CA2016324A1 - Polymer composites based cellulose - v - Google Patents
Polymer composites based cellulose - vInfo
- Publication number
- CA2016324A1 CA2016324A1 CA002016324A CA2016324A CA2016324A1 CA 2016324 A1 CA2016324 A1 CA 2016324A1 CA 002016324 A CA002016324 A CA 002016324A CA 2016324 A CA2016324 A CA 2016324A CA 2016324 A1 CA2016324 A1 CA 2016324A1
- Authority
- CA
- Canada
- Prior art keywords
- composite
- inorganic filler
- parts
- bonding agent
- isocyanate
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
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
TITLE : "POLYMER COMPOSITES BASED CELLULOSE - V"
INVENTOR: ALPHONS DANIAL BESHAY
ABSTRACT OF THE DISCLOSURE:
Polymer Composites based cellulose and polymeric matrix, which may be thermoplastic or thermosetting, or rubber. The cellulosic material is grafted with isocyanate bonding agent and may be mixed with pre-bonded inorganic filler with a bonding agent. These polymer composites are useful for most plastic articles.
+ + +
INVENTOR: ALPHONS DANIAL BESHAY
ABSTRACT OF THE DISCLOSURE:
Polymer Composites based cellulose and polymeric matrix, which may be thermoplastic or thermosetting, or rubber. The cellulosic material is grafted with isocyanate bonding agent and may be mixed with pre-bonded inorganic filler with a bonding agent. These polymer composites are useful for most plastic articles.
+ + +
Description
2 ~ 2 ~
This invention relates to polymer resin composites prepared by incorporating cellulosic fibers into a poly-meric resin or resin blends.
More specifically, the inven-tion relates to such enhanced polymeric composite per~ormances and are derived from readily available cheap materials.
Hi-therto, many kinds of thermoplastic composites have been proposed and commercialized. The additives used therein are inorganic fillers such as calcium carbonate, talc, mica, asbestos, glass fibers, asphalt, silica, gra-phite, magnesium hydroxide, aluminium hydroxide and the like. However, these additives are of high cost and of high specific gravities and their ability to improve physi-cal property of composition is not so sufficient. The other known additives used are the organic fillers such as starch, flour, wood ~lour, wood pulp and the other cellulosic fibers.
These organic fillers were added as such or af-ter treatments with surface bonding agents by impregnation methods.
The published literatures include a number of proposals9 which consist essentially of thermplastic resinous matrix having dispersed -therein cellulosic fillers mixed or not with inorganic fillers. Such materials are described for example:
- U.S. Pat. No. 3,485,777 (19~9), Gaylord~ deals with compatibilization of polyvinylchloride of polymethylmetha-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 ethyle~ically un-saturated carboxylic acid or anhydride under conditions which generate free radical on said polymer and cellulose~
- U.K. Pat. .~ppl. No. 2090849, Hishida, I., prepared composites from thermplastic 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 cellulose 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 little improvements in their mechanical streng-ths.
- J 5 Pat. ~o. 7192-4~6, Showa, teaches the addition of an unsatura~ted silane coupling agent onto the polyolefin matrix by the effect of a catalytic peroxide and then by adding wood flour as a filler, but by silylating the matrix `` ` . ` ~" ~ :
. ::
.:
L~
leads to consuming more silane than in case of silylating the filler itself. Furthermore, the composi-testperformances are not highly improved.
- U.K. Pat. Appl. No. 8705045, prepared composi-tes with j/
just coating the wood pulps with isocyanats bonding agents by assuming the formation of interfacial covalen-t bonding and in absence of any specific catalys-t leading to -the grafting of lsocyanates onto the cellulosic fibers. Further-more, no inorganic filler pretreated wi th any bonding agen-t was added to mix with the organic filler.
- The applicant~ in his U~S. Pats.Nos.4,717,742 & ~"820,749, 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 com~
posite performances are much improved.
- The Ca. Pat. No. 1252586 and the U.K. Pat. Appl. No.
2205569, Beshay, realized more improvements by mixing the silane grafted cellulosic fibers wi-th a silane bonded in-organic fillers.
In summary~ we believe to be the first to prepare composites of polymeric resin or resin blend and cellulosic fibers grafted with isocyanates by generating a free radical process and which may mix wi-th inorganic filler~s), prebonded or not, with a bonding agent; cellulosic fibers coated with isocyanates and providlng mixing with bonded inorganic filler(s) ,:, :
:.:: :
;~ .. :::, . ": . ~ :
" ': `' ;" ' ' ' ~
2~32~
with bonding agent(s).
The performances of polymer composites bas~d cellulose improved by increasing the interfacial primary bonding between the composite constituents. Said improvements show their values by mixing the cellulosic fibers coated with isocyana-tes, with prebonded inorganic filler(s) with bonding agent(s).
Furthermore, in order to prepare composites of highly im-proved performancest the cellulosic fibers are grafted wi-th isocyanates by generating a free radical process and by mixing with inorganic filler(s), whether prebonded or not9 with bonding agent(s).
The cellulosic fibers, starch, or flour, in the present invention, may be:
a) Coated with -the isocyanate as a bonding agen-t, and providing mixing wi-th prebonded inorganic filler(s) with bonded agent(s)~
b) Grafted with isocyanate by the effect of a specific catalys-t, and op-tionally mixed with inorganic filler(s), whether bonded or not with bonding agent(s).
The term coating means covering the cellulosic fibers with isocyanate bonding agent in absence of a catalyst.
The term grafting here means the formation of inter-facial primary bonding between the cellulosic molecules and the isocyanates bonding agent(s) and -the polymeric matrix, by the effect of a specific catalyst, or by generating a `
This invention relates to polymer resin composites prepared by incorporating cellulosic fibers into a poly-meric resin or resin blends.
More specifically, the inven-tion relates to such enhanced polymeric composite per~ormances and are derived from readily available cheap materials.
Hi-therto, many kinds of thermoplastic composites have been proposed and commercialized. The additives used therein are inorganic fillers such as calcium carbonate, talc, mica, asbestos, glass fibers, asphalt, silica, gra-phite, magnesium hydroxide, aluminium hydroxide and the like. However, these additives are of high cost and of high specific gravities and their ability to improve physi-cal property of composition is not so sufficient. The other known additives used are the organic fillers such as starch, flour, wood ~lour, wood pulp and the other cellulosic fibers.
These organic fillers were added as such or af-ter treatments with surface bonding agents by impregnation methods.
The published literatures include a number of proposals9 which consist essentially of thermplastic resinous matrix having dispersed -therein cellulosic fillers mixed or not with inorganic fillers. Such materials are described for example:
- U.S. Pat. No. 3,485,777 (19~9), Gaylord~ deals with compatibilization of polyvinylchloride of polymethylmetha-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 ethyle~ically un-saturated carboxylic acid or anhydride under conditions which generate free radical on said polymer and cellulose~
- U.K. Pat. .~ppl. No. 2090849, Hishida, I., prepared composites from thermplastic 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 cellulose 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 little improvements in their mechanical streng-ths.
- J 5 Pat. ~o. 7192-4~6, Showa, teaches the addition of an unsatura~ted silane coupling agent onto the polyolefin matrix by the effect of a catalytic peroxide and then by adding wood flour as a filler, but by silylating the matrix `` ` . ` ~" ~ :
. ::
.:
L~
leads to consuming more silane than in case of silylating the filler itself. Furthermore, the composi-testperformances are not highly improved.
- U.K. Pat. Appl. No. 8705045, prepared composi-tes with j/
just coating the wood pulps with isocyanats bonding agents by assuming the formation of interfacial covalen-t bonding and in absence of any specific catalys-t leading to -the grafting of lsocyanates onto the cellulosic fibers. Further-more, no inorganic filler pretreated wi th any bonding agen-t was added to mix with the organic filler.
- The applicant~ in his U~S. Pats.Nos.4,717,742 & ~"820,749, 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 com~
posite performances are much improved.
- The Ca. Pat. No. 1252586 and the U.K. Pat. Appl. No.
2205569, Beshay, realized more improvements by mixing the silane grafted cellulosic fibers wi-th a silane bonded in-organic fillers.
In summary~ we believe to be the first to prepare composites of polymeric resin or resin blend and cellulosic fibers grafted with isocyanates by generating a free radical process and which may mix wi-th inorganic filler~s), prebonded or not, with a bonding agent; cellulosic fibers coated with isocyanates and providlng mixing with bonded inorganic filler(s) ,:, :
:.:: :
;~ .. :::, . ": . ~ :
" ': `' ;" ' ' ' ~
2~32~
with bonding agent(s).
The performances of polymer composites bas~d cellulose improved by increasing the interfacial primary bonding between the composite constituents. Said improvements show their values by mixing the cellulosic fibers coated with isocyana-tes, with prebonded inorganic filler(s) with bonding agent(s).
Furthermore, in order to prepare composites of highly im-proved performancest the cellulosic fibers are grafted wi-th isocyanates by generating a free radical process and by mixing with inorganic filler(s), whether prebonded or not9 with bonding agent(s).
The cellulosic fibers, starch, or flour, in the present invention, may be:
a) Coated with -the isocyanate as a bonding agen-t, and providing mixing wi-th prebonded inorganic filler(s) with bonded agent(s)~
b) Grafted with isocyanate by the effect of a specific catalys-t, and op-tionally mixed with inorganic filler(s), whether bonded or not with bonding agent(s).
The term coating means covering the cellulosic fibers with isocyanate bonding agent in absence of a catalyst.
The term grafting here means the formation of inter-facial primary bonding between the cellulosic molecules and the isocyanates bonding agent(s) and -the polymeric matrix, by the effect of a specific catalyst, or by generating a `
3 ~ ~
free radical process.
Within -the scope of the presen-t invention and as per non li~iting examples, composites are made from wood pulp, as an example for the other cellulosic fibers. The poly-methylene polyphenyleneisocyanate (PMPPIC) is an example for the other isocyanatesO The inorganic fillers are clay and glass fibers, as examples for other inorganic fillers.
The bonding agents, which may bond the inorganic filler(s), are silane (A-llOO) and (A-189), Union Carbide, are as examples for other bonding agents. The polymeric resins are polyethylene, polyvinylchlordie and polystyrene, which are as examples for the other polymeric or copolymeric resins or resin blends, thermoplastic, thermose-tting or rubber.
These composites may also include other additives such as plasticizers.
;
The inorganic filler(s), whether bonded or not with the bonding agent(s), may mix with the cellulosic fibers, starch or flour, during or after the coating or grafting processes~ or to be mixed with the polymeric, copolymeric resin or resin blend. The inorganic filler(s) 5 may be bonded with the same isocyanate bonding agent or any other bonding agent.
This invention is not limited either to the materials or the substances used in the examples of the present in-: . ,: :-- ... :
~..... .
~, . : .:
' '; ' ' , ': '~ : ':: ' ' : ~ ' , ~ . . ., :
. ~
2 Q ~ 2 ~
vention, or to their weight percentages, but it also shows its useful advantages for the following materials to be used in any weight percent.
The cellulosic materials; the inorganic fillers, -the silylating agents and the polymeric or copolymeric resins, to be used in the present invention, are those prementioned in the U.S. No. 4,820,749.
The polymeric or copolymeric resins or resin blends, to be used in the present invention, are also those including polyethylene, polypropylene, polyvinylchloride, polystyrene, polymethylmethacrylate, polycarbonates, polyacrylonitryl bu-tadiene styrene (ABS) alloys, or other polyblends, and may be those described in U.S. Pat. No. 4,317,765, or other polymericD or copolymeric of thermoplastic9 or thermosetting resin, or resin blends or rubber.
The other bonding agents for the inorganic filler(s) are titanium ccupling agents, zirconium coupling agents, stearates, or the like.
The silylating agents may be prehydrolized and/or diluted to form a monolayer onto the inorganic filler(s) to decrease the costs.
The titanium bondlng agents are those as described in the Modern Plastic EncyclopediaJ 1986-87, pp. 128 & 130.
The isocyanates for the cellulosic fibers, or the .
' ' 2 f~
inorganic filler(s) are such as polymethylene polyphenyliso-cyanate (PMPPIC), 1,6 and hexamethylene di-isocyanate &
NC0-(CH2) 6-NC0, 2,4 toluene di-isocyanate, or their oligomers, or the like.
The grafting of isocyanate onto -the cellulosic fibers may be carried out by generating a free radical process~
The 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 sour-ces or from the chemical sources. The radiation sources are such as gamma radiation, ultraviolet radiation, laser radiation, or -the ultrasonic, or the like. The chemical initiation may be from any catalytic initiator causing the free radical reactions~ among which are -the chemical ini-tiators listed in the Polymer Hand-Book, Interseience 196~, pp. II-3 to II-51, or the like.
The ethylenically unsaturated carboxylic acid or acid anhydride may be added as auxiliaries to be used in the practice of the invention, such as those described in the U.~. 4,820,749.
Wax(es) optionally added as further filler(s) surface treatments~
The plasticizers, which may be contained in the present composites~ invention, are such as dipropylene glycol di-benzoate, di-2-ethylhexl adipate, dilsodecyl adipate; azelates, :: . . . . - ,-- - : .:
. ~ ~ -. ... . .
~ , , '' ~ . :
, 2 ~
di-2-ethylhcxyl azelate; phosphates, such as tricresyl phosphate, cresyl diphenyl phosphate, 2-ethylhe~yl di-phenyl phosphate, di-n-octyl phenyl phosphate, and tri-n-hexyl phosphate; ph-thalates, such as diethylphthalate, butyl benzyl phthalate, di-2-e-thylhexylphthalate diisodecyl phthalate; sebacates, such di-2-ethylhexyl sebacate; and terephthalates, such as di-2-e-thylhexyl tereph-thalate;
or the like.
Other additives are optionally added, such as colorants, antioxidants, lubricants, pigments, opacifiers, heat stabilizers, impact modifiers9 photos-tabilizers, antistatic agents, biostabilizers, crystal nuclea~ting agents, or the like.
T~-e filler(s), -~hether from said organic or inorganic nature may be in the for~ 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 poly-meric or copolymeric thermoplastic or thermosetting resin or resin blends, or rubber, to bond with each other by grafting with 0.1 to 20 wt.% of isocyana-te(s). The same composite material may additonally comprise from O to 10 wt.% catalytic initiator, from O to 10 wt.% ethylenically ~''' ' :
3 ~
unsaturated acid or acid anhydride. It may also comprise from 0 to 95 wt.% inorganic filler(sJ, whether bonded or not with bonding agent(s)~ and from 0 to 60 wt.% plas~ticizer(s).
Said composite material is op-tionally comprising coloran-t(s), antioxidant(s), stabilizer(s), flame-re-tardent(s), lubri-cant(s), pigmen-t(s), opacifier(s), impact-modifier(s), photo-stabilizer(s), antista-tic agent(s), and crys-tal nucleating agent(s), or the like. Furthermore, said cellulosic fibers, starch, or flour, can be coated with isocyana-te(s) as bonding agen-t(s), providing boing mixed with the said eæsentially bonded inorganic filler(s).
The inorganic filler(s), whether bonded or not with said bonding agent(s), may be mixed with the cellulosic fibers, starch or flour, before, during or after the addition step(s) of said isocyanate bonding agent(s).
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 o~ the applied materials or the sub-stances.
This invention will now be furtherly described by non limiting examples:
EXAM
100 g. of dried chemicalthermomechanical wood pulp ~CTMWP) derived from aspen and ground at mesh size 60~ are _ 9 _ , ~: ~
.
213~2~
wet-ted with acetone solution comprising 4 g. of (PMPPIC), then evapora-ting the acetone solvent and -then mixed with 10 g. of silane bonded clay or silane bonded glass fibers (A-llO0, A-17~, A-189) Union Carbide, -to form mixed filler materials.
Mixing 10, 20, 30 & 40 wt~% (based on the to-tal com-posite wt.) of these mixed filler materials (by using a roll mill or a compounding extruder) with 909 80, 70 & 60 wt.% of (hot molten) linear low density polyethylene, or polystyrene, or polyvinylchloride, (plasticizer(s) could be added such as in case of P.V.C.). Time and temperature varies according to the resin kind and resin grade, by means to prepare well compatible composite samples.
Mo]ding the resulted composites for testing according to ASTM, D1822-78. The results showing improvements from 30 to 1100% based on their related neat resins.
EXAMPLE 2:
The same type as in example No. 1, but the isocyanate/
acetone solution additionally comprising 0.8g. of dicumyl peroxide and in absence of the inorganic filler. The testing results show improvements from 35 to 1361%~ based on their related neat resins.
EXAMPLE 3:
Same -type as in example No. 2, but 90g of (CTM~P), derived from aspen, premixed with lOg. of clay. The testing . ~ :
.
2~324L
results show improvemen-ts from 37 to 1390%, based on their related neat resins.
EXAMPLE ~:
Same type as in example 3, but the inorganic filler is silane (A-llO0) bonded with glass fibers and with clay.
The testing results show improvements from 60 to 2015%, based on their related neat res,ins.
It will be understood that the above description of the present invention is susceptible to various modifica-tions, changes and adaptations, and the same are intended to be comprehended within the meaning and the scope of equi~alents of the appended claims.
... .. . .. .. . . , .. _ _ _ _ _ _ . _ . . . . . . . . . . . . , . .. . . _ _ _ _ _ _ . ~
. . : : : .
~ - - , . . . .
'.
. ~ . - - .
, , -.
. ~
., , . ~ , .
, . .;
free radical process.
Within -the scope of the presen-t invention and as per non li~iting examples, composites are made from wood pulp, as an example for the other cellulosic fibers. The poly-methylene polyphenyleneisocyanate (PMPPIC) is an example for the other isocyanatesO The inorganic fillers are clay and glass fibers, as examples for other inorganic fillers.
The bonding agents, which may bond the inorganic filler(s), are silane (A-llOO) and (A-189), Union Carbide, are as examples for other bonding agents. The polymeric resins are polyethylene, polyvinylchlordie and polystyrene, which are as examples for the other polymeric or copolymeric resins or resin blends, thermoplastic, thermose-tting or rubber.
These composites may also include other additives such as plasticizers.
;
The inorganic filler(s), whether bonded or not with the bonding agent(s), may mix with the cellulosic fibers, starch or flour, during or after the coating or grafting processes~ or to be mixed with the polymeric, copolymeric resin or resin blend. The inorganic filler(s) 5 may be bonded with the same isocyanate bonding agent or any other bonding agent.
This invention is not limited either to the materials or the substances used in the examples of the present in-: . ,: :-- ... :
~..... .
~, . : .:
' '; ' ' , ': '~ : ':: ' ' : ~ ' , ~ . . ., :
. ~
2 Q ~ 2 ~
vention, or to their weight percentages, but it also shows its useful advantages for the following materials to be used in any weight percent.
The cellulosic materials; the inorganic fillers, -the silylating agents and the polymeric or copolymeric resins, to be used in the present invention, are those prementioned in the U.S. No. 4,820,749.
The polymeric or copolymeric resins or resin blends, to be used in the present invention, are also those including polyethylene, polypropylene, polyvinylchloride, polystyrene, polymethylmethacrylate, polycarbonates, polyacrylonitryl bu-tadiene styrene (ABS) alloys, or other polyblends, and may be those described in U.S. Pat. No. 4,317,765, or other polymericD or copolymeric of thermoplastic9 or thermosetting resin, or resin blends or rubber.
The other bonding agents for the inorganic filler(s) are titanium ccupling agents, zirconium coupling agents, stearates, or the like.
The silylating agents may be prehydrolized and/or diluted to form a monolayer onto the inorganic filler(s) to decrease the costs.
The titanium bondlng agents are those as described in the Modern Plastic EncyclopediaJ 1986-87, pp. 128 & 130.
The isocyanates for the cellulosic fibers, or the .
' ' 2 f~
inorganic filler(s) are such as polymethylene polyphenyliso-cyanate (PMPPIC), 1,6 and hexamethylene di-isocyanate &
NC0-(CH2) 6-NC0, 2,4 toluene di-isocyanate, or their oligomers, or the like.
The grafting of isocyanate onto -the cellulosic fibers may be carried out by generating a free radical process~
The 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 sour-ces or from the chemical sources. The radiation sources are such as gamma radiation, ultraviolet radiation, laser radiation, or -the ultrasonic, or the like. The chemical initiation may be from any catalytic initiator causing the free radical reactions~ among which are -the chemical ini-tiators listed in the Polymer Hand-Book, Interseience 196~, pp. II-3 to II-51, or the like.
The ethylenically unsaturated carboxylic acid or acid anhydride may be added as auxiliaries to be used in the practice of the invention, such as those described in the U.~. 4,820,749.
Wax(es) optionally added as further filler(s) surface treatments~
The plasticizers, which may be contained in the present composites~ invention, are such as dipropylene glycol di-benzoate, di-2-ethylhexl adipate, dilsodecyl adipate; azelates, :: . . . . - ,-- - : .:
. ~ ~ -. ... . .
~ , , '' ~ . :
, 2 ~
di-2-ethylhcxyl azelate; phosphates, such as tricresyl phosphate, cresyl diphenyl phosphate, 2-ethylhe~yl di-phenyl phosphate, di-n-octyl phenyl phosphate, and tri-n-hexyl phosphate; ph-thalates, such as diethylphthalate, butyl benzyl phthalate, di-2-e-thylhexylphthalate diisodecyl phthalate; sebacates, such di-2-ethylhexyl sebacate; and terephthalates, such as di-2-e-thylhexyl tereph-thalate;
or the like.
Other additives are optionally added, such as colorants, antioxidants, lubricants, pigments, opacifiers, heat stabilizers, impact modifiers9 photos-tabilizers, antistatic agents, biostabilizers, crystal nuclea~ting agents, or the like.
T~-e filler(s), -~hether from said organic or inorganic nature may be in the for~ 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 poly-meric or copolymeric thermoplastic or thermosetting resin or resin blends, or rubber, to bond with each other by grafting with 0.1 to 20 wt.% of isocyana-te(s). The same composite material may additonally comprise from O to 10 wt.% catalytic initiator, from O to 10 wt.% ethylenically ~''' ' :
3 ~
unsaturated acid or acid anhydride. It may also comprise from 0 to 95 wt.% inorganic filler(sJ, whether bonded or not with bonding agent(s)~ and from 0 to 60 wt.% plas~ticizer(s).
Said composite material is op-tionally comprising coloran-t(s), antioxidant(s), stabilizer(s), flame-re-tardent(s), lubri-cant(s), pigmen-t(s), opacifier(s), impact-modifier(s), photo-stabilizer(s), antista-tic agent(s), and crys-tal nucleating agent(s), or the like. Furthermore, said cellulosic fibers, starch, or flour, can be coated with isocyana-te(s) as bonding agen-t(s), providing boing mixed with the said eæsentially bonded inorganic filler(s).
The inorganic filler(s), whether bonded or not with said bonding agent(s), may be mixed with the cellulosic fibers, starch or flour, before, during or after the addition step(s) of said isocyanate bonding agent(s).
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 o~ the applied materials or the sub-stances.
This invention will now be furtherly described by non limiting examples:
EXAM
100 g. of dried chemicalthermomechanical wood pulp ~CTMWP) derived from aspen and ground at mesh size 60~ are _ 9 _ , ~: ~
.
213~2~
wet-ted with acetone solution comprising 4 g. of (PMPPIC), then evapora-ting the acetone solvent and -then mixed with 10 g. of silane bonded clay or silane bonded glass fibers (A-llO0, A-17~, A-189) Union Carbide, -to form mixed filler materials.
Mixing 10, 20, 30 & 40 wt~% (based on the to-tal com-posite wt.) of these mixed filler materials (by using a roll mill or a compounding extruder) with 909 80, 70 & 60 wt.% of (hot molten) linear low density polyethylene, or polystyrene, or polyvinylchloride, (plasticizer(s) could be added such as in case of P.V.C.). Time and temperature varies according to the resin kind and resin grade, by means to prepare well compatible composite samples.
Mo]ding the resulted composites for testing according to ASTM, D1822-78. The results showing improvements from 30 to 1100% based on their related neat resins.
EXAMPLE 2:
The same type as in example No. 1, but the isocyanate/
acetone solution additionally comprising 0.8g. of dicumyl peroxide and in absence of the inorganic filler. The testing results show improvements from 35 to 1361%~ based on their related neat resins.
EXAMPLE 3:
Same -type as in example No. 2, but 90g of (CTM~P), derived from aspen, premixed with lOg. of clay. The testing . ~ :
.
2~324L
results show improvemen-ts from 37 to 1390%, based on their related neat resins.
EXAMPLE ~:
Same type as in example 3, but the inorganic filler is silane (A-llO0) bonded with glass fibers and with clay.
The testing results show improvements from 60 to 2015%, based on their related neat res,ins.
It will be understood that the above description of the present invention is susceptible to various modifica-tions, changes and adaptations, and the same are intended to be comprehended within the meaning and the scope of equi~alents of the appended claims.
... .. . .. .. . . , .. _ _ _ _ _ _ . _ . . . . . . . . . . . . , . .. . . _ _ _ _ _ _ . ~
. . : : : .
~ - - , . . . .
'.
. ~ . - - .
, , -.
. ~
., , . ~ , .
, . .;
Claims (14)
1. A composite material characterized by compounding from 1-98 parts of polymeric or copolymeric thermoplastic, or thermosetting resin, or resin blends or rubber, and from 1-98 parts of cellulosic fibers,or starch, or flour, to bond with each other by coating with 0.01 to 30 parts of isocyanate(s), said composite essentially comprising from 1-90 parts of inorganic filler(s), such inorganic filler(s) essentially bonded with bonding agent(s); said composite material also comprising from 0 to 10 parts of free radical initiator(s), and from 0 to 10 parts of acid/
acid anhydride and from 0 to 60 parts plasticizer(s), furtherly said composite material is optionally comprising .
colorant(s), antioxidant(s), stabilizer(s) flame re-tardent(s), lubricant(s), pigment(s), opacifier(s), impact modifier(s), photo-stabilizer(s), antistatic agent(s), and crystal nucleating agent(s).
acid anhydride and from 0 to 60 parts plasticizer(s), furtherly said composite material is optionally comprising .
colorant(s), antioxidant(s), stabilizer(s) flame re-tardent(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 isocyanate(s) with bonding agent(s) by generating free radical process.
3. The composite as defined in claim 2, wherein the inorganic filler(s) is not bonded with bonding agent(s).
4. The composite as defined in claim 1, wherein the free radical initiator is selected from radiation or chemical sources.
5. The composite as defined in claim 1 or 4, wherein the free radical initiator is dicumyl peroxide.
The composite as defined in claim 1, wherein the cellulosic fibers, or starch, or flour, are selected from chemicalthermomechanical pulp.
7. The composite as defined in claim 19 wherein the isocyana-te is selected from polymethylene polyphenyl-isocyanate.
8. The composite as defined in claim 1, wherein the inorganic filler(s) is selected from silane bonded clay and silane bonded glass fibers.
~ . The composite as defined in claim 1 or 8, wherein the bonding agent(s) for bonding the inorganic filler(s) is selected from silylating agents, titanium coupling agents, zirconium coupling agents, isocyanate coupling agents and stearate coupling agents.
10. The composite as defined in claim 1, wherein the polymerie, or copolymerie,-thermoplastic or thermosetting, resin or resin blend, or rubber, is selected from polystyrene, polyethylene, polyvinylchloride.
11. The composite as defined in claim 1, wherein the ethylenically unsaturated acid or acid anhydride is selected from maleic anhydride.
12. A shaped articles whenever made from a composition as claimed in any of claims 1 to 4.
13. A composition as claimed in claim 1, and des-cribed in any of the examples herein.
14. A compression molding made from composite in any of claims from 1 to 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/353,365 US5008310A (en) | 1989-05-15 | 1989-05-15 | Polymer composites based cellulose-V |
| US07/353,365 | 1989-05-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2016324A1 true CA2016324A1 (en) | 1990-11-15 |
Family
ID=23388798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002016324A Abandoned CA2016324A1 (en) | 1989-05-15 | 1990-05-09 | Polymer composites based cellulose - v |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US5008310A (en) |
| CA (1) | CA2016324A1 (en) |
Families Citing this family (68)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1251723B (en) * | 1991-10-31 | 1995-05-23 | Himont Inc | POLYOLEFINIC COMPOSITES AND PROCEDURE FOR THEIR PREPARATION |
| US5288772A (en) * | 1992-06-23 | 1994-02-22 | Clemson University | Pre-treated cellulosic materials for producing molded composite articles therefrom and process |
| US6004668A (en) | 1992-08-31 | 1999-12-21 | Andersen Corporation | Advanced polymer wood composite |
| CA2100320C (en) | 1992-08-31 | 2011-02-08 | Michael J. Deaner | Advanced polymer wood composite |
| CA2100319C (en) | 1992-08-31 | 2003-10-07 | Michael J. Deaner | Advanced polymer/wood composite structural member |
| US5406768A (en) | 1992-09-01 | 1995-04-18 | Andersen Corporation | Advanced polymer and wood fiber composite structural component |
| EP0596379A1 (en) * | 1992-10-31 | 1994-05-11 | Hoechst Aktiengesellschaft | Plastic moulding composition for the production of moulded parts with a colour matching decoratire effect |
| US5441801A (en) | 1993-02-12 | 1995-08-15 | Andersen Corporation | Advanced polymer/wood composite pellet process |
| DE4317692C2 (en) * | 1993-05-27 | 1999-08-26 | Biotec Biolog Naturverpack | Process for the production of composite materials from renewable raw materials |
| US5858522A (en) * | 1993-08-30 | 1999-01-12 | Formtech Enterprises, Inc. | Interfacial blending agent for natural fiber composites |
| US5516472A (en) * | 1993-11-12 | 1996-05-14 | Strandex Corporation | Extruded synthetic wood composition and method for making same |
| US5679129A (en) * | 1993-12-15 | 1997-10-21 | Clemson University | Encapsulated fertilizers and pesticides and process |
| CA2178036C (en) * | 1995-06-07 | 2008-09-09 | Kasyap V. Seethamraju | Advanced compatible polymer wood fiber composite |
| US5948524A (en) | 1996-01-08 | 1999-09-07 | Andersen Corporation | Advanced engineering resin and wood fiber composite |
| US6011091A (en) | 1996-02-01 | 2000-01-04 | Crane Plastics Company Limited Partnership | Vinyl based cellulose reinforced composite |
| US5847016A (en) | 1996-05-16 | 1998-12-08 | Marley Mouldings Inc. | Polymer and wood flour composite extrusion |
| US5827462A (en) * | 1996-10-22 | 1998-10-27 | Crane Plastics Company Limited Partnership | Balanced cooling of extruded synthetic wood material |
| US5866264A (en) * | 1996-10-22 | 1999-02-02 | Crane Plastics Company Limited Partnership | Renewable surface for extruded synthetic wood material |
| US6117924A (en) * | 1996-10-22 | 2000-09-12 | Crane Plastics Company Limited Partnership | Extrusion of synthetic wood material |
| US6180257B1 (en) | 1996-10-29 | 2001-01-30 | Crane Plastics Company Limited Partnership | Compression molding of synthetic wood material |
| US6344504B1 (en) | 1996-10-31 | 2002-02-05 | Crane Plastics Company Limited Partnership | Extrusion of synthetic wood material |
| US5938994A (en) | 1997-08-29 | 1999-08-17 | Kevin P. Gohr | Method for manufacturing of plastic wood-fiber pellets |
| US20020010229A1 (en) * | 1997-09-02 | 2002-01-24 | Marshall Medoff | Cellulosic and lignocellulosic materials and compositions and composites made therefrom |
| US20030187102A1 (en) | 1997-09-02 | 2003-10-02 | Marshall Medoff | Compositions and composites of cellulosic and lignocellulosic materials and resins, and methods of making the same |
| US6464913B1 (en) | 1997-09-05 | 2002-10-15 | Crane Plastics Company Limited Partnership | In-line compounding and extrusion system |
| US20060065993A1 (en) * | 1998-04-03 | 2006-03-30 | Certainteed Corporation | Foamed polymer-fiber composite |
| US6344268B1 (en) * | 1998-04-03 | 2002-02-05 | Certainteed Corporation | Foamed polymer-fiber composite |
| US6284098B1 (en) | 1998-07-20 | 2001-09-04 | Wwj, Llc | Lignocellulose fiber filler for thermoplastic composite compositions |
| US7258913B2 (en) * | 2002-10-28 | 2007-08-21 | Certainteed Corp. | Plastic fencing system reinforced with fiberglass reinforced thermoplastic composites |
| US20080010924A1 (en) * | 2006-07-12 | 2008-01-17 | Pietruczynik Christopher B | Exterior building material having a hollow thin wall profile and an embossed low gloss surface |
| US6337138B1 (en) | 1998-12-28 | 2002-01-08 | Crane Plastics Company Limited Partnership | Cellulosic, inorganic-filled plastic composite |
| US6153293A (en) * | 1999-02-04 | 2000-11-28 | Dahl; Michael E. | Extruded wood polymer composite and method of manufacture |
| US6265037B1 (en) | 1999-04-16 | 2001-07-24 | Andersen Corporation | Polyolefin wood fiber composite |
| US6280667B1 (en) | 1999-04-19 | 2001-08-28 | Andersen Corporation | Process for making thermoplastic-biofiber composite materials and articles including a poly(vinylchloride) component |
| US6662515B2 (en) | 2000-03-31 | 2003-12-16 | Crane Plastics Company Llc | Synthetic wood post cap |
| US6578368B1 (en) | 2001-01-19 | 2003-06-17 | Crane Plastics Company Llc | Cryogenic cooling of extruded and compression molded materials |
| US6637213B2 (en) | 2001-01-19 | 2003-10-28 | Crane Plastics Company Llc | Cooling of extruded and compression molded materials |
| US20040148965A1 (en) * | 2001-01-19 | 2004-08-05 | Crane Plastics Company Llc | System and method for directing a fluid through a die |
| US6590014B2 (en) * | 2001-06-28 | 2003-07-08 | Certainteed Corporation | Non-staining polymer composite product |
| US6758996B2 (en) | 2001-07-13 | 2004-07-06 | Kadant Composites Inc. | Cellulose-reinforced thermoplastic composite and methods of making same |
| US6846849B2 (en) | 2001-10-24 | 2005-01-25 | Temple-Inland Forest Products Corporation | Saccharide-based resin for the preparation of foam |
| US6822042B2 (en) | 2001-10-24 | 2004-11-23 | Temple-Inland Forest Products Corporation | Saccharide-based resin for the preparation of composite products |
| US6632863B2 (en) | 2001-10-25 | 2003-10-14 | Crane Plastics Company Llc | Cellulose/polyolefin composite pellet |
| US20050255305A1 (en) * | 2001-11-19 | 2005-11-17 | Jo Byong H | Thermoplastic composite building product having continuous fiber reinforcement |
| US20030096096A1 (en) * | 2001-11-19 | 2003-05-22 | Jo Byeong H. | Plastic rail system reinforced with fiberglass thermoplastic composites |
| US6780359B1 (en) | 2002-01-29 | 2004-08-24 | Crane Plastics Company Llc | Synthetic wood composite material and method for molding |
| FI122175B (en) * | 2003-12-23 | 2011-09-30 | Teknologian Tutkimuskeskus Vtt | Process for making a fiber product |
| FI121892B (en) * | 2003-12-23 | 2011-05-31 | Teknologian Tutkimuskeskus Vtt | A process for making composite fiber products |
| KR100572400B1 (en) * | 2004-05-11 | 2006-04-24 | 재단법인서울대학교산학협력재단 | plastic forming goods using vinyl Polymer particles encapsulating semiconductor nanoparticles and manufacturing method thereof |
| US7473722B2 (en) * | 2004-11-08 | 2009-01-06 | Certain Teed Corp. | Polymer-fiber composite building material with bulk and aesthetically functional fillers |
| US20060100466A1 (en) | 2004-11-08 | 2006-05-11 | Holmes Steven A | Cycloalkane base oils, cycloalkane-base dielectric liquids made using cycloalkane base oils, and methods of making same |
| US8074339B1 (en) | 2004-11-22 | 2011-12-13 | The Crane Group Companies Limited | Methods of manufacturing a lattice having a distressed appearance |
| US20060292357A1 (en) * | 2004-11-22 | 2006-12-28 | Phillips Plastics Corporation | Additives for foaming polymeric materials |
| US20060135691A1 (en) * | 2004-11-22 | 2006-06-22 | Phillips Plastics Corporation | Foaming additives |
| US20060235113A1 (en) * | 2005-03-11 | 2006-10-19 | Dorgan John R | High modulus polymer composites and methods of making the same |
| US20150328347A1 (en) | 2005-03-24 | 2015-11-19 | Xyleco, Inc. | Fibrous materials and composites |
| BR122017001970B1 (en) * | 2005-03-24 | 2020-05-19 | Xyleco Inc | method of densifying a fibrous material |
| US7708214B2 (en) | 2005-08-24 | 2010-05-04 | Xyleco, Inc. | Fibrous materials and composites |
| KR100900414B1 (en) * | 2005-08-18 | 2009-06-01 | 주식회사 엘지화학 | Process for Preparation of Composite Containing Wood Fiber Component and Polymer Resin |
| US8167275B1 (en) | 2005-11-30 | 2012-05-01 | The Crane Group Companies Limited | Rail system and method for assembly |
| US7743567B1 (en) | 2006-01-20 | 2010-06-29 | The Crane Group Companies Limited | Fiberglass/cellulosic composite and method for molding |
| US8460797B1 (en) | 2006-12-29 | 2013-06-11 | Timbertech Limited | Capped component and method for forming |
| GB2469837A (en) * | 2009-04-29 | 2010-11-03 | Task Green Ltd | Elongate composite article comprising a lignocellulose material |
| DE102011051678A1 (en) * | 2011-07-08 | 2013-01-10 | Europlast-Nycast Gmbh | Recycling plastic and/or plant materials, useful to prepare molded parts, comprises milling plastic and/or plant materials, mixing obtained granulate with adhesion promoter, followed by mixing with e.g. binding agent, water and additives |
| JP6437391B2 (en) * | 2015-07-07 | 2018-12-12 | 東洋ゴム工業株式会社 | Rubber composition for tire, tire and method for producing the same |
| MX2018012108A (en) * | 2016-04-04 | 2019-03-07 | Fpinnovations | Composite materials comprising cellulose filaments and fillers and methods for the preparation thereof. |
| JP7068891B2 (en) * | 2018-03-30 | 2022-05-17 | 大阪瓦斯株式会社 | Complex and its manufacturing method |
| USD902318S1 (en) | 2018-05-21 | 2020-11-17 | Brunswick Corporation | Safety rail for a marine vessel |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5014277B2 (en) * | 1971-09-14 | 1975-05-26 | ||
| US4376144A (en) * | 1981-04-08 | 1983-03-08 | Monsanto Company | Treated fibers and bonded composites of cellulose fibers in vinyl chloride polymer characterized by an isocyanate bonding agent |
| US4820749A (en) * | 1985-05-29 | 1989-04-11 | Beshay Alphons D | Reinforced polymer composites with wood fibers grafted with silanes |
-
1989
- 1989-05-15 US US07/353,365 patent/US5008310A/en not_active Expired - Fee Related
-
1990
- 1990-05-09 CA CA002016324A patent/CA2016324A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| US5008310A (en) | 1991-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2016324A1 (en) | Polymer composites based cellulose - v | |
| TW202100849A (en) | Decorative panel, and decorative floor covering consisting of said panels | |
| US4455398A (en) | Glass fiber reinforced polyvinyl composition | |
| US20030216496A1 (en) | Environmentally friendly polylactide-based composite formulations | |
| US20050136259A1 (en) | Environmentally friendly polylactide-based composite formulations | |
| EP1275699A1 (en) | Cellulose-reinforced thermoplastic composite and methods of making same | |
| CN113811441A (en) | Decorative panel and decorative floor covering composed of said panel | |
| US7166668B2 (en) | Method of making a finished product | |
| US20230220679A1 (en) | Decorative Panel, and Decorative Floor Covering Consisting of Said Panels | |
| CA1269187A (en) | Polymer composites based cellulose - iii | |
| WO2011130780A1 (en) | Cellulose fibre-polymer composite material | |
| CA1339711C (en) | Composites of cellulosic fibers and vinyl chloride polymer bonded by an isocyanate bonding agent | |
| US20220034097A1 (en) | Decorative Panel, and Decorative Floor Covering Consisting of Said Panels | |
| Stanaszek-Tomal | Wood-polymer composites as an alternative to the natural environment | |
| NL2025762B1 (en) | Decorative panel, and decorative floor covering consisting of said panels | |
| Misra et al. | Mohanty et al. | |
| Khongrit | Wood composite based on crosslinked polypropylene | |
| EA042504B1 (en) | DECORATIVE PANEL AND DECORATIVE FLOOR COVERING CONSISTING OF THESE PANELS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |