Europaisches Patentamt

(19)

European Patent Office

Office europeen
brevets
peen des brevets

EP

0 569

995

B1

E U R O P E A N PATENT S P E C I F I C A T I O N

(12)

(45) Date of publication and mention

of the grant of the patent:
16.12.1998 Bulletin 1998/51

(51) intci.6: C 0 8 K 5 / 0 0 , C 0 8 K 5 / 4 4 ,
C08L 2 1 / 0 0

(21) Application number: 93107840.6

(22) Date of filing: 13.05.1993
(54) Scorch retardant compositions for peroxide curable e l a s t o m e r s
Mischungen zur Verzogerung der Vorvulkanisation fur peroxidhartbare Elastomere
Melanges anti-grilleurs pour des elastomeres durcissables par les peroxides
Cornforth, David Arthur
Rochdale, Lancashire OL12-7RU (GB)
Carney, Francis Michael
Crumpsall, Manchester M8 7WR (GB)

(84) Designated Contracting States:

BE DE ES FR GB IT NL SE
(30) Priority: 14.05.1992 US 883333

(73) Proprietor: CRAY VALLEY SA

92800 Puteaux (FR)

(74) Representative: Chaillot, Genevieve

Cabinet CHAILLOT,
16-20, avenue de L' Agent Sarre,
B.P. 74
92703 Colombes Cedex (FR)

(72) Inventors:
Knowles, Eric
Thornton Cleveleys, Lanes. FY5 3JD (GB)

(56) References cited:

EP-A- 0 346 863
US-A- 3 993 633

(43) Date of publication of application:

18.11.1993 Bulletin 1993/46

EP-A- 0 504 920

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Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give
notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in
a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
99(1) European Patent Convention).
Printed byJouve, 75001 PARIS(FR)

EP 0 569 995 B1
Description
FIELD OF THE INVENTION
5

This invention is directed to scorch retardant compositions suited for the vulcanization of elastomers.
DESCRIPTION OF THE PRIOR ART

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The use of polyunsaturated monomers, and particularly polyfunctional (meth)acrylate monomer systems, for the
curing and vulcanization of peroxide-curable elastomers to enhance physical properties of the resulting elastomers is
known. Such property enhancements include high hardness, resistance to attack by sunlight, hydrocarbon solvents
as well as water, physical strength and aging. Free-radical reaction of the polyunsaturated monomers with the elastomeric compositions is conducted at elevated temperatures wherein the polyunsaturated compositions crosslinkth rough
an abstractable hydrogen atom on the elastomer.
Scorching is a problem associated with the curing of the elastomers in the presence of peroxide and scorching,
in effect, is the result of prevulcanization of the elastomer. In prevulcanization the monomer crosslinks with the elastomer at low temperature resulting in products which have a rough texture, a shriveled appearance and its surface
appearance is lumpy. Thus, they are unacceptable. To combat the problem of prevulcanization and scorching of the
elastomer, it has been customary to add scorch retardants to the polyunsaturated monomer which in turn retard the
rate of crosslinking between the elastomer and polyunsaturated monomer at low temperature. Although many types
of scorch retardants have been incorporated into the polyunsaturated monomers for subsequent peroxide curing of
elastomers, there have been problems. In terms of elastomer properties, the addition of the scorch retardants have
been relatively ineffective during high temperature vulcanization or too effective in that they have retarded vulcanization
to the extent that the resulting elastomers do not have the required physical properties. For example many have reduced
elastic modulus and increased elongation. In terms of processing the elastomers, the scorch retardants often have
extended the cure times to such an extent that costs become prohibitive or, because of their volatility, present environmental problems in the workplace due to odor and toxicity.
Several patents which disclose scorch retardant systems for inhibiting prevulcanization of elastomers including
rubber and rubber type compositions are as follows:
U.S. 3,751 ,378 discloses a mechanism for inhibiting prevulcanization of rubber crosslinked with a polyfunctional
methacrylate in the presence of peroxide. A scorch retardant of N-nitrosodiarylamine or N,N'-dinitrosodiphenyl-j>phenylenediamine is shown.
U.S. 4,857,571 discloses a method for the inhibiting the prevulcanization during free-radical curing of rubbers. The
prior art section of the patent discloses that it was known to use acidic materials such as phthalic anhydride, salicylic
acid and sodium acetate which act as retarders in sulfur vulcanization systems. Other known retarders include nitroso
and nitroaromatic amines as well as various quinones e.g. p-benzoquinone and naphthoquinone. Retarders used by
the patentees include modified alkyl-substituted aminoalkylphenols, an example of which is 2,6-di-t-butyl-4-[methyl
(phenyl)amino]-n-propylphenol.
U.S. 954,907 discloses a method for avoiding scorching of ethylene polymer based compositions vulcanized in
the presence of organic peroxide. The patentees disclose the use of monofunctional vinyl compositions as a scorch
retarding agent. Antioxidants such as sterically hindered phenols are also suggested as an adjuvant.
U.S. 3,578,647 discloses a scorch prevention process for producing ethylene-containing polymers crosslinked by
free radical generating crosslinking agents. The patentees employ the use of a chain transfer agent e.g., mercaptans
and aldehydes as a scorch retarding or scorch preventing adjuvant.
U.S. 3,335,124 discloses method for controlling the rate of vulcanization of polyethylene through the use of a
crosslinking regulator which heretofore were utilized or antioxidants. Various compositions having antioxidant activity
and suited as a crosslinking regulator include aromatic amines, phenolic compounds and ketone-aldehyde condensation products.
U.S. 3,202,648 discloses the addition of scorch inhibiting components during the free radical peroxide crosslinking
of polyethylene. Alkyl, cycloalkyl and arylalkyl nitrites having from 5 to 18 carbon atoms are used as the scorch preventing additive.
EP-A-0 346 863 relates to a mixture containing at least one organic peroxide suitable for the crosslinking of
polymers ; at least one hydroquinone derivative ; and at least one crosslinking reinforcing agent, said mixture permitting
the crosslinking of polymers while extending the scorch time.
US-A-3 993 633 describes a class of 2-(1 (2H)-phthalazinone) sulfenamides useful as inhibitors of premature vulcanization of rubber.

EP 0 569 995 B1
SUMMARY OF THE INVENTION

to

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This invention relates to a polyfunctional (meth)acrylate based scorch retardant formulation for use as a crosslinker
system for the peroxide curing of elastomer compositions vulcanizable in the presence of the peroxide catalyst and to
the curable elastomer system itself. The improved scorch retarding polyfunctional (meth)acrylate system comprises:
a polyfunctional (meth)acrylate and an effective amount of a scorch retardant mixture comprising hydroquinone and a
sulfenamide. Scorch retarding curable elastomers are formed by incorporating the polyfunctional (meth)acrylate based
scorch retardant formulations into a peroxide-curable elastomer system. There are several advantages associated
with the polyfunctional (meth)acrylate based scorch retardant compositions and the curable elastomers prepared therefrom and these include:
an ability to formulate an easily handled scorch retardant polyfunctional (meth)acrylate system for vulcanizing
peroxide-curable elastomers;
an ability to formulate storageable, scorch retardant polyfunctional (meth)acrylate systems suited for forming peroxide-curable compositions;
an ability to retard scorching of peroxide-curable elastomers during crosslinking with polyfunctional (meth)acrylate
monomers while maintaining excellent rates of cure at vulcanization temperatures; and
an ability to inhibit scorch in the vulcanization of peroxide-curable elastomers reacted with polyfunctional (meth)
acrylates without significant environmental problems due to offensive odors and particularly offensive toxicity.
A first subject-matter of the present invention is a scorch retarding polyunsaturated monomer containing system
suited for curing peroxide curable elastomers and polyethylene, polypropylene, copolymers containing ethylene units
and copolymers containing propylene units, which comprises polyunsaturated monomer, 0.2 to 6 weight percent hydroquinone based upon said polyunsaturated monomer and 1 to 50 weight percent sulfenamide based upon said polyunsaturated monomer.
A second subject matter of the present invention is a curable composition comprising an elastomer or polyethylene
or polypropylene or a copolymer containing ethylene units or a copolymer containing propylene units having an abstractable hydrogen atom crosslinkable with a polyfunctional (meth)acrylate, polyfunctional (meth)acrylate, organic
peroxide, and a scorch retarding additive which comprises from 0.2 to 6% by weight of hydroquinone based upon said
polyfunctional (meth)acrylate and from 1 to 50% by weight of a sulfenamide based upon said polyfunctional (meth)
acrylate.
DETAILED DESCRIPTION OF THE INVENTION

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This invention pertains to compositions suited for inhibiting or retarding the prevulcanization or scorching of peroxide-curable elastomers during cure with polyinsaturated monomers. The curable elastomers which are crosslinked
with the polyunsaturated monomers are elastomeric organic high polymers, e.g., rubbers which are curable via freeradical crosslinking with polymerizable vinyl unsaturated monomers. In general, the free-radical curable elastomers
are polymers having extractable hydrogen atoms which on reaction with the polymerizable monomers crosslinkthrough
carbon-carbon bonds. Representative examples of synthetic rubbery polymers formed via the polymerization of conjugated dienes, include polyisoprene, styrene-butadiene rubbers, polybutadiene rubbers, neoprene, and substituted
butyl rubbers, chlorinated polyethylene rubber. Other elastomers are based upon vinyl polymerization and include
polymers such as ethylene-propylene rubbers, butadiene-acrylonitrile elastomers, and silicone elastomers. This invention pertains also to compositions mited for inhibiting or retarding the prevulcanization or searching of peroxide-curable
polyethylene, polypropylene and copolymers containing ethylene and propylene units e.g. ethylene-vinyl acetate copolymers. The patents described in the prior art section herein suggest many representative elastomer systems.
The scorch retarding curatives for peroxide curable elastomers comprise a polyfunctional unsaturated monomer,
typically a polyfunctional (meth)acrylate monomer, and an effective amount of a scorch retardant inhibitor and vulcanizate accelerator, the scorch retarder being hydroquinone and the vulcanizate accelerator being a sulfenamide. The
polyfunctional unsaturated monomer generally is admixed with the scorch retardant additives and generally it is a
component of the scorch retarding curative; it is polyfunctional in that it has a plurality of unsaturation units for crosslinking with the elastomers. Preferably it is a liquid at temperatures below about 50C. The use of polyacrylates in the
vulcanization of peroxide curable elastomers is conventional. Examples of polyfunctional acrylates include those acrylic
and methacrylic acid esters of C2.12 polyols and alkoxylated derivatives containing from 2-6 alkyleneoxide units. Preferably the polyols have from 2-8 carbon atoms and preferably they are diols and triols. Specific polyfunctional (meth)
acrylates are : trimethylolethane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethylacrylate,
glycerol trimethyacrylate, glycerol triacrylate, 1,3-butylene glycol dimethylacrylate, ethylene glycol dimethacrylate,
1,4-butylene glycol dimethacrylate, polyethylene glycol dimethacrylate.

EP 0 569 995 B1

Other polyunsaturated monomers which may be used by themselves or in combination with the polyfunctional
(meth)acrylates include the polyallyl derivatives of polyols, such as, the allylic ethers of trimethylolpropane, pentaerythritol, ethylene glycol, glycerol, polyethylene glycol and polypropylene glycol ; triallylmellitate, diallylphthalate, diallylchlorendate, triallylcyanurate, and triallylisocyanurate,
One component of the scorch retardant system is an organosulfenamide. These compounds have been used in
rubber formulations as delayed action accelators. The sulfenamides are represented by the formulas:
I

10

wherein
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40

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RisuptoC10;
R-i is H, C-|.10 aliphatic, aryl, cycloalkyl or aralkyl;
R2 is C-|_ 10 aliphatic, aryl, cycloalkyl or aralkyl, or combined with R-, forming a heterocyclic group; and,
X is hydrogen, halogen, hydroxy, C-,.6 lower alkyl, C-,.6 alkoxy.
Examples include
N,N-dicyclohexylbenzothiazolesulfenamide;
N,N-diisopropyl-2-benzothiazolesulfenamide;
2-(4-morpholino)thiobenzothiazole (MTB);
N-t-butyl-2-benzothiazolesulfenamide; and
N-cyclohexyl-2-benzothiazolesulfenamide.
Another component of the scorch retardant system is hydroquinone. In the past, quinones have been used as
shortstop agents in polymerization processes, e.g. in the polymerization of olefins such as butadiene and styrene.
Other quinones or polymerization inhibitor, even though they act to retard the rate of vulcanization, do not give the
desired result when combined with the sulfenamide during the peroxide curing of elastomer with polyacrylates.
One highly acceptable method for incorporating the scorch retardant additive for curing of the elastomer involves
mixing the hydroquinone and sulfenamide with the polyacrylate and then coating the resulting liquid mixture onto an
inert solid phase substrate. The material then can be packaged and stored for extended periods of time at ambient
temperatures. Examples of substrates suited for coating the mixture of polyacrylates monomers and scorch retardants
include powdered silica, diatomaceous earth and clays.
The scorch retardant system of hydroquinone and sulfenamide also can be added separately or jointly to the
elastomer during milling with the polyunsaturated monomer. However, it is preferred that the scorch retardant additives
be mixed with the polyunsaturated monomer and the resultant mixture added to the elastomer.
The scorch resistant polyunsaturated monomer or polyf unctional(meth)acrylate systems for effecting vulcanization
of curable elastomeric organic high polymers typically are formulated on the basis of one hundred weight parts monomer, e.g., polyfunctional(meth)acrylate. The scorch retardant system then is incorporated into the curable elastomer
in conventional amounts from about 0.5 to 50 weight parts polyunsaturated monomer per one hundred weight parts

EP 0 569 995 B1

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elastomer. (These values may be expressed as weight percent.) When using polyallylic functional monomers, higher
levels may be used than when using polyacrylates. For polyfunctional(meth)acrylates the level of polyfunctional(meth)
acrylate vis-a-vis the curable elastomer generally is from 1 to 50 parts per 100 parts elastomer. Higher levels may be
used but seldom are for reasons of cost; the addition level is primarily at the discretion of the formulator and thus
depends on the nature of the elastomer to be produced. In formulating the scorch retardant system the range of hydroquinone based upon polyfunctional(meth)acrylate is from 0.2 to 6 parts by weight per one hundred parts by weight
polyf unctional(meth)acrylate. The sulfenamide also present in a proportion of from about 1 to 30 typically 2 to 20 weight
parts per 100 weight parts of polyf unctional(meth)acrylate. When less than about 0.2 parts hydroquinone are used in
the scorch retardant polyfunctional(meth)acrylate system, there may be insufficient inhibitor to prevent even modest
levels of scorching during cure. Higher levels may be required depending upon vulcanization temperatures and vulcanization times as well as the elastomeric organic high polymers and polyunsatured momomers themselves. Too
much hydroquinone may overly extend cure cycles and result in insufficiently cured elastomers.
Typically, the vulcanization or crosslinking of the curable elastomers is effected through free radical initiation by
the addition of a free-radical generating compound or via a radiation source, e.g., a high energy electron source.
Although many systems will cure at high temperature, high temperatures may result in unacceptable product if cure
temperature is too high. Generally, then polymerization is effected by initiating reaction through the addition of a free
radical generating compound which is usually an organic peroxide. Organic peroxides suited for abstracting hydrogen
from the elastomer are known and those conventionally used can be used in the practice of this invention for vulcanizing
elastomers. Organic peroxides which can be used include ditertiary peroxides and these include benzoyl peroxide,
1,3-bis-t-butylperoxyisopropylbenzene;
1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane;
2,5-dimethyl-2,5-bis(tbutylperoxy)hexane; di-a-cumyl peroxide; and ditertiary peroxides such as di(tert-peroxy)butane; tert-butyl-methylcyclohexyl peroxide and dibenzoyl peroxide. Other peroxides include tert-butyl perbenzoate and tert-butyl perphthalate.
Radiation of the polymers would be an acceptable method depending on use and cost over chemical free radical
initatiors. However, any conventional process may be used.
The elastomeric compositions can be processed in conventional manner typically involving the milling of a masterbatch formulations in roll mills and then curing the milled masterbatch in molds or presses. Various additives can
be added to the elastomer for imparting desirable properties thereto and examples of additives include carbon black,
antioxidants, wetting agents and reinforcing pigments and fillers. Examples of reinforcement and fillers include fine
particles, zinc oxide, calcium carbonate, calcium silicate, amorphous hydrated silica, fine clays, magnesium carbonate
and carbon black. The addition of various additives to achieve desired properties is at the discretion of the processor.
The following examples are provided and illustrate various embodiments of the invention and provide comparisons
against the prior art.
EXAMPLE 1
Scorch Retardant Systems for Elastomers Effect of Level of Scorch Retardent
Vulcanization of butadiene-acrylonitrile rubbers was carried out in conventional manner in a roll mill and then
placing the milled system into a mold. Varying levels of scorch retarding additives of hydroquinone and sulfenamide
were compared. The scorch retardant systems were formulated by mixing the hydroquinone and sulfenamide with the
trimethylolpropane triacrylate and coating the resulting mixture onto powdered silica. Scorch time to determine cure
characteristics was evaluated on the basis of Mooney scorch time according to ASTM 1646-80. The formulations were
cured at 160C and physical properties i.e. hardness measured. The conditions and results are set forth in Table 1.
The masterbatch formulation is as follows:
Parts (by wt)
NBR N367C70 Nitrile Rubber
100
FEF Carbon Black N550
40
Zinc Oxide
5
Stearic Acid
1
15
Trimethylolpropane Trimethacrylate
5
Vulcup 40KE (peroxide)
TABLE 1
N-t-butylbenzothiazolesulfenamide
TABLE 1
Hydroquinone
Nitrile Rubber is a butadiene-acrylonitrile rubber
Vulcup 40KE is 1,3-bis-t-butylperoxyisopropylbenzene at 40% activity

EP 0 569 995 B1
TABLE 1
SULFENAMIDE*

HYOROQUINONE*

SCORCH TIME AT 121 C (min)

IRHD HARDNESS

1
0.5
1
0.5
1
0.5

1
1
0.5
0.5
0.25
0.25

48
54
48
47
49.5
43.5

76.5
74.5
79
78.5
84
85

TABLE 1 shows a combination of both additives yields desirable products. A level of hydroquinone or less than
0.5% by weight of the trimethylolpropane trimethacrylate provided higher hardness levels in the cured elastomer, although all levels are acceptable.
EXAMPLE 2 (comparative)
Elastomers Cured with Trial lylcyan urate (TAC) No Sulfenamide
The procedure of Example 1 was repeated using the following masterbatch formulation. No sulfenamide was used
in the cure and delayed action was sought to be achieved through addition of hydroquinone to the methacrylate monomer. The scorch retarding monomer, TAC, was also tested for comparison.
Vistalon 7500 EPDM
100 PTS
FEF Carbon Black N550
100
45
Struckpar 2280 Process Oil
Antioxidant TMQ
1
2
Trimethylolpropane trimethacrylate
5
Vulcup 40KE (peroxide)
Vistalon 7500 EPDM is an ethylene/propylene rubber which is commercially available.
TMQ antioxidant is polymerized trimethyldihydroquinone.
Additions of hydroquinone expressed as weight percent of the trimethylolpropane trimethacrylate co-agent gave
results as follows:
TABLE 2
HQ LEVEL
1.07%
12.5%

TAC
2

SCORCH TIME AT 131C (min)

HARDNESS

11
12.5
27

56
56
55

As can be seen from Table 2, when 2 parts TAC were used as the coagent (with no added scorch retardant), the
elastomer had a scorch time of 27 min and a hardness of 55. When the methacrylates were used, the addition of
hydroquinone as the sole scorch retarder failed to give as good as a scorch retardant.
EXAMPLE 3
Ethylene-Propylene Rubbers
The procedure of Example 2 was repeated except sulfenamide was added along with polyacrylate and hydroquinone in forming the co-agent formulation. Table 3 provides data at 5 parts and 3 parts trimethylolpropane trimethacrylate
as follows. The masterbatch formulation was comprised:

EP 0 569 995 B1
Parts (by wt)
Keltan 4802 EPDM
100
FEF Black
85
30
Sunpar 2280 Process Oil
Antioxidant TMQ
1
Table 3
N-t-butylbenzothiazole sulfenamide
9
Vulcup 40KE
1.7
Hydroquinone
Kelton 4802 is an ethylene/propylene rubber which is commercially available.
TABLE 3
TRIMETHYLOLPROPANE TRIMETHACRYLATE
CO-AGENT 5 PTS
20

SULFENAMIDE LEVEL

SCORCH TIME AT 121 C (min)

HARDNESS

0.25
0.5

19.5
24.5

71
71

SCORCH TIME AT 121 C (min)

HARDNESS

CO-AGENT 3 PTS
SULFENAMIDE LEVEL
0
0.25
0.5
30

35

73
70
72

14
19
19

When comparing the results with those of Example 2, it is generally recognized that the standard methacrylate grades
give superior physical properties as evidenced by the high hardness values relative to the TAC cured product. The
methacrylate grades suffer primarily from the scorch problem. The additions of the sulfenamide to the polymethacrylate
formulation resulted in higher Mooney scorch times. Also, these results show generally longer levels of scorch time
than those obtained with hydroquinone alone, indicating that both components are required in order to confer with
desired activity.
EXAMPLE 4 (comparative)

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Comparison of Hydroquinone to Other Polymerizaton Inhibitors

The procedure of Example 1 was repeated but using a different masterbatch formulation as follows:
Nitrile Rubber BR 1042
Zinc Oxide
Stearic Acid
FEF Carbon Black
Dicumyl peroxide
Trimethylolpropane trimethacrylate

100 pts.
5 pts.
1 pt.
40 pts.
4 pts.
15 pts.

Various potential scorch additives were added at a level of 5% W/W relative to the acrylate monomer. Table 4 sets
forth the test results:
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EP 0 569 995 B1
TABLE 4
Scorch Retardant Additive

15

Mooney Scorch at 121 C Mins.

Hardness* IRHD

None
8.33
84
60
46
Hydroquinone
Antioxidant 2246
10.06
79
8.48
83
Phenyl B-naphthylamine
Santowhite Crystals
84
11.14
This demonstrates that hydroquinone is unique in its ability to extend scorch time, but that it does so at a very
unacceptable reduction of hardness when used alone at higher levels.
After 60 mins cure at 160C.
Antioxidant 2246 is 2,2-methylene bis 4,methyl,6-t-butyl phenol.
Santowhite Crystals is a Monsanto product.
EXAMPLE 5
Diethyleneglycol dimethacrylate Comparison with Triallylcyanurate Low Level Polyunsaturated Monomer in Cure

20

The procedure of Example 1 was repeated except for the use of a different masterbatch formulation. One co-agent
composition was prepared consisting of diethylene glycol dimethacrylate (83.3%), hydroquinone (1 .7%) and N-t-butylbenzthiazylsulfenamide (15%). That formulation was compared with an identical masterbatch formulation in which TAC
was substituted for the diethylene glycol dimethylacrylate and without the addition of scorch additives. Table 5 sets
forth the test results.

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Ingredients

Parts (by wt)

Vistalon 7500 EPDM

N550 Black
Paraffinic Oil
Antioxidant TMQ
Coagent Monomer
Vulcup 40KE peroxide

100
100
45
1
2
5

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TABLE 5
Coagent Monomer 2 Parts
Scorch Time at 121 C (min)
Hardness
Compression Set % (22 hr at 160C)
Elongation at break %
Tensile Strength (MN.m-2)

DIMETHACRYLATE

TAC

53
57
23.6
360
14.5

45
60
34.2
31 5
15.7

The results show that the dimethacrylate cured system had improved scorch time, compression set and elongation
compared to TAC. Hardness was slightly reduced and tensile strengths were approximately equivalent.
so

EXAMPLE 6
Low Level Trimethylolpropane trimethacrylate- TAC

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The procedure of Example 5 was repeated except only 30 pts of paraffinic oil, and a coagent consisting of trimethylolpropane trimethacrylate (83.55), N-t-butylbenzothiazolesulfenamide (15) and hydroquinone (1.45), parts were
used. Table 6 sets forth the test results.

EP 0 569 995 B1
TABLE 6
Coagent 2 Parts
METHACRYLATE

TAC

24.5
70
21.9
255
17.6

22.5
67
16.2
235
17.9

Scorch Time at 121 C

Hardness
Compression Set % (22 hrs at 160C)
Elongation at break %
Tensile Strength (MN.m-2)

The results show that even at low levels of polyacrylate addition in the form of diacrylate and triacrylate the scorch
retardant effect of the scorch retardant mixture was about equivalent to TAC and yet hardness was better and compression set somewhat poorer.
EXAMPLE 7
High Level of Process Oil Addition
The procedure of Example 6 was repeated except at higher levels of process oil addition. The system was compared to TAC systems. Using the Example 6 trimethylolpropane trimethacrylate co-agent composition in a rubber compound as above containing 65 parts of paraffinic process oil, data are as follows in Table 7.
TABLE 7
Coagent 2 parts
METHACRYLATE

TAC

77
49
27.0
480
12.0

>120
44
65.1
515
6.9

Scorch Time
Hardness
Compression Set % (22 hrs at 160C)
Elongation at break %
Tensile Strength (MN.m"2)

The advantage of the scorch retarding polyacrylate systems over TAC systems is best emphasized at the highest
loading levels of process oil. Hardness was better and tensile strength was nearly double. Compression set was considerably improved in the methacrylate system.
EXAMPLE 8 (comparative)
Scorch Retardation System in the Absence of Hydroquinone
The procedure of Example 1 was repeated except hydroquinone was omitted from the scorch retarding polyacrylate
system. The sulfenamide derivative failed to give adequate scorch protection. The formulation consisted of:
Parts (by wt)
Breon N3670 Nitrile Rubber
FEF Carbon Black
Zinc Oxide
Stearic Acid
DiCup 40C (peroxide)
Trimethylolpropane trimethacrylate
N-t-butylbenzothiazolesulfenamide

100
40
5
1
5
15
2

A Mooney Scorch of only 6 1/2 minutes and a vulcanisate hardness of 81 was obtained thus showing the need for
the scorch retarding additive, hydroquinone, in combination with the sulfenamide.

EP 0 569 995 B1
EXAMPLE 9 (comparative)
Vulcanization without Scorch Retardant Effect of Acrylate Functionality
The procedure of Example 1 was repeated except that the following masterbatch was used. No special addition
of scorch-retardant agent(s) was made. The results are in Table 8.
NBR B36C70 Nitrile Rubber
FEF Black
Zinc Oxide
Stearic Acid
Antioxidant TMQ
DiCup 40C (peroxide)
Polyacrylate Monomer (See Table 8 )

100
40
5
1
0.5
7
15

TABLE 8
MONOMER
TETRAHYDROFURFURYL
METHACRYLATE
1,3-BUTANEDIOL
DIMETHACRYLATE
TRIMETHYLOLPROPANE
TRIMETHACRYLATE

FUNCTIONALITY

SCORCH TIME AT 121 C (min)

IRHD HARDNESS

24

63

81

84

These results show that polyunsaturated monomers without a scorch retarding agent scorch times were low. The
monounsaturated monomer had better scorch time but at the expense of hardness. The appearance of the products
showed severe scorching. Scorching became more severe, as expected, with increasing functionality of the polyacrylate and such scorch times were significantly lower for the higher functional polyfunctional(meth)acrylates. However,
the polyunsaturated monomers cured elastomers had better and excellent hardness.
EXAMPLE 10 (comparative)
Effect of Hydroquinone on Vulcanization - No Sulfenamide
The procedure of Example 1 was repeated except that the percentage of hydroquinone was varied based on the
trimethylolpropane methylacrylate. No sulfenamide was used. The results are set forth in Table 9.
Table 9
% ADDITION OF HYDROQUINONE ON MONOMER

SCORCH TIME AT 121 C (min)

IRHD HARDNESS

0
0.5
1.0
3.0
5.0

7.5
16
25
58
>60

84
82
76
60
50

The increasing levels of hydroquinone based on the weight of the polyf unctional(meth)acrylate extended the scorch
time with increasing hydroquinone levels, but reduced the vulcanisate hardness. These results in terms of vulcanisate
hardness are is consistent with Example 1, and they also show the importance of sulfenamide addition.

10

EP 0 569 995 B1
EXAMPLE 11 (comparative)
Scorch Retardant Using Tetramethyl/Thiuram Monosulfide
The procedure of Example 1 was repeated, but using tetramethyl thiuram monosulfide in place of the sulfenamide.
The results obtained are set forth in Table 10.
Monosulfide

Hydroquinone

Scorch Time 121 C

Hardness

1
0.5
1
0.5

1
1
0.5
0.5

27.4
30.1
21.5
21.2

73
73.5
77
78

This demonstrates that the Monosulfide system has an interesting combination of properties, but that its performance is not as the preferred sulfenamide system.
EXAMPLE 12 (comparative)
Commercial Scorch Retardant and Effect
Two commercial scorch retardant systems were compared to the formulation of Example 1 in order to provide
comparative performance requirements. The formulation was as follows:
NBR N36C70 Nitrile Rubber
FEF Black N550
Zinc Oxide
Stearic Acid
Monomer
Vulcup 40KE peroxide

100
40
5
1
15
4

TABLE 8
MONOMER

SCORCHTIME AT121C(min)

IRHD HARDNESS

EXAMPLE 1
TRIMETHYLOLPROPANE TRIMETHACRYLATE
COMMERCIAL PRODUCT 1
COMMERCIAL PRODUCT 2

43.5
6 1/2
47.5
40.5

85
84
83
83

The results show similar scorch times and hardness for the scorch retardant systems described herein to established commercial systems.
EXAMPLE 13 (comparative)
Effect of N-Cyclohexylbenzothiazolesulfenamide
The procedure of Example 4 was repeated using the same masterbatch, but using N-cyclohexyl benzothiazolesulfenamide at a level of 5% relative to the methacrylate monomer. This formulation gave a scorch-time of 9.5
minutes at 121C and a vulcanisate hardness of 83 after cure for 60 mins at 160C. This further demonstrates that
sulfenamide by itself will not render the scorch properties adequate.
EXAMPLE 14
Effect of N-Cyclohexylbenzothiazolesulfenamide
The procedure of Example 1 was repeated except that the t-butyl-sulfenamide was replaced by N-cyclohexylben-

11

EP 0 569 995 B1
zothiazolesulfenamide at a level of 3% relative to the methacrylate monomer. However, the combination was only
slightly inferior to the commercial products of Example 11 .
Claims
1. Scorch retarding polyunsaturated monomer containing system suited for curing peroxide curable elastomers and
polyethylene, polypropylene, copolymers containing ethylene units and copolymers containing propylene units,
which comprises polyunsaturated monomer, 0.2 to 6 weight percent hydroquinone based upon said polyunsaturated monomer and 1 to 50 weight percent sulfenamide based upon said polyunsaturated monomer.
2.

The scorch retardant system of Claim 1 wherein the sulfenamide is represented by the formulas :
I

and

wherein :
R is up to C10;
R1 is H, C|_10 aliphatic, aryl, cycloalkyl or aralkyl ;
R2 is C|_10 aliphatic, aryl, cycloalkyl or aralkyl, or combined with R1 forming a heterocyclic group ; and
X is hydrogen, halogen, hydroxy, C-,.6 alkyl, C-,.6 alkoxy.
3.

The scorch retardant system of Claim 2 wherein the polyunsaturated monomer is selected from the group of polyfunctional (meth)acrylates and polyallylic monomers.

4.

The scorch retardant system of Claim 3 wherein the polyunsaturated monomer is a polyacrylic or methacrylic ester
of a C2_-|2 polyol.

5.

The scorch retardant system of Claim 4 wherein the polyol is C2.8 diol or triol.

6.

The scorch retardant system of Claim 5 wherein said sulfenamide is selected from the group consisting of N,Ndicyclohexylbenzothiazolesulfenamide ; N,N-diisopropyl-2-benzothiazolesulfenamide ; 2-(4-morpholino)thiobenzo-thiazole (MTB) ; N-t-butyl-2-benzothiazolesulfenamide ; and N-cyclohexyl-2-benzothiazolesulfenamide.

7.

The scorch retardant system of Claim 1 intended to be used in a peroxide curable elastomer selected from the
group consisting of polyisoprene, styrene-butadiene rubbers, polybutadiene, neoprene, butyl, chlorinated polyeth-

12

EP 0 569 995 B1
ylene, ethylene-propylene, and butadiene-acrylonitrile rubbers, and silicone elastomers, or in a peroxide curable
ethylene - vinylacetate copolymer.
8.

The scorch retardant system of Claim 7 wherein the weight parts hydroquinone per 100 weight parts polyfunctional
(meth)acrylate are from 0.5 to 5.

9.

The scorch retardant system of Claim 8 wherein the sulfenamide is present in an amount from 2 to 20 parts per
100 parts by weight polyfunctional (meth)acrylate.

10. The scorch retardant system of Claim 9 wherein the sulfenamide is N-t-butylbenzothiazolesulfenamide.
11. A curable composition comprising an elastomer or polyethylene or polypropylene or a copolymer containing ethylene units or a copolymer containing propylene units having an abstractable hydrogen atom crosslinkable with a
polyfunctional (meth) acrylate, polyfunctional (meth) acrylate, organic peroxide, and a scorch retarding additive
which comprises from 0.2 to 6% by weight of hydroquinone based upon said polyfunctional (meth)acrylate and
from 1 to 50% by weight of a sulfenamide based upon said polyfunctional (meth)acrylate.
12. The curable composition of Claim 11 wherein the sulfenamide is represented by the formulas :
I

and

wherein :
R is up to C10;
R1 is H, C|_10 aliphatic, aryl, cycloalkyl or aralkyl ;
R2 is C|_10 aliphatic, aryl, cycloalkyl or aralkyl, or combined with R1 forming a heterocyclic group ; and,
X is hydrogen, halogen, hydroxy, C-,.6 alkyl, C-,.6 alkoxy.
13. The composition of Claim 12 wherein the sulfenamide is represented by formula 1 and R-, is hydrogen and R2 is
aliphatic.
14. The curable composition of Claim 13 wherein the polyfunctional (meth)acrylate is a polyacrylic or methacrylic ester
of a C2.12 polyol.
15. The curable composition of Claim 14 wherein the polyol is C2.8 diol ortriol.

13

EP 0 569 995 B1
i. The curable composition of Claim 15 wherein said sulfenamide is selected from the group consisting of N,Ndicyclohexylbenzothiazolesulfenamide ; N,N-diisopropyl-2-benzothiazolesulfenamide ; 2-(4-morpholino)thiobenzo-thiazole (MTB) ; N-t-butyl-2-benzothiazolesulfenamide; and N-cyclohexyl-2-benzothiazole-sulfenamide.
'. The curable composition of Claim 16 wherein the elastomer is selected from the group consisting of polyisoprene,
styrene-butadiene rubbers, polybutadiene, neoprene, butyl, chlorinated polyethylene ethylenepropylene, and butadiene-acrylonitrile rubbers, and silicone elastomers, or wherein the copolymer containing ethylene units is ethylene
- vinyl acetate copolymer.
!. The curable composition of Claim 17 wherein the weight parts hydroquinone per 100 parts polyfunctional (meth)
acrylate are from 0.5 to 5.
i. The curable composition of Claim 18 wherein the sulfenamide is present in an amount from 2 to 20 parts per 100
weight parts polyfunctional (meth)acrylate.
i. The curable composition of Claim 19 wherein the sulfenamide is N-t-butylbenzothiazolesulfenamide.

20

Patentanspriiche
1.

Mehrfach ungesattigtes Monomer enthaltendes Scorchschutzsystem fur die Hartung von peroxidhartbaren Elastomeren und Polyethylen, Polypropylen,- Ethyleneinheiten enthaltenden Copolymeren und Propylen enthaltenden Copolymeren, enthaltend mehrfach ungesattigtes Monomer, 0,2 bis 6 Gewichtsprozent Hydrochinon, bezogen
auf das mehrfach ungesattigte Monomer, und 1 bis 50 Gewichtsprozent Sulfenamid, bezogen auf das mehrfach
ungesattigte Monomer.

2.

Scorchschutzsystem nach Anspruch 1, wobei das Sulfenamid durch die Formeln:

25

30

35

40

45

dargestellt wird, worin:

50

R fur bis zu C10 steht;

R-, fur H, C-|.10-Aliphat, -Aryl, -Cycloalkyl oder -Aralkyl steht;
RgfiirC-i.-io-Aliphat, -Aryl, -Cycloalkyl oder -Aralkyl steht oder gemeinsam mit R1 eine heterocyclische Gruppe
bildet; und
X fur Wasserstoff, Halogen, Hydroxy, C-|.6-Alkyloder C-|.6-Alkoxy steht.

55
3.

Scorchschutzsystem nach Anspruch 2, wobei das mehrfach ungesattigte Monomer aus der Gruppe der polyfunktionellen (Meth)acrylate und Polyallylmonomere stammt.

14

EP 0 569 995 B1
Scorchschutzsystem nach Anspruch 3, wobei es sich bei dem mehrfach ungesattigten Monomer urn einen Polyacryl- oder Methacrylsaureester eines C2_12-Polyols handelt.
Scorchschutzsystem nach Anspruch 4, wobei es sich bei dem Polyol urn ein C2.8-Diol oder -Triol handelt.
Scorchschutzsystems nach Anspruch 5, wobei das Sulfenamid aus der Gruppe bestehend aus N,N-Dicyclohexylbenzothiazolsulfenamid; N,N-Diisopropyl-2-benzothiazol-sulfenamid; 2-(4-Morpholino) thiobenzothiazol (MTB);
N-t-Butyl-2-benzothiazolsulfenamid und N-Cyclohexyl-2-benzothiazolsulfenamid stammt.
Scorchschutzsystem nach Anspruch 1 zur Verwendung in einem peroxidhartbaren Elastomer aus der Gruppe
bestehend aus Polyisopren, Styrol-Butadien-Kautschuken, Polybutadien-, Neopren-, Butyl-, Chlorpolyethylen-,
Ethylen-Propylen- und Butadien-Acrylnitril-Kautschuken sowie Silicon-Elastomeren oder in einem peroxidhartbaren Ethylen-vinylacetat-copolymer.
Scorchschutzsystem nach Anspruch 7, worin Hydrochinon in einer Menge von 0,5 bis 5 Gewichtsteilen pro 100
Gewichtsteile polyfunktionelles (Meth)acrylat vorliegt.
Scorchschutzsystem nach Anspruch 8, worin das Sulfenamid in einer Menge von 2 bis 20 Gewichtsteilen pro 100
Gewichtsteile polyfunktionelles (Meth)acrylat vorliegt.
Scorchschutzsystem nach Anspruch 9, wobei es sich bei dem Sulfenamid urn N-t-Butylbenzothiazolsulfenamid
handelt.
Hartbare Zusammensetzung mit einem Elastomer oder Polyethylen oder Polypropylen oder einem Ethyleneinheiten enthaltenden Copolymer oder einem Propyleneinheiten enthaltenden Copolymer, das ein abstrahierbares
Wasserstoffatom aufweist, das mit einem polyfunktionellen (Meth)acrylat vernetzbar ist, polyfunktionellem (Meth)acrylat, organ ischem Peroxid und einem Scorchschutz-additiv, enthaltend 0,2 bis 6 Gew.-% Hydrochinon, bezogen
auf das polyfunktionelle (Meth)acrylat, und 1 bis 50 Gewichtsprozent Sulfenamid, bezogen auf das polyfunktionelle
(Meth)acrylat.
Hartbare Zusammensetzung nach Anspruch 11, wobei das Sulfenamid durch die Formeln:
I

und

dargestellt wird, worin:

R fur bis zu C10 steht;
R-, fur H, C-|.10-Aliphat, -Aryl, -Cycloalkyl oder -Aralkyl steht;
R2furC-|_10-Aliphat, -Aryl, -Cycloalkyl oder -Aralkyl steht oder gemeinsam mit R-, eine heterocyclische Gruppe
bildet; und

15

EP 0 569 995 B1
X fur Wasserstoff, Halogen, Hydroxy, C-|.6-Alkyloder C-|.6-Alkoxy steht.
13. Zusammensetzung nach Anspruch 12, wobei das Sulfenamid die Formel I aufweist und R-, fur Wasserstoff steht
und R2 aliphatisch ist.
14. Hartbare Zusammensetzung nach Anspruch 13, wobei es sich bei dem polyfunktionellen (Meth)acrylat urn einen
Polyacryl- oder Methacrylsaureester eines C2_12-Polyols handelt.
15. Hartbare Zusammensetzung nach Anspruch 14, wobei es sich bei dem Polyol urn ein C2_8-Diol oder -Triol handelt.
16. Hartbare Zusammensetzung nach Anspruch 15, wobei das Sulfenamid aus der Gruppe bestehend aus N,NDicyclohexylbenzothiazolsulfenamid; N,N-Diisopropyl-2-benzothiazolsulfenamid; 2- (4-Morpholino) thiobenzothiazol (MTB); N-t-Butyl-2-benzothiazolsulfenamid und N-Cyclohexyl-2-benzothiazolsulfenamid stammt.
17. Hartbare Zusammensetzung nach Anspruch 16, wobei das -Elastomer aus der Gruppe bestehend aus Polyisopren,
Styrol-Butadien-Kautschuken, Polybutadien-, Neopren-, Butyl-, Chlorpolyethylen-, Ethylen-Propylen- und Butadien-Acrylnitril-Kautschuken sowie Silicon-Elastomeren stammt oder es sich bei dem Ethyleneinheiten enthaltenden
Copolymer urn Ethylen-vinylacetat-copolymer handelt.
18. Hartbare Zusammensetzung nach Anspruch 17, worin Hydrochinon in einer Menge von 0,5 bis 5 Gewichtsteilen
pro 100 Gewichtsteile polyfunktionelles (Meth)acrylat vorliegt.
19. Hartbare Zusammensetzung nach Anspruch 18, worin das Sulfenamid in einer Menge von 2 bis 20 Gewichtsteilen
pro 100 Gewichtsteile polyfunktionelles (Meth)acrylat vorliegt.
20. Hartbare Zusammensetzung nach Anspruch 19, wobei es sich bei dem Sulfenamid urn N-t-Butylbenzothiazolsulfenamid handelt.
Revendications
1.

Systeme anti-grilleur contenant un monomere polyinsature, approprie pour durcir des elastomeres durcissables
par un peroxyde et le polyethylene, le polypropylene, des copolymeres renfermant des motifs ethylene et des
copolymeres renfermant des motifs propylene, qui comprend un monomere polyinsature, de 0,2 a 6 pour cent en
poids d'hydroquinone, par rapport audit monomere polyinsature, et de 1 a 50 pour cent en poids de sulfenamide,
par rapport audit monomere polyinsature.

2.

Systeme anti-grilleur selon la revendication 1, dans lequel le sulfenamide est represents par les formules :
I

et

16

EP 0 569 995 B1
II

10

dans lesquelles :

is

20

25

3.

Systeme anti-grilleur selon la revendication 2, dans lequel le monomere polyinsature est choisi parmi le groupe
de (meth)acrylates polyfonctionnels et de monomeres polyallyliques.

4.

Systeme anti-grilleur selon la revendication 3, dans lequel le monomere polyinsature est un ester polyacrylique
ou methacrylique d'un polyol en C2_12.

5.

Systeme anti-grilleur selon la revendication 4, dans lequel le polyol est un diol ou triol en C2.8.

6.

Systeme anti-grilleur selon la revendication 5, dans lequel ledit sulfenamide est choisi parmi le groupe constitue
du N,N-dicyclohexylbenzothiazolesulfenamide ; du N,N-diisopropyl-2-benzothiazolesulfenamide ; du 2-(4-morpholino)thiobenzothiazole (MTB) ; du N-t-butyl-2-benzothiazolesulfenamide ; etdu N-cyclohexyl-2-benzothiazolesulfenamide.

7.

Systeme anti-grilleur selon la revendication 1, destine a etre utilise dans un elastomere durcissable par un peroxyde, choisi parmi le groupe constitue d'un polyisoprene, de caoutchoucs styrene-butadiene, d'un polybutadiene,
d'un neoprene, d'un butyle, d'un polyethylene chlore, de caoutchoucs ethylene-propylene et butadiene-acrylonitrile, et d'elastomeres a la silicone, ou dans un copolymere ethylene-acetate de vinyle durcissable par un peroxyde.

8.

Systeme anti-grilleur selon la revendication 7, dans lequel les parties en poids d'hydroquinone pour 100 parties
en poids de (meth)acrylate polyfonctionnel sont de 0,5 a 5.

9.

Systeme anti-grilleur selon la revendication 8, dans lequel le sulfenamide est present en une quantite allant de 2
a 20 parties pour 100 parties en poids de (meth)acrylate polyfonctionnel.

30

35

40

45

so

R est jusqu'en C10 ;

R-i est H, un aliphatique, un aryle, un cycloalkyle ou un aralkyle en C-|.10 ;
R2 est un aliphatique, un aryle, un cycloalkyle ou un aralkyle en C-|.10, ou combine avec R-, en formant un
groupe heterocyclique ; et
X est un hydrogene, un halogene, un hydroxy, un alkyle en C^g, un alcoxy en C^g.

10. Systeme anti-grilleur selon la revendication 9, dans lequel le sulfenamide est le N-t-butylbenzothiazolesulfenamide.
11. Composition durcissable comprenant un elastomere, ou du polyethylene, du polypropylene, un copolymere renfermant des motifs ethylene ou un copolymere renfermant des motifs propylene, ayant un atome d'hydrogene
pouvant etre elimine, et reticulable avec un (meth)acrylate polyfonctionnel, un peroxyde organique et un additif
anti-grilleur, et qui comprend de 0,2 a 6% en poids d'hydroquinone, par rapport audit (meth)acrylate polyfonctionnel,
et de 1 a 50% en poids d'un sulfenamide par rapport audit (meth)acrylate polyfonctionnel.
12. Composition durcissable selon la revendication 11, dans laquelle le sulfenamide est represents par lesformules :

55

17

EP 0 569 995 B1
I

et
II

N S

dans lesquelles :
R est jusqu'en C10 ;
R-i est H, un aliphatique, un aryle, un cycloalkyle ou un aralkyle en C-|.10 ;
R2 est un aliphatique, un aryle, un cycloalkyle ou un aralkyle en C|_10, ou combine avec R1 en formant un
groupe heterocyclique ; et
X est un hydrogene, un halogene, un hydroxy, un alkyle en C-,.6, un alcoxy en C-,.6.
13. Composition selon la revendication 12, dans laquelle le sulfenamide est represents par laformule I et R-, est un
hydrogene et R2 est un aliphatique.
14. Composition durcissable selon la revendication 13, dans laquelle le (meth)acrylate polyfonctionnel est un ester
polyacrylique ou methacrylique d'un polyol en C2_ 12.
15. Composition durcissable selon la revendication 14, dans laquelle le polyol est un diol ou triol en C2.8.
16. Composition durcissable selon la revendication 15, dans laquelle ledit sulfenamide est choisi parmi le groupe
constitue du N,N-dicyclohexylbenzothiazole-sulfenamide ; du N,N-diisopropyl-2-benzothiazole-sulfenamide ; du
2-(4-morpholino)thiobenzothiazole (MTB) ; du N-t-butyl-2-benzothiazolesulfenamide ; et du N-cyclohexyl-2-benzothiazolesulfenamide:
17. Composition durcissable selon la revendication 16, dans laquelle I'elastomere est choisi parmi le groupe constitue
d'un polyisoprene, de caoutchoucs styrene-butadiene, d'un polybutadiene, d'un neoprene, d'un butyle, d'un polyethylene chlore, de caoutchoucs ethylene-propylene et butadiene-acrylonitrile, et d'elastomeres a la silicone, ou
dans laquelle un copolymere contenant des motifs ethylene est un copolymere ethylene-acetate de vinyle.
18. Composition durcissable selon la revendication 17, dans laquelle les parties en poids d'hydroquinone pour 100
parties de (meth)acrylate polyfonctionnel sont de 0,5 a 5.
19. Composition durcissable selon la revendication 18, dans laquelle le sulfenamide est present en une quantite allant
de 2 a 20 parties pour 100 parties en poids de (meth)acrylate polyfonctionnel.
20. Composition durcissable selon la revendication 19, dans laquelle le sulfenamide est le N-t-butylbenzothiazolsulfenamide.

18