Step Growth Polymersization

Dr. S.
Ray_Chem Engg_NIT Agratala
3/20/2013
Polymerization Processes
Modern classification of polymerization according to polymerization mechanism
Step growth polymerization : Polymers build up stepwise
Chain growth polymerization : Addition polymerization molecular weights increase successively, one by one monomer
Ring-opening polymerization may be either step or chain reaction
Polymerization mechanisms - Step-growth polymerization
Polymer Processing Engineering
Dr. S.Ray_Chem Engg_NIT Agratala
3/20/2013
Condensation or step-reaction polymerization

Condensation or step-growth polymerization is entirely analogous to condensation in low-molecular-weight compounds. In polymer formation the condensation takes place between two poly-functional molecules to produce one larger poly-functional molecule, with the possible elimination of a small molecule, such as, water. The reaction continues until almost all of one of the reagents is used up; an equilibrium is established that can be shifted at will at high temperatures by controlling the amounts of the reactants and products
Stepwise (Condensation) polymerization Reaction Requirements for Step-Growth Polymerization

High monomer conversion High monomer purity High reaction yield Stoichiometric equivalence of functional groups
The characteristic features of this type of polymerization process as follow .

1-Growth occurs throughout the matrix 2-There is the rapid loss of the monomer species 3-The molecular weight slowly increases throughout the reaction 4- The same mechanism operate throughout the reaction 5-The polymerization rate decreases as the number of functional group decreases 6-No initiator is required to start the reaction
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Step-growth polymerization
In step-growth polymerization, the stepwise reaction occurs between pairs of chemically reactive or functional groups on the reacting molecules. In most cases, step-growth polymerization is accompanied by the elimination of a small molecule such as water as a by-product.
Step-Growth Polymerization
Stage 1 n n Consumption of monomer
Stage 2 Combination of small fragments
Stage 3 Reaction of oligomers to give high molecular weight polymer
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Step-growth polymerization involves a series of reactions in which any two species (monomers, dimers, trimers, etc.) can react at any time, leading to a larger molecule. Most step-growth polymerizations, involve a classical condensation reaction such as esterification, ester interchange, or amidization.
Step-growth polymerizations generally involve either one or more types of monomers. In either case, each monomer has at least two reactive (functional) groups. In cases where only one type of monomer is involved, which is known as A-B step-growth polymerization, the functional groups on the monomer are different and capable of intramolecular reactions. In those cases where more than one type of molecule is involved, the functional groups on each type of monomer are the same, but capable of intermolecular reaction with the other type of monomer. This is known as the AA/BB stepgrowth polymerization
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Step-growth polymerizations can be divided into two main categories: polycondensation, in which a small molecule is eliminated at each step,
polyaddition, in which, monomers react without the elimination of a small molecule.
Polyaddition
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Polyaddition
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Step-reaction Polymerization
A. Monomer to have difunctional group
1. One having both reactive functional groups in one molecule
A R B
R X
O
HO
CO2H
+ H 2O
O H 2N R CO2H NH R C + H 2O
2. Other having two difunctional monomers

A R A + B R'
R'
O
R'
OCN
NCO + HO
OH
O
CNH
NHCO
R'
H 2N
NH 2 + ClCO
O
'
OCCl
O
CNH
NHCO
R'
2HCl
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B. Reaction : Condensation reaction using functional group

Example - Polyesterification
O n HO CO2H O C
n
nH2O
nHO2C
CO2H O C
nHOCH2CH2OH O COCH2CH2O
n
2nH2O
C. Carothers equation
( NO : number of molecules N : total molecules after a given reaction period. NO N : The amount reacted P : The reaction conversion ) P= NO NO N Or N = NO(1 P)
( DP is the average number of repeating units of all molecules present) DP = NO/N DP = 1 1-P For example At 98% conversion DP = 1 1- 0.98
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(A) Unreacted monomer

A (a)
B B B B B B B B B B B B
(B) 50% reacted, DP = 1.3

(b) A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
(C) 75% reacted, DP = 1.7

(c) A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
(D) 100% reacted, DP = 3

A (d)
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
A
B
Step-Growth Polymerization
Great Industrial Value

Examples Polyester Linear saturated polyester: plasticizer, Linear unsaturated polyester: glass fiber laminate, casting resin, solvent-less lacquer Network polyester: surface coating
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Most of the Polycondensation reactions are the typical Step-Growth Polymerization. Polycondensation reactions are taken as examples to illustrate the Step-Growth Polymerization.
Step-Growth Polymerization: Polycondensation
Polycondensation is the abbreviation of condensation polymerization.
many times of repeated condensation
Monomers with functional group
Polymer
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B. Functionality ( f ) the number of functional groups in the molecule which take part in the reaction. (monomer,oligomer).
Step-Growth Polymerization: Polycondensation general reaction n aRa + n bRb a[RR]nb + (2n1)ab
ab functional group RRconstruction unit ab micromolecule These reactions involve two different functional groups. One type of the functional group in each monomer.
Forming linear polycondensation polymer
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1) monomers f 2 2) Changeable factors : functional groups (OH,COOH,COOR, Cl,NH2), f (linear or cross linking polycindensation) R, and R Huge sorts of polycondensation polymers 3) The polycondensation polymers are usually the heterochain polymers with N,O,S,P in the backbone and the functional groups in the end. eg.O,CONH,COOetc
Industrially, polycondensation can be divided into many types according to the group in the polymer chain. polyester, polyamide, polyether reaction
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4) The compositions and structures of the polymers are different from those of the monomer, because of the byproducts in the reaction. 5) The conversion of monomer does not increase with the reaction time in the polycondensation reactions.
Step-Growth Polymerization: Polycondensation Essentially, the key of polycondensation is the reactions between the function groups. Only with the efficient reaction, the macromolecules can be prepared. Practically, polycondensation should be described by the extent of reaction.
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2.2.4
Classifications of
Polycondensation
(2) mixed polycondensation, f = 2,2

Two kinds of bifunctional monomers. Only one type of functional group in each monomer. Example: diamine / diacid, dihydric alcohol / diacid
n H2N(CH2)6NH2
+ HOOC(CH2)4COOH
[NH(CH2)6NHOC(CH2)4CO]n + (2n1)H2O
2. By Structure of polymer linear polycondensation

Bifunctional monomer The chain increases to two directions along the ends of the chain.
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2.2.4
Classifications of
Polycondensation
Systems of f = 2 and f = 2, 2 are linear
polycondensation.
The key of linear polycondensation is to
control the molecular weight of the products.
cross linking polycondensation

At least one monomer has more than two functional groups (f = 2, 3 or 2,43,3 ) The molecule increases towards more than two directions. The crosslinking polymer forms.
Example: glycerol / phthalic anhydride alkyd resin,
phenol / formaldehyde phenolic-formaldehyde resin.
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The viscosity will be suddenly increased as reaction goes to the certain degree, forming the gel. --------gelation This critical point is called the gel point.
The key of cross-linking polycondensation is to
forecast and control the gel point
2.2.4
Classifications of
Polycondensation
3. By Thermodynamics
balanced polycondensation
the rate of reverse reaction is not equal to zero K 103 .
unbalanced polycondensation
the rate of reverse reaction is little or equal to zero K 103 .
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2.3 Characteristic of linear polycondensation
Characteristic I.
The increasement of macromolecule chain is step by step.
Any molecule with different functional group can react to each other. There are no particular active centers in the reaction. The molecular weight of the polymer gradually increases with the decrease of the number of the groups.
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The monomers dispear at the early stage of reaction far before forming any polymer with sufficiently high molecular weight for practical utility. High conversion of monomer is reached at early stage of reaction followed by the reaction between oligomers. As the time increases, conversion. Contrarily, the conversion increases with time in the chain polymerization.
X n increases instead of the
HOROH + HOOCR`COOH
dimer
HOROCOR`COOH + H2O
2
HOOCR`COOH
HOROH
HOROCOR`COOROH
HOOCR`COOROCOR`COOH
trimer tetramer
trimer
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Step-Growth Polymerization: Polycondensation Firstly, the diol and the di-acid monomer reacts to form dimer.
aAa + bBb
a [ A B ] b + ab
Then the dimer reacts with itself to form tetramer or with unreacted monomer to yield trimer.
a[A B]b + aAa a[A B]b + bBb
a[A B]b + a[A B]b
a[A B A]a + ab b[B A B]b + ab

a[A B A B]b + ab
aAa: dihydric alcohol(diol); bBb: diacid
The tetramer and trimer continues to react with themselves, with each other, and with monomer and dimer. The polymerization proceeds in the stepwise manner, resulting the continuously increases of the molecular weight of the polymer.
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All polycondensations are characterized by the stepwise. The mechanism of polycondensation is rather different to that of chain polymerization. The reactivity of a functional group is independent of the size of the molecule.
the degree of polymerization P, the fraction of the functional groups that have reacted
N0 N N = 1 N0 N0
where, N0 the total of the certain groups at the initial stage N the quantity of unreacted groups at time of t
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X n the number average of construction units in

each macromolecule
Xn =
P=
the total of construction units the number of macromo lecules
N0 N N =1 N0 N0
P=1
1 Xn
1
Xn 1 P
P0. 9 X n = 10 X = 100 ~ 200 P 0. 99 ~ 0. 995
Characteristic II.
Characteristic of linear polycondensation
Linear polycondensation is reversible equilibrium. The equilibrium constants (K) of different linear polycondensation is different.
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K410, e.g kinds of polyester the existence of micromolecule will greatly affect the degree of polymerization. K300400, e.g kinds of polyamide the existance of micromolecule will affect the degree of polymerization to some extent. K103 e.g phenol ~ methanal the reaction is irreversible It is clear that the synthesize art depends on the equilibrium constant, K, will affect.
In the closed system, the high molecular weight polymer is hardly obtained, due to the existence of byproducts and residual micromolecule. Industrially, the micromolecules can be removed by reducing pressure method in order to change the equilibrium for preparing high molecular weight polymer. e.g. The vacuum degree of the system, i.e., the quantity of residual micromolecules, control the molecular weight of polyethylene terepthalate (polyester).
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The degree of polymerization

P, the fraction of the functional groups that have reacted
N0 N N = 1 N0 N0 where, N0 the total of the certain groups at the initial stage N the quantity of unreacted groups at time of t X n the number everage of construction units in
each macromolecule
Xn = the total of construction units the number of macromo lecules
Example 1polyester reaction nHORCOOH [ORCO]n + (n1)H2O t=0the total of the initial groups COOHN0
t=tthe quantity of unreacted groups COOHN POHPCOOH N 0 N = 1 N P

N0 N0
(22)
Xn =
the total of construction units the number of macromolecules
N0 N
(23)
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Xn =
the total of construction units the number of macromolecules

1 Xn
N0 N
(23)
from (23)
N N0
(24)
substitutes (22) for (24) POHPCOOH N 0 N = 1 N P

N0 N0
(22)
P 1
1 Xn
Xn
1 1 P
(25)
Example 2HOROH + HOOCRCOOH Case : the same mole ratio t=0 OH: N0 COOH N0, the total of construction unitsN0 t=t OH: N COOH N the quantity of macromoleculesN POHPCOOH
N
N0 N N = 1 N0 N0
0 Xn N 1 P
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Step-Growth Polymerization: Polycondensation In the polycondensation reactionincrease of the degree of reaction depends on 1. prolonging the reaction time 2. increasing the reaction temperature 3. removing the micromolecule intensively 4. using high active monomer
The equilibrium constant (K) and the degree of polymerization

The equilibrium polycondensation reactions consist of a series of equilibrium reactions. As the reactivity of functional groups are assumed to be equal to each other, all reactions can be expressed by the same K COOH OH OCO OCO OCO H2O K
k1 k 1
[ OCO][ H 2 O] [ COOH ][OH ]
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COOH OH t 0 C0 C0 tt C0(1-P) C0(1-P)
OCO OCO OCO H2O C0 P C0 P
the closed system
C0 P C0 P K= C0 (1 P ) C0 (1 P)
P2 (1 P) 2
K 1 P
Xn
1 1 P
Thus, P
K K +1
(26)
Xn
K + 1
(27)
X n has relations not only with Pbut also with K.
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To polyesterK
4, P(equilibrium)2/3 X n3
X n21
To polyamide: K 400, P(equilibrium)0.95, K 104

Thus
Xn
100
1. In the closed systems especially that with small K, the high molecular weight polymer is hard to be prepared. 2. Try to remove the micromolecules is key for increasing the molecular weight of the polymer.
Example
formation of polyester
nHO nHO-R-OH + nHOOCnHOOC-R-COOH HH-(O (O-R-OOCOOC-R-CO CO-)nOH+( OH+(2 2n-1)H2O
Kinetics of condensation (step Growth ) polymerization

Consider the synthesis of polyester from a diol and a diacid. The first step is the reaction of the diol and the diacid monomers to form dimer,
HO-R-OH + HOOC-R"-COOH--> HO-R-OCO-R'-COOH + H2O
The dimer then forms trimer by the reaction with diol monomer,
HOHO -R-OCO OCO-R'R'-COOH + HOHO-R-OH OH---> > HOHO-R-OCO OCO-R' R'-COO COO-R-OH +H2O and also with diacid monomer, HOHO -R-OCO OCO-R' R'-COOH + HOOCHOOC-R' R'-COOH COOH---> > HOOCHOOC -R'R'-COO COO-R-OCO OCO-R'R'-COOH + H2O
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Kinetics of Condensation (Step-Growth) Polymerization

StepStep -Growth polymerization occurs by consecutive reactions in which the degree of polymerization and average molecular weight of the polymer increase as the reaction proceeds. Usually (although not always), the reactions involve the elimination of a small molecule (e.g., water). Condensation polymerization may be represented by the following reactions: Monomer + Monomer Dimer + H2O Monomer + Dimer Trimer + H2O Monomer + Trimer Tetramer + H2O Dimer + Dimer Tetramer + H2O Dimer + Trimer Pentamer + H2O Trimer + Trimer Hexamer + H2O Generally, the reactions are reversible, thus the eliminated water must be removed if a high molecular weight polymer is to be formed. Based on the assumption that the polymerization kinetics are independent of molecular size, the condensation reactions may all be simplified to: ~~~~COOH + HO~~~~ ~~~~COO~~~~ + H2O
Kinetic analysis
~~~~COOH + HO~~~~ ~~~~COO~~~~ + H2O Most step polymerization involve bimolecular reaction that are often catalyzed ~~~~A + B~~~~ + catalyst ~~~~AB~~~~ + catalyst The rate is accelerated according to
-d [A]
Or dt -d [A] dt I f [A] [A] = [B] By integration -d [A] dt 1 [M] 1 [M]o = k 't ** = k '[A [A] ]2 = k [A [A][B] ][B] [catalyst] = k '[A [A][B] ][B] Where k = k [catalyst]
By use the extent of the reaction P (fraction of A or B functional groups that has reacted at time t ) P = extent of the reaction = the fraction of conversion
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The concentration [M] at any time given by [M] = [M]o - [M]o P = [M]o (1 (1 - P )
By substitution in (** ) 1 = k '[A [A]o ]o t + 1 (1-p) Note that experimental data are usually linear only beyond ca. 80% conversion.
Polyesterification Without Acidic Catalyst

The rate equation is given by - d[A] Or I f [A] = [B]
dt
= k [A]2[B] -d [A] dt = k [A]3
By integration
1 [M]2 [M] =
1 [M]o2
= 2k t
**
[M]o - [M]o P = [M]o (1- P )
By substitution in (** )
1 =2 k [A]2ot + 1 (1-p)2
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Uncatalyzed Polyesterification
Note that experimental data for esterification reactions show that plots of 1/( /(1 1-p)2 vs. time are linear only after ca. 80 80% % conversion conversion. .
Polyesterification Without Acidic Catalyst (continued)

This behavior has been attributed to the reaction medium changing from one of pure reactants to one in which the ester product is the solvent. Thus, the true rate constants for condensation polymerizations should only be obtained from the linear portions of the plots (i.e., the latter stages of polymerization). For example, the kinetic plots for the polymerization of adipic acid and 1,1010-decamethylene glycol show that at 202oC, the thirdthird-order rate constant for the uncatalyzed polyesterification is k = 1.75 x 10 10-2 (kg/equiv)2 min-1.
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The Number Average Molecular Weight in Polycondensation

. The numbernumber-average degree of polymerization Xn is given as the total number of monomer molecules initially present divided by the total number of molecules present at time t, Xn = No / N = [ M ]o / [ M ] Xn = 1 / 1 - P [ M ] = [ M ]o ( 1 P )
This relationship is the Carother's Equation. Equation.
Example
If monomer conversion is 99% what is Xn ? Xn = 1 / 1 P = 1 / 1 - 0.99 = 100 If P =99.5 % Xn = 1 / 1 - 0.995 = 200 If P =99.6 % Xn = 1 / 1 - 0.996 = 250
H-(O (O-R-OOCOOC-R-CO CO-)nOH

The numbernumber-average molecular weight Mn, defined as Mn = Mo Xn + Meg = Mo / 1 P + Meg where Mo is the mean of the molecular weights of the structural units, and Meg is the molecular weight of the end groups. The latter becomes negligible at even moderate molecular weight Mn = Mo Xn + Meg = Mo / 1 P 1 = k '[A]ot + 1 (1-p) Xn= k '[A]ot + 1 X2n=2 k [A]2ot + 1
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Mn as a Function of Conversion
Molecular Weight Control in Linear Polymerization In the synthesis of polymers one is usually interested in obtaining a product of very specific molecular weight since its properties are highly dependent on its molecular weight.
The desired molecular weight can be obtained by

1-Quenching the reaction (e.g., by cooling) at the appropriate time. However, the polymer obtained in this case is unstable, since it can undergo further polymerization if it is heated. This is because the end groups on the polymer chains are still active and they can react with each other. 2-By increasing one reactant over the other. In this way the monomer in excess will block any further increase in the polymer chains.
Excess H2N-R-NH2 + HOOCHOOC-R' R'-COOH ---> ---> HH-(-NH NH-R-NHCO NHCO-R' R'-CO CO-)n-NH NH-R-NH2
The use of excess diacid accomplishes the same result; the polyamide in this case has carboxyl end groups
ExcessHOOCExcessHOOC -R' R'-COOH+H2N-R-NH2 --->HO --->HO-(-CO CO-R' R'-CONH CONH-R-NH NH-)n-CO CO-R'R'-COOH
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3- Another method of controlling the molecular weight is by adding small amounts of monofunctional monomer. (Acetic acid )
Type (2 (2)
For the polymerization of bifunctional monomers AA-A and BB-B where B B-B is present in excess, the numbers of A and B F.gs. are given by NA and NB . Notice that NA and NB are equal to twice the number of AA-A and B B-B molecules, respectively. The stoichiometric imbalance r of the two f.gs. is given by r = NA /NB. 1 The total number of monomer molecules is given by (NA+NB)/ )/2 2 or NA(1+1/r)/2 /r)/2. , the total number of polymer molecules is one half the total number of chain ends or [NA(1-p)+NB(1-rp]/2 rp]/2. The numbernumber-average DP( Xn )is the total number of AA-A and B B-B molecules initially present divided by the total number of polymer molecules: Xn = NA(1+1/r)/2 /r)/2. [NA(1-p)+NB(1-rp]/2 rp]/2.
If r = 1 Xn = 1 / 1-p Xn = 1+r 1 + r 2rP If p = 1 Xn = 1 + r / 1 - r
Example
What is Xn when P = 1 but use 0. 9800 moles of AA-A and 1. 0100 moles of B B r = NA / NB = 0.98 x 2 / 1.01 x 2 = 0.97 Xn = 1 + r / 1 r = 1.97 / 0.03 = 66
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Type (3 (3)
the molecular weight can also be controlled by adding small amounts of monofunctional monomer. Moles of AA- A = NA / 2 Moles of BB- B = NB / 2 Moles of mono functional B = NB r = NA / NB + NB = NA / NB + 2 NB
Example
Find Xn for 1 mole of A-A ,1mole of B-B and 0.01 mole of RB when P = 1 r = 1/ 1 + 2x 0.01 = 0.99 Xn 1 + r / 1 r = 1 + 0.99 / 1 0.99 = 199
The poly dispersity index Xw / Xn = 1 + P Xn = 1 /1-P Xw = 1 + p / 1 - P
1 (1-p)
= k '[A [A]o ]o t + 1
Summary
1 =2 k [A]2ot + 1 (1-p)2 Xn = No / N = [ M ]o / [ M] Mn = Mo Xn + Meg = Mo / 1 P Xn= k '[A]ot + 1 X2n=2 k [A]2ot + 1 r = NA /NB. 1 Xn = 1 + r 1 + r 2rP r = NA / NB + NB = NA / NB + 2 NB If r = 1 Xn = 1 / 1-p If p = 1 Xn = 1 + r / 1 - r Xn = 1 / 1 - P
The poly dispersity index Xw / Xn = 1 + P Xn = 1 /1-P Xw = 1 + p / 1 - P
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POLYESTER
Polyesters form a large class of commercially important polymers. A typical polyester is poly(ethylene terephthalate) (PET), the largest volume synthetic fiber. It is also used as film and in bottle applications. The traditional route for the production of commercial PET is through two successive ester interchange reactions,
POLYESTER
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POLYESTER
In the 1st step, a 1:2 molar ratio of dimethyl terephthalate to ethylene glycol is heated at temperatures near 200C in the presence of a catalyst such as calcium acetate. During this stage, methanol is evolved and an oligomeric product (x = 1 to 4) is obtained. The 2nd step involves a temperature increase to about 300C. This results in the formation of high polymer with the evolution of ethylene glycol. Poly(ethylene terephthalate) is a linear polyester obtained from the reaction of difunctional monomers. Branched or network polyesters are obtained if at least one of the reagents is tri- or multifunctional. This can be achieved either by the use of polyols such as glycerol in the case of saturated polyesters (glyptal) or by the use of unsaturated dicarboxylic acids such as maleic anhydride in the case of unsaturated polyester.
POLYESTER
In the preparation of glyptal, glycerol and phthalic anhydride react to form a viscous liquid initially, which on further reaction hardens as a result of network formation Glyptal is used mainly as an adhesive. Glyptal modi.ed with natural or synthetic oils is known as an alkyd resin, which is a special polyester of great importance in the coatings industry. A typical alkyd resin comprises of pthalic anhydride, glycerol and fatty acid. The fatty acid may be derived from vegetable drying oils (e.g., soybean, linseed oils) or from nondrying oils (e.g., coconut oil).
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POLYESTER
Branched or network polyesters
POLYAMIDES
Polyamides, as they are commonly called, are characterized by the presence of amide linkages (CONH) on the polymer main chain. Theoretically, a large number of polyamides can be synthesized based on four main synthetic routes: (1) condensation reaction between a dicarboxylic acid and a diamine, (2) reaction between a diacid chloride and a diamine, (3) dehydrationcondensation reactions of amino acids, (4) ring-opening polymerization of lactams. Chemically, polyamides may be divided into two categories: those based on synthetic routes (1) and (2); and those based on routes (3) and (4). The commercial use of polyamides is primarily centered around two products: nylon 6,6 from the first category, and nylon 6 from the second category.
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POLYAMIDES
The classical route for the synthesis of nylon 6,6 is the direct reaction between a dicarboxylic acid (adipic acid) and a diamine (hexamethylenediamine). In practice, however, to achieve an exact stoichiometric equivalence between the functional groups, a 1:1 salt of the two reactants is prepared initially and subsequently heated at a high temperature to form the polyamide. For nylon 6,6, an intermediate hexamethylene diammonium adipate salt is formed. A slurry of 60 to 80% of the recrystallized salt is heated rapidly. The steam that is released is purged by air. Temperature is then raised to 220C and finally to 270 to 280C when the monomer conversion is about 80 to 90% while maintaining the steam pressure generated during polymerization at 200 to 250 psi. The pressure is subsequently reduced to atmospheric pressure, and heating is continued until completion of polymerization. Since the polymerization reaction occurs above the melting points of both reactants and the polymer, the polymerization process is known as melt polymerization.
POLYAMIDES
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POLYAMIDES
Other polyamides of commercial importance are nylons that are higher analogs of the more common types: nylons 11; 12; 6,10; and 6,12. The numerals in the trivial names refer to the number of carbon atoms in the monomer(s). In designating AA/BB nylons, the first number refers to the number of carbon atoms in the diamine while the second number refers to the total number of carbon atoms in the acid. In 60s aromatic polyamides were developed to improve the flammability and heat resistance of nylons. Poly(m-phenyleneisophthalamide), or Nomex, is a highly heat resistant nylon obtained from the solution or interfacial polymerization of a metasubstituted diacid chloride and a diamine The corresponding linear aromatic polyamide is Kevlar aramid which decomposes only above 500C. The high thermo-oxidative stability of Kevlar is due to the absence of aliphatic units in its main chain. The material is highly crystalline and forms a fiber whose strength and modulus are higher than that of steel on an equal weight basis.
POLYAMIDES
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Formaldehyde Resins
Formaldehyde is employed in the production of aminoplasts and phenoplasts, which are two different but related classes of thermoset polymers. Aminoplasts are products of the condensation reaction between either urea (ureaformaldehyde or UF resins) or melamine (melamineformaldehyde or MF resins) with formaldehyde. Phenoplasts or phenolic (phenolformaldehyde or PF) resins are prepared from the condensation products of phenol or resorcinol and formaldehyde.
Formaldehyde Resins
Ureaformaldehyde resin synthesis consists basically of two steps. In the first step, urea reacts with aqueous formaldehyde under slightly alkaline conditions to produce methylol derivatives of urea In the second step, condensation reactions between the methylol groups occur under acidic conditions, leading ultimately to the formation of a network structure
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Step Growth Polymersization

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Step Growth Polymersization

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Dr. S.

Ray_Chem Engg_NIT Agratala

Step growth polymerization : Polymers build up stepwise

Ring-opening polymerization may be either step or chain reaction

Polymerization mechanisms - Step-growth polymerization

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

Condensation or step-reaction polymerization

Stepwise (Condensation) polymerization Reaction Requirements for Step-Growth Polymerization

The characteristic features of this type of polymerization process as follow .

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

Stage 2 Combination of small fragments

Stage 3 Reaction of oligomers to give high molecular weight polymer

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

polyaddition, in which, monomers react without the elimination of a small molecule.

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

2. Other having two difunctional monomers

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

B. Reaction : Condensation reaction using functional group

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

(A) Unreacted monomer

(B) 50% reacted, DP = 1.3

(C) 75% reacted, DP = 1.7

(D) 100% reacted, DP = 3

Great Industrial Value

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

Step-Growth Polymerization: Polycondensation

Polycondensation is the abbreviation of condensation polymerization.

many times of repeated condensation

Monomers with functional group

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

Step-Growth Polymerization: Polycondensation

Step-Growth Polymerization: Polycondensation general reaction n aRa + n bRb a[RR]nb + (2n1)ab

Forming linear polycondensation polymer

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

Step-Growth Polymerization: Polycondensation

Step-Growth Polymerization: Polycondensation

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

Step-Growth Polymerization: Polycondensation

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

(2) mixed polycondensation, f = 2,2

2. By Structure of polymer linear polycondensation

Polymer Processing Engineering

Dr. S.Ray_Chem Engg_NIT Agratala

Systems of f = 2 and f = 2, 2 are linear

The key of linear polycondensation is to

control the molecular weight of the products.

cross linking polycondensation

phenol / formaldehyde phenolic-formaldehyde resin.