CHAPTER II

COMPOSITE REQUISITE
Section A - Reinforcing Agent: Pine Cellulosic Fiber
Section B - Matrices : The resins
• Phenol - Formaldehyde

• Urea - Formaldehyde

• Phenol - Resorcinol - Formaldehyde

• Phenol ~ Lignin - Formaldehyde

The present chapter discusses on the materials required for the preparation of pine

cellulosic-based composites. The chapter is therefore, divided into two sections, i.e.

Section A and section B. Section A deals with the discussions on pine needle based

cellulosic fibers, used as reinforcing material and section B, on the chemistry,

preparation and characterization of the adhesives, used as the matrix, for the

manufacture of particle board composite.

SECTION - A

REINFORCING AGENT: PINE CELLULOSIC FIBER

The increasing demand of timber wood has forced the polymer chemists to search for

an alternative to wood and their continuous efforts in this direction led to the

development of different polymer based (particle boards) composites. The main raw

material used for the preparation of these composites, as the reinforcing agent, is the

fibrous lignocellulosic material. These materials can be obtained fi-om a variety of

naturally occurring raw materials such as wood waste in the form of round wood, saw

waste including saw dust, plainer shaving, veneering waste, or agro based industrial

residues like baggasse, rice husk, rice or wheat straw, jute sticks, etc. In recent years,

therefore, polymer composites containing wood fiber/natural fibers have received

considerable attention both in the literature and in industry. Studies have been

reported on natural fiber based composite products'. Particularly, agro based natural

fibers have attracted the attention of scientist and technologist for energy-intensive

applications since cellulosic fibers are strong lightweight, abundant, non-abrasive,

non-hazardous, renewable and inexpensive. The flexibility and reduced tear of

22
processing machinery with no health problem makes these materials as excellent

reinforcing agents for plastics^.

Over the past decade cellulose based natural fibers have found use as a potential

resource for making low cost composite materials, especially in developing tropical

countries where these fibers are abundant. Sisal and jute fibers possess moderately

high specific strengths and stiffiiess and can be used as reinforcement in polymeric

resin matrices to make usefiil structural composite materials. Lack of good interfacial

adhesion and poor resistance to moisture absorption make the use of natural fiber

reinforced composite less attractive. This problem can be over come by suitable

chemical modification of these fibers. Several studies have been reported based on

the surlace modification offibers^"^.Kuruvilla Joseph et. al^ have reported the effect

of alkaline treatment and cardanol derivatives of toluene diisocyanate .(CTDIC)

treatment on the physical and mechanical properties of sisal-LDPE composite.

Short fiber elastomer composites containing natural fibers have gained much

importance due to their renewable nature, low cost, and amenability to chemical and

mechanical modification. A considerable amount of research work has been done in

o

the field of short natural fiber reinforced rubber composites . The processing

advantage of short fiber reinforced elastomer composites has been investigated by

Foldi^. Chakraborty et. al^° have reported the properties of short jute fiber reinforced

carboxylated nitride rubber (XNBR). Short fiber strength reinforced rubber

composites have better processing advantages, high green strength, high dimensional

stability and show anisotropy in mechanical properties'\ Murty and De ^ have

studied the properties of short jute fiber reinforced SBR composites. Recently,

23
Thomas and coworkers'^''"* have reported the mechanical properties of short sisal and

coir fiber reinforced natural rubber (NR) composites. Prasantha Kumar et. al' have

evaluated the critical fiber length, the influence of fiber orientation processability and

the effect of bonding agent on the mechanical properties of sisal fiber reinforced -

styrene- butadiene rubber composites. Cost effective utilization of oil palm fibers as

reinforcement in composite materials and their mechanical properties were studied by

M.S. Sreekala et. al'^. Oil palm fibers being hard and tough, become a cost effective

replacement for synthetic fibers. Structural properties and applications of these fibers

have been reported'^. M.S. Sreekala et al'^. have analyzed the tensile, flexural and

impact performance of the composites fi-om oil palm fibers and phenol-formaldehyde

resins. Hardness of composites was also checked.

Among various natural fibers, pineapple leaf fibers (PALF), exhibit excellent

mechanical properties due to its high cellulose content and comparatively low

microfibrillar angle. Among matrix resins, unsaturated polyester, have been

commonly used for making thermoset composites especially with glass fiber'^. But

high level of moisture absorption, poor wettability and insufScient adhesion between

untreated fibers and the polymer matrix leads to debonding with

age' . Because mechanical properties of composites depend on interfacial

adhesion, it is necessary to have good adhesion between the reinforcement and the

polymer matrix^-'^'*. Mishra et.al^^ have analyzed physico-mechanical properties of

PALF-reinforced polyester composites. The high cellulose content and the low

microfibrillar angle (11 degree) of banana fiber indicate that it has also the potential

as a reinforcing material^^. Con^osites made out of banana/cotton hybrid febric has

24
been found to be useful in the preparation of low strength material^'. Effect of banana

fiber on the mechanical properties of polyester composites with reference to fiber

length and fiber content has been analyzed^^. The fiber matrix interfecial bond

strength is expected to be very poor due to hydrophilic nature of sisal fiber and

hydrophobic nature of SBR. The efficiency of sisal as reinforcement in SBR

composites can be achieved by modifying the surfece topology of sisal fiber by

suitable chemical treatment or by selecting a bonding system. Several treatments

have been reported to inprove the fiber matrix interfecial bonding^^'^^. Kokta et.al^

have reported that compiling agents like silanes and isocyanates improve the

mechanical properties and dimensional stability of cellulose fiber-PE composites. It

has been observed that mercerization of sisal fiber will enhance the bonding of fiber

with rubber matrix. Sapieha et. al^^ have reported that the addition of small amount of

DCP into cellulose fiber composites, during processing, improve their tensile

properties significantly. Prasantha and Sabu Thomas have explained the effect of

different chemical treatments of sisal fiber on the mechanical properties of short sisal

fiber- reinforced SBR composites.

Various juvenile woods have been used as reinforcing agent in different

thermosetting resins thus substituting the timber wood. However, the poor

mechanical properties as well as higher water absorption due to the incompatibility of

polymer with wood are obstacles in the fi-equent use of wood polymer composites.

Hemp and Agave fibers are employed as filler for the preparation of wood polymer

composites with high-density polyethylene (HDPE) in different ratios 55:45, 50:50,

45:55 and 60:40 (wt./wt.) respectively. The young modulus and tensile strength

25
decrease with increase in the amount of fiber concentration in wood polymer

composites.The Agave fibers showed higher strength among the fiber composites for

all ratios. The maleic anhydride treatment shows significant improvement in Young's

modulus and tensile strength over the untreated fiber/polymer composites.

Improvements in the mechanical properties are due to the compatibility of HDPE

with fibers. Recently, cellulosic plots and wastes such as shell flour, wood flour and

pulp have been used as filler in thermoplastics, and primarily to achieve cost saving

fiber reinforced plastic based composites. In feet, synthetic fibers such as nylon,

rayon, aramid, polyesters and carbon are extensively being used as the reinforcement

of plastics. But these materials are expensive and are non-renewable resources. There

is therefore, growing interest in the use of agro-based fibers as reinforcing

components in dififerent composite materials. Because of the uncertainties in the

supply and the price of petroleum-based products, it is important to use the naturally

occurring alternatives. Natural fibers are renewable resources; they are cheaper, cause

no health hazards and finally provide solution to environmental pollution by finding

new uses for waste materials. Natural fiber reinforced composites therefore, come

prior to synthetic fiber reinforced polymer composite in properties such as

biodegradability, combustibility, light weight, non toxicity, decrease environmental

pollution, low cost, ease of recyclability etc. These advantages place the natural fiber

composites among the high performance applications of natural fiber composites

having economical and environmental advantages.

Thus, natural fibers, being the source of lignocellulosic materials along with various

properties best needed for the preparation of polymeric composites, offer a renewable

26
resource material as a reinforcing agent. From the literature survey it is observed that

different natural fibers fi-om agriculture waste such as flax, baggasse, cotton, hemp

and jute stalks have been used industrially in the preparation of different

lignocellulosic polymeric composites using suitable synthetic adhesives. A review of

literature lists meager studies on utilization of pine needles, the major waste of

coniferous forests and rich source of lignocellulosic content, as a reinforcing agent in

these polymeric composites. In the present work, therefore, utilization of pine

needles, as a reinforcing agent, has been made towards the preparation of wood based

polymer composites.

Himachal Pradesh, the land of forests, is mainly covered with thick coniferous forests

with different varieties of Pinus. Pinus roxburghii is one of the common species of

Finns genera and is widely spread over the low-lying mountain ranges. It is a tall tree

with a spreading crown. The leaves of the trees are in clusters of three, which are

needle like. There is a huge fell of pine needles (leaves) in the month of April to

June, estimated to about one ton per hectare per season. About 4.0 to 5.0 kg. leaves

are shed by one tree of matured growth. The needles are the fire hazards to the forest

and an irritant to villagers, as these do not allow the grass to grow underneath for the

cattle. Utilization of these wastes in the preparation of composites would give relieve

firom these problems.

27
EXPERIMENTAL

MATERIALS AND METHOD

i) Collections of Pine needles: Pine needles of Pinus roxburgii (chil) were

collected from the forest near H.P. University, Summer Hill, Shimla, H.P.

India, between the periods April to June.

ii) Chopping of Pine needles : The dried pine needles were chopped to a size

between 0.5" to 1" in length with chopping machine. These needles were used

for further experiments.

iii) Digestions of Pine needles : The dried and weighed pine needles (5 kg.) of

0.5" to 1.0" size were put in the digester. To it was added 50 liters of 5%

aqueous solution of NaHSOs. The digester was closed air tightly and the

needles were allowed to digest for 8 hoxir under pressure. After the specific

time, the pressure was released and the needles were removed fi*om the

digester. The digested needles were thoroughly washed with water and

allowed to dry in the open. In between, while the needles were still wet, a

mild thrashing was given with a wooden hammer, to separate the cellulosic

fibers. They were further allowed to dry in air and then in the oven at 60-

70°C. The moisture content of these pine cellulosic fibers is maintained

between 6-8%. These fibers were used as a reinforcing agent in the

preparation of particleboards.

CHARACTERIZATION-The physico-chemical properties'^ of pine needles are

presented in Table 1. The pine celulosic fibers obtained after the digestion of the

pine needles have been characterized as follow:

28
m SPECTROSCOPY

FTIR of pine cellulosic fibers was taken on KBr disc on FTIR spectrophotometer.

Pine cellulosic fibers showed a broad band in the region between 3300-3600 cm'^ due

to H-bonded hydroxyl groups of the cellulose.

THERMOGRAVIMETRIC ANALYSIS

Thermo gravimetric analysis of pine cellulosic fibers was recorded on simultaneous

Schimadtzu TGA-DTG apparatus in air at a heating rate of lO^C/min. The primary

thermogram is presented in Figure 1. The initial decomposition temperature (IDT),

final decomposition temperature (FDT) and the decomposition temperature (DT) at

every 10% weight loss are presented in Table 2. The initial decomposition begins at

250°C and continues upto 296°C for next 10% weight loss. Further loss in the weight

fi-om 10% to 40% shows a fest decomposition with temperature difference lying

between 10*^C to 25°C. Beyond 40% weight loss, the decomposition slows down and

the temperature difference between each 10% weight loss i.e. fi-om 40% to 50%,

. is 25°C, fi-om 50% to 60% weight loss, it is 55°C and finally fi-om 60% to

70% weight loss, the temperature difference again reduces to 29°C. Final

decomposition begins at 458°C where about 70% weight loss has been observed and

continues upto 72% weight loss with 16% residue. Initial degradation of pine

cellulosic fibers may be due to thermo-oxidation and formation of flammable volatile

glycosan. Similar thermal behavior of different cellulosic fibers has been observed by

Kosiketal^^"*°.

29
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o

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in

o a O
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en
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ssoi iMBia/AVo L
WATER ABSORPTION BEHAVIOR

Table 3 represents the water absorption behavior of pine cellulosic fibers from

atmosphere and after immersion in water for different time periods.

0.200 g samples of pine cellulosic fibers were kept in the open for different time

periods. The moisture absorption by the samples was determined from the increase in

the initial weight of the samples. Similarly, water absorption by the samples was

determined by immersing the samples in water for different time periods. After a

definite time period, the samples were taken out of water and the adhering water was

removed by gently pressing against dry filter paper and weighed. Percent water

absorption is determined from the increase in weight of the original fiber. Results are

presented in Table 3.

30
 SECTION- B

MATRICES : THE RESINS

Phenol-Formaldehyde

Urea-Formaldehyde

Phenol-Resorcinol-Formaldehyde

Phenol-Lignm-Fonnaldehyde

This section deals with second and the most important component of composites i.e.

the matrix. It constitutes the binding material, which holds of the reinforcmg agent.

With wood or similar material forming the basis and the bulk of the particle board,

adhesive binds the fragments of the reinforcing agent together into a homogenous

mass and thus is no less important.

Adhesive are derived either from

1. The natural resources such as animals, vegetable, casein, soyabean and blood

albumin, glue or

2. They are synthetic products of chemical industries drained from petroleum,

natural gas, coal, air and water.

Glue from animals and plant cells have been known for a long time and are still

widely employed for bonding porous materials such as paper. These materials

however, have limited resistance to moisture and mould growth. These limitations of

adhesives of natural origin provided the stimulus, and are responsible for the great

expansion of new adhesives, which are based upon synthetic resins and other

materials.

31
Synthetic resin adhesives were introduced in the wood processing industry in the

early 1930's. The chief advantage of some of the synthetic adhesives is their

excellent durability, making glued wood products serviceable under more severe

exposure than was possible with natural glues. Some synthetic resin adhesives are

capable of maintaining their strength under practically any conditions of service

where wood is the suitable material. Others have only moderate resistance to heat or

moisture or both and are not suitable for use under critical severe conditions.

Between two extremes in durability, wide ranges of synthetic resins are available.

Development of synthetic resin adhesives has facilitated manufacture of many

important glued wood products, which have extensive use in various fields like

engineering, construction, architecture, furniture, housing, agriculture, boat building

and other exterior uses. Synthetic resin adhesives for wood may be thermosetting or

thermoplastic. A thermosetting resin is one that undergoes cross-linking upon

hardening and become substantially infusible. The cross-linking or hardening

reaction is catalyzed by heat or chemicals and is iaeversible. The most important

thermosetting adhesives are phenol-formaldehyde (PF), urea-formaldehyde (UF), etc.

Thermosetting plastics have a large number of uses including uses as adhesives,

coating encapsulates and molding compounds. Paints often contain a thermosetting

binder. Thermosetting polyesters can be used to mould parts for automobiles. The

traditional term ''thermosetting resin" is now generally used for all reactive system

that forms a cross-linked network. Thermosetting resins are sold in their

unpolymerized form and must be reacted during processing. The reactions consist of

a complex combination of both polymerization and cross-linking that involves

32
conversion of low molecular weight molecules into a tight three-dimensional

network. The reaction can be separated into heat activated and catalysts activated

systems. Typical temperature activated systems include PF, epoxides, polyimides etc.

The most common catalyst activated resins are liquid unsaturated esters. In general,

the properties of both types of thermosetting resins are often improved by the

addition of additives. A thermosetting plastic consists of a thermosetting polymer

resin along vAxh various additives. Each thermosetting polymer resin possesses a

unique combination of properties such as strength, stif&iess, dimensional stability,

thermal stability, processability, dielectric strength, refractive index etc. However,

many thermosetting resins would be commercial failures if they do not contain

additives.

Thermoplastic resins do not normally undergo any cross-linking during curing or

hardening but remain in a reversible state and can soften on subsequent heating. The

most important thermoplastic resin for wood adhesive is poly vinyl acetate resin.

Thermoplastic resin is usually produced by addition polymerization.

The backbone polymer provides the strength for the adhesive joint. It makes up

usually the major properties of the adhesive and also confers its name for the

formulation e.g. phenol-formaldehyde adhesive, urea-formaldehyde adhesive etc.

Although the backbone polymer provides the framework, they are to be modified by

incorporating other constituents so that it can simultaneously meet several

performance criteria favorably. However, it is a problem to make an adhesive mix,

which is adequate to meet the desired requirements. The underlying fector here is that

the adhesive mix is then not a one-component system, rather it may now frequently

33
contain as many as six or seven components. Since so many variables are involved,

the making of an adhesive mixture is. usually a trial and error processes often ending

up as a patented formulation. The various constituents and the role they play in

improving the characteristics of a polymer, so that it can function eflSciently as an

adhesive are as follows:

1. Solvents

These are needed in most adhesives to disperse the binder to a spreadable

consistency. In most wood bonding adhesives, the solvent is water. For reconstituting

PF resin powder, some alcohol is used together with water. Demineralized water is to

be preferred, although only potable water may be used.

2. Catalysts

These are the substances, which speed up the rate of curing reaction of an adhesive

when added in small proportions. A good example of a catalyst is ammonium

chloride, commonly used to speed up the curing of UF adhesives.. The proportions of

catalyst to resin are adjusted to provide a practical working life for the adhesive while

ensuring complete cure of the resin. The catalytic action may be further controlled by

the addition of modifiers. For example, buffers or retarders such as hexamine,

ammonia, tricalcium phosphate, zinc oxide, urea and melamine may be added to

control the acidity of catalyst added to UF resin.

3. Hardeners

These are substances added to an adhesive to promote or control the curing reaction

e.g. paraformaldelyde is used with resorcinol-formaldehyde and phenol-resorcinol-

34
formaldehyde resin, and ammonium chloride is the hardener for urea-formaldehyde

resins.

4. Fortifiers

These are the materials, which are added to an adhesive to improve the strength,

moisture resistance and durability of resultant bonds. They usually have some

distinct adhesive values. An example is melamine or melamine-formaldehyde resin

added to urea-formaldehyde glue to improve water resistance and durability. A

fortifier may also sometime function as an accelerator.

5. Fillers

Fillers are relatively inert substances with little or no paste forming properties and are

added in the fine powder form to the adhesive. These materials improve the spreading

characteristics of synthetic resin adhesive on conventional roller spreader and control

excessive adhesive penetration into porous wood.

6. Extenders

These are the substances having some adhesive property when added to the backbone

resin adhesive. It improves the performance quality of the backbone resin and

reduces the quantity of primary binder required per unit area of the panel products,

thus reducing the cost of the adhesive.

7. Preservatives

These are added to certain adhesives to prevent or retard decomposition by

microorganisms either while the adhesive is being stored and applied or during

service of the complete bond.

35
8. Plasticizers

These are high boiling liquids or low melting solids incorporated in the adhesives to

increase their flexibility and workability.

9. Viscosity builders

These are the materials, which when added even in a small quantities during the

production of synthetic urea-formaldehyde and phenol-formaldehyde resin adhesives

or during their application increase their viscosity enormously and this property is

exploited to decrease the extender cost of the adhesive to a large extent as well as to

improve the consistency of the resin glue.

10. Wax

Wax in the form of wax emulsion, is an additive used with phenol or urea-

formaldehyde resin adhesive during the production of particle board and fiber board.

Wax sizing is designed to confer a degree of water repellency upon the board

products.

11. Fire retardants

Fire retardants are the chemicals, which can be used to reduce the flammability of

cellulosic materials and can generally be applied with the resin. If they are insoluble

powders they can often be added in quite large amounts. But since the wood rather

than the resin needs fire proofing, the most efficient way is to treat the chips with fire

retardant before applying the resin.

12. Insecticides and fungicides

Any fire retardant chemical also have insecticidal and fungicidal properties,

especially boron and halogen compounds. Since the cellulose and not the resin is the

36
object of attack, the most effective way to control the attack is again by applying the

substance to the wood chips separately instead of mixing it with the resin.

The common resins, used as adhesives are, phenol-formaldehyde (PF), urea-

formaldehyde (UF) and melamine-formaldehyde (MF). Sometimes combinations of

these resins are also used. Recently isocyanine based resins have been used for

particle board preparations.

The chemistry and adhesive properties of some of the resins, used in the present

studies, such as phenol-formaldehyde, urea-formaldehyde, phenol-resorcinol-

formaldehyde, phenol-lignin-formaldehyde is discussed here. A comprehensive

literature of the utilization of these resins in the manufacture of the particle boards is

also reviewed.

CHEMISTRY AND ADHESIVE PROPERTIES OF SOME RESINS.

PHENOL-FORMALDEHYDE RESINS

Although phenol-formaldehyde, a synthetic resin adhesive, was invented by

Bakeland about 80 years ago, its large-scale application to the plywood industry was

a development of the thirties. Phenolic resin is the reaction products of phenol and/or

substituted phenol with formaldehyde. An unlimited variety of resins are possible

depending on (i) the choice of the phenol, (ii) the formaldehyde to phenol molar ratio,

(iii) the type and amount of catalyst used (iv) time and (v) temperature of the

reaction. The formaldehyde to phenol molar ratio, compiled with the type of catalyst

used, determines whether the polymer will be phenol-terminated or methylol (-

CH2OH) terminated. On the basis of this, two types of phenolics have been described

37
(i) phenol tenninated resin, referred to as novolac and (ii) methylol terminated resin

referred to as resol.

Novolacs are two-step resins, in which the formaldehyde necessary for cross-linking

is added in two successive steps. An acid catalyst is used and phenol-formaldehyde

ratio is usually about 1:0.8. This produces a novolac resin, which is permanantly

thermoplastic and soluble, because of the absence of free methylol groups. Moulding

powders are then prepared by mbdng the powdered resin with filler and pigments,

together with a source of sufficient methylene bridges to yield a resite upon

subsequent thermal curing. As a methylene source, paraformaldelyde or more

commonly, hexamethylene tetramine (hexamine) is added, since it liberates no water,

a desirable feature, when resins of high electrical quality are being prepared.

Methylol terminated resins i.e. resole, is a one step resin in which all the

formaldehyde is added at one time. An alkaline catalyst is used and the phenol-

formaldehyde ratio is usually about 1:1.5. Condensation is interrupted while the resin

is still thermoplastic and soluble. These spirit soluble resins are used for laminating,

although molding materials for special purposes can also be prepared from them by

adding fillers and catalyst to the carefiilly dried resol. Subsequent application of heat

completes the conversion of resite.

Phenolic resins are more durable and impact resistance to cold and hot water than

urea resins. Phenolic resins are not attacked by weak acids or alkalies and are

resistant to common organic solvents. These adhesives also show good resistance to

high temperature. These adhesives are boil proof, can be soaked indefinitely, and in

weather exposure will outlast the wood. The boil proof quality permits steaming of

38
phenolic bonded plywood to soften it for bending and foaming operations. Extreme

resistance to the action of moulds and fimgi is another important property.

However, phenolic adhesives are at a disadvantage compared to urea resin adhesives

in a number of respects including solid contents, storage life, cure speed, tacki

characteristics, compatibility with additives including wax emulsion and cost.

Furthermore, they impart color to the resulting boards. PF resin undergoes a more

gradual transition and therefore higher temperature and longer time for cure is

required. Phenol adhesives that require temperature above 100°C to effect their cure

in a reasonable length of time are considered to be high temperature setting. These

are usually set by alkali hardefner. Intermediate temperature setting adhesives

(between 25° to 100°C) are cured by either alkaline or acidic hardeners. However, the

nearly neutral or mildly alkaline adhesives are more common and are usually

preferred because of the possibility of wood weakening by strongly acid adhesives.

Apart from the slower curing rate, PF resin tends to penetrate the wood to a greater

extent than UF resins, and in order to achieve required strength characteristics, a

higher resin to wood ratio has to be employed. PF resin increases its viscosity during

storage and hence it may be necessary to adjust it to maintain the required spraying

consistency by the addition of water.

In recent years, continuous research and development to improve the properties of

phenolic resins have almost paralleled to that of urea resins. Phenolic resins require

longer press time and the color generated by phenolics is considered as a drawback.

However, phenolic resin bonded particle boards are still being made on larger scale.

Modifications of phenolic resins have also been carried out. Polyvinyl alcohol has

39
been added to PF resins to increase the viscosity and to provide pressure sensitive

character'*\

UREA-FOIUVIALDEHYDE RESINS

Urea-formaldehyde resin adhesives came on the market in middle of 1930s. UF resin

commonly, used as adhesive is a product of chemical condensation of urea and

formaldehyde. The resinous material is prepared in a soluble form, which may be

converted to the permanently infusible form by proper treatment during bonding.

These adhesives are usually obtained as highly viscous liquids of high resin content

(50-60 %), which has a limited period of stability. The resins are also available as dry

powder, which when mbted with small quantities of water, form liquid adhesives.

The resins in the form of powder have, of course, a larger shelf life. The liquid

adhesive is generally prepared by condensing urea and formaldehyde under slightly

acidic conditions to a predetermined degree, followed by the addition of alkali to

maintain the shelf life. The resins are hardened by a sufficient reduction of the pH

value. A catalyst is also used. The function of catalyst or hardener is to reinitiate the

interrupted action of condensation and to convert the low molecular weight UF resins

into high molecular weight network polymer. The rate of reaction during the

hardening process is increased considerably by acid or by a substance capable of

liberating acid when mixed with the resin. The amount and types of catalysts added

determine whether the adhesive bond is cured at room temperature or at higher

temperature range. Cure time varies from a few minutes at high temperature to a few

hours at room temperature.

40
Since the pH value falls too rapidly, pot life becomes too short and the strength of the

UF resin glued joints deteriorates with time, the direct addition of UF resin in most

cases is unsuitable. Liquid UF resin, is therefore, mixed with the hardner, such as

ammonium salt of strong acids before using with the substrate. They are cheap,

convenient to handle and has a high ratio of pot life to setting time. A frequently used

ammonium salt is ammonium chloride, which reacts with the free formaldehyde,

slowly with methylol groups available in the resin solution and forming

hexamethylene tetrammine, hydro chloride and water,

4NH4CI + 6HCHO • (CH2)6(NH2)4 + HC1 + 6H20

The liberation of acid results in an immediate decrease of pH value of the adhesives.

Additionally, the liberation of formaldehyde from methylol group causes fiirther drop

in the pH value, these are fiirther facilitated by the application of heat.

Urea resin, mostly used at elevated temperatures,should have pot life as long as

possible at room temperature and they should set very rapidly at high temperature.

From this aspect, the free formaldehyde in the urea resin solution, which governs the

amount of liberated acid and with it the reaction rate, should be bound in such a way

that it is freed again when the temperature rises. To extend the working life of UF

adhesives, a pH buffer such as ammonium hydroxide is added along with hardener to

slow dowp the rate of polymerization at room temperature. For cold hardeners,

designed for room temperature, cures the resin with in 1-1'/z hours. Free acids are

preferred to ammonium salts. The most suitable cold hardeners are organic acids

such as tartaric acid or citric acid. The hardening or curing of UF resins consists of

41
chemical curing and migration of the water, which is partly contained in the liquid

adhesives and partly chemically, liberated form the resm during the condensation

process. Both phenomena must occur simultaneously. If water is removed too quickly

or if the wood is too dry, the reaction of hardening cannot be completed due to lack

of solvent. If the decrease of water is too slow, induced by too high moisture content

of the wood or by too much water in the glue mixture, the hardening will be

terminated earlier and instead of adherent glue; a crumbling mass without cohesion

will be formed. To further improve the performance and the overall cost of the UF

resins, some additives are added during the synthesis of the resin or at the time of

applying to the mix for gluing. These may impart better water resistance, strength,

flexibility and other properties desirable and usefiil for the finished products. UF

resin is modified mainly by melamine. The product is urear-melamine-formaldehyde

copolymer resin adhesive. The material is widely applied in the production of

plywood and particle board with better bond strength and water resistance. Urea-

melamine-formaldehyde resin performs nicely. Urea-phenol-formaldehyde

copolymer adhesive has also been developed for the production of plywood and

particle boards. The adhesive strength and water resistance of the product are

between those of PF resm and UF resin bonded materials.

RESORCINOL BASED PHENOI^FORMALDEHYDE RESINS

Resorcinol based adhesive was first introduced in 1943. The polyhydroxy phenols

are, in general, much more reactive than the monohydric phenol, since the second

hydroxyl group enhances the activity of benzene ring. Probably the only polyhydric

phenol used commercially in phenol-formaldehyde resins is resorcinol i.e. m-

42
dihydroxy benzene. Resorcinol-formaldehyde resins cure at room temperature

because of its high reactivity and are prepared with only a part of formaldehyde. For

complete cure, the balance of the formaldehyde is added at the time of application of

the resin adhesives. Later it was found that the most important properties of the

resorcinol-formaldehyde adhesive can be retained, and the costs can be reduced^ if

some of the costly resorcinol is replaced by ordinary phenol. The usual replacement

is upto one half the molecular proportion of total phenolic constitutes. It may be

possible to replace more than one half but during the process of room temperature

setting, often gelation becomes progressively slower. The cost reduction is the motive

for mixing phenol to resorcinol resin glues but the principal point is that the resins

remain adequately active for hardening at lower temperature.

Resorcinol-formaldehyde glues, although quite expensive, cure at room temperature

or at slightly elevated temperature to provide water- proof products. Mixture of

phenol and resorcinol based resins as well as resorcinol-phenol- formaldehyde

copolymer resins have been in the use for the production of exterior grade of

plywood and structural timber products.

Commercially, resorcinol adhesives are available in two components as a dark

reddish liquid (50-70% solid) resin with a powdered, or at times with a liquid

hardener. This hardener is usually a mixture of paraformaldehyde and fillers. The

paraformaldehyde is selected for control of glue mix working life and curing

efficiency. Filler such as nutshell flour's siliceous fiber etc. are used to provide

suitable consistency to the mix, to form a fibrous reinforcement for the adhesive

films and to control thixotropic behavior. Once the resin and the hardener portions

43
are mixed, the usable life of the adhesive mix is limited. The viscosity increases as

the reaction continues until the adhesive becomes non-spreadable. This time is

generally termed as *pot life' and is generally determined at controlled temperature

with the aid of timing device.

Since the adhesive mixer produce exothermic reaction, the temperature of adhesive

mixes increases and the cross-linking reaction proceeds more rapidly thereby

reducing the pot life considerably. It is always advisable to remove the heat as it is

generated by stirring and cooling rapidly at or below room temperature. Resorcinol

adhesives cure at 27°C or higher, but usually are not recommended for use below

27°C. The advantage of room temperature setting of resorcinol resins over acid

catalyzed room temperature setting adhesives are several. Whereas a PF resin

requires very strong acid catalyst for curing at room temperature while resorcinol-

formaldehyde (RF) and phenol-resorcinol-formaldehyde (PRF) resin cure at nearly

neutral pH [6.5 to 7.0 (RF) and 7.0 to 7.5 (PRF)]. These limits are between pH 6 and

9, a range which is not at all harmful to wood. RF and PRF resins are mostly used as

special purpose adhesives in the assembly gluing of wood and wood products. These

adhesives withstand exposure to weather better than most timbers themselves. They

comply with the highest requirements of all specification and have outstanding

durability under most severe conditions. These adhesives are also suitable to bond

treated wood. Further, it is feasible to treat timber or plywood and then glue the

assemblies to the desired size and shape.

44
UGNEV BASED PHENOL-FORMALDEHYDE RESEV

In recent years, the need for conservation to meet the expanding requirement for the

materials, and the urge for more economical production method in the face of higher

operating costs, have added additional incentive to exploiting more efficiently the

lignin containing wastes from the pulping and wood using industries. For the pulp

and paper industry, the most profitable use of lignin would be as a component of

finished paper. Lignin consisting of 20 to 30% by weight of the dry weight of wood

is a high molecular weight polymer. It is the most important non-cellulosic portion of

the wood and is the resinous binder for the cellulosic fiber. It has structural properties

similar to phenolic resins. The structure of lignin is still only completely unknown

and the term lignin,'cannot be considered to be the designation of a constitutionally

defined compounds, it is rather a collection term for a group or system of high

molecular amorphous compounds that are chemically very closely related in the same

sense as any other natural high molecular products such as cellulose, hemicelluloses,

starch and proteins. Lignin may perhaps be defined as that incrusting material of the

plant, which is built up largely of methoxylated p-hydroxy phenyl propane stones

with varying degree of oxidation of their side chains, but how these building stones

are fiised together is still unclear. Lignin has been defined by Brauns as "that

incrusting material of the plant which built up mainly, if not entirely, of phenyl

propane building stones, it carries the major part of the methoxyl content of the

wood, it is unhydrolyzable by acid, readily oxidizable, soluble in hot alkali and

bisulphite, and readily condenses with phenol and thiocomponds."

45
 CH-CH3 (a) R = R' = H
GH
(b) R = - 0 C H 3 . R' = H

(c) R = R'=^0CH3

Investigations on the substitution of phenol with lignin, lignin rich materials and acid

hydrolyzed wood which is enriched in lignin have resulted in replacement of 30 to

60% of phenol in PF resin adhesive but the results are generally less satisfactory than

those achieved by the use of tannins'*^. It has been reported that investigation carried

out in Canada on a 100 % lignosulphonate based adhesive have given satisfactory

results. A process has recently been reported wherein high molecular weight lignin

derivatives are copolymerized with PF resin, replacing upto 40 % of resin in adhesive

mix without imdue effect on wood failure or durability. Wood flour and coconut shell

flour have been shown to be satisfactory extenders for PF resin adhesives. During

hydrolysis especially in the presence of phenol, the lignin in coconut shell flour

(CSF), wood flour and other similar lignocellulosic materials is dispersed and the

hemicellulosic and the cellulose converted at least partially into simple sugars and

aldehydes. These products of hydrolysis can be expected to react with phenol and/or

formaldehyde during subsequent resin formation. The process is applicable to both

hardwood and softwood and other lignocellulosic materials such as coconut husk,

coconut husk pith and coconut shell. It has been observed that CSF may also be

dispersed by alkali treatment. Yoshihiro and Naoki *^ prepared lignin based phenol

formaldehyde (LPF) resin adhesives. Lignin based adhesives (LRF) from a mixture

of RF and LF was the best of the other lignin-based adhesives. About 80% of the

46
resorcinol resin can be replaced by high molecular weight lignin. Arthur et. al**^ have

carried out the reactivity test of lignin with formaldehyde in order to identify

potential lignins to partially replace phenol in phenol-formaldehyde resin adhesives.

Sulphite lignins were found to be the best with reference to rate of reaction and

capacity of reaction. Fast curing copolymer resins of phenol-formaldehyde and

chemical extract from agriculture and forest residue was prepared. The copolymer

provided superior bond quality for plywood in comparison to the common phenolic

resins especially at the short press time in the preparation of veneer flake board

laminates of 2mm thickness**^.

REVIEW OF LITERATURE

The highest strength of adhesive joints bonding beech wood samples was obtained

when phenol-formaldehyde adhesive contains 16-20 phr benzene sulphonic acid as

cross-linking agent and had pH between 0.12-1.39'*^. The mechanical strength of the

phenolic adhesive obtained using MgCOa-water glass as fire proofing agent

decreased by approximately 25%. ZnO was used as water proofing agent**^. The alkyl

resorcinol-formaldehyde adhesives, DFK-l-AM and DFK-14, were prepared from

crude shale phenols. The pot life at 20°C was 1.0 and 2.5-3.0 h and resistivity 100 at

30°C and 300-500 Mpa respectively'*^. Resin useful as adhesives especially for

corrugated paper board are prepared by condensing 1 mole ketone with 5.5-6.5 mole

formaldehyde at pH > 8.5 imtil the free formaldehyde content is < 4%, adding 0.15-

0.4 mole urea and completing polymerization**^. The bonding strength of urea-

formaldehyde resin was increased by the addition of oligomeric polyethylene glycol

(PEG) or PEG-polypropylene glycol copolymer^^. Paraformaldehyde or a-

47
polyethylene fibers were used as hardeners for formaldehyde-phenol-resorcinol resin

to check the evaluation of fonnaldehyde^\ Addition of cross-linking catalysts such as

monbasic or dibasic ammonium salts to urea- formaldehyde resin reduces the curing

time with good pot life^^. Adhesives containing mainly immodified synthetic rubber

latexes, poly (vinyl alcohol), extenders, fillers, polyisocyanate cross-linking agents

and deliquescent compounds show excellent paste stability and form water proof

bonds to wood^^. Modification of urea resin adhesive with melamine and phenol and

aminoplast with isocyanate improved the strength and weather resistance of particle

boards. The amount required and kind of reinforcing component affected the board

quality^"*. An adhesive useful for bonding cellulose containing materials and textiles

is prepared by condensation of urea and formaldehyde in the presence of alkali and

alkaline earth salts and adding cross linking controlling additives to obtain desired

viscosity^^. The alkali lignin modified urea-formaldehyde resin was prepared by the

polycondensation of urea with formaldehyde in an acid medium and the reaction of

oligomer with alkali lignin at pH 9-9.5. The hot water resistance of the adhesive

joints with veneer increased^^. Resins containing <0.40 % fi'ee formaldehyde, usefiil

as wood adhesives, resistant to humidity and microorganism are manufectured by

polycondensation of 1:0.8 urea-formaldehyde mix at 90-94°C, modification of the

product with an sodium-lignosulphonate and optionally conditioning the product with

insecticide and fungicide^^. Urea-formaldehyde resins hardened by acid catalysts

especially useful in the manufacture of particle boards containing 0.5-25 % thermally

unstable inorganic or organic peroxides have higher mechanical strength caused by

gas pressure developed during hardening process . Binders giving particle boards

48
with high flexural and transverse tensile strengths and short press times contains

urea-formaldehyde resin containing 0-2 % melamine and 0-5 % phenol, ammonium

salt of (in) organic acids inert to curing compounds, urea and metal salts^^. Adhesives

from lignin containing waste for the manufacture of wood based materials were

prepared by Heinz^. The process decreased the demand for phenol and improve

environmental protection from discarded waste. Chemical modification of oligomeric

formaldehyde-urea resin with sulphate lignin gave good quality binders for plywood

and particle board manufeture^\ Physical and chemically modified lignins

contributed better characterized to kraft-lignin-phenol-formaldehyde (LPF) resin

compound with non-modified lignin especially for mechanical resistance . N-

hydroxyl methyl caprolactam is used to modify phenol-formaldehyde resin to

improve its elastic properties'^. Fire resistant adhesives for plywood were prepared

from urea resins or urea-melamine resins using NH4H2PO4 and powdered AI2O3. The

plywood showed adhesive strength of 12 kg/cm^ and acceptable flame proof

performance^. The strength and water resistance of particle boards were increased by

using urea-formaldehyde resin containing chloroacetic acid as hardener and a

complex of aluminium hydroxy pentabromide crystal solvate^^. Flame and heat

resistant phenolic resin compositions containing vinyl chloride-vinylidene chloride

copolymers with excellent-adhesion, no residual smell, and low adhesion temperature

were prepared and were usefiil as hot melt adhesives for felts, laminates and resin

bonded grinders^. Phenol resins with high lignin content and acceptable viscosity

were formulated from acid insoluble residue of wood hydrolyzed resin cure and dry

adhesive strength properties of laminated blocks glued with phenolic resins having

49
phenolic replacement levels by lignin >50% were not significantly different from

lignin free control sample^^. The use of aqueous extraction of tannin from spruce

wood and lignin from spruce and beech wood with 1% aqueous NaOH solution in the

preparation of phenolic resin, replacing phenols, has been made. Lignin extraction

from pinewoods gave better results than those from beech wood. The method of

concentration of tannins affected their reactivity with formaldehyde and good results

were obtained by spray drying the tannin extraction . Wheat straw based particle

boards were prepared by using isocyanate resin. The boards revealed good physical

and mechanical properties and were complying with the requirements of the standard

for the fiimiture particle boards^^. Fire resistant particle boards were prepared from

urea-formaldehyde resin containing oligomeric epichlorohydrin-phosphoric acid

dimethylamide copolymer and monomeric product of phosphoric acid with

cyanoguanidine and urea as the fire proofing agents'^. Recently, wood particle boards

were prepared by press curing a mixture of wood particles with portland cement as

the binder. The boards have a bending strength of 98 Mpa^\ Phenol-formaldehyde

resin mixed with self-emulsifying polyisocyanate was used to prepare wooden

fiberboard. The particle board could be removed from the press plate without

trouble . Manufacture of lignocellulosic composite particle products using lignin as

.an additives has been successfiilly carried by Pukis et. aP^. Ready to use resin-wax

emulsion adhesive was prepared by heating thermosetting phenol-formaldehyde resin

with a wax emulsion adjusted to pH within one unit to that of the phenolic resin,and

then cooling to room temperature^**. Preparation of adhesives based on tannin extracts

for febrication of wood particle boards have been carried out by Garro and Juan'^.

50
Adhesives for the manufecture of low-density particle boards consisted of

polymethylene polyphenylene isocyanate (-NCO contents 0.5-5 %) and prepolymers

of polypropylene polyols with 0.5-3 cross link density'^ Manufacture of wood

based cement-bonded boards, utilizing wood chips and industrial waste was

undertaken by Vladimir et. al ^'"'^. These included wood chip/wood dust cement

boards (Arbolite), excelsior cement boards (fibrolite) and cement bonded particle

boards.The bending strength of the manufactured cement bonded particle boards and

excelsior cement boards are upto 182 and 1 Mpa respectively. Amino resins

comprising of melamine containing 0.1-3 % (VS. Solid contents) and water soluble

organic acids offered a short adhesion time for preparing particle boards^^. Water

resistant and odorless boards showing storage ability on adhesives were prepared by

using amino resin adhesive comprising 50-70 % (based on total solid), melamine-

formaldehyde, methanol and alkali metal hydroxides (2.0-40 % based on

fin

formaldehyde) as catalyst . Gypsum slurry obtained by adding CuS04- O.5H2O

powder in water has been used as binder for manufacturing particle boards from

wood chips by Kamatsu and Nezu . Formamide, hexamethylene tetramine and

K2CO3 were evaluated as catalyst for phenol-formaldehyde resins in the manufacture

of particle boards from beggasse. The gelling point of the resin decreased by 30-35%.

The adhesive stregth of the resin was 1.8 Mpa for all catalyst! .

EXPERIMENTAL

MATERIALS AND METHOD

Phenol (CDH), Formalin (37%) (Qualigens), Urea (Nice), Resorcinol (Merck),

NaOH were used as received.

51
PREPARATION OF PHENOL-FORMALDEHYDE RESIN

Specific mole ratio (by weight) of phenol and formalin, taken in a resin kettle, was

mixed with the help of the mechanical stirrer. Meanwhile, 50 % aqueous solution of

sodium hydroxide was prepared on the basis of 5 % relative weight of sodium

hydroxide to the weight of phenol taken. Sodium hydroxide solution was added

slowly with constant stirring and heatingj to the phenol- formaldehyde mixture. Since

the reaction is exothermic, proper precaution was taken to maintain the temperature

between 50 to 60°C by circulating cold water around the resin kettle for initial 30-40

minutes. The temperature was then raised to 80° - 85°C and mixture was further

heated at this temperature. The addition of a drop from the condensing resin to the

cold water checks the setting of the resinification on appearance of turbidity.

Reaction mbcture was condensed at this temperature for another three and a half hour

after which the heating was stopped and the resin cooled.

The pH, flow time, water tolerance, curing time and solid contents of the resin were

measured and results are presented in Table 4.

PREPARATION OF UREA-FORMALDEHYDE RESIN

Urea and formalin were taken in a resin kettle in a specific mole ratio (by weight) and

were mixed with the help of mechanical stirrer. To the solution was added 50 %

aqueous solution of sodium hydroxide till the pH of the mixture is adjusted to about

7.5. The reaction mixture was heated at 65° to 70°C till the dimethylol urea was

formed (a few ml. of the solution in a test tube form white crystalline precipitates,

when the sides of the test tube w;&re scratched with the glass rod). The resultant

product was then cooled and the pH of the reaction mixture was adjusted to 6 to 6.5

52
by the addition of 50 % acetic acid solution under constant stirring. The whole mass

was heated again at 80° - 85°C till the start of the resinification (confirmed by the

turbidity test). Condensation at this temperature was continued further for 30 minutes

and then cooled to room temperature. The pH was raised to 7.5 by the dropwise

addition of 50 % aqueous solution of sodium hydroxide.

The pH, flow time, water tolerance, curing time and solid contents of the resin were

measured and results are presented in Table 4.

PREPARATION OF PHENOL-RESORCINOL-FORMALDEHYDE RESEV

Definite amount of PF resin was taken in a resin kettle and to it was added a known

amount of resorcinol slowly with constant heating and stirring. The reaction mixture

was heated between 55° to 60°C for about 50 minutes and then cooled to room

temperature. The pH, flow time, water tolerance, curing time and solid contents of

each resin were measured and results are presented in Table 4. The amoimt of

resorcinol in PF resin and corresponding % PRP is tabulated as Table 5.

PREPARATION OF UGNIN-PHENOL-FORMALDEHYDE RESIN

(i) Formation of lignin formaldehyde (LF) - The mother liquor containing

lignin extract obtained after the digestion of the pine needles was

concentrated and a definite amount of it was taken m the resin kettle. A

known amount of formaldehyde was added; the pH of the mixture was

adjusted 9.5 by the addition of aqueous 50 % NaOH solution with constant

stirring. The reaction mixture was heated at 80°-85°C for about 4 hours and

then cooled to room temperature.

53
(ii) Phenol-formaldehyde (PF) of best mole ratio (based on the properties of the

particle boards) was prepared. Definite amount of Hgnin-formaldehyde resin

and definite amount of phenol-formaldehyde resin were taken in a resin kettle

and were mixed with the help of mechanical stirrer. The reaction nuxture was

heated between 55° - 60°C for about 24h and then cooled to room

temperature. The composition of LF to PF in PLF corresponding to % PLF

resin is detailed out in Table 6.

The pH, flow time, curing time and solid contents of each resin were measured and

results are presented in Table 4.

CHARACTERIZATION OF RESINS

The resins were characterized with respect to the following properties.

1. pH: pH of each resjn was measured with the help of pH meter.

2. Viscosity: Viscosity of the resin was measiu-ed at room temperature as a

fiinction of flow time with the help of B4 cup.

3. Solid contents: Definite amount of resin was heated in a preweighed crucible

at 100*^C for one hour. After stipulated time, the resin was weighed again till

the constant weight was obtained. Percent solid content of resin was

determined from the following equation.

Wi-Wo
Percentage of solid contents = X 100
Wi

Where Wi and Wo are the weights of resin before and after heating at 100°C

respectively.

4. Curing of Resin: Curing of different resins was carried out as follows.

54
 a. Hot Curing (PF, PRF and PLF resins): 5 ml. of the resin taken in a

test tube, was placed in an oil bath maintained at 145°C. The sides of

the test tube were scratched with the help of the glass rod till a string

of the resin is formed. Time taken to form this string is noted.

b. Hot Curing (UF resin): UF resin requires the addition of ammonium

chloride to avoid the fall of pH during application. To 20 gm. of UF

was added 0.1 gm. NH4CI in 5 ml. of water and nuxed thoroughly. 5

ml. of the resin solution was taken in a test tube and placed in boiling

water. The sides of the test tube were scratched with the glass rod till

the resin solidifies. The time taken for solidification was noted.

c. Cold Curing (PRF resin): Cold curing of PRF was carried out with

the addition of formalin. To the known amount of the PRF was added

a known amount of formalin, under stirring. The temperature of the

mixture rises and the resin becomes solid. The time taken for

solidification is noted. The results are presented in Table 7.

5. Water Tolerance: Water tolerance is the appearance of turbidity in the resin

on addition of water to the resin.

Water Tolerance of PF and PRF Resins: Water fi-om the burette is added

slowly to 5 ml. of the resin (PF and PRF) taken m a beaker till the turbidity

appeared. The amount of water required in proportion to the amount of resin

taken gave the water tolerance of resin.

Water Tolerance of UF Resin; 10 ml. each of UF resin was separately taken

in four beakers. To each of the beaker was added varying amount of water

55
 under stirring. UF resin which settled first gave the least water tolerance to

resin. The ratio of UF: H2O required to settle the resin gave the water

tolerance range of the resin.

RESULTS AND DISCUSSION

Formaldehyde-based adhesive systems are based on reacting formaldehyde with

active hydrogen containing compounds such as phenol, urea or melamine (Fig.l).

This iamily of themosets has low flammability, high rigidity, good dimension

stability and low cost. These systems are heat activated and are processed using

compression or injection molding.

(a)

O O
II
H-C—H + (b) NH2 —C —NH2
NH2

N N
(C)
HX^^fT^ NH2

Fig.l: Formaldehyde can react with (a) phenol, (b) urea or (c) melamine to produce

cured thermosetting resin.

PHENOL-FORMALDEHYDE RESEV

Phenol-formaldehyde resin based polymers are prepared by the condensation of

phenol with formaldehyde. The reaction is catalyzed by acids or alkalies. The nature

56
of the product is dependent on the types of catalyst and the mole ratio of the

reactants. Novolac resins are prepared by reacting a molar excess of phenol with

formaldehyde (mole ratio 1.25:1) in the presence of an acid catalyst. In the present

work resol resins are used and are prepared by the reaction of phenol with a molar

excess of formaldehyde in the ratio of 1:1.5-2 under alkaline conditions. The

mechanism of condensation of phenol, formaldehyde in the alkaline medium is

represented as:

OH o-

+ H+

O
II
H—C—H

OH
o O OH O"

-6
.H
CH2OH .CH20H
Vx^
^v •CH2O:
" ^ ^
+

The resulting o and p-methylol phenols are more reactive towards formaldehyde than

the original phenol. They further react with formaldehyde resulting in the formation

of di and trimethylol derivatives as shown below:

57
 OH OH

HCHO r*^v^^20H ^°^*^^YV^^20H

OH OH

6 HCHO
OH
I
_
OH
I
[fVCHzOH
HOH

CH2OH
CH2OH

CH2OH CH2OH

The above reaction is repeated forming the trinuclear phenols from the dinuclear

phenol. Further heating of these initial reaction products results in the condensation

and increase in the molecular weight. Condensation takes place between the methylol

groups to form a methylene ether link (a) or between a methylol group and an active

ortho and para hydrogen atom to yield a methylene link (b)

OH OH OH
OH
A^CHjOH HOCH2s^
or CH2—O—CH2x^
X)
(a)

OH OH
OH OH
I
CHzOH CH2-A^°H
O-^ . or' CHzOH
or ^'XJ
(b)

The amount of heating determines the final focus of the product e.g. whether the resin

is less viscous (water soluble liquid), highly viscous (little or no water miscibility)or a

grindable form. Hence, the product obtained by the reaction of phenol and

58
formaldehyde in the presence of alkali is a complex mixture of mono and polynuclear

phenol in which the phenolic nuclei are linked by methylene groups. The general

structure of resol can then be represented as:

OH OH
I I OH
HOH^
-2-xy
HOHX; •—
CH2OH

UREA-FORMALDEHYDE RESIN

The preparation of urea-formaldehyde resin is sensitive to the change in pH. The pH

is maintained and adjusted with proper addition of base or acid during the reaction.

The mechanism of formation of resin follows two steps. The first step in the reaction

between urea and formaldehyde is the formation of methylol urea. As urea is tetra

functional, the initial reaction can lead to the formation of tetra methylol derivative of

urea, if the ratio of formaldehyde to urea is high enough.

NH2 NHCH2OH NHGH2OH N(CH20H:^ N(CH20H1

I HCH.O I HCHO I HCHO ' HCHO ^ ^
c=o ^ *- c=o ^ *• c=o *• c=o *• c=o
NH2 NH2 NHCH2OH NHCH2OH N(CH20H^

(I) (II) (III) (iv;

59
In this case, formation of methylol group slows the formation of another methylol

therefore; the introducti9n of subsequent methylol groups is reduced gradually. For

wood adhesives, reaction conditions, which leads mostly to the formation of

dimethylol urea are employed.

The rate at which methylol urea (I) and (II) takes place, depends on the concentration,,

temperature, pH and the ratio of formaldehyde to urea (FAJ). To control the reaction

and to favour the formation of dimethylol urea, the conditions must be slightly

alkaline and a pH of 7-8 is employed.

The methylol ureas are not adhesives. Condensation does not take place yet.

Methylol present in dilute aqueous solution must be removed by means of distillation

since it is toxic and could retard the hardening of the glue. The next step is the

condensation of monomeric methylol urea to form polymer molecules. The resin is

carried out at 90°-100°C and the reaction speed is controlled by the acidity of the

medium. Best results are obtained at a pH of 4.5-5. As the reaction proceeds larger

molecules with cross-linked structures are formed.

At a desired level, the reaction is arrested by neutralization (pH 7-8). If the reaction is

allowed to continue, the cross linking will lead to gelatinization of the resin in the

resin kettle. The condensation must, therefore, be closely watched and controlled at

all the stages of production.

Under acidic conditions, methylol ureas condense by elimination of water between

either.

i. A methylol group and a free amine group (I) yielding a product containing

methylene linkage (III)

60
ii. Two methylol groups (II) yielding product containing methylol ether linkage

(IV)

iii. Or methylol ether linkage (IV), which by loss of formaldehyde condensed to

III.

H O H O H
I ir I
—C—N—CH2OH + HN- —C—N—CH2OH + HO2HG—NH

(II) -H2O
(I) -H2O

O H H O H
II I i -HCHO
C—N—CH2—N— —C—[li—CH2—O—Chfe—NH
(111) (IV)

The product of the above kind still possesses methylol and amino groups. Thus

condensation may continue to yield polymer methylene compounds. The general

structure may be represented by:,

o H O H
' II I II I
HO2HC- -NH— C—N —CH2- - NH - C - N _ C H 2 0 H
• n

Average molecular weight ranges from 200-500 corresponding to the value of 'n' in

the above structure of about 1-5. The different steps in the formation of the resin are

shown in Table 8.

61
 Table 8.

Resin Raw State Mole Reaction Semi Reaction Product Hnal

material ratio product pH
F/U
UF Urea AMiite 1.5-1 Addition Mcffio- Craidensation UF 7.5 to
crystalline 2.0:1 metl^lol resin 8.5
Fcffinalin liquid urea and
di-
methjdol
urea

Addition Condensation

Urea + Formaldehyde Methylolurea UF resin

pH 7 to 8 pH 5.5 to 6

RESORCEVOL BASED PHENOI^FORMALDEHYDE RESIN

Resorcinol i.e. m-dihydroxybenzene is trifimctional and it readily combine with

formaldehyde to form methylene derivatives, with methylol groups occupying either

the position ortho to both hydroxyl groups or ortho to one and para to the other

OH OH OH
I
HCHO Js^CHzOH
OH
^ ^ ^ H
CH2OH

The reactivity of methylol derivative is so high that they cannot easily be obtained in

the stable form as resoles as in the case of phenolics. The reactivity of resorcinol

towards formaldehyde is such that the resins are formed in the absence of any

catalyst. When two materials are heated together, the exothermic reaction proceeding

62
vigorously to the themoset stage unless carefully controlled. In these polymers, the

resorcinol nuclei are joined together through methylene bridges to give complex

molecule.

OH OH OH OH
1 /CH2^
^CHzOH
^

yU—OH
•

ULOH TyL-OH
CH2OH CH;jOH

The greater reactivity of resorcinol compared to phenol is due to the presence of two

hydroxyl groups, meta to each others. The two groups reinforcing each other in their

activation of the ortho and para positions of the benzene ring. Since the introduction

of methylol groups onto the ring increases the activity of the ortho nuclear positions,

it is, therefore, clear why resorcinol resins have so great tendency to react as long as

there are active sites available.

UGNEV-PHENOL-FORMALDEHYDE RESIN

The preparation involves the reaction of lignin with formaldehyde to give the product

with hydroxyl groups of Ugnin reacting with formaldehyde. The resinous mass is

mixed with the resin obtained from phenol-formaldehyde. The cross linking between

the two leads to the formation of lignin based phenol- formaldehyde resin.

63
CHARACTERIZATION OF PHENOL-FORMALDEHYDE, UREA-

FORMALDEHYDE, PHENOL-RESORCEVOI^FORMALDEHYDE AND

PHENOL-UGNIN-FORMALDEHYDE RESINS

Phenol-formaldehyde and urea-formaldehyde resins were prepared with varying ratio

of phenol to formaldehyde and urea to formaldehyde respectively. Each resin sample

was characterized with respect to pH, viscosity, water tolerance, curing time and

solid content .The results are presented in Table 4.

The pH of phenol-formaldehyde resin for the F/P ratio varying between 1.74 to 2.44

is observed between 9.0 to 9.7 i.e. resin is alkaline which is due to the use of NaOH

as the catalyst. For urea-formaldehyde resin, the pH of all the samples was

maintained between 7 to 7.5 after the reaction is stopped, in order to avoid the

process of further condensation. However, lower pH value (5.9 - 6.5) is required at

the time of its use in the preparation of the board.

Viscosity measured in terms of flow time with B4 cup is found to vary with the

change in F/P and F/U ratio in the resin. The flow time initially increases with

increasing F/P and F/U ratios. At higher ratio it shows a decrease with both the

resins. Flow time of 21 sec. is observed for PF resin of 2.44 F/P mole ratio while UF

shows a flow time of 25 min. at F/U ratio 1.74, The PF resin with F/P ratios 1.97

shows the best water-tolerance (1:8.5) while at the maximum F/P ratio (2,44) the

water-tolerance value is 1:6. In the case of UF, the higher water-tolerance (1:1.2) is

observed for the lower F/U ratio (1.40) while at higher F/U (1.74) the value is 1:0.55.

The better water-tolerance at lower ratio of both PF and UF resins may be due to the

reason that since at lower ratios smaller amount of formaldehyde is used in

64
comparison to phenol and urea, which shows affinity for water. At higher ratios

almost complete condensation takes place and as such the water-tolerance value

decreases. Curing time for both PF and UF resin increases initially and decreases at

higher F/P and F/U ratio. PF and resin of F/P 2.44 ratio shows a curing time of 11.32

sec. while UF resin a curing time of 152 sec at F/U =1.74. The solid content

decreases with increasing F/P and F/U ratio.

Different samples of PRF and PLF resins were prepared with varying percentage of

resorcinol (15%, 20%, 25%) or lignin-formaldehyde (10%, 20%, 30%, 40%, 50 %)

with respect to phenol-formaldehyde resin and characterized.

The pH of PRF resin does not vary much with rise in the percentage of resorcinol. It

remains same (8.1) for 15% and 20% samples while for 25% PRF resin^pH lies at

8,3. Flow time and water-tolerance increases with increase in the percentage of

resorcinol from 15 to 25 %. Maximum flow time (252sec.) and maximum water

tolerance (1:8.5) is observed for 25% PRF resin. The curing time (13.54 min) and

solid content (62.33 %) is also higher for this resin. Table 7 represents cold

curing of PRF resin.

On determining the pH of the PLF resin, it was observed that pH remain almost same

(9.1-9.2) for all percentages of PLF resin. The flow time increases with increase m

percentage of PLF resin; the maximum (46sec.) is observed for 50% PLF resin. The

curing time also increases with increasing LF percentage in PLF resin and the

maximum (19.23min) is obtained for 50% PLF resin. Solid content also increases

with increase in LF percentage upto 40% giving maximum (58.35 %) beyond which.

65
at 50% PLF, itfellsto 54.51 %, which is due to relative amount of PF and LF present

in the PLF composition.

66
 38
TABLE 1. PHYSICO-CHEMICAL CHARACTERISTIC OF PINE NEEDLES

Physical Characteristics
1. Colour when dry = light brown
2. Length of the needles = 15-20 cm.
3. Diameter = 0.5 to 1.00 mm
4. Bulk density = 0.05 g/cm^

Chemical Characteristics
1. Extractives:
4.47 % oven dry basis (in ether)
4.81 % (in alcohol: benzene 1:2 VA'")
17.6% (in hot water)
2. Pentosan = 13.3%
3. *LiLgnin = 31.0%
4. * Holo-cellulose = 70.5 %
5. * Alpha cellulose = 42.8%
6. Ash = 2.44 %
7. Hydrochloric = 0.16%
acid insoluble

• Calculated on extractive from oven dry basis

TABLE 2. THERMOGRAVIMETRIC ANALYSIS OF PINE CELLULOSIC

FIBERS.

IDT FDT DT (""C) at every 10% weight OSS

("C) (°C) 10% 20 7. 30% 40% 50% 60% 70'/, 80^0 90%
250 458 296 320 330 350 383 429 458 - -

TABLE 3. WATER ABSORPTION STUDIES OF PINE CELLULOSIC FIBER

FROM THE ATMOSPHERE AND IMMERSION IN WATER.

Percent moisture absorption from Percent water absoi•ption by the sample

atmosphere after immersed in water af :er
24h 48h 24h 48h
3.5 6.0 221.5 225.5

67
TABLE 4. CHARACTERIZATION OF PF, UF, PRF AND PLF RESINS

S.No Resin mole ratio/% Flow Time Water Curing Solid

(Sec) Tolerance Time* Contents
ResinrH^O (%)
1. PF F/P 1.74 29 1:6.5 11.55imL. 54.24
2. 1;97 32 1:8.5 14.38niin. 56.35
3. 2.20 25.5 1:5.5 12.32 45.50
min.
4. 2.44 21 1:6 11.32 nun. 42.23
5. UF FAJ 1.40 21 10:12 175 sec 49.67
6. 1.55 27.5 10:7 189sec. 47.51
7 1.63 28 10:7.5 160 sec 45.78
8. 1.74 25 10:5.5 152^ 46.22
9. PRF % 15 194 1:7 12.45nm 54.22
10. 20 238 1:7 13.07 miiL 58.63
11. 25 252 1:8.5 13.54 miiL 62.33
12 PLF 10 22 - 12.02 min. 46.35
13 20 26 - 12.20 tnin. 48.05
14 30 30 - 13.40 mia 53.41
15 40 35 - 16.25 58.35
16 50 46 - 19.23 min. 54.51

* PF, PRF and PLF at 135''C-140°C

UFat 100°C

TABLE 5. THE AMOUNT OF RESORCINOL IN PF RESIN AND

CORRESPONDING % PRF

S.No. PF(gm) Resorcinol % of resorcinol in PRF

1 300 30 10 (Cross linked)

2 300 45 15
3 300 60 20
4 300 75 25

TABLE 6. THE COMPOSITION OF LF TO PF IN PLF CORRESPONDING

TO % PLF RESIN
S.No. LF(gm) PF(gm) %ofLFinPRF
1 50 450 10
2 100 400 20
3 150 350 30
4 200 300 40
5 250 250 50

68
TABLE 7. COLD CURING OF PRF RESINS

S.No. Amount Formalin Initial Change in Diiference Curing

of PRF added Temp. **C Temp. °C in Temp. Time (hr)
15% (ml.)
(ml)
1. 5 1 22 23 1 14
2. 5 2 22 24 2 14
3. 5 3 22 25 3 14
4. 5 4 22 23 1 24
5. 5 5 22 23 1 24
20%
1. 5 1 22 24 2 14
2. 5 2 22 25 3 13
3. 5 3 22 26 4 19
4. 5 4 22 26 4 20
5. 5 5 22 24 2 20
25%
1. 5 1 22 25 3 12
2. 5 2 22 26 4 12
3. 5 3 22 27 5 16
4. 5 4 22 26 4 20
5. 5 5 22 26 4 22

69
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