CA1269187A - Polymer composites based cellulose - iii - Google Patents
Polymer composites based cellulose - iiiInfo
- Publication number
- CA1269187A CA1269187A CA000585838A CA585838A CA1269187A CA 1269187 A CA1269187 A CA 1269187A CA 000585838 A CA000585838 A CA 000585838A CA 585838 A CA585838 A CA 585838A CA 1269187 A CA1269187 A CA 1269187A
- Authority
- CA
- Canada
- Prior art keywords
- composite
- bonding agent
- coated
- polymerizable functional
- flour
- 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.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Abstract
TITLE : POLYMER COMPOSITES BASED CELLULOSE
ABSTRACT OF THE DISCLOSURE:
Composites based cellulose and polymeric matrix which may be thermoplastic or thermosetting or rubber; the cellulosic material is co -grafted with bonding agents and polymerizable monomers together.
ABSTRACT OF THE DISCLOSURE:
Composites based cellulose and polymeric matrix which may be thermoplastic or thermosetting or rubber; the cellulosic material is co -grafted with bonding agents and polymerizable monomers together.
Description
1269~L87 This invention relates to polymer resin composites prepared by incorporating cellulosic fibers into a poly~eric resin or resin blends.
More specifically the invention relates to such enhanced polymeric composite performances and are derived from readily available cheap materials.
Hitherto~ many kinds of thermoplastic composites have been proposed and commercialized . The addltives used thereln are lnorganic flllers such as calcium carbonate, talc~ mica, asbestos, glass fibers, asphalt, silica graphite, magnesium hydroxide, aluminium hydroxide and the llke. However,these additives are Qf high cost and of high specific gravities and their ablllty to improve physlcal property of compositlon is not so sufficient. The other known addltives used are ~he organic fillers such as starch, flour, wood flour, wood pulp and the other cellulosic flbers.
The published literatures include a number of proposals, . which conslst essentially of thermoplastic resinous matrix havlng dispersed therein cellulosic fillers mlxed or not wlth lnorganic fillers. Such materials are de~crlbed for example:-
More specifically the invention relates to such enhanced polymeric composite performances and are derived from readily available cheap materials.
Hitherto~ many kinds of thermoplastic composites have been proposed and commercialized . The addltives used thereln are lnorganic flllers such as calcium carbonate, talc~ mica, asbestos, glass fibers, asphalt, silica graphite, magnesium hydroxide, aluminium hydroxide and the llke. However,these additives are Qf high cost and of high specific gravities and their ablllty to improve physlcal property of compositlon is not so sufficient. The other known addltives used are ~he organic fillers such as starch, flour, wood flour, wood pulp and the other cellulosic flbers.
The published literatures include a number of proposals, . which conslst essentially of thermoplastic resinous matrix havlng dispersed therein cellulosic fillers mlxed or not wlth lnorganic fillers. Such materials are de~crlbed for example:-
- 2 -- U.S. pat. no 3,485,777 (1969), Gaylord, deals with compatibilization of polyvinylchloride of polmethylmetha-crylate with grafted cellulose.
- U.S. pat. no 3,645,939,also shows that polyethylene or polyvinyl chloride or acrylic rubber can be compatibilized with cellulosic fibers in presence of an ethylenically unsaturated carboxylic acid or anhydride under conditions which generate free radical on said polymer and cellulose.
- U.K. pat. appl. no. 2090849, Hishida,I., prepared composites from thermoplastic resins by compatibilizing flax fibers coated with a surface treating agent such as silanes, titanates ..etc. in absence of a free radical initiator.
-U.S. pat. no. 4,554,215, Robbart, made composites coated with alkylhalogeno-silane~also in absence of an initiator.
-U.S. Pat. no. 4,374,178, Kulkarni, prepared composites by filling with calcium carbonate or sodium silicate and a microcrystalline celluluse as a carrier by coating with silane bonding agent.
-E.P. pat no. 0008143, Solvay & Cie and the Japanese pat.
no. 8011-537, showa, both teach the application of organic and inorganic fillers in presence of a peroxide and an acid anhydride, resulting composite materials having relatively lZ691~
little improvements in their mechanical strengths.
-J 5 pat. no.7192-466, Showa,teaches the addition of an unsaturated silane coupling agent onto the polyolefin matrix by the effect of a catalytic peroxide and then by addlng wood flour as a filler, but by silylating the matrix leads to consuming more silane than in case of silylating the filler itself. Furthermore the composites performances are not highly improved.
-The applicant in his U.S. pat. no. 4,717,742, Beshay, made composites by grafting the silane bonding agents onto the cellulosic fibers by generating free radicals to generate the interfacial strong bondings, from which the composite perfomances are much improved.
- The U.K. pat. appl. no.2205569 , Beshay, realized more improvements by mixing the silane grafted cellulosic fibers free radically , with a silane treated inorganic fillers.
In summary~ we believe to be the first to prepare composites of polymeric resin or resin blend and cellulosic fibers, or starch, or flour, co-grafted with a small amount of polymerizable functional monomer(s) or functional oligomer(s) and with bonding agent(s). Those composites characterized by having good physicomechanical properties, and are easy to make from the available and cheap components.
lZ691~7 The present invention is not only characterized by enhancing the composite performances from the cheap available fillers, but also characterized by its ability for making composites having properties upon the different required purposes. That may be realized by qualitative and quar.titative variations of the compGsite constituents, speci.ally for the gra~ting polymerizable functional monomer(s) or functional oligomer(s) for the same cellulose and for the same matrix.
SUMMARY OF THE INVENTION:
The cellulosic fibers ~ay well compatibilize with polymeric or copolymeric resin or resin blends of thermoplastic or thermosetting or rubber, by co-grafting with polymerizable functional monomer(s), or functional oligomer(s) and with bonding agent(s) together.
DETAILED DESCRIPTION OF THE INVENTION:
It has been found that the cellulosic fibers can well compatibilize with the matrix of the thermoplastic resin or resin blends and the strong covalent bonding between the matrix and the fibers can substantially be lZ69187 improved by improving the interfacial bonding of the cellulosic fibers.
Co-grafting said cellulosic fibers with the conventional polymerizable functional monomer(s) or functional oligomer(s) and with the bonding agent(s) together, confirms said interfacial strong bondings. The preferred grafting processes are those carried out by generating the free radicals.
The cellulosic fibers, starch, or flour may be:
a- Coated with both the polymerizable functional monomer(s) or functional oligomers, and with the bonding agent(s);
b- Grafted with said polymerizable functional monomer(s), or functional oligomer(s) and coated with the bonding agent(s);
c- Grafted with the bonding agent(s) and coated with the polymerizable functional monomer(s) or functional oligomer(s); or d- Grafted with both the polymerizable functional monomer(s), or functional oligomer(s), and with the bonding agent(s) together.
' ~Z691~7 Within the scope of the present inventlon and as per non limiting examples, composites are made from wood pulps or bagasse as examples for the other cellulosic fibers. Acrylonitrile, styrene and methylmethacrylate are as examples for the other polymerizable functional monomer(s) or fumctional oligomer(s~. Silane A-174 and A-llOO, (Union Carbide), and polymethylene polyphenylene isocyanate (PMPPIC) are as examples for the other bor.ding agents. Polyethylene, polystyrene and polyvinyl chloride are as examples for the other polymeric or copolymeric resins or resin blends of thermoplastic,thermosetting, or rubber.
This inventionmay ~so include other additives for more improvements, such as inorganic fillers and/ or plasticizers, which may mix wit~l said polymeric or copol~meric matrix.
The inorganic filler(s) may mix with the cellulosic fibers, starch , or flour befor, during, or after of any of the coating and/o~ the grafting, or the co- grafting step(s) as mentioned ab.ove. 8y means that the lnorganic filler(s) may be coated or bonded with said polymerizables and/or with said bonding agent(s).
This invention is not limited neither to the materials, nor the substances used in the examples of the lZ691~7 present invention, nor to their weight pecentages, but it shows its most usefull advantages for the following materials to be used in any weight percent:
The cellulosic material to be used in the invention includes saw dust, ground wood, wood pulps, agricultural cellulosic fibers, cotton fibers or flakes, flax fibers, rayon, bomboo fibers, bagasse, rice hulls, nut shells, wood shavings, waste papers, cartons, cellulosic cloth, also starch or flour, or the like.
The preferred cellulosic fibers for carrying out the examples of the present invention are chemicalthermomechenical wood pu].p derived from aspen and semichemical pulp of bagasse.
The polymeric or copolymeric resins or resin blends are those including polypropylene, polyvinylchloride, polyethylene, polystyrene, polymethylmethacrylate, polyacrylonitryl butadiene styrene (ABS) alloys,or other polyblends, and may be those described in U.S. pat. no.
4,317,765, or other polymeric~ or copolymeric of thermoplastic, or thermosetting resin, or resin blen~ or rubber.
~Z~93L1 3~
- The preferred matrices in the examPles of the invention are; linear low density polyethylene, polystyrene and polyvinyl chloride and polymethylmethacrylate The polymerizable functional monomer(s) or functional oligomer(s) include the vinyl monomers or the the monomers listed in the Polymer Hand Book, Interscience pub., 1966, pp.VIII-2 to VIII-26 or their re~ated oligomers, or the like.
The preferred vinyl monomers for carrying out the examples of the invention are acrylonitrile, styrene, and methylmethacrylate.
The bonding agents are silylating agents, titanium coupling agents, zirconium coupling agents, isocyanates, stearates,or the l1ke.
The silylating agents are comprising gamma-aminopropyltriethoxysilane, gamma-methacryloxypropyl-trimethoxysilane, propyltriethoxysilane, vinyltriethoxy-silane,- vinyltri(2-methoxyethoxy)silane, beta-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane gamma-mercaptopropyltrimethoxysilane, gamma- aminopropyltriethoxy-silane, n-beta-(aminoethyl), gamma-aminopropylmethoxysilane, n-beta-(aminoethoxyl)-gamma-aminopropyltrimethoxysilane, ~Z69~ ~37 gamma- chloro-propyltrimethoxysilane or any other silylating agents having the formula, - Si - R
' 2 r an oligomer ~hereof, wherein R , R and R are the same or different and are selected from the group comprising alkoxy with 1 to 6 carbon atoms, alkyl, alkenyl, cycloalkYl, with 1 to 6 carbon atoms, aryl, aralkyl, and organo-functional radicals.
The silylating agents may be prehydrolized and\or, diluted to form a monolayer onto the cellulosic fibers or the fille(s) used, and to decrease the costs.
The titanium bonding agents are those as described in the Modern Plastic Encyclopedia, 1986-87, pp. 128 & 130.
The isocyanates such as polymethylene polyphenylisocyanate (PMPPIC), l, 6, and hexamethylene di-isocyanate & NCO-(CH2 )6-NC0,2,4 toluene di-isocyanate or their oligomers or the like.
91~37 The preferred bonding agents to be used in the examples of the inventiOn are gamma-aminopropyltriethoxysllane (A-1100, Union Carbide), gamma-methacryloxypropyl trimethoxysilane, (A-174,Union Caxbide) and linear polymethylene polyphenylisocyanate (PMPPIC).
Free radicals can be generated for the purpose of forming interfacial strong bonding such as the covalent bonds. The free radical initiator may be those from the radiation sources or from the chemical sources. The radiation sources such as gamma radiation, ultraviolet radiation ,laser radiation, or the ultrasonic or the like. The chemical initiation may be from any catalytic initiatorcausing the free radical reactions, among which are the chemical initiators listed in the Polymer Hand Book, Interscience 1966, pp.II-3 to II-51, or the like.
The preferred chemical initiators for carrying out the examples of the invention are the chemicals used for the known xanthation process for graft polymerization of vinyl monomers onto cellulose, ceric ammonium sulfate, sodium bisulfite, peroxides, or the like.
The ethylenically unsaturated carboxylic acid or acid anhydride may be ~ded ~s~auxiliaries to be used in the practice of the invention. such as maleic acid, maleic 1269~8~' anhydride, fumaric acid, citraconic acid, or itaconic acid or the like. Maleic anhydride is the preferred auxiliary agent. Monocarboxylic acids such as acrylic acid or methacrylic acid may also be used.
Instead of maleic anhydride , polymaleic anhydride, succinic anhydride may also be used.
The inorganic fillers such as the hydroxyl containing group, silica, calcium carbonate, kaolin, talc, clay, mica, glass fibers, glass spheres, glass flakes, wollastonite, carbon black, graphite fibers, metal fibers, metal powders, metal hydrides, metal oxides partially hydrated or not, metal compounds, diatomaceous earth, silica, aramide, potassium titanate fibers, or the like,in-either purified or unpurified form. Said inorganic fillers are used as auxiliaries for obtaining more composite improvements.
The preferred fillers used in the examples of the invention are calcium carbonate, short glass fibers and clay.
i~:69~1~7 The p]asticizers which may be contained in the matrix such as dipropylene glycol dibenzoa~e, dl-2-ethylhexyl adipate, diisodecyl adlpate; azelates, di-2-ethylhexyl azelate; phosphates, such as tricresyl phosphate, cresyl diphenYl phosphate, 2-ethylhexyl diphenyl phosphate, di-n-octyl phenyl phosphate, and tri-n-hexyl phosphat.e;
phthalates, such as diethylphthalate, butyl benzyl phthalate, di-2-ethylhexylphthalate diisodecyl phthalate;
sebacates, such as di-2-ethylhexyl sebacate, and terephthalates, such as di-2-ethylhexyl terephthalate;or the like.
Other additives are optionally added, such as colorants, antioxidants, lubricants, pigments, opacifiers, heat stabilizers, impact modifiers, photostabilizers, antistatic agents, biostabilizers, crystal nucleating agents, or the like.
Concerning the weight percentages for the composite constituants, accordindg to the present invention?may be as follows:
The matrix resin or resin blend is....... from 1 to 98 wt.%, (based on the total composite's weight.) he celluloslc fibers, starch or flour is from 1 to 98 wt.%, (based on the total composite's weight.) The p~lymerizable functional monomer(s) or functional oligomer(s).............................. from 0.5 to 300 wt%, (based on the filler's weight.) The bonding agent(s)................... from 0.001 to 20 wt.%, (based on the filler's weight.) The inorganic filler....................... from 0 to 95 wt.%, (based on the filler's weight.) The acid anhydride......................... from 0 to 10 wt.%, (based on the filler's weight.) The chemical initiator..................... from 0 to 10 wt.%, (based on the filler's weight.) The plasticizer............................ from o to 60 wt.%, (based on the matrix' weight.) The filler(s), whether from said organic or inorganic nature may be in the form of powders, particles, crystals, fibers, sheets, woven fibers, papers, cartons, threads, cords, cloths~ gravels, chips, boards, panels preshaped forms, or the like.
A composite material may be made according to the invention by compounding from 1 to 98 wt% of cellulosic fibers or starch or flour and from 1 to 98 wt. % of 1269~7 polymeric or copolymeric thermoplastic or thermosetting resin or resin ble~sor rubber, to bond wi~h each other by coating and\or grafting, or co-grafting with both 0.5 to 300 wt. % of polymerizable functional monomer(s~ or functional oligomer(s) and with 0.001 to 20 wt.~ of bonding agent(s).
The same composite material may additionally comprise from 0 to 10 wt.% catalytic initiator, from 0 to 10 wt. %
ethylenically unsaturated acid or acid anhydride. It may also comprise from 0 to 95 wt.% inorganic filler(s) ar,d from 0 to 60 wt.% plasticizer(s). Said composite material is optionally comprising colorant(s), antioxidant(s), stabilizer(s), ~lame-retardent(s), lubricant(s), pigment(s), opacifier(s), impact-modifier(s), photo-stabilizer(s) antistatic agent(s), and crystal nucleating agent(s), or the like.
The cellulosic fibers, or starch, or flour may be grafted first with said polymerizable functional monomer(s) or functional oligomer(s) by a known free radical process or by any graft polymerization process leading to form interfacial strong bonding such as covalent bonding.
The bonding agents may coat the cellulosic fibers or starch or flour; or may graft by free radical grafting process via the effect of any initiating source as mentioned before.
~2~
The graftlng of said ~oth polymerlzabl monomer(s) or oligcmer(s) and said bonding agent(s) onto said fillers may be carried out simultaneously or successiveiy. The simultaneous grafting is recommended for the industrial economy.
The inorganic filler may be mixed wi~ the cellulosic fibers, starch or flour, befor the addition step(s) of said polymerizable(s) and said surface bonding agent(s). Said mixing may also be after or during said addition.
The inorganic filler(s) may also be bonded or coated with the said polymerizabl(s) and /or with said bonding agent(s), befor or after the mixing step.
The experimentation results in the examples of the invention could be improved or be reached their optimum values by changing the preparation conditions, and/ or the weight percentages of the applied materials or the substances.
This invention will now be furtherly describ~dby non limiting examples:
lZ~
GROUP A :
10 g. of dried chemicalthermOmechenical wood pulp derlved from aspen, ground at mesh 60 and wetted with vapor of acrylonitrile, styrene~ or methylmethacrylate monomer and silane A-174 or A-1100, or mixed with linear polymethylene polyphenylisocyanate (PMPPIC), ~ or may be dlssolved in a solvent sich as acetone, then sub~ected to a method for pol~merising said monomers onto the surface of said pulP fibers). This ls to obtain a traated or coated aspen pulp with poly acrylonitrlle- silane A-1100, - silane A -174; poly acrylonltrile - (PMPPIC);pol~styrene -silane A-1100, -silane A-174, and polystyrene - (PMPPIC) or polymethylmethacrylate- silane A-1100 or -silane A-174; an~
polymethylmethacrylate -(PMPPIC).
Mlxing 10, 20, 30 & 40 wt.% (based on the total composite wt.) of these coated pulps, (by using a roll mill or a compounding extuder) with 90, ~0, 70 & 60 wt.% of (hot molten) linear low den~ity polyethylene, or polystyrene, or polyvinylchloride, (plagt1cizer(s) could be added such as ln case o~ P.V.C.) . Molding the resulted composites to shape specim~ns for testin~ ënergy (k~ tress (mpa) and modulus (mpa) according to ASTM, D1822-78.
The examples accordin~ to the group A are as follows:
Example l;
The aspen pulp coated or treated with polyacrylonitrile &
silane A-llO0 and then compounded with LLDPE or pl~icized P.V.C. resins.
Example 2;
The aspen pulp coated or treated with polyacrylonitrile & silane A-174 and then compounded with LLDPE resin.
Example 3;
The aspen pulp coated or treated with polyacrylonitrile (PMPPIC) and then compounded with P.S. resin.
Example 4;
The aspen pulp coated or treated with polymethylmethacrylate & silane A-llO0 and then compounded with P.S. resin.
Example 5;
The aspen pulp coated or treated with polystyrene &
silane A-llO0 and then compounded with P.S. resin.
The testing values are showing improvments with no more than 60% based on their related neat resins.
- GROUP B:
Following here the same experimentaion as per group A, but the difference is by pregrafting the aspen pulp first with 20 wt.% ( based on the pulp weight) of acrylonitrile, styrene or methylmethacrylate by following any of the known graft polymerization processes such as the xanthation process. Then 10 g. of the prepared pregrafted a~pen pulp is wetted with a vapor of ( an organic solvent may be added), 0.2 g. silane-llO0, sllane-174 or mixed with 0.5 g. of PMPPIC, ( the silanes may be prehydrolized or diluted, by evapora~ing the solvent, if present) to glve aspen pulp grafted with polyacrylonitrile, polystyrene, or polymethylmethacrylate, and coated with silane A-llO0, sllane A-174, or PMPPIC; then compounding-the said resulted grafted and coated aspen pulp with the polymeric resins givlng the follwing examples:
Example 6 :
10, 20, 30, & 40 wt.% of Aspen pulp grafted with polyacrylonltrlle and coated wlth sllane A-llO0, and compounded wlth 90, 80, 70 & 60 wt.% of LLDPE, or P.V.C. (plastlclzed) resins.
Exam~le 7 :
10, 20, 30, & 40 wt.% of aspen pulp grafted with polyacrylonitrile ard coated with PMPPIC, then compounded X - 19 _ with 90, 80, 70 & 60 wt.% of P.S. resin.
Example 8 :
10, 20, 30 & 40 wt.% of aspen pulp grafted with polymethylmethacrylate and coated with silane A-1100, then compound with P.S. resin.
The testing values are showing improvements from 70 to 760% based on their related neat resin.
Group C :
'rhe experimentation as per group A,but here it is preferred to use an organic solvent which additionally co~prises ~.1 g.
benzoyl peroxide, then by subjecting to hot air current till dryness, and by mixing with the polymeric resin to give the follwing examples.
Example 9 :
10, 20, 30 & 40 wt.% of the co-grafted aspen pulp with acrylonitrile and silane A-llOO,compound with 90, 80, 70 &
60 wt.% of LLDPE, or P.S. resins.
~xample 10 :
10, 20, 30 & 40 wt.% of the co-grafted aspen pulp with polystyrene and silane A-llOO~compound with 90, 80, 70 & 60 wt.% of P.S. resin.
- 20 _ lZ6gl~7 Example 11 :
10, 20, 30 & 40 wt.% of the co-grafted aspen pulp with polyacrylonitrile and PMPPIC compound wlth 90, 80, 70 & 60 wt.% of P.S. resin.
The testing values for these examples showing improvements from 85 to 1000 %, based on their related neat resin.
Group D :
The experimentation here as per group C, but by mixing the filler with 10 of its wt.% of calcium carbonate, after the drying step to give the following examples:
Example 12 :
10, 20, 30 ~ 40 wt.% of aspen pulp co-grafted with polyacrylonitrile and silane A-llOO~and mixed with calcium carbonate, compoundi with 90, 80, 70 & 60 wt.% of LL3PE or P.S. resins.
Example 13 :
10, 20, 30 & 40 wt.% of aspen pulp co-grafted with polystyrene and silane A-llOO,mixed with calcium carbonate, compound with 90, 80, 70 & 60 wt.% of P.S. resin.
~`- lZ~
The testing values show improvements from 90 to 1050 wt.% based on their related neat resins.
Group E :
As per group D but the calcium carbonate is mixed with the aspen pulp befor the wetting step(s) to give the following examples no. 14 & 15:
Eaxample 14 :
Using the filler of group E and the same composition as per example no. 12.
Example 15 :
Using the filler of group E and the same composition as per example no. 13.
The testing values are showing improvements from 100 to 1100% based on their related resins.
Group F :
As per group B for the pregrafting step of aspen p~lp with acrylonirile, styrene and methylmethacrylate. Then 10 g. of the pregrafted aspen pulp is wetted with a vapor of an organic solution comprising, 0.2 g. silane A-1100, or 0,5 g o~ ~ PMPPIC and 0.1 g. of benzoyl peroxide, then ~9~7 by passing a current of hot air and heatlng for a certaln time and compoundins the given co-grafted aspen pulp with polymeric resins to give the following examples:
Example 16 :
10, 20, 30 ~ 40 wt.% of the prepared co-grafted aspen pulp wlth polyacrylonitrile & sialne A-llO0, are compounded with 90, 80, 70 & 60 wt.% of LLDPE or P.S. resins.
Example 17 :
10, 20, 30 ~ 40 wt.~ of the prepared co-grafted aspen pulp wlth polystyrene & PMPPIC are compounded with 90, 80, 70 &
60 wt.% of P.s. resin.
The testing values are showing improvemnts from 100 to 1100~ based on their related neat resin.
Group G :
As per group F, but by mixing the co-grafted aspen pulp with 10 wt.% ( based on the filler wt.) of short glass fibers pretreated with silane A-llO0 (as delivered), then compounding wlth polymeric resins giving the following examples:
Example 18 :
10, 20, 30 & 40 wt.% of the prepared filler of group G, wherein the aspen pulp co-grafted with polyacrylonitrile &
`- lZS9187 silane A-1100, to be compounded with 90, 80, 70 & 60 wt.% of LLDPE or P.S. resins.
Example 19 :
10, 20, 30 & 40 wt.% of the flller prepare.d as group G, wherein the aspen pulp co-grafted with polystyrene & silane A-1100 to be compounded with 90, 80, 70 ~ 60 wt.% of P.S.
resin.
The results are showing more improvement~ whic~
reached from 150 to 1200 %.
Group H ~ Example 20 :
g. of semichemical pulp of bagasse ground at mesh 60, mixed with 10 g. of clay and-sub~ e~ted to gFa~t polymorization with methylmethacrylate by the known sodium bisulfite initiation method. After dryness, the filler is rewetted wlth a vapor of 0.8 g. cf silane A-1100 in acetone solution comprising 0.4 g. of benzoyl peroxide. Hot air current passed for a certain time. Then 10, 20, 30 & 40 wt.% of the resulted filler is well compounded with 90, 80, 70 & 60 wt.%
of powdered polymethylmethacrylate by using compressionr molding processes.
The testing results give improvements from 90 to 1200 % based on the neat polymethylmethacrylate resin.
- U.S. pat. no 3,645,939,also shows that polyethylene or polyvinyl chloride or acrylic rubber can be compatibilized with cellulosic fibers in presence of an ethylenically unsaturated carboxylic acid or anhydride under conditions which generate free radical on said polymer and cellulose.
- U.K. pat. appl. no. 2090849, Hishida,I., prepared composites from thermoplastic resins by compatibilizing flax fibers coated with a surface treating agent such as silanes, titanates ..etc. in absence of a free radical initiator.
-U.S. pat. no. 4,554,215, Robbart, made composites coated with alkylhalogeno-silane~also in absence of an initiator.
-U.S. Pat. no. 4,374,178, Kulkarni, prepared composites by filling with calcium carbonate or sodium silicate and a microcrystalline celluluse as a carrier by coating with silane bonding agent.
-E.P. pat no. 0008143, Solvay & Cie and the Japanese pat.
no. 8011-537, showa, both teach the application of organic and inorganic fillers in presence of a peroxide and an acid anhydride, resulting composite materials having relatively lZ691~
little improvements in their mechanical strengths.
-J 5 pat. no.7192-466, Showa,teaches the addition of an unsaturated silane coupling agent onto the polyolefin matrix by the effect of a catalytic peroxide and then by addlng wood flour as a filler, but by silylating the matrix leads to consuming more silane than in case of silylating the filler itself. Furthermore the composites performances are not highly improved.
-The applicant in his U.S. pat. no. 4,717,742, Beshay, made composites by grafting the silane bonding agents onto the cellulosic fibers by generating free radicals to generate the interfacial strong bondings, from which the composite perfomances are much improved.
- The U.K. pat. appl. no.2205569 , Beshay, realized more improvements by mixing the silane grafted cellulosic fibers free radically , with a silane treated inorganic fillers.
In summary~ we believe to be the first to prepare composites of polymeric resin or resin blend and cellulosic fibers, or starch, or flour, co-grafted with a small amount of polymerizable functional monomer(s) or functional oligomer(s) and with bonding agent(s). Those composites characterized by having good physicomechanical properties, and are easy to make from the available and cheap components.
lZ691~7 The present invention is not only characterized by enhancing the composite performances from the cheap available fillers, but also characterized by its ability for making composites having properties upon the different required purposes. That may be realized by qualitative and quar.titative variations of the compGsite constituents, speci.ally for the gra~ting polymerizable functional monomer(s) or functional oligomer(s) for the same cellulose and for the same matrix.
SUMMARY OF THE INVENTION:
The cellulosic fibers ~ay well compatibilize with polymeric or copolymeric resin or resin blends of thermoplastic or thermosetting or rubber, by co-grafting with polymerizable functional monomer(s), or functional oligomer(s) and with bonding agent(s) together.
DETAILED DESCRIPTION OF THE INVENTION:
It has been found that the cellulosic fibers can well compatibilize with the matrix of the thermoplastic resin or resin blends and the strong covalent bonding between the matrix and the fibers can substantially be lZ69187 improved by improving the interfacial bonding of the cellulosic fibers.
Co-grafting said cellulosic fibers with the conventional polymerizable functional monomer(s) or functional oligomer(s) and with the bonding agent(s) together, confirms said interfacial strong bondings. The preferred grafting processes are those carried out by generating the free radicals.
The cellulosic fibers, starch, or flour may be:
a- Coated with both the polymerizable functional monomer(s) or functional oligomers, and with the bonding agent(s);
b- Grafted with said polymerizable functional monomer(s), or functional oligomer(s) and coated with the bonding agent(s);
c- Grafted with the bonding agent(s) and coated with the polymerizable functional monomer(s) or functional oligomer(s); or d- Grafted with both the polymerizable functional monomer(s), or functional oligomer(s), and with the bonding agent(s) together.
' ~Z691~7 Within the scope of the present inventlon and as per non limiting examples, composites are made from wood pulps or bagasse as examples for the other cellulosic fibers. Acrylonitrile, styrene and methylmethacrylate are as examples for the other polymerizable functional monomer(s) or fumctional oligomer(s~. Silane A-174 and A-llOO, (Union Carbide), and polymethylene polyphenylene isocyanate (PMPPIC) are as examples for the other bor.ding agents. Polyethylene, polystyrene and polyvinyl chloride are as examples for the other polymeric or copolymeric resins or resin blends of thermoplastic,thermosetting, or rubber.
This inventionmay ~so include other additives for more improvements, such as inorganic fillers and/ or plasticizers, which may mix wit~l said polymeric or copol~meric matrix.
The inorganic filler(s) may mix with the cellulosic fibers, starch , or flour befor, during, or after of any of the coating and/o~ the grafting, or the co- grafting step(s) as mentioned ab.ove. 8y means that the lnorganic filler(s) may be coated or bonded with said polymerizables and/or with said bonding agent(s).
This invention is not limited neither to the materials, nor the substances used in the examples of the lZ691~7 present invention, nor to their weight pecentages, but it shows its most usefull advantages for the following materials to be used in any weight percent:
The cellulosic material to be used in the invention includes saw dust, ground wood, wood pulps, agricultural cellulosic fibers, cotton fibers or flakes, flax fibers, rayon, bomboo fibers, bagasse, rice hulls, nut shells, wood shavings, waste papers, cartons, cellulosic cloth, also starch or flour, or the like.
The preferred cellulosic fibers for carrying out the examples of the present invention are chemicalthermomechenical wood pu].p derived from aspen and semichemical pulp of bagasse.
The polymeric or copolymeric resins or resin blends are those including polypropylene, polyvinylchloride, polyethylene, polystyrene, polymethylmethacrylate, polyacrylonitryl butadiene styrene (ABS) alloys,or other polyblends, and may be those described in U.S. pat. no.
4,317,765, or other polymeric~ or copolymeric of thermoplastic, or thermosetting resin, or resin blen~ or rubber.
~Z~93L1 3~
- The preferred matrices in the examPles of the invention are; linear low density polyethylene, polystyrene and polyvinyl chloride and polymethylmethacrylate The polymerizable functional monomer(s) or functional oligomer(s) include the vinyl monomers or the the monomers listed in the Polymer Hand Book, Interscience pub., 1966, pp.VIII-2 to VIII-26 or their re~ated oligomers, or the like.
The preferred vinyl monomers for carrying out the examples of the invention are acrylonitrile, styrene, and methylmethacrylate.
The bonding agents are silylating agents, titanium coupling agents, zirconium coupling agents, isocyanates, stearates,or the l1ke.
The silylating agents are comprising gamma-aminopropyltriethoxysilane, gamma-methacryloxypropyl-trimethoxysilane, propyltriethoxysilane, vinyltriethoxy-silane,- vinyltri(2-methoxyethoxy)silane, beta-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane gamma-mercaptopropyltrimethoxysilane, gamma- aminopropyltriethoxy-silane, n-beta-(aminoethyl), gamma-aminopropylmethoxysilane, n-beta-(aminoethoxyl)-gamma-aminopropyltrimethoxysilane, ~Z69~ ~37 gamma- chloro-propyltrimethoxysilane or any other silylating agents having the formula, - Si - R
' 2 r an oligomer ~hereof, wherein R , R and R are the same or different and are selected from the group comprising alkoxy with 1 to 6 carbon atoms, alkyl, alkenyl, cycloalkYl, with 1 to 6 carbon atoms, aryl, aralkyl, and organo-functional radicals.
The silylating agents may be prehydrolized and\or, diluted to form a monolayer onto the cellulosic fibers or the fille(s) used, and to decrease the costs.
The titanium bonding agents are those as described in the Modern Plastic Encyclopedia, 1986-87, pp. 128 & 130.
The isocyanates such as polymethylene polyphenylisocyanate (PMPPIC), l, 6, and hexamethylene di-isocyanate & NCO-(CH2 )6-NC0,2,4 toluene di-isocyanate or their oligomers or the like.
91~37 The preferred bonding agents to be used in the examples of the inventiOn are gamma-aminopropyltriethoxysllane (A-1100, Union Carbide), gamma-methacryloxypropyl trimethoxysilane, (A-174,Union Caxbide) and linear polymethylene polyphenylisocyanate (PMPPIC).
Free radicals can be generated for the purpose of forming interfacial strong bonding such as the covalent bonds. The free radical initiator may be those from the radiation sources or from the chemical sources. The radiation sources such as gamma radiation, ultraviolet radiation ,laser radiation, or the ultrasonic or the like. The chemical initiation may be from any catalytic initiatorcausing the free radical reactions, among which are the chemical initiators listed in the Polymer Hand Book, Interscience 1966, pp.II-3 to II-51, or the like.
The preferred chemical initiators for carrying out the examples of the invention are the chemicals used for the known xanthation process for graft polymerization of vinyl monomers onto cellulose, ceric ammonium sulfate, sodium bisulfite, peroxides, or the like.
The ethylenically unsaturated carboxylic acid or acid anhydride may be ~ded ~s~auxiliaries to be used in the practice of the invention. such as maleic acid, maleic 1269~8~' anhydride, fumaric acid, citraconic acid, or itaconic acid or the like. Maleic anhydride is the preferred auxiliary agent. Monocarboxylic acids such as acrylic acid or methacrylic acid may also be used.
Instead of maleic anhydride , polymaleic anhydride, succinic anhydride may also be used.
The inorganic fillers such as the hydroxyl containing group, silica, calcium carbonate, kaolin, talc, clay, mica, glass fibers, glass spheres, glass flakes, wollastonite, carbon black, graphite fibers, metal fibers, metal powders, metal hydrides, metal oxides partially hydrated or not, metal compounds, diatomaceous earth, silica, aramide, potassium titanate fibers, or the like,in-either purified or unpurified form. Said inorganic fillers are used as auxiliaries for obtaining more composite improvements.
The preferred fillers used in the examples of the invention are calcium carbonate, short glass fibers and clay.
i~:69~1~7 The p]asticizers which may be contained in the matrix such as dipropylene glycol dibenzoa~e, dl-2-ethylhexyl adipate, diisodecyl adlpate; azelates, di-2-ethylhexyl azelate; phosphates, such as tricresyl phosphate, cresyl diphenYl phosphate, 2-ethylhexyl diphenyl phosphate, di-n-octyl phenyl phosphate, and tri-n-hexyl phosphat.e;
phthalates, such as diethylphthalate, butyl benzyl phthalate, di-2-ethylhexylphthalate diisodecyl phthalate;
sebacates, such as di-2-ethylhexyl sebacate, and terephthalates, such as di-2-ethylhexyl terephthalate;or the like.
Other additives are optionally added, such as colorants, antioxidants, lubricants, pigments, opacifiers, heat stabilizers, impact modifiers, photostabilizers, antistatic agents, biostabilizers, crystal nucleating agents, or the like.
Concerning the weight percentages for the composite constituants, accordindg to the present invention?may be as follows:
The matrix resin or resin blend is....... from 1 to 98 wt.%, (based on the total composite's weight.) he celluloslc fibers, starch or flour is from 1 to 98 wt.%, (based on the total composite's weight.) The p~lymerizable functional monomer(s) or functional oligomer(s).............................. from 0.5 to 300 wt%, (based on the filler's weight.) The bonding agent(s)................... from 0.001 to 20 wt.%, (based on the filler's weight.) The inorganic filler....................... from 0 to 95 wt.%, (based on the filler's weight.) The acid anhydride......................... from 0 to 10 wt.%, (based on the filler's weight.) The chemical initiator..................... from 0 to 10 wt.%, (based on the filler's weight.) The plasticizer............................ from o to 60 wt.%, (based on the matrix' weight.) The filler(s), whether from said organic or inorganic nature may be in the form of powders, particles, crystals, fibers, sheets, woven fibers, papers, cartons, threads, cords, cloths~ gravels, chips, boards, panels preshaped forms, or the like.
A composite material may be made according to the invention by compounding from 1 to 98 wt% of cellulosic fibers or starch or flour and from 1 to 98 wt. % of 1269~7 polymeric or copolymeric thermoplastic or thermosetting resin or resin ble~sor rubber, to bond wi~h each other by coating and\or grafting, or co-grafting with both 0.5 to 300 wt. % of polymerizable functional monomer(s~ or functional oligomer(s) and with 0.001 to 20 wt.~ of bonding agent(s).
The same composite material may additionally comprise from 0 to 10 wt.% catalytic initiator, from 0 to 10 wt. %
ethylenically unsaturated acid or acid anhydride. It may also comprise from 0 to 95 wt.% inorganic filler(s) ar,d from 0 to 60 wt.% plasticizer(s). Said composite material is optionally comprising colorant(s), antioxidant(s), stabilizer(s), ~lame-retardent(s), lubricant(s), pigment(s), opacifier(s), impact-modifier(s), photo-stabilizer(s) antistatic agent(s), and crystal nucleating agent(s), or the like.
The cellulosic fibers, or starch, or flour may be grafted first with said polymerizable functional monomer(s) or functional oligomer(s) by a known free radical process or by any graft polymerization process leading to form interfacial strong bonding such as covalent bonding.
The bonding agents may coat the cellulosic fibers or starch or flour; or may graft by free radical grafting process via the effect of any initiating source as mentioned before.
~2~
The graftlng of said ~oth polymerlzabl monomer(s) or oligcmer(s) and said bonding agent(s) onto said fillers may be carried out simultaneously or successiveiy. The simultaneous grafting is recommended for the industrial economy.
The inorganic filler may be mixed wi~ the cellulosic fibers, starch or flour, befor the addition step(s) of said polymerizable(s) and said surface bonding agent(s). Said mixing may also be after or during said addition.
The inorganic filler(s) may also be bonded or coated with the said polymerizabl(s) and /or with said bonding agent(s), befor or after the mixing step.
The experimentation results in the examples of the invention could be improved or be reached their optimum values by changing the preparation conditions, and/ or the weight percentages of the applied materials or the substances.
This invention will now be furtherly describ~dby non limiting examples:
lZ~
GROUP A :
10 g. of dried chemicalthermOmechenical wood pulp derlved from aspen, ground at mesh 60 and wetted with vapor of acrylonitrile, styrene~ or methylmethacrylate monomer and silane A-174 or A-1100, or mixed with linear polymethylene polyphenylisocyanate (PMPPIC), ~ or may be dlssolved in a solvent sich as acetone, then sub~ected to a method for pol~merising said monomers onto the surface of said pulP fibers). This ls to obtain a traated or coated aspen pulp with poly acrylonitrlle- silane A-1100, - silane A -174; poly acrylonltrile - (PMPPIC);pol~styrene -silane A-1100, -silane A-174, and polystyrene - (PMPPIC) or polymethylmethacrylate- silane A-1100 or -silane A-174; an~
polymethylmethacrylate -(PMPPIC).
Mlxing 10, 20, 30 & 40 wt.% (based on the total composite wt.) of these coated pulps, (by using a roll mill or a compounding extuder) with 90, ~0, 70 & 60 wt.% of (hot molten) linear low den~ity polyethylene, or polystyrene, or polyvinylchloride, (plagt1cizer(s) could be added such as ln case o~ P.V.C.) . Molding the resulted composites to shape specim~ns for testin~ ënergy (k~ tress (mpa) and modulus (mpa) according to ASTM, D1822-78.
The examples accordin~ to the group A are as follows:
Example l;
The aspen pulp coated or treated with polyacrylonitrile &
silane A-llO0 and then compounded with LLDPE or pl~icized P.V.C. resins.
Example 2;
The aspen pulp coated or treated with polyacrylonitrile & silane A-174 and then compounded with LLDPE resin.
Example 3;
The aspen pulp coated or treated with polyacrylonitrile (PMPPIC) and then compounded with P.S. resin.
Example 4;
The aspen pulp coated or treated with polymethylmethacrylate & silane A-llO0 and then compounded with P.S. resin.
Example 5;
The aspen pulp coated or treated with polystyrene &
silane A-llO0 and then compounded with P.S. resin.
The testing values are showing improvments with no more than 60% based on their related neat resins.
- GROUP B:
Following here the same experimentaion as per group A, but the difference is by pregrafting the aspen pulp first with 20 wt.% ( based on the pulp weight) of acrylonitrile, styrene or methylmethacrylate by following any of the known graft polymerization processes such as the xanthation process. Then 10 g. of the prepared pregrafted a~pen pulp is wetted with a vapor of ( an organic solvent may be added), 0.2 g. silane-llO0, sllane-174 or mixed with 0.5 g. of PMPPIC, ( the silanes may be prehydrolized or diluted, by evapora~ing the solvent, if present) to glve aspen pulp grafted with polyacrylonitrile, polystyrene, or polymethylmethacrylate, and coated with silane A-llO0, sllane A-174, or PMPPIC; then compounding-the said resulted grafted and coated aspen pulp with the polymeric resins givlng the follwing examples:
Example 6 :
10, 20, 30, & 40 wt.% of Aspen pulp grafted with polyacrylonltrlle and coated wlth sllane A-llO0, and compounded wlth 90, 80, 70 & 60 wt.% of LLDPE, or P.V.C. (plastlclzed) resins.
Exam~le 7 :
10, 20, 30, & 40 wt.% of aspen pulp grafted with polyacrylonitrile ard coated with PMPPIC, then compounded X - 19 _ with 90, 80, 70 & 60 wt.% of P.S. resin.
Example 8 :
10, 20, 30 & 40 wt.% of aspen pulp grafted with polymethylmethacrylate and coated with silane A-1100, then compound with P.S. resin.
The testing values are showing improvements from 70 to 760% based on their related neat resin.
Group C :
'rhe experimentation as per group A,but here it is preferred to use an organic solvent which additionally co~prises ~.1 g.
benzoyl peroxide, then by subjecting to hot air current till dryness, and by mixing with the polymeric resin to give the follwing examples.
Example 9 :
10, 20, 30 & 40 wt.% of the co-grafted aspen pulp with acrylonitrile and silane A-llOO,compound with 90, 80, 70 &
60 wt.% of LLDPE, or P.S. resins.
~xample 10 :
10, 20, 30 & 40 wt.% of the co-grafted aspen pulp with polystyrene and silane A-llOO~compound with 90, 80, 70 & 60 wt.% of P.S. resin.
- 20 _ lZ6gl~7 Example 11 :
10, 20, 30 & 40 wt.% of the co-grafted aspen pulp with polyacrylonitrile and PMPPIC compound wlth 90, 80, 70 & 60 wt.% of P.S. resin.
The testing values for these examples showing improvements from 85 to 1000 %, based on their related neat resin.
Group D :
The experimentation here as per group C, but by mixing the filler with 10 of its wt.% of calcium carbonate, after the drying step to give the following examples:
Example 12 :
10, 20, 30 ~ 40 wt.% of aspen pulp co-grafted with polyacrylonitrile and silane A-llOO~and mixed with calcium carbonate, compoundi with 90, 80, 70 & 60 wt.% of LL3PE or P.S. resins.
Example 13 :
10, 20, 30 & 40 wt.% of aspen pulp co-grafted with polystyrene and silane A-llOO,mixed with calcium carbonate, compound with 90, 80, 70 & 60 wt.% of P.S. resin.
~`- lZ~
The testing values show improvements from 90 to 1050 wt.% based on their related neat resins.
Group E :
As per group D but the calcium carbonate is mixed with the aspen pulp befor the wetting step(s) to give the following examples no. 14 & 15:
Eaxample 14 :
Using the filler of group E and the same composition as per example no. 12.
Example 15 :
Using the filler of group E and the same composition as per example no. 13.
The testing values are showing improvements from 100 to 1100% based on their related resins.
Group F :
As per group B for the pregrafting step of aspen p~lp with acrylonirile, styrene and methylmethacrylate. Then 10 g. of the pregrafted aspen pulp is wetted with a vapor of an organic solution comprising, 0.2 g. silane A-1100, or 0,5 g o~ ~ PMPPIC and 0.1 g. of benzoyl peroxide, then ~9~7 by passing a current of hot air and heatlng for a certaln time and compoundins the given co-grafted aspen pulp with polymeric resins to give the following examples:
Example 16 :
10, 20, 30 ~ 40 wt.% of the prepared co-grafted aspen pulp wlth polyacrylonitrile & sialne A-llO0, are compounded with 90, 80, 70 & 60 wt.% of LLDPE or P.S. resins.
Example 17 :
10, 20, 30 ~ 40 wt.~ of the prepared co-grafted aspen pulp wlth polystyrene & PMPPIC are compounded with 90, 80, 70 &
60 wt.% of P.s. resin.
The testing values are showing improvemnts from 100 to 1100~ based on their related neat resin.
Group G :
As per group F, but by mixing the co-grafted aspen pulp with 10 wt.% ( based on the filler wt.) of short glass fibers pretreated with silane A-llO0 (as delivered), then compounding wlth polymeric resins giving the following examples:
Example 18 :
10, 20, 30 & 40 wt.% of the prepared filler of group G, wherein the aspen pulp co-grafted with polyacrylonitrile &
`- lZS9187 silane A-1100, to be compounded with 90, 80, 70 & 60 wt.% of LLDPE or P.S. resins.
Example 19 :
10, 20, 30 & 40 wt.% of the flller prepare.d as group G, wherein the aspen pulp co-grafted with polystyrene & silane A-1100 to be compounded with 90, 80, 70 ~ 60 wt.% of P.S.
resin.
The results are showing more improvement~ whic~
reached from 150 to 1200 %.
Group H ~ Example 20 :
g. of semichemical pulp of bagasse ground at mesh 60, mixed with 10 g. of clay and-sub~ e~ted to gFa~t polymorization with methylmethacrylate by the known sodium bisulfite initiation method. After dryness, the filler is rewetted wlth a vapor of 0.8 g. cf silane A-1100 in acetone solution comprising 0.4 g. of benzoyl peroxide. Hot air current passed for a certain time. Then 10, 20, 30 & 40 wt.% of the resulted filler is well compounded with 90, 80, 70 & 60 wt.%
of powdered polymethylmethacrylate by using compressionr molding processes.
The testing results give improvements from 90 to 1200 % based on the neat polymethylmethacrylate resin.
Claims (19)
I CLAIM:
1- A composite material is characterized by compounding from 1-98 Wt.% of cellulosic fibers or starch or flour and from 1-98 Wt.% of polymeric, or copolymeric resin or resin blend of thermoplastic, or thermosetting, or rubber, to bond with each other by applying a co-grafting, a grafting-coating, or a coating-grafting process, by using from 0.5 to 300 wt.% of polymerizable functional monomer(s) or functional oligomer(s), and with from 0.001 to 20 wt.% of bonding agent(s): said composite material additionally comprising from 0 to 10 wt.% catalytic initiator, from 0-10 wt.% ethylenically unsaturated acid or acid anhydride, from 0-95% wt.% inorganic filler(s) and from 0-60 wt.%
plasticizer(s); furtherly, said composite material is optionally comprising colorant(s), antioxidant(s), stabilizer(s), flameretardent(s), lubricant(s), pigment(s), opacifier(s), impact modifier(s), photo-stabilizer(s), antistatic agent(s), and crystal nucleating agent(s).
plasticizer(s); furtherly, said composite material is optionally comprising colorant(s), antioxidant(s), stabilizer(s), flameretardent(s), lubricant(s), pigment(s), opacifier(s), impact modifier(s), photo-stabilizer(s), antistatic agent(s), and crystal nucleating agent(s).
2- The composite as defined in claim 1, wherein the cellulosic fibers, or starch,or flour are grafted with said polymerizable functional monomer(s), or functional oligomer(s) by a free radical polymerization process and coated with said bonding agent(s).
3- The composite as defined in claim 1, wherein the cellulosic fibers or starch or flour are grafted with said bonding agent(s) by a free radical process and coated with said polymerizable functional monomer(s), or fuctional oligomer(s).
4- The composite as defined in claim 1, wherein the cellulosic fibers, starch or flour are grafted with polymerizable functional monomer(s), or functional oligomer(s) and with the said bonding agent(s) by a free radical process.
5- The composite as defined in claim 1, wherein the polymerizable functional monomer(s), or functional oligomer(s) is selected from acrylonitrile, styrene and methylmethacrylate.
6- The composite as defined in claim 1, wherein the bonding agent(s) is selected from organo-silicon compounds, organo-titanium compounds, organo-zirconium compounds, iso-cyanate bonding agents and stearate bonding agents,
7- The composite as defined in claim 1 or 6, wherein the bonding agent(s) is selected from gamma-amlnopropyltriethoxy silane, gamma-metha-cryloxypropyltrimethoxy silane and polymethylene polyphenylisocyanate.
8- The composite as defined in claim 1, wherein the cellulosic fibers, starch, or flour, is selected from chemicalthermomechanical wood pulp derived from aspen and semichemical pulp of bagasse.
9- The composite as defined in claim 1, wherein the polymeric or copolymeric thermoplastic or thermosetting resin or resin blend or rubber,is selected from polystyrene, polyethylene, polyvinylchloride and polymethylmethacrylate.
10- The composite as defined in claim 1, wherein the inorganic filler is coated or bonded with said polymerizable functional monomer(s) or functional oligomer(s).
11- The composite as defined in claim 1, wherein the inorganic filler is coated or bonded with said bonding agent(s).
12- The composite as defined in claim 1, wherein the inorganic filler is coated or bonded with said polymerizable functional monomer(s) or functional oligomer(s), and with said bonding agent(s).
13- The composite as defined in claim 1, wherein the inorganic filler is selected from calcium carbonate, short glass fibers and clay.
14- The composite as defined in claim 1 wherein the catalytic initiator is selected from organic peroxide.
15- The composite as defined in claim 1 or 14, wherein the organic peroxide is selected from benzoyl peroxide.
16- The composite as defined in claim 1, wherein the ethylenically unsaturated acid or acid anhydride is selected from maleic anhydride.
17- A shaped articles whenever made from a composition as claimed in any one of claims from 1 to 4.
18- A compression molding made from composite in any one of claims from 1 to 4.
19- An injection molding made from composite in any one of claims from 1 to 4.
+ + +
+ + +
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000585838A CA1269187A (en) | 1988-12-14 | 1988-12-14 | Polymer composites based cellulose - iii |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000585838A CA1269187A (en) | 1988-12-14 | 1988-12-14 | Polymer composites based cellulose - iii |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1269187A true CA1269187A (en) | 1990-05-15 |
Family
ID=4139285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000585838A Expired CA1269187A (en) | 1988-12-14 | 1988-12-14 | Polymer composites based cellulose - iii |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1269187A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992007009A2 (en) * | 1990-10-23 | 1992-04-30 | Beshay Alphons D | Modified waxes and applications thereof |
| WO1992007022A1 (en) * | 1990-10-23 | 1992-04-30 | Atomic Energy Of Canada Limited | Process for the preparation of cellulosic fibre-reinforced thermoplastic composite materials |
| US5164432A (en) * | 1989-06-07 | 1992-11-17 | Solvay & Cie | Moulding compositions comprising polyolefins and cellulose fibres, process for their manufacture and objects wrought from these compositions |
| EP0747419A2 (en) * | 1995-06-07 | 1996-12-11 | Andersen Corporation | Advanced compatible polymer wood fiber composite |
| EP0982110A1 (en) * | 1997-05-13 | 2000-03-01 | Du-Pont-MRC Co., Ltd. | Wood-like molding, process for preparing the same, and composition for molding |
| FR2856405A1 (en) * | 2003-06-20 | 2004-12-24 | Ulice | BIODEGRADABLE MATERIAL BASED ON POLYMERS AND PLASTICIZED CEREAL MATERIALS, MANUFACTURING METHOD THEREOF AND USES THEREOF |
| WO2006060714A1 (en) * | 2004-12-03 | 2006-06-08 | Dow Global Technologies Inc. | Wood fiber plastic composites |
| WO2007073416A1 (en) * | 2005-12-20 | 2007-06-28 | Equistar Chemicals, Lp | Cellulosic-reinforced composites having increased resistance to water absorpiton |
| CN104046051A (en) * | 2013-03-11 | 2014-09-17 | 昆山宝腾橡塑胶材料科技有限公司 | Novel production technology of plastic cement granule |
| CN111269451B (en) * | 2020-03-31 | 2022-04-19 | 江苏金材科技有限公司 | Rare earth light conversion film |
-
1988
- 1988-12-14 CA CA000585838A patent/CA1269187A/en not_active Expired
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5164432A (en) * | 1989-06-07 | 1992-11-17 | Solvay & Cie | Moulding compositions comprising polyolefins and cellulose fibres, process for their manufacture and objects wrought from these compositions |
| WO1992007009A2 (en) * | 1990-10-23 | 1992-04-30 | Beshay Alphons D | Modified waxes and applications thereof |
| WO1992007022A1 (en) * | 1990-10-23 | 1992-04-30 | Atomic Energy Of Canada Limited | Process for the preparation of cellulosic fibre-reinforced thermoplastic composite materials |
| WO1992007009A3 (en) * | 1990-10-23 | 1992-06-25 | Alphons D Beshay | Modified waxes and applications thereof |
| EP0747419A2 (en) * | 1995-06-07 | 1996-12-11 | Andersen Corporation | Advanced compatible polymer wood fiber composite |
| EP0747419A3 (en) * | 1995-06-07 | 1997-07-30 | Andersen Corp | Advanced compatible polymer wood fiber composite |
| EP0982110A1 (en) * | 1997-05-13 | 2000-03-01 | Du-Pont-MRC Co., Ltd. | Wood-like molding, process for preparing the same, and composition for molding |
| EP0982110A4 (en) * | 1997-05-13 | 2002-07-17 | Du Pont Mrc Co Ltd | Wood-like molding, process for preparing the same, and composition for molding |
| FR2856405A1 (en) * | 2003-06-20 | 2004-12-24 | Ulice | BIODEGRADABLE MATERIAL BASED ON POLYMERS AND PLASTICIZED CEREAL MATERIALS, MANUFACTURING METHOD THEREOF AND USES THEREOF |
| WO2004113433A1 (en) * | 2003-06-20 | 2004-12-29 | Ulice | Biodegradable material based on polymers and plasticized grain products, method for the production thereof, and uses of the same |
| WO2006060714A1 (en) * | 2004-12-03 | 2006-06-08 | Dow Global Technologies Inc. | Wood fiber plastic composites |
| WO2007073416A1 (en) * | 2005-12-20 | 2007-06-28 | Equistar Chemicals, Lp | Cellulosic-reinforced composites having increased resistance to water absorpiton |
| CN104046051A (en) * | 2013-03-11 | 2014-09-17 | 昆山宝腾橡塑胶材料科技有限公司 | Novel production technology of plastic cement granule |
| CN111269451B (en) * | 2020-03-31 | 2022-04-19 | 江苏金材科技有限公司 | Rare earth light conversion film |
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