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Polymer Degradation and Stability 41 (1993) 275-281

Characterization of urethane functional


hindered amine light stabilizers*
Jiangqing Pan, Yu Song
Polymer Physics Laboratory, Institute of Chemistry, Academica Sinica, Beijing, People's Republic of China

&
W. W. Y. Lau , S. H. Goh ~
aDepartment of Chemical Engineering, bDepartment of Chemistry, National University of Singapore, Republic of Singapore
(Received 2 May 1992; revised version received 6 October 1992; accepted 20 October 1992)
New polymerizable urethane-functional monomers containing hindered-amine
structures have been synthesized by reaction of m-isopropenyl-t~,otdimethylbenzyl isocyanate with hindered piperidines and their copolymers
with styrene and methyl methacrylate have been prepared by free-radical
initiation. The structures, thermal stabilities, solubility parameters and stabilizing effect of these new HALS have been assessed. The results show that the
monomers have good photoprotecting effect. The effect of the copolymers is
less good because of the lower content of the piperidine nitrogen. The
extraction resistance to water at 90C is good for the copolymers but poor for
the monomers. UV and ESR experiments confirm that the photoprotecting
mechanism is still due to the scavenging action of nitroxyl radicals.

I + II(II')

INTRODUCTION

Hindered Amine Light stabilizers (HALS) are


amongst the most effective stabilizers for
polymers and have been widely studied. 1-7
However, low molecular weight HALS vaporize
easily and have poor extraction resistance 4,5
decreasing their photostabilization effect. This
has led to a trend towards polymeric HALS. 6,7
Several commercial polymeric HALS are
available s'9 but new systems are still of interest.
In this paper we describe new functional
polymerizable urethane monomers and their
copolymers with vinyl monomers.

dibutyltin dil . . . . te
80C

III(III') + M

, III(III')

-(--II I-)w-(LM-)-.
80C

-(--III'~4~--M-)~-..

CH3

I
H2C-=C

HO

H3C ~ x . . ~ C H 3
H~C ~
CH~
CH3

CH,

H~c/C\N~__.~C=O
(i)

(II)

CH3

I
H2C--C

EXPERIMENTAL
1 Synthesis of urethane functional HALS

H~/C/CH30
~C \ N H

1,2,2,6,6-pentamethyl-4-piperidinyl-m-isopropenyl-tr, a~-dimethyl benzyl carbonate (III) was

* This work was supported by the National Natural Science


Foundation of China (NSFC).

1---~1~0. H

H3C~CH3
H~C

Polymer Degradation and Stability 0141-3910/93/$06.00


1993 Elsevier Science Publishers Ltd.

I
CH3

(Ill)
275

CH~

276

Jiangqing Pan et al.

synthesized by reaction of 1,2,2,6,6-pentamethyl4-piperidinol


(II)
and
m-isopropenyl- a~, tedimethyl benzyl isocyanate (I). This reaction is
catalysed by dibutyl tin laurate at 80C.
2,2,6,6-tetramethyl-4-piperdinyl -m -isopropenyl - a~,
benzyl carbonate (III') was synthesized in a
similar way.
Copolymers of III or III' with styrene (St) or
methyl methacrylate (MMA) were prepared by
free-radical copolymerization at 80C, using
A I B N a s initiator in benzene solution at 80C.
The copolymers were recovered by precipitation
into methanol or n-hexane.

HALS

concentration was monitored by the


1 7 1 0 c m -1 band in the IR spectrum.
Photo-oxidation studies were carried out using
a Weather-O-meter Model CS801 supplied by the
Chungqing Test E q u i p m e n t Plant as described
elsewhere, g,H Changes in carbonyl content, due
to photo-oxidation, were monitored by IR
spectroscopy.
Thermal oxidations were carried out at 120C
in an air-circulating oven and examined by
embrittlement times.

RESULTS A N D D I S C U S S I O N
2 Characterization o f HALLS

1 Determination o f H A L S structures

Infra-red measurements were taken with a


P e r k i n - E l m e r model 782 spectrometer and N M R
with a J E O L FX-100 spectrometer operating at
22C with TMS as internal standard and CDCI3
as solvent. Thermal stability m e a s u r e m e n t s were
taken using a D u p o n t T G A 9 5 1 thermogravimetric analyser operating at 20C min -1 in
nitrogen.
E S R spectra were obtained at 22C using a
Bruker E P R 300 spectrometer and U V spectra
were obtained on a Unicam 1750 instrument
using CHCI3 as solvent.
The solubility parameters for H A L S were
estimated by the literature m e t h o d of molar
attraction constants 5'1 using the formula

IR, N M R and elemental analysis data were used


to confirm the structures of the urethane
functional HALS. The main results are summarized in Tables 1 and 2 and in Fig. 1 and are
entirely consistent with the proposed structures.
From the elemental analysis it is possible to
determine the concentration of the H A L S units
in the copolymers and Table 3 summarizes the
structures and properties of all the m o n o m e r i c
and polymeric HALS.

Ec
6=--.d

Table 1. The IR absorption of groups in HALS (cm-t)

Sample

3 Polymer studies

Polymer samples were prepared by blending


polypropylene (PP) powder with a chloroform
solution of the H A L S and the solvent r e m o v e d
under reduced pressure with vigorous stirring.
The powders were dried then pressed at 190C
for 30 s to give films approximately 110 # m thick.
For extraction resistance studies a PP film
containing 1% of H A L S was extracted at 90C in
water or a 1% detergent solution. The change in

Styrene

MMA

--

--

--

--

Ill-St

1720
3 060,700-800
3 250
1540
1 720
3 060,700-800
3 250
1540
1720
3 060
3 400

3 020
700,760

III'-St

1 720
3 400

3 060

3 020
700,760

1 720
III-MMA 3 400

3 060

1 720
III'-MMA 3 400

3 060

III

where E G is the sum of the molar attraction


constants for all groups in the molecule, M is the
molecular weight and d is the density. Densities
were determined at 20C using an H 2 0 / K B r
density gradient column according to AS7M-D1505-68.

Carbamate

IIV

--

1 720-1 735
2 995

--

1 720-1 735
2 995

Table 2. Elemental analysis of HALS

Sample
C%
H%
N%

III

III'

III-St III'-St III-MMA IlI'-MMA

74.9 73.74 90.23 90.41


9.68 9.50 8.24 8.80
7.53 7.82 1-16
1.25

64-17
8-7
2-68

--2.28

Characterization of urethane functional hindered amine light stabilizers

I,,

1II'

2 T h e r m a l stability o f H A L S

jib, a

11I

In order to be useful, any stabilizer must survive


the high temperatures (220-260C) used in the
processing of PP, so that the thermal stability of
the HALS is important. Murayama 4 synthesized
more than 1000 hindered piperidine compounds
but only two were effective light stabilizers,
mainly because of the poor thermal stability of
the other compounds. Table 4 shows the thermal
stability of our HALS as measured by the
temperature of the onset of rapid weight loss. It
can be seen that the thermal stability is markedly
improved by copolymerization. With styrene the
increase is around 150C; the rather smaller
improvement with MMA is associated with the
poorer thermal stability of the MMA unit.

a'

-st

/
1,

III '-st

~"

3 Solubility p a r a m e t e r s

III ' - M M A

277

Compatibility is another important factor in the


effectiveness of HALS and can be estimated by
comparison of the solubility parameters for the
additive and the polymer; similar solubility
parameters imply good compatibility. Table 5
shows the solubility parameters of our HALS as
determined by literature methods, s,l It can be
seen that the values are all close enough to that
for PP (18.8-19.3 (Jcm-3) 1/2) to suggest good
compatibility.
4 Stabilizing e f f e c t i v e n e s s

1(3

6
4
2
Chemical shift (ppm)

Fig. 1. The N M R spectra of urethane functional H A L S .

a'

H2C__---C

gCH~

CH~ C H ~
j_~/
3

~ g ~
t II_ e/~
h~ - - N H - - C - - O - - ~ H
b

IN--CH~a

CH3 CH3
a~
a
IIl

CH3 ~

d H2~C
~ g

H3

I
g

a'
CH~ CH3 a

i V

CH~
b
III'

"

--A

CH3 C H 3
a~ a

Figure 2 shows the build up of carbonyl groups


during photo-oxidation of PP containing 0-3% of
each of the HALS and Table 6 shows the
corresponding induction periods (defined as the
time to reach a carbonyl index of 0.1). For
comparison, data are included for two commercial low-molecular-weight HALS, Tinuvin 770
and 765 (Ciba-Geigy TM) and for PDS, a
commercial polymeric HALS. 1~ The photoprotecting effect of the monomers III and III' is
comparable to that of the commercial HALS.
However, copolymers are significantly less
effective, which we attribute to the lower
concentration of the piperidine nitrogen.
Embrittlement times for HALS-containing PP
films during thermal oxidation are also given in
Table 6, together with data for the commercial
additives and for 2,6-di-t-butyl-4-methyl phenol
(BHT). All of the HALS possess anti-oxidant
action and are more effective than BHT. In

278

Jiangqing Pan et al.


Table 3. The structure and property of HALS

HALS

Structure

Vinyl
III(III')

N%"

T= (C)

3.76

82.3-83.8

cn 3

H2~

III

H3

H2C-----C
III'

3"91

116-118

III-St

19.5:1

0-58

114-116

III'-St

18:1

0"63

120-122

7:1

1-34

147-150

8.75:1

1.14

138-140

CH3

I
III-MMA

C--=O

I
I

O
CH3
CH3

I
4-cH~-~---~IU'~
III'-MMa

C=O

I
O
I

CH3

"Nitrogen of piperidine ring in HALS. Tmis melting temperature.

thermal oxidation 765, 770 and PDS all p e r f o r m


better; this m a y be associated with their better
thermal stability and higher effective nitrogen
content. 5,7,H
5 Extraction resistance

Many polymers are used in conditions w h e r e


resistance of the stabilizers to extraction is

important. Low-molecular-weight H A L S have


poor extraction resistance which limits their use
in such applications.
Figure 3 shows the extraction resistance of all
of our H A L S towards water at 90C. The
polymeric I-IALS are all highly resistant to
extraction, whereas the commercial low molecular weight additives and our m o n o m e r s III and
III' are poor; similar results w e r e obtained w h e n

Characterization of urethane functional hindered amine light stabilizers

300nm, so that the urethane-functional molecules are not able to function as UV absorbers.
The ESR signals during photo-oxidation of PP
films containing the urethane functional HALS
are shown in Fig. 4. They are the standard signals
from the nitroxide free radical in the solid
s t a t e . 7,s'12-t4A6-18 Thus the stable NO" free radical
can be formed during photo-oxidation. The g
value of the urethane-functional HALS is 2.0064,
similar to
other
low molecular weight
HALS. 1'3'7"15 Thus the stabilizing action of these
compounds remains the scavenging of alkyl

Table 4. Thenno-stability of HALS


HALS

Ill III' llI-St

Stability 148 159


(C)

llI'-St II1-MMA III'-MMA

271

271

214

225

11

1I'

118 120

samples were extracted with a 1% aqueous


detergent solution at 90C.
6 Stabilization

279

mechanism

UV spectroscopy shows that all of the HALS we


have used have no measurable absorption above

Table 5. The solubility parameter of HALS


HALS

III

III'

III-St

III'-St

III-MMA

III'-MMA

770

765

PDS

/~
Cal=/2/cm3/2

9-1

9.3

8-7

8.4

8-9

8.4

9.2

7-8

8.8

1.5~

O~ 6

13

t3

1.0
X

16

0.5

S
100

14

200

300

400
Irradiation time

//----

1400
(h)

1500

1600

1700

Fig. 2. Carbonyl formation in polypropylene film containing H A L S during photo-oxidation, (1-Ill, 2-111, 3-III-St, 6-III-St,
8-III-MMA, 13-III-MMA, 14-Tinuvin-765, 15-Tinuvin-770 and 16-PDS).

Table 6. Induction period of photo-oxidation and embrittlement time of thermo-oxidation for polypropylene containing HALS
Additives

Blank

III

III'

III-St

III'-St

IP (h)"
tem (h) b
N% c

25-5
22"5
/

1 385
85
3-76

1 480
110
3-91

122
62
0-58

44
62
0-63

III-MMA III'-MMA
80
134
1.32

76
156"5
1-14

765
1 412
540
5.5

770

PDS

264

1660
540
5-8

216
465
2-2

/
41
/

"Induction period.
h Embrittlement time.
c Content of nitrogen of piperidine ring in H A L S (effective N%).
The concentration of additive in PP is 0.3%. The structures of 765(Tinuvin-765 or 508), 770(Tinuvin-770) PDS and 264(BHT)
are in the literature. "'9.u

280

Jiangqing Pan et al.

synthesized and copolymerized with styrene and


MMA. The monomers are photostabilizers with
effectiveness equivalent to conventional HALS,
but the effect of the polymeric HALS is reduced
by their lower nitrogen content. The copolymers
exhibit much better thermal stability than the
monomers, especially when styrene is the
comonomer. They also have very much better
extraction resistance. Their photoprotecting
mechanism is apparently the same as that of the
low molecular weight HALS.

F
<

IlL

~qL

8
-" 4

ACKNOWLEDGEMENTS
n

I
20

I
40

I
60

I
80

I
100

I
120

7 9

140

We thank Ciba-Geigy AG and Beijing Third


Chemical Works for supplying samples of
Tinuvin 770, Tinuvin 765, PDS and BHT.

Extraction time (h)

Fig. 3. Extraction resistance of HALS from PP into water at


90C (1-III, 2-III', 3-Tinuvin-770, 4-Tinuvin-765, 5-III-ST,
6-III'-St, 7-III'-MMA, 8-III-MMA, 9-PDS).

radicals by nitroxides formed during photooxidation.


CONCLUSIONS
New polymerizable urethane-functional monomers containing hindered amine units have been

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10 G
i
I
rn

rn'

Tr[ - s t

Tn"-st

Trt'-MMA

m'-MMA

Fig. 4. The ESR signal of HALS (in PP film containing HALS at 0.3%, after photo-oxidation for 142.5 h)

Characterization of urethane functional hindered amine light stabilizers


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