer, causing the mixture to deposit on the fibers, and drying the treated fibers, wherein the non-aqueous portion of the mixture is present in an amount of at least 25 parts per 100 parts of fibers by weight, and the weight ratio of plasticizer to polymer in the mixture is from 2:1 to 25:1.
2. The process of Claim 1, wherein the non-aqueous portion of the mixture is present in an amount of at least 30 parts per 100 parts of fibers by weight, and the weight ratio of plasticizer to polymer in the mixture is from 2.5:1 to 15:1.
3. The process of Claim 1, wherein the non-aqueous portion of the mixture is present in an amount of at least 40 parts per 100 parts of fibers by weight, and the weight ratio of plasticizer to polymer in the mixture is from 2.8:1 to 10:1.
4. The process of Claim 1, wherein the aqueous suspension of the polymer is a latex.
5. The process of Claim 1, wherein the coagulant is added to cause the mixture to deposit on the fibers.
6. The process of Claim 1, wherein the mixture also contains a filler.
7. The process of Claim 1, wherein the mixture also contains a bonding agent.
8. The process of Claim 1, wherein the fibers are slurried in water during the step of contacting them with the mixture.
9. The process of Claim 1, wherein the fibers are in sheet form during the step of contacting them with the mixture.
10. Treated fibers produced by the process of Claim 1.
11. A composite containing treated fibers of Claim 10 dispersed in a matrix which comprises vinyl chloride polymer.
12. The composite of Claim 11, wherein the fibers are present in an amount of from 1 to 40 weight percent of cellulose based on the total weight of the composite.
13. A treated fiber comprising discontinuous cellulose fiber of aspect ratio greater than 20, vinyl chloride polymer and a plasticizer for said polymer wherein the polymer and plasticizer together are present in an amount of at least 25 parts by weight per 100 parts of cellulose fiber by weight and the weight ratio of plasticizer to polymer is from 2:1 to 25:1.
14. The treated fiber of Claim 13, wherein the aspect ratio of the cellulose fiber is within the range of 50-350.
15. The treated fiber of Claim 14, wherein the aspect ratio of the cellulose fiber is within the range of 75-200.
16. The treated fiber of Claim 13, wherein the cellulose fiber is hardwood kraft.
17. The treated fiber of Claim 13, wherein the polymer and plasticizer are present in an amount of at least 30 parts by weight per 100 parts of cellulose fiber.
18. The treated fiber of Claim 17, wherein the polymer and plasticizer are present in an amount of at least 40 parts by weight per 100 parts of cellulose fiber.
19. The treated fiber of Claim 13, wherein the weight ratio of plasticizer to polymer is from 2.5:1 to 15:1.
20. The treated fiber of Claim 19, wherein the weight ratio of plasticizer to polymer is from 2.8:1 to 10: 1.
21. The treated fiber of Claim 13, which is in sheet form.
22. A composite containing treated fibers of Claim 13 dispersed in a matrix which comprises vinyl chloride polymer.
23. The composite of Claim 22, wherein the fibers are present in an amount of from 1 to 40 weight percent of cellulose based on the total weight of the composite.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US252,514 | 1981-04-08 | ||
| US06/252,514 US4414267A (en) | 1981-04-08 | 1981-04-08 | Method for treating discontinuous cellulose fibers characterized by specific polymer to plasticizer and polymer-plasticizer to fiber ratios, fibers thus treated and composites made from the treated fibers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1189213A true CA1189213A (en) | 1985-06-18 |
Family
ID=22956333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000400652A Expired CA1189213A (en) | 1981-04-08 | 1982-04-07 | Method for treating discontinuous cellulose fibers, fibers thus treated and composites made from the treated fibers |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4414267A (en) |
| EP (1) | EP0062532B1 (en) |
| JP (1) | JPS57179226A (en) |
| AU (1) | AU545237B2 (en) |
| BR (1) | BR8202011A (en) |
| CA (1) | CA1189213A (en) |
| DE (1) | DE3268627D1 (en) |
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| CA2527325C (en) * | 2005-11-18 | 2014-05-06 | Mohini M. Sain | Manufacturing process for high performance lignocellulosic fibre composite materials |
| US8167275B1 (en) | 2005-11-30 | 2012-05-01 | The Crane Group Companies Limited | Rail system and method for assembly |
| NZ544493A (en) * | 2005-12-22 | 2008-07-31 | Nz Forest Research Inst Ltd | Method for producing wood fibre composite products |
| US7743567B1 (en) | 2006-01-20 | 2010-06-29 | The Crane Group Companies Limited | Fiberglass/cellulosic composite and method for molding |
| US20070260006A1 (en) * | 2006-05-03 | 2007-11-08 | Whitson Russell L | Rigid polyvinyl chloride polymer compositions having improved impact properties |
| EP2057243B1 (en) | 2006-08-30 | 2013-01-23 | Eastman Chemical Company | Sealant compositions having a novel plasticizer |
| CN102850968B (en) | 2006-08-30 | 2015-09-09 | 伊士曼化工公司 | As the terephthalate of softening agent in vinyl acetate polymer compositions |
| CA2560349C (en) * | 2006-09-21 | 2014-04-22 | Mohini H. Sain | Manufacturing process for hybrid organic and inorganic fibre-filled composite materials |
| US8460797B1 (en) | 2006-12-29 | 2013-06-11 | Timbertech Limited | Capped component and method for forming |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3461012A (en) * | 1961-11-13 | 1969-08-12 | Turner Brothers Asbest | Manufacture of thermoplastic sheet |
| US3265644A (en) * | 1963-02-18 | 1966-08-09 | Nat Lead Co | Particle-polymer compositions and process for making same |
| DE1544759B2 (en) * | 1964-05-13 | 1972-12-14 | Dynamit Nobel Ag, 5210 Troisdorf | PROCESS FOR THE PRODUCTION OF FILLER-CONTAINING VINYL POLYMERISATES |
| FR1582334A (en) * | 1967-09-28 | 1969-09-26 | ||
| US3836412A (en) * | 1970-04-16 | 1974-09-17 | Monsanto Co | Preparation of discontinuous fiber reinforced elastomer |
| US3697364A (en) * | 1970-04-16 | 1972-10-10 | Monsanto Co | Discontinuous cellulose reinforced elastomer |
| US3943079A (en) * | 1974-03-15 | 1976-03-09 | Monsanto Company | Discontinuous cellulose fiber treated with plastic polymer and lubricant |
| US4263184A (en) * | 1977-01-05 | 1981-04-21 | Wyrough And Loser, Inc. | Homogeneous predispersed fiber compositions |
-
1981
- 1981-04-08 US US06/252,514 patent/US4414267A/en not_active Expired - Fee Related
-
1982
- 1982-04-06 EP EP82301805A patent/EP0062532B1/en not_active Expired
- 1982-04-06 DE DE8282301805T patent/DE3268627D1/en not_active Expired
- 1982-04-07 AU AU82435/82A patent/AU545237B2/en not_active Ceased
- 1982-04-07 JP JP57056769A patent/JPS57179226A/en active Pending
- 1982-04-07 CA CA000400652A patent/CA1189213A/en not_active Expired
- 1982-04-07 BR BR8202011A patent/BR8202011A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR8202011A (en) | 1983-03-15 |
| JPS57179226A (en) | 1982-11-04 |
| US4414267A (en) | 1983-11-08 |
| EP0062532B1 (en) | 1986-01-22 |
| AU545237B2 (en) | 1985-07-04 |
| EP0062532A3 (en) | 1983-03-09 |
| EP0062532A2 (en) | 1982-10-13 |
| AU8243582A (en) | 1982-10-14 |
| DE3268627D1 (en) | 1986-03-06 |
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