Polycondensation Interfacial Polymerization of PA 6, 10 using Hexamethylene diamines & sebacic acid chloride

Prepared By: Muhammad Farooq Matriculation # 764316

INTRODUCTION
Polymerization process is generally classified into two major categories, step growth polymerization and chain growth polymerization. One major difference i n both the polymerization processes is the formation of by product for example water, which is associated to step growth polymerization. In step growth, polymerization polymer chains grow in a slow, step-wise manner forming dimers, tetramers, and pentamers leading to polymer. A very high conversation rate is required to achieve a higher molecular weight product. Two different functional groups are involved in any condensation polymerization, which typically are two different reactive groups on two monomers. Condensation polymerization is an example of Step polymerization.

In chain growth polymerization, chains grow rapidly. Free radical and photoinitiated polymerizations are examples of chain-growth reactions.

Interfacial polymerization is a unique process because we can achieve very high molecular weight polymers instantly and more surprisingly at room temperature. This reaction is named as Schotten Baumann reaction. Reaction proceeds at the interface of two immiscible liquid phases. Each phase contains one monomer. Polymerization rate is controlled by the rate of diffusion of reactants to the interface. Nylon is an example of a commercial polymer that is commonly produced via interfacial polymerization.

Nylon can be produced using different techniques and with variety of monomers. Polymerization reaction between diamines and diacid chloride is very fast. This is because acid chlorides are much more reactive than acids and this is the reason we use this particular faster rate of reaction in interfacial polymerization. The polymerization reaction is carried out in two phase system. Monomer A (Hexamethylene di amine) is dissolved in inorganic solvent (water) and monomer B (sebacic acid chloride) is dissolved in organic solvent. Since these two phases are immiscible in nature. As they meet each other at the interface they polymerize due to which this kind of polymerization is terms interfacial facial polymerization. By using a glass rod or any thin tube polymer film can be extracted out and rolled on the tube by the help of tweezers. The resulting polymer has high molecular weight.
Fig.1. Interfacial polymerization

Nylon 6, 10

Interface

REACTION MECHANISM
The reaction between amine and diacid is a nucleophilic reaction. Amine attacks the carbonyl carbon present in the sebacic acid chloride. HCl is formed as a byproduct. HCl neutralizes by reacting with Sodium Carbonate.

Fig.2. Reaction mechanism of Diacid chloride with Hexamethylene diamines

The core of this upper described reaction is the attact of nitrogen on carbonyle group. From the below schematics of the reaction it can be understood well. O R O H2 C H N

O Cl R1 NH C Cl H N R1 + HCl

R1

Fig.3. Intermediate Reaction

EXPERIMENT Following values of monomer and initiator were consumed Table 1 Sr. No 1 2 3 4 Regent & material Sebacic acid Hexamethylene di amine Na2CO3 Dichloromethane Molar Mass (g/ mol)
202.25 116.24 105.98 84.93

Amount 0.4 grams 0.5 grams 0.2 grams 10 mL

PROCEDURE Solution if sebacic acid and hexamethylene diamines were prepared according to above composition.Na2CO3 was added in hexamethylene diamines to neutralize the byproduct during the condensation reaction between the acid and amine. In our case since we used diacid chloride so, our byproduct was HCl, which was neutralized by Na2CO3, which formed the salt and the release of water with carbon dioxide.

The inorganic phase was poured on the organic phase, pouring should be in a careful uniform fashion, slowly poured all over the organic phase but we poured it in an abrupt way due to which reaction took place only at those places where the interface was formed not the other places. The polymerization process started very quickly as the phases met each other and condensation polymerization started. By the help of tweezers, we pulled out the nylon film. As we started pulling the film out of the beaker the new monomer got in touch and formed new film was produced till all the monomers were consumed.
Fig.4. Nylon 6, 10 produced in our experiment

The acid is rapidly neutralized by the carbonate in the aqueous phase. The resulting product is a pink / magenta color, which was due to the addition of phenolphthalein solution in order to visualize the interfaces, Nylon that was filtered, washed with portions of ethanol, acetone and water and dried overnight. Differential Scanning calorimetry DSC measures the thermal properties of polymeric materials by comparing the rate at which polymer sample absorbed the heat energy. Upon the absorption heat polymer undergoes morphological changes, which gives us a clear indication about the glass transition temperature, crystallization temperature, and melting point of the sample. From the below given DSC graph data we can get the values of glass transition temperature, crystallization temperature and also melting point of the Nylon 6,10.

It will be a good idea to compare standard thermal properties values of Nylon 6, 10 with the values obtained from the DSC plot during our experiment.

Temperature
Fig.5. DSC Plot of Nylon 6, 10

Table 1

Termal Properties Glass Transition temperature C Melting temperature C

Standard 45-55 215-220

Our Results ~40 ~196

Remarks Since the curve is not so linear so its really hard to determine it Lesser than the standard

Temperatures determined using DSC curve of our sample is lesser than the standard temperature. The most possible reason might be the presence of moisture in our sample and the impurities, which always add error in calculations. There is high probability that our sample contained some water or impurities. Waster can act as a plasticizer and reduce transition temperatures.

Answer No 1 Polymerization stop when we stop pulling out the layer formed at the interface. The reason behind is that in interfacial polymerization production of layer at the interface depends upon the diffusion rate of both the monomers. As both monomers meet the reaction takes place, when we dont extract the nylon layer formed The film at the interface stops further reaction by preventing the monomers from meeting each other. There is a possibility that some monomers do reach other by diffusion through the film but this is so slow that the film appears to have stopped growing. Due to which new monomer does not get the chance to meet each other to form another layer

Answer No 2 Sodium carbonate is added as a nuterlizing agent. The byproduct of the reaction between diacid and amine is HCl, which is toxic chemical and can react with monomers. Higher concentration of HCl can also produce side reaction, can tie up with diamines and make its unreacted anime salt, which can lower the polymerization reaction rate.

Following reaction shows how Sodium carbonate reacts and forms salt, water and carbon dioxide.

References Paul C. Hiemenz, Polymer Chemistry: The Basic Concepts, pp. 307-310 George Odian , Principles of Polymerization, pp. 90 - 92