GRAFTING OF STARCH BY RADICAL INITIATORS VINYL CHLORIDE

Under the supervision Submitted by Mr. RAMESH Poonam Malik

of DOGRA

Bsc-III

ACKNOWLEDGEMENT

I Poonam Malik student of BSC-III year of S D College Sector -32 C, Chandigarh gratefully acknowledge the valuable contribution of the individual involved in this project grafting of starch. The acknowledgements are due to all teachers of the department of chemistry studies. I sincerely thank Dr. Ramesh Dogra for guiding me in this project. I also thank the members of Chemistry department and my classmates who helped me a lot to prepare this project. I also took help from internet website and magazine Extra Edge. I also thank the college library for providing internet website and books. I also acknowledge the contribution of my parents for their valuable suggestions. At last I would like to thank to all the person involved to prepare this project

SANDEEP KAUR

100 80 60 40 20 0 1s t Qtr 2ndQtr 3rdQtr 4thQtr E a s t W es t N orth

S.No. 1 2 3 INTRODUTION

TOPICS

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STARCH OCCURANCE AND ISOLATION COPOLYMER COPOLYMERS GRAFT COPOLYMERS RADICAL POLYMERISATION EXPERIMENTAL SETUP EXPERIMENTAL CHARACTERISTICS STARCH OBSERVATIONS DIFFERENT TYPES OF

4 5

10 12

OF

GRAFTED 15 16

6 7

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RESULTS AND DISCUSSION EFFECT OF TIME EFFECT OF TEMPERATURE EFFECT OF MONOMER CONCENTRATION EVIDENCES OF GRAFTING REFERENCES

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INTRODUCTION
Naturally occurring organic polymers can be directed into six categories: 1. Polysaccharides, a category that includes gums, chitins, pectin, alginic, acid, starch, cellulose and many other. 2. Polypeptides or naturally occurring polyamides. This large group of macromolecules is found both in the vegetable and animal kingdom and is the major constituents of such diverse materials as silk, wool, horns, hoofs and feathers. 3. Polynucleotides or nucleic acids found in animal plant cells and in viruses. 4. Polyisoprenes, the constituent of hevea natural rubber balate and gutta percha. or

5. Lignins or polymeric material of coniferyl alcohol and related substances found in wood tissues . 6. Miscellaneous: polymeric materials found in nature such as some of the natural resins or for instance polyesters found in membranes of certain seeds and lichens. In the present dissertation attempts have been made to modify natural polymers such as starch, cellulose and wool protein by graft copolymerization. It is therefore, considered 5

worthwhile to review the chemistry of the natural polymer products.

STARCH
The word "starch" is derived from Middle English sterchen, meaning to stiffen. "amylum" is Latin for starch, from the Greek , "amylon" which means "not ground at a mill". The root amyl is used in biochemistry for several compounds related to starch. Starch or amylum is carbohydrates consisting of a large number of glucose units joined by glycosidic bonds. This polysaccharide is produced by all green plants as an energy store. It is the most common carbohydrate in the human diet and is contained in large amounts in such staple foods as potatoes, wheat, maize (corn), rice, and cassava

Starch is processed to produce many of the sugars in processed foods. Dissolving starch in warm water give which can be used as a thickening, stiffening or 6

gluing agent. The biggest industrial non-food use of starch is as adhesive in the papermaking process

Pure starch is a white, tasteless and odourless powder that is insoluble in cold water or alcohol. It consists of two types of molecules: the linear and helical amylose and the branched amylopectin. Depending on the plant, starch generally contains 20 to 25% amylose and 75 to 80% amylopectin by weight. Glycogen the glucose store of animals is a more branched version of amylopectin.

Structure of the amylose molecule

Structure of the amylopectin molecule OCCURANCE AND ISOLATION The starch industry extracts and refines starches from seeds, roots and tubers, by wet grinding, washing, sieving and drying. Today, the main commercial refined starches are cornstarch, tapioca, wheat and potato starch. To a lesser extent, sources include rice, sweet potato, sago and mung bean. Historically, Florida arrowroot was also commercialized. To this day, starch is extracted from more than 50 types of plants. Untreated starch requires heat to thicken or gelatinize. When a starch is pre-cooked, it can then be used to thicken instantly in cold water. This is referred to as a pregelatinized starch .Although starch material has been found in some bacteria protozoa and algae, its main sources are in 8

the higher plants, where the polysaccharide is laid down in the form of granules, which are insoluble in the cell medium. However, it is to be noted that the distinction between starch as the food reserve polysaccharide of plants and glycogen and the corresponding reserve polysaccharide in animals is not completely well defined, some animals can produce starch like material and some plants can produce glycogen like polymers. Starch is found in all parts of plants, the leaves stem, shoot and storage organs such as tubers rhizomers and seeds; the proportion varies from a few percent to 70 to 80% of the cereal grains. The starch granules in most plant material can be easily isolated but the extraction and purification of starches from cereal are difficult.

COPOLYMER
A heteropolymer or copolymer is a polymer derived from two (or more) monomeric species, as opposed to a homopolymer where only one monomer is used. Copolymerization refers to methods used to chemically synthesize a copolymer. Commercially relevant copolymers include ABS plastic, SBR, Nitrile rubber, styrene-acrylonitrile, styrene-isoprene-styrene (SIS) and ethylene-vinyl acetate

Types of copolymers

Different types of copolymers Since a copolymer consists of at least two types of constituent units (also structural units), copolymers can be classified based on how these units are arranged along the chain. These include:

Alternating copolymers alternating A and B units (2)

with

regular

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Periodic copolymers with A and B units arranged in a repeating sequence (e.g. (A-B-A-BB-A-A-A-A-B-B-B)n)

Statistical copolymers are copolymers in which the sequence of monomer residues follows a statistical rule. If the probability of finding a given type monomer residue at a particular point in the chain is equal to the mole fraction of that monomer residue in the chain, then the polymer may be referred to as a truly random copolymer

Block copolymers comprise two or more homopolymer subunits linked by covalent bonds (4). The union of the homopolymer subunits may require an intermediate non-repeating subunit, known as a junction block. Block copolymers with two or three distinct blocks are called diblock copolymers and triblock copolymers, respectively.

Copolymers may also be described in terms of the existence of or arrangement of branches in the polymer structure. Linear copolymers consist of a single main chain whereas branched copolymers consist of a single main chain with one or more polymeric side chains. Other special types of branched copolymers include star copolymers, brush copolymers, and comb 11

copolymers. In gradient copolymers the monomer composition changes gradually along the chain.

Graft copolymers
Graft copolymers are a special type of branched copolymer in which the side chains are structurally distinct from the main chain. A special case where the main chain and side chains are composed of distinct homopolymers. However, the individual chains of a graft copolymer may be homopolymers or 12

copolymers. Different copolymer sequencing is sufficient to define a structural difference, thus an AB diblock copolymer with A-B alternating copolymer side chains is properly called a graft copolymer.

RADICAL POLYMERISATION
A free radical is an atom, molecule or complex which contains one or more unpaired e-. This definition is very broad since it includes species such as nitric oxide NO, the chloride atom Cl, free methyl radical CH3 and atoms of transition metal which contain an 13

unpaired electron in an inner shell. The last named group is excluded from this definition of a free radical. Free radicals can exist in the gaseous and liquid phased. Radical polymerization has traditionally played a central role in the development of polymers chemistry. Many concepts of polymerization have initially been developed for radical polymerizations (1) have lent themselves very convent entry to the development of technical process they had flexibility and could be used for various processes such as bulk polymerization. Suspension polymerization and emulsion polymerization, most of which are polymerization technique based on radical process. Chemistry of radical initiators (peroxides) in vinyl polymerization and grafting. The molecules with bond energies of 25 to 35 K cal/m. should be useful radical initiator at 500C to 1500C. Several types of compounds have bonds with. Strength in this range, but for the most commonly used are those containing the peroxide O-O bond.

TABLE 1 Name Structure 14 Activatio n Energy

0

C For

t-Butyl peroxide t-BuO-OBu.t t-Butyl perbenzoate t-Buo-O-C-C6H5 Benzoyl peroxide C6H5-C-O-O-CC6H5 Acetyl peroxide CH3-C-O-O-C-CH3

37 34 30 30-32

150 125 95 85

Table 1lists some commercially available peroxides that are used as initiators. The table gives the activation energy for the dissociation reaction and the temperature at which the peroxide produces radicals with a 1 hour half life The compound listed in the table is useful because they are stable enough to be synthesized at ordinary temperature and can be stored for long periods refrigerator. They can be used as initiator at temperature at which most bonds do not undergo thermal hemolysis. BPO is one of the peroxidic compounds that has been extensively used in vinyl polymerization. The nonconceived mechanism for the unimolecular decomposition of BPO has been demonstrated many times through the interception of benzoyloxy radical by conventional scavengers including moist iodine (2) Galvinoxyl(3) and vinyl monomers(4). The later studies indicates that the activation energy for 15

decarboxylation of this intermediate must be more than 10 kal/m. BPO is believed to decompose in the following manner

When benzoyl peroxide is allowed to decompose in hot oxygen free benzene, the initially formed benzoyloxys radicals rapidly decarboxylated(5). Furthermore both benzoyloxy radicals and phenyl radicals can react by addition on by H abstraction. Conventional free radical initiators like BPO are known to effect polymerization of vinyl monomers.

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EXPERIMENTAL SETUP

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EXPERIMENTAL
Materials and method Unmodified dried soluble variety potato starch (BDH) has been used in all experiments(6). BPO was used without further purification, a weighted amount of BPO was dissolved in 1: 1 methanol-dioxane mixture. Purification of Monomer Monomers-vinyl acetate (VAc) (BDH) were purified by distillation under reduced pressure in presence of nitrogen atmosphere. Methyl acrylate (MA) (BDH) was shaken with 10% NaOH solution washed with distilled water and dried over anhydrous sodium sulphate and was then distilled under reduced pressure in presence of nitrogen. Purified monomers were store in refrigerator at 00C.

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Graft copolymerization:
Pure dry starch (2.0 g) was dispersed in 100 ml of cold deserted distilled water (600C) in a three necked flask The temperature of starch dispersion was brought to the water bath temperature Weighed amount of catalyst dissolved in appropriate solvent (1:1 Methanol-dioxene) was added to the reaction flask. . Definite amount of monomer (VAc) was added dropwise from the separatory funnel into the reaction mixture. The graft copolymerizaton was carried out under constant stirring by a magnetic stirrer. After completion of reaction, the reaction mixture was filtered and the residue was extracted for 24 hours, with boiling water for the removal of unreacted starch. The residue was then further extracted with appropriate solvent for 48 hours. Benzene was used as a solvent for Poly (VAc) and . After removal of homopolymer and unreacted starch, the residue was dried at 50C until constant weight was obtained.

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MECHANISM FOR GRAFTING OF POL(VAc) ONTO STARCH

I2 2II + M IM IMM I + Starch Starch +IH IMM+ Starch Starch + IMMH Starch + M Starch-M Starch (M)n IMM + M IM-(Mn) H Starch-(M)n + I Starch-(Mn)-I

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Characterization of grafted starch

The graft copolymers were characterized by determination of starch in graft copolymer by hydrolyzing weighed amount of graft starch. With 1 NHCl at 1100C for two hours when all the starch went into solution as glucose. The liberated glucose was estimated by titration with standard Fehling solution by using methylene blue as indicator. From the amount of starch in graft copolymer, percentage of grafting and percent efficiency has been calculated as follows: % grafting = W2/W1 x 100 % grafting efficiency = W2/W3 x 100 Where W1, W2, W3 denotes respectively, the weight of the graft copolymer after water and benzene extraction, the weight of the polymer grafted and the weight of the monomer used. Percentage of grafting and efficiency were determined as functions of time, temperature, monomer con and catalyst concentration and the results are in tables 2 21

OBSERVATION
EFFECT OF TIME
Sl No. 1. 2. 3. Conc Vac Temperature(0 (mol/L) C) -4 0.5 10 60 -4 0.510 60 -4 0.510 60 Time(min % ) Grafting 120 9.6 60 10.6 90 29.0

EFFECT OF TEMPERATURE
Sl No. 1. 2. 3. Conc.Vac (mol/L) 1.0810-4 1.0810-4 1.0810-4 Temperature(0 C) 55 65 70 Time(min % ) Grafting 90 21.1 90 27.5 90 17.4

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EFFECT OF MONOMER CONCENTRATION

Sl No. 1. 2. 3. Conc.Vac (mol/L) 1.0810-4 0.710-4 210-4 Temperature(0 C) 60 60 60 Time(min % ) Grafting 90 53.6 90 1.3 90 0.0

RESULT AND DISCUSSION

In a free radical polymerization percent conversion of the monomers is dependent upon the nature of initiator and monomer. Benzoyl peroxide is known to effect polymerization by free radical mechanism. In free radical polymerization after termination of the growing chain occurs through chain transfer. A chain transfer reaction is defined as the phenomenon in which termination of growing chain occur without destruction of the kinetic chain. Abstraction of hydrogen atom or a labile atom by growing radical is a well-recognized and extensively studied reaction is free radical vinyl polymerization. During these processes, the propagating chain terminates and a new radical is formed. When polymerization of a vinyl monomer is carried out in the presence of a backbone polymer (starch), the growing radical may abstract a hydrogen atom from the backbone polymer forming active sites upon starch where grafting may occur by the addition of 23

monomer. The following chain transfer mechanism is suggested for grafting of vinyl monomer into starch by free radical initiators I2 represents initiator molecules and M the monomer. Since starch is easily dispersible in water, it is more accessible for attack by radical initiator. Cellulose being insoluble in water is less accessible and the no. of active sites generated on starch by hydrogen abstraction is expected to be larger. Further according to the above grafting is dependent upon: 1. Nature and concentration of the 2. Nature and concentration of the 3. Type of the backbone upon occurs. 4. Nature of the reaction medium mechanism % initiator. vinyl monomer which grafting

Water has been used as medium in all the experiments and hence the effect of solvent upon percentage of grafting is ignored, since water has a low chain transfer constant. Starch has been used as a polymer backbone in all the experiments, so effect of the nature of polymer backbone is the same. Therefore in the parent study, percentage of grafting is primarily determined by nature and concentration of catalyst and by the concentration and reactivity of vinyl monomer. Since starch is easily dispersible in water (I) has a greater chance to react with starch and thus wastage of (I) by cage recombination is minimum when grafting is carried out in presence of starch. This explanation finds support in the observation with increase in concentration of BPO, 24

Vac given higher percentage of grafting than cellulose. However beyond optimum concentration of initiator. Further increase in BPO concentration leads to decrease in percent grafting .At higher concentration BPO may undergo induced decomposition. This would then decrease the radical conc. and would lead to decrease in percent grafting maximum grafting of (53.6%) of Vac was obtained at catalyst concentration of 1.8 x 10-4 mol/liters

Effect of time Table show that maximum grafting occurs within 90 min for Vac Beyond 90min, % grafting decreases. The decrease in % grafting beyond 90 min is attributed to the occurrence of induced decomposition of BPO. With increase in reaction time some initiator fragments escape from the cage and react with initiator molecule leading to decrease in concentration of radical fragments. Increase in reaction period may bring about mutual annihilation of growing radical resulting in net decrease in percent grafting. Effect of temperature It is observed from the table that with increase in temperature percent grafting increases and reaches a maximum value at 600 for Vac. This would be 25

expected since chain transfer reactions usually have higher energy of activation. Further increase in temperature leads to decrease in percent grafting due to acceleration of some of the termination process the exact nature of which remains to be elucidated. Effect of monomer concentration It can also be seen from the tables that with increase in monomer concentration percent grafting increases with Vac and reaches a maximum value. Further increase in monomer concentration leads to preferential formation of homopolymer with monomers. The growing polymeric radical at higher concentration may terminate grafting by process 8 and this should reduce % grafting. In fact it is observed from tables that when the monomer concentration exceeds 1.08 mole/L in case of Vac, % grafing decreases.

REFERENCES

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1.J.C.Bevington, Acrylonitrile in macromolecules, Acad. Press London/New York 1961

2.G.S Hammonol and L.M Sofffer , J.Am. Chem. Soc, 85 ,3613(1963)

3.Shina, J. Waters and D.Hoffmans J. Am. Chem. Soc, 85, 3613 (1963)

4.G. Ayrey Chem, Rev. 63, 645 (1963)

5.Y. Iwakura, T. Kurasaki and Y. Imai, J. Polym. sci. , A, 3, (1965)

6.E-Marck

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