CA1339711C - Composites of cellulosic fibers and vinyl chloride polymer bonded by an isocyanate bonding agent - Google Patents
Composites of cellulosic fibers and vinyl chloride polymer bonded by an isocyanate bonding agentInfo
- Publication number
- CA1339711C CA1339711C CA 513361 CA513361A CA1339711C CA 1339711 C CA1339711 C CA 1339711C CA 513361 CA513361 CA 513361 CA 513361 A CA513361 A CA 513361A CA 1339711 C CA1339711 C CA 1339711C
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- weight
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Composites are made from cellulose fibers dispersed in a matrix of plasticized vinyl chloride polymer, and bonded there to with isocyanate bonding agent dispersed in polymer matrix. The cellulose fibers may be also pretreated with plasticized vinyl chloride polymer or other compatible polymer in the presence of isocyanate bonding agent before admixture into the vinyl chloride polymer matrix to form composites. The composites may be extruded or molded as thermoplastics in order to produce useful articles.
Description
-: ' ~
1~ BACKGROUND OF THE INVENTION i ~ ~ } ~ ~ 1 .
, This invention relates to composites of cellulose based fibers dispersed in :~ a matrix of vinyl chlQride polymer and to treated cellulose fibers which have . :
improved dispersabilit~ into pol~mer and improved adhesion thereto. More specifically, it relates to such reinforced thermoplastic composites which have good strength and moulding characteristics and are derived from readily available cheap component.
- . The published literature includes a number of proposals which teach preparation of composites which consist essentially of thermosetting or ~ thermoplastic resinous matrix materials having dispersed therin inorganic ~~ reinforcing fillers such as mica platelets or flakes. Such materials are described~ for example~ ln U.S. Patent number 3,7b4~456 Woodhams issued Oct.
9. 1973; and in U.S. Patent 4~442.243 which describes Cuch mica-re~nforced .~
thermoplastic cornposites ha~ing improved durabi]ity~ physical and aesthetic properties which are prepared bY mi~ing the resin and the mica in the pl-esence ot propylene polymer wa?~-. 'I'he m~ca may be pretreated to provide funclional 35 groups thereon for subse~uent chemical reaction with the propylene polymer x .
' The use of inorganic fil]ers such as mica does however present cl?rtain technical difficulties. Mica is a difficult material to process in inakillg : , such composites. It is ai)r.isive bv nature. so that it tends to wear out "~5~ ~ 45 processing machinerY which it contacts.
' The published litera~ure contains certains referenc~c to the o~e nf cellulosic fillers as additlves for both thermopla~stic and thermosf tting :- 50 resins. Such fillers ~ v hf' derived from the finelY ground products of wood pulp, the shells of peanut~ 01' Wl]ll~lts. corn coles. rice hulls, vegl~tahle . ,~, ~ ~ 55 fibers or certain bamboo-type reeds or grasses. The great ah1lndanr e and ; i~ cheapness of such cellulo.sic materials ln every part of th-' giobe ha~ made :
~- these cellulosic rnater-ials attractive sources for producing useLul fille,-c tor ~'~ 60 '- plastics. Althou,~h the llSf' of cellnLo;,ic fillers in thermoset resins (such as ,,, ,~
"~; the phenolics) has been all accepted practice for many yea,s their use ln ~, ~ f ~s '~;
:: ' 3 'J' 7 ~ ~
-.. . .
. ,~ , '' ;5' ~- thermoplastics has been limited mainly as a result of difficulties in dlspers-ing the cellulose partic]es in thermoplastic melts~ poor adhesion (wettabili-r 5 ty) and in consequence interior mechanica] properties of the molded composi-'~' -tes.
- It has been sllown that the dispersion of discontinuous cellulose based ': 1 0 fibers into polymeric matrix can be ~reatly improved by pretreatment of the fibers with a plastic polymer and a lubricant, U.S. pat, no. 3,943,079 to -~; 15 Hamed described such pretreatment. Goettler in U.S, pat. no. 4,376,144 has - shown that the composites made from cellulose fibers dispersed in a matrix of -~ ; plasticized vinyl chloride polymer and bonded thereto with a cyclic trimer of ~- toluene dissocyanate can be molded or extructed to produce useful articles.
-.~
~ Coran et al, U.S. pat, 4~323,625 have shown that the composites can be , ~- 25 produced from grafted olefin polYmers and cellulose fibers. The polvolefin have been grafted with other polymer carrying methylol phenolic groups hefore being combined w]th cel]u]osic flbers and bonding agent such as phenoi-alde-hYde resin~ a polYisocvanate or the like, Lachowicz et al.. ii.S. pat. 4~]07~110 described thatc~ -cellulose ~lbers.
coated with a graft copolymer comprising 1,2-polybutadiene to which is ~rafted an acrylate such as butvlJnetllacrYlate could be used in reinforcing of polye-thYlene and other plastic compositions.
Fujimara et al., Jap. p31 . Kokai 137,243,178 also describe a cellulosic material, which has been acetYlated with gaseous acetic anhydride as a reinforcing agent for po]yo]er'lns.
~; Gaylord~ ~'.S. pat. 3~ 5~,77 ~1~69) descrihes compatibi]ization of poly-vinylchloride or polyrreth~ -ethaclYL;3te with grafteci cellulose.
Gaylord, U.S. pat. 3~iiiS ~'33':f a]so shows that polvethYlene or polyvinv]chlo-ride or acrylic rubber ca~ e compatlbilised with cellulosic tlbers Lll the presence of an ethylenlcrl~L~ unsaturated carboxYlic acid or a~ clridf~ ullder - ~ conditions which generate frf>e radicals nn said polYmers, wherehv said ethYle-nically unsaturated carboxv]lc acid or anhvdride reacts with all-1 couples with thermoplastic polymer and cellulose.
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~ 65 ::;
-~,", ~ 711 : ~:
: ;,r . Hse U.S. pat. 4.)09 433 have treated wood material with polyisncyanate - before mixing with ther1nosetting phenol formaldehYde resin.
: -.. ,, S
~- Lundl et al... ~.S. pat. 4.241.133 rnixed elont~ated wood flakes with binder ~i.e.polyisocyanate) and than hot:-pressed into the form of an elongated structural member as a beam~ post etc.
~ Wadeson~ Brit. pat. 1~5~5 074 describes process to manufacture ce]lulose-- ~ polyurethane material by reaction nf fibrous cellulosics with impregnated ; polyisocyanates in the presence of catalyst (zinc-octoate).
; Nakavrishi et al.... Jap. Kokai 76 97648 describe the use of cellulosics in 20 PP. Theiysohn et al..... Ger-Offen 2gl6657 presents heat resistant PP moldingcompos~tlon. Surivama et al. Jap. Kokai 79 72247 introduce heat treated wood filler for thermoplast~cs. Also Dereppe et al.. Ger. Offen. 2635957 as wel]
as Kishikawa et al. Jap. Kokai 73 45540 describe filler reinforced polypropy-lene. In summarY we he]ieve to be the first one to claim the use of polyme-30 thylene polypherlvlisocYanate as a honding agent in a composites of vin~lchlo-~- rlde polymer an-lIiscontinuous ce]lu]osic fibers. These compos~tes are havll1g --~ good strength molding chai3cteristic and are derlved fronl rea-lily av.lilahl cheap components.
, - ~
~ 40 ~7 ~ j SIJMMARY OF THE INVENTION
. . .
- It has now been foun-l thlt the cellulosic fibers can be we~l compatihllize with a matrix formed bY vlnvl chloride polymer iPVC) and the adhesion of 50 cellulosic fibers to a ratrlx can he suhstantially improved hy incorpo~atillgtherewith a certain bondirlog a~Pnt. It has been a]so found that discont]nuous cellulosic fibers~ when coate-J with polYmer give better adheslon when incnrpo-rated with polvetllvlelle matri~ if the po]ymer coat~ng includes a small anioullt - of certain bonding agellt.
' .': ' According to prese1lt in~entiol1~ composites are made ol discont-MI~lolls cellulosic fibers dispersed ln a PVC matrix which include a bonding aof~rlt ~ 3 - 65 _-':~
~ 3 ~711 .
~' .~., ,~
.. ~, ,~, -.,~ which is linear polymethylene polyphenylisocyanate (PMPPIC) of the formula:
., ,~ ~
~ ' 5 ~ / ~ C
3~ tl : ~/ L '~ ~1 \D
, - ,~
:~-. 15 ~ Composites containing from ~ to 50% of cellulosic fibers by weight~ based on the total weight of conlposites, are within the scope of invention. The PMPPIC is forming a strong adhesive (chemical~ bond with wood fibers (being ; grafted) and thus provlde the composite whi.ch has improved stren~th and stiffness.
~: The bonding agent has been found to be effective at relatively low concen-30 trations - as low as 0.1 parts by weight on 100 parts of the PVC in the -: . matrix. The invention also includes treated cellulosic wood fibers~ with aspect ratio v~rJing from to 5 (saw dust); from 12 et 50 for high yield) . 35 (Yield from 50 - 80%) and ultra high yield (yield from 80 to 95%) pu]ps and : ~ .
from 50-150 for low vield (less than 50%) chemical pulps, grafted with PMPPIC
~:. and pre-coated with PVC. The Latter material appears to have an excellent di.spersabilitY wlth PVC mat!ix.
: The present ~nventlo~ cl~ldes also -l~b hexamethylene diisocvanate~ ~CO-45 !oH2)~-NCO. Mixtures Ot othel- isocYanate materia]s can be plesent aLon~7 with PMPPIC~ but their proport-otl and eflect is inferior to thereto ln the present '::
; . S O invention.
-:
:
:, :- 55 DeTATI,~.I) DESCRIPTION OF THE INVENTION
:
The cellulosic material used in the invention includes cellulosic fibers derived from softwood and ori~nd hardwood pulps. e.g. chem]cal or mechallical , 4 ,,,~
: - 65 : - ' -' 711 , ~''' , ,~
or che,mi-mechanical or hi~h-yield or ultra-hiOh yield or therrno-mecharlica] orrefiner or stone groundwood or chemi-thermomechanical pulp nr explosion pulp;
S nut shells~ corn cobs~ rice hulls. vegetahle fibres, certain bamboo-type reeds grasses, hagasse, cotton. rayon (regenerated cellulose), sa~dust. wood .~r~ ",~
,-' shawings and the like. Preferred are wood fibers derived from wood pulp, e.g.
chemi- thermomechanical aspen pulp or thermo-mechanical pulp or sawdust.
;~rc~ There are many avai]able types of wood pulp which may be classified accordin~
1 15 to whether they were derived by chemical or mechanical treatment or cnmbina-~, ., - -' tion of both one. as well know in the pulp and paper industry. Waste pulp and recycled paper pulp can also be used. The fibers have an aspect ratio (length ~- divided by diameter) ranging from 2 to 5 for mechanical pulps as well as for sawdust wood flour and 15 for cherrli-mecllanical and cheml-thermomechanical pulps and 50 to 150 f:or low yield chemical pulps. In some instances~ it is desirable to use rnixtures of fibers having wldely differing aspect ratios.
The polymer contained in the matrix is described as being vinyl chloride , polymer and includes both vinyl ch]oride polymer and copolymer of a major ~, proportion of vinyl chloride with minor proportion of other copolvmeres ~ . . ,:
~" 35 monomers like ~,nylacetate or vinylidenchloride.
The plasticizer which can be contained in the matrix shou]d be one which is compatible with the ~invl chloride po]y~er as described. Examples of effec-tive plasticizers include adipates, such as di-2-ethylhexvl adipate and diisodecyl adipate; azelates~ such as di-2-ethYlhe~l azelate; benzoates~ such '- 45 as dipropy]ene g1ycol dibenzoate; phosphates. such as tricresyl phosphate, cresyl diphenyl phosphate, '~-ethvlhexyl diphenyl phosphate~ -n-octy] phenyl phosphate~ and ti-i-n-llexYI l~hosphate; phtalates, such as diethylpht:alate, butyl benzyl phtalate, dl-2-ethY11leYvlphthalate. and diisodecyl phth,llate.
di-2-ethylhexylp11tha1ate, arld dlisodecvl phtalate: sebacates. such as dl-2-ethylhexyl sebacate and te~epilthalates sl)cll as di-2-ethylhexYI terephth;llate.
- A compatible blend of two nr rrlore plasticizers can be used. In use. the plasticizer has the elfect not on;v on softening and modifylng the polynler, ~ 60 --~" but also on lubricating thP t~Lber surfacec, pro~oting dispersJrJIl and nini~l-~"
S
_ ?.~?i~ I ~r 65 _ , .
A
t3 !~
.'.-~, ,'.''~
I:~f,~ sing fiber breakage.
,:~.., .. ~
The cellulosic based fibeYs are described as "discontinuous" to distinguish ~ 5 "~,, from the well hnown lncorporation of contlnuous cord reinforcenent into rubber and plastic articles. The "matrix" is the material forming a continuous phase which surrounds the fibers. A "composite" is the combination of discontinuous ,~, fibers in a matri~ wherein the contained fibers may be randomly oriented~ or, .. - .
to a greater or lesser degree, aligned in a particular direction.
~ The bondlng (grattlng) agent of the invention lS llnear polymethylene -,~ polyphenylisocyanate of the formula:
~.~0 _.
, 30 identified as PMPP~C. The E~MPPIC can be of low, medium or high viscosity depending on degree of polyn,~eri~atloll, and can be in analytical as well as technical grade. The technical grade can be formed by mlxture or major ~ proportion of PMPPIC with a minor proportion of other isocyanatec~ e.g.
-; 40 4,4'-diphenylmetllane dlisocvanate or toluene diisocyanate.
The bonding a~.ent can b~ also itl form of a 1,6 hexamethylene diisocvanate.
; NC0-(CH2)Lj-NC0 and other rliisocyanates having the general for-mula NC0-(R)~NC0 - ; 45 where R represents alkvl group and n ls number varying from 2 to 10,000.
The bonding agent is used ln the composites of the invention in sufficient amount to achieve an adllesive hond between the PVC and the cellulosir based fibers. This amount can be ac little as 0.1~. by weight of PVC~ up to 10~ bY
~ weight or more, on the same basis. The arnount of bonding agent requirerl can - 55 also be expected to varY w~th the amount of cellulosic based fiber preserlt.
ln general~ with 40 weight percents of cellulosic fibers present in ,-~ 6 composites~ the best prop-~r~:ies tre obtained at 3% bY wei,~,ht ot isoc~anat,e ~, based on polYmer weight O~L ~ b~ wei,c~ht nf bonding agent bacecl on ce]]ulnslc i ~ 7 1 1 .~ . -,;
'',~, tiber weight. With 30i~.~ hY weight of cellulosic fibers. 5.5% by weight of ,.. ~ ., , bonding agent based on fiber weight are going to give optimal results.
~-- 5The precise mechanisrrl nf the bonding is not known, however, it is highlY
- probable that the active isocyanate moities in the bonding agent react with . . ~*
~ the hydroxyl groups on the cellulosic base fibers~ forming a chemical bond by '-:~ 1 0 ~ reaction well known in polyurethane industry which is as follows:
.
~' l5 - ~C0 + H0 - ~ - N - C - O -,,................................................. 1 ~1 ~-~, H
, .
~ The bonding agent can be used either as it is or in solution in a conve-'''"
, nient, compatible~ non-reactive so]vent in order to facilitate dispersion of the active material thKougho1lt the cornposities, The bonding agent can be incorporated into the cornposites of the invention 30by mixing the bonding agent therewith~ before or at the same time the fibers -- are combined with the PVC and other ingredients. If the bonding agent is added in solvent solution, the solvent will usually be rerrloved prior to the 35final shaping of the compou11d. In case when plasticizer solution form of bonding agent is emplo~ed, this step is unnecessary.
Alternatively~ the bonding agent rnay be combined with the cellulosic base fibers in a pre-treatin,o~ step. Following the idea of Gaylord U.S. Pat.
3~645,939 the fibers can be grafted with a bonding agent so as to enhance 45their dispersability llltO ,1 compos]te by admixture thereto of organic polYmer which can be processed as ther!noplastic substance~ in an amount-sufficient to reduce fiber-to-fiber aff]nity. Preferab]y~ the organic polyrrer lS PVC, although other compatible polvmer, having solubilitY parameters at midpnint of ,~, range within one unit of that of PVC, can be used. It was obsel~ved th,!t the pre-treated fibers which contain the bonding agent show a consideKable lmpro-~ ~ vernent in their dispersabi1it~ into a pol!~rnf?r matrix- over flheJs treate(l on1y - ~ with organic polymer wl ~ hOllt E~MPPIC.
.;,' ', ~ r~ 7 1 1 :
" Eventhough the used bonding agent was designed for use with nylon or '~''' polyester textile it is ver~ effective in adhering discontinllous wood fibers ~, 5 "' to a PVC polymer matrix.
:'r~ The pre-treating step can usually be preformed in an internal mixer~ such , ;,s~ ~., - , ~ 10 as a Banbury rrixer~ ~rabender mixer~ CSI-MAX mixing extruder or on Roll mill.
- '~' The order of addition of material to the mixer is not critical. The mate-, ,, rials, PVC~ fiber~ bondlng at~ent. and other ingredient, can all be charged ~;~ 15 initially. The ternperature of mixing is a function of mixtures and equipments ~ used. In general~ the temperatures used in roll-mill are 10 to 15~C higher ''' ' 20 than that used in extruder~ The proportions of the ingredi,ents are dictated by the resulting composite properties. The amount of polymer used should be high enough to prevent fibre-to-fibre interaction~ usually at least 3 parts of PVC or polymer by weight per 100 parts by weight of wood fi,bers. Usua]ly~ no ~'~ more than 15 parts of PVC by weight per 100 parts of fibers by weight will be used~ although higher polYmer level can be employed if desired. The level of bonding agent(s) wlll normal]y range from about 0.5 parts up to 15 parts or more of bonding agent(s! hv weight per 100 parts by weight of fiber. In most instances~ it will be rlore convenient to include all of the bonding agent in ~- the treated fihers~ sin-e no further additi,ons of this ingredient need he - added in making ~he t'inal composlte~ Since the treatment step coats the surface of the fibers to a certain extent~ the polymer pre~sent in the Co,Jting wi,ll be in a position to he honded to the fibers. It appears also, tha~ some additional honding ot the ~:lher to PVC in the matrix is achieved dur-il-lg the :~:
composite forrnation. The composi,tes of' the invention are usuallv~ though not - necessarily~ rnade t'rom nol1-treated fibers compoun-led with pVl' with pre-rrli,Y
bonding agent.
In any case hr)wever, t:he bondinto~ agent of the present Invention rnllst he ,, 55 present in the recommended anount in orrler t,o achieve good adhesive bonding -,; between the fiber.s and the mat,rix.
Fibers. treated or not. arl~ mi,Ye(l with po],ymer mat:rix to fonn a composite ~, 60 -, usllally in an interlla~ n-ix~m~~ ~xtruder or on a rol1 nlill. Additiona], i,ngre-,: .
: ~ , ~:' A
L
~ i~
;, dients, such as fillers~ plasticizers, stabilizers, colorants. etc. can also ~'' be added at this point, Inorganic filler material may be selected from mica, '~~'~ 5 talc, CaC03, silica, glass flbers. asbestos or wollastonite.
The following speciflc examples illustrate the use of PMPPIC or others coupling as well as grafting a, ents for cellulosic fibers.
. ., , ~-: 15 eXAMPLE 1.
The wood pulp, chemitherrr.o-mechanical aspen pulp, having properties as ~ ~ 20 x~ f,~l~ described in Table 1. was predried i.n circulating air oven for 12 hours at . ~ ~
,- 65 C.
The polymer matrix~ PVC a.lreadv plasticized, supplied by Baron Caoutchouc ~~ Co., was pre-mixed at room temperature with 0.5 to 5% of polymethylene polyphenylisocyanate based on polymer weig~ht.
' ~:
Preparation of composites.
Mixing of polYrrler and fiber was done in CSI-max extruder, Model CS-194 with different weight percent3~oes (varying from lO to 507~) of cel]ulosic t~-ibers.
~:- The mixing temperatures used were hetween 140-150~C. The extruder composite was allowed to ('')G. down to room temperature and ground to mesh size 20.
The above prepared polvmer-r~iber Inixture was molded into the shoulder type test speciments (6-24 at the same time), in a mold~ which was covered b~ rnetal plates on both sides.
The weight of rrlater-ia] tor one specimen was 0.5 g when mo].ded at a tempera-':- 50 :'- ture of 160~C tor 25 rnillutes at a pressure of 2 . 7 MPi3 . l:he starting te~l~pera-ture was 93.3"C and coolln,. t~ waS 15 rninutes at pressure 0.5 ~Pa.
S5 The samples were tak-~n ~-ut ~ rorn t-h~ rnold after a 15 minnto cooling period and then allowed tn starld "t ll~ast 3 to 4 hours in the testing room which was Icept at 230C ancl 50~ re~atlve h~ iditv.
. 60 , g ,, - _ ; '' ,. ' ' 7 .,, q~
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;~''.V ~
~ Mechanical tests . ~ ;, . .
Mechanical measurements were made on an Instrom tester (Model 4201) at 23~C
and 50% RH. The rate ot elongation was 100%/min in all cases. All samples -~, were 3.175 mm in width and B.4 cm in length (1.7 cm between grips~. The thickness of samples was usoallY 0.158 cm, ,~ 10 Dimensions of al] samp]es were measured with a micrometer. All experimen-tal data reported is an avera~e of at least four measurements.
:~
Mechanical properties reported for this work, are those measured usualy at maximum, break. stress proof point or otherwise specified. The properties.
-- measured using Instrom 4201. were automatically calculated by HP86B using the ~~- Instrom 4479-521 Plastic Tensile Test Program. The elastic modulus was ~ ,-measured at 0.1% strain. Average coefficients of variation for mechanical properties were as follows: stress, 3.5~0; strain, 5%; energy, 8.3%; modullls~
- ~, ~ 2.3%.
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TABLE I
,: .
Properties Aspen CTMP pulp Drainage index (CSF). ml 119 Brightness, Elrepllo (%) 60.9 Opacity. (~o)91.4 Br,lklng 1ength~ km 4.46 longation~ 1.79 Tear index, m~.m2/g 7.2 Burst index~ kP,~.~n~/g 2.6 Yield, (~o! 92 Lignin, (%)17.9 :
~:
~ - 55 _ Tensile data are presented ~n Tab1e II.
~ 60 :--- . . . .
,~
:'' Y t It is quite obvious~ that the PMPPIC bonding agent lead to the increase of 5- strentgh properties as well as modulus. The stress values have increased from 2 MPa to 2.36 MPa when CTMP aspen fibers were used or to 7.7 MPa when the CTMP
aspen fibers were used with PVC and 2% PMPPIC, at 30% weight percent nf fiber addition. I'his enormous strength increase which indicated good adhesion and bonding between fibers and matrix was accompanied bY increase in modulus from h,44 MPa of PVC to 37 MPa when CTMP aspen were mixed with PVC and to 4~.7 MPa , 15 in case of 30% weight percent CTMP aspen fibers were mixed with PVC in which 2'~ weight percent of PMPPIC wer dispersed. It is interesting to see that the ' ~ " 20 energy has also increased from 0.032J for PVC 0.127J for PVC with 2% PMPPIC
- , and 30% of CTMP aspen fiber. Mesh 60.
' '-, ~-.
eXAMPLE II
The composites were prepared and evaluated as indicated in Example I but : . -aspen Kraft pulp~ Mesh ~0~ were used in place of CTMP Aspen pulp (Mesh 60).
- 35 The tensile data are represented in Table III.
-~ The tensile properties were evaluated at maximum values. at break as well - 40 as at stress proof point.
The tensile values of PVC composites of Aspen Kraft are compared to that of -~
PVC composite with 2% PMPPIC and aspen kraft pulp.
- 45 It is clear~ that there is verv positive effect of the presence of PMPPIC
especially on values of stress and modul1)s, At stress proof point. stress value of 3.25 MPa ïor E'V(, has increased to 3.~ ME~a for cnmposites without bonding agent but to ~ !n case when 2~ of PMPPIC were premixed with P~7C
hefore the addition of 30',~c ot' aspen 1<raft pnlp fibers.
In the case when the E'VC was premlxed with 0.7% of dioctylphtalate an-i 0.3~
of PMPPIC before fibers additinn there has heen also considerable impro~ement of stress and modulus. from 3.''5 MPa to f~.l MPa for stress and from 4.4v MPa to 58 MPa for modulus.
. . ,.~, _ - ~ ..
.~' ,...
~ '"~i'' . '.~
~i .
.3 -~ 7 ~:3 - eXAMPLE III
- The composites were prepared and eva]uated as indlcated in Example I. hut low -~ yield spruce sulphite pu]p (Mesh 60) were used in p]ace of CTMP aspen pulp (Mesh 60). The tensile results are presented in Table IV.
, -, The tensile properties improved particularly at stress proof point. Stress has increased from 3.25 MPa for PVC to 8.5 MPa for PVC premixed with 2% of ,,,,, 15 PMPPIC and 30~ low yield sulphite pulp.
:
'~; 20 , ~ EXAMPLE IV
,~ "
~ 25 The composites were prepared and evaluated as indicated in Example T, but .~
aspen sawdust (M60) was used instead of CTMP aspen pulp (M60). The tensile results are presented i,n Table IV. When compared to PVC the composites with aspen sawdust have shown improvement registered at stress proof point a,s far as stress is concerned as well as in case of modulus and energy, all at 30 ~, , weight percents of fibers present.
"
~,; 40 ~-~, EXAMPLE V
The composites were prepared and evaluated as indicated in Example 1~ but cotton cellulosic fibers (M~0) were used instead of CTMP aspen pulp (M601.
~- 50 The tensile resu],ts are presetlted at Table V for different percentagec "f bonding agent as well as fibers used.
Results show the pos3tive effect of renforcement of P~C by cel1ulosic fibers especial],Y in the preccllce of bolldillg agent. For example, at stress proof point stress has inrreace(l fl~om 3.25 MPa for PVC to 8.~S M~a for corlpos-ites in the presence of ~,i of PMPFIC arld rnodulus has increased from 4.i4 MF'ato 5.65 MPa.
~:- A
"'~,' .
;
,,~ . .
~S
. ' ,~
~, EXAMPLE VI
,, S
The composites were prepared and evaluated as indicated in Example I~ hut ':''' ' ' ,~," ~ PVC, identified by trade mark "GE0~ 110 x 334" of B.F. Goodrich. plasticized ~' 10 with 20% of diocty]phtha1ate was used in p]ace of PVC Baron Caoutchouc Company. The tensile properties. evaluated at maximum values. are presented ---- in Table VI and properties. eva]uated at yield point are presented in Table ~ 15 e~ VII. These results show signlficant improvement of composite properties when , bonding agent was used in weight percentages varying from 0.5 to 5% based on '"";' 20 polymer weight.
'' ;~' ' ~," 25 EXAMPLE VII
:
~- 30 The composites were prepared and evaluated as indicated in Example Vl~ but - the bondin~ isocvanate agent used was l,6 - hexamethylene diisocyanate ,,~~~ (HMDIC). The tensi,le properties are presented in Table VIII.
, The HMDIC lead to significant increases of stress as well as modulus at ~" stress values measured at stress proof point as well as at maximum. The ~; ., - , 40 stress values at stress proof point more then doubled and modulus. measured at 0.4% classification (at stress proof point) has increase from 368.4 MPa to 831 MPa.
, ~
EXAMPLE VIII
The composi,tes were prepared and evaluated as in Example I but 10~7 yiel( spruce sulphlte pulp was used ln place of CTMP aspen pulp and PvC. identitied , -~ by trade mark "GEUN 110 x 334" was used instead of PVC of Baron Caoutchouc Co.
The tensile properties are presented in Table IX. The good adhesiol-l in composites bonded by 0.'; of PMYPIC is demonstrated bY increases in ,ctress .. ,, ~ .
~ A
s ';3 3 ~ i -L :l :: ' ~ ,~
, measured at maximum, hreak as we]l as at stress proof pOillt (at 0.4~).
The stress has increased at SPP from 5.43 MPa to 13.6 MPa. modulus from 368.4 MPa to ~69 MPa and both elongation as well as energy at SPP at 30 weight percents of fiber presents have shown increases when compared to PVC, : .:
'~''~,'' ~; EXAMPLE IX
~i, 15 - The composites were prepared and evaluated as in Example I but vinyl : ..:
~ 20 chloride polymer used was PVC identified by trade mark "DALVIN 1467" of ; ~ ~ovacor Chemicals Ltd instead of PVC of Baron Caoutchouc Co.
The tensile properties are presented in Table X. The tensile properties 25 are compared between that of PVC, PVC with fibers and PVC + 0.52 of PMPPIC +
fibers. At 30~ of fibers presents, the stress measured at SPP increased from 30 original 6.4 MPa to 10.7 MPa (PVC + fibers) or to 11.8 MPa (PVC + PMPPIC +
flbers~. The modulus has increased from 305.4 MPa to 818 MPa or 814 MPa respectively. The presence of bonding agent lead to higher values of stress, elongation as well as energY when cornpared to composites without PMPFIC at maximum as well as at break va]ues.
Although the fore~,oing invention has been described in come details by the f way of examples for purposes of clarity of understanding, it will be obvious _- ~ that certain changes and modification may be practiced within the scope of the ~ 45 appended claims.
::~,, "
" 50 : , ~ 14 . . , -A
TABLE II
SAMPLE FORCE (N) STRESS (MPa) ENERGY (J) STRAIN (%) MODULUS (MPa) ~ of fiber~ 10 20 30 10 20 30 10 20 30 10 20 30 10 20 30 P~C __ 9.7 _ _ _ 2.0 ___ _ 0.032 _ _ 20 __ _ _ __ 4.44 _ _ PVC+FIBER
CTMP-ASPEN j.l4 12.g6 13.61 1.87 2.3 2.36 0.018 0.0hl 0.064 20 11.0 17.3 37.0 CTMP-ASPEN 16.70 27.40 39.20 3.60 5.90 7.70 0.038 0.058 0.072 20 17.2 32.6 49.7 + 2% PMPPIC
u~ CTMP-ASPEN 20 5 32.16 35.80 4.10 6.40 7.40 0.046 0.069 0.127 20 18.7 39.8 78.3 + 8% PMPPIC
CTMP-ASPE~
+ 1% DOP 15.124.90 28.30 3.30 5.40 6.10 0.047 0.067 0.078 20 14.0 30.0 49.0 PMPPIC
CTMP-ASPEN
0 S~. 15-924.03 30.53 3.27 4.87 6.486 0.039 0.0i0 0.119 20 13.6 30.0 51.() ~_ PMPPIC ~~
PVC..... vinyl chloride polymer. plasticized by Baron Caoutchouc Co. ~C~
Tensile properties ~easured at 20% of elongation. _~
DqP..... dioctylphtAlate. r !
TABLE III
COMPOSITE STRESS (MPa) MODULUS (MPa) ELONGATION (%) ENERGY (J~
% ~f 10 20 30 10 20 30 10 2030 10 20 30 tlbers AT .AX 13.12 4.44 439 2.90 PVC AT B~EAK 12.65 444 2.93 AT STRESS
PROOF POINT 3.25 " 17.1 0.033 p~ ~ AT MAX~1.8l 6.46.0 l~.2 34.2 54.4241 12644.71.33 0.53 0.1~3 ASPEN AT BREAK 9.25.3 3.5 " 248132 52 1.39 0.6 0.2 KRAFT PULP AT SPP1.92 2.33.'3 " 6.15 4.8 6.10.011 0.010 0.017 PVC + 2% AT MAX10.8 12.011.4 19.234.5 51.2143 6035 0.340.42 0.23 + ASPEN AT BREAK9.7 10.49.2 " 151 6738 1.010.48 0.26 KRAFT PULT AT SPP4.3 5.16.2 " 17.4 11.8 10.g0.042 0.034 0.038 PVC t 0.7% DOP AT MAXlO.l 12.29.4 17.539.7 58 140 5225 0.860.36 0.14 + ASPEN AT SPP3.8 6.56.1 " 15.8 13.8 9.70.035 0.047 0.034 KRAFT PUt.P
PVC.... vinyl chloride poly~er, plasticized by Baron Ca~utchouc Co.
DOP.... dioctYlphtalate i--TABLE IV
COMPOSITE STRESS (MPa) MODULUS (MPa) ELONGATION (%) ENERGY (J) % ~f 10 2030 10 20 30 10 20 30 10 20 30 fibers AT MAX 13.12 4.44 439 2.9 AT BREAK 12.65 4.44 444 2.93 PVC
AT STRESS
PROOF POINT 3.25 4.44 17.1 0.033 AT MAX10.2 12.615.2 21.1 36.5 69 137 5S 38.60.~5 0.414 0.330 PVC ~ 2% PMPPIC
+ LOW YIELD AT BREAK 8.410 14.2 " 144 66.544.1 0.91 0.49 0.36 SULPHITE P~LP
AT STKESS
PROOF POINT 3.0 6.5 8.5 " 10.3 14.3 11.8 0.021 0.047 0.052 PVC + 5% AT MAX 7.8 7.59.3 11.4 20.6 65 170 88 42 O.Y17 0.49 0.27 SAWDUST (M60) 6.8 6.1 7.6 " 178 101 49 0.98 0.58 0.33 AT SPP 2.1 2.45.5 " 11.2 8.6 11.9 0.02 0.018 0.042 PVC.... vinyl chloride polymer, plasticlzed by Baron Caoutchouc Co.
TABLE V
COMPOSITE STRESS (MPa) MODULUS (MPa) ELONGATION (%) ENERGY (J) % of ibers 10 20 30 10 20 3010 20 30 10 20 30 AT MA.Y 13.12 4.44 439 2.9 AT BREAK 12.65 " 444 2.93 pVC
AT STRESS
PROFF POrNT 3.25 " 17.1 0.033 AT ~X. 9.7 7.9 6.3 16.3 34 44.3214.5145.559.3 1.2 0.8 0.25 PVC
+ COT'rON AT BREAK9.0 6.9 5.1 " 221153 69.7 1.22 0.8 0.3 (~160~
AT SPP 2.4 3.1 3.8 " 8.76.6 6.6 0.016 0.015 0.018 PVC + 2% AT MAX.10.312.1 14.5 16.2 30.1 54 16474.3 49.3 1.011 0.52 0.41 PMPPIC
+ COTTON AT BREAK9.2 10 12.4 " 17285.2 53.3 1.07 0.62 0.46 (MhO) AT SPP 3.8 4.4 5.8 16.612.2 10.4 0.037 0.033 0.038 PVC + 5~ AT MAX.11.212.3 15 20.8 34 56.5131.365.441.0 0.883 0.4h 0.34 PMPPLC
+ COTTON AT BREAK10.110.713.6 " 141.672.343.6 0.97 O.S3 0.37 (M60) AT SPP 3.9 5.0 8.8 " 15.412.3 14.5 0.036 0.036 0.063 ~_~
PVC.... vinyl chloride polymer, plasticized bv Baron Caoutchouc Co.
;_~
, . ...... . .. .
TABLE VI
COMPOSITE % OF FORCE (N) STRESS (MPa) MODULUS (MPa) PV~ 127.75 _ _ _ __ 24.4 _ 368.4 CTMP-ASPEN (M60~ 89.7 83.5 98.4 18.2 17 20.3 569 670.9 912 CTMP-ASPEN t 0.5~0 104.1 130.2 133.8 21,4 27 27.5 401 718 782.9 PMPPTC
CTMP-ASP~N + 1% 105.3 127.8 134.7 21.4 25.9 27.3 398 742 808 PMPPIC
_ CTMP-ASPEN 3% 109.3 122.7 128.4 22.12 24.9 25.9 474 568 662 _~ PMPPIC
CTMP-ASPEN 5% 116.3 136.2 150.0 22.5 26.14 28.7 427 664 852 PMPPIC
*CTMP-ASPEN 1.84% 131136.4 124.8 25.2 27.1 24.5 608 636 594 PMPPIC
*CTMP-ASPEN 4.61~ 95.8 - 142.7 19.6 - 29.3 288 _ 871 *Molding time: 20 minutes instead of 15 minutes. ~_~
PVC of B.-F. Goodrich identified by trade mark "GEON 110 x 334", plasticized with 20% of dioctylphtalate. , Tensile properties measured at ~aximum.
.. .. _ . _ TABLE VII
COMPOSITE FORCE (N) STRESS (MPa) ENERGY (J) STRAIN (%~ MODULUS (MPa) % ~f 10 20 3010 20 30 10 20 30 10 20 3010 20 30 fibers PVC-~IBER
'-PVC-PURE 49.19 _ 10.25 0.030 5.51 _ 368.4 CTMP-ASPEN 83.3 36.2 88.0 16.9 l7.5 21.0 0.048 0.040 0.036 5.64 5.22 3.44 585 670 924 CTMP-ASPEN-~ 0.5l/o 50 ~5 110 10.3 17.5 Y2.7 0.026 0.031 0.05~ 4.18 3.55 3.52 397 790 791 PMPPIC
Q~
c CTMp-AspEN
~ 1~ 48 31 82 9.8 18.6 16.6 0.023 0.039 0.030 4.05 4.08 2.9 388 743 808 PMPPIC
CTMP-ASPEN
+ 3% 62.6 73.8 87.5 12.7 14.3 17.7 0.040 0.046 0.054 5.0 5.0 5.0 460 5~2 652 PMPPIC
CTMP-ASPEN
+ 5% 57.7 82.5 110.6 11.2 15.8 21.2 0.036 0.05 0.068 5.0 5.0 5.0 ~27 599 ~l7 PMPPIC
pVC of B.-F. Goodrich, identified by trade mark "GEON 110 x 334" with 20% of di-octylphtalate ~-~
Properties measured at yield point.
\
TABLE VIII
COMPOSITE STRESS (MPa) MODULUS (MPa) ELONGATION (%) ENERGY (J) % ~f 10 20 30 10 20 3010 20 30 10 20 30 fibers AT MAX. 24.4 368.4 145.8 2.37 AT BREAK 21.0 " 149.8 2.S5 PVC
AT STRESS
PROOF POINT 5.43 " 1.31 0.006 PVC + 0.5~ AT MAX 13.2 21.2 24.4 146 670 831 82.3 12.8 8.6 0.78 0.19 0.14 HMDIC AT BREAK 11.6 17.3 22.8 " 86.8 21.2 10.5 0.81 0.33 0.18 + CTMP
of ASPEN AT STRESS
PROOF POINT 2.910.7 12.3 " 1.1371.447 1.363 0.003 0.011 0.012 -'iModulus measured at 0.4% of elon~ation.
PVC of B.-F. Goodrich, identified by trade mark "GEON 110 x 334", plasticized with 20% of dioctylphtalate.
HMDIC.... 1,6 - hexamethylene diisocyanate.
C~
'~;.
TABLE IX
COMPOSITE STRESS (MPa) MODULUS* (MPa) ELONGATION (%) ENeRGY (J) % ~f 10 20 30 10 20 30 10 20 30 10 20 30 flbers AT MAX. 24.4 368.4 145.8 2.37 PVC AT BREAK 21.0 " 149.8 2.45 AT STRESS
PROOF POINT 5.43 " 1.31 0.0()~
PVC + 0.5~ AT MAX.19.1 27.1 30.6 324 841 969 60.2 21 13.7 0.73 0.40 0.28 PMPPIC AT BREAK 16.9 25.3 29.3 " 66.7 26 15.3 0.88 0.51 0.32 SULPHITE AT STRESS
PULP PROOF POINT 5.1 12.8 13.6 " 1.32 1.52 1.39 0.05 0.013 0.013 *Modulus measured at 0.4% of elongation.
PVC.... vinyl chloride polymer identified by trade mark "GEON 110 x 334" of B.-F. Goodrich plasticized with 20% of dioctylphtalate.
' I .
TABLE X
'~
COMPOSITE STRESS (MPa) MODULUS* (MPa) ELONGATION (%) ENERGY (J) % ~f 10 20 30 10 20 30 10 20 30 10 20 30 flbers AT MAX. 24.7 305.4 129 2.037 PVC AT BREAK 21.6 305.4 133.2 '.117 AT STRESS
PROOF POINT 6.4 305.4 2.27 0.00-1 AT MAX.17.5 "O 18.2 287 765 818 84.7 5.0 4.7 1.058 0.064 0.053 PVC
+ CTMP ASPENAT BREAK 14.5 11.3 13.2 " go 12.2 8.7 1.134 0.173 0.07 AT SPP4.4 10.7 10.7 " 1.335 1.378 1.320 0.005 0.011 0.011 PVC + 0.5% AT MAX.19.123.h25.3 211 726 814 82.4 23.7 11.8 0.99 0.40 0.20 PMPPIC AT BREAK15.821.724.3 211 726 814 87 27 12.7 l.06 0.45 0.22 + CTMP ASPEN AT SPP 3.6 10.3 11.8 211 726 814 1.3 1.37 1.41 0.004 0.01 0.012 *Measured at 0.4% of elongation.
PVC.... vinyl chloride polymer identified by trade mark "Dalvin 1467", Novacor Chemicals Ltd, viscositv O.g2, K value: 67 plastified with 20% of dioctylphtalate. ~_~
.. ...
1~ BACKGROUND OF THE INVENTION i ~ ~ } ~ ~ 1 .
, This invention relates to composites of cellulose based fibers dispersed in :~ a matrix of vinyl chlQride polymer and to treated cellulose fibers which have . :
improved dispersabilit~ into pol~mer and improved adhesion thereto. More specifically, it relates to such reinforced thermoplastic composites which have good strength and moulding characteristics and are derived from readily available cheap component.
- . The published literature includes a number of proposals which teach preparation of composites which consist essentially of thermosetting or ~ thermoplastic resinous matrix materials having dispersed therin inorganic ~~ reinforcing fillers such as mica platelets or flakes. Such materials are described~ for example~ ln U.S. Patent number 3,7b4~456 Woodhams issued Oct.
9. 1973; and in U.S. Patent 4~442.243 which describes Cuch mica-re~nforced .~
thermoplastic cornposites ha~ing improved durabi]ity~ physical and aesthetic properties which are prepared bY mi~ing the resin and the mica in the pl-esence ot propylene polymer wa?~-. 'I'he m~ca may be pretreated to provide funclional 35 groups thereon for subse~uent chemical reaction with the propylene polymer x .
' The use of inorganic fil]ers such as mica does however present cl?rtain technical difficulties. Mica is a difficult material to process in inakillg : , such composites. It is ai)r.isive bv nature. so that it tends to wear out "~5~ ~ 45 processing machinerY which it contacts.
' The published litera~ure contains certains referenc~c to the o~e nf cellulosic fillers as additlves for both thermopla~stic and thermosf tting :- 50 resins. Such fillers ~ v hf' derived from the finelY ground products of wood pulp, the shells of peanut~ 01' Wl]ll~lts. corn coles. rice hulls, vegl~tahle . ,~, ~ ~ 55 fibers or certain bamboo-type reeds or grasses. The great ah1lndanr e and ; i~ cheapness of such cellulo.sic materials ln every part of th-' giobe ha~ made :
~- these cellulosic rnater-ials attractive sources for producing useLul fille,-c tor ~'~ 60 '- plastics. Althou,~h the llSf' of cellnLo;,ic fillers in thermoset resins (such as ,,, ,~
"~; the phenolics) has been all accepted practice for many yea,s their use ln ~, ~ f ~s '~;
:: ' 3 'J' 7 ~ ~
-.. . .
. ,~ , '' ;5' ~- thermoplastics has been limited mainly as a result of difficulties in dlspers-ing the cellulose partic]es in thermoplastic melts~ poor adhesion (wettabili-r 5 ty) and in consequence interior mechanica] properties of the molded composi-'~' -tes.
- It has been sllown that the dispersion of discontinuous cellulose based ': 1 0 fibers into polymeric matrix can be ~reatly improved by pretreatment of the fibers with a plastic polymer and a lubricant, U.S. pat, no. 3,943,079 to -~; 15 Hamed described such pretreatment. Goettler in U.S, pat. no. 4,376,144 has - shown that the composites made from cellulose fibers dispersed in a matrix of -~ ; plasticized vinyl chloride polymer and bonded thereto with a cyclic trimer of ~- toluene dissocyanate can be molded or extructed to produce useful articles.
-.~
~ Coran et al, U.S. pat, 4~323,625 have shown that the composites can be , ~- 25 produced from grafted olefin polYmers and cellulose fibers. The polvolefin have been grafted with other polymer carrying methylol phenolic groups hefore being combined w]th cel]u]osic flbers and bonding agent such as phenoi-alde-hYde resin~ a polYisocvanate or the like, Lachowicz et al.. ii.S. pat. 4~]07~110 described thatc~ -cellulose ~lbers.
coated with a graft copolymer comprising 1,2-polybutadiene to which is ~rafted an acrylate such as butvlJnetllacrYlate could be used in reinforcing of polye-thYlene and other plastic compositions.
Fujimara et al., Jap. p31 . Kokai 137,243,178 also describe a cellulosic material, which has been acetYlated with gaseous acetic anhydride as a reinforcing agent for po]yo]er'lns.
~; Gaylord~ ~'.S. pat. 3~ 5~,77 ~1~69) descrihes compatibi]ization of poly-vinylchloride or polyrreth~ -ethaclYL;3te with grafteci cellulose.
Gaylord, U.S. pat. 3~iiiS ~'33':f a]so shows that polvethYlene or polyvinv]chlo-ride or acrylic rubber ca~ e compatlbilised with cellulosic tlbers Lll the presence of an ethylenlcrl~L~ unsaturated carboxYlic acid or a~ clridf~ ullder - ~ conditions which generate frf>e radicals nn said polYmers, wherehv said ethYle-nically unsaturated carboxv]lc acid or anhvdride reacts with all-1 couples with thermoplastic polymer and cellulose.
r~"
~ 65 ::;
-~,", ~ 711 : ~:
: ;,r . Hse U.S. pat. 4.)09 433 have treated wood material with polyisncyanate - before mixing with ther1nosetting phenol formaldehYde resin.
: -.. ,, S
~- Lundl et al... ~.S. pat. 4.241.133 rnixed elont~ated wood flakes with binder ~i.e.polyisocyanate) and than hot:-pressed into the form of an elongated structural member as a beam~ post etc.
~ Wadeson~ Brit. pat. 1~5~5 074 describes process to manufacture ce]lulose-- ~ polyurethane material by reaction nf fibrous cellulosics with impregnated ; polyisocyanates in the presence of catalyst (zinc-octoate).
; Nakavrishi et al.... Jap. Kokai 76 97648 describe the use of cellulosics in 20 PP. Theiysohn et al..... Ger-Offen 2gl6657 presents heat resistant PP moldingcompos~tlon. Surivama et al. Jap. Kokai 79 72247 introduce heat treated wood filler for thermoplast~cs. Also Dereppe et al.. Ger. Offen. 2635957 as wel]
as Kishikawa et al. Jap. Kokai 73 45540 describe filler reinforced polypropy-lene. In summarY we he]ieve to be the first one to claim the use of polyme-30 thylene polypherlvlisocYanate as a honding agent in a composites of vin~lchlo-~- rlde polymer an-lIiscontinuous ce]lu]osic fibers. These compos~tes are havll1g --~ good strength molding chai3cteristic and are derlved fronl rea-lily av.lilahl cheap components.
, - ~
~ 40 ~7 ~ j SIJMMARY OF THE INVENTION
. . .
- It has now been foun-l thlt the cellulosic fibers can be we~l compatihllize with a matrix formed bY vlnvl chloride polymer iPVC) and the adhesion of 50 cellulosic fibers to a ratrlx can he suhstantially improved hy incorpo~atillgtherewith a certain bondirlog a~Pnt. It has been a]so found that discont]nuous cellulosic fibers~ when coate-J with polYmer give better adheslon when incnrpo-rated with polvetllvlelle matri~ if the po]ymer coat~ng includes a small anioullt - of certain bonding agellt.
' .': ' According to prese1lt in~entiol1~ composites are made ol discont-MI~lolls cellulosic fibers dispersed ln a PVC matrix which include a bonding aof~rlt ~ 3 - 65 _-':~
~ 3 ~711 .
~' .~., ,~
.. ~, ,~, -.,~ which is linear polymethylene polyphenylisocyanate (PMPPIC) of the formula:
., ,~ ~
~ ' 5 ~ / ~ C
3~ tl : ~/ L '~ ~1 \D
, - ,~
:~-. 15 ~ Composites containing from ~ to 50% of cellulosic fibers by weight~ based on the total weight of conlposites, are within the scope of invention. The PMPPIC is forming a strong adhesive (chemical~ bond with wood fibers (being ; grafted) and thus provlde the composite whi.ch has improved stren~th and stiffness.
~: The bonding agent has been found to be effective at relatively low concen-30 trations - as low as 0.1 parts by weight on 100 parts of the PVC in the -: . matrix. The invention also includes treated cellulosic wood fibers~ with aspect ratio v~rJing from to 5 (saw dust); from 12 et 50 for high yield) . 35 (Yield from 50 - 80%) and ultra high yield (yield from 80 to 95%) pu]ps and : ~ .
from 50-150 for low vield (less than 50%) chemical pulps, grafted with PMPPIC
~:. and pre-coated with PVC. The Latter material appears to have an excellent di.spersabilitY wlth PVC mat!ix.
: The present ~nventlo~ cl~ldes also -l~b hexamethylene diisocvanate~ ~CO-45 !oH2)~-NCO. Mixtures Ot othel- isocYanate materia]s can be plesent aLon~7 with PMPPIC~ but their proport-otl and eflect is inferior to thereto ln the present '::
; . S O invention.
-:
:
:, :- 55 DeTATI,~.I) DESCRIPTION OF THE INVENTION
:
The cellulosic material used in the invention includes cellulosic fibers derived from softwood and ori~nd hardwood pulps. e.g. chem]cal or mechallical , 4 ,,,~
: - 65 : - ' -' 711 , ~''' , ,~
or che,mi-mechanical or hi~h-yield or ultra-hiOh yield or therrno-mecharlica] orrefiner or stone groundwood or chemi-thermomechanical pulp nr explosion pulp;
S nut shells~ corn cobs~ rice hulls. vegetahle fibres, certain bamboo-type reeds grasses, hagasse, cotton. rayon (regenerated cellulose), sa~dust. wood .~r~ ",~
,-' shawings and the like. Preferred are wood fibers derived from wood pulp, e.g.
chemi- thermomechanical aspen pulp or thermo-mechanical pulp or sawdust.
;~rc~ There are many avai]able types of wood pulp which may be classified accordin~
1 15 to whether they were derived by chemical or mechanical treatment or cnmbina-~, ., - -' tion of both one. as well know in the pulp and paper industry. Waste pulp and recycled paper pulp can also be used. The fibers have an aspect ratio (length ~- divided by diameter) ranging from 2 to 5 for mechanical pulps as well as for sawdust wood flour and 15 for cherrli-mecllanical and cheml-thermomechanical pulps and 50 to 150 f:or low yield chemical pulps. In some instances~ it is desirable to use rnixtures of fibers having wldely differing aspect ratios.
The polymer contained in the matrix is described as being vinyl chloride , polymer and includes both vinyl ch]oride polymer and copolymer of a major ~, proportion of vinyl chloride with minor proportion of other copolvmeres ~ . . ,:
~" 35 monomers like ~,nylacetate or vinylidenchloride.
The plasticizer which can be contained in the matrix shou]d be one which is compatible with the ~invl chloride po]y~er as described. Examples of effec-tive plasticizers include adipates, such as di-2-ethylhexvl adipate and diisodecyl adipate; azelates~ such as di-2-ethYlhe~l azelate; benzoates~ such '- 45 as dipropy]ene g1ycol dibenzoate; phosphates. such as tricresyl phosphate, cresyl diphenyl phosphate, '~-ethvlhexyl diphenyl phosphate~ -n-octy] phenyl phosphate~ and ti-i-n-llexYI l~hosphate; phtalates, such as diethylpht:alate, butyl benzyl phtalate, dl-2-ethY11leYvlphthalate. and diisodecyl phth,llate.
di-2-ethylhexylp11tha1ate, arld dlisodecvl phtalate: sebacates. such as dl-2-ethylhexyl sebacate and te~epilthalates sl)cll as di-2-ethylhexYI terephth;llate.
- A compatible blend of two nr rrlore plasticizers can be used. In use. the plasticizer has the elfect not on;v on softening and modifylng the polynler, ~ 60 --~" but also on lubricating thP t~Lber surfacec, pro~oting dispersJrJIl and nini~l-~"
S
_ ?.~?i~ I ~r 65 _ , .
A
t3 !~
.'.-~, ,'.''~
I:~f,~ sing fiber breakage.
,:~.., .. ~
The cellulosic based fibeYs are described as "discontinuous" to distinguish ~ 5 "~,, from the well hnown lncorporation of contlnuous cord reinforcenent into rubber and plastic articles. The "matrix" is the material forming a continuous phase which surrounds the fibers. A "composite" is the combination of discontinuous ,~, fibers in a matri~ wherein the contained fibers may be randomly oriented~ or, .. - .
to a greater or lesser degree, aligned in a particular direction.
~ The bondlng (grattlng) agent of the invention lS llnear polymethylene -,~ polyphenylisocyanate of the formula:
~.~0 _.
, 30 identified as PMPP~C. The E~MPPIC can be of low, medium or high viscosity depending on degree of polyn,~eri~atloll, and can be in analytical as well as technical grade. The technical grade can be formed by mlxture or major ~ proportion of PMPPIC with a minor proportion of other isocyanatec~ e.g.
-; 40 4,4'-diphenylmetllane dlisocvanate or toluene diisocyanate.
The bonding a~.ent can b~ also itl form of a 1,6 hexamethylene diisocvanate.
; NC0-(CH2)Lj-NC0 and other rliisocyanates having the general for-mula NC0-(R)~NC0 - ; 45 where R represents alkvl group and n ls number varying from 2 to 10,000.
The bonding agent is used ln the composites of the invention in sufficient amount to achieve an adllesive hond between the PVC and the cellulosir based fibers. This amount can be ac little as 0.1~. by weight of PVC~ up to 10~ bY
~ weight or more, on the same basis. The arnount of bonding agent requirerl can - 55 also be expected to varY w~th the amount of cellulosic based fiber preserlt.
ln general~ with 40 weight percents of cellulosic fibers present in ,-~ 6 composites~ the best prop-~r~:ies tre obtained at 3% bY wei,~,ht ot isoc~anat,e ~, based on polYmer weight O~L ~ b~ wei,c~ht nf bonding agent bacecl on ce]]ulnslc i ~ 7 1 1 .~ . -,;
'',~, tiber weight. With 30i~.~ hY weight of cellulosic fibers. 5.5% by weight of ,.. ~ ., , bonding agent based on fiber weight are going to give optimal results.
~-- 5The precise mechanisrrl nf the bonding is not known, however, it is highlY
- probable that the active isocyanate moities in the bonding agent react with . . ~*
~ the hydroxyl groups on the cellulosic base fibers~ forming a chemical bond by '-:~ 1 0 ~ reaction well known in polyurethane industry which is as follows:
.
~' l5 - ~C0 + H0 - ~ - N - C - O -,,................................................. 1 ~1 ~-~, H
, .
~ The bonding agent can be used either as it is or in solution in a conve-'''"
, nient, compatible~ non-reactive so]vent in order to facilitate dispersion of the active material thKougho1lt the cornposities, The bonding agent can be incorporated into the cornposites of the invention 30by mixing the bonding agent therewith~ before or at the same time the fibers -- are combined with the PVC and other ingredients. If the bonding agent is added in solvent solution, the solvent will usually be rerrloved prior to the 35final shaping of the compou11d. In case when plasticizer solution form of bonding agent is emplo~ed, this step is unnecessary.
Alternatively~ the bonding agent rnay be combined with the cellulosic base fibers in a pre-treatin,o~ step. Following the idea of Gaylord U.S. Pat.
3~645,939 the fibers can be grafted with a bonding agent so as to enhance 45their dispersability llltO ,1 compos]te by admixture thereto of organic polYmer which can be processed as ther!noplastic substance~ in an amount-sufficient to reduce fiber-to-fiber aff]nity. Preferab]y~ the organic polyrrer lS PVC, although other compatible polvmer, having solubilitY parameters at midpnint of ,~, range within one unit of that of PVC, can be used. It was obsel~ved th,!t the pre-treated fibers which contain the bonding agent show a consideKable lmpro-~ ~ vernent in their dispersabi1it~ into a pol!~rnf?r matrix- over flheJs treate(l on1y - ~ with organic polymer wl ~ hOllt E~MPPIC.
.;,' ', ~ r~ 7 1 1 :
" Eventhough the used bonding agent was designed for use with nylon or '~''' polyester textile it is ver~ effective in adhering discontinllous wood fibers ~, 5 "' to a PVC polymer matrix.
:'r~ The pre-treating step can usually be preformed in an internal mixer~ such , ;,s~ ~., - , ~ 10 as a Banbury rrixer~ ~rabender mixer~ CSI-MAX mixing extruder or on Roll mill.
- '~' The order of addition of material to the mixer is not critical. The mate-, ,, rials, PVC~ fiber~ bondlng at~ent. and other ingredient, can all be charged ~;~ 15 initially. The ternperature of mixing is a function of mixtures and equipments ~ used. In general~ the temperatures used in roll-mill are 10 to 15~C higher ''' ' 20 than that used in extruder~ The proportions of the ingredi,ents are dictated by the resulting composite properties. The amount of polymer used should be high enough to prevent fibre-to-fibre interaction~ usually at least 3 parts of PVC or polymer by weight per 100 parts by weight of wood fi,bers. Usua]ly~ no ~'~ more than 15 parts of PVC by weight per 100 parts of fibers by weight will be used~ although higher polYmer level can be employed if desired. The level of bonding agent(s) wlll normal]y range from about 0.5 parts up to 15 parts or more of bonding agent(s! hv weight per 100 parts by weight of fiber. In most instances~ it will be rlore convenient to include all of the bonding agent in ~- the treated fihers~ sin-e no further additi,ons of this ingredient need he - added in making ~he t'inal composlte~ Since the treatment step coats the surface of the fibers to a certain extent~ the polymer pre~sent in the Co,Jting wi,ll be in a position to he honded to the fibers. It appears also, tha~ some additional honding ot the ~:lher to PVC in the matrix is achieved dur-il-lg the :~:
composite forrnation. The composi,tes of' the invention are usuallv~ though not - necessarily~ rnade t'rom nol1-treated fibers compoun-led with pVl' with pre-rrli,Y
bonding agent.
In any case hr)wever, t:he bondinto~ agent of the present Invention rnllst he ,, 55 present in the recommended anount in orrler t,o achieve good adhesive bonding -,; between the fiber.s and the mat,rix.
Fibers. treated or not. arl~ mi,Ye(l with po],ymer mat:rix to fonn a composite ~, 60 -, usllally in an interlla~ n-ix~m~~ ~xtruder or on a rol1 nlill. Additiona], i,ngre-,: .
: ~ , ~:' A
L
~ i~
;, dients, such as fillers~ plasticizers, stabilizers, colorants. etc. can also ~'' be added at this point, Inorganic filler material may be selected from mica, '~~'~ 5 talc, CaC03, silica, glass flbers. asbestos or wollastonite.
The following speciflc examples illustrate the use of PMPPIC or others coupling as well as grafting a, ents for cellulosic fibers.
. ., , ~-: 15 eXAMPLE 1.
The wood pulp, chemitherrr.o-mechanical aspen pulp, having properties as ~ ~ 20 x~ f,~l~ described in Table 1. was predried i.n circulating air oven for 12 hours at . ~ ~
,- 65 C.
The polymer matrix~ PVC a.lreadv plasticized, supplied by Baron Caoutchouc ~~ Co., was pre-mixed at room temperature with 0.5 to 5% of polymethylene polyphenylisocyanate based on polymer weig~ht.
' ~:
Preparation of composites.
Mixing of polYrrler and fiber was done in CSI-max extruder, Model CS-194 with different weight percent3~oes (varying from lO to 507~) of cel]ulosic t~-ibers.
~:- The mixing temperatures used were hetween 140-150~C. The extruder composite was allowed to ('')G. down to room temperature and ground to mesh size 20.
The above prepared polvmer-r~iber Inixture was molded into the shoulder type test speciments (6-24 at the same time), in a mold~ which was covered b~ rnetal plates on both sides.
The weight of rrlater-ia] tor one specimen was 0.5 g when mo].ded at a tempera-':- 50 :'- ture of 160~C tor 25 rnillutes at a pressure of 2 . 7 MPi3 . l:he starting te~l~pera-ture was 93.3"C and coolln,. t~ waS 15 rninutes at pressure 0.5 ~Pa.
S5 The samples were tak-~n ~-ut ~ rorn t-h~ rnold after a 15 minnto cooling period and then allowed tn starld "t ll~ast 3 to 4 hours in the testing room which was Icept at 230C ancl 50~ re~atlve h~ iditv.
. 60 , g ,, - _ ; '' ,. ' ' 7 .,, q~
::
~ ~ ;3 ~
;~''.V ~
~ Mechanical tests . ~ ;, . .
Mechanical measurements were made on an Instrom tester (Model 4201) at 23~C
and 50% RH. The rate ot elongation was 100%/min in all cases. All samples -~, were 3.175 mm in width and B.4 cm in length (1.7 cm between grips~. The thickness of samples was usoallY 0.158 cm, ,~ 10 Dimensions of al] samp]es were measured with a micrometer. All experimen-tal data reported is an avera~e of at least four measurements.
:~
Mechanical properties reported for this work, are those measured usualy at maximum, break. stress proof point or otherwise specified. The properties.
-- measured using Instrom 4201. were automatically calculated by HP86B using the ~~- Instrom 4479-521 Plastic Tensile Test Program. The elastic modulus was ~ ,-measured at 0.1% strain. Average coefficients of variation for mechanical properties were as follows: stress, 3.5~0; strain, 5%; energy, 8.3%; modullls~
- ~, ~ 2.3%.
::
TABLE I
,: .
Properties Aspen CTMP pulp Drainage index (CSF). ml 119 Brightness, Elrepllo (%) 60.9 Opacity. (~o)91.4 Br,lklng 1ength~ km 4.46 longation~ 1.79 Tear index, m~.m2/g 7.2 Burst index~ kP,~.~n~/g 2.6 Yield, (~o! 92 Lignin, (%)17.9 :
~:
~ - 55 _ Tensile data are presented ~n Tab1e II.
~ 60 :--- . . . .
,~
:'' Y t It is quite obvious~ that the PMPPIC bonding agent lead to the increase of 5- strentgh properties as well as modulus. The stress values have increased from 2 MPa to 2.36 MPa when CTMP aspen fibers were used or to 7.7 MPa when the CTMP
aspen fibers were used with PVC and 2% PMPPIC, at 30% weight percent nf fiber addition. I'his enormous strength increase which indicated good adhesion and bonding between fibers and matrix was accompanied bY increase in modulus from h,44 MPa of PVC to 37 MPa when CTMP aspen were mixed with PVC and to 4~.7 MPa , 15 in case of 30% weight percent CTMP aspen fibers were mixed with PVC in which 2'~ weight percent of PMPPIC wer dispersed. It is interesting to see that the ' ~ " 20 energy has also increased from 0.032J for PVC 0.127J for PVC with 2% PMPPIC
- , and 30% of CTMP aspen fiber. Mesh 60.
' '-, ~-.
eXAMPLE II
The composites were prepared and evaluated as indicated in Example I but : . -aspen Kraft pulp~ Mesh ~0~ were used in place of CTMP Aspen pulp (Mesh 60).
- 35 The tensile data are represented in Table III.
-~ The tensile properties were evaluated at maximum values. at break as well - 40 as at stress proof point.
The tensile values of PVC composites of Aspen Kraft are compared to that of -~
PVC composite with 2% PMPPIC and aspen kraft pulp.
- 45 It is clear~ that there is verv positive effect of the presence of PMPPIC
especially on values of stress and modul1)s, At stress proof point. stress value of 3.25 MPa ïor E'V(, has increased to 3.~ ME~a for cnmposites without bonding agent but to ~ !n case when 2~ of PMPPIC were premixed with P~7C
hefore the addition of 30',~c ot' aspen 1<raft pnlp fibers.
In the case when the E'VC was premlxed with 0.7% of dioctylphtalate an-i 0.3~
of PMPPIC before fibers additinn there has heen also considerable impro~ement of stress and modulus. from 3.''5 MPa to f~.l MPa for stress and from 4.4v MPa to 58 MPa for modulus.
. . ,.~, _ - ~ ..
.~' ,...
~ '"~i'' . '.~
~i .
.3 -~ 7 ~:3 - eXAMPLE III
- The composites were prepared and eva]uated as indlcated in Example I. hut low -~ yield spruce sulphite pu]p (Mesh 60) were used in p]ace of CTMP aspen pulp (Mesh 60). The tensile results are presented in Table IV.
, -, The tensile properties improved particularly at stress proof point. Stress has increased from 3.25 MPa for PVC to 8.5 MPa for PVC premixed with 2% of ,,,,, 15 PMPPIC and 30~ low yield sulphite pulp.
:
'~; 20 , ~ EXAMPLE IV
,~ "
~ 25 The composites were prepared and evaluated as indicated in Example T, but .~
aspen sawdust (M60) was used instead of CTMP aspen pulp (M60). The tensile results are presented i,n Table IV. When compared to PVC the composites with aspen sawdust have shown improvement registered at stress proof point a,s far as stress is concerned as well as in case of modulus and energy, all at 30 ~, , weight percents of fibers present.
"
~,; 40 ~-~, EXAMPLE V
The composites were prepared and evaluated as indicated in Example 1~ but cotton cellulosic fibers (M~0) were used instead of CTMP aspen pulp (M601.
~- 50 The tensile resu],ts are presetlted at Table V for different percentagec "f bonding agent as well as fibers used.
Results show the pos3tive effect of renforcement of P~C by cel1ulosic fibers especial],Y in the preccllce of bolldillg agent. For example, at stress proof point stress has inrreace(l fl~om 3.25 MPa for PVC to 8.~S M~a for corlpos-ites in the presence of ~,i of PMPFIC arld rnodulus has increased from 4.i4 MF'ato 5.65 MPa.
~:- A
"'~,' .
;
,,~ . .
~S
. ' ,~
~, EXAMPLE VI
,, S
The composites were prepared and evaluated as indicated in Example I~ hut ':''' ' ' ,~," ~ PVC, identified by trade mark "GE0~ 110 x 334" of B.F. Goodrich. plasticized ~' 10 with 20% of diocty]phtha1ate was used in p]ace of PVC Baron Caoutchouc Company. The tensile properties. evaluated at maximum values. are presented ---- in Table VI and properties. eva]uated at yield point are presented in Table ~ 15 e~ VII. These results show signlficant improvement of composite properties when , bonding agent was used in weight percentages varying from 0.5 to 5% based on '"";' 20 polymer weight.
'' ;~' ' ~," 25 EXAMPLE VII
:
~- 30 The composites were prepared and evaluated as indicated in Example Vl~ but - the bondin~ isocvanate agent used was l,6 - hexamethylene diisocyanate ,,~~~ (HMDIC). The tensi,le properties are presented in Table VIII.
, The HMDIC lead to significant increases of stress as well as modulus at ~" stress values measured at stress proof point as well as at maximum. The ~; ., - , 40 stress values at stress proof point more then doubled and modulus. measured at 0.4% classification (at stress proof point) has increase from 368.4 MPa to 831 MPa.
, ~
EXAMPLE VIII
The composi,tes were prepared and evaluated as in Example I but 10~7 yiel( spruce sulphlte pulp was used ln place of CTMP aspen pulp and PvC. identitied , -~ by trade mark "GEUN 110 x 334" was used instead of PVC of Baron Caoutchouc Co.
The tensile properties are presented in Table IX. The good adhesiol-l in composites bonded by 0.'; of PMYPIC is demonstrated bY increases in ,ctress .. ,, ~ .
~ A
s ';3 3 ~ i -L :l :: ' ~ ,~
, measured at maximum, hreak as we]l as at stress proof pOillt (at 0.4~).
The stress has increased at SPP from 5.43 MPa to 13.6 MPa. modulus from 368.4 MPa to ~69 MPa and both elongation as well as energy at SPP at 30 weight percents of fiber presents have shown increases when compared to PVC, : .:
'~''~,'' ~; EXAMPLE IX
~i, 15 - The composites were prepared and evaluated as in Example I but vinyl : ..:
~ 20 chloride polymer used was PVC identified by trade mark "DALVIN 1467" of ; ~ ~ovacor Chemicals Ltd instead of PVC of Baron Caoutchouc Co.
The tensile properties are presented in Table X. The tensile properties 25 are compared between that of PVC, PVC with fibers and PVC + 0.52 of PMPPIC +
fibers. At 30~ of fibers presents, the stress measured at SPP increased from 30 original 6.4 MPa to 10.7 MPa (PVC + fibers) or to 11.8 MPa (PVC + PMPPIC +
flbers~. The modulus has increased from 305.4 MPa to 818 MPa or 814 MPa respectively. The presence of bonding agent lead to higher values of stress, elongation as well as energY when cornpared to composites without PMPFIC at maximum as well as at break va]ues.
Although the fore~,oing invention has been described in come details by the f way of examples for purposes of clarity of understanding, it will be obvious _- ~ that certain changes and modification may be practiced within the scope of the ~ 45 appended claims.
::~,, "
" 50 : , ~ 14 . . , -A
TABLE II
SAMPLE FORCE (N) STRESS (MPa) ENERGY (J) STRAIN (%) MODULUS (MPa) ~ of fiber~ 10 20 30 10 20 30 10 20 30 10 20 30 10 20 30 P~C __ 9.7 _ _ _ 2.0 ___ _ 0.032 _ _ 20 __ _ _ __ 4.44 _ _ PVC+FIBER
CTMP-ASPEN j.l4 12.g6 13.61 1.87 2.3 2.36 0.018 0.0hl 0.064 20 11.0 17.3 37.0 CTMP-ASPEN 16.70 27.40 39.20 3.60 5.90 7.70 0.038 0.058 0.072 20 17.2 32.6 49.7 + 2% PMPPIC
u~ CTMP-ASPEN 20 5 32.16 35.80 4.10 6.40 7.40 0.046 0.069 0.127 20 18.7 39.8 78.3 + 8% PMPPIC
CTMP-ASPE~
+ 1% DOP 15.124.90 28.30 3.30 5.40 6.10 0.047 0.067 0.078 20 14.0 30.0 49.0 PMPPIC
CTMP-ASPEN
0 S~. 15-924.03 30.53 3.27 4.87 6.486 0.039 0.0i0 0.119 20 13.6 30.0 51.() ~_ PMPPIC ~~
PVC..... vinyl chloride polymer. plasticized by Baron Caoutchouc Co. ~C~
Tensile properties ~easured at 20% of elongation. _~
DqP..... dioctylphtAlate. r !
TABLE III
COMPOSITE STRESS (MPa) MODULUS (MPa) ELONGATION (%) ENERGY (J~
% ~f 10 20 30 10 20 30 10 2030 10 20 30 tlbers AT .AX 13.12 4.44 439 2.90 PVC AT B~EAK 12.65 444 2.93 AT STRESS
PROOF POINT 3.25 " 17.1 0.033 p~ ~ AT MAX~1.8l 6.46.0 l~.2 34.2 54.4241 12644.71.33 0.53 0.1~3 ASPEN AT BREAK 9.25.3 3.5 " 248132 52 1.39 0.6 0.2 KRAFT PULP AT SPP1.92 2.33.'3 " 6.15 4.8 6.10.011 0.010 0.017 PVC + 2% AT MAX10.8 12.011.4 19.234.5 51.2143 6035 0.340.42 0.23 + ASPEN AT BREAK9.7 10.49.2 " 151 6738 1.010.48 0.26 KRAFT PULT AT SPP4.3 5.16.2 " 17.4 11.8 10.g0.042 0.034 0.038 PVC t 0.7% DOP AT MAXlO.l 12.29.4 17.539.7 58 140 5225 0.860.36 0.14 + ASPEN AT SPP3.8 6.56.1 " 15.8 13.8 9.70.035 0.047 0.034 KRAFT PUt.P
PVC.... vinyl chloride poly~er, plasticized by Baron Ca~utchouc Co.
DOP.... dioctYlphtalate i--TABLE IV
COMPOSITE STRESS (MPa) MODULUS (MPa) ELONGATION (%) ENERGY (J) % ~f 10 2030 10 20 30 10 20 30 10 20 30 fibers AT MAX 13.12 4.44 439 2.9 AT BREAK 12.65 4.44 444 2.93 PVC
AT STRESS
PROOF POINT 3.25 4.44 17.1 0.033 AT MAX10.2 12.615.2 21.1 36.5 69 137 5S 38.60.~5 0.414 0.330 PVC ~ 2% PMPPIC
+ LOW YIELD AT BREAK 8.410 14.2 " 144 66.544.1 0.91 0.49 0.36 SULPHITE P~LP
AT STKESS
PROOF POINT 3.0 6.5 8.5 " 10.3 14.3 11.8 0.021 0.047 0.052 PVC + 5% AT MAX 7.8 7.59.3 11.4 20.6 65 170 88 42 O.Y17 0.49 0.27 SAWDUST (M60) 6.8 6.1 7.6 " 178 101 49 0.98 0.58 0.33 AT SPP 2.1 2.45.5 " 11.2 8.6 11.9 0.02 0.018 0.042 PVC.... vinyl chloride polymer, plasticlzed by Baron Caoutchouc Co.
TABLE V
COMPOSITE STRESS (MPa) MODULUS (MPa) ELONGATION (%) ENERGY (J) % of ibers 10 20 30 10 20 3010 20 30 10 20 30 AT MA.Y 13.12 4.44 439 2.9 AT BREAK 12.65 " 444 2.93 pVC
AT STRESS
PROFF POrNT 3.25 " 17.1 0.033 AT ~X. 9.7 7.9 6.3 16.3 34 44.3214.5145.559.3 1.2 0.8 0.25 PVC
+ COT'rON AT BREAK9.0 6.9 5.1 " 221153 69.7 1.22 0.8 0.3 (~160~
AT SPP 2.4 3.1 3.8 " 8.76.6 6.6 0.016 0.015 0.018 PVC + 2% AT MAX.10.312.1 14.5 16.2 30.1 54 16474.3 49.3 1.011 0.52 0.41 PMPPIC
+ COTTON AT BREAK9.2 10 12.4 " 17285.2 53.3 1.07 0.62 0.46 (MhO) AT SPP 3.8 4.4 5.8 16.612.2 10.4 0.037 0.033 0.038 PVC + 5~ AT MAX.11.212.3 15 20.8 34 56.5131.365.441.0 0.883 0.4h 0.34 PMPPLC
+ COTTON AT BREAK10.110.713.6 " 141.672.343.6 0.97 O.S3 0.37 (M60) AT SPP 3.9 5.0 8.8 " 15.412.3 14.5 0.036 0.036 0.063 ~_~
PVC.... vinyl chloride polymer, plasticized bv Baron Caoutchouc Co.
;_~
, . ...... . .. .
TABLE VI
COMPOSITE % OF FORCE (N) STRESS (MPa) MODULUS (MPa) PV~ 127.75 _ _ _ __ 24.4 _ 368.4 CTMP-ASPEN (M60~ 89.7 83.5 98.4 18.2 17 20.3 569 670.9 912 CTMP-ASPEN t 0.5~0 104.1 130.2 133.8 21,4 27 27.5 401 718 782.9 PMPPTC
CTMP-ASP~N + 1% 105.3 127.8 134.7 21.4 25.9 27.3 398 742 808 PMPPIC
_ CTMP-ASPEN 3% 109.3 122.7 128.4 22.12 24.9 25.9 474 568 662 _~ PMPPIC
CTMP-ASPEN 5% 116.3 136.2 150.0 22.5 26.14 28.7 427 664 852 PMPPIC
*CTMP-ASPEN 1.84% 131136.4 124.8 25.2 27.1 24.5 608 636 594 PMPPIC
*CTMP-ASPEN 4.61~ 95.8 - 142.7 19.6 - 29.3 288 _ 871 *Molding time: 20 minutes instead of 15 minutes. ~_~
PVC of B.-F. Goodrich identified by trade mark "GEON 110 x 334", plasticized with 20% of dioctylphtalate. , Tensile properties measured at ~aximum.
.. .. _ . _ TABLE VII
COMPOSITE FORCE (N) STRESS (MPa) ENERGY (J) STRAIN (%~ MODULUS (MPa) % ~f 10 20 3010 20 30 10 20 30 10 20 3010 20 30 fibers PVC-~IBER
'-PVC-PURE 49.19 _ 10.25 0.030 5.51 _ 368.4 CTMP-ASPEN 83.3 36.2 88.0 16.9 l7.5 21.0 0.048 0.040 0.036 5.64 5.22 3.44 585 670 924 CTMP-ASPEN-~ 0.5l/o 50 ~5 110 10.3 17.5 Y2.7 0.026 0.031 0.05~ 4.18 3.55 3.52 397 790 791 PMPPIC
Q~
c CTMp-AspEN
~ 1~ 48 31 82 9.8 18.6 16.6 0.023 0.039 0.030 4.05 4.08 2.9 388 743 808 PMPPIC
CTMP-ASPEN
+ 3% 62.6 73.8 87.5 12.7 14.3 17.7 0.040 0.046 0.054 5.0 5.0 5.0 460 5~2 652 PMPPIC
CTMP-ASPEN
+ 5% 57.7 82.5 110.6 11.2 15.8 21.2 0.036 0.05 0.068 5.0 5.0 5.0 ~27 599 ~l7 PMPPIC
pVC of B.-F. Goodrich, identified by trade mark "GEON 110 x 334" with 20% of di-octylphtalate ~-~
Properties measured at yield point.
\
TABLE VIII
COMPOSITE STRESS (MPa) MODULUS (MPa) ELONGATION (%) ENERGY (J) % ~f 10 20 30 10 20 3010 20 30 10 20 30 fibers AT MAX. 24.4 368.4 145.8 2.37 AT BREAK 21.0 " 149.8 2.S5 PVC
AT STRESS
PROOF POINT 5.43 " 1.31 0.006 PVC + 0.5~ AT MAX 13.2 21.2 24.4 146 670 831 82.3 12.8 8.6 0.78 0.19 0.14 HMDIC AT BREAK 11.6 17.3 22.8 " 86.8 21.2 10.5 0.81 0.33 0.18 + CTMP
of ASPEN AT STRESS
PROOF POINT 2.910.7 12.3 " 1.1371.447 1.363 0.003 0.011 0.012 -'iModulus measured at 0.4% of elon~ation.
PVC of B.-F. Goodrich, identified by trade mark "GEON 110 x 334", plasticized with 20% of dioctylphtalate.
HMDIC.... 1,6 - hexamethylene diisocyanate.
C~
'~;.
TABLE IX
COMPOSITE STRESS (MPa) MODULUS* (MPa) ELONGATION (%) ENeRGY (J) % ~f 10 20 30 10 20 30 10 20 30 10 20 30 flbers AT MAX. 24.4 368.4 145.8 2.37 PVC AT BREAK 21.0 " 149.8 2.45 AT STRESS
PROOF POINT 5.43 " 1.31 0.0()~
PVC + 0.5~ AT MAX.19.1 27.1 30.6 324 841 969 60.2 21 13.7 0.73 0.40 0.28 PMPPIC AT BREAK 16.9 25.3 29.3 " 66.7 26 15.3 0.88 0.51 0.32 SULPHITE AT STRESS
PULP PROOF POINT 5.1 12.8 13.6 " 1.32 1.52 1.39 0.05 0.013 0.013 *Modulus measured at 0.4% of elongation.
PVC.... vinyl chloride polymer identified by trade mark "GEON 110 x 334" of B.-F. Goodrich plasticized with 20% of dioctylphtalate.
' I .
TABLE X
'~
COMPOSITE STRESS (MPa) MODULUS* (MPa) ELONGATION (%) ENERGY (J) % ~f 10 20 30 10 20 30 10 20 30 10 20 30 flbers AT MAX. 24.7 305.4 129 2.037 PVC AT BREAK 21.6 305.4 133.2 '.117 AT STRESS
PROOF POINT 6.4 305.4 2.27 0.00-1 AT MAX.17.5 "O 18.2 287 765 818 84.7 5.0 4.7 1.058 0.064 0.053 PVC
+ CTMP ASPENAT BREAK 14.5 11.3 13.2 " go 12.2 8.7 1.134 0.173 0.07 AT SPP4.4 10.7 10.7 " 1.335 1.378 1.320 0.005 0.011 0.011 PVC + 0.5% AT MAX.19.123.h25.3 211 726 814 82.4 23.7 11.8 0.99 0.40 0.20 PMPPIC AT BREAK15.821.724.3 211 726 814 87 27 12.7 l.06 0.45 0.22 + CTMP ASPEN AT SPP 3.6 10.3 11.8 211 726 814 1.3 1.37 1.41 0.004 0.01 0.012 *Measured at 0.4% of elongation.
PVC.... vinyl chloride polymer identified by trade mark "Dalvin 1467", Novacor Chemicals Ltd, viscositv O.g2, K value: 67 plastified with 20% of dioctylphtalate. ~_~
.. ...
Claims (11)
1. A composite comprising from 1 to 50% of discontinuous wood cellulose fibers dispersed in polyvinylchloride being bonded to each other by 0.1 to 10% by weight based on the total composition of linear polymethylene polyphenylisocyanate or 1,6-hexamethylene isocyanate, the composite optionally further including up to 50% by weight (based on the total composite) of plasticizer or inorganic filler or combination of plasticizer and inorganic filler.
2. A composite according to claim 1 wherein the fibers are pretreated by precoating with a material of the matrix.
3. A composite according to claim 2 wherein fiber material of the precoated fibers is up to 50% by weight of the total composite.
4. A composite according to claim 1, claim 2 or claim 3 wherein the cellulosic fibers are from hardwood or softwood pulps or their mixtures.
5. A composite according to claim 1, claim 2 or claim 3 wherein the cellulosic fibers are from wood flour, sawdust or shavings or their mixtures.
6. A composite according to claim 1, claim 2 or claim 3 wherein the fibers have a fiber aspect ratio from 2 to 150.
7. A composite according to claim 1, claim 2 or claim 3 wherein the inorganic filler of claim 1 is present and is mica, talc, calcium carbonate, silica, glass.
8. A composite according to claim 1, claim 2 or claim 3 wherein the cellulosic fibers are 40% by weight of the composite and the bonding agent is present at 7.5% by weight based on the cellulosic fibers.
9. A composite according to claim 1, claim 2 or claim 3 wherein the cellulosic fibers are 30% by weight on the composite and the bonding agent is present at 5.5% by weight based on the cellulosic fibers.
10. A treated discontinuous wood cellulosic fiber treated with polyvinylchloride containing 0.5 to 15% by weight, based on the fiber, of 1,6-hexamethylene isocyanate or linear polymethylene polyphenyl isocyanate, the weight ratio between polyvinylchloride and fiber being not higher than 15:100.
11. A compression or an injection molding made from a composite of any one of claims 1 to 10.
D
D
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 513361 CA1339711C (en) | 1986-07-09 | 1986-07-09 | Composites of cellulosic fibers and vinyl chloride polymer bonded by an isocyanate bonding agent |
| GB8705045A GB2192398B (en) | 1986-07-09 | 1987-03-04 | Composites of cellulosic fibres and vinyl chloride polymer bonded by an isocyanate bonding agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 513361 CA1339711C (en) | 1986-07-09 | 1986-07-09 | Composites of cellulosic fibers and vinyl chloride polymer bonded by an isocyanate bonding agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1339711C true CA1339711C (en) | 1998-03-17 |
Family
ID=4133526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 513361 Expired - Fee Related CA1339711C (en) | 1986-07-09 | 1986-07-09 | Composites of cellulosic fibers and vinyl chloride polymer bonded by an isocyanate bonding agent |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1339711C (en) |
| GB (1) | GB2192398B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3134580A1 (en) * | 2022-04-19 | 2023-10-20 | Valoops | extrudable composition containing PVC and cotton fibers – material and associated products |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2178036C (en) * | 1995-06-07 | 2008-09-09 | Kasyap V. Seethamraju | Advanced compatible polymer wood fiber composite |
| AU2003250844A1 (en) * | 2002-06-24 | 2004-01-06 | Fagerdala Deutschland Gmbh | Method for producing parts from high-grade lignocellulose fiber-filled thermoplastics |
| US7390846B2 (en) | 2004-11-30 | 2008-06-24 | Crompton Corporation | Wood sizing agents for PVC composites |
| RU2527468C1 (en) * | 2013-05-16 | 2014-08-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Казанский государственный архитектурно-строительный университет" КГАСУ | Method of producing highly filled polyvinyl chloride-based wood-polymer composition |
| CN109206769B (en) * | 2017-06-16 | 2022-06-28 | 合肥杰事杰新材料股份有限公司 | Rice hull powder modified regenerated polyvinyl chloride composition and preparation method thereof |
| CN109233134A (en) * | 2017-07-10 | 2019-01-18 | 合肥杰事杰新材料股份有限公司 | A kind of PVC modified composite material and preparation method of regeneration |
| CN109721878A (en) * | 2017-10-31 | 2019-05-07 | 合肥杰事杰新材料股份有限公司 | A kind of wood powder modification regeneration polychloroethylene composition and preparation method thereof |
| CN109721867B (en) * | 2017-10-31 | 2022-07-12 | 合肥杰事杰新材料股份有限公司 | Regenerated polystyrene modified composite material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3943079A (en) * | 1974-03-15 | 1976-03-09 | Monsanto Company | Discontinuous cellulose fiber treated with plastic polymer and lubricant |
| 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 |
| US4414267A (en) * | 1981-04-08 | 1983-11-08 | Monsanto Company | Method for treating discontinuous cellulose fibers characterized by specific polymer to plasticizer and polymer-plasticizer to fiber ratios, fibers thus treated and composites made from the treated fibers |
| DE3279475D1 (en) * | 1981-12-21 | 1989-04-06 | Dow Chemical Co | Composite panels derived from scrap plastics |
-
1986
- 1986-07-09 CA CA 513361 patent/CA1339711C/en not_active Expired - Fee Related
-
1987
- 1987-03-04 GB GB8705045A patent/GB2192398B/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3134580A1 (en) * | 2022-04-19 | 2023-10-20 | Valoops | extrudable composition containing PVC and cotton fibers – material and associated products |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2192398A (en) | 1988-01-13 |
| GB2192398B (en) | 1990-02-14 |
| GB8705045D0 (en) | 1987-04-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |
Effective date: 20140317 |