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2021年2月15日发(作者：2014年感恩节)

Improving

Easy

Care

Nonformaldehyde

Finishing

Performance

Using

Polycarboxylic

Acids

via

Precationization

of

Cotton

Fabric

A.

Hebeish,

M.

Hashem,

A.

Abdel- Rahman,

Z.

H.

El- Hilw

National

Research

Centre,

Textile

Research

Division,

Dokki,

Cairo,

Egypt

Received

7

February

2005;

accepted

26

April

2005

DOI

10.1002/app.22916

Published

onli

ne

9

February

2006

in

Wiley

InterScience

().

ABSTRACT:

Cott

on

fabric

were

first

subjected

to

quaternization

(cationization)

reaction

using

3

-chloro-2- hyd

roxypropyl

trimethyl

ammonium

chloride

commercially

known

as

Quat

-188.

Cationization

was

carried

out

under

different

conditions

for

optimization

of

the

preparation

of

cationized

cotton

with

different

degrees

of

cationization,

using

the

pad-batch

method.

Also,

establish

ed

was

the

optimal

condition

for

cationization

that

involves

Quat-188/

NaOH

molar

ratio

1/2

at

70°

C

for

4

h.

Besides,

a

thorough

investigation

of

factors

affecting

reaction

of

thes

e

cationized

cotton

with

citric

acid

(CA)

or

1,2,3,4-butanetetracarboxylic

acid

(BTCA)

was

carried

out

with

a

view

of

improving

the

ease

of

care

characteristics

of

nonformaldehyde

fi

nishing.

The

dependence

of

fabric

performance

as

measured

by

strength

properties,

dry

wrinkle

recovery

angles,

whiteness

index,

and

dyeability

with

reactive

dyes

was

also

evalu

ated.

It

was

postulated

that

reaction

of

cationized

cotton

with

either

CA

or

BTCA

involve

s

estercrosslinking

as

well

as

ionic

crosslinking.

This,

indeed,

was

largely

positively

reflect

ed

on

the

fabric

performance

especially

when

the

properties

of

both

uncationized

cotton

w

ere

compared

with

those

of

the

cationized

cotton.

©

2006

Wiley

Periodicals,

Inc.

J

Appl

Polym

Sci

100:

2697

–

2704,

2006

Key

words:

crosslinking;

cotton;

cationization;

esterification;

finishing

INTRODUCT

ION

Since

the

identification

of

formaldehyde

as

a

probable

human

carcinogen,

extensive

efforts

have

been

made

to

find

formaldehyde

-free

crosslinking

agents

for

cotton

to

replace

the

traditional

N-methylol

reagents.1

In

1988,

Welch

reported

that

1,2 ,3,4-butan

etetracarboxylic

acid

(BTCA)

was

able

to

provide

effective

crosslinking

for

cotton

cellulos

e.2

In

recent

years,

multifunctional

carboxylic

acids

have

been

used

as

nonformaldehyde

d

urable

press

finishing

agents

for

cotton.3–

5

Among

the

various

polycarboxylic

acids

investi

gated,

BTCA

is

the

most

effective

crosslinking

agent

for

cotton.6

Crosslinking

of

cotton

c

ellulose

imparts

wrinkle

resistance,

but

reduces

mechanical

strength

of

the

treated

cotton

fa

bric.

Severe

tensile

strength

loss

and

yellowing

have

been

the

major

obstacles

for

applicati

ons

of

polycarboxylic

acids

in

durable

press

finishing

processes

to

a

wider

range

of

cellul

ose

fabrics.

On

the

other

hand,

crosslinking

of

cotton

cellulose

with

either

N-methylol-base

d

agents

or

polycarboxylic

acids

alters

both

chemical

and

physical

properties

of

the

cotCor

respondence

to:

M.

Hashem

(mhashem22@).

Journal

of

Applied

Polymer

Science,

V

ol.

100,

2697

–

2704

(2006)

©

2006

Wiley

Periodicals,

Inc.

ton.

Such

chemical

treatments

eliminate

or

greatly

restrict

the

ability

of

the

cellulosic

fiber

s

to

absorb

dyes

of

various

classes.

Dyeing

properties

are

adversely

affected

because

of

th

e

inability

of

the

crosslinked

fiber

to

swell

sufficiently

in

an

aqueous

environment.

Under

such

circumstances,

dyeability

of

finished

co

tton

is

markedly

reduced.7

Several

studies

hav

e

been

made

to

decrease

the

mechanical

strength

loss

and

yellowing

of

durable

press

finis

hed

cotton

fabric.8

–

13

With

polycarboxylic

acids,

all

such

trials

have

varying

degree

of

s

uccess.

In

another

studies,

dye

sorption

by

crosslinked

cotton

is

greatly

improved

by

inclu

sion

of

reactive

hydroxyalkyl

nitrogenous

agents

in

finishing

bath.14

–

19

The

present

work

was

designed

to

tackle

problems

associated

with

finishing

of

cotton

fabric

with

polycarbo

xylic

acids,

such

as

fabric

yellowing

high

tensile

strength

losses

and

difficult

dyeability.

T

o

achieve

the

goal,

cationic

groups

were

introduced

in

the

molecular

structure

of

cotton

c

ellulose

prior

to

polycarboxylic

finishing

treatments.

Hence,

cationization

of

cotton

fabric

u

sing

3-chloro-2-hydroxypropyl

trimethyl

ammonium

chloride

(Quat

-188)

in

alkaline

mediu

m

was

carried

out

under

a

variety

of

conditions.

This

was

done

to

discover

the

optimum

cationization

conditions

of

cotton

fabric.

Following

this,

crosslinking

of

the

so-obtained

cat

ionized

cotton

fabric

(CCF)

was

effected

at

elevated

temperatures

using

polycarboxy-

2698

HEBEISH

ET

AL.

lic

acid

along

with

sodium

hypophosphite

(SHP)

as

catalyst.

1,2,3,4-Butanetetracarboxylic

a

cid

(BTCA)

and

citric

acid

(CA)

were

independently

used

as

crosslinkers

for

CCF.

Fabric

performance

was

assessed

through

monitoring

wrinkle

recovery

angle,

strength

properties,

and

dyeability

before

and

after

the

crosslinking

treatments.

EXPERIMENTAL

Materials

Co

tton

fabric

Mill

desized,

scoured,

and

bleached

100%

cotton

fabric

(poplin)

was

supplied

b

y

Misr

Company

for

Spinning

and

Weaving,

Mehala

El-Kura,

Egypt.

The

fabric

has

the

f

ollowing

specification:

Plan

weaved,

warp

36

yarn/cm,

weft

30

yarn/cm,

fabric

weight,

15

0

g/m2.

The

fabric

was

further

pur

ified

in

the

laboratory

by

washing

at

100°C

for

60

min

using

a

solution

containing

2

g/L

Na2CO3

and

1

g/L

Egyptol

(nonionic

wetting

agent

ba

sed

on

ethylene

oxide

condensate).

The

fabric

was

then

washed

several

times

with

boiling

water,

then

with

cold

water,

and

finally

dried

at

ambient

conditions.

Chemicals

Sodium

h

ydroxide,

sodium

carbonate,

acetic

acid,

citric

acid

(CA),

1,2,3,4-butanetetracarboxylic

acid

(BTCA),

acetone,

and

sodium

hypophosphite

(SHP)

were

of

analytical

grade.

3-Chloro-2-

hydroxypropyl

trimethyl

ammonium

chloride

(65

wt

%

aqueous

solution

under

a

commerci

al

name

Quat

-188)

was

kindly

supplied

by

DOW

Chemical

Company,

USA.

Cationization

of

cotton

fabric

Cationization

of

cotton

fabric

was

carried

out

as

per

pad-batch

method

u

sing

Quat-188

as

follows.

The

fabric

was

padded

in

solution

containing

Quat-188

(5

–

20

g/

L)

and

NaOH

(0

–

10

g/L)

then

squeezed

between

two

nips

and

dips

to

a

wet

pick

up

10

0%.

The

fabric

was

then

batched

in

plastic

bag

at

different

temperature

(30

–

90°

C)

for

di

fferent

time

intervals.

And

then,

the

cationized

fabric

was

washed

several

times

with

water,

acidified

with

1%

acetic

acid,

and

finally

washed

with

water

and

dried

at

ambient

conditi

ons.

Acetone

and

acetone/water

mixture

at

different

ratios

were

also

used

to

establish

the

most

appropriate

cationization

media.

Ester

crosslinking

of

cationized

cotton

by

polycarbox

ylic

acid

BTCA

and

CA

were

separately

used

as

an

ester

crosslinker

for

CCF.

The

CCF

was

first

impregnated

in

a

solution

containing

BTCA

or

CA

along

with

65

g/L

SHP

as

catalyst.

All

concentrations

of

BTCA

and

CA

presented

here

were

based

on

weight

of

bath.

No

softener

or

wetting

agents

were

used

in

the

formulation.

The

fabric

was

squeezed

to

a

wet

pick

up

of

ca.

10

0%.

The

fabric

was

then

dried

at

85°

C

for

5

min,

and

th

en

cured

at

a

specified

temperat

ure

in

a

curing

oven.

Then,

the

fabric

was

washed

several

times

with

cold

water

and

drie

d

at

ambient

conditions.

No

salt

dyeing

of

cationized

ester

crosslinked

cotton

fabric

Dyein

g

of

cationized

ester

crosslinked

cotton

fabric

without

addition

of

salt

was

carried

out

usin

g

a

reactive

dye

namely,

Suncion

Red

HE3B

(C.I:

Reactive

Red

52).

Thus,

0.25

g

of

the

dye

was

dissolved

in

1000-mL

water

at

room

temperature.

The

fabric

sample

was

then

i

ntroduced

into

this

dye

solution.

A

material

to

liquor

ratio

1:100

was

employed

(in

this

c

ase,

the

dye

shade

will

be

2.5%

based

on

weight

of

fabric).

The

aqueous

solution

of

the

dye

containing

the

sample

was

put

in

shaking

water

bath

and

the

temperature

kept

at

30°

C

for

10

min,

then

20

g/L

Na2CO3

was

added.

The

temperature

was

raised

to

80°

C

and

kept

at

this

temperature

for

60

min.

Slow

heating

rate

was

exercised,

and

shaking

was

adj

usted

at

120

rpm.

At

the

end

of

dyeing,

the

sample

was

washed

several

times

with

boilin

g

water

and

1

g/L

Egyptol

(

nonionic

wetting

agent)

and

finally

washed

with

cold

water

a

nd

dried

at

ambient

conditions.

Dyeing

with

Sumofix

Supra

Brilliant

Red

F3B

(C.I:

Reacti

ve

Red

194)

was

performed

under

conditions

similar

to

those

described

earlier,

except

that

the

temperature

was

raised

to

50°

C.

Testing

and

analysis

•

•

•

•

•

•

Nitrogen

content

of

the

cationized

samples

was

determined

by

the

Microkjeldahl

method.2

0

Carboxyl

content

(expressed

as

meq/100

g

fabric)

was

determined

according

to

reported

method.21

Tensile

strength

and

elongation

at

break

were

determined

according

to

ASTM

s

tandard

test

method.22

Wrinkle

recovery

angles

of

the

treated

and

untreated

sample

were

determined

according

to

AATCC

standard

test

method.23

Whiteness

index

(WI),

expressed

as

CIE

unit,

was

measured

as

per

AA

TCC

standard

test

method.24

K/S

of

the

dyed

fabric

was

measured

using

spectrophotometer

type

Milton

Roy

Color

Mate.

RESULTS

AND

DI

SCUSSION

Reaction

of

Quat-188

with

cotton

fabric

The

reaction

of

cotton

cellulose

with

3-chloro-2-h

ydroxypropyl

trimethyl

ammonium

chloride

(Quat-

IMPROVING

EASY

CARE

NONFORMALDEHYDE

FINISHING

2699

TABLE

I

Factors

Affecting

the

Reaction

Between

Quat-188

and

Cotton

Fabric

NaOH

conc.

(%)

Temp

(°

C)

Time

(h)

Quat-188

conc.

(%)

Solvent

used

(acetone/

water

ra

tio)

0

(0)

50

(0.39)

1

(0.25)

5

(0.07)

0:100

(0.44)

4

(0.28)

60

(0.41)

2

(0.32)

10

(0.19)

25:75

(0.46)

6

(0.35)

70

(0.44)

3

(0.41)

15

(0.32)

33.5:66.5

(0.48)

8

(0.43)

80

(0.43)

4

(0.44)

20

(0.45)

50.50

(0.52)

10

(0.40)

90

(0.31)

5

(0.44)

12

(0.34)

66.5:33.5

(0.57)

75:25

(0.73)

Conditions

used:

The

effect

of

NaOH

conc.,

temp,

and

time

was

carried

out

in

aqueous

s

olution

and

each

factor

was

studied

while

keeping

other

factors

constant.

Values

in

parent

heses

are

N

(%)

values.

188)

requires

the

addition

of

alkali

in

a

multistep

process,

which

is

time,

temperature,

and

pH-dependent

reaction

process.

During

the

reaction

of

Quat-188

with

cotton

cellulose,

several

reaction

steps

occur

simultaneously

as

suggested

by

eqs.

(1)

–

(3).

(1)

(2)

(3)

Considering

the

above

reaction

scheme,

the

magnitude

of

quaternization

(cationization)

of

cotton

fabric

would

rely

on

NaOH

concentration,

reaction

temperature,

reaction

time,

so

lvent

used,

and

method

of

application.

The

extent

of

the

quaternization

reaction

was

expre

ssed

as

nitrogen

content

of

the

CCF

and

summarized

in

Table

I.

Results

of

Table

I

highli

ght

the

following

points:

i.

Increasing

NaOH

concentration

from

4

to

8%

is

accompanied

by

an

increase

in

N%

of

the

CCF

from

0.28

to

0.43%.

Further

increase

in

NaOH

concent

ration

decreases

the

N%

of

CCF.

Logically,

higher

NaOH

concentrations

enhance

the

hydr

olysis

of

Quat-188

[eq.

(3)].

ii.

Raising

the

batching

temperature

from

50

to

80°

C

increas

es

the

N%

from

0.03

to

0.19%.

Further

increase

in

temperature

decreases

the

N%

of

cati

onized

cotton.

Here

too,

higher

temperature

seems

to

act

in

favor

of

alkaline

hydrolysis

[e

q.

(3)].

iii.

The

N%

increases

by

prolonging

duration

of

quaternization

up

to

3

h

then

lev

els

of

where

further

prolongation

of

duration

has

practically

no

effect

on

the

extent

of

rea

ction

between

Quat-188

and

cotton

fabric.

This

could

be

associated

with

depletion

in

Quat

-188

concentration

and

shortage

of

accessible

cellulose

hydroxyls

as

the

reaction

proceeds.

However,

changes

in

the

physical

or

chemical

structure

of

cotton

or

both

during

cationiza

tion

and

the

onset

of

this

on

the

ability

of

cotton

to

react

further

with

Quat-88

cannot

be

ruled

out.

iv.

Increasing

Quat-188

concentration

is

accompanied

by

increasing

the

N%

of

CCF;

a

point

that

can

be

interpreted

in

terms

of

greater

availability

of

Quat-188

molecul

es

that

are

mobile

in

the

proximity

of

the

immobilized

cellulose

hydroxyls

at

higher

Quat-

88

concentrations.

v.

When

the

reaction

between

Quat-188

and

cotton

fabric

was

conducte

d

in

aqueous

medium,

the

obtained

CCF

exhibits

nitrogen

content

of

2700

HEBEISH

ET

AL.

0.44%.

The

nitrogen

content

of

the

cationized

cotton

increases

upon

using

a

mixture

of

ac

etone

and

water.

This

increase

in

N%

depends

on

acetone/water

ratio.

For

instance

increas

ing

the

acetone/water

ratio

from

25/75

to

75/25

increases

the

N%

from

0.46

to

0.73%.

It

was

also

observed

that

no

reaction

between

Quat-188

and

cotton

cellulose

takes

place

in

1

00%

acetone.

This

means

that

presence

of

water

in

the

reaction

medium

is

essential

to

di

ssolve

NaOH

and

Quat-188

and

help

to

establish

swelling

of

the

cotton

fabric.

Furthermor

e,

current

results

are

in

accordance

with

previous

studies

reported

by

us,

as

well

as

by

ot

hers.25

–

32

Effect

of

easy

care

finishing

conditions

with

CA

or

BTCA

on

nitrogen

content

of

CCF

Ta

ble

II

shows

the

nitrogen

content

of

CCFs

before

and

after

crosslinking

with

CA

or

BTC

A.

It

is

clear

that:

(a)

at

the

same

carboxyl

content,

the

N%

increases

as

the

Quat-188

co

ncentration

increases.

This

is

observed

when

the

CCFs

were

treated

independently

with

C

A

and

BTCA

and

(b)

at

the

same

Quat-188

concentration,

increasing

the

concentration

of

CA

or

BTCA

increases

the

carboxyl

content

of

the

treated

cotton

fabric

while

keeping

the

nitrogen

content

practically

intact.

On

the

basis

of

the

aforementioned

observations,

it

ma

y

be

concluded

that

finishing

treatment

of

CCF

with

CA

or

BTCA

in

the

presence

of

SH

P

at

160°

C

using

the

pad- dry-cure

method

has

no

noticeable

effect

on

the

N%

of

CCF.

T

hat

is,

the

CCFs

undergo

no

change

in

their

N%

when

they

are

subjected

to

finishing

tre

atments

using

CA

or

BTCA

as

crosslinkers

in

the

presence

of

S

HP

catalyst.

Dry

wri

nkle

recovery

angle

Table

III

shows

the

combined

effect

of

both

polycarbox

ylic

acid

(CA

or

BTCA)

and

Quat-188

concentrations

on

wrinkle

recovery

a

ngle

of

crosslinked-CCF.

Zero

Quat-188

concentration

represents

uncationize

d

cotton

fabric.

Results

of

Table

III

reveal

that

the

DWRA

of

the

cotton

fa

bric

(not

treated

with

PCA)

is

increased

when

it

was

treated

with

increasin

g

amounts

of

Quat-188.

This

could

be

attributed

to

two

reasons:

the

first

is

the

ionic

interaction

between

the

cationic

group

in

Quat-

Crosslinking

of

CCF

with

CA

and

BTCA

Bleached

cotton

fabrics

were

subj

ected

to

cationization

reaction

using

different

concentrations

of

Quat-188

to

obtain

CCF

having

different

degree

of

cationization,

which

was

monitored

a

nd

calculated

as

N%

as

detailed

in

the

preceding

section.

Cotton

fabric

trea

ted

at

zero

Quat-188

concentration

represents

the

noncationized

cotton

fabric.

Cationized

and

noncationized

cotton

fabrics

were

subjected

to

fin

ishing

trea

tment

using

different

concentrations

of

either

CA

or

BTCA.

These

two

acid

s

serve

as

nonformaldehyde

crosslinkers.

The

effect

of

concentration

of

the

said

polycarboxylic

acids

on

the

N%

of

CCF

was

examined,

and

the

onset

of

this

on

fabric

performance

was

assessed.

Assessment

of

fabric

performan

ce

was

made

through

monitoring

dry

wrinkle

recovery

angle

(WRA),

WI,

te

nsile

strength

(TS),

elongation

at

break

(E),

and

dyeability.

TABLE

II

Nitrogen

Content

of

Cationized

Cotton

Fabric

with

Different

Lev

els

Before

and

After

Crosslinking

with

Citric

Acid

(CA)

or

1,2,3,4

Butanete

tracarboxylic

Acid

(BTCA)

N%

Polycarboxylic

acid

conc.

(%)

Blank

(untreated)

CA

3

5

8

10

BTCA

4

6

8

10

Carboxylic

content

(meq/l00

g)

4.25

Quat-188

conc.

(%)a

0

0

5

0.

41

10

0.54

15

0.61

20

0.73

19.704

30.903

55.106

78.307

0

0

0

0

0.41

0.42

0.41

0.42

0.53

0.54

0.55

0.54

0.61

0.60

0.62

0.62

0.71

0.72

0.73

0.72

30.2

65.40

95.13

108.98

0

0

0

0

0.41

0.43

0.42

0.41

0.53

0.52

0.51

0.53

0.62

0.63

0.62

0.61

0.75

0.74

0.73

0.72

a

Polycarboxylic

acid

concentration

was

calculated

based

on

weight

of

bath.

Conditions

used:

Cationization

procedures

were

carried

out

in

aqueous/aceto

ne

(1:3)

solution

at

70°

C

for

4

h.

Finishing

with

CA

or

BTCA

are

detailed

in

the

Experimental

Section.

IMPROVING

EASY

CARE

NONFORMALDEHYDE

FINISHING

2701

TABLE

III

Dry

Wrinkle

Recovery

Angle

of

Cotton

and

Cationized

Cotton

with

Different

Levels

Before

and

After

Crosslinking

with

CA

or

BTCA

Dry

wrinkle

recovery

angle

(W

Polycarboxyl

acid

content

conc.

(%)

Blank

(untreated)

CA

3

5

8

10

BTCA

4

6

8

10

a

F)

15

194

20

200

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