Peroxidic compositions

Details Peroxidic compositions Peroxidic compositions

1999-12-14

2001-09-18

Yoon, Tae H. (Department: 1714)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C525S263000, C525S264000, C525S313000, C252S186420

Reexamination Certificate

active

06291617

ABSTRACT:

The present invention relates to peroxidic compositions usable for the elastomer and polyolefin curing in general, having an improved scorch resistance without negatively affecting in a meaningful way the curing efficiency.
More specifically it relates to compositions having a longer scorch time as shown by the ts
5
and ts
10
values combined with a good curing density as shown by the MH values and having t
90
curing times of the same order.
It is well known that organic peroxides are used for the elastomer and polyolefin curing. However it is desirable to have available compositions with higher scorch times in order to increase the compound processability avoiding precuring phenomena.
In order to solve this technical problem organic peroxides having a longer half-time could be used, however this has the drawback to lengthen also the curing times (t
90
), to the detriment, therefore, of the productivity, in order to maintain the same curing value (MH).
Adding additives to the peroxidic compositions to increase the scorch time is also known. See for example DE 2,553,145 and 2,553,094 wherein peroxides with different scorch times are mixed but the drawback is that the curing times become longer with the above mentioned disadvantages.
Also amine-based additives are known, but today they cannot be used any longer since they are considered toxicologically dangerous due to their cancerogenous effects.
There are also known hydroquinones, e.g. di-t-butyl or di-t-amyl, sulphur-based compounds, or antioxidants in general as scorch retardants in the peroxidic curing, in this way however the final properties of the cured product are poor since the MH value becomes worse.
In U.S. Pat. No. 5,292,791 and U.S. Pat. No. 5,245,084 a peroxidic composition having scorch retardant properties is described, which comprises:
a) a peroxide
b) an hydroquinone derivative
c) a curing promoter.
A scorch resistant composition, stable upon storage, is also known from the EP 785,229 in the name of the Applicant wherein a powdered peroxide or in the form of grain or masterbatch is mixed at the time of use with a masterbatch comprising an inhibitor and a curing promoter. In the above compositions of the European Patent Application and of the U.S. Pat. No. '791 and '084 two additives are used. One mainly acts as inhibitor (scorch resistant) but has a negative effect on the curing degree.
In order to maintain the curing degree a curing promoter is added.
From the EP 533,089 peroxidic compositions are known wherein a solid peroxide bis(alpha t-butyl-peroxy-isopropyl)-benzene, known as PEROXIMONO F, is mixed with bis (alpha t-amyl peroxy-isopropyl)-benzene, known as PEROXIMON® 180. Said compositions are liquid also at temperatures of 15° C. or lower and show a low volatility. The advantage of said compositions consisted in having available particularly desired liquid compositions in compounding application according to continous (not batch) processes or in peroxide additions carried out by direct absorption on the polymers. The drawback of these compositions is that even though they maintain good MH values, they are not scorch resistant.
The need was felt to have available compositions with improved scorch time without notably lower the curing density (MH) with comparable t
90
curing times.
The Applicant has unexpectedly and surprisingly found compositions for the polymer curing which give the above mentioned property combination comprising:
a) one or more organic peroxides selected from the following general formulae:
(R
1
—C(CH
3
)
2
—OO—C(CH
3
)
2
)
n
—R
2
  (I)
 wherein R
1
is an alkyl, aryl and aryl-alkyl-substituted group having from 1 to 9 carbon atoms; R
2
is selected from phenylene, ethylene, —C═C—, —C═C—, alkyl, aryl and aryl-alkyl-substituted group; said groups having from 1 to 9 carbon atoms; n is an integer equal to 1 or 2;
wherein the two R
3
substituents are independently alkyl, aryl, aryl-alkyl-substituted groups having from 1 to 9 carbon atoms, R
4
and R
5
are independently linear or branched, when possible, alkyl groups, having from 1 to 6 carbon atoms or —(CH
2
)
m
—C(O)OR
6
wherein R
6
is an alkyl group from 1 to 4 carbon atoms; m is an integer from 1 to 3, or they jointly form a not substituted or substituted cyclohexane or cyclododecane ring with 1 up to 3 alkyl groups having from 1 to 4 carbon atoms; and
b) 3,7-Dimethyl-1,3,6-Octatriene (OCIMENE).
The preferred type a) components are: dicumylperoxide (PEROXIMONO® (DC)), t-butyl-cumylperoxide (PE-ROXIMON® 801), bis(&agr;-t-butylperoxyisopropyl)benzene (PEROXIMOND® F), 2,5-di(t-butylperoxy)-2,5-dimethylhexane (Luperoxo 231), 2,5-di(t-butylperoxy)-2,5-dimethylhexine-3 (Luperox® 130), diterbutylperoxide (Luperox® DI), 1,1-di(terbutylpero-xy)-3, 3,5-trimethylcyclohexane (Luperox®101), n-butyl-4,4-di-(terbutylperoxy)valerate (Luperox® 230), 1,1-di-terbutylpe-roxycyclohexane (Luperox® 331), isopropylcumylterbutylperoxide (PEROXIMON® DC 60), bis(&agr;-teramylperoxyisopropyl)benzene (PEROXIMON® 180). All these peroxides are commercialized by Elf Atochem.
The component b) amount for one hundred parts by weight (100 phr) of elastomer or polyolefin to be cured is in the range 0.05-1.7, preferably 0.1-1.3.
The weight ratio between the component a) and the component b) is in the range 1:0.02 to 1:0.7, preferably 1:0.05 and 1:0.6.
The compound b) is usually a mixture of isomers cis/trans as sold by Fluka in the name of ocimene.
It is also possible to prepare formulations (in inert fillers and/or predispersions in a polymer) containing the (a+b) mixture in an amount generally higher than or equal to 30% to be used as additives to be dispersed in the polymer to be cured. The preferred range for said formulations is from 30 to 70% of (a+b) mixture. Said formulations are well known and can be prepared according to EP 785,229 herein incorporated by reference.
The polymers which can be cured according to the present invention are ethylene-based polymers. More specifically polyethylene having average, low, high density, poly-butene-1, ethylene/vinyl-acetate copolymers, acrylic ester/ethylene copolymers, ethylene/propylene copolymers, ethylene/butene-1 copolymers, ethylene/4-methyl-pentene-1 copolymers and propylene/butene-1 copolymers; furthermore ethylene/propylene EP or EPDM type elastomeric polymers or copolymers, butyl rubber, chlorinated polyethylene and propylene/butene-1 copolymer, can be mentioned. Also mixtures of two or more polymers can be used.
The final compound ready for curing (polymer+peroxide a)+additive b)+mineral and non mineral fillers, antioxidants, curing coagents, etc., see the above mentioned EP 785,229, is preferably used to produce manufactured articles extruded in a continous way and/or injection and/or compression molded.
Curing can be carried out by heat and can be directly performed in the molding in the case of compression or injection molding; in the case of continuous extrusion with the known methods, for example vapour, nitrogen, melted salt baths, autoclaves curing lines, etc.
The polymer characterization in terms of scorch resistance (ts
5
and ts
10
), curing rate (t
90
) and curing density (MH) of the cured product, is reported in Example 1.


REFERENCES:
patent: 5245084 (1993-09-01), Groepper et al.
patent: 5292791 (1994-03-01), Groepper et al.
patent: 5405915 (1995-04-01), Hess et al.
patent: 25 53 145 (1976-08-01), None
patent: 25 53 094 (1976-08-01), None
patent: 0 533 089 B1 (1995-11-01), None
patent: 0 785 229 A1 (1997-07-01), None
patent: 838963 (1960-06-01), None

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