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The use of vinyl esters of branched carboxylic acids derived from propylene tetramer in copolymer latices.

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Die Angewandte Makromolekutare Chemie 12 (1970) 145-156 (Nr. 152)
From the Research Institute for Synthetic Resins and Lacquers
and the University of Chemical Technology, Pardubice, 6SSR
The Use of Vinyl Esters of Branched
Carboxylic Acids Derived from Propylene Tetramer
in Copolymer Latices*
By JAR OM^ &YPLREK JR. and JOSEF
~
Z
N
A
(Eingegangena m 15. Oktober 1969)
SUMMARY:
Branched carboxylic acids were prepared via carboxylation of propylene tetramer, using formic acid and sulphuric acid, this waa followed by hydrolysis. Vinyl
esters of these acids were prepared via transesterificetion with vinyl acetate. The prepared monomer is a mixture of similar components having the same polymerization
activity. This monomer waa copolymerized with vinyl acetate and the reactivity
ratios were determined. The found values of rl and rz were near to 1.0. Copolymer
latices were prepared by emulsion polymerization and some properties of coating
films were evaluated in dependence on the composition of the copolymers.
ZUSAMMENFASSUNG:
Verzweigte Carbonsiiuren d e n durch Carboxylierung von Tetrapropylen mit
Hilfe von Ameiseneiiure und SchwefeWure und durch nachfolgende Hydrolym hergeetellt. Vinylester am diesen Sauren d e n durch Umvinylierung mit Vinylacetat
synthetisiert. Daa hergestellte Monomere ist eine Mischung von ahnlichen Komponenten mit gleicher Polymerisationsaktivitlit.Dieaes Monomere wurde mit Vinylacetat copolymerisiert. Die Copolymerisationsparameter d e n bestimmt ; die
Werte r1 und rz d e n nahe 1,0 gefunden. Copolymer-Laticeswurden durch Emulsionspolymerisationhergestellt ;die Eigenschaften der Anstrichfilme wurden in Abhiingigkeit von der Zuaammensetzung der Copolymeren ermittelt.
Int~ocEuCtion
Latices based on copolymers of vinyl acetate and vinyl esters of branched arboxylic acids Versetic 911 and Versatic 10 were developed by the
Shell Co. These vinyl esters specified as VeoVa 911 and VeoVa 10 are used as
* Presented at the IUPAC International Symposium on Macromolecular Chemistry,
25th-30th Aug. 1969, Budapest.
146
J. ~ ~ J P L R EJr.K and J. MLEZIVA
internal plasticizers and, in comparison with other types of polyvinyl acetate
dispersions, distinctly improve the alkali resistance of coating materials prepared from these latices1*293.In our studies we copolymerized vinyl acetate
with similar vinyl esters of branched carboxylic acids derived from a mixture
of propylene tetramers (VPT) having the formula
R'
I
R~-C-COOCH=CHZ.
I
R3
Preparation of comomer
Branched carboxylic acids from propylene tetramer were prepared by carboxylation of propylene tetramer by the method, suggested by H. K o c E ~ - ~ .
This method consists of the addition of carbon monoxide to the double bond of
the olefin in the presence of acid catalysts, followed by hydrolysis:
Rl-CH=CH-R2
H@
0
+ Rl-CHa-CH-R2
co
-+
R'-CHa-CH-R2
1
@co
I +H2O
1 -H@
R'-CH2-CH-R2
I
COOH
As a source of carbon monoxide formic acid with an excess of concentrated sulphuric acid was used.
I
Vinyl esters of these acids wer$ prepared by transesterification with vinyl
acetate in the presence of mercuric acetate according to the following scheme
7.8,Q:
R-COOH
+ CH&OOCH=CH2 + Hg(OCOCH3)a
It
CH&OO -Hg-CHaCH
<zzzH3
+ CHsCOOH
It
CHsCOOH
+ R -COOCH=CHa + Hg(OCOCHs)2
Deteminatwn of the reactivity ratios
The composition of the copolymer during the polymerization is defined by
the known copolymer composition equationlo:
146
Vinyl Esters i n Copolymer Latices
dM1
ml
For low conversions
= -,
where ml and m2 represent the polymer comdM2 m2
position.
FINEMAN
and Ross have simplified the copolymer equation for low conversionsll as follows:
F
F2
--(f-
f
l)=rl*f
- 12
where f = mllmz and F = Ml/M2.
If two monomers are polymerized in different proportions to low conversions,
then the values of F/f (f - 1)plotted against the values of F2/f give a straight
line with the slope rl and the intercept -r2. The reactivity ratios evaluated by
means of copolymerization parameters Q and e, which are characteristic for the
given monomer, are defined by the ALFREY-PRICE
equationl2, and by using the
known values 8 2 and e2 the values Q1 and el can be figured out according t o re-
-
lations
el = e2 f ( - In r1r2)1/2
&a
81 = -exp. [ - ea (ea - el)].
ra
For the calculation the known values of Q and e for vinyl acetate (Q = 0.026,
e = - 0.22) were used13.
Experimental
Prepraticm of acids frmn propykne tetramer
In a 10 1 round-bottomed four-neckedflask provided with a stirrer (1200 clmin),
a reflux condenser, a thermometer and feeding instrument, were placed 6480 g of
concentrated sulphuric acid cooled to 0-5 "C.Then 1 200 g of formic acid and 1 032 g
of propylene tetramer were added simultaneously a t such a rate as to maintain the
temperature of the reaction mixture a t a max. of 5°C. The addition was finished after 2 hrs. The reaction was completed after stirring for 1.5 hrs. a t 20°C. T h e mixture
was poured on 3 kg of ice, and the separated fatty acids were washed with water,
neutralized by a slight excess of KOH solution. The soaps were boiled for 1 hr. After
cooling they were treated with 160 ml of hexane to extract unreacted propylene tetrgmer. Fatty acids were r e l e d by acidification with HCl to pH = 1, and washed
with water. The remaining water, HCl and low boiling acids were recovered by distillation at atmospheric pressure. Distillation was completed a t the pressure of 3 torr
and the fraction 160-26OoC/3torr wm collected.
147
J. %JFLREK Jr. and J. MLEZIVA
Prepration of vinyl esters
In a 2 1 round-bottomed three-necked flask provided with a thermometer, a reflux condenser and a nitrogen inlet tube were placed 1030 g (12moles) of freshly
distillei vinyl acetate, 460 g (2moles) of acids derived from propylene tetramer and
8 g of mercuric acetate. The mixture was shaken for about 30 min and 0.8 ml of concentrated sulphuric acid were added. The solution was heated under reflux for
3hrs., then 4.16 g of sodium acetate were added to neutralize the sulphuric acid. The
excess of vinyl acetate and the main pert of acetic acid (which was formed during
the reaction) were recovered by distillation at atmospheric pressure. Distillation was
completed a t the pressure of 3 torr. The crude product, shaken three times with the
10 yo solution of sodium carbonate, was pured by distillation at a pressure of 3 torr.
The fraction 20-12OoC/3torr was collected during the first distillation (ethylidene
diacetate and other low boiling products were involved). The fraction 96-l1O0C/3
torr was collected during the second distillation. The product was stabilized by the
addition of 5 ppm of the monomethyl ether of hydroquinone.
Prepration of copolymers for determination of reactivity ratios
Dibenzoyl peroxide (0.01g) was placed into 10-12 ml g k tubes. The tubes were
closed by rubber serum caps and were flushed for 20 min with nitrogen. Before being
placed into topped tubes, with the aid of an injection syringe, the monomers were
stripped by N2 for 6 hrs. The net weight of both comonoihers was about 9 g. The
monomers were frozen by liquid nitrogen and the tubes were sealed. The tubes were
placed in a 80°C water bath until a 10-16 yoconversion had occured, as indicated by
determination of the solid content. (The viscosity of the reaction mixture was used
as an approximate indioation of conversion). When the required conversion was
reached (after 10-16 min), the tubes were cooled and opened. The reaction mixtures
were diluted in 10 ml of benzene and were precipitated with hexane and cold methanol, respectively. The polymers were reprecipitated five times. Finally the polymers
were dissolved in a small amount of benzene, frozen and freeze-dried for 60 hrs. a t
1-2 torr at room temperature. (Evaporation kept the solution frozen). The polymer
was obtained as a spongy m w and was analysed for carbon.
&
s.
chromatography
The gas chromatography analyses were performed on a PYE Panchromatograph.
The experimental details were as follows:
Flame ionisstion detector,
2.7 metre column, 4 mm i.d.,
~
Support: Celite 0.2-0.26 I I ~ I Id.,
Stationary phew : 20 % polyethyleneglycol d p e t e ,
Temperature : 146"C,
Carrier gas: Na a t 76 ml/min.
Results and discussion
Characterisation of the comorunners
Due to the fact that the starting propylene tetramer is a mixture of about 60
substances, the resulting vinyl esters form also a mixture of similar substances.
148
The relative polymerization activity of individual components was determined
from their loss during the polymerization ascertained by gas chromatography.
In crude vinyl esters one nonreactive component was found. This component
was identified by means of elementary analysis, values of some physical constants and its infrared spectrum as ethylidene diacetatel4. Its formation can be
explained by the following reaction :
CH&OOH
+ CH&OOCH =CHa + Hg(0COCHs)a
TI
OCOCHs
CHsCOO -Hg -CH&H<
OCOCHs
+ CHsCOOH
it
Fig. 1. Decrease of the components
of VPT during the polymerization.Gaa
ohromatogrem.
0
$mersion:a-5%, b-60%, c - 9 0 % . d-Q9%
149
J. &
~ P ~ EJr.
K and
J. MLEZIVA
Ethylidene &acetate and other low boiling components were separated by
distillation and the relative polymerization activity of the remaining components waa further investigated by means of gas chromatography (Fig. 1). Since
these components decrease according to their proportion in the mixture, their
polymerization activity is similar and this mixture can be handled aa a chemical
individual.
Some physical constants af the vinyl esters prepared from propylene tetramew are given in the following Table 1. Infrared spectra and gas chromatograms of VeoVa 10, VeoVa 911 and VPT are given in Fig. 2 and 3.
Fig. 2.
4ot
I
XMQ
zwo
3000 ernef
t
loo00
2000
3000 ern-‘
1
I
Veovo sn
Infrared spectra of VeoVa Q11, VeoVa 10 and VPT.
vinyl Ester8 in Copolymer Laticee
Table 1. Some properties of VPT.
Colour
Odour
Specific gravity di:
Viscosity, cP, 20°C
Refractive index n g
Acid number (mg KOH/g)
Bromine number (g Br/l 000 g)
Miscibility with vinyl acetate
Freezing point "C
Boiling range "C/3 torr (6-96 yo)
colourless, clear liquid
ester type
0.8897
4.4
1.44398
less than 2
670
complete
l e a than -30
97-110
Fig. 3. Gea chromatograms of VeoVa
911, VeoVa 10 and VPT.
Reactivity ratioe
The experimentalresults are given in TaLe 2. The copolymerizationdiagram
and the plotted FINEMAN-ROSS
relation are given in Fig. 4 and 6. The values of
the reactivity ratios for copolymerization of vinyl acetate with VPT are
rI = 1.06 f 0.17 and r2 = 1.02 f 0.16. The values Q = 0.027 and e = - 0.48
were calculated from the ALFREY-PRICErelation.
161
1
2
3
4
5
6
No.
7.41509
6.84605
6.55598
5.23160
4.71360
1.94820
(B)
(9)
1.23019
2.13747
3.05024
3.38605
4.33845
6.99480
Mz
Mi
5.841
12.030
14.817
19.484
28.780
57.443
Mi
(mole-%)
58.30
60.40
61.25
62.89
64.83
69.54
lymer (yo)
c in c o p 5.774
11.691
14.402
20.261
28.510
67.979
mi
(mole-%)
F
0.06203
0.13675
0.17394
0.24199
0.40588
1.34979
Table 2. Bulk copolymerization of VPT (Mi)and vinyl m e t a b (Mz)at 80°C.
0.06128
0.13239
0.16825
0.25602
0.39880
1.37976
f
-0.95023
-0.89622
-0.86986
-0.70323
-0.61189
+0.37151
F
-(f-1)
f
0.06283
0.14125
0.17985
0.22873
0.41309
1.32047
f
F2
F5
4
BP
?
4
r.
3'
9
Vinyl Esterr, i n Copolymer Latices
mol. % M,
in
mmomer mixture
Fig. 4. Copolymer compositioncurve for
vinyl acetate - VPT copolymerizetion.
plot for copolyFig. 5. FINEMAN-ROSS
merization of vinyl acetate - VPT.
The values found correspond to the results published recently by TESSand
TSATSOS.
These authors have evaluated the reactivity ratios of vinyl esters of
some branched acids with vinyl acetate15 :
vinyl pivalate : Q = 0.027, e = - 0.77
VeoVa 9
: Q = 0.028, e = - 0.64
VeoVa 10
: Q = 0.028, e = - 0.63
VeoVa 9 and VeoVa 10 are vinyl esters of branched carboxylic acids derived
from diiaobutylene and propylene trimer, respectively.
It is evident, that the reactivity ratios of vinyl esters of tertiary carboxylic
acids copolymerized with vinyl acetate are essentially independent of the molecular weight of the acids and their values move around 1.0. The vinyl esters of
tertiary carboxylic acids behave during their copolymerization with vinyl acetate in a similar way as the vinyl esters of fatty acids having a linear chain. For
example for vinyl butyrate the values Q = 0.026 and e = - 0.32 were foundl5.
Monomer pairs, which have the reactivity ratios approximately 1.0 form copolymers, the composition of which is equal to the composition of the starting
monomer mixture. Thus also the composition of vinyl acetate - VPT copolymers is identical with the composition of the starting monomer mixture.
163
J. S N U P ~ EJr.
K and J. MLEZIVA
Influence of VPT content on propertiea of VPT - VAc copolymer films
VPT waa copolymerized with vinyl acetate by emulsion technique using the
method commonly recommended for the preparation of VeoVa-vinyl acetate
copolymers16917.
The system anionactive - nonionic emulsXers and protective colloid waa
used. The content of VPT has a considerable influence on the mechanical properties of the copolymers. The influence of the VPT content on the tensile
strength and elongation a t break is presented in Fig. 6. With a higher content
of VPT the glass transition temperature decreases, T, of the VPT homopolymer is - 12 "C (F'ig. 7). Coating films containing more than 20 yo VPT exhibit an excellent resistance to diluted alkali (F'ig. 8).
Fig. 6. Tensile properties of vinyl acetate - VPT copolymers.
1
154
Gless transition
Fig. 7.
temperaturesof vinyl acetate
- VPT copolymers.
Vinyl Eatera in Copolymer Laticea
Fig. 8. Alkali resistance
of vinyl acetate - VPT
copolymera at 2OOC.
It is possible to conclude that 1)all components of VPT have the same polymerization activity, 2) the reactivity ratios for the copolymerization of VPT
with vinyl acetate move about 1.0, that means that the composition of the copolymers is identical with the composition of the starting monomer mixture, 3)
VPT acts aa a plastifying comonomer, 4) VPT considerably improves the alkali
resistance of coating films, 6) VPT decreases T, of copolymer more than VeoVa
10 and VeoVa 911 and the alkali resistance remains unchanged down to the
content of 20 % VPT.
The authors wish to thank Dip1.-Ing. V. B~EZINA
for the preparation of the
acids from propylene tetramer, Dip1.-Ing. K. &SPAR for the gas chromafbgraphy data and the Shell Co. for the samples of VeoVa monomers.
1
P. BRUIN,H. A. OOSTERHOF,
G. C. VEQTERand E. J. W. VOOELZANQ,
VII. FA-
2
TIPEC-Kongress 1964, 49.
A. Mc INTOSH
and C. E. L. READER,
J. Oil Colour Chemists’ Assoc. 49 (7) (1966)
525.
3
4
5
6
7
8
Q
10
C. E. L. READERand G. GASTINEAU,
Double Liaison 129 (1966) 642.
H. KOCH,Brennstoff-Chem.86 (1955) 321.
H. KOCH,Fette Seifen einschl. Anstrichmittel 59 (1957) 493.
H. KOCHand W. HM, Liebigs Ann. Chem. 618 (1958) 251.
J. &JP&EK,
J. MLEZIVAand V. B ~ Z I N A
Chem.
,
Prumysl (in press).
W. H. WATANABE
and L. E. CONLON,
J. Amer. chem. SOC. 79 (1967) 2828.
D. SWERNand E. F. JORDAN,Organic Syntheaes, Coll. Vol. 4 (1963) 977.
T. ALFREYand G. GOLDFINGER,
J . chem. Physics 12 (1944) 205.
166
J. & U P ~ E K Jr. and J. MLEZIVA
M. FINEMAN
and S. D. ROSS,
J. Polymer Sci. 5 (1950) 259.
T.ALPgEy and C. C. PRICE,
J. Polymer Sci. 2 (1947) 101.
1s L.J. YOUNO,
J. Polymer Sci. 54 (1961) 411.
14 J. &JP~REK and J. MLEZIVA,
Chem. Prumysl (inpress).
15 R. W.TESS and W.T.TSATSOS,
h e r . chem. SOC., Div. of Org. Coatings and
Plastics Chemistry Pepers Vol. 26/2 (1966) 276 (Meeting, New York, Sept.
11
12
12-16, 1966).
16
17
Vinyl Ester of Versetic 911, T e c h . Bull. (Shell).
J. & J P ~ K and J. MLEZIVA, Chem. Prumysl (inpress).
156
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