Advanced Process Control and Simulation for Chemical Engineers

Update on Application

of Response Surface

Methodology-Part I

11

CONTENTS

11.1 Introduction ..................................................................................................... 121

11.2 Experimental .................................................................................................... 123

11.2.1 Case 1: Synthesis, Characterization, and Application of HBP to PET

Fabrics................................................................................................... 123

11.2.2 Synthesis ............................................................................................... 124

11.2.3 Case 2: Experimental Design and Optimization of Treatment

Conditions ............................................................................................. 127

11.3 Discussion and Results .................................................................................... 130

11.3.1 Synthesis of Hyperbranched Polymer .................................................. 130

11.3.2 FTIR Spectroscopy Characterization .................................................... 130

11.3.3 NMR Spectroscopy Characterization ................................................... 132

11.3.4 UV-vis Spectroscopy ............................................................................ 134

11.3.5 Solubility Properties ............................................................................. 135

11.4 Contact Angle Measurement ........................................................................... 135

11.4.1 HBP Contact Angle .............................................................................. 135

11.4.2 HBP Treated PET Fabrics Contact Angle ............................................. 136

11.5 X-ray Diffraction (XRD) ................................................................................. 136

11.6 Zeta Potential ................................................................................................... 138

11.7 Dyeing Properties of HBP Treated Polyester Fabric ....................................... 139

11.8 Fastness Properties .......................................................................................... 141

11.8.1 HBP Treatment Fastness ....................................................................... 141

11.8.2 Dyeing Fastness .................................................................................... 142

11.9 The Analysis of Variance (ANOVA) and Optimization .................................. 142

11.10 Conclusion ..................................................................................................... 146

Keywords ................................................................................................................. 147

References ................................................................................................................ 147

11.1 INTRODUCTION

In recent years, dendritic polymers have attracted increasing attention due to their

unique chemical and physical properties. These polymers consist of three subsets

122 Advanced Process Control and Simulation for Chemical Engineers

namely hyperbranched polymers (HBPs), dendrigraft polymers, and dendrimers. The

HBPs are highly branched, polydisperse, and 3D macromolecules synthesized from a

multifunctional monomer to produce a molecule with dendritic structure [1-10].

Dendrimers are well-defi ned and needed a stepwise route to construct the perfectly

symmetrical structure. Hence, synthesis of dendrimers is time-consuming and expen-

sive procedures. Although HBPs are irregularly shaped and not perfectly symmetrical

like dendrimers, HBPs rapidly prepared and generally synthesized by one-step process

via polyaddition, polycondensation, radical polymerization, and so on, of AB

x

type

monomers and no purifi cation steps are needed for their preparation. Therefore, HBPs

are attractive materials for industrial applications due to their simple production pro-

cess [1-4, 11-19]. In general, according to molecular structures and properties, HBPs

represent a transition between linear polymers and perfect dendrimers. Comparison

of HBPs with their linear analogues indicated that HBPs have remarkable properties,

such as low melt and solution viscosity, low chain entanglement, and high solubility,

as a result of the large amount of functional end groups and globular structure [10-16].

In recent years, many functional HBPs with various terminal groups such as hy-

droxyl, amine, carboxyl, acetoxy, and vinyl have been suggested as excellent candi-

date for use in drug delivery [20, 21], gene therapy vectors [21, 22], coatings [23, 24],

additives [25], catalysis [26], gas separation [27], nanotechnology, supramolecular

science [28], and many more.

Some examples of modifi cation of fi bers with HBPs were successful. For instance,

the dyeability of modifi ed polypropylene (PP) fi bers by HBP was investigated [29].

The results showed that the incorporation of HBP prior to fi ber spinning considerably

improved the color strength of PP fi ber with C.I. Disperse Blue 56 and has no signifi -

cant effect on physical properties of the PP fi bers.

The synthesized amino-terminated HBP was found to be used as salt-free dyeing

auxiliary for treated cotton fabrics [30]. The washing fastness, rubbing fastness, and

leveling properties of HBP treated cotton fabrics were better than untreated cotton

fabrics. In the study on applying amino-terminated HBP to cotton fabric, it was dem-

onstrated that HBP treatment on cotton fabrics has no undesirable effect on mechani-

cal properties of fabrics. Dyeing of treated cotton fabrics with direct and reactive dyes

in the absence of electrolyte showed that the color strength of treated samples were

better than untreated cotton fabrics. Furthermore, application of HBP to cotton fabrics

reduced UV transmission and showed good antibacterial activities [31-34].

In recent years, there has been considerable research to improve polyethylene tere-

phthalate (PET) fabrics dyeability. It is known that PET fabrics are usually dyed using

disperse dyes in the presence of a carrier or at elevated temperatures. Many attempts

have been made during the last two decades to replace environmentally unfriendly

carriers with non-toxic chemicals [35]. Modifi cation of PET fabrics by attaching addi-

tives or functional groups to the polymer molecules via grafting and copolymerization

are the common methods to enhance the dyeability of PET fabrics.

Literature review showed that there has not been a previous report regarding the

treatment of amine terminated HBPs on PET fabric and study of its dyeability with

acid dyes. In the most recent investigation in this fi eld, fi ber grade PET was com-

pounded with polyesteramide HBP and dyeability of resulted samples with disperse