Poly(monoperoxycarbonates) of the structure: ##STR1## where R, R.sup.1 and n are defined in the summary of the invention such as 1,1,1-tris(t-butylperoxycarbonyloxymethyl)ethane, intermediates for their preparation as well as processes for their preparation and use are disclosed. The monoperoxycarbonate compounds are useful in initiating the polymerization of ethylenically unsaturated monomers, particularly styrene, curing of unsaturated polyester resins, and in modifying the molecular weight of polymers such as by crosslinking or controlled chain degradation.

This Application claims priority from Provisional Application Ser. No. 
60/025,206, filed Aug. 23, 1996. 
BACKGROUND OF THE INVENTION 
a) Field of the Invention 
This invention relates to new and novel compositions of matter classified 
in the art of chemistry as poly(monoperoxycarbonate) compounds of 
Structure A: 
##STR2## 
The definitions of n, R and R.sup.1 are given in the SUMMARY OF THE 
INVENTION!, to processes for their preparation and use and to 
intermediates used in the preparation processes. 
There is a need in the polymer industry for efficient, free-radical 
initiators for polymerizing ethylenically unsaturated monomers, such as 
styrene, at faster production rates while retaining polymer molecular 
weight and polymer physical properties, e.g., tensile properties. In 
general, use of more active free-radical initiators and increase of 
polymerization temperatures to enhance production rates of polymers (e.g., 
polystyrene) result in the desired enhancement of production rates but 
also undesirably result in reduced polymer molecular weights and reduced 
tensile properties. There also is a need to increase the molecular weight 
of commercial polymers in order to enhance polymer physical properties. 
Reduction of polymerization temperatures, reduction in initiator use 
levels and use of less active initiators generally achieve the goal of 
increasing polymer molecular weight, however, polymer production rates are 
reduced. In the 1980s, the art of polymerizing styrene was advanced. Use 
of diperoxyketals, such as 1,1-bis(t-butylperoxy)cyclohexane, as 
initiators in place of standard initiators, such as dibenzoyl peroxide and 
t-butyl peroxybenzoate, for commercial styrene polymerizations resulted in 
enhanced polystyrene molecular weight and/or enhanced production of 
polystyrene. The current applicants further advanced the art and found 
that the novel poly(monoperoxycarbonate) compositions of Structure A of 
this invention can be used as initiators for polymerizing ethylenically 
unsaturated monomers to produce polymers (e.g., polystyrene) having 
significantly increased polymer molecular weights while simultaneously 
retaining or increasing polymerization rates or to produce polymers at 
significantly enhanced rates while retaining polymer molecular weights, 
and that the compositions of the instant invention were superior to 
diperoxyketals, such as 1,1-bis(t-butylperoxy)cyclohexane. Thus, the novel 
poly(monoperoxycarbonate) compositions of the instant invention are 
capable of satisfying the polymerization needs of polymer industry. 
There also is a need in the polyester industry for free-radical initiators 
that cure unsaturated polyester resins faster and/or at lower 
temperatures. The novel poly(monoperoxycarbonate) compositions of the 
instant invention are also capable of satisfying this polymer industry 
need. 
b) Description of the Prior Art 
U.S. Pat. No. 3,652,631 (to PPG, Mar. 28, 1972) discloses 
bis(monoperoxycarbonates 1 derived from t-butyl hydroperoxide, 
##STR3## 
(where R.sup.1 and R.sup.3 are alkyl up to 10 carbons, optionally 
substituted with halogen or nitro groups, and R.sup.2 is the divalent 
residue of an organic diol containing up to 12 carbon atoms and up to 
three ether linkages), 
t-amyl hydroperoxide or t-hexyl hydroperoxide and bis(chloroformates) and 
the use of these compositions to polymerize monomers such as styrene. The 
bis(monoperoxycarbonate) composition, 
1,5-bis(t-butylperoxycarbonyloxy)-3-oxapentane, is covered by U.S. Pat. 
No. 3,652,631. The applicants of the instant invention found that the 
novel poly(monoperoxycarbonate) compositions of Structure A were better 
initiators for polymerizing styrene than 
1,5-bis(t-butylperoxycarbonyloxy)-3-oxapentane as they produced 
polystyrenes with significantly increased molecular weights under the same 
polymerization conditions. 
U.S. Pat. No. 4,136,105, Jan. 23, 1979 (to Pennwalt Corp.) discloses 
O-alkyl OO-t-octyl monoperoxycarbonates 2, 
##STR4## 
(where n is an integer from 1 to 4, preferably 1; when n is 1, R is 
selected from alkyl of 1-16 carbons, cycloalkyl of 5-12 carbons, aryl of 6 
to 14 carbons, aralkyl of 7-14 carbons, alkenyl of 3-10 carbons, 
cycloalkenyl of 5-10 carbons, and alkynyl of 3-14 carbons; when n is 2, R 
is selected from alkylene of 2-12 carbons, cycloalkylene of 4-12 carbons, 
arylene of 6-14 carbons, alkenylene of 2-12 carbons, alkynylene of 4-12 
carbons, methylenephenylmethylene, methylenecyclohexylmethylene, --R.sup.1 
XR.sup.1 --, and --R.sup.2 YR.sup.2 --, where R.sup.1 is alkylene of 2-6 
carbons, R.sup.2 is phenylene, X is --O-- or --S--, and Y is --O--, --S--, 
--CH.sub.2 -- or --C(CH.sub.3).sub.2 --; when n is 3, R is R.sup.3 
C(CH.sub.2 --).sub.3, --CH(CH.sub.2 --).sub.2, and --CH.sub.2 
CH(--)CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 --, where R.sup.3 is alkyl of 
1-5 carbons; and when n is 4, R is C(CH.sub.2 --).sub.4.) 
and the use of these compositions for initiating the polymerization of 
vinyl monomers and for curing of unsaturated polyester resins. This art 
covers tris- and tetrakis(mono-t-octylperoxycarbonates) derived from 
t-octyl hydroperoxide but does not disclose the novel 
poly(monoperoxycarbonate) compositions of the instant invention that are 
derived from t-butyl and t-amyl hydroperoxides. 
U.S. Pat. No. 5,314,970, (to Elf Atochem, May 24, 1994) discloses 
OO-t-alkyl O-polycaprolactone monoperoxycarbonates, i.e., 
polycaprolactones end-capped with OO-t-alkylperoxycarbonate groups 3 
derived from t-alkyl hydroperoxides and chloroformates of 
##STR5## 
m is an integer from 0 to 3, n is an integer from 1 to 4, m+n is an 
integer from 1 to 4, R.sup.1 and R.sup.2 are the same or different and are 
alkyl of 1 to 4 carbons, R.sup.3 is alkyl of 1 to 12 carbons or alkynyl of 
2 to 12 carbons, y is an integer from 0 to about 10,000, x is an integer 
from 4 to about 22,000, (y)(m)+(x)(n) is an integer from 4 to about 
22,000, X and X' are independently selected from --O-- or --N(R.sup.4 --), 
R.sup.4 being hydrogen, substituted or unsubstituted aliphatic of 1 to 20 
carbons, substituted or unsubstituted acyclic of 5 to 18 carbons, 
substituted or unsubstituted aromatic of 6-14 carbons, and substituted or 
unsubstituted araliphatic of 7 to 22 carbons, and R is a substituted or 
unsubstituted aliphatic, alicyclic aromatic or araliphatic radical, 
diradical, triradical or tetraradical), 
hydroxy-terminated polycaprolactones and the use of these compositions for 
initiating the polymerization of vinyl monomers, for curing of unsaturated 
polyester resins, for preparing polycaprolactone block copolymers, for 
crosslinking polyolefins, for curing of elastomers, for modifying 
polypropylene, for grafting polycaprolactone blocks onto polyolefins, for 
preparation of interpenetrating polymer networks, and for preparation of 
graft polyols. 
The only monoperoxycarbonate compositions that were disclosed in the 
examples were bis(t-butyl monoperoxycarbonates) and bis(t-amyl 
monoperoxycarbonates) derived from diols. The only utility disclosed in 
the examples and the utility emphasized in the abstract, the specification 
and the claims was the use of the bis(monoperoxycarbonates) for preparing 
polycaprolactone-polystyrene block and graft copolymers for use as 
compatibilizing agents for blends of polymers. Since the most effective 
block copolymers for compatibilizing polymer blends were those with larger 
block segments, the most preferred poly(e-caprolactones) were 
dihydroxy-terminated poly(e-caprolactones) of approximately 3,000 to 
15,000 molecular weight (U.S. Pat. No. 5,314,970, column 12, lines 30-33). 
The hydroxy-terminated poly(e-caprolactone) starting materials of the 
instant invention are confined to polyhydroxy-terminated 
poly(e-caprolactones) except in the special cases when novel 
peroxide-substituted bis(monoperoxycarbonates) are made by reacting the 
bis(haloformates) of bishydroxy-terminated poly(e-caprolactones with 
1,1,4-trimethyl-4-(t-butylperoxy)pentyl hydroperoxide or with 
1,1,4-trimethyl-4-(t-amylperoxy)pentyl hydroperoxide. Furthermore, the 
polyhydroxy starting materials (i.e., diols, triols and higher polyols) 
for the compositions of the instant invention must have molecular weights 
of less than about 1000, less than about 1000 and less than about 1300, 
respectively. 
U.S. Pat. No. 5,314,970 suggests no advancement in the art of polymerizing 
styrene with the bis(monoperoxycarbonate) compositions of the patent. The 
bis(t-butyl monoperoxycarbonate) derived from TONE.RTM. 200 is a 
composition of U.S. Pat. No. 5,314,970. The applicants of the instant 
invention found that the novel poly(monoperoxycarbonate) compositions of 
Structure A were better initiators for polymerizing styrene as they 
produced polystyrenes with significantly higher molecular weights under 
the same polymerization conditions than were produced with the bis(t-butyl 
monoperoxycarbonate) of TONE.RTM. 200. 
U.S. Pat. No. 5,455,321 (to The Dow Chemical Company, Oct. 3, 1995) 
discloses a process for producing a monovinylidene aromatic polymer (e.g., 
polystyrene) having molecular weight greater than 275,000 which comprises 
polymerizing a monovinylidene aromatic monomer (e.g., styrene) in the 
presence of, a) 10 to 2000 ppm by weight of at least one free-radical 
generating, branching polymerization initiator of the structure: 
EQU R'((CO).sub.n OOR).sub.m 
where n is 0 or 1, m is 3 to 6, R' is a multifunctional organic radical of 
up to 25 non-hydrogen atoms, and R is C.sub.1-15 tertiary alkyl or 
C.sub.7-15 tertiary aralkyl groups, and, b) 10 to 2000 ppm of one or more 
organic gel-reducing agents selected from the group consisting of I) 
mercaptans, terpenes, halocarbons and halohydrocarbons having up to 20 
carbons, ii) a recycle liquid generated by devolatilization of the 
polymerized monomer mixture, and, iii) mixture of the organic gel-reducing 
agents from I) and ii). A preferred free-radical generating, branching 
polymerization initiator was 
2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane: 
##STR6## 
Other free-radical generating, branching polymerization initiators 
disclosed by this patent were tri-t-alkyl 1,3,5-benzenetricarboperoxoic 
acid esters, tetra-t-alkyl 1,2,4,5-benzenetetracarboperoxoic acid esters 
and 2,4,6-tri-t-alkylperoxy-1,3,5-triazines, 
2-(4-isopropenylphenyl)-2-propyl t-alkyl peroxides, t-alkyl 
4-isopropenylperoxybenzoates, di-t-alkyl diperoxymaleates and 
diperoxyfumarates, and OO-t-alkyl O-alkyl monoperoxymaleates and 
monoperoxyfumarates. U.S. Pat. No. 5,455,321 does not disclose the novel 
poly(monoperoxycarbonates) of the instant invention nor the novel 
processes using them in polymer applications. 
U.S. Pat. No. 5,266,603 (to Huels Aktiengesellschaft, Nov. 30, 1993) 
discloses a process for the production of expandable styrene homopolymers 
or copolymers by a) providing an aqueous suspension of styrene monomer and 
a peroxide initiator system comprising at least one aliphatic or 
cycloaliphatic diperoxyketal (e.g., 2,2-bis(t-butylperoxy)butane or 
1,1-bis(t-butylperoxy)cyclohexane) or monoperoxycarbonate initiator (e.g., 
OO-t-butyl O-(2-ethylhexyl) monoperoxycarbonate or OO-t-amyl 
O-(2-ethylhexyl) monoperoxycarbonate) and a peroxide initiator having a 
shorter half-life than an aliphatic or cycloaliphatic diperoxyketal or 
monoperoxycarbonate initiator (e.g., dibenzoyl peroxide), b) heating the 
stirred suspension from 80.degree. C. to 100.degree. C. for a first period 
of time to effect initial polymerization, c) adding a C.sub.3-6 
hydrocarbon propellant to the stirred suspension, d) increasing the 
temperature of the resulting suspension to a temperature from 100.degree. 
C. to 130.degree. C. for a second period of time to effect final 
polymerization and produce an expandable polystyrene resin. In this 
patent, no bis-, tris- or higher poly(monoperoxycarbonates) are employed, 
only mono(monoperoxycarbonates) such as OO-t-butyl O-(2-ethylhexyl) 
monoperoxycarbonate or OO-t-amyl O-(2-ethylhexyl) monoperoxycarbonate. 
As a whole, the above art does not disclose the poly(monoperoxycarbonate) 
compositions of Structure A. 
c) Definitions 
A diol is defined as the structure R(--OH).sub.2, where R is a diradical, 
e.g., R(--).sub.2. A triol is defined as the structure R(--OH).sub.3, 
where R is a triradical, e.g., R(--).sub.3. A polyol is defined as a 
structure R(--OH).sub.n, where R is a polyradical, e.g., R(--).sub.n, and 
n is an integer.gtoreq.2. A tetraol is defined as the structure 
R(--OH).sub.4, where R is a tetraradical, e.g., R(--).sub.4. 
When any generalized functional group or index, such as R, R.sup.1, 
R.sup.2, x, n, etc., appears more than once in a general formula or 
structure, the meaning of each is independent of one another. 
SUMMARY OF THE INVENTION 
The invention provides in its first composition aspect, a 
poly(monoperoxycarbonate) compound of Structure A: 
##STR7## 
where n is an integer from 3 to 8, R.sup.1 is selected from the group 
consisting of t-alkyl radicals of 4 to 12 carbons, 
1,1,4-trimethyl-4(t-butylperoxy)pentyl radical, 
1,1,4-trimethyl-4(t-amylperoxy)pentyl radical, t-cycloalkyl radicals of 6 
to 10 carbons, t-aralkyl radicals of 9 to 13 carbons and 
3-methyl-1-butyn-3-yl and 3-methyl-1-pentyn-3-yl, and with the proviso 
that when R.sup.1 is selected from 1,1,4-trimethyl-4(t-butylperoxy)pentyl 
radical and 1,1,4-trimethyl-4(t-amylperoxy)pentyl radical, n can also have 
a value of 2; 
when n is 2, R is a diradical selected from alkylene of 2 to 12 carbons, 
alkenylene of 4 to 8 carbons and diradical structures (n) and (o), 
##STR8## 
where R.sup.9 is an alkylene diradical of 2 to 8 carbons; when n is 3, R 
is a triradical selected from 1,3,5-cyclohextriyl, R.sup.2 C(CH.sub.2 
--).sub.3, --CHR.sup.2 CH(--)CH.sub.2 -- and structures (a), (b), (c), (d) 
and (e), 
##STR9## 
where R.sup.2 is selected from hydrogen and an alkyl radical of 1 to 6 
carbons, R.sup.3 is a triradical selected from the group consisting of 
R.sup.2 C(CH.sub.2 --).sub.3, --CHR.sup.2 CH(--)CH.sub.2 -- and structures 
(a) and (b), R.sup.4 and R.sup.5 are the same or different and are 
selected from hydrogen and alkyl radicals of 1 to 4 carbons, x, y and z 
are integers from 0 to 5 with the proviso that the sum of x, y and z is 
from 2 to 8, and r, s and t are integers from 0 to 6 with the proviso that 
the sum of r, s and t is from 3 to 18, and when n is 4 to 8, R is a 
polyradical selected from C(CH.sub.2 --).sub.4 and structures (f), (g), 
(h), (i), (j), (k) and (l), 
##STR10## 
where R.sup.6 is a tetraradical selected from C(CH.sub.2 --).sub.4 and 
structure (f), R.sup.7 is a diradical selected from alkylene of 2 to 6 
carbons and 1,2-, 1,3- and 1,4-phenylene, R.sup.8 is the sucrose-based 
octaradical of structure (m), 
##STR11## 
p is an integer from 1 to 3, v is an integer from 0 to 5 with the proviso 
that the sum of v, x, y and z is from 3 to 10, and q is an integer from 0 
to 4 with the proviso that the sum of q, r, s and t is from 2 to 16, and 
with the further proviso that when R is R.sup.3 C(CH.sub.2 --).sub.3, 
structure (b) or C(CH.sub.2 --).sub.4, R.sup.1 is not t-octyl; such novel 
poly(monoperoxycarbonate) of Structure A being synthesized from a diol, 
trial or a higher polyol of Structure AA: 
##STR12## 
having a molecular weight of less than about 1000, less than about 1000 or 
less than about 1300, respectively. The invention provides in a subgeneric 
composition aspect, a compound of Structure A' wherein in Structure A, 
when n is 3, R is a triradical selected from 1,3,5-cyclohextriyl, R.sup.2 
C(CH.sub.2 --).sub.3, --CHR.sup.2 CH(--)CH.sub.2 --, and structures (a), 
(b), (d) and (e) as defined above. 
The invention provides in a second subgeneric composition aspect, a 
compound of Structure A" wherein in Structure A when n is 3, R is as 
defined above for the first subgeneric composition aspect of the invention 
and when n is 4 to 8, R is a polyradical selected from C(CH.sub.2 
--).sub.4, and structures (f), (g), (i), (j), (k) and (l) as defined 
above. 
The compositions of the first composition aspect of the invention have the 
inherent physical properties of being amorphous solids or viscous liquids 
said solids being white to light straw colored and said liquids being 
colorless to light straw colored. The solids exhibit melting ranges and 
all compositions exhibit infra red spectra and peroxide active oxygen 
content positively confirming the structures sought to be patented. 
The compositions of the first composition aspect of the invention possess 
the inherent applied use characteristic of being initiators for the 
polymerization of ethylenically unsaturated monomers, particularly styrene 
and for the modification of the molecular weight of polymers such as 
unsaturated polyesters, thermoplastic polymers, elastomeric polymers and 
mixtures of such polymers. 
The invention provides in a first process aspect, a process for 
free-radical initiated modification of a substrate selected from the group 
consisting of ethylenically unsaturated monomers, and polymers susceptible 
to free radical induced molecular weight modification which comprises the 
treatment of said substrates under conditions effective to initiate free 
radical induced modification of said substrates with one or more compounds 
of Structure (A) in effective initiating amounts. 
Special mention is made of the following free radical induced molecular 
weight modification processes: 
a. polymerizing ethylenically unsaturated monomer compositions (such as 
styrene, ethylene, allyl diglycol carbonate (ADC), and the like known to 
the art as susceptible to such polymerization), optionally in the presence 
of an unsaturated elastomer (such as polybutadiene, polyisoprene, and the 
like known in the art to be useful when present in such polymerizations). 
b. curing of unsaturated polyester resin compositions, 
c. crosslinking and curing of thermoplastic polymer and elastomeric polymer 
compositions, and, 
e. modifying the molecular weight of polyolefin compositions, 
The invention provides in a second process aspect, a process for 
free-radical initiated polymerization of ethylenically unsaturated monomer 
compositions (such as styrene, ethylene, allyl diglycol carbonate (ADC), 
and the like), known in the art to be susceptible to such polymerization 
optionally in the presence of an unsaturated elastomer (such as 
polybutadiene, polyisoprene, and the like), known in the art to be useful 
when present in such polymerizations under conditions effective to 
initiate free-radical induced polymerization, with one or more compounds 
of Structure A in combination with other free-radical initiators selected 
from the group consisting of monoperoxides and diperoxides (such as diacyl 
peroxides, diperoxyketals, peroxyesters, monoperoxycarbonates and dialkyl 
peroxides), in effective initiating amounts. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
Novel Poly(monoperoxycarbonate) Compositions of Structure A--Preparative 
Methods 
The novel poly(monoperoxycarbonate) compositions of Structure A can be 
prepared by reacting one or more t-alkyl hydroperoxides of Structure B. 
EQU R.sup.1 --OOH B 
with poly(haloformates) of Structure C, at -30.degree. C. to 50.degree. C., 
##STR13## 
wherein R, R.sup.1 and n are as defined for Structure A optionally in the 
presence of an inorganic or organic base, and optionally in the presence 
of one or more solvents. Non-limiting examples of suitable optional bases 
include triethylamine, tributylamine, N,N-diisopropylethylamine, 
2,2,6,6-tetramethylpiperidine, N,N-dimethylaniline, 
N,N-dimethylaminopyridine, 2,4,6-colidine, urea, tetramethylurea, sodium 
hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium 
hydroxide, potassium carbonate, potassium hydrogen carbonate, calcium 
hydroxide, magnesium hydroxide, barium hydroxide, calcium carbonate and 
trisodium phosphate. 
Non-limiting examples of suitable optional solvents include pentane, 
hexanes, heptanes, dodecanes, odorless mineral spirits mixtures, toluene, 
xylenes, cumene, methylene chloride, ethyl acetate, 2-ethylhexyl acetate, 
isobutyl isobutyrate, dimethyl adipate, dimethyl succinate, dimethyl 
glutarate (or mixtures thereof), dimethyl phthalate, dibutyl phthalate, 
benzyl butyl phthalate, diethyl ether, methyl t-butyl ether (MTBE), 
2-methoxyethyl acetate, tetrahydrofuran (THF) and others. 
The suitable hydroperoxides of Structure B that can be reacted with 
poly(haloformates) of Structure C include t-butyl hydroperoxide, t-amyl 
hydroperoxide, 2-methyl-2-pentyl hydroperoxide, 3-methyl-3-pentyl 
hydroperoxide, 3-methyl-1-butyn-3-yl hydroperoxide, 3-methyl-1-pentyn-3-yl 
hydroperoxide, 2-methyl-2-hexyl hydroperoxide, 1,1,3,3-tetramethylbutyl 
hydroperoxide, 1,1,4-trimethyl-4(t-butylperoxy)pentyl hydroperoxide, 
1,1,4-trimethyl-4(t-amylperoxy)pentyl hydroperoxide, 1-methyl-1-cyclohexyl 
hydro-peroxide, paramenthane hydroperoxide, .alpha.-cumyl hydroperoxide, 
4-methyl-.alpha.-cumyl hydroperoxide, 3-methyl-.alpha.-cumyl hydroperoxide 
and diisopropylbenzene monohydroperoxide. 
Non-limiting examples of suitable poly(haloformates) of Structure C that 
can be reacted with hydroperoxides of Structure B include 
1,1,1-tris(chlorocarbonyloxymethyl)ethane, 
1,1,1-tris-(chlorocarbonyloxymethyl)propane, 
1,1,1-tris(chlorocarbonyloxymethyl)butane, 
1,2,3-tris(chlorocarbonyloxy)propane, 1,2,3-tris(chlorocarbonyloxy)hexane, 
1,2,3-tris(chlorocarbonyloxy)heptane, 1,2,4-tris(chlorocarbonyloxy)butane, 
1,2,6-tris(chlorocarbonyloxy)hexane, 
1,3,5-tris(chlorocarbonyloxy)cyclohexane, 
tetrakis(chlorocarbonyloxymethyl)methane, 
1,2,3,4-tetrakis(chloro-carbonyloxy)butane, 
1,1,1,5,5,5-hexa(chlorocarbonyloxymethyl)-3-oxapentane, and 
1,1,1,5,5,9,9,9-octa(chlorocarbonyloxymethyl)-3,7-dioxanonane. 
Also included as suitable poly(haloformates) of Structure C are tris- and 
tetrakis(chloroformates) of Structures D and E: 
##STR14## 
that are derived from polycaprolactone triols and tetraols (Structures F 
and G, respectively); 
##STR15## 
such as those manufactured by Union Carbide Corporation and sold using the 
trade name TONE.RTM., e.g., TONE.RTM. 0301, TONE.RTM. 1303, TONE.RTM. 
0305, TONE.RTM. 0310 and TONE.RTM. 4411), and tris- and 
tetrakis(chloroformates) of Structures H and I: 
##STR16## 
that are derived from polyether triols and tetraols (Structures J and K, 
respectively); 
##STR17## 
some of which are manufactured by BASF Corporation under the trade name 
PLURACOL.RTM.; where R.sup.4 is methyl and R.sup.5 is hydrogen, e.g., 
PLURACOL.RTM. GP-730, PLURACOL.RTM. TP-740, PLURACOL.RTM. PeP 450, 
PLURACOL.RTM. PeP 550 and PLURACOL.RTM. PeP 650, and others which are 
manufactured by the Dow Chemical Company under the trade name 
VORANOL.RTM.; such as Structure J, where R.sup.4 and R.sup.5 are hydrogen, 
e.g., VORANOL.RTM. 234-630, and still others which are manufactured by 
Arco Chemical Company under the trade name ARCOL.RTM.; such as Structure J 
where R.sup.4 is methyl and R.sup.5 is hydrogen, e.g., ARCOL.RTM. LG-650 
and ARCOL.RTM. LHT-240. The molecular weights of the TONE.RTM., 
PLURACOL.RTM., VORANOL.RTM. and ARCOL.RTM. polyols as stated by the 
manufacturers are given below: 
______________________________________ 
MOLECULAR 
POLYOL TYPE STRUCTURE WEIGHT 
______________________________________ 
TONE .RTM. 0301 
Triol F 300 
TONE .RTM. 1303 
Triol F 425 
TONE .RTM. 0305 
Triol F 540 
TONE .RTM. 0310 
Triol F 900 
TONE .RTM. 4411 
Tetraol G 1006 
PLURACOL .RTM. GP-730 
Triol J 730 
PLURACOL .RTM. TP-740 
Triol J 730 
PLURACOL .RTM. PeP 450 
Tetraol K 405 
PLURACOL .RTM. PeP 550 
Tetraol K 500 
PLURACOL .RTM. PeP 650 
Tetraol K 594 
VORANOL .RTM. 234-630 
Triol J 267 
ARCOL .RTM. LG-650 
Triol J 260 
ARCOL .RTM. LHT-240 
Triol J 700 
______________________________________ 
When R.sup.1 of Structure A is 1,1,4-trimethyl-4(t-butylperoxy)pentyl 
radical or 1,1,4-trimethyl-4(t-amylperoxy)pentyl radical and n is 2, 
bis(haloformates) derived from diols can be used to produce polyperoxide 
compositions of Structure A. Non-limiting examples of diol precursors to 
the bis(haloformates) include ethylene glycol, 1,2- and 1,3-propylene 
glycols, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, diethylene glycol, 
triethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, 
TONE.RTM. diols and others. 
The definitions of R.sup.3, R.sup.6, q, r, s, t, v, x, y, and z are given 
in the SUMMARY OF THE INVENTION section. 
The above poly(haloformates) can be prepared by reacting 0% to 100% excess 
carbonyl dihalides (such as the dibromide or the dichloride, i.e., 
phosgene) with the corresponding polyol, i.e., (HO).sub.n R, in the 
presence or absence of a tetraalkylurea (e.g., tetramethylurea), in the 
presence or absence of a solvent, until the reaction is completed. The 
excess carbonyl dibromide or phosgene is removed by stripping or by 
distillation. Non-limiting examples of suitable polyols that react with 
carbonyl dihalides to form the tri- and poly(haloformates) of Structure C 
include 1,1,1-tris(hydroxymethyl)ethane, 1,1,1-tris(hydroxymethyl)propane, 
1,1,1-tris(hydroxymethyl)butane, glycerol, 1,2,3-trihydroxyhexane, 
1,2,3-trihydroxyheptane, 1,2,4-trihydroxy-butane, 1,2,6-trihydroxyhexane, 
1,3,5-trihydroxycyclohexane, pentaerythritol, 1,2,3,4-tetrahydroxybutane, 
1,1,1,5,5,5-hexa(hydroxy-methyl)-3-oxapentane, 
1,1,1,5,5,9,9,9-octa(hydroxymethyl)-3,7-di-oxanonane, and polycaprolactone 
triols and tetraols of Structures F and G, respectively, and polyether 
triols and tetraols of Structures J and K, respectively. 
Alternately, the novel poly(monoperoxycarbonate) compositions of Structure 
A can be prepared by reacting t-alkylperoxy haloformates of Structure L, 
##STR18## 
with a polyol, i.e., (HO).sub.n R, in the presence of an inorganic or 
organic base, and optionally in the presence one or more solvents. The 
t-alkylperoxy haloformates of Structure L can be prepared by reacting a 
t-alkyl hydroperoxide of Structure B with excess carbonyl dihalide 
(carbonyl dibromide or phosgene) and removal of excess carbonyl dihalide 
by stripping or distillation. 
Non-limiting examples of inorganic or organic bases, optional solvents, 
polyols, and t-alkyl hydroperoxides are listed above. Non-limiting 
examples of suitable t-alkylperoxy haloformates of Structure L include 
t-butylperoxy chloroformate, t-amylperoxy chloroformate, 
2-methyl-2-pentylperoxy chloroformate, 3-methyl-3-pentylperoxy 
chloroformate and 3-methyl-1-butyn-3-ylperoxy chloroformate. 
Novel peroxide-substituted bis(monoperoxycarbonates) of Structure A, where 
R.sup.1 is selected from 1,1,4-trimethyl-4(t-butylperoxy)pentyl radical 
and 1,1,4-trimethyl-4(t-amylperoxy)pentyl radical, and where n is 2, can 
be prepared by reacting a hydroperoxide, selected from 
1,1,4-trimethyl-4(t-butylperoxy)pentyl hydroperoxide and 
1,1,4-trimethyl-4(t-amylperoxy)pentyl hydroperoxide, with a 
bis(haloformate) of Structure C (where n=2), at -30.degree. C. to 
50.degree. C., optionally in the presence of an inorganic or organic base, 
and optionally in the presence of one or more solvents. 
Non-limiting examples of suitable bis(haloformates) of Structure C (where 
n=2), that can be reacted with 1,1,4-trimethyl-4(t-butylperoxy)pentyl 
hydroperoxide or 1,1,4-trimethyl-4(t-amylperoxy)pentyl hydroperoxide, 
include 1,2-bis(chlorocarbonyloxy)ethane, 1,2- and 
1,3-bis(chlorocarbonyloxy)propanes, 
2,2-dimethyl-1,3-bis(chlorocarbonyloxy)propane, 
1,6-bis(chlorocarbonyloxy)hexane, 1,5-bis(chlorocarbonyloxy)-3-oxapentane, 
1,4-bis(chlorocarbonyloxy)-2-butene and bis(monoperoxycarbonates) of 
Structures HH and II, 
##STR19## 
The above bis(haloformates) can be prepared by reacting 0% to 100% excess 
carbonyl dihalides (such as the dibromide or the dichloride, i.e., 
phosgene) with the corresponding diol in the presence or absence of a 
tetraalkylurea (e.g., tetramethylurea) and in the presence or absence of a 
solvent, until the reaction is completed. The excess carbonyl dibromide or 
phosgene is removed by stripping or by distillation. 
Non-limiting examples of suitable diols that react with carbonyl dihalides 
to form the bis(haloformates) of Structure C (where n=2) include 
1,2-ethanediol, 1,2- and 1,3-propanediols, 1,2-, 1,3- and 1,4-butanediols, 
2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 
2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, diethylene glycol, 
dipropylene glycol, and polycaprolactone diols of Structure JJ (TONE.RTM. 
##STR20## 
diols, such as TONE.RTM. 200 and TONE.RTM. 210; manufactured by Union 
Carbide Corporation) and polyalkylene glycols of Structure KK, 
##STR21## 
Novel Poly(monoperoxycarbonate) Compositions of Structure A--Illustrative 
Examples 
Non-limiting examples of the novel poly(monoperoxycarbonate) compositions 
of Structure A, in addition to those in the working examples, include the 
following: 
1,1,1-tris(t-amylperoxycarbonyloxymethyl)ethane, 
1,1,1-tris(t-amyl-peroxycarbonyloxymethyl)propane, 
1,1,1-tris(t-amylperoxycarbonyl-oxymethyl)butane, 
1,1-bis2-(t-amylperoxycarbonyloxy)ethoxymethyl!-1-2-(t-butylperoxycarbon 
yloxy)ethoxymethyl)propane, 
1-2-(t-amylperoxycarbonyloxy)ethoxymethyl!-1,1-bis2-(t-butylperoxycarbon 
yloxy)ethoxymethyl!propane, 1,2,3-tris(t-amylperoxy-carbonyloxy)propane, 
1,2,3-tris(t-butylperoxycarbonyloxy)hexane, 
1,2,3-tris(t-butylperoxycarbonyloxy)heptane, 
1,2,4-tris(t-butylperoxycarbonyloxy)butane, 
1,2,6-tris(t-butylperoxycarbonyloxy)hexane, 
1,3,5-tris(t-butylperoxycarbonyloxy)cyclohexane, 
tetrakis-(t-amylperoxycarbonyloxymethyl)methane, 
1,2,3,4-tetrakis(t-amyl-peroxycarbonyloxy)butane, 
1,1,1,5,5,5-hexa(t-butylperoxycarbonyl-oxymethyl)-3-oxapentane, 
1,5-bis1,1,4-trimethyl-4(t-amylperoxy)pentylperoxycarbonyloxy!-3-oxapenta 
ne, 
1,1,1-tris1,1,4-trimethyl-4(t-butylperoxy)pentylperoxycarbonyloxymethyl!p 
ropane, 
1,1,1,5,5,9,9,9-octa(t-butylperoxycarbon-yloxymethyl)-3,7-dioxanonane, and 
the tris- and tetrakis(t-alkyl monoperoxycarbonates) of polycaprolactone 
triols and tetraols and polyether triols and tetraols, i.e., compositions 
of Structures M, N, O and P, respectively: 
##STR22## 
where t-C.sub.5 H.sub.11 is t-amyl, t-C.sub.6 H.sub.13 is 
2-methyl-2-pentyl or 3-methyl-3-pentyl and t-C.sub.8 H.sub.17 - is 
2-methyl-2-heptyl or 1,1,3,3-tetramethylbutyl. 
Novel Poly(monoperoxycarbonate) Compositions of Structure A--Utility 
A. Polymerization of Ethylenically Unsaturated Monomers 
In the free-radical polymerizations of ethylenically unsaturated monomers 
at suitable temperatures and pressures the novel peroxide compositions of 
Structure A of this invention were found to be effective initiators with 
respect to efficiency (reduced initiator requirements, etc.). 
Ethylenically unsaturated monomers include olefins, such as ethylene, 
propylene, styrene, alpha-methylstyrene, p-methylstyrene, chlorostyrenes, 
bromo-styrenes, vinylbenzyl chloride, vinylpyridine and divinylbenzene; 
diolefins, such as 1,3-butadiene, isoprene and chloroprene; vinyl esters, 
such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl benzoate and 
divinyl carbonate; unsaturated nitriles, such as acrylonitrile and 
methacrylonitrile; acrylic acid and methacrylic acid and their anhydrides, 
esters and amides, such as acrylic acid anhydride, allyl, methyl, ethyl, 
n-butyl, 2-hydroxyethyl, glycidyl, lauryl and 2-ethylhexyl acrylates and 
methacrylates, and acrylamide and methacrylamide; maleic anhydride and 
itaconic anhydride; maleic, itaconic and fumaric acids and their esters; 
vinyl halo and vinylidene dihalo compounds, such as vinyl chloride, vinyl 
bromide, vinyl fluoride, vinylidene chloride and vinylidene fluoride; 
perhalo olefins, such as tetrafluoro-ethylene, hexafluoropropylene and 
chlorotrifluoroethylene; vinyl ethers, such as methyl vinyl ether, ethyl 
vinyl ether and n-butyl vinyl ether; allyl esters, such as allyl acetate, 
allyl benzoate, allyl ethyl carbonate, triallyl phosphate, diallyl 
phthalate, diallyl fumarate, diallyl glutarate, diallyl adipate, diallyl 
carbonate, diethylene glycol bis(allyl carbonate) (i.e., ADC); acrolein; 
methyl vinyl ketone; or mixtures thereof. 
In the free-radical graft polymerization of ethylenically unsaturated 
monomers onto polymers at suitable temperatures and pressures the novel 
peroxide compositions of Structure A of this invention are also effective 
initiators with respect to grafting efficiency. Ethylenically unsaturated 
monomers include: styrene monomers such as styrene, alpha-methylstyrene, 
p-methylstyrene, chlorostyrenes, bromostyrenes and vinylbenzyl chloride; 
unsaturated nitriles, such as acrylonitrile and methacrylonitrile; acrylic 
acid and methacrylic acid esters, such as allyl, methyl, ethyl, n-butyl, 
2-hydroxyethyl, glycidyl, lauryl and 2-ethylhexyl acrylates and 
methacrylates; and maleic anhydride. Graftable polymers include 
polybutadiene and polyisoprene. Two important polymeric compositions that 
are prepared by grafting of ethylenically unsaturated monomers onto 
polymers backbones are high-impact polystyrene (HIPS) and 
acrylonitrile-butadiene-styrene (ABS). HIPS is produced by the 
free-radical grafting of styrene onto polybutadiene whereas ABS is 
produced by the free-radical grafting of acrylonitrile and styrene onto 
polybutadiene. Such polybutadiene-modified compositions have impact 
resistances that are superior to the unmodified polymers. 
Temperatures of 0.degree. C. to 190.degree. C., preferably 20.degree. C. to 
175.degree. C., more preferably 30.degree. C. to 160.degree. C. and levels 
of tris- and poly(monoperoxycarbonates) of Structure A (on a pure basis) 
of 0.002 to 10% or more, preferably 0.0050% to 2%, more preferably 0.01% 
to 1% by weight based on monomer, are normally employed in conventional 
polymerizations and copolymerizations of ethylenically unsaturated 
monomers, and in grafting of ethylenically unsaturated monomers onto 
polymer backbones. The novel peroxide compositions of this invention can 
be used in combination with other free-radical initiators such as 
1,5-di(t-butylperoxycarbonyloxy)-3-oxapentane, 
2,5-dimethyl-2,5-di-(2-ethylhexanoylperoxy)hexane, 
2,5-dimethyl-2,5-di(isopropoxycarbonylperoxy)hexane, 
2,5-dimethyl-2-(2-ethylhexoxycarbonylperoxy)-5-(t-butylperoxy)hexane, 
t-butyl peroxybenzoate, t-amyl peroxybenzoate, di-t-butyl 
diperoxyphthalate and some of those listed at the bottom of column 4 and 
the top of column 5 of U.S. Pat. No. 4,525,308 (to Pennwalt Corporation, 
Jun. 25, 1985). Using the peroxide compositions of this invention in 
combination with these initiators adds flexibility to the processes of 
polymer producers and allows them to "fine tune" their polymerization 
processes. 
B. Curing of Unsaturated Polyester Resins 
In the curing of unsaturated resin compositions by heating at suitable 
curing temperatures in the presence of free-radical curing agents, the 
novel poly(monoperoxycarbonate) compositions of Structure A of this 
invention exhibit enhanced curing activity in the curable unsaturated 
polyester resin compositions. Unsaturated polyester resins that can be 
cured by the novel poly(monoperoxycarbonate) compositions of this 
invention usually include an unsaturated polyester and one or more 
ethylenically unsaturated monomers. 
The unsaturated polyesters are, for instance, polyesters as they are 
obtained by esterifying at least one ethylenically unsaturated di- or 
higher polycarboxylic acid, anhydride or acid halide, such as maleic acid, 
fumaric acid, glutaconic acid, itaconic acid, mesaconic acid, citraconic 
acid, allylmalonic acid, tetrahydrophthalic acid, and others, with 
saturated and unsaturated di- or higher polyols, such as ethylene glycol, 
diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediols, 1,2-, 
1,3- and 1,4-butanediols, 2,2-dimethyl-1,3-propanediol, 
2-hydroxymethyl-2-methyl-1,3-propanediol, 2-buten-1,4-diol, 
2-butyn-1,4-diol, 2,4,4- trimethyl-1,3-pentanediol, glycerol, 
pentaerythritol, mannitol and others. Mixtures of such di- or higher 
polyacids and/or mixtures of such di- or higher polyols may also be used. 
The ethylenically unsaturated di- or higher polycarboxylic acids may be 
partially replaced by saturated di- or polycarboxylic acids, such as 
adipic acid, succinic acid, sebacic acid and other, and/or by aromatic di- 
or higher polycarboxylic acids, such as phthalic acid, trimellitic acid, 
pyromellitic acid, isophthalic acid and terephthalic acid. The acids used 
may be substituted by groups such as halogen. Examples of such suitable 
halogenated acids are, for instance, tetrachlorophthalic acid, 
tetrabromophthalic acid, 
5,6-dicarboxy-1,2,3,4,7,7-hexachlorobicyclo(2.2.1)-2-heptene and others. 
The other component of the unsaturated polyester resin composition, the 
polymerizable monomer or monomers, can preferably be ethylenically 
unsaturated monomers, such as styrene, alpha-methylstyrene, 
p-methylstyrene, chlorostyrenes, bromostyrenes, vinylbenzyl chloride, 
divinylbenzene, diallyl maleate, dibutyl fumarate, triallyl phosphate, 
triallyl cyanurate, diallyl phthalate, diallyl fumarate, methyl acrylate, 
methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, ethyl 
acrylate, and others, or mixtures thereof, which are known in the art as 
copolymerizable with said unsaturated polyesters. A preferred unsaturated 
polyester resin composition contains as the unsaturated polyester 
component the esterification product of 1,2-propanediol (a polyol), maleic 
anhydride (an anhydride of an unsaturated polycarboxylic acid) and 
phthalic anhydride (an anhydride of an aromatic dicarboxylic acid) as well 
as the monomer component, styrene. 
Other types of unsaturated polyester resin compositions can be cured using 
the novel peroxide compositions of this invention as curing catalysts. 
These resins, called unsaturated vinyl ester resins, consist of a vinyl 
ester resin portion and one or more polymerizable monomer components. The 
vinyl ester resin component can be made by reacting a chloroepoxide, such 
as epichlorohydrin, with appropriate amounts of a bisphenol such as 
Bisphenol A (i.e., 2,2-(4-hydroxyphenyl)propane), in the presence of a 
base, such as sodium hydroxide, to yield a condensation product having 
terminal epoxy groups derived from the chloroepoxide. Subsequent reaction 
of the condensation product with polymerizable unsaturated carboxylic 
acids, such as acrylic acid and methacrylic acid, in the presence or 
absence of acidic or basic catalysts, results in formation of the vinyl 
ester resin component. Normally, styrene is added as the polymerizable 
monomer component to complete the preparation of the unsaturated vinyl 
ester resin composition. 
Temperatures of about 20.degree. C. to 200.degree. C. and levels of novel 
poly(monoperoxycarbonates) of Structure A of about 0.05% to 5% or more, 
preferably 0.10% to 4%, more preferably 0.25% to 3% by weight of curable 
unsaturated polyester resin composition are normally employed. 
The unsaturated polyester resin compositions described above can be filled 
with various materials, such as sulfur, glass, carbon and boron fibers, 
carbon blacks, silicas, metal silicates, clays, metal carbonates, 
antioxidants (AO's), heat, ultraviolet (UV) and light stabilizers, 
sensitizers, dyes, pigments, accelerators, metal oxides, such as zinc 
oxide, blowing agents, nucleating agents and others. 
C. Curing of Allyl Diglycol Carbonate (ADC) Resins 
In the curing or polymerizing of diethylene glycol bis(allyl carbonate 
(ADC), 
##STR23## 
by heating ADC monomer at suitable curing temperatures in the presence of 
free-radical curing agents, the novel poly(monoperoxycarbonate) 
compositions of Structure A of this invention exhibit enhanced curing or 
polymerizing activity for ADC monomer compositions. ADC was introduced 
commercially as CR-39 monomer (CAS Reg. No. 142-22-3) by Pittsburgh Plate 
Glass Company (PPG) and is produced by reacting diethylene glycol 
bis(chloroformate) with allyl alcohol in the presence of alkali (R. 
Dowbenko, in J. I. Kroschwitz and M. Howe-Grant, eds., 
Kirk--Othmer--Encyclopedia of Chemical Technology, "Allyl Monomers and 
Polymers," Fourth Edition, Vol. 2, Wiley-Interscience Publication, John 
Wiley & Sons, Inc., New York, 1992, pp 163-168). The ADC monomer can be 
cured or polymerized alone or with other co-monomers such as acrylic acid 
esters, methacrylic acid esters, allyl esters, diallyl dicarboxylates 
(e.g., diallyl phthalate), maleic anhydride and other monomers to produce 
clear castings or lenses that are transparent, tough, break-resistant and 
solvent-resistant. Curing or polymerizing of ADC monomer compositions are 
carried out in bulk (no solvent present). In general, curing or 
polymerizing of ADC monomer compositions to form cast sheets or lenses is 
carried out in two stages. The first stage involves the major part of the 
polymerization and occurs in the presence of the curing initiator at 
temperatures of 35.degree. C. to 150.degree. C. Curing or polymerization 
times of the first stage vary from about 5 hours to 50 hours. The second 
stage of the curing or polymerizing of ADC monomer compositions involves 
post-curing or annealing of the ADC resin for one to several hours at 
100.degree. C. to 170.degree. C. 
Levels of the novel poly(monoperoxycarbonate) compositions of Structure A 
about 1% to 6% or more, preferably 2% to 5%, more preferably 2.5% to 4% by 
weight of curable or polymerizable ADC monomer composition, are normally 
employed. 
The ADC resin compositions described above can be filled with various 
materials, such as antioxidants (AO's), heat, ultraviolet (UV) and light 
stabilizers, tints, photochromic additives and dyes. In addition, the ADC 
resin compositions can contain additives such as acrylic polymers and the 
anti-shrink, low molecular weight acrylic resins disclosed in U.S. Pat. 
No. 4,217,433 (to Pennwalt Corporation, Aug. 12, 1980). Such anti-shrink 
additives are employed to counter shrinkage that occurs when ADC monomer 
is polymerized. 
D. Curing of Elastomers and Crosslinking of Thermoplastic Polymers 
In the curing of elastomeric compositions, and the crosslinking of polymer 
compositions, by heating at suitable curing and crosslinking temperatures 
in the presence of free-radical curing and crosslinking agents, the novel 
and poly(monoperoxycarbonate) compositions of Structure A of this 
invention exhibit curing and crosslinking activities. 
Elastomeric resin compositions that can be cured by the novel 
poly(monoperoxycarbonate) compositions of this invention include 
elastomers such as ethylene-propylene copolymers (EPR), 
ethylene-propylene-diene terpolymers (EPDM), polybutadiene (PBD), silicone 
rubber (SR), nitrile rubber (NR), neoprene, fluoroelastomers and 
ethylene-vinyl acetate copolymer (EVA). 
Polymer compositions that can be cross-linked by the novel 
poly(monoperoxycarbonate) compositions of this invention include olefin 
thermoplastics such as chlorinated polyethylene (CPE), low density 
polyethylene (LDPE), linear-low density polyethylene (LLDPE), and high 
density polyethylene (HDPE). Other cross-linkable thermoplastic polymers 
include polyvinyl chloride (PVC), polystyrene, poly(vinyl acetate), 
polyacrylics, polyesters, polycarbonate, etc. 
Temperatures of about 80.degree. C. to 310.degree. C. and 
poly(monoperoxycarbonate) levels of about 0.1% to 10%, preferably 0.5% to 
5%, more preferably 0.5% to 3% based on weight of curable elastomeric 
resin composition or cross-linkable olefin polymer composition, are 
normally employed. 
The curable elastomeric resin composition or cross-linkable polymer 
composition can be optionally filled with the materials listed above for 
use with the conventional unsaturated polyester resin compositions. 
E. Modification of Polyolefins and Other Polymers 
In the processes for modifying polyolefins (e.g., beneficial degradation of 
polypropylene (PP) by reducing the polymer molecular weight and reducing 
the polymer molecular weight distribution of PP and enhancing the 
molecular weight and film forming properties of linear low density 
polyethylene (LLDPE)) and copolymers, the novel poly(monoperoxycarbonate) 
compositions of Structure A of this invention exhibit polyolefin 
modification activity. Other polymers that can be modified with tris- and 
poly(monoperoxy-carbonates) include high density PE (HDPE), 
ethylene-propylene copolymer, etc. 
Temperatures of about 140.degree. C. to 340.degree. C. and tris- and 
poly(monoperoxycarbonate) levels of about 0.001% to 1.0%, preferably 0.01% 
to 1.0%, more preferably 0.01% to 0.5% based on weight of modifiable 
polyolefins or copolymers are normally employed. Optionally, up to 1% by 
weight of molecular oxygen can be employed as a modification co-catalyst. 
Novel Poly(monoperoxycarbonate) Compositions of Structure A--Preparative 
and Utility Examples

The following examples further illustrate the best methods contemplated for 
practicing the instant invention, and are presented to provide detailed 
preparative and utility illustrations of the invention and are not 
intended to limit the breadth and scope of the invention. 
EXAMPLE 1 
Preparation of 1,1,1-Tris(t-butylperoxycarbonyloxymethyl)ethane, (I-1) 
##STR24## 
In this example the product was prepared in two synthetic steps. In the 
first step 1,1,1-tris(hydroxymethyl)ethane (0.15 mole) was reacted with 
excess phosgene (0.85 mole) in 175 mL of 1,4-dioxane at 
0.degree.-8.degree. C. 1,1,3,3-Tetramethylurea (0.4 g) was added to 
suppress cyclic carbonate formation. Upon completion of the reaction, the 
excess phosgene and the solvent were stripped from the product at 
15.degree.-30.degree. C. and reduced pressure to produce 
1,1,1-tris(chlorocarbonyloxymethyl)ethane, a liquid, having an assay of 
89.3% and in a corrected yield of 74.6%. 
In the second step, 1,1,1-tris(chlorocarbonyloxymethyl)ethane was reacted 
with t-butyl hydroperoxide, in the presence of aqueous potassium hydroxide 
and a surfactant, to yield the product as described below: 
A 300 mL water-jacketed reactor, equipped with a mechanical stirrer, a 
thermometer and an addition funnel, was charged with 70.0 g (0.25 mole) of 
20% aqueous potassium hydroxide solution, 25 g (0.25 mole) of 90.2% 
t-butyl hydroperoxide and 10 drops of TERGITOL.RTM. NP-10 a surfactant 
mixture containing poly(oxy-1,2-ethanediyl), 
.alpha.-(4-nonylphenyl)-.omega.-hydroxy-; CAS registry No., 26027-38-3, 
and poly(oxy-1,2-ethanediyl), .alpha.-hydro-.omega.-hydroxy-; CAS registry 
No., 25322-68-3; manufactured by Union Carbide! and the resulting solution 
was stirred at 25.degree. C. for 10 minutes. To the stirred mixture at 
22.degree.-29.degree. C. was slowly added 17.2 g (0.05 mole) of 89.3% 
1,1,1-tris(chlorocarbonyloxymethyl)ethane over a period of 25 minutes. 
After the addition was completed the reaction mass was stirred for 3 hours 
at 30.degree.-35.degree. C. after which 150 mL MTBE was added and the 
reaction mass was stirred one minute at 30.degree.-35.degree. C. The lower 
aqueous layer was then separated and the organic layer was cooled to 
17.degree. C. and was washed with 100 mL of aqueous 10% potassium 
hydroxide. The organic layer was then washed three times with 50 mL 
portions of aqueous 10% sodium hydrogen sulfite solution, then with 100 mL 
of 10% aqueous sodium hydroxide solution, and then with saturated aqueous 
sodium sulfate solution to a pH of 7-8. The product solution was dried 
over 5% by weight of anhydrous MgSO.sub.4, and, after separation of the 
spent desiccant by filtration, the solvent was removed in vacuo leaving 
7.4 g (31.6% of theory, uncorrected) of white solid, 
mp=55.degree.-60.degree. C. An infra red (IR) spectrum of the product 
showed a major monoperoxycarbonate carbonyl band at 1790 cm.sup.-1 and a 
major carbonate carbonyl band at about 1755 cm.sup.-1. There was no OH 
band in the IR spectrum. The product contained 9.42% active oxygen 
(theory, 10.25%) according to a peroxyester active oxygen method, 
therefore, the assay of the product was 91.9% and the corrected yield was 
29.1%. 
Based on the method of preparation, yield data, and IR spectral data the 
product obtained in this reaction was the desired title product. 
EXAMPLE 2 
Preparation of 1,1,1-Tris(t-butylperoxycarbonyloxymethyl)propane, (I-2) 
##STR25## 
In this example the product was prepared in two synthetic steps. In the 
first step 1,1,1-tris(hydroxymethyl)propane (0.10 mole) was reacted with 
excess phosgene (0.60 mole) in 200 mL of 1,4-dioxane at 
2.degree.-8.degree. C. 1,1,3,3-Tetramethylurea (0.3 g) was added to 
suppress cyclic carbonate formation. Upon completion of the reaction, the 
excess phosgene and the solvent were stripped from the product at 
20.degree.-30.degree. C. and reduced pressure to produce 
1,1,1-tris(chlorocarbonyloxymethyl)propane, a liquid, having an assay of 
87.7% and in a corrected yield of 95.6%. 
In the second step, 1,1,1-tris(chlorocarbonyloxymethyl)propane was reacted 
with t-butyl hydroperoxide, in the presence of aqueous potassium hydroxide 
and a surfactant, to yield the product as described below: 
A 300 mL water-jacketed reactor, equipped with a mechanical stirrer, a 
thermometer and an addition funnel, was charged with 56.0 g (0.20 mole) of 
20% aqueous potassium hydroxide solution and 19.5 g (0.20 mole) of 92% 
t-butyl hydroperoxide and the resulting solution was stirred at about 
25.degree. C. To the stirred mixture at 23.degree.-31.degree. C. was 
slowly added a solution of 18.3 g (0.05 mole) of 87.7% 
1,1,1-tris(chlorocarbonyloxymethyl)propane and 50 mL of MTBE over a period 
of 30 minutes. After the addition was completed the reaction mass was 
stirred for 3 hours at 30.degree.-32.degree. C. after which 50 mL MTBE was 
added and the reaction mass was stirred one minute at 
30.degree.-32.degree. C. The lower aqueous layer was then separated and 
the organic layer was cooled to 12.degree. C. and was washed with 50 mL of 
aqueous 10% sodium hydrogen sulfite solution. The resulting organic layer 
was then washed twice with 50 mL portions of 3% aqueous sodium hydrogen 
carbonate solution. The product solution was dried over 5% by weight of 
anhydrous MgSO.sub.4, and, after separation of the spent desiccant by 
filtration, the solvent was removed in vacuo leaving 10.8 g (44.8% of 
theory, uncorrected) of a clear, colorless liquid. An IR spectrum of the 
product showed a major monoperoxycarbonate carbonyl band at 1792 cm.sup.-1 
and a major carbonate carbonyl band at about 1767 cm.sup.-1. There was 
only a trace of an OH band in the IR spectrum. The product contained 8.65% 
active oxygen (theory, 9.95%) according to a peroxyester active oxygen 
method, therefore, the assay of the product was 86.9% and the corrected 
yield was 38.9%. 
Based on the method of preparation, yield data, and IR spectral data the 
product obtained in this reaction was the desired title product. 
EXAMPLE 3 
Preparation of Polycaprolactone Tris(mono-t-butylperoxycarbonate), I-3 
##STR26## 
(where the sum of x, y and z is about 2 and R.sup.3 is a triradical) 
In this example the product was prepared in two synthetic steps. In the 
first step 0.12 mole of a polycaprolactone triol (C-1), (TONE.RTM. 0301; 
molecular weight=300; manufactured by Union 
##STR27## 
(where the sum of x, y and z is about 2 and R.sup.3 is a triradical) 
Carbide Corp.), was reacted with excess phosgene (0.60 mole) at 
5.degree.-10.degree. C. Upon completion of the reaction, the excess 
phosgene was stripped from the product at 15.degree.-25.degree. C. and 
reduced pressure to produce a polycaprolactone tris(chloroformate), a 
light pink viscous liquid, having an assay of 91.0% and in a corrected 
yield of 84.2%. 
In the second step, the polycaprolactone tris(chloroformate) was reacted 
with t-butyl hydroperoxide, in the presence of aqueous potassium 
hydroxide, to yield the product as described below: 
A 250 ml water-jacketed reactor, equipped with a mechanical stirrer, a 
thermometer and an addition funnel, was charged with 28.0 g (0.10 mole) of 
20% aqueous potassium hydroxide solution, 12.9 g (0.10 mole) of aqueous 
70% t-butyl hydroperoxide and 3 drops (ca. 0.1 g) of TERGITOL.RTM. NP-10 
at 20.degree.-30.degree. C. The resulting solution was stirred at about 
25.degree. C. To the stirred solution at 23.degree.-29.degree. C. was 
slowly added 16.1 g (0.03 mole) of 91.0% polycaprolactone 
tris(chloroformate) over a period of 20 minutes. About 50 mL of MTBE was 
added in order to maintain good stirring. After the addition was completed 
the reaction mass was stirred for 3 hours at 30.degree. C. during which 
more MTBE (50-60 mL) was added. The reaction mass was then allowed to 
separate into liquid phases. The lower aqueous layer was then separated 
and the remaining organic layer was cooled to 15.degree. C. and was washed 
with 50 mL of aqueous 10% sodium hydrogen sulfite solution, then washed 
with 50 mL of aqueous 10% potassium hydroxide solution and with 50 mL 
portions of saturated aqueous sodium sulfate solution until the pH was 
7-8. The product solution was dried over 5% by weight of anhydrous 
MgSO.sub.4, and, after separation of the spent desiccant by filtration, 
the solvent was removed in vacuo leaving 19.6 g (ca. 100% of theory, 
uncorrected) of a colorless liquid. An IR spectrum of the product showed a 
major monoperoxycarbonate carbonyl band at 1785 cm.sup.-1 and a major 
carbonate or ester carbonyl band at about 1740 cm.sup.-1. There was no OH 
band in the IR spectrum. The product contained 6.69% active oxygen 
(theory, 7.40%) according to a peroxyester active oxygen method, 
therefore, the assay of the product was 90.4% and the corrected yield was 
91.3%. 
Based on the method of preparation, yield data, and IR spectral data the 
product obtained in this reaction was the desired title product. 
EXAMPLE 4 
Preparation of Polycaprolactone Tris(mono-t-butylperoxycarbonate), I-4 
##STR28## 
(where the sum of x, y and z is about 4 and R.sup.3 is a triradical) 
In this example the product was prepared in two synthetic steps. In the 
first step 0.05 mole of a polycaprolactone triol (C-2), (TONE.RTM. 0305; 
molecular weight=540; manufactured by Union 
##STR29## 
(where the sum of x, y and z is about 4 and R.sup.3 is a triradical) 
Carbide Corp.), was reacted with excess phosgene (0.45 mole) at 
3.degree.-7.degree. C. Upon completion of the reaction, the excess 
phosgene was stripped from the product at 15.degree.-25.degree. C. and 
reduced pressure to produce a polycaprolactone tris(chloroformate), a 
light pink liquid, having an assay of 97.9% and in a corrected yield of 
93.3%. 
In the second step, the polycaprolactone tris(chloroformate) was reacted 
with t-butyl hydroperoxide, in the presence of aqueous potassium 
hydroxide, to yield the product as described below: 
A 200 mL water-jacketed reactor, equipped with a mechanical stirrer, a 
thermometer and an addition funnel, was charged with 15.7 g (0.07 mole) of 
25% aqueous potassium hydroxide solution and 9.0 g (0.07 mole) of aqueous 
70% t-butyl hydroperoxide. The resulting solution was stirred at about 
25.degree. C. To the stirred solution at 24.degree.-28.degree. C. was 
slowly added 14.8 g (0.02 mole) of 97.9% polycaprolactone 
tris(chloroformate) over a period of 15 minutes. After the addition was 
completed the reaction mass was stirred for 3.5 hours at 
28.degree.-32.degree. C. after which 80 mL MTBE was added and the reaction 
mass was stirred one minute at 28.degree.-32.degree. C., then allowed to 
separate. The lower aqueous layer was then separated and the organic layer 
was cooled to 15.degree. C. and was washed with 25 mL of aqueous 10% 
sodium hydrogen sulfite solution. The resulting organic layer was then 
washed with 25 mL of aqueous 10% potassium hydroxide solution and with 50 
mL portions of saturated aqueous sodium sulfate solution until the pH was 
7-8. The product solution was dried over 5% by weight of anhydrous 
MgSO.sub.4, and, after separation of the spent desiccant by filtration, 
the solvent was removed in vacuo leaving 17.4 g (98% of theory, 
uncorrected) of a colorless liquid. An IR spectrum of the product showed a 
major monoperoxycarbonate carbonyl band at 1785 cm.sup.-1 and a major 
carbonate or ester carbonyl band at about 1730 cm.sup.-1. There was only a 
trace of an OH band in the IR spectrum. The product contained 5.00 % 
active oxygen (theory, 5.40%) according to a peroxyester active oxygen 
method, therefore, the assay of the product was 92.6% and the corrected 
yield was 90.7%. 
Based on the method of preparation, yield data, and IR spectral data the 
product obtained in this reaction was the desired title product. 
EXAMPLE 5 
Preparation of the 
1,1,1-Tris2-(t-butylperoxycarbonyloxy)ethoxymethyllpropane, I-5 
##STR30## 
In this example, the product (i.e., 
1,1,1-tris2-(t-butyl-peroxycarbonyloxy)ethoxymethyl!propane, I-5) was 
prepared in two synthetic steps. In the first step 0.15 mole of a 
polyether triol (i.e., 1,1,1-tris2-hydroxyethoxymethyl!propane, C-3), a 
commercial triol product (VORANOL.RTM. 234-630; molecular weight=267; 
##STR31## 
produced by Dow Chemical), was reacted with excess phosgene (0.65 mole) at 
3.degree.-7.degree. C. The reaction mixture was then stirred for 4 hours 
at 0.degree.-10.degree. C. and allowed to stand overnight at 
20.degree.-25.degree. C. The excess phosgene was then stripped from the 
product at 20.degree.-25.degree. C. and at reduced pressure for 5 hours to 
produce a polyether tris(chloroformate), a clear, viscous liquid, having 
an assay of 97.4% and in a corrected yield of 94.8%. 
In the second step, the polyether tris(chloroformate) was reacted with 
t-butyl hydroperoxide, in the presence of aqueous potassium hydroxide, to 
yield the product as described below: 
A 200 ml water-jacketed reactor, equipped with a mechanical stirrer, a 
thermometer and an addition funnel, was charged with 29.4 g (0.105 mole) 
of 20% aqueous potassium hydroxide solution, 13.5 g (0.105 mole) of 
aqueous 70% t-butyl hydroperoxide and 3 drops (ca. 0.1 g) of TERGITOL.RTM. 
NP-10 at 20.degree.-30.degree. C. The resulting solution was stirred at 
about 25.degree. C. To the stirred solution at 23.degree.-29.degree. C. 
was slowly added a solution consisting of 14.0 g (0.03 mole) of 97.4% 
polyether tris(chloroformate) and 20 ml of MTBE over a period of 15 
minutes. After the addition was completed the reaction mass was stirred 
for 2.5 hours at 30.degree. C. after which 80-90 ml MTBE was added and the 
reaction mass was stirred one minute at 30.degree. C., then allowed to 
separate into liquid phases. The lower aqueous layer was then separated 
and discarded. The organic layer was cooled to 15.degree. C. and was 
washed with 50 ml of aqueous 10% potassium hydroxide solution. The crude 
product solution was then washed with 50 ml of aqueous 10% sodium hydrogen 
sulfite solution. The resulting organic layer was then washed with 50 ml 
of saturated aqueous potassium hydrogen carbonate solution. The organic 
solution was then washed with 50 ml of saturated aqueous sodium sulfate 
solution to a pH of about 7. The product solution was dried over 5% by 
weight of anhydrous MgSO.sub.4, and, after separation of the spent 
desiccant by filtration, the solvent was removed in vacuo leaving 18.3 g 
(ca. 100% of theory, uncorrected) of a colorless liquid product. An IR 
spectrum of the product showed a major monoperoxycarbonate carbonyl band 
at 1785 cm.sup.-1 and a major carbonate band at about 1735 cm.sup.-1. 
There was no OH band in the IR spectrum. The product contained 7.52% 
active oxygen (theory, 7.81%) according to a peroxyester active oxygen 
method, therefore, the assay of the product was 94.2% and the corrected 
yield was 93.7%. 
Based on the method of preparation, yield data, and IR spectral data the 
product obtained in this reaction was the desired title product. 
EXAMPLE 6 
Preparation of Polycaprolactone Tetrakis(mono-t-butylperoxycarbonate), I-6 
##STR32## 
(where the sum of v, x, y and z is about 8 and R.sup.6 is a tetraradical) 
In this example the product was prepared in two synthetic steps. In the 
first step 0.03 mole of a polycaprolactone tetraol (C-4), an experimental 
caprolactone oligomeric tetraol (TONE.RTM. 4411; 
##STR33## 
(where the sum of v, x, y and z is about 8 and R.sup.6 is a tetraradical) 
molecular weight=1006; produced by Union Carbide Corp.), was reacted with 
excess phosgene (0.35 mole) at 3.degree.-7.degree. C. The reaction mixture 
was then stirred for 5 hours at 10.degree.-20.degree. C. and allowed to 
stand overnight at 20.degree.-25.degree. C. The excess phosgene was then 
stripped from the product at 20.degree.-25.degree. C. and at reduced 
pressure for 5 hours to produce a polycaprolactone 
tetrakis(chloroformate), a clear, viscous liquid, having an assay of 97.3% 
and in a corrected yield of 91.9%. 
In the second step, the polycaprolactone tetrakis(chloroformate) was 
reacted with t-butyl hydroperoxide, in the presence of aqueous potassium 
hydroxide, to yield the product as described below: 
A 200 ml water-jacketed reactor, equipped with a mechanical stirrer, a 
thermometer and an addition funnel, was charged with 11.2 g (0.05 mole) of 
25% aqueous potassium hydroxide solution and 6.4 g (0.05 mole) of aqueous 
70% t-butyl hydroperoxide at 20.degree.-30.degree. C. The resulting 
solution was stirred at about 25.degree. C. To the stirred solution at 
24.degree.-31.degree. C. was slowly added a solution consisting of 12.9 g 
(0.01 mole) of 97.3% polycaprolactone tetrakis(chloroformate) and 30 ml of 
MTBE over a period of 15 minutes. After the addition was completed the 
reaction mass was stirred for 3 hours at 30.degree.-35.degree. C. after 
which 70 ml MTBE was added and the reaction mass was stirred one minute at 
30.degree.-35.degree. C., then allowed to separate. The lower aqueous 
layer was then separated and the organic layer was cooled to 15.degree. C. 
and was washed with 50 ml of aqueous 10% potassium hydroxide solution. The 
crude product solution was then washed with 50 mL of aqueous 10% sodium 
hydrogen sulfite solution. The resulting organic layer was then washed 
with aqueous 10% potassium hydrogen carbonate solution to a pH of about 7. 
The product solution was dried over 5% by weight of anhydrous MgSO.sub.4, 
and, after separation of the spent desiccant by filtration, the solvent 
was removed in vacuo leaving 14.9 g (ca. 100% of theory, uncorrected) of a 
viscous, colorless liquid. An IR spectrum of the product showed a major 
monoperoxycarbonate carbonyl band at 1785 cm.sup.-1 and a major carbonate 
or ester carbonyl band at about 1730 cm.sup.-1 There was no OH band in the 
IR spectrum. The product contained 3.73% active oxygen (theory, 4.35%) 
according to a peroxyester active oxygen method, therefore, the assay of 
the product was 85.7% and the corrected yield was 86.9%. 
Based on the method of preparation, yield data, and IR spectral data the 
product obtained in this reaction was the desired title product. 
EXAMPLE 7 
Preparation of Polyether Tetrakis(mono-t-butylperoxycarbonate), I-7 
##STR34## 
(Where the sum of q, r, s and t is about 6-7) 
In this example the product was prepared in two synthetic steps. In the 
first step 0.075 mole of polyether tetraol (C-5), 
##STR35## 
(Where the sum of q, r, s and t is about 6-7) (PLURACOL.RTM. PeP 550; 
molecular weight=500; manufactured by BASF Corporation), was reacted with 
excess phosgene (0.60 mole) at 3.degree.-7.degree. C. The reaction mixture 
was then stirred for 2-3 hours at 10.degree.-20.degree. C. and allowed to 
stand overnight at 20.degree.-25.degree. C. The excess phosgene was then 
stripped from the product at 20.degree.-30.degree. C. and at reduced 
pressure to produce a polyether tetrakis(chloroformate), a clear liquid, 
having an assay of 100% and in a corrected yield of 97.4%. 
In the second step, the polyether tetrakis(chloroformate) was reacted with 
t-butyl hydroperoxide, in the presence of aqueous potassium hydroxide, to 
yield the product as described below: 
A 250 ml water-jacketed reactor, equipped with a mechanical stirrer, a 
thermometer and an addition funnel, was charged with 29.2 g (0.13 mole) of 
25% aqueous potassium hydroxide solution and 16.7 g (0.13 mole) of aqueous 
70% t-butyl hydroperoxide at 22.degree.-29.degree. C. The resulting 
solution was stirred at about 25.degree. C. To the stirred solution at 
23.degree.-28.degree. C. was slowly added 18.8 g (0.025 mole) of 100% 
polyether tetrakis(chloroformate) over a period of 15 minutes. After the 
addition was completed the reaction mass was stirred for 3 hours at 
25.degree.-30.degree. C. after which 100 ml MTBE was added and the 
reaction mass was stirred one minute at about 30.degree. C., then allowed 
to separate into liquid phases. The lower aqueous layer was then separated 
and the remaining organic layer was cooled to 12.degree. C. and was washed 
with 50 ml of aqueous 10% sodium hydrogen sulfite solution, then washed 
with 50 ml of aqueous 10% potassium hydroxide solution and with 50 ml 
portions of saturated aqueous sodium sulfate solution until the pH was 
7-8. The product solution was dried over 5% by weight of anhydrous 
MgSO.sub.4, and, after separation of the spent desiccant by filtration, 
the solvent was removed in vacuo leaving 22.4 g (92.9% of theory, 
uncorrected) of a colorless liquid. An IR spectrum of the product showed a 
major monoperoxycarbonate carbonyl band at 1785 cm.sup.-1 and a major 
carbonate or ester carbonyl band at about 1752 cm.sup.-1. There was only a 
trace of an OH band in the IR spectrum. The product contained 6.16% active 
oxygen (theory, 6.64%) according to a peroxyester active oxygen method, 
therefore, the assay of the product was 92.8% and the corrected yield was 
86.3%. 
Based on the method of preparation, yield data, and IR spectral data the 
product obtained in this reaction was the desired title product. 
EXAMPLE 8 
Preparation of a Polycaprolactone Bis(mono-t-butylperoxycarbonate), A-1 
##STR36## 
(where the sum of x and y is about 4 and R.sup.z is a diradical) 
In this example the product was prepared in two synthetic steps. In the 
first step 0.03 mole of a polycaprolactone diol (C-6) (TONE.RTM. 0200 
diol; molecular weight=530; manufactured by 
##STR37## 
(where the sum of x and y is about 4 and R.sup.z is a diradical) Union 
Carbide Corp.), was reacted with excess phosgene by the 
previously-described process. Obtained was polycaprolactone 
bis(chloroformate), a pink, viscous liquid, having an assay of 100%. 
In the second step, the polycaprolactone bis(chloroformate) was reacted 
with t-butyl hydroperoxide, in the presence of aqueous potassium 
hydroxide, to yield the product as described below: 
A 400 mL water-jacketed reactor, equipped with a mechanical stirrer, a 
thermometer and an addition funnel, was charged with 14.9 g (0.12 mole) of 
45% aqueous potassium hydroxide solution, 10.0 g of water and 14.1 g (0.11 
mole) of aqueous 70% t-butyl hydroperoxide at 20.degree.-30.degree. C. The 
resulting solution was stirred at about 25.degree. C. To the stirred 
solution at 23.degree.-31.degree. C. was slowly added 32.7 g (0.05 mole) 
of 100% polycaprolactone bis(chloroformate) over a period of about 25 
minutes. After the addition was completed 75 mL of MTBE was added and the 
reaction mass was stirred for about 2 hours at 30.degree..+-.2.degree. C. 
after which 125 mL of additional MTBE was added and the reaction mass was 
stirred one minute at 30.degree. C., then allowed to separate into liquid 
phases. The lower aqueous layer was then separated and discarded. The 
organic layer was cooled to 15.degree. C. and was washed with 50 mL of 
aqueous 10% sodium hydrogen sulfite solution at 15.degree.-25.degree. C. 
Separation of the resulting mass into two liquid phases was very slow. 
Addition of sodium sulfate enhanced the rate of separation into phases. 
The lower aqueous phase was removed and discarded. The upper organic 
solution was then washed twice with 50 mL portions of aqueous 20% 
potassium hydroxide solution at 20.degree.-30.degree. C. The resulting 
organic layer was then washed with saturated aqueous sodium sulfate 
solution to a pH of about 7. The organic product solution was then dried 
over 5% by weight of anhydrous MgSO.sub.4, and, after separation of the 
spent desiccant by filtration, the solvent was removed in vacuo leaving 
33.8 g (ca. 89% of theory, uncorrected) of a viscous, colorless liquid. An 
IR spectrum of the product showed a major monoperoxycarbonate carbonyl 
band at 1785 cm.sup.-1 and a major carbonate or ester carbonyl band at 
about 1731 cm.sup.-1. There was no OH band in the IR spectrum. The product 
contained 3.97% active oxygen (theory, 4.20%) according to a peroxyester 
active oxygen method, therefore, the assay of the product was 94.5% and 
the corrected yield was 84.1%. 
Based on the method of preparation, yield data, and IR spectral data the 
product obtained in this reaction was the desired title product. 
EXAMPLE 9 
Preparation of the 
1,1,1-Tris2-(t-amylperoxycarbonyloxy)ethoxymethyl!propane, I-8 
##STR38## 
In this example, the product (i.e., 
1,1,1-tris2-(t-amylperoxycarbonyloxy)ethoxymethyl!propane, I-8) was 
prepared by reacting the polyether tris(chloroformate) of VORANOL.RTM. 
234-630 (Example 5), t-amyl hydroperoxide and aqueous potassium hydroxide, 
as described below: 
A 200 mL water-jacketed reactor, equipped with a mechanical stirrer, a 
thermometer and an addition funnel, was charged with 19.6 g (0.070 mole) 
of 20% aqueous potassium hydroxide solution, 8.0 g (0.070 mole) of 91% 
t-amyl hydroperoxide and 3 drops (ca. 0.1 g) of TERGITOL.RTM. NP-10 at 
about 20.degree.-25.degree. C. The resulting solution was stirred at about 
25.degree. C. To the stirred solution at 24.degree.-32.degree. C. was 
slowly added 9.3 g (0.020 mole) of 98.7% polyether tris(chloroformate) 
(from VORANOL.RTM. 234-630) over a period of 15 minutes. During the 
addition, 50 mL of MTBE was added. The reaction mass was then stirred for 
3.0 hours at about 30.degree. C. At the end of the reaction period, an 
additional 50 mL of MTBE was added and, after stirring for an additional 2 
minutes, the reaction mass was allowed to separate into liquid phases. The 
lower aqueous layer was then separated and discarded. The organic layer 
was cooled to 20.degree. C. and was washed with 50 mL of aqueous 20% 
potassium hydroxide solution. The crude product solution was then washed 
with 50 mL of aqueous 15% sodium hydrogen sulfite solution. The resulting 
organic layer was then washed with saturated aqueous sodium hydrogen 
carbonate solution to a pH of about 7. The product solution was dried over 
5% by weight of anhydrous MgSO.sub.4, and, after separation of the spent 
desiccant by filtration, the solvent was removed in vacuo leaving 10.8 g 
(ca. 82.2% of theory, uncorrected) of a colorless liquid product. An IR 
spectrum of the product showed a major monoperoxycarbonate carbonyl band 
at 1785 cm.sup.-1 and a major carbonate band at about 1753 cm.sup.-1. 
There was a small OH band in the IR spectrum. The product contained 7.52% 
active oxygen (theory, 7.31%) according to a peroxyester active oxygen 
method, therefore, the assay of the product was 79.9% and the corrected 
yield was 65.7%. 
Based on the method of preparation, yield data, and IR spectral data the 
product obtained in this reaction was the desired title product. 
EXAMPLE 10 
Preparation of Polyether Tetrakis(mono-t-amylperoxycarbonate), I-9 
##STR39## 
(Where the sum of q, r, s and t is about 6-7) 
In this example the product was prepared in two synthetic steps. In the 
first step polyether tetraol (C-5), (PLURACOL.RTM. PeP 550), was reacted 
with excess phosgene to produce a polyether tetrakis(chloroformate) of 
Example 7. 
In the second step, the polyether tetrakis(chloroformate) was reacted with 
t-amyl hydroperoxide, in the presence of aqueous potassium hydroxide, to 
yield the product as described below: 
A 250 mL water-jacketed reactor, equipped with a mechanical stirrer, a 
thermometer and an addition funnel, was charged with 28.1 g (0.10 mole) of 
20% aqueous potassium hydroxide solution, 10.1 g (0.09 mole) of 92.6% 
t-amyl hydroperoxide and 2 drops (ca. 0.1 g) of ALIQUAT.RTM. 336 
(tricaprylylmethylammonium chloride, manufactured by Henkel Corporation) 
and the resulting solution was stirred at about 25.degree. C. To the 
stirred solution at 43.degree.-45.degree. C. was slowly added 15.2 g 
(0.020 mole) of 100% polyether tetrakis(chloroformate) over a period of 10 
minutes. After the addition was completed the reaction mass was stirred 
for 5 hours at about 35.degree.-40.degree. C. after which 75 mL MTBE was 
added, the reaction mass was cooled to 25.degree. C., stirred one minute, 
then allowed to separate into liquid phases. The lower aqueous layer was 
then separated and the remaining organic layer was washed with 50 mL of 
aqueous 20% potassium hydroxide solution, then with 50 g of aqueous 
buffered sodium sulfite solution (made by dissolving 1.2 g of acetic acid, 
2.5 g of sodium acetate and 4.3 g of sodium sulfite in 42.0 g of water). 
The aqueous layer was discarded and the organic layer was washed with 100 
g of saturated sodium chloride solution. The product solution was dried 
over 5% by weight of anhydrous MgSO.sub.4, and, after separation of the 
spent desiccant by filtration, the solvent was removed in vacuo leaving 
18.0 g (88.2% of theory, uncorrected) of a colorless liquid. The product 
contained 5.56% active oxygen (theory, 6.27%) according to a peroxyester 
active oxygen method, therefore, the assay of the product was 88.7% and 
the corrected yield was 80.0%. 
Based on the method of preparation, yield data, the product obtained in 
this reaction was the desired title product. 
EXAMPLE 11 
Preparation of Polyether Tris(mono-t-butylperoxycarbonate), I-10. from 
PLURACOL.RTM. TP-740 
##STR40## 
(Where the sum of r, s and t is about 6-7) 
In this example the product was prepared in two synthetic steps. In the 
first step 0.06 mole of polyether triol (C-7), 
##STR41## 
(Where the sum r, s and t is about 10-11) (PLURACOL.RTM. TP-740; molecular 
weight=730; manufactured by BASF Corporation), was reacted with excess 
phosgene (0.28 mole) at 3.degree.-7.degree. C. The reaction mixture was 
then stirred for 2-3 hours at 10.degree.-20.degree. C. and allowed to 
stand overnight at 20.degree.-25.degree. C. The excess phosgene was then 
stripped from the product at 20.degree.-30.degree. C. and at reduced 
pressure to produce polyether tris(chloroformate) A, a clear liquid, 
having an assay of 100% and in a corrected yield of 93.8%. 
In the second step, polyether tris(chloroformate) A was reacted with 
t-butyl hydroperoxide, in the presence of aqueous potassium hydroxide, to 
yield the product as described below: 
A 250 mL water-jacketed reactor, equipped with a mechanical stirrer, a 
thermometer and an addition funnel, was charged with 19.6 g (0.07 mole) of 
25% aqueous potassium hydroxide solution and 9.0 g (0.07 mole) of aqueous 
70% t-butyl hydroperoxide at 22.degree.-29.degree. C. The resulting 
solution was stirred at about 25.degree. C. To the stirred solution at 
33.degree.-40.degree. C. was slowly added 18.3 g (0.02 mole) of 100% 
polyether tris(chloroformate) A over a period of 15 minutes. After the 
addition was completed the reaction mass was stirred for 1.5 hours at 
40.degree. C. after which 17 g of ethylbenzene (EB) was added and the 
reaction mass was stirred two minutes at about 30.degree. C., then allowed 
to separate into liquid phases. The lower aqueous layer was then separated 
and the remaining organic layer was cooled to 25.degree. C. and was washed 
with 50 g of aqueous 20% potassium hydroxide solution, then washed with 50 
g of aqueous buffered sodium sulfite solution (made by dissolving 1.2 g of 
acetic acid, 2.5 g of sodium acetate and 4.3 g of sodium sulfite in 42.0 g 
of water) and with 50 g of saturated sodium chloride solution. The product 
solution was dried over 1.7 g of anhydrous MgSO.sub.4, and, after 
separation of the spent desiccant by filtration, 35.7 g of a colorless 
liquid was obtained. The product solution contained 2.49% active oxygen 
(theory, 4.45%) according to a peroxyester active oxygen method, 
therefore, the assay of the product was 55.96% and the corrected yield was 
92.4%. 
Based on the method of preparation and yield data the product obtained in 
this reaction was the desired title product as a 55.9% solution in EB. 
EXAMPLE 12 
Preparation of Polyether Tris(mono-t-butylperoxycarbonate), I-11, from 
PLURACOL.RTM. GP-730 
##STR42## 
(Where the sum of r, s and t is about 10-11) 
In this example the product was prepared in two synthetic steps. In the 
first step 0.05 mole of polyether triol (C-8), 
##STR43## 
(Where the sum of q, r, s and t is about 10-11) (PLURACOL.RTM. GP-730; 
molecular weight=730; manufactured by BASF Corporation), was reacted with 
excess phosgene (0.40 mole) at 3.degree.-7.degree. C. The reaction mixture 
was then stirred for 2-3 hours at 10.degree.-20.degree. C. and allowed to 
stand overnight at 20.degree.-25.degree. C. The excess phosgene was then 
stripped from the product at 20.degree.-30.degree. C. and at reduced 
pressure to produce polyether tris(chloroformate) B, a clear liquid, 
having an assay of 100% and in a corrected yield of 96.3%. 
In the second step, polyether tris(chloroformate) B was reacted with 
t-butyl hydroperoxide, in the presence of aqueous potassium hydroxide, to 
yield the product as described below: 
A 250 mL water-jacketed reactor, equipped with a mechanical stirrer, a 
thermometer and an addition funnel, was charged with 19.6 g (0.07 mole) of 
25% aqueous potassium hydroxide solution and 9.0 g (0.07 mole) of aqueous 
70% t-butyl hydroperoxide at 22.degree.-29.degree. C. The resulting 
solution was stirred at about 25.degree. C. To the stirred solution at 
23.degree.-28.degree. C. was slowly added 18.3 g (0.02 mole) of 100% 
polyether tris(chloroformate) B over a period of 15 minutes. After the 
addition was completed the reaction mass was stirred for 3 hours at 
25.degree.-30.degree. C. after which 100 mL MTBE was added and the 
reaction mass was stirred one minute at about 30.degree. C., then allowed 
to separate into liquid phases. The lower aqueous layer was then separated 
and the remaining organic layer was cooled to 12.degree. C. and was washed 
with 50 mL of aqueous 10% sodium hydrogen sulfite solution, then washed 
with 50 mL of aqueous 10% potassium hydroxide solution and with 50 mL 
portions of saturated aqueous sodium sulfate solution until the pH was 
7-8. The product solution was dried over 5% by weight of anhydrous 
MgSO.sub.4, and, after separation of the spent desiccant by filtration, 
the solvent was removed in vacuo leaving 20.3 g (94% of theory, 
uncorrected) of a colorless liquid. The product contained 4.23% active 
oxygen (theory, 4.45%) according to a peroxyester active oxygen method, 
therefore, the assay of the product was 95.1% and the corrected yield was 
89.3%. 
Based on the method of preparation and yield data, the product obtained in 
this reaction was the desired title product. 
EXAMPLE 13 
Preparation of 
1,5-Bis(1,1,4-trimethyl-4-(t-butylperoxy)pentylperoxycarbonyloxy)-3-oxapen 
tane, I-12 
##STR44## 
In this example the product was prepared by reacting diethylene glycol 
bis(chloroformate) (C-9) with 
##STR45## 
1,1,4-trimethyl-4-(t-butylperoxy)pentyl hydroperoxide (C-10) 
##STR46## 
and aqueous potassium hydroxide, to yield the product as described below: 
A 250 mL water-jacketed reactor, equipped with a mechanical stirrer, a 
thermometer and an addition funnel, was charged with 8.0 g (0.05 mole) of 
25% aqueous sodium hydroxide solution and 11.0 g (0.043 mole) of 91% 
1,1,4-trimethyl-4-(t-butylperoxy)pentyl hydroperoxide at 
22.degree.-29.degree. C. The resulting solution was stirred at about 
25.degree. C. To the stirred solution at 23.degree.-28.degree. C. was 
slowly added 5.8 g (0.025 mole) of 99% diethylene glycol 
bis(chloroformate) (C-9) over a period of 15 minutes. After the addition 
was completed the reaction mass was stirred for 3.5 hours at 
30.degree.-35.degree. C. after which 50 mL MTBE was added and the reaction 
mass was stirred one minute at about 30.degree. C., then allowed to 
separate into liquid phases. The lower aqueous layer was then separated 
and the remaining organic layer was cooled to 17.degree. C. and was washed 
with 50 mL of aqueous 10% sodium hydrogen sulfite solution, then washed 
with 50 mL of aqueous 20% sodium hydroxide solution and with 50 mL 
portions of saturated aqueous sodium sulfate solution until the pH was 
7-8. The product solution was dried over 5% by weight of anhydrous 
MgSO.sub.4, and, after separation of the spent desiccant by filtration, 
the solvent was removed in vacuo leaving 14.7 g (88.6% of theory, 
uncorrected) of a colorless liquid. An IR spectrum of the product showed a 
major monoperoxycarbonate carbonyl band at 1785 cm.sup.-1 and a major 
carbonate or ester carbonyl band at about 1752 cm .sup.1. There was only a 
trace of an OH band in the IR spectrum. The product contained 4.48% active 
oxygen (theory, 5.10%) according to a peroxyester active oxygen method, 
therefore, the assay of the product was 87.0% and the corrected yield was 
77.0%. 
Based on the method of preparation, yield data, and IR spectral data the 
product obtained in this reaction was the desired title product. 
EXAMPLE 14 
280.degree. F. (138.degree. C.) SPI Exotherm Data for Polycaprolactone 
Tris(mono-t-butylperoxycarbonate), I-4 
The unsaturated polyester resin composition employed in this example was a 
mixture of an unsaturated polyester and styrene monomer. The unsaturated 
polyester was an alkyd resin made by esterifying the following components: 
______________________________________ 
COMPONENT QUANTITY (MOLES) 
______________________________________ 
Maleic Anhydride 
1.0 
Phthalic Anhydride 
1.0 
Propylene Glycol 
2.2 
______________________________________ 
0.013% by weight of hydroquinone inhibitor was added to the resulting 
resin. The alkyd resin had an Acid No. of 45-50. Seven (7) parts by weight 
of the above unsaturated polyester alkyd resin were diluted with three (3) 
parts by weight of styrene monomer. The resulting unsaturated polyester 
resin composition had the following properties: 
Viscosity (Brookfield No. 2 at 20 r.p.m.)--13.0 poise 
Specific Gravity--1.14 
Gelation and cure characteristics of t-butyl peroxybenzoate (A-2), (a 
commercial peroxide product used to cure unsaturated polyester resin 
compositions), and polycaprolactone tris(mono-t-butylperoxycarbonate), 
I-4, a novel poly(monoperoxycarbonate) composition of the instant 
invention, were determined using the Standard SPI Exotherm Procedure 
(Suggested SPI Procedure for Running Exotherm Curves-Polyester Resins, 
published in the Preprint of the 24th Annual Technical 
Conference--Reinforced Plastics/Composites Division, Society of the 
Plastics Industry, Inc., 1969). Using this procedure at 28.degree. F. 
(138.degree. C.), A-2 and I-4 were comparatively evaluated. The amount of 
I-4 employed was equivalent in active oxygen content to 1.0 g of pure A-2 
per 100 g of unsaturated polyester resin. The results of this 
investigation are given in Example 14 Table and showed that I-4 gelled and 
cured the resin much more rapidly than A-2, hence, I-4 was more active in 
curing the unsaturated polyester resin than was the commercial peroxide 
catalyst A-2. 
______________________________________ 
EXAMPLE 14 TABLE 
280.degree. F. (138.degree. C.) SPI EXOTHERM DATA 
CURING G/100 G GEL, CURE, PEAK BARCOL 
AGENT RESIN MINS. MINS. EXO, .degree.F. 
HARDNESS 
______________________________________ 
I-4 1.64 0.9 1.85 428 35-40 
A-2 1.0 1.3 2.0 443 40-45 
______________________________________ 
EXAMPLE 15 
Enhanced Polymerizations of Styrene Employing Novel Tris- and 
Poly(monoperoxycarbonate) Compositions as Free-Radical Initiators 
Styrene polymerizations were carried out using a monomer solution 
containing 95% styrene and 5% ethylbenzene (EB). 
Initiators employed were 1,1-di(t-butylperoxy)cyclohexane (A-3), i.e., 
Lupersol 331 (manufactured by Elf Atochem North America, Inc.; the 
commercial initiator used currently to produce high molecular weight 
polystyrene at enhanced polymerization rates), 
1,5-bis(t-butylperoxycarbonyloxy)-5-oxapentane (A-4; a 
bis(monoperoxycarbonate) composition of the art; U.S. Pat. No. 3,652,631), 
polycaprolactone bis(mono-t-butylperoxycarbonate) (A-1) (a 
bis(monoperoxycarbonate) composition of the art; U.S. Pat. No. 5,314,970) 
and several poly(monoperoxycarbonate) compositions of the instant 
invention, i.e., 1,1,1-tris(t-butylperoxycarbonyloxymethyl)ethane (I-1), 
1,1,1-tris(t-butylperoxycarbonyloxymethyl)propane (I-2), polycaprolactone 
tris(mono-t-butylperoxycarbonate) (I-3), polycaprolactone 
tris(mono-t-butylperoxycarbonate) (I-4), 
1,1,1-tris2-(t-butyl-peroxycarbonyloxy)ethoxymethyl!propane (I-5) and 
polycaprolactone tetrakis(mono-t-butylperoxycarbonate) (I-6). 
Preparation of Styrene/Initiator Solutions 
To solutions of 95% styrene and 5% ethylbenzene at room temperature were 
added levels of free-radical initiators equal to 0.00277 mole of active 
oxygen per 1000 g of styrene solution (or 0.00252 mole of active oxygen 
per liter of styrene solution). The resulting styrene solutions were 
purged with nitrogen prior to being sealed in glass ampules (10 mm O.D., 8 
mm I.D.). 
Styrene Polymerization Procedure 
Ampules containing the styrene solutions (several for each solution) were 
immersed in a circulating oil bath in which the temperature was regulated 
through a temperature programmer unit. Samples were subjected to a 
100.degree. C. to 151.degree. C. linear temperature ramp, at a programmed 
rate of 0.17.degree. C./minute (5-hour program). Samples of each solution 
were withdrawn from the bath at 1-hour intervals during the 5-hour program 
and cooled by immersion in an ice-water bath. The styrene solutions were 
then removed from the ampules and analyzed for polystyrene weight average 
molecular weight (M.sub.w) and residual styrene monomer content. 
Results 
The performances of tris(mono-t-butylperoxycarbonates) I-1, I-2, I-3, I-4, 
and I-5 tetrakis(mono-t-butylperoxycarbonate) I-6 were compared to art 
compositions A-1, A-3 and A-4 according to the above-described 
methodology. The results obtained are summarized 5 Table: 
______________________________________ 
EXAMPLE 15 TABLE - STYRENE POLYMERIZATIONS 
Polystyrene 
Initiator Weight Ave. 
Residual 
(Level, Polym. Molecular Styrene 
ppm)* Time, hours Weight, M.sub.w 
Monomer, % 
______________________________________ 
A-3 1 244,000 82.8 
(361) 2 245,000 65.0 
3 285,000 42.3 
4 293,000 26.9 
5 278,000 17.8 
A-4 1 285,000 83.2 
(469) 2 274,000 67.8 
3 294,000 43.8 
4 307,000 18.9 
5 297,000 12.0 
A-1 3 294,000 39.2 
(1062) 5 288,000 10.6 
I-1 1 298,000 85.1 
(433) 2 306,000 68.9 
3 356,000 43.1 
4 371,000 20.6 
5 348,000 12.1 
______________________________________ 
______________________________________ 
EXAMPLE 15 TABLE - STYRENE POLYMERIZATIONS 
Polystyrene 
Initiator Weight Ave. 
Residual 
(Level, Polym. Molecular Styrene 
ppm)* Time, hours Weight, M.sub.w 
Monomer, % 
______________________________________ 
I-2 1 274,000 84.6 
(446) 2 291,000 68.6 
3 335,000 42.0 
4 343,000 19.0 
5 339,000 11.5 
I-3 3 357,000 41.8 
(599) 5 356,000 10.1 
I-4 1 303,000 80.6 
(821) 2 304,000 69.7 
3 362,000 39.0 
4 390,000 16.4 
5 374,000 10.1 
I-5 3 354,000 40.5 
(568) 5 347,000 10.4 
I-6 1 240,000 81.8 
(1019) 2 245,000 61.1 
3 306,000 27.3 
4 339,000 9.7 
5 331,000 5.0 
______________________________________ 
*Parts per million parts of styrene solution. 
Based on polystyrene weight average weight (M.sub.w) results, use of the 
tris- and poly(monoperoxycarbonate) compositions of the instant invention 
i.e. I-1, I-2, I-3, I-4, I-5, and I-6, as styrene polymerization 
initiators resulted in significantly higher M.sub.w values (330,000 to 
375,000) after the 5-hour polymerization program than were obtained with 
art compositions A-1 (M.sub.w, ca. 290,000), A-3 (M.sub.w, ca. 280,000) 
and A-4 (M.sub.w, ca. 300,000). A-1 (a bis(monoperoxycarbonate) 
composition of the art) was considerably less effective in enhancing the 
molecular weight of polystyrene (maximum M.sub.w was ca. 290,000) than 
were the tris- and poly(monoperoxycarbonate) compositions of the instant 
invention (M.sub.w ca. 330,000 to 375,000). Thus, the tris- and 
poly(monoperoxycarbonate) compositions of the instant invention 
significantly advance the art of polymerizing ethylenically unsaturated 
monomers such as styrene. 
EXAMPLE 16 
Enhanced Polymerizations of Styrene Employing Novel Tris- and 
Poly(monoperoxycarbonate) Compositions as Free-Radical Initiators 
Styrene polymerizations were carried out using the procedure outlined in 
Example 15. Evaluated as free-radical initiators compared to 
1,1-di(t-butylperoxy)cyclohexane (A-3) were several additional 
poly(monoperoxycarbonates) of Structure A: polyether 
tetrakis(mono-t-butylperoxycarbonate) (I-7), polyether 
tetrakis(mono-t-amylperoxycarbonate) (I-9), polyether 
tris(mono-t-butylperoxycarbonate) (I-10) from PLURACOL.RTM. TP-740, 
polyether tris(mono-t-butylperoxycarbonate) (I-11) from PLURACOL.RTM. 
GP-730 and 
1,5-bis(1,1,4-trimethyl-4-(t-butylperoxy)pentylperoxycarbonyloxy)-3-oxapen 
tane (I-12). The levels of free-radical initiators employed in this example 
were equal to 0.00277 mole of active oxygen per 1000 g of styrene solution 
(or 0.00252 mole of active oxygen per liter of styrene solution). 
Styrene Polymerization Procedure 
Ampules containing the styrene solutions (several for each solution) were 
immersed in a circulating oil bath in which the temperature was regulated 
through a temperature programmer unit. Samples were subjected to a 
100.degree. C. to 151.degree. C. linear temperature ramp, at a programmed 
rate of 0.17.degree. C./minute (5-hour program). Samples of each solution 
were withdrawn from the bath at 1-hour intervals during the 5-hour program 
and cooled by immersion in an ice-water bath. The styrene solutions were 
then removed from the ampules and analyzed for polystyrene weight-average 
molecule weight (M.sub.w) and residual styrene monomer content. 
Results 
The performances of poly(monoperoxycarbonates) I-7, I-9, I-10, I-11, and 
I-12 were compared to art composition A-3 according to the above-described 
methodology. The results obtained are summarized below in Example 16 
Table: 
______________________________________ 
EXAMPLE 15 TABLE - STYRENE POLYMERIZATIONS 
Polystyrene 
Initiator Weight Ave. 
Residual 
(Level, Polym. Molecular Styrene 
ppm)* Time, hours Weight, M.sub.w 
Monomer, % 
______________________________________ 
A-3 1 244,000 82.8 
(361) 2 245,000 65.0 
3 285,000 42.3 
4 293,000 26.9 
5 278,000 17.8 
I-7 3 400,000 37.5 
(669) 5 391,000 10.3 
I-9 1 254,000 80.1 
(707) 3 368,000 31.8 
4 354,000 17.3 
5 341,000 10.5 
I-10 1 262,000 82.8 
(997) 2 270,000 67.6 
3 322,000 32.3 
4 328,000 14.9 
5 318,000 9.0 
I-11 1 259,000 89.4 
(997) 2 273,000 71.5 
3 317,000 35.4 
4 332,000 15.6 
5 318,000 9.4 
I-12 3 304,000 50.3 
(435) 5 297,000 5.5 
______________________________________ 
Based on polystyrene weight-average molecular weight (M.sub.w) results, use 
of the poly(monoperoxycarbonate) compositions of the instant invention, 
i.e., I-7, I-9, I-10, I-11 and I-12, as styrene polymerization initiators 
resulted in significantly higher M.sub.w values (ca. 300,000 to 390,000) 
after the 5-hour polymerization program than were obtained with art A-3 
(M.sub.w, ca. 280,000). In addition, at the end of 5 hours, the residual 
styrene levels for styrenes produced by the novel 
poly(monoperoxycarbonate) compositions of the instant invention were 
significantly lower than the polystyrene produced by A-3 (5-10% residual 
styrene versus 17-18% residual styrene). I-12 was especially attractive in 
this respect. These results show that the poly(monoperoxycarbonate) 
compositions of the instant invention significantly advance the art of 
polymerizing ethylenically unsaturated monomers such as styrene. 
EXAMPLE 17 
Enhanced Polymerizations of Styrene Employing Poly(monoperoxycarbonate) 
Compositions in Combination with 1,1-di(t-butylperoxy)cyclohexane (A-3) 
Styrene polymerizations were carried out using a monomer solution 
containing 95% styrene and 5% ethylbenzene (EB). The polymerization 
methodology employed in this example was a modification of the procedure 
outlined in Example 15. In this example, combinations of two free-radical 
initiators were employed in which one of the initiators of the combination 
was a novel poly(monoperoxycarbonate) of the instant invention i.e., 
1,1,1-tris2-(t-butyl-peroxycarbonyloxy)ethoxymethyl!propane (I-5) or 
polyether tetrakis(mono-t-butylperoxycarbonate) (I-7). The second 
initiator of the initiator combinations was 
1,1-di(t-butylperoxy)cyclohexane (A-3), an art composition. 
Preparation of Styrene/Initiator Solutions 
The levels of the combinations of free-radical initiators employed in this 
example were equal to a total of 0.00230 mole of active oxygen per 1000 g 
of styrene solution (or 0.00209 mole of active oxygen per liter of styrene 
solution). 
Styrene Polymerization Procedure 
Ampules containing the styrene solutions (several for each solution) were 
immersed in a circulating oil bath in which the temperature was regulated 
through a temperature programmer unit. Samples were subjected to a 
100.degree. C. to 145.6.degree. C. linear temperature ramp, at a 
programmed rate of 0.19.degree. C./minute (4-hour program). At the end of 
the 4-hour period the samples were withdrawn from the bath and cooled by 
immersion in an ice-water bath. The styrene solutions were then removed 
from the ampules and analyzed for polystyrene weight-average molecular 
weight (M.sub.w). 
Results 
Example 17 Table summarizes the polystyrene weight average molecular 
weights that were obtained when Initiator Combination A (I-5 and A-3) and 
Initiator Combination B (I-7 and A-3) were employed as free-radical 
initiator systems: 
______________________________________ 
EXAMPLE 17 TABLE 
STYRENE POLYMERIZATIONS INITIATED BY 
INITIATOR COMBINATIONS 
______________________________________ 
Polystyrene 
INITIATOR Weight-Average 
COMBINATION A 
Mole of ActO!* from: 
Molecular 
(I-5/A-3) I-5 A-3 Weight, M.sub.w 
______________________________________ 
0.0 0.00230 267,000 
0.00092 0.00138 277,000 
0.00138 0.00092 288,000 
0.00184 0.00046 303,000 
0.00230 0.0 319,000 
______________________________________ 
Polystyrene 
INITIATOR Weight-Average 
COMBINATION B 
Mole of ActO!* from: 
Molecular 
(I-7/A-3) I-7 A-3 Weight, M.sub.w 
______________________________________ 
0.0 0.00230 267,000 
0.00092 0.00138 290,000 
0.00138 0.00092 310,000 
0.00184 0.00046 328,000 
0.00230 0.0 355,000 
______________________________________ 
*Per 1000 g of 95% styrene/5% Ethylbenzene solution; Total level of 
initiator in combination was equal to 0.00230 mole of active oxygen. 
The results show that the polystyrene weight-average molecular weight can 
be adjusted upward by replacing some of initiator A-3 with either I-5 or 
I-7, or adjusted downward by replacing some of either I-5 or I-7 with 
initiator A-3. Hence, polystyrene producers can use the novel 
poly(monoperoxycarbonates) of the instant invention in Combination with 
other free-radical initiators in order to adjust the molecular weight of 
polystyrene, thus adjusting the physical properties of polystyrene. 
EXAMPLE 18 
Enhanced Polymerizations of Styrene Employing Polyether 
Tetrakis(mono-t-butylperoxycarbonate) (I-7) in Combination with t-Butyl 
Peroxybenzoate (A-2) 
Styrene polymerizations were carried out using a monomer solution 
containing 95% styrene and 5% ethylbenzene (EB). The polymerization 
methodology employed in this example was a modification of the procedure 
outlined in Example 15. In this example, a combinations of two 
free-radical initiators was employed in which one of the initiators of the 
combination was a novel poly(monoperoxycarbonate) of the instant invention 
i.e., polyether tetrakis(mono-t-butylperoxycarbonate) (I-7) and the second 
initiator of the initiator combinations was an art monoperoxide, i.e., 
t-butyl peroxybenzoate (A-2). 
Preparation of Styrene/Initiator Solutions 
The total levels of free-radical initiators employed in this example were 
equal to a total of 0.00277 mole of active oxygen per 1000 g of styrene 
solution (or 0.00230 mole of active oxygen per liter of styrene solution). 
Styrene Polymerization Procedure 
Ampules containing the styrene solutions (several for each solution) were 
immersed in a circulating oil bath in which the temperature was regulated 
through a temperature programmer unit. Samples were subjected to a 
100.degree. C. to 151.degree. C. linear temperature ramp, at a programmed 
rate of 0.17.degree. C./minute (5-hour program). At the end of the 5-hour 
period the samples were withdrawn from the bath and cooled by immersion in 
an ice-water bath. The styrene solutions were then removed from the 
ampules and analyzed for polystyrene weight-average molecular weight 
(M.sub.w). 
Results 
Example 18 Table summarizes the polystyrene weight average molecular 
weights that were obtained when Initiator Combination C (I-7 and A-2) was 
employed as a free-radical initiator system: 
______________________________________ 
EXAMPLE 18 TABLE 
STYRENE POLYMERIZATIONS INITIATED BY 
INITIATOR COMBINATIONS 
______________________________________ 
Polystyrene 
INITIATOR Weight-Average 
COMBINATION C 
Mole of ActO!* from: 
Molecular 
(I-7/A-2) I-7 A-2 Weight, M.sub.w 
______________________________________ 
0.0 0.00277 212,000 
0.001385 0.001385 279,000 
0.00277 0.0 391,000 
______________________________________ 
Polystyrene 
Weight-Average 
Molecular 
A-3 Mole of ActO!* from: 
Weight, M.sub.w 
______________________________________ 
0.00277 278,000 
______________________________________ 
*Per 1000 g of 95% styrene/5% Ethylbenzene solution; Total level of 
initiator in combination was equal to 0.00277 mole of active oxygen. 
The results in Example 18 Table show that the polystyrene weight-average 
molecular weight can be adjusted upward by replacing some of art 
monoperoxide A-2 with I-7, or adjusted downward by replacing some of I-7 
with art monoperoxide A-2. Hence, polystyrene producers can use the novel 
poly(monoperoxycarbonates) of the instant invention in combination with 
other monoperoxide initiators in order to adjust the molecular weight of 
polystyrene, thus adjusting the physical properties of polystyrene. 
The subject matter which the applicants regard as their invention is 
particularly pointed out and distinctly claimed as follows: