Patented June 12, 1951 2,556,488

UNITED STATES PATENT OFFICE

2,556,488
MANUEFACTURE OF POLYSTYRENE
Leslie Ernest Wakeford and Donald Helmsley
Hewitt, London, England; Ernest Booth and
Richard Hartlebury Buckle, executors of said
Donald Helmsley Hewitt, deceased, assignors,
by mesne assignments, to The Sherwin
Willians Company, Cleveland, Ohio, a corpo
ration of Ohio
No Drawing. Application October 22, 1945, Serial
No. 623,887. In Great Britain November 3,
1944 -
17 Claims. (CI. 260-29.8)
This invention relates to the manufacture of vents consisting of or comprising monocyclic or
polystyrene and has particular reference to the dicyclic alpha, terpenes has a marked effect on
production of styrene polymers of low molecular the polymerisation of monomeric styrene and en
Weight from monomeric styrene. ables polymers of low molecular weight to be ob
. It is known that the polymerisation of mono 5 tained without the disadvantages previously re
meric styrene by heating it in various solvents ferred to.
produces polystyrenes of different molecular Whilst it will be appreciated that the actual
weights dependent upon the particular solvent molecular weight of the polystyrene produced
employed, and that with equal concentrations by the improved process according to the present
of styrene, not only do different Solvents lead to invention is dependent upon the relative propor
the production of polystyrenes of different tions of the styrene and terpene solvent, the
molecular weights, but the respective rates of nature of the latter and the conditions under
polymerisation of the styrene vary in accordance which the polymerisation reaction is carried out,
With the nature of the Solvent employed. the use of solvents consisting of or comprising
5 monocyclic or dicyclic alpha, terpenes results in
Further the production of polystyrenes of rela
tively low molecular weight by heating mono all cases in the production of a polystyrene of a
meric Styrene in solvents that are useful for the relatively low molecular weight, for example of
production of paints, warnishes, lacquers and the the order of about 9,000 to 12,000, as compared
like has hitherto been accomplished most. Suc with polystyrenes having a considerably higher
cessfully by polymerising the monomeric styrene 20 molecular weight, for example of the Order of
in the presence of catalysts, particularly those, about 50,000 to 70,000, produced by polymerisa
Such as benzoyl peroxide, which are Soluble in the tion of the styrene in an equal concentration of
polymer and its Solutions, or others, such as Xylene.
fuller's earth or activated clay, which are in Furthermore, in the case where the polystyrene
25 is to be employed in the manufacture of film
Soluble therein. Catalysts of the kind just men forming compositions, such as warnishes, lacquers
tioned are disadvantageous because the insoluble and paints, the presence of a monocyclic or di
ones require removal by filtration after the poly cyclic alpha terpene solvent is particularly bene
merisation has been effected, or, if, like benzoyl
peroxide, they remain in the final product the ficial, as various solvents of this nature (such
value of the latter is impaired for many purposes. 30 as turpentine and dipentene) are already exten
The present invention has for its objects to Sively used in paint and Warnish manufacture,
Overcome the disadvantages above mentioned in and are known to confer on films good brush
the production of polystyrenes of low molecular ing and drying properties, whilst at the same
Weight and to simplify the manufacture of these time possessing good Wetting and dispersing
products whilst at the same time enabling a more 35 properties. In this connection it may be re
effective control to be exercised over the molecul marked that, in the process described in the
lar weight of the polystyrene finally obtained. Specification of Our Copending application Serial
For this purpose according to the present inven No. 496.780, filed July 30, 1943, now U. S. Patent
tion polystyrene of a relatively low molecular No. 2,392,710, for the production of interpoly
weight is obtained by effecting the polymerisa 40 mers of aromatic vinyl hydrocarbons with poly
tion of monomeric styrene in a solvent or mixture hydric alcoholic mixed esters containing substan
of solvents consisting of or comprising one or tial proportions of unsaturated fatty acid radi
more alpha terpenes of the monocyclic or dicyclic cles, mineral spirits and turpentine are mentioned
type. Thus the solvent in which the polymerisa amongst the various Solvents instanced as be
tion of the monomeric styrene is carried out may 45 ing suitable for effecting the polymerisation
consist of one or more terpenes alone of the kind treatment of the mixture of aromatic vinyl hy
just mentioned, or may comprise an admixture drocarbon (such as styrene) and partially poly
of one or more of the said terpenes with another - merised polyhydric alcoholic mixed esters. (Such
Solvent, Such as an aromatic hydrocarbon, for as linseed stand oil, dehydrated castor oil etc.),
instance xylene, and/or an aliphatic hydrocar 50 and in certain cases it was stated that use of
bon, for instance mineral spirits. Dipentene and these Solvents might yield homogeneous solutions
alpha pinene may be mentioned as examples re of reaction products of particular value in the
spectively of the monocyclic and dicyclic alpha, manufacture of paints and varnishes. It is to
terpenes for use in connection with the present be understood therefore that the present inven
proceSS. tion does not include within its scope the manu
We have found that the employment of sol facture of interpolymers of styrene with poly
 2,556,488
3 4.
hydric alcoholic mixed esters by any of the The following table illustrates the effect of the
processes, particularly that mentioned above in different Solvents upon the polymerisation of
Wolving the use of turpentine as a Solvent, de styrene, the reaction being carried out in the
Scribed in the aforementioned U. S. Patent No. manner described in the aforementioned experi
2,392,710, of which this application is a con ment:
Title 1

Percent Wiscosity of
age of Percentage of Solvent TEFE- Time of Percentage solution in
Styrene Employed (by which heating of Poly- benzene of
(by weight) weight) heated in hours merisation the poly
styrene

oC. Seconds
10% Xylene.----------- 80-180 155 94 425
10% Dipentene- 80-80 153 90 235
20%-Xylene---- 75-150 27 80 500
20%. Dipentene 75-150 27 60 240
75%. Mineral Spir - i40 30 68 28
75% Dipentene-------- 140 30 35 18

tinuation-in-part. In the above table the viscosity of the poly

In illustration of the results obtained by the 20 mers obtained in the first four experiments by
process according to the present invention, the heating in the respective solutionS. is expreSSed as
following experiment shows the comparative ef the tirine, in Seconds, taken for a 1 per cent Solu
fects of commercial dipentene, xylene and min tion of the polymer in benzene to flow through a
eral Spirits on the polymerisation of styrene. No. 1 Ostwald viscometer, whilst the Viscosity of
Mixtures of styrene and commercial dipentene 25 the polymers obtained in the last two experie
(which latter actually contains fairly large inents is expressed as the time, in Seconds, taken
amounts of alpha terpinene and alpha terpinolene for a 2 per cent Solution of the polymer in ben
in addition to dipentene) in various proportions Zene to flow through a No. 2 Ostwald VisCOneter,
were made up. Samples were poured into test all the Wiscosities being measured at 20° C.
tubes previously drawn out at the top, so that they 30 The time of flow in Seconds through the vis
could be sealed in the blow pipe flame. The Cometer has not been interpreted in actual
sealed tubes were then immersed in a heated oil terms of molecular weights, but the values of the
bath, the temperature of which was elec respective viscosities in column 6 of Table 1, how
trostatically controlled, along with Sealed tubes ever, are Sufficient to. Show that the molecular
containing Samples of Styrene and Xylene, or 35 Weights of the polystyrene obtained in the pres:
styrene and mineral Spirits of equal Styrene ence of dipentene are very much less than those
concentrations. For the samples with high obtained in xylene or mineral Spirits.
concentrations of styrene the temperature was It may be noted that in the case of the experi
then raised gradually over a long period of ment With mineral Spirits (line 5 of Table) the
time, whilst for the mixtures with low con 40 polymer Was Soluble in the hot Solution but came
centrations of Styrene (about 25 per cent by Out of Solution. On Cooling, whilst when using
weight) the temperature was held at 140° C. for Xylene, and dipentene.as solvents the polymer was
about 30 hours. After heating the tubes for a Soluble both in the hot and cold. From the re
given time, they were taken out, broken, and a Sults given in the above table it will be noted
weighed amount of the mixture poured into ex that in addition to the lower molecular. Weight of
cess of petroleum ether. The ether was poured the polymers formed in dipentene, the terpene
off the precipitated polymer, Which was Washed solvent reduced the rate of polymerisation of the
with fresh ether and dried under Vacuum up to styrene.
200° C. The polymers were then dissolved in pure In Table 2 there are shown the results of an
benzene so as to give a 1 per cent solution and other series of comparative experiments carried
the time taken to flow through a No. 1 Ostwald out On lines similar to those previously described
viscometer determined at 20° C. In the case of (the results of which were given in Table 1), but
the samples prepared from styrene and dipentene in Which the terpene Solvent employed was alpha,
in which the proportion of Styrene Was consider pinene instead of dipentene. The sample of alpha,
ably less than that of the dipentene, the low 55 pinene Was Substantially pure, such as is nor
molecular Weight polymer produced after heat mally used in the manufacture of camphor.
Table 2

Wiscosity of
Psi- Percentage of Solvent Terps" Time of Percentage solution in
styrene Employed (by if heating of Poly. benzene of
(by weight) weight) heated in hours Enerisation 'EEE

oC. Seconds
50--------- 50% Xylene---------- 100-80 20 64 370
50--- - 50% Alpha Pinene---- 00-180 20 92 230
25- - - -- 75%. Mineral Spirits--- 140 30 68 28
25--------- 75% Alpha Pinene---- 40 30 76 17.5

ing the mixture appeared to be partly Soluble in 70. In the above Table 2 the viscosity of the poly
petroleum ether, So in place of the latter alcohol mers obtained in the first two experiments, where
was substituted for the precipitating medium; it the percentage of styrene initially mixed with
was found that the polymer came down very Well, the solvent amounted to 50 per cent, is expressed
especially if the alcohol was warned slightly as the time in Seconds taken for a 1 per cent Solt
after adding...the Solution theretO. 75 tion of the polymer in benzene to flow through a
 5 s
2,556,488
6
No. 1 Ostwald viscometer, whilst the viscosity of 8. A process as claimed in claim 1 in which
the polymers obtained in the last two experiments the polymerization of the styrene is effected in
where the initial concentration of the styrene a solvent containing an admixture of a mono
amounted to 25 per cent is expressed as the time cyclic alpha terpene and an aliphatic hydro
in Seconds taken for a 2 per cent Solution of the carbon.
polymer in benzene to flow through a No. 2 9. A proceSS as claimed in claim 1 in which
Ostwald viscometer, all the viscosities being the polymerization of the styrene is effected in
measured at 20° C. a Solvent containing an admixture of a mono
From the details given in Table 2 it will be cyclic alpha terpene and Xylene.
Seen that the viscosity of the polystyrene pro O 10. A process as claimed in claim 1 in which
duced in the presence of alpha, pinene is con the polymerization of the styrene is effected in
Siderably lower than the Wiscosity of the polymers a Solvent containing an admixture of a mono
formed in Xylene or mineral Spirits; from these cyclic alpha terpene and mineral spirits.
Wiscosity figures it is apparent therefore that 11. A process as claimed in claim 1 in which
alpha pinene exerts an effect similar to that of 15 the polymerization of the styrene is effected in
dipentene in producing polystyrenes of relatively a solvent containing an admixture of a dicyclic
low molecular weight. Further from the figures alpha terpene and an aromatic hydrocarbon.
of percentage of polymerisation given in Table 12. A process as claimed in claim 1 in which
2, it will be noted that alpha pinene appears to the polymerization of the styrene is effected in
give a Somewhat faster rate of reaction than 20 a solvent containing an admixture of a dicyclic
Xylene or mineral Spirits for the production of alpha terpene and an aliphatic hydrocarbon.
the polystyrene. 13. A process as claimed in claim 1 in which
In a third series of comparative experiments, the polymerization of the styrene is effected in
a Sample of commercial dipentene was fraction a Solvent containing an admixture of a dicyclic
ally distilled to yield pure dipentene, alpha ter 25 alpha terpene and xylene.
pinene and alpha teipinolene and each of these 14. A process as claimed in claim 1 in which
products WaS separately tested in mixture with the polymerization of the styrene is effected in
Styrene in experiments similar to those previously a solvent containing an admixture of a dicyclic
described in connection with Table 1 and found alpha terpene and mineral Spirits.
to give polystyrenes of low molecular weight, 30 15. A process as claimed in claim 1 in which
as shown by the results given in Table 3 below: the quantity of solvent employed is equal to the
Table 3
Wiscosity of
E Percentage of Solvent Type- Time of Percentage solution in
She Fmpeg,
weig (by which ag merisation
in hours of Poly- E.
epolyaOf
(by weight) heated styrene

oC. Seconds
50--------- 50% Xylene----------- 100-80 25 78 365
50--------- 50% Limonene.------- 100-180 25 63 220
50 --- 50%. Alpha Terpinene. 100-180 25 31 220
50--------- 50%. Alpha Terpino- 100-180 25 26 230
lene.

In the above Table 3 the viscosity of the poly quantity of styrene subjected to the polymer
mers obtained by heating in the respective solu 45 ization reaction.
tions is expressed as the tine, in seconds, taken 16. A process as claimed in claim 1 in which
for a 1 per cent Solution of the polymer in ben the quantity of solvent employed is less than the
Zene to iow through a No. 1. Ostwald viscometer, quantity of styrene subjected to the polymeri
all the viscosities being measured at 20° C. zation reaction.
What We claim and desire to secure by Letters 50 17. A proceSS as claimed in claim 1 in Which
Patent of the United States is: the quantity of solvent employed is greater than
1. A process for the production of polystyrene the quantity of styrene subjected to the poly
of a relatively low molecular weight in the order merization reaction.
of 9,000 to 12,000 which consists in effecting the 55 LESLIE ERNEST WAKEFOR.D.
polymerization by heating, in the absence of a DONALID HELMSLEY HEWITT.
polymerization catalyst, monomeric styrene in a
Solvent containing at least one terpene of the REFERENCES CTED
class consisting of monocyclic and dicyclic alpha The following references are of record in the
terpenes in an amount sufficient to control the 60 file of this patent:
molecular weight of the product.
2. A proceSS as claimed in claim 1 wherein UNITED STATES PATENTS
the terpene consists of dipentene. NameNumber Date
3. A process as claimed in claim 1 wherein the 1910,846 Maximoff ---------- May 23, 1933
terpene consists of alpha pinene. 65 2,313,728 Austin et al. ------- May 16, 1943
4. A process as claimed in claim 1 wherein the 2,383,084 Rummelsburg ------ Aug. 21, 1945
terpene consistS of limonene. 2,392,710 Wakeford et al. ----- Jan. 8, 1946
5. A process as claimed in claim 1 wherein the FOREIGN PATENTS
terpene consists of alpha terpinene.
6. A process as claimed in claim 1 wherein Number Country Date
the terpene consists of alpha terpinolene. 278,486 Germany.------- May 24, 1913
7. A process as claimed in claim 1 in which OTHER REFERENCES
the polymerization of the styrene is effected in
Synthetic Resins and Allied Plastics, R. S.
a solvent containing an admixture of a mono 7 Morrell
cyclic alpha terpene and an aromatic hydro (Oxford Univ. Press) 1937, page 321,
carbon, s