POLYMERS

Definition- poly-many, mer-part Polymer consist of many small molecular weight molecules, called monomers, linked together to form large molecules called macromolecules. A polymer is material whose molecule contain a very large number of atoms linked by covalent bond which makes molecule macromolecule. Polymer consist of same or different units

Eg: polybutadiene-synthetic rubber polymer Mol.wt-20,0000. Gaseous compound butadiene combines nearly 4000 times(mol.wt-54) which gives polymer polybutadiene. Butadiene (4000 molecules) Polybutadiene (200000) General properties of polymer 1. 2. 3. 4. 5. 6. 7. 8. 9. Can be very resistance to chemicals Thermal and electric insulators. Light in weight and varying degrees of strength. Can be proceed in various ways to produce thin fibers Should be inert and compatible with the environment. Should be non-toxic. Should be easily administered. Should be easy and inexpensive to fabricate. Should have good mechanical strength .

Monomer: molecule that combines with others (identical or different) to form a polymer Ex. ethylene (PE polyethylene) Oligomer: low molecular weight polymer, constituted of at least two monomers. Indicates a chain of n units Degree of Polymerization (D.P)=number of repeat units (N). Mechanical properties increases with D.P In practice: limitation because processing becomes difficult with high M (relation viscosity M) Classification Based on 1. 2. 3. 4. 5. 6. 7. 8. Form of network Reaction polymerization Physical property to heat Type of monomer Origin Shape Nature Interaction with water D.P=N

A)based on form of network 1) one dimensional linear a)Crystalline b)amorphous 2) two dimensional sheet eg: graphite 3) Three dimensional bulk B)reaction polymerization/Carothers classification 1)Addition polymersa)Free radical polymers b)Anionic polymers c)Cationic polymers d)Coordination polymers 2)Condensation polymers C)physical property to heat/Baekelands 1)Thermoplastics a)Crystalline b)Semi crystalline c)amorphous 2)Thermosets 3)elastomers D)Type of monomer 1)Homopolymer 2)Copolymer a)Alternating gradient copolymer b)Random copolymer c)Block coplymer d)Graft copolymer E)Origin 1)Natural polymer 2)Synthetic polymer 3)Semi synthetic polymer 1)Linear 2)Branched 3)crosslinked 1)Organic polymer 2)Inorganic polymer a)homochain inorganic polymer b)Heterochain polymer

F)Shaped

G)Nature

H) ON BASIS OF INTERACTION WITH WATER: 1)Non-biodegradable hydrophobic Polymers- E.g. polyvinyl chloride, polyethylene vinyl acetate 2)Soluble Polymers - E.g. HPMC, PEG 3)Hydrogels -E.g. Polyvinyl pyrrolidine

I) Based on Bio-stability : a) Bio-degradable Polymers : e.g. polyesters, proteins, carbohydrates, etc b) Non biodegradable Polymers : e.g. ethyl cellulose, HPMC, acrylic polymers, silicones. A)Form of network 1)one dimensional linearoccur when2 reacting chains join to make a chain. if long chain packed regularly, side by side, they form crystalline polymers. eg: fibers, single crystals polyethylene. If irregularly tangled ,polymer is amorphous. eg: rubbers, polystyrene 2) two dimensional sheet eg: graphite condition is to have 3 or more active grp. all directed in same plane and capable of forming a planar network. low shear strength , good lubricating property. 3)Three dimensional bulk-eg: crystalline diamond in which carbon is linked to 4 corners of tetrahedra and these are packed with long range range order in space to form a lattice. B)physical property to heat/ Baekeland classification 1)ThermoplasticsIn this molecules are held with weak inter molecular forces. -Get soft when heated and solidifies when cooled. -Particular solvents can be used to dissolved thermoplastic polymers. -One dimensional polymers. Mostly produced by chain polymerisation. Eg: PVC , PP,PE Can be formed and reformed in so many shapes so widely used Eg: food packing, credit cards. 2)Thermosets : Simultaneous polymerization and fabrication steps produced thermosetting polymers. Not reshaped by heating. Strong and durable. High degree of cross linked, so it restricts motion and get rigid. No solvent to dissolved polymer. Primarily used in automobile and construction to make toys ,varnishes ,boat hulls ,glue. On heating physical bonds get breaks and material get soft, but not primary bonds. they bonds allow thermoplastics to deform if subjected to stress and allow redistribution of load at point of stress condition. 3)Elastomers : body returns to its original state instantaneously upon removal of stress. Flexible at room temperature, they are cross linked. Eg; rubber bands In their natural condition, elastomers behave in a similar manner to thermoplastics (viscoelastic) i.e. applying a force causes the chains to uncoil and stretch, but they also slide past each other causing permanent deformation. This can be prevented by cross-linking the polymer chains. a)Crystalline polymer : Polymer which possess long range,3-dimensional structure, are called as crystalline polymer. Rigid, high melting, less affected by solvent penetration. The ability of a polymer to crystallize is affected by: Complexity of the chain: Crystallization is easiest for simple polymers (e.g. polyethylene) and harder for complex polymers (e.g. with large side groups, branches, etc.)

Cooling rate: Slow cooling allows more time for the chains to align Annealing: Heating to just below the melting temperature can allow chains to align and form crystals Degree of Polymerization: It is harder to crystallize longer chains b)amorphouspolymer chains with branches or irregular pendant group cannot pack together regularly enough to form crystals, called as amorphous polymer. This region made up of randomly coiled and entangled chains. Softer, low melting point. Solvent penetration is more than crystalline polymer. c)Semi crystalline they have both crystalline and amorphous regions. It is desirable property for plastics. it is tough with ability to bend without breaking. If polymer as having distinct crystalline and amorphous region then % of polymer that is crystalline is called % crystallinity, has an important influence on properties of polymer. C)polymerizations/Carothers classification: Process of joining together small molecule or monomer by covalent bonds to form large molecules with or without formation of other products is known as polymerization. Occurs with same or different monomeric compound 1)Addition polymerization: molecules just add to form polymer.Requires initiator to start growth of reaction. Monomers retains its structural identity when it gets converted to polymer. eg: ethylene ------------> polyethylene This can be represented as- A-A-A-A-A Several chemical reactions takes places -initiation reactionR-O-O-R 2RO* Initiator light/ active species -Propagation 2RO*+CH2=CHX ROCH2-C*HX monomer activated monomer -Termination RO-(-CH2-C*HX)n + (XHC*-CH2-)m-OR

RO-(-CH2-CHX)m + n- OR polymer

Note-in complete polymer all double bonds converted to single bonds. Eg: ethylene peroxide(catalyst) LDPE 5000C,1000atm press LDPE-transperant, highly branched, low density. 2) Condensation polymer/c polymerization/stepwise polymerization: Monomers consisting of two functional group(-OH,-COOH,-NH2)react with each other to form covalent bonds. it also release molecule like water or ammonia. n OH-CH2-CH2-OH + n COOH-B-COOH OH(-CH2-CH2-O-C0-B-CO-)-H + H2O Monomer monomer polymer Eg: ethylene glycol + terephthalic acid polyethylene terephthalate

D)Origin 1)Natural polymer-Natural polymers remains the primary choice of formulator because - They are natural products of living organism - Readily available - Relatively inexpensive - Capable of chemical modification Moreover, it satisfies most of the ideal requirements of polymers. But the only and major difficulty is the batch- to-batch reproducibility and purity of the sample. Eg:gelatin, arabic gum ,cotton 2)Synthetic polymer- polymers which are synthesized from low molecular weight compound. eg:PVC, PE 3)Semi synthetic polymer(cellulose derivative)-Eg: HPMC E)Type of monomer 1)Homopolymer-consist of chains with identical bonding linkages to each monomer unit. represented as - A-A-A-A-A 2)Copolymer- A polymer with two different monomers is known as a copolymer. Represented as- -A-B-A-B-A-Ba)Alternating copolymer-in this monomer units get repeated. and represented as A-B-A-B-A-Bb)Random copolymer-monomers repeated units arrange randomly. and represented as A-A-A-B-B-A-A-B-A-Bc)Block copolymer-have chain with long sequence of each repeating unit along the main polymer chain. Represented as A-A-A-A-B-B-B-B-A-A-A-A-B-B-B-B d)Grafted copolymer-consist of A side chain grafted on to B chain. F)Shaped 1)Linearthese are generally randomly coiled.The occupied volume of random coil is larger than that of constituted atom. 2)Branched polymerDue to result of side chain reaction during polymerization. 3)Cross linked polymer- form network structure with monomer that have more than one functional group during polymerization. G)Nature 1)Organic polymer-polymer whose backbone chain made up of carbon atoms is called as organic polymer. PVC,PE,PP. 2)Inorganic polymer- they contain no carbon atom in their chain back bone.Eg: glass, silicone rubber H)Bioderadable polymersBiodegradable polymers are defined as polymers comprised of monomers linked to one another through functional groups and have unstable links in the backbone. eg:collagen,gelatin. They slowly disappear from the site of administration in response to a chemical reaction such as hydrolysis. Molecular weight of polymers Related to the length of the Chains Units: generally - g/mol Mechanical properties with M, but processing becomes more difficult Commercial polymers: large distribution of molecular weights

Depending on methodof determination different molecular weight obtained: 1 Number of average molecular weight (Mn) 2 Weight average molecular weight (Mw) 3 Viscosity average molecular weight (Mv) 4 Z average molecular weight (Mz.) For mono dispersed system Mn=Mw=Mv=Mz But not for polydispersed. Properties dependent on Molecular Weights and Molecular Weight Distributions (MWD) Melt Viscosity Tensile Strength Toughness or Impact Strength Resistance to heat Corrosive Properties Number Average Molecular Weight (M) 1)Physical method a)cryoscopic method (freezing point depression) b)Ebulliometry method (boiling point elevation) c)osmometry method 2)Chemical method- chemical reactivity is the direct function of number of molecules present in sample a)End group analysis. a)cryoscopic method (freezing point depression) Used the phenomenon-depressing the freezing point of liquid by addition of solute. extent of freezing point depression depends on no of solute molecule dissolved per unit volume of solution. Eg: water freezing point is0C, get depressed by adding CaCl2 or NaCl. Molecular weight up to 30000 can be measured. Calculated as-lim

co

Tf = RT f 2 c Hf

1 M

Where C- concentration of solution. - density of solvent Tf - change in freezing point Hf- Heat of fusion of solvent. R-universal gas constant. Tf- - freezing point of solvent

b)Ebulliometry method (boiling point elevation) It is based on BP of solution (of non volatile solute)is higher than that of pure solvent. Molecular weight up to 30000 can be measured. Calculated as lim co Tb = RT b 2 c Hv 1 M

Where Tb BP of solvent. Hv -Heat of vaporization. Problem-in measurement of extremely small change in temperature.

Membrane Osmometry In the case of a dilute polymer solution of a low finite concentration separated from the pure solvent by a semipermeable membrane. The chemical potential of the solvent (s) in solution is less than that (o) of pure solvent and therefore, to keep the system in equilibrium, the chemical potential of the solvent on the two sides of the membrane requires to be balanced and made equal. This is readily done by applying an excess pressure, , called the osmotic pressure

Fig-Operating Principle and Schematic Presentation of a Membrane Osmometer Calculated aslim co c = RT M

Where osmotic pressure. Types of membrane osmometer 1)Fuoss-mead block osmometer 2)pinner-stabin glass osmometer 3)Stabin shell automatic osmometer 4)reiff osmometer Static equilibrium method are simple but have some draw back like diffusion through membrane is very slow so time consuming. On the basis of dynamic principle (HSMO) high speed membrane osmometer is available. It takes 5-7 min to attain equilibrium. But no availability of true semipermiable membrane. Currently available membrane1)Gel-cellophone membrane 2)Bacterial cellulose membrane 3)Denitrated collodion membrane

2) End group analysis method Use for polymer samples whose molecule contains reactive functional group at one end or both end. Mn = functionality Functional group equivalent Functionality of polymer- number of reactive functional group present in molecule. Average Molecular Weight M generally expressed as

M = f1 M1 + f2 M2 + f3 M3 + ------ = fi Mi (1)
Here, M1 , M2 , M3 etc. refer to molecular weights of different sizes of molecules and the coefficients f1 , f2 , f3 etc. are fractions . Average molecular weight assumes importance in the context of various bulk properties of polymers, particularly the rheological and resistance properties Another methods are1)Ultra centrifugation methoda)sedimentation velocity method b) Sedimentation equilibrium method 2)Light scattering methodLight scattering photometers employ photoelectric technique for measurements of scattering data. The specified scattering glass cell is placed on the fixed center table and centre on the axis of rotation of the receiver photomultiplier tube assembly; this assembly can be rotated and fixed at desired angular positions for measurements of the scattered light. Besides the measurements of intensities of incident and scattered light, i.e. the turbidity. , it is necessary to determine the refractive index n of solvent and the parameter (n / c) using a differential refractometer.

Operating Line and Principle of Light Scattering Photometer The choice of solvent is also important. The difference in the refractive index between the polymer and the solvent should be as large as possible. Molecular weights ranging from 10,000 to 10,000,000 are measurable by this technique. Calculated as: KC = 1 R Mw Where R -rayleigh ratio at 90observation angle. K=constant K = 2 n (dn/dc) Where n= refractive index 4 NA dn/dc= change in refractive index. NA= Avogadro's number = wavelength of incident light

Ultracentrifugation method: The ultra centrifugation techniques are somewhat complicated and much less commonly employed for molecular weight measurements of synthetic polymers. Use centrifugal force to separate suspended particles from liquid. a)sedimentation velocity method: Solution is subjected to very high gravitational fields. Due to high centrifugal force polymer molecules will starts sediments.

M = SRT D(1- V)
Where, S= sedimentation constant D =diffusion constant V=specific volume of polymer solution b)sedimentation equilibrium method: thermodynamic equilibrium is achieved by practically equalizing sedimentation and diffusion. The Z-average molecular weight is commonly measured by sedimentation equilibrium method using an ultracentrifuge.Mz is expressed as : Mz

= Ni Mi 3 Ni Mi 2

the molecular weight M is expressed as M= 2 RT ln ( c2 / c1 ) (1 v ) 2 (r22 r12) where c1 and c2 are the concentration at two points corresponding to distances r1 and r2 in the cell , is the angular velocity of rotation, v the partial specific volume of the polymer Viscosity Average Molecular Weight: The viscosity of a polymer solution ( ) is higher than that ( o ) of the pure solvent at a specified temperature and the increase in medium viscosity on dissolving the polymer in the solvent is a function of both molecular weight and concentration of the polymer solute. the viscosity average molecular weight (M) is given by the semi empirical Mark Houwink equation : Lt . c o , sp / c = *+ = K M a . where , sp =specific viscosity A ,k =constant for particular polymer/ solvent/ temperature system. sp =(n/no-1) n/no = t/t0 (t, to are flow time of solution and pure solvent respectively) Two types of viscometer are use: a. Ostwald Viscometers b. Ubbelohde Viscometers

Fig-Logarithmic Plot of [ ] vs. M

a) Ostwald type and (b) Ubbelohde type Capillary Viscometers

M = Average Number of Repeating Units n or dp Examples: (1) Find M for (Cl2P=N)n if n = 10,000? 2 X Cl = 70.9 1 X P = 31.0 1 X N = 14.0 Molecular Weight of repeating Unit = 115.9 ~116 M = n or dp x Mol. Weight of repeating units = 10,000 X 116 = 11,600,00 (2) Find M for (F2P=N) Where n = 5,000?

F=2x19=38 P=1x31=31 N=1x14=14

Total

= 83 = 83x5000 Answer= 415,000 Applications The polymer can protect the drug from the physiological environment & hence improve its stability The pharmaceutical applications of polymers range from their use as binders in tablets Viscosity and flow controlling agents in liquids, suspensions and emulsions Polymers are also used as film coatings to disguise the unpleasant taste of a drug, to enhance drug stability and to modify drug release characteristics in vivo Method of preparation of synthetic polymer Synthetic polymer Polymers which are synthesized from low molecular weight compound are called synthetic polymers. Eg : polyethylene ,PVC, nylon, terylene. Preparations of polymer: 1)Monomer purification 2)Preparation method 3)Isolation and purification Precaution during preparation of polymers: Avoid direct contact with skin Chemicals are toxic ,corrosive so handle with care Exp should carried out in fume hoods Protective appliance should be used Polymerization reactions are exothermic and can get out of control leading to fire so conducted in laboratory safety screen. 1)monomer purification: Monomers are require to purify because during transport and storage it under goes polymerization so to avoid it inhibitors are added eg : hydroquinone , tertiary butyl catechol . To remove these inhibitors monomers get purified by Washing with dil alkali Distillation under reduced pressure.

Process For water in soluble polymer: Monomer+5% KOH in separating funnel Inhibitor react with KOH form water soluble product.So monomer can remove from solution . in most case alkaline solution is colored so washing stop when no coloration occur.

Washed with water, dried using CaCl2 ,NaSO4 , NaHCO3 Method of preparation of synthetic polymers 1. Bulk polymerization 2. Solution polymerization 3. Suspension polymerization 4. Emulsion polymerization 5. Precipitation polymerization 6. Interfacial polymerization 7. Electrochemical polymerization 8. Graft polymerization 9. plasma polymerization 10. Solid and gas polymerization 1)Bulk polymerization Conversion of monomer to polymer in absence of diluents or dispensing agents is known as bulk polymerization. This require simply heating of monomer with initiator under suitable condition to form polymer. Disadvantage: 1)As polymerization Viscosity , mixing get difficult. 2) Diffusibility of growing chain is restricted due to viscosity, so collision of chain is less so active species accumulated. and polymerization rate suddenly. 3)On industrial scale it is impracticable because of problem of heat generated during polymerization. Eg: VC PVC styrene polystyrene Procedure for polystyrene: 50 mg freshly recrystalised dry inhibitor azobisisobutyronitrile (AIBN)+10 ml styrene in 100 ml RBF Shake to dissolved it. +40 ml styrene +500 mg dodecyl mercaptan (DDM)(chain modifier ) Flush flask with N2 for 15 min. Water condenser fitted to flaskand place at cost temperature 7010c. shake for 5 min After 40 min viscosity of content indicate polymerization progress. When flask attain high viscosity, content empty in beaker containing toluene 250ml. stir with glass rod to form soln Pour in 2L methanol with constant stirring to recover polymer. Filter and washed with methanol , dried at vacuum 600c.

Fig: assembly for preparation of polymer Solution polymerization Monomer + inert solvent + initiator + chain transfer agent + ionic catalyst. Inert solvent help to control viscosity. 1)Pseudo solvent system 2) true solvent system 1)Pseudo solvent system: System in which monomer is in true solution but polymer separates as swallone phase. It is similar to bulk polymerization. Solvents : methanol , cyclohexane. 2) true solvent system: monomer polymer solvent are in true solution. True solvents: THF- tetrahydrofuran, chlorobenzene,1L dichloroethane. SUSPENSION POLYMERISATION Represent polymerization of macroscopic droplets in medium (aq) to produce microscopic polymer which are readily separate from reaction medium. Used with water in soluble monomer or partially water soluble monomer. Particle size is depend on: 1) Ratio of monomer to water 2) Rate of agitation 3) Nature and concentration of suspending agent 4) Nature of monomer. Suspending agents : gelatin, starch, PVA, calcium phosphate ,gums Inhibitors: AIBN benzoyl peroxide , persulphates. Polystyrene is made in a process known as suspension polymerization. After styrene is produced by combining ethylene and benzene, it is merged with water and a mucilaginous substance to form droplets of polystyrene. Next, the droplets are heated and combined with an initiator, which begins the process of polymerization. The droplets combine to form chains, which in turn combine into beads. Stopping the process with terminators.

Eg : PVC methyl methacrylate : Inhibitor: benzoyl peroxide(0.1g) Emulsifier: cetyl dimethyl benzyl ammonium chloride.(0.02g) Protective collide: PVA(0.05g) 0 Temperature: 75 1 c Washing: warm water

EMULSION POLYMERISATION Produced polymer in form of stable lyophobic colloide. Emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water,, monomer and surfactant. The most common type of emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer (the oil) are emulsified (with surfactants) in a continuous phase of water. Water-soluble polymers, such as certain polyvinyl alcohols or hydroxyethyl celluloses, can also be used to act as emulsifiers/stabilizers. When water-soluble polymers are used as stabilizers instead of soap, the repulsion between particles arises because these water-soluble polymers form a 'hairy layer' around a particle that repels other particles, because pushing particles together would involve compressing these chains.

Fig :Emulsion Polymerization Polymerization of styrene: 180 ml of DW+100 mg potassium persulfate (initiator) in 3 necked 1 L RBF +100 mg NaHPO4 (buffer)+ 1g SLS (emulsifier)+ 100ml styrene Fitted with condenser, stirrer To flush N2 inlet tube dipped in content (7010c) stir for 4-6 hrs Content of flasked attain latex, removed it

+50 ml 3%sol aluminium sulfate , stir Latex coagulated Washed with warm water and methanol and dried. PREPARATION OF CARBAPOL COATED NANOPARTICLES BY EMULSION POLYMERIZATION TECHNIQUE MATERIALS : Methyl methacrylate ,Carbapol Ammonium persulphate (inhibitor)

Preparation of Carbapol coated nanoparticles: prepared by emulsion polymerization technique in a closed 100ml flask. Carbapol was dissolved in 100 ml water under magnetic stirring at 400-500 rpm. 1% (w/v) of the monomer methyl methacrylate was dissolved in the above mixture at 75oc and APS solution was added. The reaction was completed after 24 hrs. Advantages of emulsion polymerization include: High molecular weight polymers can be made at fast polymerization rates The continuous water phase is an excellent conductor of heat and allows the heat to be removed from the system. Since polymer molecules are contained within the particles, viscosity remains close to that of water and is not dependent on molecular weight. The final product can be used as is and does not generally need to be altered or processed

Disadvantages : Surfactants and other polymerization adjuvant remain in the polymer or are difficult to remove For dry (isolated) polymers, water removal is an energy-intensive process Emulsion polymerizations are usually designed to operate at high conversion of monomer to polymer. This can result in significant chain transfer to polymer. Application: in adhesives, paints, paper coating and textile coatings. Precipitation polymerization : in this polymer is precipitate from solution as it is in soluble in solvents. Acrylonitrile: 50 mg AIBN +50 ml Acrylonitrile +200 ml toluene flushed with N2 70 1oC After some time turbidity developed i.e polymer starts precipitate and settle at bottom Filter, washed with methanol and dried Interfacial polymerization: Reaction is carried out at interface of two immiscible solvents , having very reactive functional group so react at ambient temperature . Variables involved in this are: Organic solvents : control partition and diffusion of reactants between two immiscible phases, reaction rate solubility and swelling of growing polymer. Composition of solvents should be such that it does not allow ppt till require high molecular wt is achieved Solvents: chlorinated and aromatic hydro carbon. Advantages: Low temperature process, so polymers which are unstable in melt polymerization can be handle. Random and block polymer can be form. Eg: nylon 66 Polymerization of terephthaloyl chloride and ethylene diamine. 20 g terephthaeloyl chloride +200 ml CCl4 In 500ml beaker In another beaker 50 mlwater+2-3pallets of NaOH +5g ethylene diamine This solution added to acid chloride solution care taken during adding that it add by side not at center so form layer. After some time film form at inter face between organic and in organic layers. film is polyamide which form by condensation between acid chloride and amine at interface.

Electrochemical polymerization: involves generation of propagation center by electrolysis of conducting solution of monomer in bulk or polar solvent The difficulty is electro active/conductive polymer films can be generated on electrode surfaces by the oxidation of aromatic compounds such as benzene, and heterocycles. This phenomenon is used to advantage in coating of metal surface electronic and electro chromic devices, In counter electrode in electrolytic capacitors chromatographic stationary phases, light-weight batteries, membrane separation. Fig: electrochemical polymerization.. in book Graft polymerization: Consist of A side chain grafted on to B chain. In case one polymer is dissolved in another and mixture is then subjected to polymerization, then chain transfer between growing chain of monomer and molecule of polymer. The long chain of one type of unit are joined to back bone chain consisting of other unit such polymerization called as graft polymerization. Kennedy divided these reaction in to 2 main group: 1)Grafting on to reaction in which propagating macrocations terminated on polymerized backbone. 2)Grafting from reaction in which polymeric backbone is employed as micro initiators for cationic polymerization. Eg: poly (dimethylamino styrene) and poly(2-vinyl pyridine) Solid gas polymerization : solid polymerization is restricted to chain polymerization . radiation or photo activation is required. Eg: trioxane Gas phase polymerization is known to few olefinic compound. Two method are used 1)spraying catalyst in gaseous monomer 2)feeding monomer in fluidised bed containing catalyst. Eg: ethylene gas pass through fluidised bed containing zeigler catalyst(titanium chloride + alkyl ammonium in pentane) At RT and pressure at 4-5 atm polymer form is collected as free flowing powder . Plasma polymerization: Plasma : Any ionized gas containing positively charge molecules and atoms and negatively charge electron is said to be plasma state. Glow discharge: DC current pass through gas at low pressure between two electrode then it produced glow discharge. The plasma polymer does not contain regularly repeating units, the chains are branched and are randomly terminated with a high degree of cross linking. The cross linking in plasma polymer increases with the intensity and energy of bombarding ions. Basic operating mechanism Plasma polymerization (or glow discharge polymerization) uses plasma sources to generate a gas discharge that provides energy to activate or fragment gaseous or liquid monomer

Figure 1. Schematic representation of basic internal electrode glow discharge polymerization apparatus Production: Combustion ,flames, controlled nuclear reaction, electric discharge can produced plasma. Electric discharge maintain plasma state for longer period glow discharge is favorable for polymerization. At pressure of 0.1to 10 torr further in pressure positive glow disappear leaving negative glow

Fig. Normal glow discharge

Density of plasma in negative glow is 100 times more than positive glow. Ionization with electron energy. during this they excited to higher state and looses energy and return to ground state. Electron act as carriers of energy but capyure by molecules to form negative ions. The overall power input in plasma polymerization is used for two things: for creating the plasma and for fragmentation of monomer. The major polymer deposition occurs onto the substrate surface that makes contact with the glow. Not all glow discharges yield polymer deposition though. The plasmas of Ar, Ne, O2, N2 are non-polymer forming and as such can be used to maintain the glow in the vacuum chamber while the monomer vapor is used efficiently for polymer conversion. Common monomers Thiophene , Pyridine , Acrylonitrile ,Furan Styrene ,Acetylene,2-Methyloxazoline Tetramethyldisiloxane PROCESSES EGS. Bulk polymerization Solution polymerization Suspension polymerization Emulsion polymerization Interfacial polymerization Methyl methacrylate , nylon 66, Styrene in ethyl benzene, propylene in hydrocarbon VC, acrylonitrile in water Butadiene , styrene Isophthaloyl dichloride in methylene chloride ,m-pheneylene diamine in water

3)Isolation and purification of polymers: For Precipitation polymerization: as polymer get ppt out ,obtained as fine polymer. For Suspension polymerization: polymer obtained in beads so by filter/centrifugation separates and washed with water or suitable solvents. For Bulk and Solution polymerization: polymer is in solution. so purification done by Precipitating polymer using nonsolvents which is miscible with monomer and solvent. for good precipitation polymer solution is diluted to 3-5% concentration and add in large amount of non-solvent slowly with stirring. polymers separates as solid lumps. reprecitate to improve purity. For Emulsion polymerization: polymer isolated by breaking emulsion with electrolyte eg: HCL, NaCl, alum, or by freezing. Then washed with water and again reprecipitate to get purified. Purified polymers are dry in vacuum or in inert atmosphere to temperature as low as possible say 60oC. polymer solubility characteristics uses Brand name hydroxyethyl cellulose soluble in water, ethylene glycol. Insoluble in ethyl ether discolors and becomes used as an emulsifier, insoluble with thermal stabilizer, thickener and film aging former in many types of solutions such as foods, cosmetics, paints and glazes. It is also used as a sizing agent and consolidant resistant to alkalis, good impact, tensile fibers, paints, films, foams, and and insoluble in and flexural strengths, molded parts most organic elasticity, and wear solvents. Soluble resistance as well as in hot phenols, low water absorption cresols and mineral acids soluble or miscible can remain tacky and solvents, plasticizers, in water and most attract dirt consolidants organic solvents soluble in most hydrocarbon solvents, oils, ketones, esters, inorganic acids soluble in aromatics, ketones, aldehydes and chlorinated solvents inexpensive; good stability, stiffness, and impact strength; degrades in UV light approved for contact with food; used in insulation, toys, appliances, cabinets, containers, and furniture Natrosol [Aqualon]; Cellosize [Union Carbide];

nylon (polyamide)

Akulon; Caprolan: Celon; Durethan; Nylon 66; Nylon #66; fiber 66:

polyethylene glycol

Carbowax [Union Carbide]; Polywax [Huls] Styrofoam [Dow]; Luran; Styron; Lustrex; Fome-Cor; Algil [Polymers, Inc.]; Permene [Modglin Co.]; Shalon Geon [B.F.Goodrich]; Koroseal [B.F.Goodrich]; Tygon; Vinagel; Elaston; Trovidur; Bexan

polystyrene

polyvinylchlo ride

resistant to ignition, corrosion and stains.

gramophone records, sheeting, gaskets, tubing, raincoats, waterproof coatings

 Thermal characterization - Glass transition temperature - Glassy solids and glass transition - Transitions and associated properties - Factors influencing glass transition temperature - Glass transition temperature and molecular weight - Glass transition temperature and melting point - Importance of glass transition temperature - Determination of glass transition temperature - Heat distortion temperature GLASS TRANSITION TEMPERATURE What is glass transition temperature? Consider a rubber ball if it is cooled below -70c it becomes hard and brittle and will break into pieces like a glass falling on hard surface same like that there is a temperature boundry for all polymers which it becomes soft, flexible and rubbery and below which it becomes hard brittle and glassy. The temperature below which polymer is hard and above which it is soft, is called as Glass transition temperature. Hard, brittle state- Glassy state Soft, flexible state- Rubbery state or viscoelastic state . On further heating ,the polymer becomes a highly viscous liquid and starts flowing, this state is termed as viscofluid state and temperature is termed as Flow temperature. Glassy state (Brittle plastics) Rubbery state/Viscoelastic State (Rubbers/ plastics) Visco fluid state (polymer melts)

Tg

Tf

GLASSY SOLIDS AND GLASS TRANSITION States of aggregation- Low molecular compouds- Solids, Liquids and Gases Polymers- Solids and Liquids Molecules occupy definite positions within crystal lattice This arrangement is repeated several times in all three dimensions Long range order of crystalline solid Posses vibrational motion, not molecular translational motion

External force Increase in temperature

As the molecules are in rigid state,plane formed by this system is also rigid and inflexible Kinetic energy is added to the system Individual molecules start vibrating more and more vigorously and move out of their position(brownian movement) More vigorous brownian movement.No well defined pattern of molecular arrangement,long range order is lost If force applied,will flow(liquid state)

High temperature

Temperature at which change in the state occurs is termed as Melting point. In polymers Polymer long chain molecule comprised of localisd units ( Chain segments) Two types of motions exhibited by polymeric material Segmental motion (Internal or micro brownian movement) Molecular motion ( External or macro brownian movement)

Increase in the temperature At higher temperature activated both motions poymeric chains start moving apart and system flows. At higher temperature when both movements are activated,the individual polymer chain starts moving apart and there will be flow of material(liquid state). Polymers

Solid state (Brownian movements are frozen)

Liquid state ( Brownian movements are activated)

Rubbery state States of phases A phase is simply a part of a system separated from the other part of the same system by an interface. Low molecular weight substance (crystalline solid) Solid phase (Long range order) Liquid phase (Absence of long range order)

Molecular mobility is Molecular mobility is frozen activated - no long range order - no long range order - exists as a physical solid, unable to crystallise. - amorphous solid(Glassy solid) An amorphous substance cannot exhibit crystallinity but can exist as a glassy solid(liquid phase state) and transition from glassy solid to molten liquid occurs at a temperature, known as glass transition temperature.

TRANSITIONS AND ASSOCIATED PROPERTIES When a polymer passes from one state to other state, there is change in many of its properties. Among them, specific volume is most significant property and is frequently used to determine the transition temperature of the polymer. The changes in specific volume of a polymeric sample with temperature are measured using a diatometer. The bulb of the instrument containing the sample along with a confined liquid can be heated or cooled to measure the change in volume of the sample with temperature. When sample expands or contracts with temperature, a corresponding amount of liquid is displaced and the quantity displaced is measured in a graduated capillary tube.

Plot showing variation of specific volume with temperature for crystalline(1),amorphous(2) Factors influencing glass transition temperature The presence or absence of segmental and molecular motions decides whether a polymer is in a solid, rubbery or molten state. The nature and the magnitude of these motions depend on the size and geometry of polymeric chain, flexibility of chain segments and type of molecular aggregates formed. Polymers with a symmetrical or stereo-regular structure are crystalline and those with irregular chain backbone are non-crystallisable. Segmental and chain mobilities are easier in non-crystallisable or amorphous polymers than in crystalline polymers. Flexibility of the chain segments is determined by the degree of freedom with which different segments along the chain backbone can rotate around the covalent bonds. Linear polymer chains made up of C-C,C-O,C-N single bonds have a high degree of freedom for rotation. The presence of aromatic or cyclic structure in the chain backbone or of bulky side groups on the backbone C atoms hinders the freedom for rotation. The higher the freedom to rotate,the more flexible are the chain segments,hence higher the segmental mobility. Highly crystalline polymers possesing a regular chain geometry show a high glass transition temperature. Bulky groups come in the way of segmental motion and increase the Tg of the polymer. e.g. Polyethylene, hydrocarbon polymer and has Tg of -125oC (low) where as nylon 6,a polyamide has a high glass transition temperature i.e 50oC because of presence of a large number of polar groups in the molecules. Tg of polymethylstyrene is larger than polystyrene as CH3 group in polymethylstyrene comes in the way of free rotation around C-C. GLASS TRANSITION TEMPERATURE AND MOLECULAR WEIGHT Glass transition temperature of polymer is influenced by its molecular weight,at least up to around a value of 20,000;beyond this, effect of molecular weight is not pronounced.

Tg = Tg - k/Mn

1/Tg = 1/Tg + A/Mn

where Tg is the glass transition at infinite molecular weight and k and A are arbitary constants. As we know that mobility of chain segments influences the glass transition temperature, low molecular weight sample will have more chain end segments than high molecular weight sample.The larger the number of chain end segments, larger will be the effective segmental motion. Tg value will be lower for low molecular weight polymers. GLASS TRANSITION TEMPERATURE AND PLASTICIZERS Plasticizers are low molecular weight non-volatile substance(mostly liquids)which when added to a polymer, improves its flexibility,processibility. Addition of plasticizer reduces Tg of polymer due to reduction in cohesive forces of attraction between polymer chains. Plasticizer molecules being small in size as compared to polymer molecules penetrate into polymer matrix and establish polar attractive forces between it and chain segments. These attractive forces reduce the cohesive forces between the polymer chains Increases segmental mobility thus reduces glass transition temperature. Example Dibutyl pthalate,dioctyl sebacate,diisooctyl phthalate,tricresyl phosphate. GLASS TRANSITION TEMPERATURE AND COPOLYMERS The net effect of the interaction between two monomeric components of a copolymer on the Tg value is as though the copolymer is mixture of two homopolymers. The Tg value of random copolymers depends on the Tg value of individual homopolymers and on the ratio of two monomeric components

1/Tg(AB) = WA /Tg(A)+WB /Tg(B)

where,Tg(A),Tg(B) and Tg (AB) are glass transition temperature of homopolymers A,B and copolymer AB. WA and WB are weight fractions of respective monomers components in copolymer. Glass transition temperature of copolymer will be between those of respective homopolymers. Glass transition temperature of many homopolymers can be decreased by copolymerisation with small quantities suitable monomer termed as internal plasticisation. GLASS TRANSITION TEMPERATURE AND MELTING POINT Factors those affect the Tg will also affect Tm Tg = 1/2 Tm(symmetrical polymers) Tg = 2/3 Tm (unsymmetrical polymers) Range Tg /Tm = 1/2< Tg /Tm<2/3

METHODS FOR DETERMINATION OF GLASS TRANSITION TEMPERATURE

Dilatometric method

Calorimetric method

Thermomechanical method

IMPORTANCE OF GLASS TRANSITION TEMPERATURE Acts as measure for evaluating the flexibility of polymer molecule. It decides whether the polymer at use temperature will behave like a rubber or plastic . It gives an indication of temperature region at which a polymeric material transforms from rigid solid to soft viscous state and helps to select right processing temperature.

HEAT DISTORTION TEMPERATURE It indicates the temperature range over which the polymer begins to soften and get deformed under the influence of a load. RHEOLOGY OF POLYMERS The word Rheology is defined as the science of deformation and flow, was coined by Prof Bingham in 1920s . Rheology involves measurements in controlled flow, mainly the viscometric flow in which the velocity gradients are nearly uniform in space. In these simple flows, there is an applied force where the velocity (or the equivalent shear rate) is measured, or vice versa. They are called viscometric as they are used to define an effective shear viscosity from the measurments,

=xy/
where xy is the shear stress (measured or applied) and is the shear rate (applied or measured). Viscosity is measured in Pa-s (Pascal second). Rheology is not just about viscosity, but also about another important property,namely the elasticity. The modulus of elasticity is defined as G = xy/ where is called the strain or the angle of the shearing deformation. G is measured in Pa (Pascal). G for most polymeric fluids is in the range 10104 Pa Visual and Measurable Phenomena Some of the striking visual phenomena are associated with flow behaviour of polymeric liquids. Few of them are described as below : Weissenberg Rod Climbing Effect When a liquid is stirred using a cylindrical rod, the liquid that wets the rod begins to climb up the rod and the interface with the surrounding air assumes a steady shape dangling to the rod, so long as there is a continuous rotation.

Rod climbing is exhibited by liquids that show a normal stress differences.Polymeric liquids, upon application of shear flow, begin to develop normal stress differences between the flow and flow-gradient directions .

Extrudate or Die Swell This phenomenon is observed when polymeric melts are extruded through a die. The diameter of liquid as it exits a circular die can be three times larger than the diameter of the die, One of the important reasons for this phenomena is again the normal stress difference induced by the shear flow in the die. Contraction Flow Sudden contraction in the confining geometry leads to very different streamline patterns in polymeric liquids. In polymeric liquids, including in dilute polymer solutions, different patterns of secondary flow are observed. These include large vortices and other instabilities. These flows are undesirable in many situations in polymer processing as it leads to stagnation and improper mixing of the fluid in the vortices. Tubless Siphon In a typical syphoning experiment, a tube filled with liquid drains a container containing the liquid at a lower pressure, even though the tube goes higher than the liquid surface. When the tube is lifted off the surface of the liquid, the flow immediately stops. In the case of polymeric liquids, the liquid continues to flow with a free surface with the air without the tube, as the tube is taken of the surface. Elastic Recoil A sheet of polymeric liquids pouring down from a vessel can be literally cut with a pair of scissors. Relaxation time and Dimensionless Numbers One of the simplest and most important characters of polymeric liquids is the existence of an observable microscopic time scale. For regular liquids the timescales of molecular motion are in the order of 1015 seconds, associated with molecular translation. In polymeric liquids, apart from this small time scale, there is an important timescale associated with large scale motions of the whole polymer itself. The large scale microscopic motions are usually associated with the elastic character of the polymeric liquids. The relaxation time is the time associated with large scale motion (or changes) in the structure of the polymer, it is denoted by . The microscopic timescale should be compared with the macroscopic flow time scales. The macroscopic time scales arises from two origins. One is simply the kinematic local rate of stretching of the fluid packet (strain rate). This is measured by the local shear rate . The other is a dynamic timescale associated with the motion of the fluid packets themselves. Weissenberg Number The ratio of the microscopic time scale to the local strain rate is called as the Weissenberg Number, Wi = Note that the strain rate is the inverse of the kinematic timescale. Flows in which the Wi are small, Wi <<1, are in which elastic effects are negligible. Most of the flow effects are seen around Wi ~ 1. For large Wi >> 1, the liquid behaves almost like an elastic solid. Weissenberg number is used only in situations where there is a homogeneous stretching of the fluid packet in the flow. That is the strain rates are uniform in space and time. Deborah Number In most practical applications the fluid packets undergo a non-uniform stretch history. This means that they could have been subjected to various strain rates at various times in their motion. Therefore no unique strain rate can be associated with the flow. In these cases it is customary to refer to the Deborah number defined as the ratio of the polymeric time scale to then dynamic or flow timescale.

De = /td For small De<< 1, the polymer relaxes much faster than the fluid packet transverses a characteristic distance. On the other hand for De ~ O (1), the polymer has not sufficiently relaxed.

Biodegradable polymers:
Chitosan Chitosan is a natural polymer obtained by deacetylation of chitin. After cellulose, chitin is the second most abundant polysaccharide in nature. It is biologically safe, non toxic, biocompatible & biodegradable polysaccharide. CS has been used as a safe excepient in drug formulations. Due to its bioadhesive property, it can adhere to hard and soft tissues and has been used in dentistry, orthopedics and ophthalmology and in surgical release medium. It adheres to epithelial tissues and to the mucus coat present on the surface of the tissues. It also has a fungistatic or bacteriostatic, anticancerogen and anticholestermic action.