CA2029727A1 - Process for production of cellulose fiber filled-polystyrene composites characterized by lignin/mixture of lignin and isocyanate bonding agents - Google Patents
Process for production of cellulose fiber filled-polystyrene composites characterized by lignin/mixture of lignin and isocyanate bonding agentsInfo
- Publication number
- CA2029727A1 CA2029727A1 CA 2029727 CA2029727A CA2029727A1 CA 2029727 A1 CA2029727 A1 CA 2029727A1 CA 2029727 CA2029727 CA 2029727 CA 2029727 A CA2029727 A CA 2029727A CA 2029727 A1 CA2029727 A1 CA 2029727A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- composite
- lignin
- fiber
- polystyrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT
Under study were the method of preparation of composites comprising polystyrene and cellulose fiber using a coupling agent, such as lignin, or the mixtures of coupling agents, e.g. lignin and isocyanate. An alternative method for incorporating cellulosic fibers into polystyrene matrix is also provided by precoating the fibers with a compatible polymer and a single coupling agent or the mixture of coupling agents.
Under study were the method of preparation of composites comprising polystyrene and cellulose fiber using a coupling agent, such as lignin, or the mixtures of coupling agents, e.g. lignin and isocyanate. An alternative method for incorporating cellulosic fibers into polystyrene matrix is also provided by precoating the fibers with a compatible polymer and a single coupling agent or the mixture of coupling agents.
Description
7 2 '7 BACKGIROUNl) OF THE INVENTION
This invention relates to a process for bonding of cellulosic fiber with a matrix of polystyrene by using a single coulping agent or a mixtures of coupling agants ancl 0to composite systems obtained thereby. More specifically, it r~lates to such reinforced thermoplastic composites which have good mechanical properties and are derived from readily available cheap component.
The published literature includes a number of proposals which teach the various way of dispersing and compatibilizing discontinuous cellulose fibers in 20thermoplastic matrix. Duchateau, France Patant number 2,471,274 used wood fibers having diameter of 0.1 to about 1mm length as the filler of PE or PS composites.Gueret, France Patent number 2,413,20~ described the injection molding of PP-sawdust composites by the control of pre- and post-pot temperatures at increased levels (up to 210C).
Nakabayashi, Japan Patent Kokai number 233,134/8~ prepared uncoated reclaimed paper and PP composites.
Duperrier, France Patent number 2,563,462 prepared composite product from wood particles or the like and thermoplastic binder by a screw-type extruder process 40to produce a rod or bar of composite materials.
Hamed, lu'.S Patent number 3,943,079 described the pretreatment of cellulose fibers with a plastic polymer and a lubricant.
Varteressian described that sawdust wood chips, or similar particle materials can be mixed with a solution of plastic (e.g. PS) in a solvent (e.g. trichloroethylene), 5 and the resulting composition is subjected to heat treatment to evaporate andrecover the solvent, and then to molding. The resulting product can be used as aconstruction material or as a fuel.
Goettler, U.S. Patent number 4,376,144 showed advantageous to combine the bonding agent, like isocyanate, with the cellulose fibers in a pre-treament step of ~ ~ ~ e3~ ~
cellulose-PVC composites.
Kokta, U.K. Patent number 2,193,503 adopted the post-coating procedura of the cellulose fiber with polystyrene and isocyanate bonding agent before mixing the cellulose fiber with polystyrene composites.
Lund, U.S. Patent number 4,241,133 mixed elongated woo~ flakes with a binder (e.g. a polyisocyanate), formed into a mat and hot-pressecl to forrn an elongat~d structural member such as a builcling beam, post, or the like.
Fujimura, Japan Patent Kokai number I37,243/78 described that a cellulosic material, e.g. straw, which has been acetylated with gaseous acetic anhydride is a 2 o good reinforcing filler for polyethylene.
Hishida, IJ.K. Patent number 2,090,503 described the surface coating of jute fibers with various coupling agents, e.g. stearate, silane, titanate, acrylics and so on, and prepared the composites of polypropylene and polystyrene.
Gaylord, U.S. Patent number 3,485,777 showed the compatibilization of grafted cellulose fibers with polyvinyl chloride or polymethylmethacrylate matrices.
Gaylord, U.S. Patent number 3,645,939 also showed good compatibilization of plastics, like polyethylene, polyvinyl chloride or acrylic rubber with cellulose by precoating the fibers with a thermoplastic, ethylenically unsaturated carboxylic acid or anhydride and a free radical initiator.
Dainippon Ink and Chemical Inc., Japan Patent Kokai number 79,064/85 described the use of copolymer of maleic anhydride, phthalic anhydride, and the like - and banzoyl peroxide, as a good prepreg with ~ood blocking registance on decorative laminated sheets.
Pleska, France patent number 2,456,133 showed that a mixture of polyolefin fibril and polyolefin grafted with a polar monomer (e.g. maleic anhydride) exhibited good compatibility with cellulose fibers.
Coran et al., U.S. Patent number 4,323,625 prepared the composites comprise discontinuous celiuiose fibers mixed with certain modified polymer, which have 2~2~
methylol phenolic group grafted thereto in presence of a bonding agent, like isocyanate.
Hse, U.S. Patent number 4,209,433 describecl the preparation of particle board using as binder a composition including a phenolic compound and a polyisocyanate.
Improved tolerance of the binder to wood were achieved by applying the n polyisocyanate to the wood were achieved by applying the polyisocyanate to the wood material prior to applying the phenolic resin.
Janiga, U.S. Patent number 4,701,383 prepared sructural materials, such as particle or like, using an improved lignosulfonate-phenol-formaldehycle resin as a 20 binder or adhesive. Lgnosulphonate, which was obtained from spend sulfite liquor (SSL) or sulfite black liquor frorn alkaline pulping is mixed with phenol and HCHO.
Eldin, Canadian Patent number 1,192,398 describes both or~anic and inorganic fibers composites prepreg coated with two different rssins, like maleic acid (derivatives)/hydrantoin vinylether copolymers.
Kokta, U.K. Patent numbers 2,192,397; 2,192,398 and 2,203,743 described the precoating of cellulose fibers with a compati~le polymer in presence of silane or isocyanate couplin~ agents and the composites of polyvinyl chloride or polyetylene and coated fibers.
Beshay, U.S. Patent number 4,717,742 reported the silane graHed cellulose pulp and polyethylene composites.
Kansai Kogyo Co. Ltd., Japan Patent Kokai number 217,552/83 prepared extruded composites containing PP, wood flour and citric acid ester to give a composite sheet with high flexural strength and high heat distortion tempera~ure.
Lachowicz et at., U.S. Patent number 4,107,110 described that o~-cellulose fibers, coated with graft coplymer comprising 1,2-polybutadine to which an acylate such as butylmethacrylate is grafted could be used in reinforcing of PE and other plastic compositions.
2~?~72ri SUMMARY C)F THE IIIVENTION
It has now been found that the dispersion of discontinuous cellulose fibers in polystyrene rnatrix can be promoted by incorporating therewith a oertain bonding 0 agent or the mixture of bonding agents.
It has been also found that cellulose fibers, when coated with polymer give better adhesion when incorporated with polystyrene matrix if the polymer coatingincludes a smal! amount of certain bonding agent or the mixtur~ of bondin~ agents.
According to present invention, composites are made of discontinuous cellulose 20 fibers dispersed in a polystyrene matrix which include a bonding agent which is organosolv lignin (OSL).
The invention includes composites are made of discontinuous cellulose fibers dispersed in polystyrene matrix in the presence of the mixture of OSL and poly[methylene (polyphenyl isocyanate)~ (PMPPIC) of the formula:
N=C=O N=C-O N=C-O
~3 CH2--_ [3 CH2- [~?= 2.7) The bonding a~ent has been found to be effective at low concentrations as low as 0.5 parts by weight on 100 parts of the polystyrene in the matrix.
The invention also includss treated cellulosic fibers pre-coatecl with polystyrene in the presence of small amount of OSL and ~PMPPIC).
3ETAILED DESCPIIPTIC)N OF THE INVENTION
The ceilulosic material used in the invention includes cellulosic fibers derived from softwood or/and hardwood pulps, e.g. chemical or mechanical or chemi-7 2 r~J
mechanical or refiner or stone groundwood or thermo-mechanical or chemithermo-mechanical or ~xplosion or low yield or high yield or ultla high yield pulp, nut shells, corn cobs, rice hulls, vegitable fibers, certain bambootype reeds, grasses, bagasse, cotton, rayon (regenerated cellulose), sawdust, wood flour, wood shavings and the l 0 like.
Preferred are cellulose fibers derived from woocl sawdust, wood flour, wood pulps, e.g. mechanical pulps or ohemi-thermomechanical aspen pulps. There are many available types of wood pulp which may be classified according to where they were derived by chemical or mechanical or thermal treatments as well as known in20 the pulp and paper industry. Waste pulp and/or recycled pulp can also be used. The fibers have an aspect ratio (length divided by diameter~ ranging from 2 to ~ forsawdust, wood flour as well as for mechanical pulps, and 15 to 50 for cherni-mechanical and chemi-thermomechanical pulps, and 50 to 150 for low yield chemical pulps (e.g. kraft, soda or bisulfite).
In some instances, it is desirable to use mixtures of fibers having widely different aspect ratios.
The polymer contained in the matrix is described as being "polystyrene" and inoludes both polys~yrene polymer and copolymer of a major proportion of polystyrsne with minor proportion of other vinyl polymer. The polymer "polystyrene"
includes polystyrene of different densities as well as different propoltion of crystallin0 and amorphous fractions.
Lignin coupling agent used in the practice of this invention is milled wood lignin (MWL)I acid hydrolysis linin (AHL), Kraft lignin (KL)I steam explosion lignin (SEL) 50 and organosolv lignin (OSL). A more detailed compilation of lignin which may be used is set ~orth at pages 921 to 930 of "J. Agric. Food Chem.", vol. 31, No. 5 (Glasser et al. 1983)1 the disclosure of which is incorporated herein by reference.
The organosolv Ignin which is identified as OSL, is the preferred coupling agent.
The lignosu3fonatel such as relatively pure lignosulfonate or may contain a 2~2~2~
substantial quantity of up to about 80% impurities, may also be used.
The isocyanate coupling agent of the invention is linear poly{methylene-(polyphenyl isocyanate)}, which is identi~ied as PMPPIG. The PMPPIC can be of low, medium or high viscosity depending on degree of polymerization, can be in l0 analytical as well as technical grade. Other di-isocanatas, e.g. toluene di-isocyanate, may also be used.
Lignin is known as a natural wood binder. The attachment of lignin and its derivatives to hydroxy-rich surface of lignocellulosic materials has proven a convenient way to increase the strength of reconstructed fiber and particle materials 0 (Glasser et al. 19~2).
It is reported (Glasser et al. 1982) that lignin and hydroxy propylatecl lignin derivatives can react with diisocyanate in the pr0sence of cellulose fiber. Hydroxy propylated lignin derivatives are capable of contributing equal or even greater strength to relignified fiber composites than does polymeric isocyanate alone.
The bonding agent is used in the composites of the invention in sufficient amount to achieve an adhesive bond between the thermoplastics and the cellulosicbased fibers. This amount can be as little as 0.5% by weight of thermoplastic, up to 10% by weight or more, on the same basis. The amount of bonding agent required 40 can also be expected to vary with the amount of cellulosic fiber present.
The coupling agent can be incorporated into the composites of the invention by mixing the coupling agent therewith, before or at the same time the fibers are combined with the polystyrene and other ingredients.
The coupling agent can be used either as it is or in solution in a convenient, 5 compatible, non-reactlve solvent in order to facilitate dispersion of the reactive material throughout the composites. If the bonding agent is added in solvent solution, the solvent will usually be removed prior to the final shapin~ of the compound. In case when plasticizer solution form of bonding agent is employed, this step is unnecessary.
2~727 The bonding agent may be also at first incorporated by mixing with 5 to 15 parts by weight of polystyrene basecl on total polystyrene weight, than mixed with cellulosic fibers on roll mill; the precoated cellulosic fiber may ba than re-mixed with the rest of polymeric matrix. The bondin~ agent may be incorporat~d totaly in the l~) pre-mixing stage or it can also be added to remaining polymer befor~ fiber addition.
The polymer is mixed with cellulose flblqr to form a composite usually in an internal mixer, extruder or in a roll mill. A,dditional ingredients, such as fillers, plasticizers, stabilizers, colorants, etc., can also be added at this point. Inorganic fillers material may be selected from mica, talc, glass fibers, etc.
The following specific examples illustrate the use of lignin or mixture of lignin and PMPPIC) for cellulose fibers.
EXAMPLE I
High impact polystyrene (PS 525) was supplied by Polysar Limited, Sarnia, Ontario, Canada.
Organosolv lignin (ALCELL) was supplied by Repap Technologies Inc., Valley Forge, Pennsylvania, U.S.A.
Hardwood species aspen (Populus tremuloides Michx) was used in the form of chemithermomechanical pulp (CTMP). CTMP was prepared in a Sund Defibrator an have the properties as described in U.K. Patent number 2,193,503 to Kokta.
Both sawdust aspen and sawdust spruce fibers were used as the filler. Chips for making sawdust and CTMP aspen pulp were dried in an air circulating oven at 55C for 48 hours and then ~round to a mesh size 60 mixture: 60.5%, mesh 60;
20.2%, mesh 80;15.5%, mesh 100; and 3.5%, mesh 200, with a Granu Grinder, C.
W. Brabender, Instruments Inc., U.S.A.
q~
Preparation of the_cc~
Usually, a 25 gram mixture of cellulosic fiber (15-35% by weight of composite) and polymer were mixed in the roll mill at 1 75C. After mixing 5-10 times, the resulting mixtures were reground to mesh size 20. The mixtures were then molded n (24 at a time) into shoulder-shapecl test specimens (ASTM D-638, Type V).
Standard molding conditions are: temperature, 175C; pressure during heating andcooling, 3.8 MPa; heating time, 20 min; cooling time, 15 min. Width and thickness of each specimen were measured with the help of a micrometer.
20 Mechanical tests The mechanical properties (e.g. tensile strength at yield point and the corresponding elongation and energy as well tensile modulus at 0.1% strain) of all the samples were measured with an Instron Tester (Model 4201) following ASTM D-638 and mechanical properties were automatically calculated by a HP-86B computer.
The strain rate was 1.5 mm/min. The impact strength (Izod, un-notched) was tested with an Impact Tester (Model TMI, No 43-01) of Tasting Machines Inc., U.S.A. Thesamples were tested after conditioning at 23iO.5~C and 50% R.H. for at least 18 hours in a controlled atmosphere. Mechanical properties were reported after taking 40 the statistical average of six measurements. The coefficients of variation 2.5-8.~%
were taken into account for each set of tests.
Mechanical properties of cellulosic fiber-filled PS 52~ composites, treated withlignin (0-10 weight percent based on composite used) are presented in Tables I and Il. Properties of the composites are compared to that of virgin polystyrene as well as 50 to those filled with fibers without the use of lignin. It is obvious, that the mechanical properties of polystyrene based composites improved compared to those of both the original polymer and non-treated composites. For CTMP based composites strength increased from 16.8 MPa (virgin PS) to 23.5 MPa in case of 25 weight percentage of fiber addition and at 2 % level of lignin. In same time, the modulus has increased 2 l from 1.4 GPa to 1.8 GPa; elongation from 1.5% to 2.4~/o and energy from 17.2 mJ
to 41.9 mJ. On the other hand, impact strength diminised comparod to that of virgin polymer, but the same properties improved compared to that Qf non-trea~ed composites. Mechanical properties of both sawdust aspen and sawdust spruce have l0 shown the samilar general trend at 4% level of lignin.
EXAMPLE ll The composites were prepared and evaluated as described in Example I but polystyrene used at this time was high heat crystal polystyrene (PS 201) of Polysar 2 0 Limited of Canada. Mechanical properties are presented in Tables lll and IV. It appears from these tables that mechanicai properties of lignin treated composites increased in many cases for 15 weight % of fiber level compared to those of non-treated composites.
EXAMPLE lll The composites were prepared and evaluated as described in Example I but coupling agent used at this tirne was mixtures of lignin and PMPPIC. Properties are presented in Tables V and Vl. These tables indicate that the proper'lies are ,~0 enhanced further thanks to the addition of PMPPIC cornpared to that of only lignin treated composites.
EXAMPLE IV
The fibers were precoated with PS 201 (10 weight % of fiber) and lignin (4-8 50 weight % of fiber)/mixtures of lignin and PMPPIC (total 8 weight % of fiber) with th help of a Laboratory Roll Mill (C.W. Brabender, Model No. 065) at 1 75C. The mixtures were colected and mixed repeatedly 8-10 times for homogsneous coating.
Finally, the coated fiber were ground to mesh size 20. The cornposites of coated cellulose fiber and PS 201 were prepared and evaluated as described in Example 1.
~ ~ ?, ~3~
Properties are presented in Tables Vll and Vlll. These tables reveal that the properties of the composite materials improved due to such coating treatment compared to those of virgin polymer and those of non-tre~ted composites.
Althougth the foregoing invention has been described in some details by the lo way of illustration and example for purposes of clarity of understanding, it will be obvious that certain changes and modifications may be practiced within the scope of the appended claims.
2~2~72~
REFERENICES
1. Gaylord, N.G., U.S. Patent, 3,485,777, Dec. 23, 1969.
2. Gaylord, N.G., U.S. Pa~ent, 3,645,939, Feb. 29, 1972.
This invention relates to a process for bonding of cellulosic fiber with a matrix of polystyrene by using a single coulping agent or a mixtures of coupling agants ancl 0to composite systems obtained thereby. More specifically, it r~lates to such reinforced thermoplastic composites which have good mechanical properties and are derived from readily available cheap component.
The published literature includes a number of proposals which teach the various way of dispersing and compatibilizing discontinuous cellulose fibers in 20thermoplastic matrix. Duchateau, France Patant number 2,471,274 used wood fibers having diameter of 0.1 to about 1mm length as the filler of PE or PS composites.Gueret, France Patent number 2,413,20~ described the injection molding of PP-sawdust composites by the control of pre- and post-pot temperatures at increased levels (up to 210C).
Nakabayashi, Japan Patent Kokai number 233,134/8~ prepared uncoated reclaimed paper and PP composites.
Duperrier, France Patent number 2,563,462 prepared composite product from wood particles or the like and thermoplastic binder by a screw-type extruder process 40to produce a rod or bar of composite materials.
Hamed, lu'.S Patent number 3,943,079 described the pretreatment of cellulose fibers with a plastic polymer and a lubricant.
Varteressian described that sawdust wood chips, or similar particle materials can be mixed with a solution of plastic (e.g. PS) in a solvent (e.g. trichloroethylene), 5 and the resulting composition is subjected to heat treatment to evaporate andrecover the solvent, and then to molding. The resulting product can be used as aconstruction material or as a fuel.
Goettler, U.S. Patent number 4,376,144 showed advantageous to combine the bonding agent, like isocyanate, with the cellulose fibers in a pre-treament step of ~ ~ ~ e3~ ~
cellulose-PVC composites.
Kokta, U.K. Patent number 2,193,503 adopted the post-coating procedura of the cellulose fiber with polystyrene and isocyanate bonding agent before mixing the cellulose fiber with polystyrene composites.
Lund, U.S. Patent number 4,241,133 mixed elongated woo~ flakes with a binder (e.g. a polyisocyanate), formed into a mat and hot-pressecl to forrn an elongat~d structural member such as a builcling beam, post, or the like.
Fujimura, Japan Patent Kokai number I37,243/78 described that a cellulosic material, e.g. straw, which has been acetylated with gaseous acetic anhydride is a 2 o good reinforcing filler for polyethylene.
Hishida, IJ.K. Patent number 2,090,503 described the surface coating of jute fibers with various coupling agents, e.g. stearate, silane, titanate, acrylics and so on, and prepared the composites of polypropylene and polystyrene.
Gaylord, U.S. Patent number 3,485,777 showed the compatibilization of grafted cellulose fibers with polyvinyl chloride or polymethylmethacrylate matrices.
Gaylord, U.S. Patent number 3,645,939 also showed good compatibilization of plastics, like polyethylene, polyvinyl chloride or acrylic rubber with cellulose by precoating the fibers with a thermoplastic, ethylenically unsaturated carboxylic acid or anhydride and a free radical initiator.
Dainippon Ink and Chemical Inc., Japan Patent Kokai number 79,064/85 described the use of copolymer of maleic anhydride, phthalic anhydride, and the like - and banzoyl peroxide, as a good prepreg with ~ood blocking registance on decorative laminated sheets.
Pleska, France patent number 2,456,133 showed that a mixture of polyolefin fibril and polyolefin grafted with a polar monomer (e.g. maleic anhydride) exhibited good compatibility with cellulose fibers.
Coran et al., U.S. Patent number 4,323,625 prepared the composites comprise discontinuous celiuiose fibers mixed with certain modified polymer, which have 2~2~
methylol phenolic group grafted thereto in presence of a bonding agent, like isocyanate.
Hse, U.S. Patent number 4,209,433 describecl the preparation of particle board using as binder a composition including a phenolic compound and a polyisocyanate.
Improved tolerance of the binder to wood were achieved by applying the n polyisocyanate to the wood were achieved by applying the polyisocyanate to the wood material prior to applying the phenolic resin.
Janiga, U.S. Patent number 4,701,383 prepared sructural materials, such as particle or like, using an improved lignosulfonate-phenol-formaldehycle resin as a 20 binder or adhesive. Lgnosulphonate, which was obtained from spend sulfite liquor (SSL) or sulfite black liquor frorn alkaline pulping is mixed with phenol and HCHO.
Eldin, Canadian Patent number 1,192,398 describes both or~anic and inorganic fibers composites prepreg coated with two different rssins, like maleic acid (derivatives)/hydrantoin vinylether copolymers.
Kokta, U.K. Patent numbers 2,192,397; 2,192,398 and 2,203,743 described the precoating of cellulose fibers with a compati~le polymer in presence of silane or isocyanate couplin~ agents and the composites of polyvinyl chloride or polyetylene and coated fibers.
Beshay, U.S. Patent number 4,717,742 reported the silane graHed cellulose pulp and polyethylene composites.
Kansai Kogyo Co. Ltd., Japan Patent Kokai number 217,552/83 prepared extruded composites containing PP, wood flour and citric acid ester to give a composite sheet with high flexural strength and high heat distortion tempera~ure.
Lachowicz et at., U.S. Patent number 4,107,110 described that o~-cellulose fibers, coated with graft coplymer comprising 1,2-polybutadine to which an acylate such as butylmethacrylate is grafted could be used in reinforcing of PE and other plastic compositions.
2~?~72ri SUMMARY C)F THE IIIVENTION
It has now been found that the dispersion of discontinuous cellulose fibers in polystyrene rnatrix can be promoted by incorporating therewith a oertain bonding 0 agent or the mixture of bonding agents.
It has been also found that cellulose fibers, when coated with polymer give better adhesion when incorporated with polystyrene matrix if the polymer coatingincludes a smal! amount of certain bonding agent or the mixtur~ of bondin~ agents.
According to present invention, composites are made of discontinuous cellulose 20 fibers dispersed in a polystyrene matrix which include a bonding agent which is organosolv lignin (OSL).
The invention includes composites are made of discontinuous cellulose fibers dispersed in polystyrene matrix in the presence of the mixture of OSL and poly[methylene (polyphenyl isocyanate)~ (PMPPIC) of the formula:
N=C=O N=C-O N=C-O
~3 CH2--_ [3 CH2- [~?= 2.7) The bonding a~ent has been found to be effective at low concentrations as low as 0.5 parts by weight on 100 parts of the polystyrene in the matrix.
The invention also includss treated cellulosic fibers pre-coatecl with polystyrene in the presence of small amount of OSL and ~PMPPIC).
3ETAILED DESCPIIPTIC)N OF THE INVENTION
The ceilulosic material used in the invention includes cellulosic fibers derived from softwood or/and hardwood pulps, e.g. chemical or mechanical or chemi-7 2 r~J
mechanical or refiner or stone groundwood or thermo-mechanical or chemithermo-mechanical or ~xplosion or low yield or high yield or ultla high yield pulp, nut shells, corn cobs, rice hulls, vegitable fibers, certain bambootype reeds, grasses, bagasse, cotton, rayon (regenerated cellulose), sawdust, wood flour, wood shavings and the l 0 like.
Preferred are cellulose fibers derived from woocl sawdust, wood flour, wood pulps, e.g. mechanical pulps or ohemi-thermomechanical aspen pulps. There are many available types of wood pulp which may be classified according to where they were derived by chemical or mechanical or thermal treatments as well as known in20 the pulp and paper industry. Waste pulp and/or recycled pulp can also be used. The fibers have an aspect ratio (length divided by diameter~ ranging from 2 to ~ forsawdust, wood flour as well as for mechanical pulps, and 15 to 50 for cherni-mechanical and chemi-thermomechanical pulps, and 50 to 150 for low yield chemical pulps (e.g. kraft, soda or bisulfite).
In some instances, it is desirable to use mixtures of fibers having widely different aspect ratios.
The polymer contained in the matrix is described as being "polystyrene" and inoludes both polys~yrene polymer and copolymer of a major proportion of polystyrsne with minor proportion of other vinyl polymer. The polymer "polystyrene"
includes polystyrene of different densities as well as different propoltion of crystallin0 and amorphous fractions.
Lignin coupling agent used in the practice of this invention is milled wood lignin (MWL)I acid hydrolysis linin (AHL), Kraft lignin (KL)I steam explosion lignin (SEL) 50 and organosolv lignin (OSL). A more detailed compilation of lignin which may be used is set ~orth at pages 921 to 930 of "J. Agric. Food Chem.", vol. 31, No. 5 (Glasser et al. 1983)1 the disclosure of which is incorporated herein by reference.
The organosolv Ignin which is identified as OSL, is the preferred coupling agent.
The lignosu3fonatel such as relatively pure lignosulfonate or may contain a 2~2~2~
substantial quantity of up to about 80% impurities, may also be used.
The isocyanate coupling agent of the invention is linear poly{methylene-(polyphenyl isocyanate)}, which is identi~ied as PMPPIG. The PMPPIC can be of low, medium or high viscosity depending on degree of polymerization, can be in l0 analytical as well as technical grade. Other di-isocanatas, e.g. toluene di-isocyanate, may also be used.
Lignin is known as a natural wood binder. The attachment of lignin and its derivatives to hydroxy-rich surface of lignocellulosic materials has proven a convenient way to increase the strength of reconstructed fiber and particle materials 0 (Glasser et al. 19~2).
It is reported (Glasser et al. 1982) that lignin and hydroxy propylatecl lignin derivatives can react with diisocyanate in the pr0sence of cellulose fiber. Hydroxy propylated lignin derivatives are capable of contributing equal or even greater strength to relignified fiber composites than does polymeric isocyanate alone.
The bonding agent is used in the composites of the invention in sufficient amount to achieve an adhesive bond between the thermoplastics and the cellulosicbased fibers. This amount can be as little as 0.5% by weight of thermoplastic, up to 10% by weight or more, on the same basis. The amount of bonding agent required 40 can also be expected to vary with the amount of cellulosic fiber present.
The coupling agent can be incorporated into the composites of the invention by mixing the coupling agent therewith, before or at the same time the fibers are combined with the polystyrene and other ingredients.
The coupling agent can be used either as it is or in solution in a convenient, 5 compatible, non-reactlve solvent in order to facilitate dispersion of the reactive material throughout the composites. If the bonding agent is added in solvent solution, the solvent will usually be removed prior to the final shapin~ of the compound. In case when plasticizer solution form of bonding agent is employed, this step is unnecessary.
2~727 The bonding agent may be also at first incorporated by mixing with 5 to 15 parts by weight of polystyrene basecl on total polystyrene weight, than mixed with cellulosic fibers on roll mill; the precoated cellulosic fiber may ba than re-mixed with the rest of polymeric matrix. The bondin~ agent may be incorporat~d totaly in the l~) pre-mixing stage or it can also be added to remaining polymer befor~ fiber addition.
The polymer is mixed with cellulose flblqr to form a composite usually in an internal mixer, extruder or in a roll mill. A,dditional ingredients, such as fillers, plasticizers, stabilizers, colorants, etc., can also be added at this point. Inorganic fillers material may be selected from mica, talc, glass fibers, etc.
The following specific examples illustrate the use of lignin or mixture of lignin and PMPPIC) for cellulose fibers.
EXAMPLE I
High impact polystyrene (PS 525) was supplied by Polysar Limited, Sarnia, Ontario, Canada.
Organosolv lignin (ALCELL) was supplied by Repap Technologies Inc., Valley Forge, Pennsylvania, U.S.A.
Hardwood species aspen (Populus tremuloides Michx) was used in the form of chemithermomechanical pulp (CTMP). CTMP was prepared in a Sund Defibrator an have the properties as described in U.K. Patent number 2,193,503 to Kokta.
Both sawdust aspen and sawdust spruce fibers were used as the filler. Chips for making sawdust and CTMP aspen pulp were dried in an air circulating oven at 55C for 48 hours and then ~round to a mesh size 60 mixture: 60.5%, mesh 60;
20.2%, mesh 80;15.5%, mesh 100; and 3.5%, mesh 200, with a Granu Grinder, C.
W. Brabender, Instruments Inc., U.S.A.
q~
Preparation of the_cc~
Usually, a 25 gram mixture of cellulosic fiber (15-35% by weight of composite) and polymer were mixed in the roll mill at 1 75C. After mixing 5-10 times, the resulting mixtures were reground to mesh size 20. The mixtures were then molded n (24 at a time) into shoulder-shapecl test specimens (ASTM D-638, Type V).
Standard molding conditions are: temperature, 175C; pressure during heating andcooling, 3.8 MPa; heating time, 20 min; cooling time, 15 min. Width and thickness of each specimen were measured with the help of a micrometer.
20 Mechanical tests The mechanical properties (e.g. tensile strength at yield point and the corresponding elongation and energy as well tensile modulus at 0.1% strain) of all the samples were measured with an Instron Tester (Model 4201) following ASTM D-638 and mechanical properties were automatically calculated by a HP-86B computer.
The strain rate was 1.5 mm/min. The impact strength (Izod, un-notched) was tested with an Impact Tester (Model TMI, No 43-01) of Tasting Machines Inc., U.S.A. Thesamples were tested after conditioning at 23iO.5~C and 50% R.H. for at least 18 hours in a controlled atmosphere. Mechanical properties were reported after taking 40 the statistical average of six measurements. The coefficients of variation 2.5-8.~%
were taken into account for each set of tests.
Mechanical properties of cellulosic fiber-filled PS 52~ composites, treated withlignin (0-10 weight percent based on composite used) are presented in Tables I and Il. Properties of the composites are compared to that of virgin polystyrene as well as 50 to those filled with fibers without the use of lignin. It is obvious, that the mechanical properties of polystyrene based composites improved compared to those of both the original polymer and non-treated composites. For CTMP based composites strength increased from 16.8 MPa (virgin PS) to 23.5 MPa in case of 25 weight percentage of fiber addition and at 2 % level of lignin. In same time, the modulus has increased 2 l from 1.4 GPa to 1.8 GPa; elongation from 1.5% to 2.4~/o and energy from 17.2 mJ
to 41.9 mJ. On the other hand, impact strength diminised comparod to that of virgin polymer, but the same properties improved compared to that Qf non-trea~ed composites. Mechanical properties of both sawdust aspen and sawdust spruce have l0 shown the samilar general trend at 4% level of lignin.
EXAMPLE ll The composites were prepared and evaluated as described in Example I but polystyrene used at this time was high heat crystal polystyrene (PS 201) of Polysar 2 0 Limited of Canada. Mechanical properties are presented in Tables lll and IV. It appears from these tables that mechanicai properties of lignin treated composites increased in many cases for 15 weight % of fiber level compared to those of non-treated composites.
EXAMPLE lll The composites were prepared and evaluated as described in Example I but coupling agent used at this tirne was mixtures of lignin and PMPPIC. Properties are presented in Tables V and Vl. These tables indicate that the proper'lies are ,~0 enhanced further thanks to the addition of PMPPIC cornpared to that of only lignin treated composites.
EXAMPLE IV
The fibers were precoated with PS 201 (10 weight % of fiber) and lignin (4-8 50 weight % of fiber)/mixtures of lignin and PMPPIC (total 8 weight % of fiber) with th help of a Laboratory Roll Mill (C.W. Brabender, Model No. 065) at 1 75C. The mixtures were colected and mixed repeatedly 8-10 times for homogsneous coating.
Finally, the coated fiber were ground to mesh size 20. The cornposites of coated cellulose fiber and PS 201 were prepared and evaluated as described in Example 1.
~ ~ ?, ~3~
Properties are presented in Tables Vll and Vlll. These tables reveal that the properties of the composite materials improved due to such coating treatment compared to those of virgin polymer and those of non-tre~ted composites.
Althougth the foregoing invention has been described in some details by the lo way of illustration and example for purposes of clarity of understanding, it will be obvious that certain changes and modifications may be practiced within the scope of the appended claims.
2~2~72~
REFERENICES
1. Gaylord, N.G., U.S. Patent, 3,485,777, Dec. 23, 1969.
2. Gaylord, N.G., U.S. Pa~ent, 3,645,939, Feb. 29, 1972.
3. Hamed, P., U.S. Patent, 3,943,079, Mar. 15, 1976.
4. Varteressian, (:i., France Patent, 2,291,021, June 11, 1976.
5. Imagawa, T. and Endo, N., U.S. Patent, 4,029,847, June. 14, 1977.
6. Lachowicz, D.R. and Holder, C.B., U.S. Patent, 4,107,110, Aug. 15, 197~.
7. Fujimura, T. and Suto, S.l., Japan PatenIt Kokai, 137,243/78, Nov. 30, 1978.
8. Gueret, J.L., France Patent, 2,413,205, July 27, 1979.
~. Hse, C.Y., U.S. Patent, 4,209,433, June 24,1980.
10. Pleska, J.P., France Patent, 2,456,133, Dec. 5, 1980.
11. Lund, A.E., Kruger, G.P., Nicholas, l).D. and Adams, R.D., U.S. Patent, 4,241,133, Dec. 23, 1980.
12. Duchateau, H., France Patent, 2,471,274, June 19, 1981.
13. Hishida, I., U.K. Patent, 2,090,849, Jul. 21, 1982.
14. Koran, A.Y., U.S. Patent, R., 4,323,62~, Apr. 6, 1982.
15. Glasser, W.G., Saraf, V.P. and Newman, W.H., J. Adhesion, 14, 233 (1982).
16. Goettler, L.A., U.S. Patent, 4,376,144, Mar. 8, 1983.
17. Coran A.Y. and Goettler, L.A., U.S. Patent, 4,414,2~7, Nov. 8, 1983.
18. Kansai Kogyo Co. Ltd., Japan Patent Kokai, 217,552/83, Dec. 17, 1983.
19. Dainippon Ink and Chemical Ino., Japan Patent Kokai, 79,064/85, May 4, 198~.
20. Eldin, S.H., Candian Patent, 1,192,102, Aug. 20, 1985.
21. Duperrier, P., France Patent, 2,563,462, Oct. 31, 1985.
22. Nakabayashi, H., Ishikawa, Y. and Matsubara, T., Japan Patent Kokai, 233,134/8~, Nov. 19, 198~.
23. Janiga, E.R., U.S. Patent, 4,701,383, C)ct. 20, 1987.
24. Beshay, A.D., IJ.S. Patent, 4,717,742, Jan. 5, 1988.
25. Kokta, B.V. and Beland, P., U.K. Patent, 2,192,398, Jan. 13, 1988.
26. Kokta, B.V., U.K. Patents: 2,192,397, Jan. 13, 1988; 2,193,503, Feb. 10, 1988;
2,203,743, Oct. 26,1988.
2 ~3 2 ~ r~
TABLEI
Composite Te~sile ~ensill! Impact strength modulus str~ngth Polym~r/ Lignin~ (HPa) (GPa) (J/m) fiber lwt.%) Weight % of ~iber: 15 25 35 15 25 35 15 25 35 PS 525 - 16.8 1.4 25.2 10 CTMP-A - 18.9 22.3 21.5 1.8 2.0 2.312.011.3 7.0 CTMP-A 2 20.0 23.5 18.4 1.6 1.8 1.811.013.9 10.4 CTMP-A 4 18.3 19.9 16.2 1.6 1.7 1.811.612.1 10.7 CTMP-A 7 17.7 19.3 15.8 1.5 1.7 1.911.410.1 8.4 CTMP-A 10 15.3 16.3 15.7 1.5 1.7 1.911.910.4 9.3 S.D.-A - 16.2 18.3 17.2 1.6 1.8 2.017.311.2 9.8 S.D.-A 4 17.3 17.5 16.1 1.4 1.5 1.610.511.5 g.7 20 S.D.-S - 17.2 18.~ 17.8 1.7 1.9 2.011.811.4 6.7 S.D.-S 4 17.8 18.9 15.5 1.4 1.4 1.610.4 9.9 9.2 ~ By weight of composite.
S.D.: Sawdust. A: Aspen. S: spruce.
TABLE II
_ Composites ~longation Energy 1~ % ) (mJ) Polymer/ Lignin~
fiber (wt.%) Weight % of fiber: 15 25 35 15 25 35 .
PS 525 - 1.5 17.~
CTMP-A - 1.6 1.7 2.2 22.9 25.1 39.7 CTMP-A 2 3.1 2.4 1.2 49.7 41.9 12.6 CTMP-A 4 2.7 2.1 1.1 42.5 32.2 10.4 CTMP-A 7 2.5 1.4 1.0 37.4 16.4 9.3 50CTMP-A 10 1.1 1.1 1.0 11.1 9.8 9.3 S.D.-A - 1.6 1.7 1.6 17.0 20.7 19.2 S.D.-A 4 1.3 1.2 1.1 13.7 13.4 11.3 S.D.-S - 1.8 1.8 1.6 22.7 25.0 21.3 S.D.-S 4 1.4 1.8 1.4 16.5 23.5 17.0 __ By weight of composite.
S.D.: Sawdust. A: Aspen. S: spruce.
TABLEIII ~ ~ 2 .~ ~ 2 7 Composite Tensile TensileImpact strength ~odul~lsstrength Polymer/ Lignin^(MP~) (GPa) (J/m) fiber (wt.%) Weight ~ of fiber: 15 25 35 15 25 35 15 25 35 I PS 201 - ~1.5 1.9 7.8 CTMP-A - 36.0 35.8 33.81.9 2.0 2.2 6.3 6.1 4.9 CTMP-A 4 38.9 35.0 33.01.6 1.7 1.8 5.9 5.7 5.4 S.D.-A - 35.6 32.6 30.62.2 2.3 2.4 6.9 6.6 6.2 S.D.-A ~ 38.~ 30.7 27.01.6 1.6 1.7 5.4 6.0 6.5 S.D.-S - 38.4 38.1 33.32.0 2.0 2.2 6.5 6.3 5.8 S.D.-S 4 39.3 32.4 27.31.6 1.7 1.8 5.5 6.7 5.7 _ .
^ By weight o~ composite.
S.D.: Sawdust. A: Aspen. S: spruce.
TABLE IV
Composites Elongation Energy Polymer~ Lignin^
fiber ~Wt.%) Weight % of fiber: 15 25 35 15 25 35 _ ~ PS 201 - 3.3 80.5 CTMP-A - 2.7 2.6 2.2 63.7 57.9 44.1 CTMP-A 4 2.7 2.0 2.0 64.6 39.7 38.8 S.D.-A - 2.5 2.2 2.1 54.7 49.1 40.1 S.D.-A 4 2.5 1.9 1.4 56.2 32.4 20.8 S.D.-S - 2.8 2.7 2.3 71.0 66.9 51.6 S.D.-S 4 2.4 1.9 1.5 54.4 34.5 24.0 .
~ By weight of composite.
S.D.: Sawdust. A: Aspen. S: spruce.
/~
TABL~V 202972~
.. ... ...... . . .
Composite Tensile T~nsile Impact str~ngth modulus strength Polymer~ Lignin: (MPa) (GPa) (J/m) fiber PMPPIC^ _ _ _ twt. ratio) Weight ~ of fiber: 15 25 35 ]5 25 35 15 25 35 PS 525 - 16.8 1.4 25.2 CTMP-A - 18.9 22.3 21.5 1.8 2.02.3 12.0 11.3 7.0 CTMP-A 2:2 22.6 22.4 i902 1.4 1.51.5 12.9 13.0 10.2 CTMP-A 4:1 20.2 19.9 18.3 1.4 1.51.5 15.7 10.9 9.8 CTMP-A 4:3 21.2 19.5 19.0 1.5 1.51.5 11.6 11.7 9.9 CTNP-A 7:3 20.9 19.6 17.4 1.3 1.41.5 9.0 10.8 9.0 ^ By weight of composite.
A: Aspen.
TABLE VI
.
Composites Elongation Energy (%~ (mJ3 Polymer/ Lignin:
fiber PMPPIC
(wt. ratio3 Weight ~ of fiber~ 15 25 35 15 25 35 PS 525 - 1.5 17.2 CTMP-A - 1.6 1.7 2.2 22.9 25.1 39.7 CTMP-A 2:2 3.8 2.2 1.3 66.5 34.5 15.5 CTMP-A 4:1 2.8 2.0 1.3 44.1 27.7 13.7 CTMP-A 4:3 3.3 2.0 1.4 57.0 27.2 17.1 CTMP-A 7:3 3.2 1.8 1.3 51.0 24.6 1305 b By weight of composite.
A: Aspen.
2~2~727 TABLE VII
coating Tensile Tensil~3 Impact compositions^ strenth modulus strength ~wt.96) Fiber (MPa) ((;Pa ) ~ J/m ) A B C _ _ ____ Weight 96`0f ~iber: 15 25 35 15 25 35 15 25 35 10PS~01 41.5 1.9 7.8 - - - D 36.0 35.8 33.8 1.9 2.0 2.2 6.3 6.1 4.9 8 - D 41.7 ~1.6 31.2 2.0 2.2 ~.2 5.5 6.5 5.7 4 4 D 42.4 44.3 31.5 1.8 2.0 2.2 7.4 7.3 6.0 - - - E 35.6 32.6 30.6 2.2 2.3 2.4 6.9 6.6 6.2 8 - E 38.6 38.5 29.1 2.û 2.2 2.3 5.7 5.9 6.5 4 4 E 36.5 37.4 39.9 1.7 1.9 2.1 6.1 6.6 5.4 - - F 38.4 38.1 33.3 2.0 2.0 2.2 6.5 6.3 5.8 8 - F 40.5 43.7 37.9 1.7 1.8 2.1 5.5 6.5 5.9 4 4 F 36.6 41.3 42.1 1.7 1.8 2.1 6.3 7.3 5.6 By weight of fiber. A: PS 201. B: Lignin. C: PMPPIC.
D: CTMP aspen. E: Sawdust aspen. F: Sawdust spruce.
TABI,E VIII
Coating FiberElongation Energy composil:ions~ (%) ~m;r) O . .
A B C
Weight % of fiber- 15 ~5 35 15 25 35 PS 201 3.3 80.5 - - - D 2.72.6 2.2 63.757.9 44.1 8 - D 2.82.5 1.7 68.261.4 30.9 4 4 D 2.62.6 1.7 62.564.9 30.4 50_ _ - E 2.52.2 2.1 54.749.1 40.1 8 - E 2.62.3 1.6 58.352.3 26.2 4 4 E 2.32.2 2.2 49.246.8 44.2 - - - F 2.82.7 2.3 71.066.3 51.6 8 - F 2.73.1 2.2 67.584.4 48.3 4 4 F 2.72.3 2.1 62.652.5 40.2 By weight of fiber. A: PS 201. B: Lignin. Co PMPPIC.
D: CTMP aspe~. E: Sawdust aspen. F: Sawdust spruce.
~. Hse, C.Y., U.S. Patent, 4,209,433, June 24,1980.
10. Pleska, J.P., France Patent, 2,456,133, Dec. 5, 1980.
11. Lund, A.E., Kruger, G.P., Nicholas, l).D. and Adams, R.D., U.S. Patent, 4,241,133, Dec. 23, 1980.
12. Duchateau, H., France Patent, 2,471,274, June 19, 1981.
13. Hishida, I., U.K. Patent, 2,090,849, Jul. 21, 1982.
14. Koran, A.Y., U.S. Patent, R., 4,323,62~, Apr. 6, 1982.
15. Glasser, W.G., Saraf, V.P. and Newman, W.H., J. Adhesion, 14, 233 (1982).
16. Goettler, L.A., U.S. Patent, 4,376,144, Mar. 8, 1983.
17. Coran A.Y. and Goettler, L.A., U.S. Patent, 4,414,2~7, Nov. 8, 1983.
18. Kansai Kogyo Co. Ltd., Japan Patent Kokai, 217,552/83, Dec. 17, 1983.
19. Dainippon Ink and Chemical Ino., Japan Patent Kokai, 79,064/85, May 4, 198~.
20. Eldin, S.H., Candian Patent, 1,192,102, Aug. 20, 1985.
21. Duperrier, P., France Patent, 2,563,462, Oct. 31, 1985.
22. Nakabayashi, H., Ishikawa, Y. and Matsubara, T., Japan Patent Kokai, 233,134/8~, Nov. 19, 198~.
23. Janiga, E.R., U.S. Patent, 4,701,383, C)ct. 20, 1987.
24. Beshay, A.D., IJ.S. Patent, 4,717,742, Jan. 5, 1988.
25. Kokta, B.V. and Beland, P., U.K. Patent, 2,192,398, Jan. 13, 1988.
26. Kokta, B.V., U.K. Patents: 2,192,397, Jan. 13, 1988; 2,193,503, Feb. 10, 1988;
2,203,743, Oct. 26,1988.
2 ~3 2 ~ r~
TABLEI
Composite Te~sile ~ensill! Impact strength modulus str~ngth Polym~r/ Lignin~ (HPa) (GPa) (J/m) fiber lwt.%) Weight % of ~iber: 15 25 35 15 25 35 15 25 35 PS 525 - 16.8 1.4 25.2 10 CTMP-A - 18.9 22.3 21.5 1.8 2.0 2.312.011.3 7.0 CTMP-A 2 20.0 23.5 18.4 1.6 1.8 1.811.013.9 10.4 CTMP-A 4 18.3 19.9 16.2 1.6 1.7 1.811.612.1 10.7 CTMP-A 7 17.7 19.3 15.8 1.5 1.7 1.911.410.1 8.4 CTMP-A 10 15.3 16.3 15.7 1.5 1.7 1.911.910.4 9.3 S.D.-A - 16.2 18.3 17.2 1.6 1.8 2.017.311.2 9.8 S.D.-A 4 17.3 17.5 16.1 1.4 1.5 1.610.511.5 g.7 20 S.D.-S - 17.2 18.~ 17.8 1.7 1.9 2.011.811.4 6.7 S.D.-S 4 17.8 18.9 15.5 1.4 1.4 1.610.4 9.9 9.2 ~ By weight of composite.
S.D.: Sawdust. A: Aspen. S: spruce.
TABLE II
_ Composites ~longation Energy 1~ % ) (mJ) Polymer/ Lignin~
fiber (wt.%) Weight % of fiber: 15 25 35 15 25 35 .
PS 525 - 1.5 17.~
CTMP-A - 1.6 1.7 2.2 22.9 25.1 39.7 CTMP-A 2 3.1 2.4 1.2 49.7 41.9 12.6 CTMP-A 4 2.7 2.1 1.1 42.5 32.2 10.4 CTMP-A 7 2.5 1.4 1.0 37.4 16.4 9.3 50CTMP-A 10 1.1 1.1 1.0 11.1 9.8 9.3 S.D.-A - 1.6 1.7 1.6 17.0 20.7 19.2 S.D.-A 4 1.3 1.2 1.1 13.7 13.4 11.3 S.D.-S - 1.8 1.8 1.6 22.7 25.0 21.3 S.D.-S 4 1.4 1.8 1.4 16.5 23.5 17.0 __ By weight of composite.
S.D.: Sawdust. A: Aspen. S: spruce.
TABLEIII ~ ~ 2 .~ ~ 2 7 Composite Tensile TensileImpact strength ~odul~lsstrength Polymer/ Lignin^(MP~) (GPa) (J/m) fiber (wt.%) Weight ~ of fiber: 15 25 35 15 25 35 15 25 35 I PS 201 - ~1.5 1.9 7.8 CTMP-A - 36.0 35.8 33.81.9 2.0 2.2 6.3 6.1 4.9 CTMP-A 4 38.9 35.0 33.01.6 1.7 1.8 5.9 5.7 5.4 S.D.-A - 35.6 32.6 30.62.2 2.3 2.4 6.9 6.6 6.2 S.D.-A ~ 38.~ 30.7 27.01.6 1.6 1.7 5.4 6.0 6.5 S.D.-S - 38.4 38.1 33.32.0 2.0 2.2 6.5 6.3 5.8 S.D.-S 4 39.3 32.4 27.31.6 1.7 1.8 5.5 6.7 5.7 _ .
^ By weight o~ composite.
S.D.: Sawdust. A: Aspen. S: spruce.
TABLE IV
Composites Elongation Energy Polymer~ Lignin^
fiber ~Wt.%) Weight % of fiber: 15 25 35 15 25 35 _ ~ PS 201 - 3.3 80.5 CTMP-A - 2.7 2.6 2.2 63.7 57.9 44.1 CTMP-A 4 2.7 2.0 2.0 64.6 39.7 38.8 S.D.-A - 2.5 2.2 2.1 54.7 49.1 40.1 S.D.-A 4 2.5 1.9 1.4 56.2 32.4 20.8 S.D.-S - 2.8 2.7 2.3 71.0 66.9 51.6 S.D.-S 4 2.4 1.9 1.5 54.4 34.5 24.0 .
~ By weight of composite.
S.D.: Sawdust. A: Aspen. S: spruce.
/~
TABL~V 202972~
.. ... ...... . . .
Composite Tensile T~nsile Impact str~ngth modulus strength Polymer~ Lignin: (MPa) (GPa) (J/m) fiber PMPPIC^ _ _ _ twt. ratio) Weight ~ of fiber: 15 25 35 ]5 25 35 15 25 35 PS 525 - 16.8 1.4 25.2 CTMP-A - 18.9 22.3 21.5 1.8 2.02.3 12.0 11.3 7.0 CTMP-A 2:2 22.6 22.4 i902 1.4 1.51.5 12.9 13.0 10.2 CTMP-A 4:1 20.2 19.9 18.3 1.4 1.51.5 15.7 10.9 9.8 CTMP-A 4:3 21.2 19.5 19.0 1.5 1.51.5 11.6 11.7 9.9 CTNP-A 7:3 20.9 19.6 17.4 1.3 1.41.5 9.0 10.8 9.0 ^ By weight of composite.
A: Aspen.
TABLE VI
.
Composites Elongation Energy (%~ (mJ3 Polymer/ Lignin:
fiber PMPPIC
(wt. ratio3 Weight ~ of fiber~ 15 25 35 15 25 35 PS 525 - 1.5 17.2 CTMP-A - 1.6 1.7 2.2 22.9 25.1 39.7 CTMP-A 2:2 3.8 2.2 1.3 66.5 34.5 15.5 CTMP-A 4:1 2.8 2.0 1.3 44.1 27.7 13.7 CTMP-A 4:3 3.3 2.0 1.4 57.0 27.2 17.1 CTMP-A 7:3 3.2 1.8 1.3 51.0 24.6 1305 b By weight of composite.
A: Aspen.
2~2~727 TABLE VII
coating Tensile Tensil~3 Impact compositions^ strenth modulus strength ~wt.96) Fiber (MPa) ((;Pa ) ~ J/m ) A B C _ _ ____ Weight 96`0f ~iber: 15 25 35 15 25 35 15 25 35 10PS~01 41.5 1.9 7.8 - - - D 36.0 35.8 33.8 1.9 2.0 2.2 6.3 6.1 4.9 8 - D 41.7 ~1.6 31.2 2.0 2.2 ~.2 5.5 6.5 5.7 4 4 D 42.4 44.3 31.5 1.8 2.0 2.2 7.4 7.3 6.0 - - - E 35.6 32.6 30.6 2.2 2.3 2.4 6.9 6.6 6.2 8 - E 38.6 38.5 29.1 2.û 2.2 2.3 5.7 5.9 6.5 4 4 E 36.5 37.4 39.9 1.7 1.9 2.1 6.1 6.6 5.4 - - F 38.4 38.1 33.3 2.0 2.0 2.2 6.5 6.3 5.8 8 - F 40.5 43.7 37.9 1.7 1.8 2.1 5.5 6.5 5.9 4 4 F 36.6 41.3 42.1 1.7 1.8 2.1 6.3 7.3 5.6 By weight of fiber. A: PS 201. B: Lignin. C: PMPPIC.
D: CTMP aspen. E: Sawdust aspen. F: Sawdust spruce.
TABI,E VIII
Coating FiberElongation Energy composil:ions~ (%) ~m;r) O . .
A B C
Weight % of fiber- 15 ~5 35 15 25 35 PS 201 3.3 80.5 - - - D 2.72.6 2.2 63.757.9 44.1 8 - D 2.82.5 1.7 68.261.4 30.9 4 4 D 2.62.6 1.7 62.564.9 30.4 50_ _ - E 2.52.2 2.1 54.749.1 40.1 8 - E 2.62.3 1.6 58.352.3 26.2 4 4 E 2.32.2 2.2 49.246.8 44.2 - - - F 2.82.7 2.3 71.066.3 51.6 8 - F 2.73.1 2.2 67.584.4 48.3 4 4 F 2.72.3 2.1 62.652.5 40.2 By weight of fiber. A: PS 201. B: Lignin. Co PMPPIC.
D: CTMP aspe~. E: Sawdust aspen. F: Sawdust spruce.
Claims (24)
1. A composite comprising from 1 to 50% by weight of discontinuous cellulose fibers dispersed in a matrix from 1-95% by weight of polystyrene being bonded to each other by reaction with 0.5 to 10% by weight of bonding agent and comprising from 0 to 50% by weight of plasticizer and from 0-40% by weight of inorganic filler.
2. The composite as defined in claim 1 wherein the bonding agent is lignin.
3. The composite as defined in claim 1 wherein the cellulosic fiber is selected from softwood pulp or hardwood pulp or mixture of hardwood and softwood pulp or sawdust or wood flour.
4. The composite as defined in claim 1 wherein the cellulosic fiber is selected from non-wood plants, e.g. bagasse, nutshells, corn cobs, jute and the like.
5. The composite as defined in claim 1 wherein the inorganic filler material is selected from mica, talc, calcium carbonate, silica, glass fibers, asbestos or wollastonite.
6. A composite comprising from 1 to 50% by weight of discontinuous cellulose fibers dispersed in a matrix from 1-95% by weight of polystyrene being bonded to each other by reaction with 0.5 to 10% by weight of mixtures of bonding agents and comprising from 0-50% by weight of plasticizer and from 0-40% by weight of inorganic filler.
7. The composite as defined in claim 6 wherein the bonding agents are various weight ratios of lignin and linear poly[methylene (polyphenyl isocyanate)].
8. The composite as defined in claim 6 wherein the cellulosic fiber is selected from softwood pulp or hardwood pulp or mixture of hardwood and softwood pulp or sawdust or wood flour.
9. The composite as defined in claim 6 wherein the cellulosic fiber is selected from non-wood plants, e.g. bagasse, nutshells, corn cobs, jute and the like.
10. The composite as defined in claim 6 wherein the inorganic filler material isselected from mica, talc, calcium carbonate, silica, glass fibers, asbestos or wollastonite.
11. A treated discontinuous cellulosic fibers comprising from 1 to 25% by weight of polystyrene to each other by reaction with 0.5 to 10% by weight of bonding agent.
12. The treated fiber as defined in claim 11 wherein the bonding agent is lignin.
13. The treated fiber as defined in claim 11 wherein the cellulosic fiber is selected from softwood pulp or hardwood pulp or mixture of hardwood and softwood pulp or sawdust or wood flour.
14. The treated fiber as defined in claim 11 wherein the cellulosic fiber is selected from non-wood plants, e.g. bagasse, nutshells, corn cobs, jute and the like.
15. A composite comprising from 1 to 50% by weight of discontinuous treated cellulose fibers as defined in claims 11 to 14, dispersed in a matrix from 1-95% by weight of polystyrene and comprising from 0-50% by weight of plasticizer and from 0-40% by weight of inorganic filler.
16. The composite as defined in claim 15 wherein the inorganic filler material is selected from mica, talc, calcium carbonate, silica, glass fibers, asbestos or wollastone.
17. A treated discontinuous cellulosic fibers comprising from 1 to 25% by weight of polystyrene to each other by reaction with 0.5 to 10% by weight of mixtures of various weight ratios of bonding agents.
18. The treated fiber as defined in claim 17 wherein the bonding agents are lignin and linear polymethylene polyphenyl isocyanate.
19. The treated fiber as defined in claim 18 wherein the cellulosic fiber is selected from softwood pulp or hardwood pulp or mixture of hardwood and softwood pulp or sawdust or wood flour.
20. The treated fiber as defined in claim 18 wherein the cellulosic fiber is selected from non-wood plants, e.g. bagasse, nutshells, corn cobs, jute and the like.
21. A composite comprising from 1 to 50% by weight of discontinuous treated cellulose fibers as defined in claims 18 to 20, dispersed in a matrix from 1-95% by weight of polystyrene and comprising from 0-50% by weight of plasticizer and from 0-40% by weight of inorganic filler.
22. The composite as defined in claim 21 wherein the inorganic filler material is selected from mica, talc, calcium carbonate, silica, glass fibers, asbestos or wollastone.
23. A compression molding made from a composite according to any of claims 1-5 or 6-10 or 15 or 21.
24. An injection molding made from a composite according to any of claims 1-5 or 6-10 or 15 or 21.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2029727 CA2029727A1 (en) | 1990-11-13 | 1990-11-13 | Process for production of cellulose fiber filled-polystyrene composites characterized by lignin/mixture of lignin and isocyanate bonding agents |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2029727 CA2029727A1 (en) | 1990-11-13 | 1990-11-13 | Process for production of cellulose fiber filled-polystyrene composites characterized by lignin/mixture of lignin and isocyanate bonding agents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2029727A1 true CA2029727A1 (en) | 1992-05-14 |
Family
ID=4146395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2029727 Abandoned CA2029727A1 (en) | 1990-11-13 | 1990-11-13 | Process for production of cellulose fiber filled-polystyrene composites characterized by lignin/mixture of lignin and isocyanate bonding agents |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2029727A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5693131A (en) * | 1996-03-19 | 1997-12-02 | Paul Wunning | Decomposable and compostable natural substance granulates from primarily late growth raw materials |
| US5750201A (en) * | 1995-04-13 | 1998-05-12 | Imperial Chemical Industries Plc | Process for binding lignocellulosic material |
| US20210363330A1 (en) * | 2014-06-27 | 2021-11-25 | GranBio Intellectual Property Holdings, LLC | Nanocellulose-polymer composites, and processes for producing them |
-
1990
- 1990-11-13 CA CA 2029727 patent/CA2029727A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5750201A (en) * | 1995-04-13 | 1998-05-12 | Imperial Chemical Industries Plc | Process for binding lignocellulosic material |
| US5693131A (en) * | 1996-03-19 | 1997-12-02 | Paul Wunning | Decomposable and compostable natural substance granulates from primarily late growth raw materials |
| US20210363330A1 (en) * | 2014-06-27 | 2021-11-25 | GranBio Intellectual Property Holdings, LLC | Nanocellulose-polymer composites, and processes for producing them |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4791020A (en) | Bonded composites of cellulose fibers polyethylene | |
| KR101487644B1 (en) | Manufacturing process for high performance lignocellulosic fibre composite materials | |
| Kalia et al. | Pretreatments of natural fibers and their application as reinforcing material in polymer composites—a review | |
| US6758996B2 (en) | Cellulose-reinforced thermoplastic composite and methods of making same | |
| US4717742A (en) | Reinforced polymer composites with wood fibers grafted with silanes - grafting of celluloses or lignocelluloses with silanes to reinforce the polymer composites | |
| Flandez et al. | Management of corn stalk waste as reinforcement for polypropylene injection moulded composites | |
| US5120776A (en) | Process for chemical treatment of discontinuous cellulosic fibers and composites of polyethylene and treated fibers | |
| RU2437894C2 (en) | Binding agents for polyolefins filled with natural fibres and compositions thereof | |
| Feldman | Lignin and its polyblends—a review | |
| Maldas et al. | Composites of polyvinyl chloride—wood fibers: IV. Effect of the nature of fibers | |
| Maldas et al. | Thermoplastic composties of polystyrene: Effect of different wood species on mechanical properties | |
| Maldas et al. | Influence of maleic anhydride as a coupling agent on the performance of wood fiber‐polystyrene composites | |
| Akinyemi et al. | Durability and strength properties of particle boards from polystyrene–wood wastes | |
| Ishak et al. | Effect of silane‐based coupling agents and acrylic acid based compatibilizers on mechanical properties of oil palm empty fruit bunch filled high‐density polyethylene composites | |
| Beg | The improvement of interfacial bonding, weathering and recycling of wood fibre reinforced polypropylene composites | |
| Karina et al. | Physical and mechanical properties of recycled polypropylene composites reinforced with rice straw lignin | |
| US6114416A (en) | Flax shives reinforced thermosetting resin composition | |
| Tufan et al. | Potential use of hazelnut husk in recycled high-density polyethylene composites | |
| Chowdhury et al. | Compatibilizer selection to improve mechanical and moisture properties of extruded wood-HDPE composites | |
| CA2029727A1 (en) | Process for production of cellulose fiber filled-polystyrene composites characterized by lignin/mixture of lignin and isocyanate bonding agents | |
| CA1340707C (en) | Cellulose based fibers and bonded composites of the fibers in vinyl chloride polymer characterized by a silane bonding agent | |
| GB2192398A (en) | Composites of cellulosic fibers and vinyl chloride polymer bonded by an isocyanate bonding agent | |
| CA1334558C (en) | Cellulose based fibers and bonded composites of the fibers in polystyrene polymers characterized by an isocyanate bonding agent | |
| CA1340708C (en) | Cellulose based fibers and bonded composites of the fibers in polyehtylene characterized by a silane bonding agent | |
| Solala et al. | Composites of high-temperature thermomechanical pulps and polylactic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |