CA1340707C - Cellulose based fibers and bonded composites of the fibers in vinyl chloride polymer characterized by a silane bonding agent - Google Patents

Abstract

Cellulose fibers are treated with silane bonding agent or silane bonding agent and peroxyde. Composites are made from cellulose fibers dispersed in a matrix of plasticized vinyl chloride polymer, and bonded thereto with silane bonding agent. The composites can be molded or extruded to produce useful articles.

Description

CELLULOSE BASED FIBERS AND BONDED COMPOSITES OF THE FIBERS

This invention relates to composites of cellulose based fibers dispersed in a matrix of vinyl chloride polymer and to treated cellulose fibers which have improved disperability into polymer and improved adhesion thereto. More specifically, it relates to such reinforced thermoplastic composites which have good strength a:nd moulding characteristics and are derived from readily available cheap component.
The published literature includes a number of proposals which teach preparation of comF~osites which consist essentially of thermosetting or thermoplastic resinous matrix materials having dispersed therein inorganic reinforcing fillers, such as mica platelets or flakes. Such materials are described, for example, in U.S. Patent number 3,764,456 Woodhams issued) Oct.
9) 1973; and :in U.S. Patent 4,442,243 which describes such mica-reinforced thermoplastic composites having improved durability, physical and aesthetic Properties which are ~arepared by mixing the resin and the mica in the presence of propylene polymer was. The mica may be pretreated to provide functional groups thereon for subsequent chemical reaction with the propylene polymer wax.
The use of inorganic fillers such as mica does however present certain technical difficulties. Mica is a difficult material to process in making such composites. I1;. is abrasive by nature) so that it tends to wear out processing machinery which it contacts.
The published literatures certain references to the use of cellulosic fillers as additives for both thermoplastic and thermosetting resins. Such fillers may be derived from the finely ground products of wood pulp, the shells of peanuts or walnuts) corn cobes, rice hulls) vegetable fibers or 134U~07 certains bamboo-type reeds or grasses.
The great abundance and cheapness of such cellulosic materials in every part of the globe ha:> made these cellulosic materials attractive sources for producing useful fillers for plastics. Although the use of cellulosic fillers in thermoset resins (ouch as the phenolics) has been an accepted practise for '.
many years, their use in thermoplastics has been limited mainly as a result of difficulties in dispersing the cellulose particles in thermoplastic melts, poor adhesion (wettability) and in consequence inferior mechanical properties of the molded composites.
It has been shown that the dispersion of discontinuous cellulose based fibers into polymeric matrix can be greatly improved by pretreatment of the fibers with a plastic: polymer and a lubricant) U.S. Patent number 3,943,079 to Hamed described such pretreatment. Goettler in U.S. Patent number 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 dilsocyanate can be molded or extruded to produce useful articles.
Coran et al., U.S. Patent number 4, 323,625 have shown that the composites can be produced from grafted olefin polymers and cellulose fibers. The Polyolefin have been grafted with other polymer carrying methylol phenolic groups before being combined with cellulosic fibers and bonding agent such as phenol-aldehyde resin., a polyisocyanate or the like.
Lachowicz et al.) iJ.S. Patent number 4,107,110 described that a-cellulose fibers, coated with a graft copolymer comprising 1,2 - polybutadiene to which an acrylate such as buthylmethacrylate is grafted could be used in reinforcing of PE and other plastic compositions.
Fujimara et al., Jap. Patent Kokai 137,243178 also describe a cellulosic material, which has been acetylated with gaseous acetic anhydride as a reinforcing agent for polyo:lei'ins.
Gaylord) U.S. Patent :number 3,485,777 (1969) describes compatibilization of polyvivylchloride or polymethylmethacrylate with grafted cellulose.

1340~10~
Gaylord, U.S. Patent number 3,645,939 also shows that polyethylene or polyvinylchloride or acrylic rubber can be compatibilised with cellulosic fibers in the presence of an ethylenically unsaturated carboxylic acid or anhydride under conditions which generate free radicals on said polymers) whereby said ethylenically unsaturated carboxylic acid or anhydride reacts with and couples with thermoplastic polymer and cellulose.
Hse, U.S. Patent number 4,209,433 have treated wood material with polyiso-cyanate before mixing with thermosetting phenol formaldehyde resin.
Lundl and ai.) U.;i. Patent number 4,241,133 mixed elongated wood flakes with binder (e.g, polyisocyanate) and than hot-pressed into the form of an elongated structural member as a beam, post) etc.
Wadeson) Brit. Patent number 1,585,074 describes process to manufacture cellulose-polyurethane material by reaction of fibrous cellulosics with impregnated polyisocyanates in the presence of catalyst (zinc octoate).
Nakavishi et al.) Jap. Patent Kokai 76 97648 describe the use of cellulo-sics ini PP. Theiysok:n et ai.) Ger-Offen 291 6657 presents heat resistant PP
molding composition. Suriyama et al., Jap. Kokai 79 72247 introduces heat treated wood filler for thermoplastics. Also Dereppe et al., Ger. Offen 263 5957 as well as Kishikawa et al., Jap. Kokai 73 45540 describe filler rein-forced polypropylene.
In summary) we believe to be the first to prepare composites of polyvinyl-chloride and discontinuous cellulosic fibers in the presence of small amount of silane bonding agemt. These composites are having good strength) molding characteristic and are derived from readily available cheap components.
SUMMARY OF THE INVENTION
It has now been found that the cellulosic fibers can be well compatibilize with a matrix formed by vinyl chloride polymer and the adhesion to cellulosic fibers to a matrix can be substantially improved by improving the interfacial -~ 13t~0'7 ~ 7 adhesion by pretreatment of the filler with a conventional silane coupling agent alone or even better in combination of silane coupling agent in the presence of a free-radical source.
According to pre;~ent invention) composites are made of discontinuous cellulosic fibers) pre-reacted with silane bonding agent identified by following trade marks like "A-174" or "A-172" or "A-1100" of Union Carbide Corporation) without or in the presence of peroxide like benzoylperoxide or butylperoxide or dicumylperoxi.de.
Composites containing from 1 to 60% of cellulosic fibes by weight) based on the total weight of composite are within the scope of convention.
The silane coupling agent identified by the following trade marks "A-174"
(gramma - Methacrylo:!cy-propyltrimethoxy silane) or "A-172" (vinyltri (2 -methoxyethoxysilane) or "A-1100" (gamma-aminopropyltriethoxysilane) without or in the presence of free-radical source is forming a strong adhesive bond with wood fibers and possibly with vinylchloride polymer matrix and thus provide the composite which ha.s improved strength and stiffness.
The bonding agent ihas been found to be effective at relatively low concen-trations - as low as 0.1 parts by weight on 100 parts of the vinylchloride polymer in the matrix. The free-radical source is used at concentration from 0.1 to 3 parts by weight based on 100 parts of the vinylchloride polymer.
The invention also includes treated (precoated) discontinous cellulosic fibers with aspect ratio varying from 2 to 5 (sawdust); from 12 to 50 (high yield and ultra high yield pulps) and from 50 to 150 (for low yield chemical cellulosic pulps) bonded chemically with one to ten parts of vinyl chloride polymer based on fiber weight in the presence of U.5 to 10 parts of anhydride, 0.1 to 5 parts of peroxide and from 0.1 to 4 parts of silanes) all weight parts related to 100 weight parts of filler.
It has been also mound that discontinuous cellulosic fibers, when pre-coated with polymer gives better adhesion when incorporated with vinyl certain bonding agent.
chloride polymer matrix if the polymer coating includes a small amount of B-L

1340'~0'~
The later material has also an excellent dispensability with vinyl chloride polymer matrix.

134070' DIETAILED DESCRIPTION OF THE INVENTION
The cellulosic material used in the invention includes cellulosic fibers derived from solfwood or/and hardwood pulps, e.g, chemical or mechanical or chemi-mechanical or refiner or stone groundwood or thermo-mechanical or chemi-thermomechanica.l or explosion or low yield or high yield or ultra high yield pulp, nut shells, corn cobs) rice hulls) vegetable fibers, certain bamboo-type reeds, grasses) bagasse) cotton) rayon (regenerated cellulose), sawdust, wood flour, wood shavings and the like.
Preferred are cellulosic fibers derived from wood sawdust, wood flour) wood pulps, e.g, mechanical pulps or chemi-thermomechanical aspen pulps. There are many available types of wood pulp which may be classified according to where they were derived by chemical or mechanical or thermal treatment or combina lion of treatments as. well known in the pulp and paper industry. Waste pulp and/or recycled pulp can also be used. The fibers have an aspect ratio (length divided by diameter) ranging from 2 to 5 for sawdust, wood flour as well as for mechanical pulps and 15 to 50 for chemi-mechanical and chemi-thermomec:hanical pulps and 50 to 150 for low yield chemical pulps (e.
g.
kraft) soda or bisulfite).
In some instances, it is desirable to use mixtures of fibers having widely different aspect ratios.
The polymer contained in the matrix is described as being "vinyl chloride polymer" and includes both vinyl chloride polymer and copolymer of a major proportion of vinyl chloride polymer with minor proportion of other copoly merizable monomers such as vinyl acetate or vinylidene chloride.
The plasticizer which can be contained in the matrix should be one which is compatible with the vinyl ch:Loride polymer as described. Examples of effec-live plasticizers include adipates) such as di-2-ethylhexyl adipate and diisodecy'1 adipate; a.?elates) such as di-2-ethylhexyl azelate; benzoates, such as dipropylene glycol dibenzoate; phosphates, such as tricresyl phosphate .._ :."

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cresyl diphenyl phosphate) 2-ethylhexyl diphenyl phosphate, di-n-octyl phenyl phosphate) and tri-n~-hexyl phosphate; phtalates, such as diethylphtalate) butyl benzyl phtalate) di-2-ethylhexylphthalate) and diisodecyl phtalate) di-2-ethylhexylphth.alate) and diisodecyl phthalate; sebacates) such as di-2-ethylhexyl sebaca~te and terephthalates such as di-2-ethylhexyl terephtha late. A compatible blend of two or more plasticizers can be used. In use) the plasticizer has the effect not only on softening and modifying the polymer) but also of lubricating the fiber surface) promoting dispersion and minimising fiber breab:age.
The cellulosic based fibers are described as "discontinuous" to distinguish from the well known incorporation of continuous cord reinforcement into rubber and plastic articles. The "matrix" is the material forming a continuous phase which surrounds the fibers. A "composites" is the combination of disconti nuous fibers in a matrix wherein the contained fibers may be randomly orient-ed) or) to a greater or lesser degree, aligned in a particular direction.
Silane coupling agents) R'Si (OR)3 which can be used in this invention) are characterized by dual functionality: R' represents an organo-functional group (such as amino) merca~pto, vinyl) epoxy, or methacrylate) and OR represents a hydrolyzable group attached to silicon. R' is usually bonded to the silicon atom by a short alkyl chain.
In use) the alkoxy groups hydrolyse to form silanols that react with (or otherwise condense in the presence) of filler or fiber surface. At the other end of the silane coupling agent molecule, the functional organic groups (such as vinyl, epoxy, and amino) react with the organic matrix resin. The coupling agent may be applied 1to the filler in a separate pre-treatment step or it may be added to the polymer during compounding. In general) improved processing is obtained with pretreatment.
The following sil;rne coupling agents identified by the following trade marks: "A-174", "A-172") "A-1100") "A-151", "A-186", "A-187") "A-189", "A-1120" and "A-1160" can be used in the scope of this invention.

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The bonding agent "A-174" has the formula:

l II
CHz = CH - C - OCH2 CHz CH2 Si (OCH,)3 gamma - Methacrylaxypropyltrimethoxysilane Silane "A-172" has the following structure:
CH2 = CH - Si (OCz H4 OCH3)3 Viny:Ltri (2 - rnethoxyethoxy) silane Silane "A-1100" of Union Carbide as gamma - Aminopropyltriethoxysilane having the formula:
H2 NC, H6 Si (OCHz CH,)3 Silane "A-151" of Union Carbide, vinyltriethoxysilane having the formula:
CH2 = CH Si (OCHZ CH,), Silane "A-186" of Union Carbide) beta - (3,4 - Epoxycyclohexyl) ethyltrime thoxy silane of formula:
i\
- CHI CH2 Si (OCH,), Silane "A-187" of Union Carbide) gamma-glycidoxypropyl-trimethoxysilane of formula:

CHa - CH CH2 OCH2 CHz CH2 Si (0CH3)s Silane "A-189" of Union Carbide, gamma - Mercaptopropyltrimethoxysilane of formula:
HSCH2 CHz CH2 Si (OCH3)s Silane "A-1120" of Union Carbide) N-beta - (Aminoethyl) gamma - aminopropyl-trime toxysilane of formula.:
H, NC2 H4 NHC3 H6 Si (OCH3)a Silane "A-1160" of Union Carbide, ureido - modified amino coupling agent in solution of formula:

NH2- CNHC3 H6 Si (OCH, CH,), The bonding agent :is used in the composites of the invention in sufficient amount to achieve an adhesive bond between the vinyl chloride polymer and the cellulosic fiber. This amount can be as little as 0.1 part by weight up to 5 parts by weight. based on 100 parts by weight of fiber. The amount of bonding agent required can also be expected to vary with the amount of cellulosic fibers present. The free radical source among others is benzoylperoxide or dicumylperoxide or d-tert-butyl peroxide in proportion varying from 0.1 to 5 parts by weight related to 100 weight parts of filler.
The coupling may bf~ applied to the filler in a separate pre-treatment step or it may be added directly to the resin during compounding. In general improved processing is obtained with pretreatment in the presence of peroxide.
Alternatively) the bonding agent may be combined with the cellulosic base fiber in pretreatment and precoating step. Following the idea of Gaylord U.S.
Patent number 3,645,9'.!9 the fibers can be grafted with a silane bonding agent so as to enhance their dispersability into a composite by admixture thereto of organic polymer which can be processed as thermoplastic in an amount suffi d ent to reduce fiber-to-fiber affinity. Preferably) the organic polymer is vinyl chloride polymer) although other compatible polymer having solubility parameters at midpoint of range within one unit of that of vinyl chloride polymer can be used. The precoating step is divided on prereacting of silane with ceilulosic fibers, in the presence of peroxide prereacting of 3 to 10 1.340707 weight parts of vinyl chloride polymer based on 100 parts weight of fiber) with 1-3 parts of arnsaturated anhydride of bicarboxylic acid (e. g. malefic anhydride) in the presence of 1-3 parts of peroxide) (e. g, dicumyl peroxide, benzoylperoxide, methylethylketone peroxide, di-t-benzyl peroxide, and 2,5-dimethyl-2,5i-di(tbuty:L peroxide hexane)) followed by combining the products from the prereacting steps (cellulosic fibers silane treated +
carboxylated polymer). Resulted precoated cellulosic fiber show excellent dispersability in polymeric matrix.
The ethylenically unsaturated carboxylic acid or anhydride coupling agent used in the practise of this invention is preferably dicarboxylic on such as malefic acid or anhydride fumaric acid) citraconic acid, or itaconic acid.
Malefic anhydride is the preferred coupling agent. Monocarboxylic acids, such as acrylic acid and methacrylic acid, may also be used.
In addition to peroxides mentionned above a more detailed compilation of free radical initiators which may be used is set forth at pages II-3 to II-51 of "Polymer Handbook", Interscience Publishers (1966).
The combining of prereacted product can be accomplished in an internal mixer) such as a Banbury mixer, Brabender mixer) CSI-Max mixing extruder or on Roll Mill. The temperature of mixing is a function of mixtures and equipement used. The proportions of the ingredients are dictated by the resulting composite properties. The amount of polymer used should be high enough to prevent fiber to fiber interaction) usually at least 3 parts of vinyl chloride Polymer by weight per 100 parts by weight of cellulosic fibers. Usually, no more than 10 parts of vinyl chloride polymer by weight per 100 parts of fibers by weight will be used, although higher polymer level for fiber precoating can be employed if desired.
The fibers pretreated with silane or the one precoated with polymer are mixed with polymer matrix to form a composite usually in an internal mixer) extruder or an a roll mill. Additional ingredients) such as fillers) plas-ticizers) stabilizers, colorant etc, can also be added at this point.
The following specific examples illustrate the use of silane coupling agent si .--134070?
for cellulosic fibers.

EXAMPLE
I

Materials:Plasticized vinyl polymer, supplied by Baron Caoutchouc chloride Co..

The chemithermomechanical pulp of aspen or birch used,in this work was prepared a Sund Defibrator in and have the properties described in Table 1.

Properties Aspen CTMP pulp Drainage index (CSF),119 mi ,rightness, Elrepho 60.9 (%) ~pacity) (%) 91.4 Breaking length, km 4.46 Elongation, (%) 1.79 Tear index, mN.rn2/g 7.2 Burst index, kPa.m2/g2.6 Yield) (%) 92 Lignin) (~.) 17.9 -x::

-- ~~~0707 Coupling agents:
i- Vinyltri (2- Methoxy Ethoxy) Silane CH2 = CH - Si (0 CZH4 0 CH,), known as "A-172"
ii- Gamma - Methacryloxy - Propyltrimethoxy Silane CH, = C - C - OCHz - CH2 - CH2 - Si (OCH3)3 known as "A-174"
25 iii- Gamma - Amino Propyl Triethoxy Silane H2N - C,HE, - Si (0 CHz - CH3), known as "A-1100"
were supplied by Union Carbide Co.) Montreal.
BONDING OF FIBERS WITH SILANES "A-172" AND "A-174"
a) 20 g of fibers, si;:e Mesh 60) placed in 500 ml flask with 150 ml of carbon tetrachloride and (0.8-2~) of peroxide based on oven dried pulp, followed by addition of 1 to 4,°6 bw weight of silane "A-172" or silane "A-174".
The whole mixture was heated to reflux at 70-75°C while agitated by magnetic stirrer for 3 hrs. After cooling, CC14) was evaporated and mixture was dried at 55°C for 24 hrs.
Preparation of com osites Mixing of polymer and fiber' was done in CSI-max extruder, Model CS-194 with different weight percentages (varying from 10 to 50~) of cellulosic fibers.
The mixing temperatures used were between 140-150°C. The extruded composite was allowed to cool down to room temperature and ground to Mesh size 20.

134Q'~07 The above prepared polymer-fiber mixture was molded into the shoulder type test specimens, (6-24 at the same time)) in a mold, which was covered by metal plates on both sides.
The weight of mate:cial for one specimen was 0.9 g when molded at a tempera ture of 160°C for 25 minutes at a pressure of 2.7 MPa. The starting tempe rature was 93.3°C and cooling time was 15 minutes at pressure 0.5 MPa.
The samples were taken out from the mold after a 15 minute cooling period and then allowed to stand at least 3 to 4 hours in the testing room which was kept at 23C and 50% relative humidity.
Mechanical Tests Mechanical measurements were made on an Instron tester (Model 4201) at 23°C
and 50% RH. The rate of elongation was 100%/min in all cases. All samples were 3.175 mm in width and 6.4 cm in length (1.7 cm between grips). The thickness of samples Haas usually 0.158 cm.
Dimensions of all samples were measured with a micrometer. All experimen-tal data reported is an average of at least four measurements.
Mechanical properties) reported for this work, are those measured at yield point. The properties) were automatically calculated by HP86B using the Instron 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%; strain: 4.9%; energy: 8,3%;
modulus: 2.3%.
Results in Table :? demonstrate that CTMP aspen fibers) bonded either with silane "A-174") or "A-172", or "A-1100" were very effective on increasing the strength of resulting composites.

The composites were prepared and evaluated as in Example 1 but PVC used was vinyl chloride polymer of tratde mark GEON 110-334 supplied byi B.F. Goodrich.
The vinyl chloride polymer was plasticized with 20 weight percents of dioc-tylphthalate.
In addition, aspen sawdust replaced CTMP aspen pulp. The tensile results are presented in Table 3. The results indicate reinforcing effect of cellulo-sic fibers in form of sawdust (Mesh 60) of aspen. At 30% of fiber addition) the strength has increased from 5.5 MPa to 11.5 MPa in case of "A-172" or to 7.5 MPa in case of si:lane A-174. The modulus has also increased from 370 MPa of PVC to 810 MPa ("A-172") or 620 MPa ("A-174")) The simultaneous improve ment in stress) modulus, energy and elongation indicate excellent adhesion between fibers and matrix.

134070' The composite were made and evaluated as in Example 1 but the silane treatment step was carried out without the presence of peroxide as follows:
Coupling agent treatment The wood fibers were treated using silane coupling agents in dilute ethanol solution as follows:
0.8 g silane "A-1100" or "A-174" was dissolved in 15 ml of ethanol (90%) and was added by drop; for 5 minutes to 20 g of CTMP aspen pulp) or aspen sawdust (Mesh 60) while stirring. After this addition stirring continued for ten minutes. The mixture was left at 105°C in the oven to dry for 2 hours before mixing with vinyl chloride polymer.
Tensile data are presented in Table 4.
There is improvement in both stress as well as modulus when compared to vinyl chloride polymer values. On the other hand, the absolute values are inferior to that found in Table 2 where fibers were silane treated in the presence of peroxide.

This time) the co~r,posite were made and evaluated as in Example 1, but the fiber were precoated with polymer before being mixed with polymer matrix. The precoating procedure were divided in the following steps:
a) 20 g of fibers) ;size Mesh 60, placed in 500 ml flask; + 150 ml of carbon tetrachloride; + :?% of benzoyl or lauroyl peroxide (0.4 g) followed with addition of 1 to 4% of silane A-1100. The whole mixture heated to reflux at 70 to 75°C whi:Le agitated by magnetic stirrer for 3 hrs.
After cooling) CC 4 evaporated and mixture was dried at 55C for 24 hrs.
b) 2 g PVC placed in a round bottom flask and 100m1 of p-xylene was added +
0.1 gm of benzovl or lauroyl peroxide (5% on PVC) + 0.2 g of malefic anhydride (10% on PVC).
The whole mixture was kept under reflux while being agitated by the magnetic stirrer for 3 hrs.
c)The whole content (a + b) was put under reflux at 80-85°C, stirred for 2 hrs. The content left to cool down) at room temperature) than poured in a centered glass funnel to filter, washed with dist. water, then dried at 105°C for 12 hrs and at 55°C for 24 hrs, then grinded again to the desired mesh size. Followed by mixing with PVC in percentages 10, 20) 30 and 40%
on the roll mill as described in Example 1.
The tensile results for precoated samples are presented in Table 5. It is evident) that precoating of cellulosic fibers lead to excellent adhesion d .; , 1.3~D?0'?
between fibers and matrix and to excellent resulting properties of composites.

The composites were made and evaluated as in Example 4) but PVC-Baron was substituted with pVC of trade mark GEON-110-334 of B.F. Goodrich, plasticized with 20% of di-octyl-phthalate and CTMP aspen was substituted with aspen sawdust (Mesh 60). The tensile properties) presented in Table 6 show improve ment of stress from 5.5 to 8.5 MPa) modulus from 370 to 635 MPa and energy from 5.9 x 10-' to 8.0 x 10-3J when original PVC was compared to composites at 35% of fibers addition. These values again confirm excellent reinforcing properties of cellul~osic fibers in the presence of silane and carboxylic bonding agents.
Although the foregoing invention has been described in some details by the way of examples for purposes of clarity of understanding, it will be obvious that certain changes and modification may be practised within the scope of the appended claims.

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Claims (45)

1. A composite comprising from 1 to 95% by weight of discontinuous wood cellulose fibers dispersed in a matrix comprising from 1 to 95% by weight plasticized vinyl chloride polymer wherein the fibers are bonded to the matrix with silane bonding agent in amount comprising from 0.1 to 10% by weight.

2. A composite as defined in claim 1 comprising from 1 to 95% by weight of discontinuous wood cellulose fibers dispersed in a matrix from 1 to 95% by weight of vinyl chloride polymer being bonded to each other by reaction with 0.1 to 10% by weight of silane comprising from 0 to 50% by weight of plasticizer and from 0 to 40 of inorganic filler and also comprising from with 0.1 to 5% by weight of peroxide and from 0 to 10% by weight of ethylenicaly unsaturated carboxylic acid or anhydride.

3. The composite as defined in claim 1 and 2 wherein the silane is of that of trade mark "A-151 ".

4 The composite as defined in claim 1 and 2 wherein the silane is of that of trade mark "A-172"..

5. The composite as defined in claim 1 and 2 wherein the silane is of that of trade mark "A-174".

6. The composite as defined in claim 1 and 2 wherein the silane is of that of trade mark "A-186".

7. The composite as defined in claim 1 and 2 wherein the silane is of that of trade mark "A-187".

8. The composite as defined in claim 1 and 2 wherein the silane is of that of trade mark "A-189".

9. The composite as defined in claim 1 and 2 wherein the silane is of that of trade mark "A-1100".

10. The composite as defined in claim 1 and 2 wherein the silane is of that of trade mark "A-1120".

11. The composite as defined in claim 1 and 2 wherein the silane is of that of trade mark "A-1160".

12. The composite as defined in claim 1 and 2 wherein the fibers as softwood pulp.

13. The composite as defined in claim 1 and 2 wherein the fibers are hardwood pulp

14, The composite as defined in claim 1 and 2 wherein the fibers have an fiber aspect ratio from 2 to 150.

15. The composite as defined in claim 2 wherein the inorganic filler material is selected from mica, tale, calcium carbonate, silica, glass fibers, asbestos and wollastonite

16. A composite as defined in claim 2 comprising from 1 to 95% by weight of discontinuous wood cellulose fibers dispersed in a matrix comprising from 1 to 95%
by weight to vinyl chloride polymer, being bonded to each other by reaction with 0.1 to 10% by weight of silane and with 0.1 to 5% by weight of peroxide and also comprising from 0 to 60% by weight of plasticizes and from 0 to 5 by weight of inorganic filler

17 The composite as defined in claim 1 and 16 wherein the silane is selected from silanes identified by the following trade marks: "A-151", "A-172", "A-174", "A-186", "A-187", "A-189", "A-1100", "A-1120" and "A-1160".

18. The composite as defined in claim 2 and 16 wherein the peroxide is selected from dicumyl peroxide, benzoyl peroxide, hydrogen peroxide, sodium peroxide, di-ter-butyl peroxide, lauroyl peroxide, 2,5 - dimethyl - di -t-butyl-peroxy hexane.

19. The composite is defined in claim 1 and 16 wherein the wood cellulose fiber is selected from softwood pulp, hardwood pulp, mixture of hardwood and softwood pulps, wood flour, sawdust or wood shavings.

20 The composite as defined in claim 1 and 16 wherein the fibers have a fiber aspect ratio from 2 to 150.

21. The composite as defined in claim 2 and 16 wherein the inorganic filler material is selected from mica, talc, calcium carbonate, silica, glass fibers, asbestos wollastonite.

22. A composite as defined in claim 2 comprising from 1 to 95% by weight of discontinuous wood cellulose fibers dispersed in a matrix comprising from 1 to 95%
by weight of vinyl chloride polymer, being bonded to each other by reaction with 0.1 to 10% by weight of silane and with 0.1 to 5% by weight of peroxide and with 0.1 to 10% by weight of ethylenicaly unsaturated carboxylic acid or anhydride and also comprising from 0 to 60% by weight of plasticizer and from 0 to 50% by weight of inorganic filler.

23. The composite as defined in claim 22 wherein the silane is selected from that identified by the following trade marks: "A-151", "A-174", "A-186", "A 187", "A-189", "A-1100", "A-1120" and "A-1160".

24. The composite as defined in claim 22 wherein the peroxide is selected from dicumyl peroxide, benzoyl peroxide, hydrogen peroxide, di-t-butyl peroxide, lauroyl peroxide, 2,5 - dimethyl - 2,5 - di -t-butyl peroxy hexane.

25. The composite as defined in claim 22 wherein the ethylenicaly unsaturated carboxylic acid or anhydride is selected from malefic acid, malefic anhydride, fumaric acid, citraconic acid, itaconic acid, acrylic acid or methacrylic acid.

26. The composite as defined in claim 1 and 22. wherein the discontinuous wood cellulose fiber is selected from softwood pulp, hardwood pulp, mixture of softwood and hardwood pulps, wood flour, sawdust or wood shavings.

27. The composite as defined in claim 1 and 22 wherein the fibres have a fiber aspect ratio from 2 to 150.

28. The composite as defined in claim 22 wherein the inorganic filler material is selected from mica, talc, calcium carbonate, silica, glass fibers, asbestos or wollastonite.

29. A treated discontinuous wood cellulose fibers comprising from 1 to 25% by weight of vinyl chloride polymer or pVC compatible polymer bonded to each other by reaction with 0.1 to 10% by weight of silane bonding agent and with 0 to 5% by weight of peroxide and with 0 to 10% by weight of ethylenicaly unsaturated carboxylic acid or anhydride.

30. The treated fiber as defined in claim 29 wherein the bonding agent is selected from silanes identified by trade marks: "A-151" or "A-174" or "A-187" or "A-1100" or "A-1120" or "A-1160".

31. The treated fiber as defined in claim 29 wherein the peroxide is selected from dicumyl peroxide benzoyl peroxide, hydrogen peroxide, di-t-butyl peroxide, lauroyl peroxide, 2,5 - dimethyl - 2,5 - di. t-butyl peroxy) hexane

32. The treated fiber as defined in claim 29 wherein the ethylenicaly unsaturated carboxylic acid or anhydride is selected from malefic acid, malefic anhydride, fumaric acid, citraconic acid, itaconic acid, acrylic acid or methacrylic acid.

33. The treated fiber as defined in claim 29 wherein the discontinuous wood cellulose fiber is select from softwood or hardwood pulps, mixture of softwood and hardwood pulps, wood flour, sawdust or wood shavings.

34. A composite as defined in claim 2 comprising from 1 to 50% by weight discontinuous treated wood cellulose fibers prepared as defined in claim 29 dispersed in a matrix from 1 to 95% by weight of vinyl chloride polymer being bonded to each other by reaction with 0 to 10% by weight of bonding agent and comprising from 0 to 5% of peroxide and from 0 to 50% by weight of plasticizer and from 0 to 40% by weight of inorganic filler.

35. The composite as defined in claim 2 and 34 wherein the bonding agent is selected from silanes identified by trade marks: "A-151 ", "A-174", "A-187", "A-1100", "A-1120" or "A-1160".

36. The composite as defined in claim 34 wherein the peroxide is selected from dicumyl peroxide, benzoyl peroxide, hydrogen peroxide, di-t-butyl peroxide, lauroyl peroxide, 2,5 dimethyl - 2,5 - di- t-butyl peroxide hexane.

37. The composite as defined in claim 34 wherein the inorganic filler material is selected from mice, talc, calcium carbonate, silica, glass fibers, asbestos or wollastonite.

38. A compression molding made from the composite of claim 1 and 2.

39. An injection molding made from the composite of claim 1 and 2.

40. A compression molding made from the composite of claim 16.

41. An injection molding made from the composite of claim 16.

42. A compression molding made from the composite of claim 22.

43. An injection molding made from the composite of claim 22.

44. A compression molding made from the composite of claim 34.

45. An injection molding made from the composite of claim 34.