Studies on Diazo Type Process. VIII

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3) U.S.P. 3,205,157. 4) B.P. 893, 063. 5) H. Ito and C. G. Wilson, SPE Regional Tech- nical Conference on Photopolymers (Ellenville,. New York, Nov. 1982), p.

J. Soc. Photogr. Sci. Technol. Japan,





Studies

on Diazo

Vol. 47, No. 5, 1984

Type

Process.

VIII

Quantitative Analysis of Boron Trifluoride generated by Photodecomposition of Benzene Diazonium Tetrafluoroborate Kieko

HARADA,

Nobuo and

Department

UENO,

Shin

Kazuyuki

SUGITA

SUZUKI

of Image Science and Technology, Faculty of Engineering, 1-33, Yayoi-cho, Chiba City

(Received 15th August,

1984.

Accepted

for Publication

Chiba University

23th October,

1984)

Abstract Boron

trifluoride,

(BDTFB), an

was

insoluble

could

be

because

the

determined of

by

indirectly

1.0

in

by

dioxane

from

the

it

completely

in

weeks.

This

pound

detects

was IPA

decomposition

as

of

decomposed

analytical selectively

the

the

BF3

IPA

which

the

60%

is

of

the

useful

of spectral

as

BF3

cationic

Introduction

Since Schlessinger extended the use of BF3 which was photogenerated from diazonium tetrafluoroborate as the initiator of cationic

mer

polymerization1), many reports have been published on the application of such an initiator to photocurable cationic systems for surface coatings and printing plates2)-4), and to radiation-degradable systems for EB and X-ray resists". The former system involves the use of the photoinitiator in epoxy resisns, and an example of the latter is the radiation initiated depolymerization of polyaldehyde. They are favorable to get high sensitivity through chemical amplification. The amount of BF3 determines the rate of poly-

cured

and

W. by

and

sensitivity

as

important

nium

the

is

by

the

with

pounds9)-12), titative As

•\ 351—

BF3

was

place

in

dimethylamino

2

com-

storage

molecular of

it

the

resolving amount

may

BF3

funcit

much

generated

are of are

many

diazonium

sysdiazo-

reports com-

about

photogene•\ration of

the the

diazonium few

is

boron

in of

There

the

of

Therefore,

photolysis

rate

power of

how

actually

stability

the

property

photodecomposition

on

to

the

depolymerization

catalyst5).

there

polyIn

relates

In

the

the

reaction6)-8).

determine

but study

the

generated

mechanical

compound.

dealing

in-

BDTFB

no

took

the

and by

to

trifluoride tem

been

material.

controlled

tioned

was that

distribution

the

coating

be

was

determined

found

system,

curing

dimethyl-

depolymerization,

M.

obtained

the

BDTFB

hand,

a

a

initiator.

polymerization of

of

have

of

BF3

N-dimethyl-

was

which

or

weight,

p-(N,

BF3

other

BDTFB

merization

1.

to

the

change

the

of

It was

On

directly So

of

of

mole

ring

detected

electrons

20•Ž.

products.

of

be

presence

in

benzene

products.

stability

at

decomposition use

the

storage

that

to

pair

1.0

dioxane

and

thermal

in

dioxane, the

or

3 weeks,

by

out

or

decomposition

complete method

carried

able other

lone

decomposed

containing

not of

to

Then, in

in in

the

was

dispersion

was those

coordination

compound. a

BF3

tetrafluoroborate was

products

with

isopropanol

diazonium compound

decomposition But

by

benzene

diazonium

band

change

solution

detected after

and

characteristic

diazonium

keeping

BDTFB

detected

the a

from the

spectrophotometry.

spectral

When

of

reactant

the

from

in

mole

vestigated

UV of

amino)-fluorobenzene from

photogenerated When

residual

overlapping

compound.

was

quantitatively.

solvent,

determined amino

which

analysed

quanof

BF3. com-

•\

K. HARADA, N. UENO, K. SUGITA and S. SUZUKI

352•\—

pound

is

poor

on

composition,

it

amount

of

catalyze

the

In

paper,

a

was

use

able

to

and

was

of

diazonium

studied,

thermal

the

the

analysis

benzene

storage

of

be

quantitative

by

during

the

to

deout

system.

from

generation

thermal find

trifluoride

tetrafluoroborate

BDTFB

its to

photo-imaging

photogenerated

BF3

of

essential

boron

this

BF3

account is

J. Soc. Photogr. Sci. Technol. Japan

then

the

decomposion

of

investigated

by

analytical

method

above-

mentioned. 2.

Experimental

2.1

Materials Benzene

diazonium

obtained

by

rafluoroborate

aqueous

to

benzene

diazonium

aniline.

The

and

aqueous

used

were

of

of

by

The

extra

Photodecomposition

from

purified

methanol.

were

tet-

solution prepared

precipitates from

materials

was

hydrogen

chloride

recrystallization

2.2

tetrafluoroborate

adding

pure

and

other

grade.

UV

Spectro-

Fig.

photometry Benzene

diazonium

tetrafluoroborate

TFB)

powders

dispersed

vent

(isopropanol

or

with

a

A

part

a of

was

a

of

diluted

measured

with

a

Spectrophotometer was

partly

was

dissolved

3. 3.1

and

is

tion sorption

in

and

are

at

that

275

nm

of

BDTFB persed

the

in

IPA

Fig.

the

absorpAbethyl

were

1.

was

an

dioxane13). trifluoride

measured

The

molar

calculated value

of

to 9.3

in

abbe

6.6

dioxane

literature. of

Tetrafluoroborate

IPA

BF3

nm

and

IPA

powders in

BDTFB

water.

shows

Photodecomposition zonium

BDTFB

of

boron

in

from in

When

BF3

275

dioxane

in

reported 3.2

at

shown

sorptivity

and Beam

residual

with

Spectrum

spectra

etharate

solvent Double

the

dilution

reported

maximum

50

20•Ž.

Discussion

Absorption It

the

Shimazu

UV-180.

Results

at

photodecomposition

decomposed, by

mmƒ³ •~

kept

with

(0.019 (3 ml)

Benzene in

g,

were

in

IPA ƒÃ=6.6

dioxane *

R

. Havey,

Anal.

of

BF3(C2H5)20 -

e =9.3 Chim.

Acta.

at

275

nm

at

275

...... nm*

67,

2448

(1973)

Toshiba

(10

3 cm

sol-

Spectrum

irradiated

lamp, cell

of

solution

was

were

quartz

distance the

products

insoluble

mercury

in

at

an

dioxane),

high-pressure

SHL-100UV, mm)

in

(BD-

1

Dia-

IPA

1 •~ 10-4 irradiated

mole)

diswith

a high-pressure mercury lamp. While irradiation, little bubbles were generated from the surface of powders and BDTFB gradually dissolved into IPA. After complete dissolution of BDTFB powders, an aliquot of the IPA solution was taken and analysed by UV spectrophotometry. UV spectra of decomposition products and some expected model compounds (fluorobenzene; a mixture of fluorobenzene and phenol; and a mixture of fluorobenzene, phenol and boron trifluoride ethyl etherate) are shown in Fig. 2. The spectrum of decomposition products coincided with that of a mixture of fluorobenzene, phenol and boron trifluoride ethyl etherate; absorption bands at 248-270 nm were assigned to fluorobenzene and phenol, respectively. From the spectral intensity, it was estimated that these compounds were produced in a molar ratio shown in Eq. (1) :

Vol. 47,

Studies

No. 5, 1984

on Diazo

Type

Process.

•\ 353•\—

VIII

the fact that BF3 coordinates to the lone pair electrons of the dimethylamino group and that interaction is interrupted between the lone pair electrons and r electrons of benzene ring14) (see Eq. (2 )).

(2) The

quantitative

tempted of

the

the

is

so

form

the

is

the

visible

at

azo

the

dye,

In

was

line,

and

p-

reaction is

occurs

deduced at

order

to

from

405

nm

in

prevent

the

from

being

N-dimethylamino)-fluoroben-

used

instead

BF3

diazonium

be

unsubstituted

compound

p-(N,

with may

N-Dimethylani-

which

region.

When contact

appeared

N-dimethylamino

zene

N,

coupling

peak

coupled,

in

at-

change

former

latter.

the

an

was

compounds.

reactive

absorption

BF3

spectral

the

that

an

N,

Products compounds

the

compound

with

position to

of

of

N-dimethylaniline,

line

Spectra of Photodecomposition of BDTFB and some model

use

dimethylamino

coupled

2

the

diazonium

N,

Fig.

analysis

by

of

N,

N-dimethylani-

photo-generated

from

tetrafluoroborate

was

benzene

determined

quantitatively.

(1)

3.3.1

The

The

spectral

Calibration

Curve

change

of

solutions

of

N-dimethylamino)-fluorobenzene The

sum

of

moles

containing nol

and

mined

to

be

equal

BF3 because

sorption

band at

275

phenol

at

tivity

of

was

nm,

those

of

and

of

(ƒÃ= 6.6)

s =1,700

at

small

When

BF3

nm)

the

zene.

The

and

other 262

nm

;

was

Presence

added

to

(DMA)

or

of

that spectral

a solution p-(N,

(DMAFB)

spectrum

of of

DMA

or

benzene change

As

308

pair

electrons peak

er

lowered.

248

or is

in

ascribed

Fig.

4. of

of It

in

248

BF3

is of

concentration

considthe

was

lone when

no

long-

absorbances

at

concentration 4. is

the

of

The

calibra-

also

shown

plot

fluorobenzene

standard

was

nm

Fig.

of

nm be-

group

fluorobenzene slope

248

to

initial

shown

was

at

fluorobenzene

3].

at

in

• (C2115)2O

spectrum

coordinated

vs.

curve

the

that

minimum

nm

and

BF3

dimethylamino

The

of

the

various shown

peaks and

Fig.

DMAFB

the

calibration

the

of

The

DMAFB

of

has

are

curve

derivative to

with

308

tion

fore,

DMAFB fluoroben-

)'

with is of

to

BF3

of

and

peak N-

maximum

decreased

(7 that

adding

• (C2115)2O

the

similar

ered

by

BF3

concentration

quite

the

IPA

the

nm

DMAFB the

Fluorobenzene

• (C2H5)2O

into

at

in of

[compare

absorp-

with

3.

came

.

in

N-dimethylaniline

changed

nm,

molar

dimethylamino)-fluorobenzene IPA,

262

=1,400

275

and

products

at

M/l)

increased,

photo-

detected of the ab-

other

compared

Photodecomposition Dimethylamino

be

Fig.

reactant

the

10-4

concentrations

deter-

of

not able to of overlapping

(fluorobenzene, ƒÃ

phenol,

N,

mole

fluorobenzene

nm)

BF3

was the

(0.9 •~

phe-

However,

with

275

products

of

products

(fluorobenzene,

to

employed.

generated directly,

3.3

decomposition ring

p-hydroxy-azobenzene)

originally

(BF3

of

benzene

p-(N,

(DMAFB)

of

derivative coincided

with

fluorobenzene. of

regarded fluorobenzene.

the to

be

in

248

nm

from that

of

Therefluorobenzene equal

to

Absorbance

that

K. HARADA, N. UENO, K. SUGITA and S. SUZUKI

•\ 354•\

Fig. 3

Spectral change BF3(C2H5)2O

of DMAFB by adding

J. Soc. Photogr. Sci. Technol. Japan

Fig. 5 Relation between concentration of (CH3)2N

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