Poly-sulphonyloxyurethanes of the formula EQU A[O--CO--NH--O--SO.sub.2 --R].sub.n (1) wherein A is a linking group to which the oxygen atoms are attached at alkyl, cycloalkyl or aryl carbon atoms, n is an integer of value at least 2, and each R which may be the same or different, is an optionally substituted alkyl or aryl group, and their salts, especially salts with cations based on tertiary amines, are useful cross-linking or chain-extending agents for natural or synthetic polymers, or may be used as adhesives for binding these materials to each other or to metal substrates.

This invention relates to nitrogen-containing compounds and more 
particularly to poly-sulphonyloxyurethanes and their salts, and to their 
use as cross-linking and bonding agents for polymers. 
According to the invention there are provided poly-sulphonyloxyurethanes of 
the formula: 
EQU A [O--CO--NH--O--SO.sub.2 --R].sub.n ( 1) 
wherein A is a linking group to which the oxygen atoms are attached at 
alkyl, cycloalkyl or aryl carbon atoms, n is an integer of value at least 
2, and each R which may be the same or different, is an optionally 
substituted alkyl or aryl group. 
The invention also provides salts of these poly-sulphonyloxyurethanes of 
the formula: 
EQU A [O--CO--N--O--SO.sub.2 --R].sub.n (B.sup.m+).sub.n/m ( 2) 
Where B is a cation of valency m. 
As linking groups represented by A there may be mentioned alkylene groups 
such as ethylene, 1,2- and 1,3-propylene, tetramethylene, hexamethylene, 
octamethylene, decamethylene, and dodecamethylene; cycloalkylene such as 
1,4-cyclohexylene; arylene such as m- and p- phenylene; alkarylene groups 
derived from combinations of the foregoing groups such as 
methylene-bis-4-phenyl, 2,2-propylene-bis-4-phenyl-, m- and p-xylylene; 
groups derived from one or more of the foregoing groups linked by 
heteroatoms or groups containing heteroatoms, e.g. 
bis-(alkyleneoxy)phenylene groups; or radicals derived from polyalkylene 
oxides such as polyethylene oxides, condensates of alkylene oxides with 
glycols and other compounds containing two or more hydroxyl groups such as 
glycerol, 1,4-bis-(.beta.-hydroxyethoxycarbonyl)benzene, mannitol, 
sorbitol and sucrose; unsaturated polyvalent groupings e.g. as derived 
from pentaerythritol dialkyl ether, and polymeric chains to which the 
oxycarbonyl groups are attached directly or through pendant groups, as for 
example in addition polymers and copolymers of alkyl esters of acrylic or 
methacrylic acids in which the oxycarbonyl group is attached to the alkyl 
radical of the ester group. 
As optionally substituted alkyl or aryl groups which may be represented by 
R, there may be mentioned alkyl groups preferably containing from 1 to 4 
carbon atoms such as ethyl, n- and iso-propyl, n-butyl, and especially 
methyl, but also n-octyl, n-decyl, n-dodecyl and n-octadecyl, and 
substituted derivatives of these such as chloroethyl, trifluoromethyl and 
perfluorooctyl, and aryl groups such as phenyl and o-, m- and p-tolyl and 
substituted aryl especially substituted phenyl groups such as nitrophenyl, 
chloro-, bromo-, iodo- and fluoro-phenyl and alkoxyphenyl, e.g. 
methoxyphenyl. 
The preferred meaning for the radical A is the group consisting of alkylene 
radicals of the formula (CH.sub.2).sub.m where m has a value of 2 to 10, 
or bis-(ethyleneoxy)phenylene radicals of the formula 
##STR1## 
or polyalkyleneoxy radicals of the formula: 
EQU --CH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2).sub.p 
where p has a value 1 or 2. 
The preferred meaning for the radical R is the group consisting of methyl, 
phenyl, tolyl and nitrophenyl. 
Thus, as preferred examples of formula (1) there may be mentioned: 
1,4-bis[N-(p-nitrobenzenesulphonyloxy)carbamoyloxy]butane alternatively 
named as butane-1,4-bis-(p-nitrobenzenesulphonyloxy)urethane, 
1,4-bis-[N-(m-nitrobenzenesulphonyloxy)carbamoyloxy]butane, 
1,4-bis-[N-(benzenesulphonyloxy)carbamoyloxy]butane, 
1,4-bis-[N-(p-toluenesulphonyloxy)carbamoyloxy]butane, 
1,4-bis-[N-(methanesulphonyloxy)carbamoyloxy]butane, 
1,4-bis-[N-(benzenesulphonyloxy)carbamoyloxyethoxy]benzene, 
1,2-bis-[N-(m-nitrobenzenesulphonyloxy)carbamoyloxy]ethane, 
.beta.,.beta.'-bis-[N-(m-nitrobenzenesulphonyloxy)carbamoyloxy]ethyl ether, 
1,2-bis-[N-(m-nitrobenzenesulphonyloxy)carbamoyloxyethoxy]ethane, 
1,6-bis-[-(m-nitrobenzenesulphonyloxy)carbamoyloxy]hexane, 
1,10-bis-[N-(m-nitrobenzenesulphonyloxy)carbamoyloxy]dodecane. 
The value of n is preferably 2. 
As examples of cations represented by B, there may be mentioned alkali 
metal cations, e.g. sodium and potassium; however these salts tend to 
decompose at the usual ambient temperatures and it is preferred that B 
should represent an organic cation, derived from primary, secondary and 
especially tertiary amines, e.g. thiouronium or diethylammonium. but 
preferably trialkylammonium salts as derived e.g. from tertiary amines 
such as triethylamine, dimethylbenzylamine, triethanolamine, pyridine, 
1,4-diazabicyclo-2,2,2-octane, or other tertiary amino compounds such as 
tetraalkylthioureas, tetraalkyl-thiuram mono- and di-sulphides, and 
dialkyldithiocarbamates, especially zinc dialkyldithiocarbamate and 
benzthiazyl derivatives. As a general rule, it is preferred that the 
cation should be derived from an amino compound of low volatility at 
ambient temperatures, since these are more stable than either the alkali 
metal salts or the salts formed by volatile amino compounds. All the salts 
are thermally unstable, the instability being increased by the presence of 
electron withdrawing substituents, e.g. halogen atoms or nitro groups in 
the group R. 
The invention also provides a process for manufacture of the 
poly-sulphonyloxyurethanes of formula (1) which comprises reacting a 
poly-(hydroxyurethane) of the formula: 
EQU A [O--CO--NHOH].sub.n ( 3) 
with n moles of a sulphonyl chloride of the formula: 
EQU R -- SO.sub.2 Cl (4) 
the symbols A, R and n having the meanings stated above, in the presence of 
an acid-binding agent which is added at a rate sufficient to neutralise 
the mineral acid formed whilst keeping the pH of the mixture below 7. 
The above process can conveniently be carried out by mixing the 
poly-(hydroxyurethane) and the sulphonyl chloride in an inert solvent, 
e.g. diethyl ether or dioxan, and adding the acid-binding agent at such a 
rate that the pH of the mixture is maintained at below 7. The reaction is 
preferably carried out at a temperature below 10.degree. C, more 
especially from 0.degree. C to 5.degree. C. 
Excess of the sulphonyl chloride should be avoided, since otherwise a 
further reaction may take place whereby sulphon-acylation of the imino 
group is effected. This reaction can also take place in preference to 
reaction with the hydroxyl group if the pH of the mixture is allowed to 
rise to 7 or above. 
As examples of acid-binding agents which can be used in the above process 
there may be mentiond alkali metal carbonates, bicarbonates and 
hydroxides, but more especially tertiary amines e.g. trialkylamines, 
tris-(hydroxyalkyl)amines, pyridine or its homologues. As particular 
examples of all these, there may be mentioned: 
sodium and potassium bicarbonated, carbonates and hydroxides 
triethyl- and tri-n-butyl amines 
triethanolamine 
1,4-diaza-2,2,2-bicyclooctane 
N-methylpiperidine 
quinoline and the picolines. 
As examples of sulphonyl chlorides of formula (4) which may be used in the 
above process, there may be mentioned: 
methane sulphonyl chloride 
benzene sulfonyl chloride 
p-tolyl sulphonyl chloride m- and p-nitrobenzene sulphonyl chlorides, and 
.alpha. or .beta.-naphthalene sulphonyl chloride. 
The poly-(hydroxyurethanes) of formula (3) used in the above process can be 
obtained by reacting a polyol of the formula A(OH).sub.n with excess 
phosgene to form a poly-chloroformate of the formula A(O--CO--Cl).sub.n 
and reacting the latter with hydroxylamine. 
As examples of polyols of formula A(OH).sub.n which may be used, there may 
be mentioned: aliphatic glycols and higher polyols, e.g. 
ethylene glycol 
1,2- and 1,3-propylene glycols 
1,4-, 1,3- and 2,3-butylene glycols 
hexamethylene and decamethylene glycols 
glycerol 
trimethylolethane 
trimethylolpropane 
pentaerythritol 
araliphatic glycols e.g. 
m- or p-xylylene glycols 
di-(.beta.-hydroxyethyl)hydroquinone; 
polyethers formed by the addition of alkylene oxides of 2-4 carbon atoms, 
e.g. ethylene oxide, propylene oxide or tetrahydrofuran, on aliphatic or 
araliphatic polyols as described above, or on aromatic polyols e.g. 
hydroquinone, catechol, resorcinol or carbohydrate polyols, e.g. glucose, 
fructose, sorbitol, mannitol, sucrose; polyesters formed by the 
esterification of di- or poly-carboxylic acids e.g. adipic or phthalic 
acid, with aliphatic glycols or higher polyols of the kinds described 
above, especially .beta.-hydroxyethyl terephthalates; hydroxyl-ended 
polyolefines e.g. polyethylene or polypropylene containing terminal OH 
groups, addition polymers of ethylene compounds containing a hydroxyl 
group, e.g. polyvinyl alcohol, poly-.beta.-hydroxyethyl acrylate or 
poly-.beta.-hydroxyethylmethacrylate. 
The poly-sulphonyloxyurethanes of the invention are oils or solids, 
depending on the values of A, R and n, soluble in many organic solvents. 
They may be converted to the salts of formula (2) by treatment with a 
suitable basic compound, containing the cation B.sup.+. 
The poly-sulphonyloxyurethane salts of the invention may be used as 
cross-linking agents for polymers, as chain extending agents for e.g. 
polyepoxides and other polyfunctional compounds, as bonding agents and 
adhesives for use with polymers or other materials, and as coating agents. 
As polymers which may be cross-linked there may be mentioned natural 
rubber, synthetic rubbers such as styrene-butadiene (SBR), 
acrylonitrile-butadiene, ethylene-propylene rubbers (EPDM), stereo-regular 
polyisoprene, high or low density polyethylene, polypropylene, nylons, 
polyesters and polyurethanes. Any of the above polymers for example 
styrene-butadiene rubber may be bonded to the same polymer, or a different 
polymer as for example stereo-regular polyisoprene, or to other materials 
such as polyethylene terephthalate, nylon-6, nylon-6,6, rayon and metal 
substrates such as copper, brass and steel, by means of the 
poly-sulphonyloxyurethane salts of the invention. 
The poly-sulphonyloxyurethane salts may be incorporated into the polymer by 
for example blending with the polymer in any conventional manner, such as 
on a two-roll mill, this type of procedure being especially suitable when 
the poly-sulphonyloxyurethane salt is to be used as a cross-linking agent 
and must be present throughout the bulk of the polymer. The polymer is 
thereafter shaped, for example in a mould, and heated to a temperature 
above 50.degree. C, and preferably between 100.degree. C and 250.degree. 
C, to bring about cross-linking. The salt may be pre-formed and added to 
the polymer or may be formed in situ by adding a poly-sulphonyloxyurethane 
of formula (1) and at least an equivalent weight of a basic compound 
providing the cation B.sup.+. 
For use as a bonding agent or adhesive, in which cases application of the 
poly-sulphonyloxyurethane salt is usually necessary only at the surfaces 
of the polymer, it is generally more convenient and economical to treat 
the polymer in shaped form, e.g. in filament, yarn, fabric, sheet or 
massive form, with the poly-sulphonyloxyurethane and basic compound in 
solution form, and then heat the treated polymer to drive off the solvent, 
bring the surfaces to be bonded, e.g. polyester cord and rubber, into 
contact, and then heat more strongly to effect bonding. An auxiliary 
bonding agent such as an epoxy resin and resorcinol/formaldehyde reaction 
product may also be present to aid adhesion. 
As basic compounds which may be used in conjunction with the 
poly-sulphonyloxyurethanes in polymers there may be mentioned any of the 
basic compounds used to form salts of the poly-sulphonyloxyurethanes. 
Volatile amines may have the disadvantage of causing porosity in polymers 
treated in the mass, and non-volatile amino compounds are more suitable 
for this purpose. Certain amines, such as tetramethylthiourea or the 
tetramethylthiuram monosulphides and disulphides and various 
dialkyldithiocarbamates, which are commonly used as vulcanisation 
accelerators may be more suitable for this purpose, especially for use in 
rubber. 
It is most convenient to add the poly-sulphonyloxyurethane and basic 
compound independently to the polymer but similar effects may be obtained 
by mixing the poly-sulphonyloxyurethane and basic compound together before 
addition or to react them to form the salt. The last two procedures 
however may have the disadvantage that the mixture or the salt may not be 
stable to storage. 
The amount of basic compound is suitably equimolar to that of the 
sulphonyloxyurethane groups present in the poly-sulphonyloxyurethane 
added, but less or more may be used if desired. 
The uses of the poly-sulphonyloxyurethanes described above and polymers so 
treated represent further features of the invention. 
The invention is illustrated but not limited by the following Examples in 
which all parts and percentages are by weight unless otherwise stated.

EXAMPLE 1 
A solution of 360 parts of 1,4-butanediol in 200 parts of chloroform is 
added over 2 hours to a stirred solution of 900 parts of phosgene in 500 
parts of methylene dichloride at a temperature of 0.degree. C under a 
reflux condenser cooled with solid carbon dioxide. The reaction mixture is 
then stirred at 5.degree. C for 1 hour and at 25.degree. C for 3 hours 
after which the condenser is removed and a stream of dry nitrogen is 
passed to remove hydrogen chloride and excess phosgene. The methylene 
dichloride and chloroform are distilled off under reduced pressure and 850 
parts of 1,4-butane bis-chloroformate are obtained by distillation at 
97.degree. C under a pressure of 1 mm of mercury. On analysis the compound 
was found to contain carbon 34.1%, hydrogen 4.1% and chlorine 32.7%, the 
theoretical figures being carbon 33.5%, hydrogen 3.7% and chlorine 33.0%. 
A solution of 276.4 parts of potassium carbonate in 250 parts of water and 
215 parts of 1,4-butane bis-chloroformate are added separately at 
equivalent rates over 1 hour to a stirred suspension of 139 parts of 
finely ground hydroxylamine hydrochloride in 700 parts of diethyl ether at 
a temperature between 0.degree. and 5.degree. C. After a further 3 hours 
stirring at 0.degree. C and 18 hours at 25.degree. C the suspension is 
filtered and the filter cake washed with water until free from chloride. 
170 parts of butane-1,4-bis-N-hydroxycarbamate, a white solid melting at 
150.degree. C, are obtained. On analysis the compound was found to contain 
carbon 35.5%, hydrogen 5.9% and nitrogen 13.0%, the theoretical figures 
being carbon 34.6%, hydrogen 5.8% and nitrogen 13.5%. 
A mixture of 20.8 parts of butane-1,4-bis-N-hydroxycarbamate, 44.4 parts of 
p-nitrobenzenesulphonyl chloride and 250 parts of dioxan is stirred at a 
temperature of 0.degree.-5.degree. C while a solution of 18.4 parts of 
triethylamine in 50 parts of dioxan is added over about 1 hour at such a 
rate that the pH is maintained between 3 and 6. After a further 12 hours 
stirring at a temperature of 25.degree. C the mixture is added to 1500 
parts of 4% aqueous sodium chloride solution. The oily product is 
separated in 500 parts of chloroform which is washed with water, dried and 
evaporated under reduced pressure at 40.degree. C. The residue is washed 
with toluene and dried under reduced pressure to give 26 parts of 
butane-1,4-bis(p-nitrophenylsulphonoxyurethane), a yellowish solid melting 
at 105.degree. C. On analysis the product was found to contain carbon 
36.7%, hydrogen 3.0%, nitrogen 9.7% and sulphur 11.0 %, the theoretical 
figures being carbon 37.4%, hydrogen 3.1%, nitrogen 9.7% and sulphur 
11.1%. 
EXAMPLE 2 
4 parts of butane-1,4-bis(p-nitrophenylsulphonoxyurethane) and 2 parts of 
tetramethylthiourea were milled in succession into 100 parts of a 27:73 
styrene-butadiene copolymer (SBR) at 50.degree.-60.degree. C to give a 
pale yellow sheet. The compounded rubber sheet was cured at 190.degree. C 
for 10 minutes to give a cross-linked rubber in which the extension at 
break was 600%. The styrene-butadiene copolymer cured without the 
additives has an extension at break of 130%. 
Similar results were obtained when the tetramethylthiourea was replaced by 
3 parts of tetramethylthiuram monosulphide or zinc 
diethyl-dithiocarbamate. The maximum modulus torque recorded by 
Oscillating Disc Rheometer was 48, 43 and 46 units respectively, vs. 17 
for the untreated rubber after 54 minutes cure. Similar treatment of 
ethylene-propylene copolymer using tetramethylthiuram mono-sulphide gave a 
maximum torque modulus 57 vs. "no cure" for the untreated rubber. 
EXAMPLE 3 
Repetition of the final stage of Example 1 using m-nitrobenzenesulphonyl 
chloride instead of p-nitrobenzenesulphonyl chloride afforded 
butane-1,4-bis(m-nitrophenylsulphonoxyurethane), a viscous oil. On 
analysis the product was found to contain carbon 41.2%, hydrogen 3.9%, 
nitrogen 9.6% and sulphur 11.2%, the theoretical figures being carbon 
39.4%, hydrogen 3.1%, nitrogen 9.7% and sulphur 11.1%. 
EXAMPLE 4 
Repetition of the procedure of Example 2 using tetramethylthiourea and 
butane-1,4-bis(m-nitrophenylsulphonoxyurethane) instead of the p-nitro 
isomer afforded a cross-linked rubber in which the extension at break had 
been increased by approximately 600%, i.e. 130% for untreated SBR to 900%. 
Using zinc diethyl dithiocarbamate in place of tetramethylthiourea gave a 
peak torque 32 after 4 minutes at 180.degree. C, vs. "no cure" for the 
untreated sample. 
EXAMPLE 5 
Repetition of the final stage of Example 1 using 35.3 parts of benzene 
sulphonyl chloride instead of p-nitrobenzenesulphonyl chloride gives 
butane-1,4-bis(phenylsulphonyloxyurethane), a colourless viscous oil. On 
analysis the product was found to contain carbon 45.0%, hydrogen 4.3%, 
nitrogen 5.0% and sulphur 15.3%, the theoretical values being carbon 
44.3%, hydrogen 4.1%, nitrogen 5.7% and sulphur 13.1%. 
EXAMPLE 6 
Repetition of the procedure of Example 2 using tetramethylthiourea and 
butane-1,4-bis(phenylsulphonyloxyurethane) afforded a cross-linked rubber 
in which the extension at break was 900%, an increase of 600% over the 
untreated rubber. Using zinc diethyl dithiocarbamate at 180.degree. C gave 
a product with peak torque of 28 after 1.5 minutes. 
A similar result is obtained if the butane-1,4-bis 
(phenylsulphonyloxyurethane) and tetramethylthiourea are ground together 
with cooling and the mixture is milled into 100 parts of styrene-butadiene 
rubber at 50.degree.-60.degree. C, and the latter is then cured at 
190.degree. C for 10 minutes. 
EXAMPLE 7 
Repetition of the final stage of Example 1 using 38.2 parts of p-toluene 
sulphonyl chloride in place of the p-nitrobenzene sulphonyl chloride 
affords butane-1,4-bis(p-toluenesulphonyloxyurethane) as a white solid, 
m.p. 122.degree. C. On analysis the product was found to contain carbon 
45.9%, hydrogen 4.8%, nitrogen 5.3% and sulphur 12.4%, the theoretical 
values being carbon 46.5%, hydrogen 4.6%, nitrogen 5.4% and sulphur 12.4%. 
EXAMPLE 8 
Repetition of Example 2, using butane-1,4-bis(p-toluene 
sulphonyloxyurethane) and tetramethylthiourea gave a cross-linked product 
having an extension of break 600% greater than the original. A product 
having a peak torque of 25 was obtained after 2.5 minutes at 180.degree. C 
using zinc diethyl dithiocarbamate. 
EXAMPLE 9 
Rubber master batches based on Natural Rubber (NR) and Styrene/Butadiene 
Rubber (SBR), as detailed below, are prepared by mixing the ingredients 
together in a BR size Banbury mixer. 
______________________________________ 
MB/1 MB/2 
______________________________________ 
Natural Rubber (SMR 5) 100 
Styrene/Butadiene Rubber (Solprene 1204) 
-- 100 
N-330 Carbon Black 50 50 
______________________________________ 
(figures quoted are parts by weight). 
To separate portions of each of the masterbatches the products of Example 1 
and Example 5 are added together with zinc diethyldithiocarbamate on a 
laboratory mill. Test pieces are vulcanised at 153.degree. C for the times 
given in Table I. The properties of the vulcanisates are then measured. 
Full details of the amounts used and the test results obtained are given 
in Table I. A conventional curing system is included for comparison. 
Table I 
__________________________________________________________________________ 
/1 /2 /3 /4 /5 /6 
__________________________________________________________________________ 
MB/1 150 150 150 -- -- -- 
MB/2 -- -- -- 150 150 150 
Zinc diethyldithiocarbamate 
4.0 4.0 -- 4.0 4.0 -- 
Product of Example 1 
4.0 -- -- 4.0 -- -- 
Product of Example 2 
-- 4.0 -- -- 4.0 -- 
N-cyclohexylbenzthiazole 
-- -- 0.5 -- -- 1.2 
sulphenamide 
Sulphur -- -- 2.5 -- -- 1.8 
Zinc oxide.sup.1 -- -- 5.0 -- -- 5.0 
Stearic acid -- -- 3.0 -- -- 1.0 
Rheometer at 153.degree. C 
Minimum viscosity (in.-lbs.) 
17 15.8 14.9 26 23.3 17.6 
Induction time T.sub.2 (minutes) 
1.8 1.5 4.3 1.1 1.3 7.9 
State of cure at peak (in.-lbs) 
50 58 86 78 87 110 
Time to 95% peak cure (minutes) 
14 11 16 6 7 16 
Cure at 153.degree. C (minutes) 
15 10 15 10 10 15 
Physical Properties 
Tensile strength (kg/cm.sup. 2) 
232 260 269 128 106 120 
Elongation at Break (%) 
490 480 395 350 240 190 
Modules at 200% (kg/cm.sup.2) 
52 74 150 60 88 -- 
Resilience at R.T. (%) 
56 58 67 55 59 59 
Hardness (BS.degree.) 
52 56 67 68 70 74 
Compression Set (%) 
34 30 36 28 15 24 
after 24 hrs. at 70.degree. C 
(25% Compression) 
__________________________________________________________________________ 
EXAMPLE 10 
Repitition of the final stage of Example 1 using 36.5 parts of 
butane-1,4-bis-N-hydroxycarbamate and 40.1 parts of 
methanesulphonylchloride instead of p-nitrobenzenesulphonylchloride gives 
36 parts of butane-1,4-bis(methylsulphonyloxyurethane), a colourless 
viscous oil. On analysis the product was found to contain carbon 25.7%, 
hydrogen 4.2%, sulphur 18.3%; the theoretical figures being carbon 26.4%, 
hydrogen 4.4% and sulphur 17.6%. 
EXAMPLE 11 
Repitition of Example 5 using phenylene-1,4-bis-oxyethanol instead of 
1,4-butane diol at the first stage afforded 
phenylene-1,4-bis(oxyethoxyphenylsulphonyloxyurethane), a pale yellow oil. 
On analysis the product was found to contain carbon 43.7%, hydrogen 4.3%, 
nitrogen 3.5%, sulphur 10.6%; the theoretical figures being carbon 43.4%, 
hydrogen 4.0%, nitrogen 4.7% and sulphur 10.7%. 
EXAMPLE 12 
Repitition of Example 3 using ethylene glycol instead of 1,4-butane diol 
afforded ethane 1,2-bis-(m-nitrophenylsulphonoxyurethane) a pale yellow 
glass. On analysis the product was found to contain carbon 35.6%, hydrogen 
2.9%, nitrogen 7.9%, sulphur 11.6%; the theoretical figures being carbon 
34.9%, hydrogen 2.55%, nitrogen 10.2% and sulphur 11.6%. 
EXAMPLE 13 
Repitition of Example 3 using diethylene glycol instead of 1,4-butane diol 
afforded ethoxyethyl-bis(m-nitrophenyl sulphonoxyurethane), a pale yellow 
viscous oil. On analysis the product was found to contain carbon 36.8%, 
hydrogen 5.5%, sulphur 11.0%; the theoretical figures being carbon 37%, 
hydrogen 3% and sulphur 10.8%. 
EXAMPLE 14 
464 parts of 2-hydroxyethylacrylate is added over 1 hour to a stirred 
mixture of 250 parts of calcium carbonate, 500 parts of phosgene and 500 
parts of methylene dichloride at a temperature of 0.degree. C under a 
reflux condenser cooled with solid carbon dioxide. The reaction mixture is 
then stirred at 10.degree. C for 6 hours and at 25.degree. C for 18 hours 
after which the condenser is removed and a stream of dry nitrogen is 
passed to remove hydrogen chloride and excess phosgene. The reaction 
mixture is then filtered to remove calcium salts and methylene dichloride 
is distilled off under reduced pressure and 494 parts of 
2-chlorocarbonyloxyethylacrylate are obtained. On analysis the compound 
was found to contain carbon 39.7%, hydrogen 4.2% and chlorine 18.3%; the 
theoretical figures being carbon 40.3%, hydrogen 3.9% and chlorine 19.8%. 
A solution of 80 parts of sodium hydroxide in 120 parts of water and 178.5 
parts of 2-chlorocarbonyloxyethylacrylate are added separately at 
equivalent rates over 1 hour to a stirred suspension of 69.5 parts of 
finely ground hydroxylamine hydrochloride in 600 parts of tertiary butanol 
at a temperature of 10.degree. C. After a further 20 hours stirring at 
25.degree. C the reaction mixture is filtered to remove sodium chloride 
and the butanol layer is separated. Butanol is distilled off under reduced 
pressure and the residue is extracted into 500 parts of ethyl alcohol. The 
alcohol solution is filtered to remove sodium chloride and ethyl alcohol 
is distilled off under reduced pressure to give 148 parts of 
2-(N-hydroxycarbamoyloxy)-ethylacrylate, a red oil. On analysis the 
compound was found to contain carbon 41.3%, hydrogen 6.3%, nitrogen 7.9%; 
the theoretical figures being carbon 41.1%, hydrogen 5.1% and nitrogen 8%. 
A mixture of 87.5 parts of 2-(N-hydroxycarbamoyloxy)-ethylacrylate, 110.7 
parts of m-nitrobenzenesulphonylchloride and 300 parts of dioxan are 
stirred together at a temperature of 0.degree.-5.degree. C while 50.5 
parts of triethylamine is added over 2 hours at such a rate that the pH is 
maintained between 3 and 6. After a further 18 hours stirring at a 
temperature of 25.degree. C the mixture is added to 2000 parts of water. 
The oily product is separated into 1000 parts of chloroform which is 
washed with water, dried and evaporated under reduced pressure at 
40.degree. C to give 178 parts of 
.beta.-acryloyloxyethyl-N-(m-nitrophenylsulphonoxy)urethane, a brown oil. 
On analysis the product was found to contain carbon 37.3%, hydrogen 3.2%, 
nitrogen 5.9%, sulphur 10%; the theoretical figures being carbon 40.0%, 
hydrogen 3.3%, nitrogen 7.7% and sulphur 8.9%. 
Solutions of 29.4 parts of butylacrylate in 50 parts of ethylene 
dichloride, 27 parts of 
.beta.-acryloyloxyethyl-N-(m-nitrophenylsulphonyloxy)urethane in 50 parts 
of ethylene dichloride and 1 part of .alpha.,.alpha.'-diisobutyronitrile 
in 20 parts of toluene are added dropwise and concomitantly over 11/2 
hours to a preheated flask at 85.degree. C containing 50 parts ethylene 
dichloride and covered with nitrogen. The reaction is stirred for 5 hours 
and solvent removed under reduced pressure to give 42 parts of a 
co-polymer of butyl acrylate and 
.beta.-acryloyloxyethyl-N-(m-nitrophenylsulphonoxy)urethane in molecular 
ratio 3:1, a viscous brown oil. On analysis the compound was found to 
contain carbon 51.9%, hydrogen 6.4%, nitrogen 3.7%, sulphur 5.3%; the 
theoretical figures being carbon 53%, hydrogen 6.5%, nitrogen 3.9% and 
sulphur 4.3%. 
EXAMPLES 15-19 
The procedure of Example 2 was repeated using the products of Examples 
10-14 in place of the product of Example 1 and the amount of zinc 
diethylcarbamate or tetramethylthiourea indicated in Table 2. The 
extension at break or peak torque with and without the additives is given 
in columns 5 to 8. 
TABLE 2 
__________________________________________________________________________ 
Zinc Extension 
diethyldithio- 
at Peak 
Example 
Additive 
carbamate 
TMTU 
Break Blank 
torque Blank 
__________________________________________________________________________ 
15 10 3 -- -- -- 73 (190.degree./2 min) 
38 (190.degree./54 min) 
16 11 -- 2 900% 130% 
17 12 4 -- 700% 130% 
32.5 (153.degree./8 min) 
17 (153.degree./54 min.) 
18 13 3 -- 900% 130% 
43 (153.degree./8 min) 
17 (153.degree./54 min) 
19 14 4 31 (160.degree./9 min) 
no cure 
__________________________________________________________________________ 
EXAMPLE 20 
8.4 parts of butane-1,4-bis-(p-nitrophenylsulphonoxy)urethane is cooled to 
0.degree. C and ground with 5.3 parts of tetramethylthiourea. The mixture 
reacted exothermically to form a bright yellow oil which solidified on 
cooling to give 13.7 parts of bright yellow crystals. 
EXAMPLE 21 
6 parts of the product of Example 20 were milled into 100 parts of a 27:73 
styrene-butadiene copolymer (SBR) at 55.degree.-60.degree. C to give a 
pale yellow sheet. The compounded rubber was cured at 190.degree. C for 10 
minutes to give a cross-linked rubber in which the extension at break was 
700%. The styrene-butadiene copolymer cured without the additive has an 
extension at break of 130%.