CN1336939A - Tack free surface cures of polymers by organic peroxides in the presence of air - Google Patents

Abstract

Compositions are disclosed which comprise mixtures of at least one compound selected from silicone elastomers, bis-, tri- or higher polymaleimides and/or bis-, tri- or higher polycitraconimides, and at least one compound selected from p-phenylene-diamine based antiozonants, sulfur compounds capable of accelerating sulfur vulcanization of polymers capable of being crosslinked by sulfur and polysulfide polymers which when compounded into polymers curable by free radical initiators in the presence of free radical initiators permit substantially tack free surface cure of the polymers by decomposition of the free radical initiator in the presence of molecular oxygen. Compositions containing the above ingredients and at least one free radical initiator, curable compositions containing the combination and processes for making and using the compositions are also disclosed.

Description

Polymer carries out non-adhesive surface by organic peroxide and solidifies in the presence of air

Present patent application requires the priority of the temporary patent application 60/164,488 of application on November 9th, 1999.

The background of invention

The present invention relates in chemical industry, be categorized as the composition of following substances: two-, three-or higher poly maleimide, two-, three-or higher poly-citraconimide, silicone elastomer, p-phenylene-two amido antiozonant, for can being carried out by sulphur the organic compounds containing sulfur of promoter of the sulfur curable (crosslinked) of crosslinked polymer, and be the sulfur-containing compound of polysulfide polymer. The present invention also relates to contain the compoistion and method of use of said components and the goods of being made by described method.

Known have good performance with radical initiator (organic peroxide and/or azo initiator) crosslinked polymer and copolymer, especially the crosslinked polymer by sulfur curable. These performances comprise high resistance to thermal deterioration performance, low compression set, metal or metallic sheet reduction staining property and crosslinked during and the articles colored produceability that has colour stability between the long-term operating period. These performances are so that use peroxide cure that very large actual importance is especially arranged, because crosslinkedly undertaken by carbon-carbon bond, rather than undertaken by the key of sulfur-bearing, and the difference of this keyed jointing can improve heat aging property and compression set. Be used for always having such defective from the free radical cure polymer of organic peroxide and azo initiator, if there is air in the setting up period material surface, will form because the tacky surfaces that the molecular oxygen inhibition is solidified to form.

For fear of adopting this body surface toughness of being made by organic peroxide and/or azo initiator radical crosslinking, when being curing, conventional method stops air contacting surface, suppress to solidify with the oxygen of avoiding being present in the atmosphere. The test of getting rid of molecular oxygen can increase cost and the complexity of curing schedule, and in steam autoclave with under the situation that tube interior solidifies, sometimes is difficult to guarantee complete deaeration and molecular oxygen composition thereof. In some cases, the producer would rather change into peroxide cure from sulphur, uses existing hot-air oven curing room. Under these situations, it is infeasible being cured with conventional peroxide systems, because can form tacky surfaces.

For cost and the complexity of simplifying and reduce curing schedule, various prevention molecular oxygens suppress surface cure during radical crosslinking method has been proposed. Because a variety of causes, these methods almost can not satisfy the needs of practical operation or unsuccessful. Especially be that the cryogenic property of prior art is compared with about 100 ℃, although best physical property, 150 ℃ of good compression sets of 70 hours that they provide peroxide (azo) to solidify can not provide non-adhesive surface.

Prior art

United States Patent (USP) 4983685 has disclosed and has used the compound that is selected from following classification: (a) imidazolium compounds, (b) thiourea compound, (c) thiazolium compounds, (d) thiuram compound, (e) dithio carbamate compounds, (f) phenolic compound, (g) triazole compounds and (h) amines, they are the sulfur vulcanization promoter of elastomer in the presence of optional antioxidant, anti-aging compound etc., and they can reduce surface viscosity in the presence of molecular oxygen in elastomeric peroxide cure. In this case, can be used as in the optional components of the possible component in the formulation in proposition, increasing crosslinked component is N, N '-meta-phenylene-dimaleimide.

It is not preferred optional adjuvants, when among the embodiment actual use be the dimethylacrylate compound time. Do not recognize that latter's dimaleimide compound can reduce to the free radical setting up period of some compound in (a)-(h) in the presence of molecular oxygen the ability generation humidification of surface viscosity. In the document, use various sulphur promoter especially with peroxide, cure polymer can form the surface of non-adhesive surface or viscosity reduction, but the important physical properties that is formed by peroxide cure of expection has also descended. United States Patent (USP) 4983685 is not recognized, if in free polymer readical solidifies, the antiozonant of silicone elastomer of the present invention, dimaleimide and two citraconimides and p-phenylenediamine base, the sulfur vulcanization promoter of sulfur-bearing and antioxidant and/or polysulfide polymer mix use, can form non-adhesive surface and improved physical property, and do not mention in all above-mentioned crosslinking coagents, only the compound of these particular types has described effect.

Day patent application № of the present disclosure flat 9 (1997)-169873 has disclosed benzimidazole type and 2,2,4-trimethyl-1, the antioxidant of 2-EEDQ type and the crosslinking coagent of standard be the preferred ingredient N of methacrylate, triallyl cyanurate and maleimide such as this invention for example, the crosslinked peroxide of N '-meta-phenylene dimaleimide and standard is used in combination, and can form the peroxide crosslinkable elastomer of surperficial noncohesive curing in the presence of air. Do not mention the sulphur promoter and/or the polysulfide polymer that comprise p-phenylenediamine base antiozonant, silicone elastomer, any type.

United States Patent (USP) 4,334,043 enlightened in air crosslinked with the organic peroxide cross-linked evocating agent before, with organo-metallic compound, inorganic metal salt or lanthanide series curable polymeric composition is carried out surface treatment, to prevent crosslinked rear surface toughness. Thereby stop it to contact with rubber surface the technology that is solidified into non-adhesive surface except previously known by deaeration simply, do not mention the method for other control surface viscosity.

United States Patent (USP) 4814384 and 4973627 has disclosed and has adopted sulphur and peroxide combination curing mode that the rubber blend on tire tread and sidewall is solidified. Also adopted sulphur promoter. Do not mention the auxiliary agent of any type, the curing under the air existence is not discussed yet. In these workings of an invention, need to use element sulphur. But the final physical property that we find to use element sulphur can adversely affect curing elastomer is namely compared with peroxide cure to such degree, and they more typically show as sulfur curable.

United States Patent (USP) 4743656 has also been discussed elastomeric sulphur/peroxide mixed curing agent, and described curing agent also contains sulphur promoter and elementary sulfur and peroxide. Do not mention auxiliary agent, aerial crosslinked and surface viscosity is not discussed yet.

Hindered phenol antioxygen, the slaine of dithiocarbamate and the particular composition of meta-phenylene-dimaleimide are used in what is claimed is of United States Patent (USP) 4575552, so that the polymer that is applied to the peroxide crosslinking with good hydrolysis and heat endurance under the Geothermal Conditions to be provided. Not mentioning air exists, forbids crosslinked under the air or forbid the surface viscosity that air forms.

United States Patent (USP) 5849214 has disclosed in the presence of radical initiator and has mixed during the free radical crosslinkable polymer, uses sulphur compound, sulphur promoter and hydroquinones and the optional crosslinking coagent that exists in scorch-delaying. Not concrete dimaleimide and two citraconimides discussed are not mentioned for any composition of discussing yet, at the setting up period that molecular oxygen (air) exists, and the impact of their possibility effects on surface viscosity.

In addition, also have patent to adopt various compounds that the physics coating is carried out on the crosslinkable elastomeric surface, with deaeration (oxygen), for example United States Patent (USP) 4439388 had enlightened before hot-air solidifies and has used boric acid, boric anhydride to carry out surface treatment. This surface-coated technology is labour-intensive type, because after the end of cross-linking reaction step, it must remove and process.

Above-mentioned document, no matter alone or in combination, the applicant's solution is not all proposed, and require such right: polymer during for example organic peroxide and azo initiator carry out free radical curing agent by free radical curing agent because deaeration makes the surface inviscid, the physical property that provides again simultaneously desired peroxide (azo) to solidify, for example, the compression set value that is obtained by the expection of the peroxide cure of standard, and under about 150 ℃ of temperature 70 hours test compression permanent deformations.

The general introduction of invention

First aspect present invention provides a kind of composition, and said composition contains:

A) at least a compound (A), it is selected from silicone elastomer and has the compound of following formula (I):

(I) wherein n is 1 or 2, R is divalence or trivalent, it is selected from the non-annularity of 2-16 carbon atom aliphatic group approximately, the alicyclic group of 5-20 carbon atom is arranged approximately, have approximately the aryl peace treaty of 6-18 carbon atom that the alkaryl of 7-24 carbon atom is arranged, wherein these divalence or trivalent group can contain the hetero atom replacement carbon atom (one or more) of one or more O of being selected from, N and S, and each R₁Identical, be a hydrogen or 1-18 carbon atom alkyl;

(b) at least a compound (B), it is selected from p-phenylene-two amido antiozonant and organic compounds containing sulfur, and this organic compounds containing sulfur is selected from the mixture that can promote to be undertaken by sulphur organic compounds containing sulfur (" sulphur promoter "), polysulfide polymer and the described sulfur-containing compound of the sulfur vulcanization of crosslinked polymer.

The composition of the clear and definite embodiment of first aspect present invention has so inherent application characteristic, it is the inhibitor that polymer is obstructed by the surface of free radical initiation curing in the presence of gaseous molecular oxygen (being the oxygen that exists in the atmosphere), can make thus polymer in the presence of air, carry out inviscid curing by free radical curing agent, the final physical property that can keep conventional peroxide cure to have simultaneously.

Provide a kind of composition aspect first aspect present invention composition secondary, it forms by mixing at least a compound (A) and at least a compound (B) that its solvent is the first aspect present invention composition.

Second aspect present invention provides a kind of composition, and it contains the described composition of first aspect and is selected from the radical initiator of organic peroxide and azo initiator.

The clear and definite embodiment composition of second aspect present invention has so inherent application characteristic, be that it is curing agent or the crosslinking agent of following polymer, described polymer can be undertaken crosslinked by radical initiator, and can in the presence of air (molecular oxygen), implement this curing, and the curing that can not make polymer stands owing to the existence of air to be obstructed in the surface, the substantially noncohesive curing in surface or cross-linked polymer are provided thus, and do not need during curing to make described surface to avoid contacting with air (molecular oxygen).

The secondary aspect of second aspect present invention composition is that described composition is by making with at least a compound (A) of random order mixing first aspect present invention composition and the radical initiator of at least a compound (B) and second aspect present invention composition.

Third aspect present invention provides a kind of curable compositions, and it contains the polymer of available radical initiator curing and the composition of second aspect present invention.

The composition of third aspect present invention has so inherent application characteristic, be that it can form the goods with shape, then can be crosslinked during with contact with air (molecular oxygen) on the surface of described goods with shape, form surperficial substantially noncohesive crosslinked products with shape.

The secondary aspect of third aspect present invention composition provides a kind of curable compositions, the radical initiator of its at least a compound (A) by mixing the first aspect present invention composition with random order and at least a compound (B) and the described composition of second aspect present invention with can carry out crosslinked polymer by radical initiator and make.

First aspect present invention also provides the method for preparing the second aspect present invention composition, and it comprises with random order mixes at least a compound (A) of first aspect present invention composition and the radical initiator of at least a compound (B) and the described composition of second aspect present invention.

Second aspect present invention also provides the method for preparing the third aspect present invention composition, and it comprises with random order and mixes the radical initiator of at least a compound (A) of first aspect present invention composition and at least a compound (B), the described composition of second aspect present invention and can carry out crosslinked polymer by radical initiator.

Will mention especially the embodiment of the several aspects of the present invention, wherein said compound (A) is selected from dimaleimide and compound (B) is selected from sulphur promoter; Compound (A) is selected from two citraconimides and compound (B) is selected from sulphur promoter; Compound (A) is selected from dimaleimide and compound (B) is selected from polysulfide polymer; Compound (A) is selected from two citraconimides and compound (B) is selected from polysulfide polymer; Compound (A) is selected from silicone elastomer and compound (B) is selected from polysulfide polymer.

Also to mention the embodiment of the several aspects of the present invention, wherein except compound (A) and (B), also contain haloflex and/or chlorosulfonated polyethylene as optional supplemental components.

Detailed description of the invention

Below with reference to particular implementation, describe this invention preparation of inventor's plan and the best mode that uses in detail, that is:

Use bis-pentamethylenethiuram tetrasulfide (Sulfads), N, N '-meta-phenylene dimaleimide (HVA-2) and 1,1-two (t-butyl peroxy)-3, the mixture of 3,5-trimethyl-cyclohexane (LUPEROX  231XL) solidifies ethylene-propylene copolymer (VISTALON  504) in hot-air.

In order to prepare the mixture of Sulfads, HVA-2 and LUPEROX231XL, can mix with random order all is each component (form of LUPEROX  231XL is that 40% (weight) peroxide is scattered in the calcium carbonate) of dry powder-shaped, then sneak into VISTALON  polymer by standard method (Banbury, mill, extruder etc.). Sulfads, HVA-2 and LUPEROX231XL also can directly sneak into VISTALON simultaneously or with random order successively. Any two components among Sulfads, HVA-2 and the LUPEROX231XL can be mixed, respectively or together sneak into VISTALON with the third component simultaneously. This mixing also can add component in the polymer with random order if carry out respectively, but preferably adds at last peroxide.

In case mix end with VISTALON, the mixture that just can will blend together is very simply put into temperature, and suitable hot-air oven solidifies, curing is caused by peroxide breakdown, in this case, be to solidify the long enough time at about 365 °F (about 185 ℃) easily, make to produce the desired degree of cross linking, in this case, for thin sample, at room temperature to solidify during beginning about 10 minutes easily.

Technical staff in the industry will appreciate that other compounds in the formula I scope that falls into the first aspect present invention composition all are solid materials, all be three maleimides, dimaleimide, three citraconimides or two citraconimides, and can both be mixed by similar conventional method with other raw materials that the present invention plans. Plan can have been bought as dimaleimide and two citraconimides of raw material, or can be easily synthetic by well-known method in the industry. Referring to United States Patent (USP) 5484948 for example, 5616666 and 5292815 and the document quoted, can see more common synthetic method.

If poly maleimide and the citraconimide of three maleimides and three citraconimides and Geng Gao can't buy, can be by similar technology preparation. For example three maleimides, N, " CAS number of (1,3,5-triazines-2,4,6-three bases) three maleimides is CAS (67460-81-5) for N ', N.

Some be suitable for synthetic two-, three-be for example for example polypropyleneoxide diamine and polyoxypropylene triamine of melamine and various polyoxypropylene amine of multifunctional primary amine with the primary amine of higher poly maleimide and similar citraconimide, with the JEFFAMINE trade name available from Huntsman Corporation.

Except the N that upper mask body is mentioned, N '-meta-phenylene-dimaleimide, above-mentioned patent beyond described be applicable to the present invention and general other dimaleimides that can not limit following formula (I) are:

N, N '-ethylene maleimide, N, N '-hexa-methylene dimaleimide, N, N '-ten dimethylene dimaleimide, N, N '-(2,2, the 4-tri-methyl hexamethylene) dimaleimide, N, N '-(oxygen-dipropylene) dimaleimide, N, N '-(amino dipropylene) dimaleimide, N, N '-(ethylidene dioxy-dipropylene) dimaleimide, N, N '-(1, the 4-cyclohexylidene) dimaleimide, N, N '-(1, the 3-cyclohexylidene) dimaleimide, N, N '-(methylene-1,4-two cyclohexylidenes) dimaleimide, N, N '-(isopropylidene-1,4-two cyclohexylidenes) dimaleimide, N, N '-(oxygen-1,4-two cyclohexylidenes) dimaleimide, N, N '-p-(phenylene) dimaleimide, N, N '-(ortho-, meta-or p-phenylene) dimaleimide, N, N '-(1, the 3-naphthylene) dimaleimide, N, N '-(1, the 4-naphthylene) dimaleimide, N, N '-(1, the 5-naphthylene) dimaleimide, N, N '-(3,3 '-dimethyl-4,4 '-phenylene) dimaleimide, N, N '-(3,3-two chloro-4,4 '-diphenylene) dimaleimide, N, N '-(2,4-pyridine radicals) dimaleimide, N, N '-(2, the 6-pyridine radicals) dimaleimide, N, N '-(Isosorbide-5-Nitrae-Ya anthraquinonyl) dimaleimide, N, N '-(meta-tolyl) dimaleimide, N, N '-(p-tolyl) dimaleimide, N, N '-(4,6-dimethyl-1, the 3-phenylene) dimaleimide, N, N '-(2,3-dimethyl-Isosorbide-5-Nitrae-phenylene) dimaleimide, N, N '-(4,6-two chloro-1, the 3-phenylene) dimaleimide, N, N '-(5-chloro-1, the 3-phenylene) dimaleimide, N, N '-(5-hydroxyl-1,3-phenylene) dimaleimide, N, N '-(5-methoxyl group-1, the 3-phenylene) dimaleimide, N, N '-(meta-xylylene) dimaleimide, N, N '-(p-xylylene) dimaleimide, N, N '-(methylene two-p-phenylene) dimaleimide, N, N '-(oxygen two-p-phenylene) dimaleimide, N, N '-(sulfo-two-p-phenylene) dimaleimide, N, N '-(two sulfo-s two-p-phenylene) dimaleimide, N, N '-(sulfo group two-p-phenylene) dimaleimide, N, N '-(carbonyl two-p-phenylene) dimaleimide, α, α-two-(4-maleimide aminophenyl)-m-diisopropyl benzene, α, α-two-(the p-phenylene of 4-) dimaleimide and α, α-two-(4-maleimide aminophenyl)-p-diisopropyl benzene.

In the present composition and method, two or more dimaleimide combinations, or dimaleimide and three maleimides and also be considered equivalent with the combination of higher poly maleimide, technical staff in the industry can understand these three and higher poly maleimide, with the substituent of these maleimides of be used for implementing the present invention's Compounds and methods for as herein described also be equivalent, also in the scope of the present invention's consideration.

With reference to above-mentioned N, N-metaphenylene dimaleimide, two citraconimides that can all or part of replacement comprise following representative example:

1,2-N, N '-dimethylene two citraconimides;

1,2-N, N '-trimethylene two citraconimides;

1,5-N, N '-(2-methyl-pentamethylene)-two citraconimides; With

N, N '-methylphenylene two citraconimides.

The mixture of the mixture of two citraconimides and dimaleimide and two citraconimides and comprise that the said mixture of three maleimides also is regarded as equivalent of the present invention.

Two citraconimides of considering all are well-known compounds, and in situation about can not buy, they are synthetic by the method that the industry describes in detail easily. United States Patent (USP) 5,292,815 the 4th hurdles provide the inventory of these methods. As mentioned above, three or higher poly-citraconimide can prepare by similar approach, they also can all or part ofly be substituted in composition of the present invention, these compounds and substituent are understood by the technical staff of the industry, the equivalent of the compound that specifies of this paper, also in the present invention is thought of as the scope of equivalent.

Think that in each side of the present invention useful silicone elastomer is the silicone derivative elastomer of the dimethyl vinyl replacement of available peroxide crosslinking, it is well-known in the industry. For example referring to " Kirk Othmer Eneyclopedia of Chemical Technology ", 20 volumes, the p43-page or leaf, John Wiley﹠ Sons ,@1982.

The organic compounds containing sulfur that can accelerate the polymer sulfur vulcanization also is that the industry is well-known, and it is crosslinked that these polymer can be considered for Sulfur of the present invention. Many these dissimilar compounds are known, and they all are regarded as equivalent.

" The Vanderbilt Rubber Handboot (the 13rd edition, 1990, R.T.Vanderbilt Company, Inc) " in list many types. The example of these types is derivatives of benzothiazole, thiadiazoles (thiadiazoles), sulfenamide, sulfenimide, dithiocarbamate, thiuram, imidazoles, xanthate and thiocarbamide. The sulphur promoter that also is contained in such sulphur compound is sulfide, disulphide (for example diallyl disulfide), polysulfide and aryl polysulfide, for example the amyl phenol polysulfide is such as the VULTAC  product available from ATOFINA Chemicals Inc., with other sulfide, the compound of polysulfide phosphate, dithiophosphates and/or phosphorous and sulfur-bearing that the sulphur that for example disulphide and/or other are known promotes. Other are known but can not contribute the organic compounds containing sulfur of sulphur also to be regarded as equivalent at curing temperature owing to what the cost reason was used for such reaction at present. Their example is compound 2-(2,4-cyclopentadiene-1-subunit)-1, the 3-dithiolane.

Or rather, being applicable to a class sulphur promoter of the invention process is the salt of dibasic aminodithioformic acid.

These salt have following formula:Wherein X is selected from the ion that the metal of nickel, cobalt, iron, chromium, tin, zinc, copper, lead, bismuth, cadmium, selenium and tellurium forms, or X is quaternary ammonium ion, and n can change between 1-6, and it equals the positive charge on the X ion, R₁And R₂Each is the alkyl of 1-7 carbon atom naturally.

Two examples that replace the salt of aminodithioformic acid are:

Bismuth dimethyl dithiocarbamate;

Cadmium diethyl dithiocarbamate;

The diamyl dithiocarbamate cadmium;

Cupric dimethyldithio carbamate;

Lead diamyldithiocarbamate;

Lead dimethyl dithiocarbamate;

Selenium diethyl dithiocarbamate;

Selenium dimethyl dithiocarbamate;

Tellurium diethyl dithiocarbamate;

The dithiocarbamate-based piperidines of pentamethylene;

Zinc diamyldithiocarbamate;

Zinc diisobutyldithiocarbamate;

PZ;

Zinc diethyl dithiocarbamate;

Copper dibutyldithiocarbamate;

SDD;

Sodium diethyldithiocarbamate;

NB sodium dibutyl dithiocarbamate;

Zinc dibutyl dithiocaarbamate;

Zinc dibenzyl dithiocarbamate;

Be applicable to Equations of The Second Kind sulphur promoter of the present invention and comprise thiuram. They are made by secondary amine and carbon disulfide, and have the structure of following general formula:

R wherein₃1 alkyl to about 7 carbon atoms, or the R on each specific nitrogen-atoms₃Group can couple together, and together forms 5,6 or 7 yuan of heterocycles that contain respectively 4,5 or 6 carbon atoms with the nitrogen-atoms that is connected with them, and n can be more than 0 to as high as 6 on the occasion of.

The general example of thiuram sulphur promoter is:

Four sulfuration and dipentamethylenethiuram hexasulfides;

Tetrabutylthiuram disulfide;

Tetramethylthiuram disulfide;

Tetraethylthiuram disulfide;

Single sulfuration tetra methylthiuram;

Curing isobutyl group thiuram;

Dibenzyl disulfide base thiuram;

Tetra-benzyl thiram disulfide;

Curing four isobutyl group thiurams;

Single sulfuration isobutyl group thiuram;

Single sulfuration dibenzyl thiuram;

Single sulfuration tetra-benzyl thiram;

Single sulfuration four isobutyl group thiurams.

The more much higher sulfide of various thiurams also is the sulphur donor.

Thiadiazoles (thiadiazoles) derivative is but is not limited to single benzoyl derivative of dimercaptothiodiazole (2,5-dimethyl-1,3,4-thiadiazoles); The proprietary trade mark of Vanderbilt Rubber Company is the thiadiazoles of VANAX  189; 1,2,4-thiadiazoles, 5-ethyoxyl-3-(trichloromethyl) thiadiazoles; With alkyl thiol thiadiazoles methyl mercapto thiadiazoles for example.

The derivative of benzothiazole has following formula:Wherein M is direct-connected key, H between two sulphur atoms, or is selected from the ion of the metal formation of nickel, cobalt, iron, chromium, tin, zinc, copper, lead, bismuth, cadmium, selenium and tellurium; When M was H, x was 1; When M is between two sulphur atoms during direct-connected key, x is 1 or 2; When M was the ion of metal formation, x equaled the positive valence mumber of metal ion; If M is direct-connected key between two sulphur atoms, and x is 1, also is connected with the 4-morpholinyl with second sulphur atom of M keyed jointing so.

The compound of example is:

2-(4-morpholino two sulphur) benzothiazole, benzothiazole disulfide, 2-sulfydryl-benzothiazole, curing 2-mercaptobenzothiazoler, Vencide (sodium-2-mercaptobenzothiazolate), 2-sulfydryl-benzopyrene zinc, 2-sulfydryl-benzothiazole copper, 2-N-cyclohexyl aminobenzothiazole, vulcanize N-cyclohexyl amino-2-[4-morpholinodithio, 2-bisbenzothiazole-2 more, 2-polysulfide and 2-bisbenzothiazole-2,2-disulphide, two (2,2 '-the benzothiazole based bisulfide).

Sulfenamide accelerators also is well-known. Exemplary example is: N-oxygen diethylidene-2-[4-morpholinodithio sulfenamide, N-oxygen diethylidene sulfo-carbamyl-N-oxygen diethylidene sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, the N-tert-butyl group-2-[4-morpholinodithio sulfenamide, N-cyclohexyl-2-[4-morpholinodithio base sulfenamide, N, N-dicyclohexyl benzothiazolyl sulfenamide, the N-tert-butyl group-2-[4-morpholinodithio sulfenamide. Also has for example N-tert-butyl group benzo thiazole-2-sulfenimide of sulfenimide compound.

General imidazoles is: the zinc salt of 2-mercaptobenzimidazole, 2 mercaptomethyl benzimidazole, 2-mercaptobenzimidazole.

Zinc isopropyl xanthate is general xanthates sulphur promoter.

General thiocarbamide is: trimethyl thiourea, 1, the blend of 3-diethyl thiourea and 1,3-dibutyl thiourea, ethylene thiourea, dialkyl thiourea, rhenocure CA, di-o-tolyl thiocarbamide, dimethyl sulfourea, diethyl thiourea, dibutyl thiourea.

The example of the sulphur promoter of alkyl phenol disulphide type is with trade name VULTAC  2, VULTAC3 and the VULTAC5 compound available from ATOFINA ChemicalsInc..

The example of thiophosphate sulphur promoter is dialkyl dithiophosphoric acid copper, zinc dialkyl dithiophosphate, phosphordithiic acid amine zinc, zinc dibutyl dithiophosphate, O, O-diisopropyl--phosphordithiic acid copper, O, O-diisopropyl-zinc dithiophosphate.

Other various sulphur promoter comprise 4,4-dithio morpholine, curing N, N '-caprolactam, dibutyl xanthogen disulfide (dibutylxanthogen disulfide).

The polymer that can solidify (crosslinked) in the presence of molecular oxygen comprises that all can be by capturing hydrogen (or other can extract the fluoroelastomer that atom for example replaces with iodine and bromine) or carrying out crosslinked natural and synthetic polymer by double-bond polymerization.

At present, thinking can not be crosslinked by these mechanism, and produced by organic peroxide and azo initiator following, and substantially should non-existent free radical in curable compositions of the present invention in the presence of can degraded polymer comprise: polyvinyl chloride, polypropylene, butyl rubber, epichlorohydrin polymers and chloropropylene oxide ethylene oxide polymer. In this paper and claims, when mentioning the polymer of the suitable use relevant with the present invention, do not having under the contrary situation, when no matter when mentioning one group of polymer, " containing " of employing, " substantially by ... form ", " by ... form " vocabulary all represents not comprise the non-free radical cross-linked polymer of Duoing than a small amount of (1% (weight) or following).

Can carry out crosslinked polymer by the free radical that following organic peroxide and azo initiator form and comprise ethylene-propylene terpolymer (EPDM), ethylene-propylene copolymer (EPM), natural polyisoprene rubber (NR), SBR styrene butadiene rubbers (SBR), polybutadiene rubber (BR), synthetic polyisoprene rubber (IR), polyethylene (PE), ethane-acetic acid ethyenyl ester (EVA), acrylonitrile-butadiene-styrene (ABS) (ABS), unsaturated polyester (UP), SBS (SBS), SIS (SIS), neoprene (CR), acrylonitrile-butadiene rubber (NBR), polysulfide rubber (T), haloflex (CM), polyurethane (AU, EU), 1,1-fluoride copolymers (CFM), silicon rubber (PMQ), vinylsiloxane rubber (VMQ, PVMQ), polyacrylate (ACM), chlorosulfonated polyethylene (CSM) and fluorosioloxane rubber (FVMQ).

Be applicable to radical initiator of the present invention (organic peroxide and azo initiator) and comprise that all are suitable for solidifying (crosslinked) thermoplastic and the organic peroxide of two kinds of polymer of elastomer and the initator of azo initiator class.

Azo initiator is the known azo initiator that can be produced by thermal decomposition the free radical that can cause desired curing (crosslinked) reaction in the industry, for example 2,2 '-azo two-(2-acetyl Ethylene Oxide). Azo initiator in the United States Patent (USP) 3862107 and 4129531 also is suitable for, and this patent is incorporated by reference here.

Except hydroperoxides and liquid peroxy two carbonic esters, the organic peroxide that all known thermal decompositions produce the free radical that can cause desired curing (crosslinked) reaction all is considered to be applicable to the present invention. Peroxide two carbonic esters of dialkyl peroxide, diperoxy ketal, single peroxy carbonates, cyclic ketone peroxide, diacyl peroxide, organic sulfonyl-peroxide, peroxy esters and solid, ambient-temp-stable are preferred initators. Most preferred initator is dialkyl peroxide, peroxy ketal, cyclic ketone peroxide and diacyl peroxide.

At Jose Sanchez and Terry N, Myers is published in " Ke Erke of chemical technology-Ao Simo encyclopedia " (1996,18 volumes, the 4th edition) article " organic peroxide " in, can find document, important peroxide title and the physical property of all these organic peroxide types can be provided.

The example of dialkyl peroxide initator is:

Di-tert-butyl peroxide;

Tert-butyl group cumyl peroxide;

2,5-two (cumyl peroxide)-2, the 5-dimethylhexane;

2,5-two (cumyl peroxide)-2,5-dimethyl hexin-3;

4-methyl-4-(t-butyl peroxy)-2-amylalcohol;

4-methyl-4-(tertiary pentyl peroxide)-2-amylalcohol;

4-methyl-4-(cumyl peroxide)-2-amylalcohol;

4-methyl-4-(t-butyl peroxy)-2 pentanone;

4-methyl-4-(tertiary pentyl peroxide)-2 pentanone;

4-methyl-4-(cumyl peroxide)-2 pentanone;

2,5-dimethyl-2,5-two (t-butyl peroxy) hexane;

2,5-dimethyl-2,5-two (tertiary pentyl peroxide) hexane;

2,5-dimethyl-2,5-two (t-butyl peroxy) hexin-3;

2,5-dimethyl-2,5-two (tertiary pentyl peroxide) hexin-3;

2,5-dimethyl-2-t-butyl peroxy-5-hydrogen peroxide hexane;

2,5-dimethyl-2-cumyl peroxide-5-hydrogen peroxide hexane;

2,5-dimethyl-2-tertiary pentyl peroxide-5-hydrogen peroxide hexane;

Between/p-α, α-two [(t-butyl peroxy)-isopropyl] benzene;

1,3,5-three (t-butyl peroxy isopropyl) benzene;

1,3,5-three (tertiary pentyl peroxy isopropyl base) benzene;

1,3,5-three (cumyl peroxy isopropyl base) benzene;

Two [1,3-dimethyl-3-(t-butyl peroxy) butyl] carbonic ester;

Two [1,3-dimethyl-3-(tertiary pentyl peroxide) butyl] carbonic ester;

Two [1,3-dimethyl-3-(cumyl peroxide) butyl] carbonic ester;

Two-tertiary pentyl-peroxide;

The tertiary pentyl cumyl peroxide;

2,4,6-three (butyl peroxy)-S-triazine (2,4,6-tri (butylperoxy)-s-triazine);

1,3,5-three [1-(t-butyl peroxy)-1-Methylethyl] benzene;

1,3,5-three-[(t-butyl peroxy)-isopropyl] benzene;

1,3-dimethyl-3-(t-butyl peroxy) butanols;

1,3-dimethyl-3-(tertiary pentyl peroxide) butanols, and composition thereof.

The solid of example, the peroxide of ambient-temp-stable two carbonic esters are, but are not limited to:

Two (2-benzene oxygen ethyl) peroxide two carbonic esters; Two (4-tert-butylcyclohexyl) peroxide, two carbonic esters; Myristyl peroxide two carbonic esters; Dibenzyl peroxide two carbonic esters; Two (isobornyl) peroxide, two carbonic esters.

Can use separately or be selected from the compound that is expressed from the next with another kind of preferred dialkyl peroxide that other radical initiators of plan of the present invention are used in combination:

R wherein₄And R₅Between can each leisure in position or the contraposition, can be identical or different, and be selected from the straight or branched alkyl of hydrogen or 1-6 carbon atom. Dicumyl peroxide and isopropyl cumyl cumyl peroxide are exemplary examples.

Other dialkyl peroxide is:

Methacrylic acid 3-cumyl peroxide-1,3-dimethyl butyl ester;

Methacrylic acid 3-t-butyl peroxy-1,3-dimethyl butyl ester;

Methacrylic acid 3-tertiary pentyl peroxide-1,3-dimethyl butyl ester;

Three (1,3-dimethyl-3-t-butyl peroxy butoxy) vinyl silanes;

1,3-dimethyl-3-(t-butyl peroxy) butyl N-(1-{3-(1-methyl ethylene)-phenyl }-the 1-Methylethyl) carbamate;

1,3-dimethyl-3-(tertiary pentyl peroxide) butyl N-(1-{3-(1-methyl ethylene)-phenyl }-the 1-Methylethyl) carbamate;

1,3-dimethyl-3-(cumyl peroxide) butyl N-(1-{3-(1-methyl ethylene)-phenyl }-the 1-Methylethyl) carbamate.

In one group of diperoxy ketal initator, preferred initator is:

1,1-two (t-butyl peroxy)-3,3, the 5-trimethyl-cyclohexane;

1,1-two (t-butyl peroxy) cyclohexane;

4,4-two (tertiary pentyl peroxide) n-butyl pentanoate;

3,3-two (t-butyl peroxy) ethyl butyrate;

2,2-two (tertiary pentyl peroxide) propane;

3,6,6,9,9-pentamethyl-3-ethoxy carbonyl methyl isophthalic acid, 2,4,5-, four oxonane (tetraoxacyclononane);

4,4-two (t-butyl peroxy) n-butyl pentanoate;

3,3-two (tertiary pentyl peroxide) ethyl butyrate; And composition thereof.

Other peroxide that fall into total class of the present invention comprise benzoyl peroxide; The OO-tert-butyl group-O-hydrogen-single peroxide-succinate and OO-tertiary pentyl-O-hydrogen-single peroxide-succinate.

Exemplary cyclic ketone peroxide is to have following general formula (II), (III) and/or compound (IV).

(II)

(III) (IV) R wherein₁-R ₁₀Be selected from separately hydrogen, C₁-C ₂₀Alkyl, C₃-C ₂₀Cycloalkyl, C₆-C ₂₀Aryl, C₇-C ₂₀Aralkyl and C₇-C ₂₀Alkaryl, these groups can comprise line style or branched alkyl, and each R₁-R ₁₀Can be with one or more hydroxyl, C of being selected from₁-C ₂₀Alkoxyl, line style or side chain C₁-C ₂₀Alkyl, C₆-C ₂₀The group of aryloxy group, halogen atom, ester, carboxyl, nitride and amide groups replaces, and the active oxygen total amount that is used for the peroxide mixture of cross-linking reaction preferably at least 20% comes from have formula (II), (III) and/or compound (IV).

Some examples of suitable cyclic ketone peroxide are:

3,6,9-triethyl group-3,6,9-trimethyl-Isosorbide-5-Nitrae, 7-three peroxide nonanes (or methyl-ethyl-ketone peroxide cyclic trimer) and methyl-ethyl-ketone peroxide cyclic dimer;

3,3,6,6,9,9-vegolysen, 2,4,5-, four oxonane (tetraoxacyclononane);

Suitable peroxy esters example is:

2,5-dimethyl-2,5-two (benzoyl peroxide) hexane;

T-butyl perbenzoate;

T-butyl peroxy-acetate;

T-butyl peroxy-2 ethyl hexanoic acid ester;

The benzylhydroperoxide tert-pentyl ester;

The peracetic acid tert-pentyl ester;

T-butyl peroxy-isobutylate;

3-hydroxyl-1,1-dimethyl t-butyl peroxy-2 ethyl hexanoic acid ester;

OO-tertiary pentyl-O-hydrogen-single peroxysuccinic acid ester;

The OO-tert-butyl group-O-hydrogen-single peroxysuccinic acid ester;

Diperoxy phthalic acid di tert butyl carbonate;

T-butyl peroxy (3,3,5-tri-methyl hexanoic acid ester);

Isosorbide-5-Nitrae-two (t-butyl peroxy carbonyl) cyclohexane;

T-butyl peroxy-3,5,5-tri-methyl hexanoic acid ester;

T-butyl peroxy-(cis-3-carboxyl) propionic ester;

3-methyl-3-t-butyl peroxy allyl butyrate.

The example of single peroxy carbonates is:

The OO-tert-butyl group-O-isopropyl list peroxy carbonates;

The single peroxy carbonates of the OO-tert-butyl group-O-(2-ethylhexyl);

1,1,1-three [2-(t-butyl peroxy-ketonic oxygen) ethoxyl methyl] propane;

1,1,1-three [2-(tertiary pentyl peroxide-ketonic oxygen) ethoxyl methyl] propane;

1,1,1-three [2-(cumyl peroxide-ketonic oxygen) ethoxyl methyl] propane;

OO-tertiary pentyl-O-isopropyl list peroxy carbonates;

The example of diacyl peroxide is:

Two (4-methyl benzoyl) peroxide;

Two (3-methyl benzoyl) peroxide;

Two (2-methyl benzoyl) peroxide;

Didecanoyl peroxide; Dilauroyl peroxide;

2,4-, two bromo-benzoyl peroxide;

Succinic acid peroxide;

The dibenzoyl peroxide;

Two (2,4-, two chloro-benzoyls) peroxide.

The described imino group peroxide type of PCT patent application WO9703961A1 (on February 6th, 1997) also is considered to be applicable to the present invention.

Those skilled in the art can easily select one's own profession for various an amount of components of the present invention, and by a series of bench-scale testings, in the polymer samples that will solidify (crosslinked), increase constituent content, just can easily optimize soon concentration. From same test, also can determine best processing (mixing) time and temperature etc., as optimum curing time and temperature.

The general compound of employing formula (a) (dimaleimide and two citraconimides) in the present composition, consumption is about 0.2-10.0 part (weight), take 100 parts of (weight) polymer as benchmark (phr), preferred about 1.0-5.0phr, most preferably from about 1.5-3.0phr.

The general organic compounds containing sulfur that can promote to be undertaken by sulphur the sulfur vulcanization of crosslinked polymer that in the present composition, adopts. Consumption is about 0.01-20phr, preferably about 0.1-1.0phr, most preferably from about 0.1-0.5phr. Those skilled in the art can understand that these compounds are two types one's own profession. They are to vulcanizing the compound of contributing sulphur and the compound that only promotes sulfur vulcanization. Every compounds or their mixture all are considered to equivalent of the present invention.

When the alkyl phenol disulphide polymer of VULTAC  type used separately, consumption is about 0.5-20phr preferably, when perhaps being used in combination with other sulphur promoter, and the about 0.1-10phr of consumption.

The general radical initiator (organic peroxide and/or azo initiator) that adopts, consumption is about 0.04-10phr, preferably is about 1-4phr.

Solidify required Time-temperature condition and greatly depend on the structure of free radical curing agent. For azo initiator, appropraite condition is as described in United States Patent (USP) 3632107 and 4129531.

For the present composition, the suitable time of crosslinked specific aggregation compositions and temperature conditions can be determined by such mode: carry out the good flow graph research of a small amount of control, and from these results of study, select numerical value, wherein time/temp relation be the radical initiator half-life in this system 5-15 doubly.

The conventional additives that the present invention has also planned other for example antioxidant (preferred hindered phenol and quinoline polymer), aliphatic processing oil and other processing aids, pigment, dyestuff, tackifier, wax, reinforcing agent, UV stabilizing agent, blowing agent, activator and antiozonant also can during the curing schedule and before, be present in composition afterwards.

The polysulfide polymer of plan of the present invention is by α, the known polysulfide polymer that the reaction of ω-dihalo alkyl (or the assorted alkyl of dihalo) compound and metal preferred as alkali polysulfide is made. The polysulfide polymer of buying commonly used is liquid or solid, take mercaptan or hydroxyl as terminal, comes from by 1,2-dichloroethanes, 2,2 '-two chloro-diethyl ether or two (2-chloroethyl) formal and alkali metals polysulfide (MSx_x) the material made of reaction, MSx_xIn M be alkali metal ion, preferably formed by sodium, x is to as high as about 6 number more than 1.

Plan polysulfide polymer of the present invention can be used for replacing other compounds (B) or mix with it, and consumption equates with these compound aforementioned quantities. Because think that excessive polysulfide polymer can be unharmful to enforcement of the present invention, also having planned them can and choose wantonly and radical initiator (one or more) premixed with compound (A) (one or more), forms solid-state or liquid masterbatch. Polysulfide polymer also can be premixed in the polymer that will solidify, and the operator also can select simultaneously or subsequently mixing cpd (A) (one or more) and radical initiator (one or more). Be used in combination polysulfide polymer with other sulphur promoter of plan of the present invention, can reduce the consumption of sulphur promoter required for the present invention.

Similarly, those skilled in the art can understand one's own profession, if compound (A) is present in the curable compositions, even another kind of compound (B) does not exist, polysulfide polymer self also can be solidified into non-adhesive surface by radical initiator in the presence of molecular oxygen. Therefore, it is considered herein that this curable compositions is the equivalent of the described composition of second aspect present invention.

Usually adopt sulfur vulcanization to be cured with large gauging and/or carbon black-filled crosslinkable elastomeric composition (being commonly referred to high increase-volume elastomer formulation), rather than radical initiator. Free radical solidifies more difficult, because the free radical that forms lacks selectivity, can also can react with elastomer with filler and oil. This can reduce the efficient of radical initiator.

Find, use haloflex and/or chlorosulfonated polyethylene as the supplemental components of each side composition of the present invention, can unexpectedly improve the curing efficiency of free radical in high increase-volume elastomer formulation, and make the surface viscosity reduction of free radical curing system or do not have viscosity. In the first aspect present invention composition, be used as the chlorination of supplemental components and/or the consumption of chlorosulfonated polyethylene and can be about 1-50% (weight), preferred 15-40% (weight), more preferably 20-35% (weight).

In some cases, in the preparation of second aspect present invention composition, contain such two kinds of polymer as a supplement component can reduce the working concentration of first aspect present invention composition.

The following examples further illustrate the best mode for carrying out the invention of inventor plan, they are interpreted as exemplary rather than restriction the present invention.

Embodiment

Embodiment 1

On the evaluation of the prior art compositions of crosslinked EPM and the impact of effects on surface viscosity and the degree of cross linking thereof under the air existence

In the present embodiment, estimated in solidifying with organic peroxide various known auxiliary curing agent for example unsaturated monomer crosslinking coagent, elementary sulfur or for the compound of sulphur. The elastomer that uses in the present embodiment is ethylene-propylene copolymer (EPM), and commodity are called Exxon VISTALON  504. The special sulfur-containing compound of high-load (2.5-20 part) is used in what is claimed is being with or without of prior art (United States Patent (USP) 4983685) under the optional unsaturated monomer, be used in the presence of air, using the peroxide crosslinking elastomer, and form non-sticky surface. Other documents adopt sulphur. In the present embodiment, separately or in the presence of some monomer auxiliary agents, estimated low content sulphur or confession sulphur compound. These formulations of the data declaration of table 1 form tacky surfaces, but also form the good (M of physical property_HMoment of torsion is higher) cross-linking products. Also estimated the mixture (by the enlightenment of prior art) of optional monomer auxiliary agent, high-load sulphur compound and peroxide. When there was lower cross-linked elastomer in air, it formed non-adhesive surface, still, compares with the monomer crosslinked formulation of the peroxide of routine, and physical property is defective.

In table 1 formulation, the carbon black formulation of Application standard. Carbon black (N774), the Sunpar  LW150 processing oil available from Sun, zinc oxide, antioxidant (AgeRite MA) are sneaked among the EPM. In addition, all formulations contain all that the organic peroxy ketal peroxide, ATOFINA Chemicals Inc. of 8 part 40% mensuration usefulness sell is dispersed in LUPEROX  231XL[40%1 on the calcium carbonate, 1-two (butyl peroxy)-3,3, the 5-trimethyl-cyclohexane]. Adopt the Flexsys MDR  2000E mould rheometer measurement alive degree of cross linking. Sample also solidified 10 minutes in 365 °F in hot-air, after taking out from baking oven, put from the teeth outwards paper handkerchief with moderate with consistent pressure at once, judged surface viscosity. Surface viscosity is divided into 1-10 grade, and 1: inviscid, 10: very sticking.

When solidifying in hot-air, the composition of the Minor element sulphur of peroxide and 0.3 part (general EPM solidifies) (table 1, numbering 1) forms the crosslinked (according to M of good level_H), but surperficial toughness. 2 parts of HVA-2 (Du Pont sells for N, N '-phenylene dimaleimide) auxiliary agent is used in combination with peroxide (table 1, numbering 2), forms grade raising crosslinked (according to M of expection_H), but surperficial toughness unfortunately, for poor. Illustrate: under every kind of situation, all use 1 part of antioxidant AgeRite MA (quinoline of the polymerization that R.T.Vanderbilt sells), this is the standard content that does not affect the surface. 0.3 the composition of part elementary sulfur and 2 parts of HVA-2 (table 1, numbering 5) can form crosslinked (the comparing with the numbering 2 of only using HVA-2) that grade further improves, but unfortunately, also can form high surface viscosity (7 in 10 grades). Therefore, the mixture of auxiliary agent and Minor element sulphur can improve crosslinked, but does not improve surface viscosity. The prior art enlightenment needs 2.5-20 part sulphur promoter or its equivalent. When solidifying in hot-air, it is good crosslinked to use HVA-2 auxiliary agent and peroxide to form in the carbon black EPM of oil-containing and antioxidant formulation, still unfortunately, also forms tacky surfaces. 4 parts of monomer auxiliary agent SR-350  and 0.3 part of elementary sulfur together use, and can form the crosslinked of highest ranking, but poor surface viscosity (seeing Table 1, numbering 4) is arranged. SR-350 is trimethylol-propane trimethacrylate, and Sartomer sells.

Number the combination of 3,1.2 parts of Sulfads  and peroxide in the table 1, can form underproof surface viscosity, 6 in 10 grades, and form the bad curing of grade, according to M_H Sulfads is 98% bis-pentamethylenethiuram tetrasulfide, and R.T.Vanderbilt sells; Therefore, the actual addition of bis-pentamethylenethiuram tetrasulfide is 1.2 * 0.98-1.18 part. At last, when there be lower curing in air, 1.2 parts of Sulfads were used in combination with 2 parts of HVA-2 and peroxide and can form good surface, unfortunately, and desired crosslinked physical property decline, as the low M that obtains_HShown in the value.

The present embodiment explanation, during the lower curing of air existence, qualified crosslinked the maintenance simultaneously, hang down under the purpose of surface viscosity keeping grade, do not measure in advance for example mixed effect of peroxide, monomer auxiliary agent and elementary sulfur or sulfur-containing compound of different auxiliary curing agents. Can suppose, if can improve crosslinked total grade with various auxiliary agents and peroxide, so, in the presence of air, just can improve surface viscosity. But our data show, when there be lower curing in air, can improve crosslinked grade, but can not improve simultaneously surface viscosity.

In addition, when the enlightenment that utilizes prior art, when surface viscosity is descended, find total crosslinked bad. Surface-crosslinked under crosslinked (having got rid of air) in the sample and the air existence is two independently operations. Increase or reduce the amount of crosslinking coagent, perhaps different auxiliary curing agents and peroxide are used in combination and cause the result that can not estimate. Crosslinking coagent for example HVA-2 helps to increase the crosslinked grade of peroxide cure, still, in air set, forms poor surface viscosity. When using the monomer auxiliary agent, HVA-2 or SR350 and other auxiliary curing agents are when for example elementary sulfur or sulphur donor/promoter compound are used in combination, as described in the prior art, we find, final physical property significantly descends, and therefore, has negated the advantage of monomer auxiliary agent-peroxide cure system.

Table 1

Numbering	1	2	3	4	5	6
							VISTALON  504EPM elastomer	100	100	100	100	100	100
Below various components (Phr) add umber (weight) take 100 parts of rubber as benchmark, namely need not proofread and correct measuring.
							N774 (phf) carbon black	75	75	75	75	75	75
LW150 oil (phr)	10	10	10	10	10	10
							ZnO(phr)	5	5	5	5	5	5
AgeRite MA (antioxidant)	1	1	1	1	1	1
							LUPEROX  231XL40% peroxide	8	8	8	8	8	8
SR-350(phr)	-	-	-	4.0	-	-
							HVA-2	-	2.0	-	-	2.0	2.0
Sulphur	0.3	-	-	0.3	0.3	-
							Sulfads(98％)	-	-	1.2	-	-	1.2
150 ℃ crosslinked, MDR2000E mould flow graph alive
							M H(in-lb)	29	39	20	44	43	29
In 365 °F of hot-airs, solidified 10 minutes, determine surface viscosity
							Surface viscosity*	7	7	6	10	7	1

^*Surface viscosity grade: 1-10, wherein 10 is very sticking, and 1 is not sticking.

Embodiment 2

Crosslinked entirely saturated (not having two keys in the polymer chain) elastomeric prior art peroxide formulation mixes the comparison that mixes with novel peroxide formulation

When crosslinked in the presence of air, novel peroxide formulation forms the good physical behavior that conventional peroxide cure has, and unexpected non-sticky surface.

In the present embodiment, being scattered in 40% on the clay measures the dicumyl peroxide of usefulness and is used for crosslinked EPM (polyethylene propylene copolymer), VISTALON  707 (Exxon). The mixture that numbering 1 has been estimated dicumyl peroxide and SR206 (GDMA) in the table 2 crosslinked compression set % and the surface viscosity that in hot-air, solidifies in MDR. Illustrate: prior art (United States Patent (USP) 4983685) uses SR206 as optional monomer auxiliary agent in an embodiment. The mixture of this peroxide and auxiliary agent in hot-air 400 °F when solidifying forms good curing (M_H) and compression set %, the surface is very sticking. What is claimed is in peroxide SR206 mixture of prior art adds 2.5 parts of Sulfads  (98% bis-pentamethylenethiuram tetrasulfide) improvement surface, but damaged total compression set %, numbers 2 in the table 2.

Numbering 4 adopts 0.8 part of Sulfads described in prior art United States Patent (USP) 4983685 specifications to form good surface with 2.2 parts of optional HVA-2 auxiliary agents, the mixture of 5 parts of DC40 in the table 2, but compression set % is very poor. Illustrate: sulfur vulcanization rather than peroxide crosslinking can estimate to reach the compression set value of 100-60%.

Number 3 in the table 2,5 parts of Vanox ZMTI (93%2-sulfydryl-mebendazole (toluimidazole) zinc) of prior art enlightenment can improve compression set with optional SR-206 auxiliary agent, but form underproof very sticking surface.

Unexpectedly, low content bis-pentamethylenethiuram tetrasulfide (0.4 part of content does not fall into United States Patent (USP) 4983685 scopes), 0.4 part of Durax (98%N-cyclohexyl-2-[4-morpholinodithio sulfenamide) and 5 parts of DC40 (40% dicumyl peroxide) of numbering 5 in the table 2, when in hot-air oven, solidifying, form non-adhesive surface, have 41% compression set and the better crosslinked grade of raising.

Numbering 6 in the table 2 shows, unexpectedly, 0.4 part of Durax, 0.4 part of Vanax A (98%4,4 '-dithio morpholine), 2.2 parts of HVA-2 (monomer auxiliary agent) and 5 parts of DC40 (40% dicumyl peroxide), form non-adhesive surface, have 31% compression set. Find to use in the prior art Durax and/or Vanax A and peroxide and dimaleimide type auxiliary agent to be used for enlightenment that elastomer is solidified in hot-air. Numbering 7 uses 0.8 part of Durax to replace the Durax/Vanax mixture in the table 2, and 400 °F of hot-airs form more unexpected good compression set 21% and non-adhesive surface when solidifying.

Last numbering 8 in the table 2 adopts the model mixture of 2.2 parts of HVA-2,0.4 part of VULTAC5,0.4 part of Durax and 5 parts of DC40, has obtained unexpected good result, good non-adhesive surface and well 18% extremely low compression set. Do not enlighten VULTAC5 (75% alkyl phenol disulphide polymer is available from Elf Atochem) in the prior art and together be used for elastomeric hot-air curing with peroxide and dimaleimide type auxiliary agent. Illustrate: be equivalent to 0.3 part of alkyl phenol disulphide polymer of adding because analysis is 75%, 0.4 part of VULTAC5.

The present embodiment explanation, the prior art formulation adopts for example mixture of bis-pentamethylenethiuram tetrasulfide and optional monomer auxiliary agent of compound that peroxide and high-load select, in fact form non-adhesive surface, but crosslinked elastomeric final physical property is very poor. For the peroxide cure formulation, the 0.8 part of thiuram preferred compound that adopts prior art United States Patent (USP) 4983685 to enlighten, but be lower than 2.5-20 part of claim, can form the very poor cross-linked elastomer of heat aging performance.

The crosslinked polymer of high compression permanent deformation value explanation prior art of 60%+ can be assigned 70 hours permanent deformation 150 ℃ of applied pressure effects, and this is the standard testing (ASTM D-395-61) of peroxide cure. For unsaturated polymer, in hot-air, can access non-adhesive surface by sulfur vulcanization, but form poor heat aging performance. If physical property is low M for example_HAnd/or high (poor) percentage of consolidation permanent deformation value do not have notable difference, and the peroxide cure system of solidifying in hot-air is so compared with sulfur vulcanization does not just have advantage. Traditionally, most high temperature and performance application are selected peroxide cure. Peroxide crosslinking forms carbon-carbon bond, and this makes cross-linked polymer manufacturer can use whole elastomer process capabilitys.

Table 2

Numbering	1	2	3	4	5	6	7	8
									VISTALON707EPM	100	100	100	100	100	100	100	100
Below the umber (weight) of various components take 100 parts of rubber as benchmark (phr) add, namely need not proofread and correct measuring.
									N774 (phr) carbon black	75	75	75	75	75	75	75	75
LW150 processing oil (phr)	30	30	30	30	30	30	30	30
									ZnO	5	5	5	5	5	5	5	5
Stearic acid	1	1	1	1	1	1	1	1
									AgeRite MA	1	1	1	1	1	1	1	1
DC40	8.0	8.0	8.0	5.0	5.0	5.0	5.0	5.0
									SR-206	2.0	2.0	2.0	-	-	-	-	-
HVA-2	-	-	-	2.2	2.2	2.2	2.2	2.2
									Sulfads(98％)	-	2.5	-	0.8	0.4	-	-	-
ZMTI(93％)	-	-	5.0	-	-	-	-	-
									Vanax A(98％)	-	-	-	-	-	0.4	-	-
VULTAC5(75％)	-	-	-	-	-	-	-	0.4
									Durax(98％)	-	-	-	-	0.4	0.4	0.8	0.4
170 ℃ of MDR solidify
									M H(in-lb)	17	9	16	17	18	17	16	16
T S1Minute	1.04	1.56	1.06	1.20	1.11	0.61	0.58	0.63
									T C90Minute	5.8	7.5	5.5	6.6	5.2	5.9	4.1	4.2
400 °F of air sets 12 minutes
									The surface	10	1.5	7	1.5	2	2.5	2.5	2
70 hours compression set of 150 ℃ of temperature
									Compression set %	25	100	35	63	41	31	21	18

Embodiment 3

Novel peroxide-compositions of additives forms physical property cross-linked elastomer solid or foamed material that for example the percentage of consolidation permanent deformation is good in hot-air, also form non-adhesive surface when solidifying in the presence of air simultaneously.

Used elastomer is to contain 4% bicyclopentadiene as the Uniroyal  X3378EPDM of the 3rd monomer in the present embodiment. Peroximon DC40KEP (40% dicumyl peroxide on the clay) is as peroxide cross-linking agent. In the present embodiment, change the content of Sulfads  (98% bis-pentamethylenethiuram tetrasulfide), VULTAC  5 (75% alkyl phenol disulphide polymer) and Durax  (98%N-cyclohexyl-2-benzothiazole sulfenamide), keep peroxide and HVA-2 auxiliary agent constant (table 3, numbering 2-6).

Illustrate: add 0.5 part of (phr) Sulfads and be equivalent to 0.49 part of bis-pentamethylenethiuram tetrasulfide, take 100 parts of rubber as benchmark. Referring to numbering 2,3,4, be surprised to find that when with the bis-pentamethylenethiuram tetrasulfide that is lower than 0.5phr (take sterling as benchmark) and HVA-2 and peroxide, to have good compression set and non-adhesive surface.

When changing Sulfads (98% bis-pentamethylenethiuram tetrasulfide), VULTAC5 and Durax concentration, the unexpected discovery uses our novel peroxide/compositions of additives to solidify solid and the foamed material that can form cross-linked elastomer by hot-air. When the pure bis-pentamethylenethiuram tetrasulfide that is lower than 0.5phr and VULTAC5 or Durax together used, the cross-linked elastomer foamed material that can obtain to have non-adhesive surface saw Table and numbers 2,3 and 4 in 3. Use the mixture of VULTAC5 or VULTAC5 and Durax can form crosslinked EPDM solid, the numbering 5 and 6 in the table 3. Under every kind of situation (the numbering 2-6 in the table 2), accident obtains good compression set fraction values, in fact is equivalent to conventional peroxide cure, the numbering 1 in the table 2.

Under 100-120 ℃ of temperature, measure sulfur vulcanization compression set, seldom 150 ℃ of lower measurements, because performance is usually very poor under the high temperature. The compression set value proved in 150 ℃, 70 hours preferably at present, and the novel peroxide-compositions of additives of these shown in the invention process can form the unexpected good crosslinked EPDM of heat aging performance. In addition, novel peroxide-compositions of additives unexpectedly provides and has formed solid-state and method foam articles.

Although do not want to be fettered, but it is believed that in curing just interim, the very fast time of scorch relevant with producing unexpected cross-linked network is faster than emitting to form solid-state cured article in the gas self-curing system, is difficult under this low pressure conditions in the baking oven different from close die. When described time of scorch postponed, emitting of gas can occur simultaneously with the formation of cross-linked network. In addition, except these unexpected processing and technical advantage, when solidifying in the presence of air, these novel peroxide formulations also can form complete non-adhesive surface.

Table 3

Numbering	1	2	3	4	5	6
							Uniroyal X3378 EPM	100	100	100	100	100	100
Below the umber (weight) of various components take 100 parts of rubber as benchmark (phr) add, namely need not proofread and correct measuring.
							The N774 carbon black	100	100	100	100	100	100
Sunpar2280 oil	30	30	30	30	30	30
							ZnO	4	4	4	4	4	4
Stearic acid	0.5	0.5	0.5	0.5	0.5	0.5
							AgeRite D	1	1	1	1	1	1
The DC40KEP40% dicumyl peroxide	8.0	5.2	5.2	5.2	5.2	5.2
							HVA-2	-	2.0	2.0	2.0	2.0	2.0
Sulfads(98％)	-	0.5	0.3	0.3	-	-
							VULTAC5(75％)	-	-	-	0.5	0.8	0.5
Durax(98％)	-	0.3	0.5	-	-	0.3
							170℃MDR
M H(in-lb)	24	30	30	31	32	31
							T S1Minute	0.53	0.83	0.76	0.69	0.55	0.54
T C90Minute	7.9	5.9	5.6	5.5	4.9	4.7
							150 ℃ of compression sets in 70 hours
Compression set %	21	30	24	27	22	19
							400 °F solidified 10 minutes in air
The surface	10	1	1	1	1	1
							Venting	Nothing	Have	Have	Have	Nothing	Nothing

Embodiment 4

Use dicumyl peroxide and HVA-2 in the table 4, adopt the soon EPDM (Royalene 509EPDM) of curing, higher ethene, study novel peroxide-compositions of additives

The formulation of prior art (numbering 2 and 3 in the table 4) forms good surface after hot-air solidifies, but unfortunately, the compression set physical property was very poor in 150 ℃/70 hours, and emitted bad stink. These 61% with 71% compression set value to can be resulting similar by sulfur vulcanization rather than peroxide cure. In addition, prior art sample #2 and 3# use 2.5 parts of Sulfads , a large amount of bubbles can be clipped in the central authorities of cured article, and this is considered to underproof curing defective.

On the contrary, adopt all samples (numbering 5-12) of the novel peroxide-compositions of additives of the present invention's enlightenment can obtain good physical property, i.e. very low compression sets in 150 ℃/70 hours are to the control reaction that adopts peroxide, used additives or sulfur additives (numbering 1 in the table 1) are resulting very not similar. In this control reaction, although solidifying, hot-air has very sticking surface (10 in 10 grades), can obtain 15% compression set. Good compression permanent deformation value in 120 ℃/70 hours probe temperatures that the mixture of HVA-2 auxiliary agent and peroxide (numbering 4) and antioxidant AgeRite D (generally the operation as standard adds in the rubber formulation) can be reduced, but unfortunately, when crosslinked under air exists, surface very poor (7 in 10 grades). The all samples of the numbering 5-12 that the present invention is included when solidifying, all can obtain the good physical that peroxide cure has in the presence of air, and the surface is inviscid.

Table 4

	1	2	3	4	5	6	7	8	9	10	11	12
													Royalene521EPDM	100	100	100	100	100	100	100	100	100	100	100	100
Below the umber (weight) of various components take 100 parts of rubber as benchmark (phr) add, namely need not proofread and correct measuring.
													N550	50	50	50	50	50	50	50	50	50	50	50	50
N990	25	25	25	25	25	25	25	25	25	25	25	25
													LW150 oil	20	20	20	20	20	20	20	20	20	20	20	20
ZnO	4	4	4	4	4	4	4	4	4	4	4	4
													Stearic acid	1	1	1	1	1	1	1	1	1	1	1	1
AgeRiteD	1	1	1	1	1	1	1	1	1	1	1	1
													DC40KEP40％	7.2	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0
HVA-2	-	2.2	-	2.2	2.2	2.2	2.2	2.2	2.2	2.2	2.2	2.2
													SR-206	-	-	2.2	-	-	-	-	-	-	-	-	-
Sulfads98％	-	2.5	2.5	-	0.5	0.3	0.3	-	0.3	0.3	0.3	0.3
													VanaxA98％	-	-	-	-	-	-	-	0.3	-	-	-	-
M.Tuads98％	-	-	-	-	-	0.2	-	-	-	-	-	-
													Durax98％	-	-	-	-	-	-	0.2	0.2	-	-	-	-
Unads98％	-	-	-	-	-	-	-	-	0.2	-	-	-
													M.Zimate98％	-	-	-	-	-	-	-	-	-	0.2	-	-
M.Niclate98％	-	-	-	-	-	-	-	-	-	-	0.2	-
													M.Cumate98％	-	-	-	-	-	-	-	-	-	-	-	0.2
170 ℃, 1 ° radian MDR
													M H	39	43	27	45	40	38	40	42	38	38	41	37
T S1	0.4    5	0.6    8	0.7     5	0.3    8	0.6    0	0.6    2	0.5   8	0.4   2	0.6   5	0.4   6	0.5   6	0.5    3
													T C90	7.1	4.3	2.5	4.6	4.8	5.3	4.6	4.9	4.8	5.1	4.8	5.2
400 °F solidified 12 minutes in air
													The surface	10	1	1	7	1	1	1	1	1	1	1	1
Lower 70 hours compression set % of 120 ℃ of temperature
													Compression set %	11	46	-	8	16	18	14	-	15	-	-	-
Lower 70 hours compression set % of 150 ℃ of temperature
													Compression set %	15	61	71	-	-	-	19	17	-	21	17	21

Embodiment 5

To use uniquely dimaleimide auxiliary agent and the additive selected, be used to provide overall good peroxide type physical property and can be in the presence of air the evaluation of the general type auxiliary agent of curing rubber surperficial (non-adhesive surface)

Dimaleimide and Sulfads  and VULTAC  5 combinations together are used for crosslinked fast curing type EPDM (Royalene  509EPDM) with dicumyl peroxide, and dimaleimide is estimated.

Prior art has been enlightened the various auxiliary agents that use two types of monomer and non-monomers, and improving cross-linking efficiency, but the effect during with their ingresss of air is irrelevant. We find, compare with the dimaleimide type, use these different auxiliary agents only may improve reaction with oxygen, and make rubber surface more tacky after the curing in the presence of the air.

In table 5, HVA-2 (auxiliary agent of dimaleimide type) together can form non-adhesive surface with the mixture of 0.3 part of Sulfads and 0.2 part of VULTAC5. Use other auxiliary agents can form tacky surfaces, for example TAC (triallyl cyanurate), SR-350 (trihydroxy methyl propane trimethyl acrylate), 1.2BR (1,2 liquid butadiene rubber), Santolink XI-100 (allyl glycidyl ether alcohol resin), TAP (TAP) and pBQ (1,4-benzoquinone).

Table 5

Numbering	1	2	3	4	5	6	7	8	9
										Royalene509EPDM	100	100	100	100	100	100	100	100	100
Below the umber (weight) of various components take 100 parts of rubber as benchmark (phr) add, namely need not proofread and correct measuring.
										N550	50	50	50	50	50	50	50	50	50
N990	25	25	25	25	25	25	25	25	25
										LW150 oil	20	20	20	20	20	20	20	20	20
ZnO	4	4	4	4	4	4	4	4	4
										Stearic acid	1	1	1	1	1	1	1	1	1
AgeRite D	1	1	1	1	1	1	1	1	1
										DC40KEP	5.4	5.4	5.4	5.4	5.4	5.4	5.4	5.4	5.4
Sulfads98％	-	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3
										VULTAC5 98％	-	0.2	0.2	0.2	0.2	0.2	0.2	0.2	0.2
HVA-2	-	-	2.0	-	-	-	-	-	-
										TAC	-	-	-	3.0	-	-	-	-	-
SR-350	-	-	-	-	4.0	-	-	-	-
										1,2BR	-	-	-	-	-	6.0	-	-	-
Santolink XI-10	-	-	-	-	-	-	4.0	-	-
										TAP	-	-	-	-	-	-	-	4.0	-
pBQ	-	-	-	-	-	-	-	-	1.0
										170 ℃ of MDR solidify
M HIn-lb	32	27	42	26	32	27	19	23	22
										T C90Minute	7.7	6.6	4.5	7.6	6.7	8.2	7.0	7.2	9.5
200 ℃ of air sets
										The surface	10	4	1	7	7	4	4	4	4

Embodiment 6

Use the low content sulphur promoter of prior art and the mixture of HVA-2 and dicumyl peroxide can not form non-adhesive surface. The compound of selecting that uses prior art low content compound and HVA-2 during crosslinked fast curing EPDM (Royalene  509), unexpectedly forms non-adhesive surface in the presence of air.

Use 0.2 part of Methyl Zimate (98% PZ) or 0.2 part of Unads (98% single sulfuration tetra methylthiuram) when solidifying in the presence of air with HVA-2, can form poor solidified surface (tacky surfaces). Therefore, be used in combination compound and HVA-2 (N, N '-phenylene dimaleimide) auxiliary agent and the peroxide of the very low content of prior art, to form non-adhesive surface be not apparent to cross-linked elastomer in the presence of air.

As VULTAC  5 (75% alkyl phenol disulphide polymer) or Vanax  A (98%4,4 '-dithio morpholine) for example Methyl Zimate or Unads mix with the low content compound of these prior aries, when crosslinked in the presence of air, can unexpectedly obtain non-adhesive surface.

Therefore, unique mixture of peroxide, HVA-2 auxiliary agent and low content dithiocarbamate or thiuram and VULTAC5 or VanaxA can form the cross-linked polymer of surface cure in the presence of air. In addition, notice not produce bubble, therefore can form solid-state crosslinking component with these model mixtures.

Table 6

Numbering	1	2	3	4	5	6	7	8	9
										Royalene509EPDM	100	100	100	100	100	100	100	100	100
Below the umber (weight) of various components take 100 parts of rubber as benchmark (phr) add, namely need not proofread and correct measuring.
										N774	75	75	75	75	75	75	75	75	75
Sunpar2280 oil	20	20	20	20	20	20	20	20	20
										ZnO	5	5	5	5	5	5	5	5	5
Stearic acid	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
										DC40KEP40％	7.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0
HVA-2	-	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5
										M.Zimate98％	-	0.2	0.2	0.2	0.2	-	-	-	-
Unads98％	-	-	-	-	-	0.2	0.2	0.2	0.2
										Vanax A98％	-	-	0.5	-	-	-	0.5	-	-
Sulphur	-	-	-	0.15	-	-	-	0.15	-
										VULTAC 575％	-	-	-	-	0.67	-	-	-	0.67
170℃MDR
										M HIn-lb	43	42	41	43	41	43	40	42	41
T S1Minute	0.38	0.34	0.45	.042	0.40	0.47	0.50	0.47	0.49
										T C90Minute	7.2	4.6	4.8	4.4	4.4	4.5	5.3	4.7	4.5
420 °F air set 8 minutes
										The surface	10	7	1	4	1	7	1	4	1
Bubble	Nothing	Nothing	Nothing	Nothing	Nothing	Nothing	Nothing	Nothing	Nothing

Embodiment 7

Use the Minor element sulphur of prior art and the low content Sulfads  of prior art, together use the HVA-2 monomer auxiliary agent that maybe need not choose wantonly, in hot-air, can form good surface cure, but the physical property poor (61% and 49% compression set) that forms.

Therefore, use the known low content sulphur compound of prior art and the idea of the auxiliary agent of advising and peroxide to be not easy to obtain the combination property of good surface cure and desired expection physical property.

Table 7

	1	2	3	4
					Keltan 4906EPDM	100	100	100	100
Below the umber (weight) of various components take 100 parts of rubber as benchmark (phr) add, namely need not proofread and correct measuring.
					N774	80	80	80	80
N330	20	20	20	20
					LW150 oil	40	40	40	40
ZnO	6	6	6	6
					Stearic acid	1	1	1	1
AgeRite D	1	1	1	1
					DC40P(40％)	5	5	5	5
HVA-2	-	-	1.8	1.8
					Sulphur	-	0.2	-	0.2
Sulfads98％	-	0.4	-	0.4
					420 °F solidified 8 minutes in air, surface viscosity (1-10), and 10 is viscosity	10	1	10	1
The compression set in 70 hours of 120 ℃ of temperature
					Compression set %	25	61	12	49

Embodiment 8

In the present embodiment, illustrated that the effect of novel peroxide-compositions of additives in the EPDM formulation of filling and non-filling is fine.

Numbering #2 only contains EPDM, and the novel peroxide-additive of preparation, does not namely have oil, carbon black, ZnO or stearic acid. Illustrate: as enforcement of the present invention enlightens, when novel formulation solidifies, can form complete noncohesive surface (1 in 10 grades) in the presence of air, wherein 10 is viscosity. The carbon black and the oil (numbering 4) that add constant form good non-adhesive surface in the presence of air. For the curing of organic peroxide type, use the very carbon black of high-load (amount that exceeds used EPDM) and high amounts of oil, shown in numbering 6 and 8 in the table 8, can as expection, reduce the degree of cross linking (M_H). But when the amount of peroxide-additive agent mixture increased, there was the lower surface cure that forms unexpectedly good (4 in 10 grades) in air, as numbers shown in the of 8. As everyone knows, high amounts of oil and carbon black can adversely affect the curing of peroxide. Peroxide radical can easily be captured hydrogen from oil and rubber. When oil concentration increased, this can significantly reduce the efficient of peroxide cure. This can be by the M of the decline of two kinds of peroxide testers that do not contain additive_HObtain explanation (relatively number 3 constant oil and carbon black and number 5 high amounts of oil and carbon black).

Table 8

Numbering	1	2	3	4	5	6	7	8
									Royalene509EPDM	100	100	100	100	100	100	100	100
Below the umber (weight) of various components take 100 parts of rubber as benchmark (phr) add, namely need not proofread and correct measuring.
									The N774 carbon black	-	-	75	75	130	130	130	130
Sunpar 2280 oil	-	-	20	20	60	60	60	60
									ZnO	-	-	5.0	5.0	5.0	5.0	5.0	5.0
Stearic acid	-	-	0.5	0.5	0.5	0.5	0.5	0.5
									DC40KEP40％	7.00	5.00	7.00	5.00	7.00	5.00	10.5	7.50
HVA-2	-	1.50	-	1.50	-	1.50	-	2.25
									VULTAC575％	-	0.67	-	0.67	-	0.67	-	1.00
B.Zimate98％	-	0.2	-	0.2	-	0.2	-	0.30
									170 ℃, the 1 ° crosslinked MDR of radian solidifies
M HIn-lb	40	31	43	41	18	24	26	31
									T S1Minute	0.45	0.46	0.38	0.40	0.54	0.50	0.43	0.44
T C90Minute	8.3	5.8	7.2	4.4	7.0	4.2	6.6	3.8
									375 °F solidified 14 minutes in air
The surface	7	1	10	1	10	6	10	4

Embodiment 9

Novel peroxide-additive agent mixture is used for hot-air and solidifies highly-filled EPDM

This highly-filled EPDM contains a large amount of carbon blacks and oil. This formulation only is used for sulfur vulcanization, generally is not used in peroxide cure. Successful Application in these embodiments shows that these novel peroxide-additive agent mixtures have unexpected very large application. In addition, the effectiveness of this system also adopts the embodiment of 4 kinds of different organic peroxides to be illustrated by providing. They are LUPEROX  231-XL=40%3,3,5-trimethyl-1,1-two (t-butyl peroxy) cyclohexane; LUPEROX230-XL=40% normal-butyl-4,4-two (t-butyl peroxy) valerate; Peroximon DC40KEP=40% dicumyl peroxide and Peroximon F40KEP40% two (t-butyl peroxy) diisopropyl benzene.

When peroxide tester (numbering 1,3,5,7 in the table 9) is crosslinked in the presence of air, because uncured surface, so toughness all. Also contain the part bubble in sample interior. The novel peroxide that uses among the present invention-additive formulation forms completely crued surface (non-sticky) when crosslinked in the presence of air, see Table and number 2,4,6,8 in 9. These formulations are unexpectedly curable to the higher degree of cross linking, to the degree of still (bubble). When therefore novel peroxide formulation solidifies, can form better surperficial noncohesive solid-state crosslinking component in hot-air. Because used peroxide is different, so can change hardening time, although used mass filler and oil, total surface is unexpectedly inviscid.

Table 9

Numbering	1	2	3	4	5	6	7	8
									Nordel 2470EPDM	100	100	100	100	100	100	100	100
Below the umber (weight) of various components take 100 parts of rubber as benchmark (phr) add, namely need not proofread and correct measuring.
									N762	100	100	100	100	100	100	100	100
N650	100	100	100	100	100	100	100	100
									2280 oil	100	100	100	100	100	100	100	100
Lup231KE40％	16.0	10.0	-	-	-	-	-	-
									Lup230XL40％	-	-	16.0	10.0	-	-	-	-
Per DC40P40％	-	-	-	-	16.0	10.0	-	-
									Per F40P40％	-	-	-	-	-	-	16.0	10.0
HVA-2	-	4.0	-	4.0	-	4.0	-	4.0
									Vanax A98％	-	0.3	-	0.3	-	0.3	-	0.3
Durax98％	-	0.2	-	0.2	-	0.2	-	0.2
									VULTAC575％	-	1.5	-	1.5	-	1.5	-	1.5
The MDR temperature	150℃		165℃		170℃		180℃
									M HIn-lb	11	26	11	23	14	26	20	29
T S1Minute	0.50	0.48	0.53	0.49	0.52	0.56	0.38	0.38
									T C90Minute	4.6	5.4	4.4	4.5	7.0	5.0	5.4	3.1
Air set 14 minutes
										360°F		390°F		400°F		415°F
The surface	10	2	10	1	10	1	10	1
									Bubble	Seldom measure	Nothing	On a small quantity	Nothing	On a small quantity	Nothing	On a small quantity	Nothing

Embodiment 10

ADA (Celogen Az) is the blowing agent that forms foamed product

In table 10, use ADA to be formed in the crosslinked EPDM sponge that freely increases of solidifying in the hot-air, adopt novel peroxide of the present invention-additive formulation to form non-adhesive surface. The peroxide tester numbering 1 of additive-free or ADA also is provided in the table 10. Illustrate: according to the mould flow graph (MDR2000E, 200 ℃, 1 ° of radian) of living, the degree of cross linking is M_H=19.8 in-lbs. Yet, illustrate that when crosslinked in the presence of air, the surface is very sticking. The tan δ value (peroxide tester) of numbering 1 is 0.064, is desired low value. MDR can measure tan δ, and viscous modulus just can be determined this value divided by elastic modelling quantity. The tan δ that solidifies sizing material is very low, will be very flexible and show low hysteresis. Tan δ is higher, and polymer chain can forever move or be out of shape behind the expression stress application. Numbering 2 provides peroxide and ADA in the table 10, does not have other additives, M_H=17.6 in-lbs, ADA seem to have reduced the degree of cross linking, although air pressure also can affect reading, compare with numbering 1, have formed again tacky surfaces.

Numbering 3 has been used peroxide, ADA and agent mixture N in the table 10, N '-meta-phenylene dimaleimide (HVA-2) and 1, after 3-two (citraconimide methyl) benzene (Perkalink900) solidifies in hot-air, the cross-linking properties that is improved is according to higher M_H24.9 in-lb, but surface very sticking (7 in 10 grades). Auxiliary agent and peroxide together help to improve curing, but because the inhibitory action of air has formed again poor surface.

Numbering 4 in the table 10, some low content additive, ADA, without auxiliary agent and peroxide one coexist solidify in the hot-air after, can improve surface (4-5 in 10 grades), but crosslinked very low (M_H=14.9 in-lbs), tan δ value is bad, is 0.095.

When using agent mixture (HVA-2 and Perkalink900) in hot-air, to solidify according to the present invention with low content additive, peroxide and the ADA blowing agent selected, unexpectedly obtain good crosslink density (M_HBe 22.2 in-lbs) and well surperficial (2 in 10 grades) (numbering 5 in the table 10). Illustrate: having made density is 30 pounds/foot³Even foamed material EPDM.

Enlighten such as prior art, the numbering 7 in the table 10 is when using Vanox ZMTI (93%2-sulfydryl-mebendazole (toluimidazole) zinc) and ADA to solidify in hot-air under the 5phr peroxide, can form non-adhesive surface, but compare with numbering 5, unfortunately, M_HBe worth low, 16.9 in-lbs only, and corresponding tan δ is poor.

According to prior art, the numbering 8 in the table 10 is used Captax (98%2-mercaptobenzothiazoler), also can form non-adhesive surface, but crosslinked final physical property (M_HWith tan δ) can further descend.

Table 10

Numbering	1	2	3	4	5	6	7	8
									RoyaleneX3378EPDM	100	100	100	100	100	100	100	100
Below the umber (weight) of various components take 100 parts of rubber as benchmark (phr) add, namely purely need not proofread and correct analyzing.
									The N774 carbon black	100	100	100	100	100	100	100	100
Sunpar228 oil	40	40	40	40	40	40	40	40
									ZnO	2	2	2	2	2	2	2	2
Stearic acid	2	2	2	2	2	2	2	2
									DC40KEP40％	9.0	9.0	9.0	9.0	9.0	4.5	9.0	9.0
HVA-2	-	-	0.5	-	0.5	2.0	-	-
									Perkalink900	-	-	1.5	-	1.5	-	-	-
Sulfads98％	-	-	-	0.3	0.3	0.3	-	-
									Unads98％	-	-	-	0.2	0.2	0.2	-	-
Vanox ZMTI93％	-	-	-	-	-	-	5.0	-
									Captax98％	-	-	-	-	-	-	-	5.0
Celogen Az ADA	-	4.0	4.0	4.0	4.0	4.0	4.0	4.0
									200 ℃, 1 ° radian is crosslinked in MDR
M HIn-lb	19.8	17.6	24.9	14.9	22.2	19.6	16.9	6.7
									tanδ	0.064	0.068	0.037	0.095	0.046	0.64	0.093	0.247
T S5Minute	0.34	0.36	0.26	0.39	0.33	0.38	0.39	-
									T C90Minute	0.78	0.78	0.57	0.69	0.60	0.61	0.75	0.98
400 °F solidified 7 minutes in hot-air
									The surface	10	5	7	4	1	1	1	4
Density (pound/foot3)	74	21	48	22	30	26	29	43
									400 °F of curing of@are 12 minutes in hot-air
The surface	9	9	9	5	2	1	1	1
									Density (pound/foot3)	71	24	54	22	30	28	29	41

Embodiment 11

With ordinary adjuvants and LUPEROX  101-XL[45%2,5-dimethyl-2,5-two (t-butyl peroxy) hexane] together add sulphur donor-accelerator mixture and estimate

These peroxide-auxiliary agents-accelerator mixture is used for solidifying the EPDM of standard, auxiliary agent, HVA-2 or the Vanax MBM that the maleimide type is described be proof only can be at the mixture of all main combination properties of the good solidification that forms non-adhesive surface in the presence of the air during crosslinked EPDM.

Generally speaking, compare with Royalene509 in embodiment 4/ table 4, auxiliary agent is more effective in Royalene  521EPDM. Referring to table 11, numbering 5 only has HVA-2, when being used for enforcement of the present invention, can form non-adhesive surface, and has the MDR moment of torsion than the peroxide contrast object height of numbering 1 in the table 11. Although the minority auxiliary agent can provide the improvement of some bad repetitions, the auxiliary agent that the dimaleimide type only arranged and the low content additive of selecting together can unexpectedly form the excellent comprehensive performance of surface cure and physical property.

In addition, aforementioned data explanation in table 5 and the table 11, HVA-2 has the fastest hardening time in all auxiliary agents, in the invention process, can together play a role well with the low content additive simultaneously, shorten the time in air set, the non-adhesive surface that formation has good final physical property. Should help the producer to boost productivity the hardening time that shortens, and make better product.

The various components that are used for table 11

LUPEROX101-XL (45%2,5-dimethyl-2,5-two (t-butyl peroxy) hexane)

Sulfads (98% bis-pentamethylenethiuram tetrasulfide)

SantocureTBSI (the N-tert-butyl group-2-[4-morpholinodithio sulfenamide)

TAIC (cyanacrylate)

SR-350 (trihydroxy methyl propane trimethyl acrylate)

HVA-2 (N, N '-meta-phenylene dimaleimide)

DAM (mellitic acid diallyl)

Table 11

Numbering	1	2	3	4	5	6	7	8	9	10
											Royalene521E PDM	100	100	100	100	100	100	100	100	100	100
Below the umber (weight) of various components take 100 parts of rubber as benchmark (phr) add, namely need not proofread and correct measuring.
											N660	80	80	80	80	80	80	80	80	80	80
2280 oil	10	10	10	10	10	10	10	10	10	10
											Stearic acid	1	1	1	1	1	1	1	1	1	1
Lup 101XL45％	4.5	4.5	4.5	4.5	4.5	4.5	4.5	4.5	4.5	4.5
											Sulfads98％	-	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3
TBSI	-	0.15	0.15	0.15	0.15	0.15	0.15	0.15	0.15	0.15
											TAIC	-	-	2.00	-	-	-	-	-	-	-
SR-350	-	-	-	2.00	-	-	-	-	-	-
											HVA-2	-	-	-	-	2.00	-	-	-	-	-
ZnDMA	-	-	-	-	-	2.00	-	-	-	-
											DAM	-	-	-	-	-	-	2.00	-	-	-
SR-206	-	-	-	-	-	-	-	2.00	-	-
											Perkalink900	-	-	-	-	-	-	-	-	2.00	-
Sulphur	-	-	-	-	-	-	-	-	-	0.20
											185℃MDR
M H	37	27	32	35	41	27	32	33	31	28
											T S1	0.34	0.40	0.39	0.41	0.37	0.31	0.40	0.44	0.41	0.42
T C90	4.2	3.7	4.3	3.4	2.4	3.7	4.2	4.0	3.6	3.5
											420 °F solidified 8 minutes in air
The surface	10	5	4	2	1	1	4	4	4	1

Embodiment 12

Will be for surface viscosity (quality) and the compression set percentage of the various peroxide of other application-sulfur curable mixture in air set, with model mixture of the present invention and standard peroxide and sulfur curable relatively, carried out commenting grade.

The novel peroxide cure system of numbering 2 unexpectedly can form good non-adhesive surface (1 in 10 grades) in the table 12 in air, has significant compression set, with equating of the peroxide cure of numbering 1,3 and 6 very sticking after air set (10 in 10 grades) in the table 12. The sulfur additives of numbering 4 and 5 does not contain HVA-2 in the table 12, forms poor surface and higher bad compression set value. Numbering 7 and 8 adopts half EV (sulfur sulfide system of half efficient) of Minor element sulphur in table 12, forms the surface (non-sticky) of the improvement of expection, but the compression set that shows the difference of this EV sulfur curable. The compression set value of the difference of standard sulfur sulfide system is 77% and 71%, numbering 9 and 10 in the table 12, form good non-adhesive surface, this from form good 14-16% compression set but to number 1,3 and 6 peroxide tester in the very sticking table 12 in surface different.

Table 12

The comparison of the peroxide (numbering 1,3 and 6) of model mixture of the present invention (numbering 2) and various peroxide-sulfur curable system (numbering 4,5,7 and 8) and standard and the sulfur curable (numbering 9 and 10) of standard

                   Royalene 521EPDM    100

                   N660Black            75

2280 oil 20

Stearic acid 1

Numbering	1	2	3	4	5	6	7	8	9	10
											ZnO	1.00	1.00	1.00	1.00	1.00	3.00	3.00	3.00	3.00	3.00
DC40KEP	6.00	6.00	7.50	7.50	7.50	8.00	6.00	4.00	-	-
											SR-206	2.00	-	-	-	-	-	-	-	-	-
HVA-2	-	2.00	-	-	-	-	-	-	-	-
											Sulfads98％	-	0.24	-	-	-	-	0.70	1.40	-	2.80
M.Niclate98％	-	0.24	-	-	-	-	-	-	-	-
											Altax	-	-	-	-	-	-	0.40	0.80	1.00	1.60
Unads	-	-	-	-	-	-	0.40	0.80	1.50	1.60
											Durax	-	-	-	0.10	0.20	-	-	-	-	-
Sulphur	-	-	-	0.20	0.40	-	0.10	0.20	2.00	0.40
											170℃MDR
M H(inchpound)	26	31	26	25	25	27	21	26	31	29
											T S(minute)	0.74	0.50	0.47	0.45	0.50	0.47	0.85	0.99	1.02	0.93
T CSO(minute)	7.1	4.1	7.2	5.3	5.1	7.1	4.3	3.4	3.0	2.6
											70 hours compression set of 150 °F of temperature
Compression set %	14	16	16	28	42	15	62	73	77	71
											400 °F solidified 8-12 minute in air
The surface	10	1	10	10	7	10	2	1	1	1

Embodiment 13

The seasoning stability of novel peroxide formulation

These powder compositions can get up for future use in premix merging seasoning, can loss of activity. In table 13, numbering 3 and 5 is respectively aged at room temperature 3 months mixture 1 and mixture 2. Compare these aging mixtures and freshly prepd peroxide mixture (shown in numbering 2 and 4 in the table 13). In experimental error, the flow graph moment of torsion of these two kinds of mixtures and time graph and the crosslinked surface of in hot-air, solidifying identical in quality. React between aging period such as fruit component, MDR moment of torsion, time and surface are just more near tester (numbering 1) so. In enforcement of the present invention, can add various components, then add peroxide, but the various additives of premixed can make it more feasible and/or be easier to use.

Table 13

Novel peroxide compositions can premixed, and seasoning for future use, can loss of activity or performance. With two kinds of different peroxide formulation seasonings 3 months.

Mixture 1 mixture 2

              DC40P        64.6％        64.6％

              HVA-2        27.8％        22.8％

              Sulfads       3.8           -

              Unads         3.8           -

              VULTAC5        -           8.8

              Durax          -           3.8

                   Keltan 4506EPDM    100

                   N660Black           50

                   N550Black           50

2280 oil 35

                   ZnO                3.0

Stearic acid 1.5

Numbering	1	2	3	4	5
						Wearing out of mixture	0	0	3 months	0	3 months
DC40P	8.0	-	-	-	-
						Mixture 1	-	7.9	-	-	-
Mixture 1	-	-	7.9	-	-
						Mixture 2	-	-	-	7.9	-
Mixture 2	-	-	-	-	7.9
						Adopt 170 ℃, 1 ° radian of MDR@crosslinked
M H(in-lb)	21.3	25.0	24.6	25.6	25.2
						T S4(minute)	0.38	0.56	0.55	0.38	0.39
T C90(minute)	6.8	4.6	4.5	4.4	4.3
						400 °F solidified 14 minutes in air
The surface	10	2	1.5	3	2

Embodiment 14

Low content antioxidant (metallic salt of phenols, dimethyl dithiocarbamic acid) is used in combination with dimaleimide auxiliary agent and low content sulphur donor, in the presence of air during curing elastomer, form good non-adhesive surface, also obtain better final physical property (being low compression set)

The antioxidant that also can be comprised low content by peroxide (one or more), dimaleimide auxiliary agent (one or more), novel peroxide air curing formulation that the sulphur donor-the sulphur accelerator system forms. In above-described embodiment 4, number 11 (M.Niclate in the table 4, being Methyl Niclate) nickel dimethyldithiocarbamate uses with the low consumption of 0.2phr, together use other for example zinc (M.Zimate) and dimethyl dithiocarbamate and the Sulfads  of copper (M.Cumate) type, successfully made the good non-adhesive surface of physical property (compression set). Described Methyl Niclate, its chemical name are nickel dimethyldithiocarbamate, sell as antioxidant.

In present embodiment 14 and table 14, numbering 3 is used the low content Methyl Niclate of 0.28phr, contrasts with phenolic antioxidant and sulfenamide accelerators; See numbering 6 MBPC (2,2 '-methylene-two-4-methyl-6-tert-butylphenol), and number 7 Santocure TBSI (the N-tert-butyl group-2-[4-morpholinodithio sulfenimide). According to the present invention, under every kind of situation, also contain HVA-2 and Sulfads in the formulation.

According to number in the table 14 2,3 and 4, Methyl Niclate (nickel dimethyldithiocarbamate) and Sulfads (98% bis-pentamethylenethiuram tetrasulfide) or Morfax (98% curing 4-morpholinyl-2-[4-morpholinodithio) be acceptable composition. MBPC (2,2 '-methylene two-4-methyl-6-butylphenol) or Santocure TBSI (the N-tert-butyl group-2-[4-morpholinodithio sulfenimide) replace the Niclate (nickel dimethyldithiocarbamate) can to form good surface and have better low compression set physical property. Therefore, in novel peroxide compositions of the present invention, the phenolic antioxidant of low content and sulphinyl amide accelerant can together play a role well with other sulphur promoter of HVA-2 and low content. According to the enlightenment of prior art, these low content compounds effectively are non-obvious. Use the formulation example of acrylic compounds auxiliary agent SR-206 (GDMAs) in the prior art shown in numbering 9 and 10 in the table 14, much higher antioxidant, the Vanox MBPC (99%2 of content in this formulation, 2 '-methylene two-4-methyl-6-tert-butylphenol) and Vanox ZMTI (93%2-sulfydryl-mebendazole (toluimidazole) zinc) effects on surface solidify and it seems bad impact, also have bad higher compression set value, especially number 10.

Table 14

                Royalene 521EPDM   100

                N660Black          75

2280 oil 20

                ZnO                1

Stearic acid 1

Numbering	1	2	3	4	5	6	7	8	9	10
											DC40KEP	7.5	6.0	5.0	5.0	5.0	5.0	5.0	6.0	6.0	6.0
SR-206	-	-	-	-	-	-	-	2.0	2.0	2.0
											HVA-2	-	2.0	2.0	2.0	2.0	2.0	2.0	-	-	-
Sulfads	-	0.24	0.20	-	-	0.20	0.20	-	-	-
											Methyl Niclate	-	0.24	0.28	0.28	-	-	-	-	-	-
Morfax	-	-	-	0.20	0.48	-	-	-	-	-
											TBSI	-	-	-	-	-	-	0.28	-	-	-
MBPC	-	-	-	-	-	0.28	-	-	-	2.5
											ZMTI	-	-	-	-	-	-	-	-	2.5	-
170℃MDR
											M H	26	31	29	28	28	29	30	26	26	13
T S1	0.47	0.50	0.51	0.42	0.43	0.55	0.54	0.74	0.73	1.44
											T C90	7.2	4.1	3.7	3.8	3.9	3.9	4.1	7.1	6.7	11.6
400 °F solidified 12 minutes in air
											The surface	10	1.5	2	2	4	1	1	10	8	10
The compression set in 70 hours of 150 ℃ of temperature
											Compression set %	16	16	16	15	19	17	19	14	22	49

Embodiment 15

Crosslinked fully saturated elastomer (ethylene-octene copolymer)

Available from ethylene-octene (24%) the copolymer G8100 of Dupont dow with and situation without HVA-2-VULTAC  5-Butyl Zimate under, solidify in flow graph with the dicumyl peroxide of 2 content, thin sample solidifies in hot-air. The formulation of this increase-volume is rubber-like, but slight thermoplasticity is arranged, and can not vulcanize.

In table 15, numbering 3 and 4 only has slight viscosity after curing, and this is very large improvement because most thermoplastic ethylene's polymer can be very sticking in this test, only because these polymer can melting under such temperature/softening. Add oil to reduce rigidity, still can make the surface more tacky. Under the situation of described low sizing content, can not comprise oil. When being cooled to room temperature, these samples (numbering 3 and 4) are not sticking.

Table 15

Crosslinked fully saturated elastomer (ethylene-octene copolymer)

                EG8100       100

                N660Black    60

2280 oil 5

                ZnO          3

Stearic acid 1

                AgeRite MA   0.5

Numbering	1	2	3	4
					DC40P	7.0	10.0	4.00	5.72
HVA-2	-	-	1.50	2.14
					VULTAC5	-	-	0.55	0.79
B.Zimate	-	-	0.25	0.36
					170℃MDR
M H(in-lb)	22	30	30	37
					T S4(minute)	0.43	0.39	0.49	0.44
T C90(minute)	7.6	6.9	5.3	5.0
					Surface viscosity grade in air set
420 °F/8 minutes	10	10	5	5
					375 °F/18 minutes	10	10	4	4

Embodiment 16

Be used for can be in the presence of air cross-linked elastomer make it to have the evaluation of different dimaleimide compounds of the novel peroxide formulation of non-adhesive surface

In table 16, estimated several different dimaleimide compound in the invention process. All these dimaleimide compounds all unexpectedly provide good cross-linking efficiency and non-adhesive surface, and test is to take out after 8 minutes from 410 °F hot-air curing to carry out at once. With the meta-phenylene-dimaleimide of 2phr (MBM) contrast, (considered the quantity of unsaturated degree of functionality) on the mole foundation and estimated various auxiliary agents waiting. The structure of these different compounds is as described below:Abbreviation: MBM N, N '-1,3-phenylene dimaleimide

Abbreviation: MPBM 1-1 '-(methylene-two-4,1-phenylene) dimaleimideAbbreviation: MMBM N, N '-(4-methyl isophthalic acid, 3-phenylene) dimaleimide is as described below for the rubber formulation of these experiments: rubber formulation umber Keltan 2506EPDM (DSM copolymer) 100 N660 carbon blacks (Huber), 75 Sunpar 2280 (Sun Oil) 15 Peroximon DC40KEP 5 auxiliary agents are equivalent to 2.0phr MBM^*Molal quantity Vanax A (, T.Vanderbilt) 0.2 VULTAC5 (Elf Atochem) 0.7 Durax (R.T.Vanderbilt) 0.1^*Considered the unsaturated group number of every kind of auxiliary compound.

Table 16

Numbering	1	2	3	4
					The auxiliary agent that uses	Nothing	MBM	MPBM	MMBM
170 ℃, the 1 ° crosslinked DSM copolymer of radian Keltan 2506EPDM in MDR2000E
					M L(lbin)	2.270	2.280	2.140	2.180
M H(lbin)	34.90	32.47	27.51	30.08
					M H-M L(lbin)	32.63	30.19	25.37	27.90
T S0.2(minute)	0.310	0.330	0.370	0.345
					T S0.4(minute)	0.350	0.370	0.430	0.390
T S1.0(minute)	0.440	0.465	0.550	0.490
					T C90(minute)	6.850	4.870	5.890	5.260
In hot-air oven 410 °F crosslinked 8 minutes
					Surface viscosity, 1-10 level (10 is the poorest)	10	1	3	2
The compression set % that@150 ℃/70 is little	--	27	46	36

Illustrate: when used additives not, in order to reduce surface viscosity, in formulation, used the dicumyl peroxide more than 30%. But, even numbering 1 has increased peroxide, surface viscosity or very poor (10 in 10 grades).

Finished after the MDR2000E test, tested AIR solidified surface viscosity. All samples all in the pressure baking oven 410 °F the heating 8 minutes. After 8 minutes, take out sample, paper handkerchief is pressed onto on the hot sample. After the cooling, remove paper handkerchief with uniform speed, detect viscosity. Illustrate, after the crosslinked sample of hot-air is cooled to room temperature, the viscosity very little (except numbering the peroxide cure of 1 tester) on surface, all samples has very similar low surface viscosity. All samples has also demonstrated they self foaming height, illustrates that each AIR solidified sample inside can foam really to a certain degree. This part depends on used low mooney viscosity EPDM.

Embodiment 17

Further estimated be used for can be in the presence of air cross-linked elastomer make it the different dimaleimide compounds of surperficial noncohesive novel peroxide formulation

Estimated and be used for to make elastomer crosslinked and form the N of the novel peroxide compositions of completely crued non-adhesive surface in the presence of air, 1,2,1,3 and Isosorbide-5-Nitrae of N '-phenylene dimaleimide (neighbour,, to) isomers. The elastomer that is used for present embodiment is Nordel  IP EPDM NDR-4640. This is a kind of in the EPDM elastomer of new Dupont Dow metallocene type.

According to numbering 5,6 and 7 in the table 17, when various dimaleimide auxiliary agents together use with the low content additive of selecting according to the present invention, can form well good non-adhesive surface. All these new compositions have all used unique mixture of low content sulfur-containing additive (Sulfads , VULTAC  5 and Unads ) and dimaleimide auxiliary agent and peroxide.

Illustrate that when the individual components of independent use peroxide formulation, the surface cure that obtains is poor, sees Table to number 1,2,3,4 and 8 in 17. Numbering 1 is independent peroxide, and numbering 2-4 is auxiliary agent and peroxide, and numbering 8 is mixtures of peroxide and sulphur promoter. Under every kind of situation, when solidifying in 400 °F of hot-airs, the surface of these formulations is toughness all.

Table 17

The evaluation of various dimaleimide compounds in the invention process crosslinked Nordel IP NDR-4640EPDM in hot-air oven

Numbering	1	2	3	4	5	6	7	8
									DCKEP	7.00	4.20	4.20	4.20	4.20	4.20	4.20	7.00
1,2PDM	-	2.10	-	-	2.10	-	-	-
									1,3PDM	-	-	2.10	-	-	2.10	-	-
1,4PDM	-	-	-	2.10	-	-	2.10	-
									Sulfads	-	-	-	-	0.28	0.28	0.28	0.28
VULTAC5	-	-	-	-	0.28	0.28	0.28	0.28
									Unads	-	-	-	-	0.14	0.14	0.14	0.14
MDR2000E, 175 ℃, 1 ° radian
									M H(lbin)	33.8	27.6	37.2	43.3	24.1	34.5	36.2	24.8
T S.4(minute)	0.29	0.29	0.26	0.27	0.45	0.44	0.44	0.37
									T C90(minute)	4.59	5.26	3.06	2.94	4.59	3.26	5.18	4.22
140℃
									M L	3.26	3.28	3.32	3.30	3.28	3.29	3.29	3.15
T S.4	2.01	2.04	1.79	1.99	3.37	3.32	3.29	2.67
									T S.1	3.33	2.91	2.39	2.72	4.85	4.76	4.78	3.97
195℃
									M H	30.5	23.5	34.1	39.7	20.5	31.7	34.2	22.7
M L	2.47	2.45	2.71	2.63	2.14	2.14	2.16	2.19
									T S.4	0.19	0.20	0.17	0.17	0.26	0.25	0.25	0.22
T C90	1.01	1.08	0.75	0.75	1.00	0.81	1.09	0.96
									400 °F of curing of@are 12 minutes in hot-air
The surface viscosity grade	10	8	8	8	4	1	3	10
									Hardness	60	60	62	65	60	62	62	58

Prescription: Nordel 4,640 100^*The surface viscosity grade:

N774 80 1: inviscid; 4: slight viscosity,

N990 20 7: medium; 10: toughness

  Sunpar 2280    25

  ZnO            1

Stearic acid 1 PDM=N, N-(1,2 or 1,3 or Isosorbide-5-Nitrae)-phenylene dimaleimide

Embodiment 18

Various dimaleimide compounds in the invention process, have further been estimated

Table 18 has illustrated that according to enforcement of the present invention 4 kinds of auxiliary agent dimaleimide compounds form the evaluation result of the effect of surperficial noncohesive curing elastomer together using with peroxide and the low content sulphur promoter of selecting when solidifying in hot-air oven. In the present embodiment, Dupont Dow Nordel IP NDR-4640 metallocene EPDM is elected to be the elastomer of estimating usefulness.

Monomeric compound is: 1,1 ' (3,3-dimethyl-1,1 '-xenyl-4,4 '-two bases)-dimaleimide, N, N-(1,1 '-biphenyl-4,4 '-dimaleimide), 1,2-two maleimide aminoethanes and 1,6-, two maleimide aminohexanes. In table 18, they have compared does not have N, N '-1,3-phenylene dimaleimide or Vanax MBM. The formulation that adopts the present invention preferably to be formed by dicumyl peroxide, Sulfads, VULTAC5 and Unads, the various dimaleimide auxiliary agents of numbering 2-6 are compared with peroxide tester numbering 1 in our the unexpected discovery table 18, can form good non-adhesive surface, and the latter forms very sticking surface.Abbreviation: DMBPDB 1,1 ' (3,3-dimethyl-1,1 '-biphenyl-4,4 '-two bases)-dimaleimideAbbreviation: BPDB N, N '-(1,1 '-biphenyl-4,4 '-two bases)-dimaleimideAbbreviation: BH 1,6-two maleimide aminohexanes

Abbreviation: BE 1,2-two maleimide aminoethanes

Table 18

Agent mixture is in the research of air set Nordel NDR-4640

Numbering	1	2	3	4	5	6
							DC40KEP	7.00	5.00	5.00	5.00	5.00	5.00
Vanax BM	-	1.50	1.00	1.00	1.00	1.00
							DMBPDB	-	-	-	0.25	-	-
BPDP	-	-	-	0.25	-	-
							BE	-	-	-	-	0.50	-
BH	-	-	-	-	-	0.50
							Sulfads	-	0.28	0.28	0.28	0.28	0.28
VULTAC5	-	0.48	0.48	0.48	0.48	0.48
							Unads	-	0.14	0.14	0.14	0.14	0.14
MDR2000E，175℃
							M H(lbin)	44.0	40.8	36.9	40.1	40.2	39.8
T S.4(minute)	0.27	0.38	0.38	0.38	0.39	0.39
							T C90(minute)	4.53	3.05	3.15	3.51	3.20	3.07
MDR195℃
							M H	40.2	38.0	34.3	37.0	36.6	36.9
M L	2.94	2.62	2.55	2.60	2.57	2.60
							T S.4	0.18	0.23	0.23	0.22	0.22	0.23
T C90	1.02	0.79	0.80	0.83	0.78	0.79
							MDR140℃
M L	3.85	3.95	3.81	3.91	3.90	3.85
							T S.4	1.74	2.86	2.85	2.83	2.82	2.79
400 °F of surfaces of curing cross-linked EPDM8-12 minute are estimated in hot-air oven, viscosity grade 1-10,10=surface toughness
							8 minutes	10	2.5	4	2.5	3	4
12 minutes	10	1	2.5	1	1	1
							Shore hardness	65	67	66	66	66	66

Prescription: Nordel 4,640 100

      N774                  60

      N990                  60

      2280                  20

      ZnO                    1

Stearic acid 1

DMBPDB:1,1 ' (3,3-dimethyl-1,1 '-biphenyl-4,4-two bases)-dimaleimide

BPDB:N, N '-(1,1 '-biphenyl-4,4 '-two bases)-dimaleimide

BE:1,2-two maleimide aminoethanes

BH:1,6-two maleimide aminohexanes

Embodiment 19

To the 2-(2 as the additive that is used for novel peroxide formulation, 4-cyclopentadiene-1-subunit)-1, the evaluation of 3-dithiolane, described formulation are used for cross-linked elastomer in hot-air oven, form good surface cure (non-adhesive surface) and good physical property

Unsaturated sulfur-containing compound and dimaleimide auxiliary agent and peroxide combination are estimated. Compound 2-(2,4-cyclopentadiene-1-subunit)-1, the 3-dithiolane has replaced the mixture of Durax, Vanax A and VULTAC5, and described mixture is and N that N '-meta-phenylene-dimaleimide (HVA-2) auxiliary agent and dicumyl peroxide are used in combination. According to the data in the table 19, when this uniqueness formulation solidifies 8 minutes in 410 °F of hot-airs, can carry out effectively crosslinkedly, have good non-adhesive surface.2-(2,4-cyclopentadiene-1-subunit)-1, the 3-dithiolane

Except the good cross-linking properties under the air existence, can solve thus the inhibitory action of air (oxygen), find that final cross-linked elastomer also has good final physical property, according to better low compression set percentage, it obtains after crosslinked EPDM70 hour 150 ℃ of heat ageings.

Table 19

Numbering	1	2
			DSM2506EPDM	100	100
The N660 carbon black	75	75
			Sunpar2280	15	15
Dicumyl peroxide 40% on the clay	5	5
			N, N '-meta-phenylene dimaleimide	2	2
Vanax A	0.2	-
			VULTAC5	0.7	-
Durax	0.1	-
			2-(2,4-cyclopentadiene-1-subunit)-1, the 3-dithiolane	-	1.0
170 ℃, 1 ° radian of MDR2000E
			M H-M L(in-lb)	32	30
T S4Minute	0.36	0.34
			T C90	5.23	5.44
400 °F of curing in hot-air
			The grade of surface viscosity	2	1
150 ℃, 70 hours compression set %	27％	14％

Embodiment 20

Polysulfide is used in combination with the halogenated polymer of selecting or silicon rubber (as additive), with peroxide, sulphur promoter and dimaleimide auxiliary agent, makes the non-adhesive surface in the high increase-volume EPDM formulation

Nordel IP 4520 (Dupont Dow Elastomers) with etc. weight carbon black and high amounts of oil mix, be difficult to use common peroxide cure, it is typical sulfur curable hose sizing compound formulation. Wherein carbon black and or the high increase-volume EPDM formulation that almost equates with the EPDM consumption of oil content, be the very difficult formulation that solidifies well with organic peroxide. When solidifying the high EPDM that fills in the presence of air, peroxide radical meeting attack oil and carbon black as attack rubber, therefore, want to obtain good curing grade and keep non-adhesive surface just very difficult in the presence of air.

Adopt the novel sulphur promoter of the present invention and the mixture of dimaleimide, we have also added on a small quantity (FA) polysulfide polymer and (SE6160) silicon rubber, as being used for new additive agent of the present invention. We find, the mixture of polysulfide polymer and silicon rubber or haloflex or Hypalon (chlorosulfonated polyethylene) and peroxide, dimaleimide auxiliary agent and the low content sulphur promoter selected can form suitable inviscid solidified surface in the presence of air. Therefore, this model mixture can provide the method for solidifying these high increase-volume EPDM formulations that usually solidify with sulfur vulcanization. Illustrate that the various sulfur sulfide systems that use in the prior art are insensitive to oil and the carbon black of higher concentration, can solidify high extended rubber formulation fully.

Therefore we estimate, the polymer master batch of the sulphur promoter of can prepare peroxide, selecting, dimaleimide auxiliary agent, polysulfide, wherein can add haloflex and or chlorosulfonated polyethylene as other additive, as a part of the present invention.

Illustrate, use silicon rubber and do not have polysulfide polymer to can be made into moderately viscous surface. Use fluoroelastomer as additive of the present invention, be not used in combination with polysulfide and can form suitable surface.

Table 20

Polymeric additive is on the impact of air curing Nordel IP4520

	1	2	3	4	5	6
							4520EPDM	100	100	100	100	100	100
N660	100	100	100	100	100	100
							N990	60	60	60	60	60	60
LW150 oil	60	60	60	60	60	60
							Stearic acid	0.50	0.50	0.50	0.50	0.50	0.50
DCKE40％	10.0	8.0	8.0	8.0	8.0	8.0
							MBM	-	1.35	1.35	1.35	1.35	1.35
Vanax A	-	0.15	0.15	0.15	0.15	0.15
							VULTAC5	-	0.45	0.45	0.45	0.45	0.45
Durax	-	0.05	0.05	0.05	0.05	0.05
							Polysulfide	-	-	1	1	1	1
Silicon rubber	-	4.00	4.00	-	-	-
							CPE	-		-	4.00	-	-
Hai Pulong	-		-	-	4.00	-
							Fluoroelastomer	-		-	-	-	4.00
RPA170C, 0.2 ° of radian, 60cpm
							Maximum S ' (in-lb)	4.57	5.66	5.82	6.41	7.61	5.94
T S.5	0.64	0.46	0.44	0.41	0.35	0.46
							T C90	7.46	4.36	4.69	4.89	3.88	4.63
							The surface	Toughness	Medium	Slightly	Nothing	Nothing	Medium

The surface:

Toughness: very sticking; Slightly; Slight viscosity is only arranged; Nothing: inviscid; Medium: viscosity is medium.

Embodiment 21

In the present embodiment, we show the more data that height that curing " is difficult to use peroxide cure " is filled the EPDM formulation

In the Ben Teding formulation, we use the carbon black (total consumption is 180 parts) of Duoing than EPDM rubber (total consumption is 100 parts). The model mixture of the sulphur promoter (listing with mixture 1) of using peroxide, MBM and selecting, when crosslinked in the presence of air, compare under lower curing agent total concentration with standard peroxide (numbering 1), can form good surface (numbering 2). Again explanation, it is that the height that is difficult to solidify with organic peroxide is filled the EPDM formulation. Those of ordinary skill in the industry can not expected this formulation that together uses with organic peroxide, only can use the sulfur vulcanization curing system.

When crosslinked in the presence of hot-air, use a small amount of chlorosulfonated polyethylene (Hai Pulong is available from Dupont Dow) as being used for the used new additive agent of the invention process (numbering 3), can further improve surface cure. The mixture that uses polysulfide and Hypalon (numbering 4) notices that surface cure has obtained further improvement during as the new polymers additive in the invention process.

Table 21 uses chlorosulfonated polyethylene and polysulfide as new additive agent, uses organic peroxide to exist

There is the lower crosslinked high EPDM that fills in air, and forms non-adhesive surface

	1	2	3	4
					DCKEP	15.00	-	4.00	4.00
Mixture 1	-	10.00	8.00	8.00
					AgeRite MA	-	-	-	-
MTBHQ	-	-	-	-
					*Hai Pulong 40	-	-	5.00	5.00
Polysulfide	-	-	-	1.00
					RPA solidifies under 170C, 0.2 ° of radian, 60cpm
Maximum S ' (in-lb)	5.77	6.75	8.72	8.32
					T S.5Minute	0.42	0.53	0.35	0.35
T C90Minute	6.07	4.41	3.46	3.69
					400 °F solidified 8-12 minute in hot-air
Surface viscosity	Toughness	Slightly	Very slight	Nothing

Rubber compounding: mixture 1:

4570 EPDM 80 ^*    DCKE  60％

4770  EPDM 20    MBM        27％

N660       120   Vanax A    3％

N990       60    VULTAC5   9％

LW150      80    Durax     1％

Stearic acid 0.8

^*A small amount of Hai Pulong (consumption is as implied above) replaces the 4570EPDM of equivalent

Embodiment 22

In the present embodiment, we show several new chemistry and polymeric additives for exploitation peroxide formulation of cross-linked elastomer in the presence of hot-air

They are specifically: Vanax 6H (N-cyclohexyl-N '-phenyl-p-phenylenediamine) CAS101-87-1, the antiozonant of diene-based polymer, polysulfide (PTE) and silicon rubber (VMQ). Vanax 6H (R.T.Vanderbilt)

We have illustrated that antiozonant is used for replacing sulfur-containing compound in the invention process. Plan of the present invention with this antiozonant and material with analog structure as the complete equivalent that is contained in other interior compounds of compound (B) range of definition. In addition, polysulfide (PTE) also is used for same purpose.

At last, as polymeric additive, use peroxide by the unexpected mixture of two kinds of polymer P TE and VMQ, just can in the presence of hot-air, make non-adhesive surface. Illustrate, do not use dimaleimide and sulphur compound or antiozonant additive.

Table 22

Crosslinked Royalene 501EPDM uses polysulfide and silicon rubber, also uses antiozonant N-cyclohexyl-N '-phenyl-p-phenylenediamine (Vanax 6H). Elastomeric basic recipe: 100 parts of Royalene 501EPDM, 70 parts of N550 carbon blacks, 30 parts of N-990 carbon blacks, 20 parts of Sunpar LW150 oil, 1 part of zinc oxide, 1 part of stearic acid.

Additive	1	2	3	4	5	6	7
								DCP40KE	7.5	4.6	4.6	4.6	4.6	4.6	7.5
MBM	-	2.2	2.2	2.2	2.2	2.2	-
								Vanax A	-	-	0.7	-	-	-	-
Vanax 6H	-	-	-	0.7	-	-	-
								Polysulfide	-	-	-	-	0.7	2.2	3.0
VMQ	-	-	-	-	-	-	7.0
								Adopt MDR2000E, 175 ℃, 1 ° radian is crosslinked
M H(in-lb)	35.6	37.8	40.1	36.1	33.3	36.0	27.7
								T S.04Minute	0.3	0.26	0.29	0.34	0.26	0.26	0.30
T C90Minute	4.39	2.98	3.46	3.63	2.51	2.89	3.98
								400 °F of curing (8-12 minute) in hot-air
Surface viscosity (heat test)	Have	Have	Nothing	Nothing	Nothing	Nothing	Nothing

Embodiment 23

Use the example of various other dialkyl group type peroxide

In the present embodiment, we have used the crosslinked Metallocenyl EPDM of different organic peroxides (Nordel IP4640). Illustrate that under every kind of situation the peroxide that does not have various additives during crosslinked EPDM elastomer formulation, can not form non-adhesive surface in the presence of hot-air. The peroxide of listing in the table 23 is:

The peroxide chemical name

Lup101 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane

MTBPP 4-methyl-4-(t-butyl peroxy)-2 pentanone

Luperox F/R two (t-butyl peroxy) diisopropyl benzene

DAPDIB two (tertiary pentyl peroxide) diisopropyl benzene

Present embodiment is used for illustrating that by deep the most frequently used dialkyl peroxide, the dicumyl peroxide of estimating, other dialkyl peroxide also can be used in the invention process except in the aforementioned embodiment.

Table 23

Use other dialkyl peroxide curing cross-linked Nordel IP4640EPDM in hot-air

	1	2	3	4	5	6	7	8
									Nordel46 40	100	100	100	100	100	100	100	100
N330	60	60	60	60	60	60	60	60
									N990	40	40	40	40	40	40	40	40
LW150	35	35	35	35	35	35	35	35
									ZnO	1	1	1	1	1	1	1	1
Stearic acid	1	1	1	1	1	1	1	1
									Lup101 92.8％	3.60	2.20	-	-	-	-	-	-
MTBPP 84.4％	-	-	4.90	3.00	-	-	-	-
									Luperox F/R	-	-	-	-	3.60	2.20	-	-
DAPDIB 79.7％	-	-	-	-	-	-	4.90	3.00
									Vanax MBM	-	2.40	-	2.40	-	2.40	-	2.40
Sulfads	-	0.32	-	0.32	-	0.32	-	0.32
									Vultac5	-	0.32	-	0.32	-	0.32	-	0.32
Unads	-	0.16	-	0.16	-	0.16	-	0.16
									Adopt 200 ℃, 1 ° radian of MDR2000E@crosslinked
M H	27.4	30.9	21.1	30.7	32.7	34.9	26.3	29.9
									T S.4	0.18	0.24	0.19	0.24	0.17	0.22	0.17	0.21
T C90	1.07	0.76	1.16	0.85	0.91	0.72	0.79	0.58
									400 °F of curing of@in hot-air, the surface viscosity grade
Surface viscosity (heat test)	Have	Nothing	Have	Nothing	Have	Nothing	Have	Nothing

Peroxide: chemical name:

Lup101 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane

MTBPP 4-methyl-4-(t-butyl peroxy)-2 pentanone

Luperox F/R two (t-butyl peroxy) diisopropyl benzene

DAPDIB two (tertiary pentyl peroxide) diisopropyl benzene

Those of ordinary skill will appreciate that composition of the present invention also can be mixed with the masterbatch of being convenient to process and sneak into polymer and be used for crosslinked in the presence of molecular oxygen in the industry. General masterbatch carrier comprises for example polymer of microwax, polycaprolactone, ethylene-propylene-diene monomers (EPDM), ethylene-propylene monomer polymer (EPM), vinyl-vinyl alkoxide polymer (EVA), polyethylene (PE) or their mixture.

Specifically note that in appending claims the applicant is considered as its subject matter of an invention and clearly proposes claim.

Claims (27)

1. composition, it contains:

A) at least a compound (A), it is selected from silicone elastomer and has the compound of following formula (I):

(I) wherein n is 1 or 2, R is divalence or trivalent, it is selected from the non-annularity of 2-16 carbon atom aliphatic group approximately, the alicyclic group of 5-20 carbon atom is arranged approximately, have approximately the aryl peace treaty of 6-18 carbon atom that the alkaryl of 7-24 carbon atom is arranged, wherein these divalence or the trivalent group hetero atom that can contain one or more O of being selected from, N and S replaces one or more carbon atoms, and each R₁Identical, be a hydrogen or 1-18 carbon atom alkyl;

(b) at least a compound (B), it is selected from antiozonant and the organic compounds containing sulfur of p-phenylenediamine base, and this organic compounds containing sulfur is selected from the mixture that can promote to be undertaken by sulphur organic compounds containing sulfur, polysulfide polymer and the described sulfur-containing compound of the sulfur vulcanization of crosslinked polymer.

2. composition as claimed in claim 1, it also contains the radical initiator that is selected from organic peroxide and azo initiator.

3. composition, the polymer that it contains composition as claimed in claim 2 and can be solidified by radical initiator.

4. method, it comprises the goods that composition formation claimed in claim 3 is had shape, then in the presence of molecular oxygen, make it stand to be enough to cause the temperature that radical initiator decomposes, obtain thus the substantially noncohesive cured article with shape in surface.

5. composition, it requires 1 described compound (A) by hybrid right and (B) forms.

6. composition, it by require with the random order hybrid right 1 described compound (A) and (B) and organic peroxide form.

7. composition as claimed in claim 1, wherein said compound (A) is selected from dimaleimide, and compound (B) is selected from sulphur promoter.

8. composition as claimed in claim 1, wherein said compound (A) is selected from two citraconimides, and compound (B) is selected from sulphur promoter.

9. composition as claimed in claim 1, wherein said compound (A) is selected from dimaleimide, and compound (B) is selected from polysulfide polymer.

10. composition as claimed in claim 1, wherein said compound (A) is selected from two citraconimides, and compound (B) is selected from polysulfide polymer.

11. composition as claimed in claim 1, wherein said compound (A) is selected from silicone elastomer, and compound (B) is selected from polysulfide polymer.

12. composition as claimed in claim 1, it also contains the sizing material that is selected from haloflex and chlorosulfonated polyethylene.

13. composition as claimed in claim 2, wherein said radical initiator is selected from organic peroxide.

14. the noncohesive cure polymer in surface, it is cured by decomposing the free radical that produces such as the radical initiator in the described composition of claim 3 in the presence of molecular oxygen.

15. method for preparing surperficial noncohesive cure polymer, described cure polymer is cured by the free radical that the radical initiator decomposition that is contained in wherein produces in the presence of molecular oxygen, the method comprises mixes described polymer with composition claimed in claim 2, and supply with enough heats radical initiator is decomposed, introduce in the polymer thus.

16. one kind prepares the method that can be solidified into the curable compositions of non-adhesive surface in the presence of molecular oxygen by radical initiator, it comprises that can carry out crosslinked polymer by radical initiator mixes with composition claimed in claim 2.

17. one kind prepares the method that can be solidified into the curable compositions of non-adhesive surface in the presence of molecular oxygen by radical initiator, it is included in radical initiator and exists lower mixing energy to carry out crosslinked polymer by the radical initiator that contains the described composition of claim 1.

18. composition as claimed in claim 1, wherein said compound (A) is selected from one or more dimaleimides, and compound (B) is selected from four sulfuration dialkyl group thiurams, four sulfuration diaryl thiurams, curing alkyl phenol, single sulfuration tetraalkyl thiuram, single sulfuration four aryl thiurams and their mixture.

19. composition as claimed in claim 2, wherein said radical initiator is selected from dialkyl peroxide or peroxy ketal.

20. composition as claimed in claim 18, it also contains the radical initiator that is selected from dialkyl peroxide or peroxy ketal.

21. composition as claimed in claim 1, wherein said compound (A) is selected from one or more dimaleimides, compound (B) is selected from 4,4-dithiomorpholine, non-annularity alkyl-2-[4-morpholinodithio sulfenamide, cycloalkyl-2-[4-morpholinodithio sulfenamide, aryl-2-[4-morpholinodithio sulfenamide, curing alkyl phenol and their mixture.

22. composition as claimed in claim 21, it also contains the radical initiator that is selected from dialkyl peroxide or peroxy ketal.

23. composition as claimed in claim 2, it contains dicumyl peroxide, N, N-phenylene dimaleimide, 4,4-dithiomorpholine, curing alkyl phenol and N-cyclohexyl-2-[4-morpholinodithio sulfenamide.

24. composition as claimed in claim 2, it contains dicumyl peroxide, N, N-phenylene dimaleimide, bis-pentamethylenethiuram tetrasulfide, curing alkyl phenol and single sulfuration tetra methylthiuram.

25. composition as claimed in claim 2, it contains dicumyl peroxide, N, N-phenylene dimaleimide, bis-pentamethylenethiuram tetrasulfide, curing alkyl phenol and the N-tert-butyl group-benzothiazole-2-sulfenimide.

26. composition as claimed in claim 1, it is mixed with masterbatch at the carrier that is selected from microwax, polycaprolactone, EPDM, EPM, EVA, PE and composition thereof.

27. composition as claimed in claim 2, it is mixed with masterbatch at the carrier that is selected from microwax, polycaprolactone, EPDM, EPM, EVA, PE and composition thereof.