# Patent

## Title
Low polarity dimerate and trimerate esters as plasticizers for elastomers

## Abstract

An elastomeric composition including a natural or synthetic rubber, and a cyclic dimerate ester and/or a cyclic trimerate ester plasticizer.

## Background
CROSS REFERENCE TO RELATED APPLICATION
This claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application Ser. No. 60/396,453, filed Jul. 17, 2002, the entire disclosure of which is incorporated herein by reference.


FIELD OF THE INVENTION
The present invention is directed to low polarity dimerate and/or trimerate esters for plasticizing elastomers, including natural and/or synthetic rubbers.
BACKGROUND
A number of elastomers are very difficult to plasticize. For example, elastomers, such as EPDM, are difficult to plasticize since it is difficult to find plasticizers that are sufficiently compatible to avoid the plasticizer exuding (bleeding) to the surface of the elastomer upon cooling and solidification of the elastomer. Usually, hydrocarbon oils such as naphthenic oils or paraffinic oils are used to plasticize elastomers such as EPDM. While hydrocarbon-based processing oils can be used with partial success, the resulting plasticized compositions lack advantageous low temperature properties and the processing oils have a tendency to exude (bleed) to the surface of the elastomeric article. Attempts to use conventional linear dibasic acid esters, such as dioctyl adipate, dioctyl sebacate, and di-2-ethylhexyl sebacate, or phthalate esters, such as di-2-ethylhexyl phthalate, have also been unsuccessful since such conventional ester plasticizers are either incompatible with the elastomer, resulting in exudation of the plasticizer, or are too volatile for many elastomer uses.
U.S. Pat. No. 5,290,886 teaches using organic ester plasticizers to plasticize thermoplastic elastomers comprising a blend of a thermoplastic polyolefin and an elastomer to lower the glass transition temperature (Tg) of both the elastomer and the polyolefin phases and to improve impact strength at low temperatures. The '886 patent neither discloses nor suggests using the cyclic dimerate and/or cyclic trimerate esters disclosed herein, and found that “polymeric dibasic esters and aromatic esters were found to be significantly less effective” (column 3, lines 62–64).
Dimer acid esters have been proposed as plasticizers for high temperature resistant fluorocarbon polymers (see U.S. Pat. No. 4,078,114) and for plasticizing anhydride-functionalized polymers (see U.S. Pat. No. 5,169,716) but have not been suggested for plasticizing non-fluorocarbon polymers, non-anhydride-functionalized polymers, or elastomers. It is preferred that the elastomers plasticized with the dimerate and/or trimerate esters disclosed herein are not fluorocarbon polymers, fluorocarbon elastomers, anhydride-functionalized polymers, or anhydride-functionalized elastomers.
Surprisingly and unexpectedly, dimerate and/or trimerate esters designed to have very low polarity act as efficient plasticizers for elastomers. The resulting plasticized compositions have excellent low temperature properties and exhibit little or no tendency of the plasticizer to exude or bleed to the surface of the elastomer composition. Use of the dimerate and/or trimerate esters as disclosed herein provides an advantageous balance of flexibility, impact resistance, and strength to the plasticized elastomers.
SUMMARY OF THE INVENTION
In brief, it has been found that the use of cyclic dimerate and/or trimerate esters, formed from mono-, di-, and/or tri-carboxylic acids containing one, two, or three C3–C24 radicals or fatty acid residues and C3–C24 alkyl alcohols, in a natural or synthetic vulcanizable rubber, unexpectedly increases the low temperature properties of the rubber for uses such as, hoses, belts, conveyor belts, motor mounts, gaskets, automotive drive train belts, including transmission belts, roofing compounds, and the like. By adding one or more cyclic dimerate and/or trimerate esters (di- and/or tri-esters), particularly dimerate esters derived from C18 fatty acids and C3–C24 alcohols, preferably, C3–C18 alcohols, more preferably, C6–C18 alcohols, the low temperature properties of the elastomer are surprisingly improved. Preferably, the esters are formed by reacting a C3–C18 alcohol with a mixture of mono-, di-, and tri-fatty acids, e.g., primarily C18 carboxylic acids, and their dimers and trimers.


DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The cyclic dimerate and/or trimerate ester plasticizers described herein are added to one or more natural or synthetic rubbers, preferably together with a vulcanizing agent. Surprisingly, the cyclic ester plasticizers disclosed herein significantly increase the low temperature properties of the rubber composition and provide an excellent and unexpected balance of flexibility, impact resistance, and strength to the elastomer composition.
The cyclic esters may be diesters, triesters, or mixtures thereof, including saturated or unsaturated hydrocarbon chains, straight chain or branched, having zero to six double bonds in the hydrocarbon chains. While cyclic monoesters are less preferred, they also may successfully be used in accordance with the present disclosure.
Many of the cyclic diester and/or cyclic triester materials are formed from self reaction of naturally derived fatty acid mixtures containing oleic, linoleic, and linolenic acids, and consequently are blends of mono-, di-, and tri-carboxylic acid esters. The blends may further include other compounds that do not adversely affect the advantages imparted to elastomers by the subject cyclic dimerate and/or trimerate esters described herein.
Ranges may be expressed herein as from “about” or “approximately” one particular value and/or to “about” or “approximately” another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment.
The cyclic diesters, referred to herein as dimerates, have a formula I, as follows:




    wherein R5 and R7, same or different, are C3–C24, preferably C6–C24, more preferably C8–C18 hydrocarbon chains, straight chain or branched, either saturated or containing 1 to 6, preferably 1 to 3, carbon-to-carbon double bonds;
    R6 and R8, same or different, are C3–C24, preferably C3–C18, more preferably C6–C18 alkyl, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and
    R10 and R11, same or different, are C3–C24, preferably C3–C18, more preferably C6–C18 saturated hydrocarbon chain, straight chain or branched; or an unsaturated C3–C24, preferably C3–C18, more preferably C6–C18 hydrocarbon chain, straight chain or branched, containing 1 to 6, preferably 1 to 3, carbon-to-carbon double bonds.


The cyclic triesters, referred to herein as trimerates, have a formula II, as follows:




    wherein R12, R14 and R18, same or different, are C3–C24, preferably C6–C24, more preferably C8–C18 hydrocarbon chain, straight chain or branched, either saturated or containing 1 to 6, preferably 1 to 3, carbon-to-carbon double bonds;
    R13, R15 and R19, same or different, are C3–C24 alkyl, preferably C3–C18 chains, more preferably C6–C18 alkyl, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and
    R16, R17 and R20, same or different, are C3–C24, preferably C3–C18, more preferably C6–C18 saturated hydrocarbon chains, straight chain or branched; or unsaturated C3–C24, preferably C3–C18, more preferably C6–C18 hydrocarbon chains, straight chain or branched, containing 1 to 6, preferably 1 to 3, carbon-to-carbon double bonds.


The low polarity of the cyclic ester compounds disclosed herein is important for successfully plasticizing elastomeric compositions. Low polarity cyclic ester compounds, e.g., ester compounds formed from dimer acids and alcohols having a single hydroxyl group are preferred. Similarly, it is preferred that R6, R8, R13, R15, and R19 of formulas I and II do not contain hydroxyl substituents. Dimerate esters formed from dimer acids and glycol type alcohols, for example, glycol alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, and other polyethylene glycols, would be too polar to plasticize elastomeric compositions while simultaneously providing superior low temperature properties. Additionally, esters prepared by reacting dimer acids with the glycol functionalized monomers and oligomers set forth in U.S. Pat. No. 4,054,561 would also be too polar for use as plasticizers.
Useful cyclic diesters falling within formula I include dimerate ester structures formed by the reaction of C36 dimer acid derived from tall oil fatty acids and C3–C24, preferably C3–C18, more preferably C6–C18 alcohols, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds. Examples of such cyclic esters include the following structures, wherein the dimer acid corresponding to structure A is formed by self reaction of linoleic acid, the dimer acid corresponding to structure B is formed by reacting linoleic acid with oleic acid, and the dimer acid corresponding to structure C is formed by reacting linoleic acid with linolenic acid:




wherein each R, same or different, in formulas (A), (B), and (C) is a C3–C24 preferably C3–C18 hydrocarbon chain, more preferably C6–C18, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds.

RX-13804 and RX-13824 are the subject plasticizers of several of the exemplified compositions reported in the Examples, and are additional examples of dimerate esters in accordance with formula I. RX-13804 is formed by the reaction of a predominantly C36 dimer acid with 2-ethylhexyl alcohol. RX-13824 is formed by the reaction of a predominantly C36 dimer acid with tridecyl alcohol. An additional example of a plasticizer in accordance with formula I is formed by the reaction of a predominantly C36 dimer acid with oleyl alcohol.
A representative example of the triester (trimerate ester) of formula II is the following structure (D):




wherein each R1, R2, and R3, same or different, is a C3–C24, preferably C3–C18, more preferably C6–C18 hydrocarbon chain, straight chain or branched, saturated or unsaturated containing 1 to 3 carbon-to-carbon double bonds.

In the present description, the term dimerate is sometimes used by itself when referring to a blend including structures of formulas I and II (i.e., blend including dimerates and trimerates).
The cyclic ester plasticizers of formula I, II, or mixtures thereof are typically added to an elastomer composition comprising natural and/or synthetic rubber in an amount of about 0.1 parts to about 50 parts by weight, preferably from ranges about 2 parts to about 40 parts, more preferably from about 10 parts to about 35 parts per 100 parts by weight of rubber.
A particularly useful blend of carboxylic acids for forming cyclic esters in accordance with the disclosure is a blend of carboxylic acids having CAS#: 61788-89-4, and known as dimer acid. Dimer acid is a blend including primarily C36 and C54 dimer and trimer acids, and predominantly (more than 50% by weight) C36 dimer acid.
The fatty acid residues or hydrocarbon chains R5, R7, R12, R14 and R18 of the esters of formulas I and II can be any C3–C24, preferably C6–C24, more preferably C8–C18 hydrocarbon chain, either saturated or containing 1 to 6, preferably 1 to 3, carbon-to-carbon double bonds, and may be derived from animal or vegetable fatty acids such as butter; lard; tallow; grease; herring; menhaden; pilchard; sardine; babassu; castor; coconut; corn; cottonseed; jojoba; linseed; oiticica; olive; palm; palm kernel; peanut; rapeseed; safflower; soya; sunflower; tall; and/or tung. Examples are the hydrocarbon chain residues from the following fatty acids, where the number in parentheses indicates the number of carbon atoms, and the number of double bonds, e.g., (C24-6) indicates a hydrocarbon chain having 24 carbon atoms and 6 double bonds: hexanoic (C6-0); octanoic (C8-0); decanoic (C10-0); dodecanoic (C12-0); 9-dodecenoic (CIS) (C12-1); tetradecanoic (C14-0); 9-tetradecenoic (CIS) (C14-1); hexadecanoic (CIS) (C16-0); 9-hexadecenoic (CIS) (C16-1); octadecanoic (C18-0); 9-octadecenoic (CIS) (C18-1); 9,12-octadecadienoic (CIS, CIS) (C18-2); 9,12,15-octadecatrienoic (CIS, CIS, CIS) (C18-3); 9,11,13-octadecatrienoic (CIS, TRANS, TRANS) (C18-3); octadecatetraenoic (C18-4); eicosanoic (C20); 11-eicosenoic (CIS) (C20-1); eicosadienoic (C20-2); eicosatrienoic (C20-3); 5,8,11,14-eicosatetraenoic (C20-4); eicosapentaenoic (C20-5); docosanoic (C22); 13-docosenoic (CIS) (C22-1); docosatetraenoic (C22-4); 4,8,12,15,19-docosapentaenoic (C22-5); docosahexaenoic (C22-6); tetracosenoic (C24-1); and 4,8,12,15,18,21-tetracosahexaenoic (C24-6).
Commercially available blends of useful polybasic acids that can be reacted with C3–C24, preferably C3–C18, more preferably C6–C18 alcohols, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds to produce the dimerate and trimerate esters, as blends, include the following: EMPOL® 1010 Dimer Acid; EMPOL® 1014 Dimer Acid; EMPOL® 1016 Dimer Acid; EMPOL® 1018 Dimer Acid; EMPOL® 1022 Dimer Acid; EMPOL® 1024 Dimer Acid; EMPOL® 1040 Trimer Acid; EMPOL® 1041 Trimer Acid; EMPOL® 1052 Polybasic Acid; and similar PRIPOLTM products from Uniqema as well as UNIDYME® products from Arizona Chemical.
Particularly useful ester additives are made by reacting any of the long chain mono, dimer and/or trimer acids with one or more straight chain or branched C3–C24, preferably C3–C18, more preferably C6–C18 alcohols to produce esters in accordance with formulas I and II. The above dimer, trimer, and polybasic acids are produced by dimerizing, trimerizing, and polymerizing (oligomerizing) carboxylic acids, typically C18 fatty acids. The fatty acids are typically mixtures. For example, the dimer acid produced from a C18 carboxylic acids (e.g., a mixture of stearic, oleic, linoleic, and linolenic) will result in a blend of numerous cyclic dimerate and trimerate esters, as in formulas I and II, some saturated and some containing hydrocarbon chains having 1 to 6, generally 1 to 3 carbon-to-carbon double bonds. Any one or any blend of the esters that include the cyclic dimerate and/or cyclic trimerate esters in accordance with formulas I or II will function to plasticize elastomers, and provide a balance of flexibility, strength, and low temperature properties, with essentially no bleeding of the plasticizer to the surface of an elastomeric article. Particularly, the plasticized elastomeric compositions described herein are characterized in that the low temperature properties are improved to provide a balance of good flexibility and strength at low temperatures.
Rubbers useful in the compositions described herein can be natural rubbers (NR) and/or synthetic rubbers.
Synthetic rubbers include homopolymers of conjugated diene compounds such as isoprene, butadiene, chloroprene, and the like, for example, polyisoprene rubber (IR), polybutadiene rubber (BR), polychloroprene rubber, and the like; copolymers of the above described conjugated diene compounds with vinyl compounds such as styrene, acrylonitrile, vinyl pyridine, acrylic acid, methacrylic acid, alkyl acrylates, alkyl methacrylates, and the like, for example, styrene-butadiene copolymeric rubber (SBR), vinylpyridine-butadiene-styrene copolymeric rubber, acrylonitrile-butadiene copolymeric rubber, acrylic acid-butadiene copolymeric rubber, methacrylic acid-butadiene copolymeric rubber, methyl acrylate-butadiene copolymeric rubber, methyl methacrylate-butadiene copolymeric rubber, acrylonitrile-butadiene-styrene terpolymer, and the like; copolymers of olefins, such as ethylene, propylene, isobutylene, and the like with dienes, for example, isobutylene-isoprene copolymeric rubber (IIR); copolymers of olefins with non-conjugated dienes such as ethylene propylene diene monomer (EPDM), for example, ethylene-propylene-cyclopentadiene terpolymer, ethylene-propylene-5-ethylidene-2-norbornene terpolymer and ethylene-propylene-1,4-hexadiene terpolymer; polyalkenamer obtained by ring opening polymerization of cycloolefins, for example, polypentenamer; rubbers obtained by ring opening polymerization of oxirane ring, for example, polyepichlorohydrin rubber and polypropylene oxide rubber which can be vulcanized with sulfur, and the like. Furthermore, halides of the above-described various rubbers, for example, chlorinated isobutylene-isoprene copolymeric rubber (Cl-IIR), brominated isobutylene-isoprene copolymeric rubber (Br-IIR), fluorinated polyethylene, and the like are similarly included.
Particularly, the compositions described herein are characterized in that low temperature properties of natural rubber (NR), and synthetic rubbers, e.g. styrene-butadiene copolymeric rubber (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), isobutylene-isoprene, copolymeric rubber, halides of these rubbers (Cl-IIR, Br-IIR) and copolymers of olefins with non-conjugated dienes are improved to provide the rubbers with a balance of good flexibility and strength at low temperatures. Of course, the present invention can be applied to other rubbers. All these rubbers may be kneaded with compounding agents conventionally used for compounding with rubber, for example, fillers, such as carbon black, silica, calcium carbonate, lignin and the like, softening agents, such as mineral oils, vegetable oils, prior to vulcanization and then vulcanized.
In order to cure a rubber composition a vulcanizing agent such as a sulfur or peroxide vulcanizing agent is dispersed throughout the composition. The amount of vulcanizing agent, e.g., sulfur, in the composition is typically from about 2 to about 8 parts, for example from about 3 to about 6, by weight per 100 parts by weight of natural and/or synthetic rubber, but lesser or larger amounts, for example, from about 1 to 7 or 8 parts may be employed on the same basis. A preferred range is from about 2.5 to about 6 parts per 100 parts by weight of rubber. Representative examples of sulfur vulcanizing agents include elemental sulfur (S8), amine disulfides, polymeric polysulfides, and sulfur olefin adducts. Preferably, the sulfur vulcanizing agent is elemental sulfur.
The term “vulcanization” used herein means the introduction of three dimensional cross-linked structures between rubber molecules. Thus, thiuram vulcanization, peroxide vulcanization, quinoid vulcanization, resin vulcanization, metal salt vulcanization, metal oxide vulcanization, polyamine vulcanization, radiation vulcanization, hexamethylenetetramine vulcanization, urethane cross-linker vulcanization and the like are included in addition to sulfur vulcanization, which is usual and most important.
Accelerators may be used to control the time and/or temperature required for vulcanization and to improve the properties of the vulcanizate. The accelerator(s) may be used in total amounts ranging from about 0.3 parts to about 4 parts, for example about 0.3 parts to about 1.5 parts, preferably from about 0.4 parts to about 1.0 parts, and more preferably from about 0.5 parts to about 0.8 parts by weight per 100 parts by weight of natural and/or synthetic rubbers. Suitable types of accelerators that may be used are amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates, and xanthates. If included in the rubber composition, the primary accelerator preferably is typically a sulfenamide. If a second accelerator is used, the secondary accelerator is preferably a guanidine, dithiocarbamate, or thiuram compound. Specific examples of vulcanization accelerators which can be used in the rubber compositions described herein are thiazole-based accelerators, for example 2-mercaptobenzothiazole, bis(2-benzo-thiazolyl)disulphide, 2(2′,4′-dinitro-phenylthio)benzothiazole, benzothiazole-2-sulphenamides, for instance N-isopropyl-benzothiazole-2-sulphenamide, N-tert-butyl-benzothiazole-2-sulphenamide, N-cyclo-hexylbenzo-thiazole-2-sulphen-amide, and 2(morpholinothio)benzothiazole, and thiocarbamylsulphenamides, for example N,N-dimethyl-N′,N′-dicyclohexylthiocarba-moylsulphenamide, and N(morpholinothiocarbonylthio)morpholine.
The commonly employed carbon blacks used in conventional rubber compounding applications can be used as the carbon black in this invention. Representative examples of such carbon blacks include N110, N121, N220, N231, N234, N242, N293, N299, S315, N326, N330, M332, N339, N343, N347, N351, N358, and N375.
The rubber compositions described herein are compounded by methods generally known in the rubber compounding art, such as mixing the various sulfur-vulcanizable or peroxide-vulcanizable constituent rubbers with various commonly used additive materials such as, for example, sulfur donors, curing aids, such as activators and retarders, and processing additives, such as oils, resins including tackifying resins and other conventional plasticizers, fillers, pigments, fatty acid, zinc oxide, waxes, antioxidants and antiozonants, retarders, and peptizing agents. As known to those skilled in the art, the additives mentioned above are selected and commonly used in conventional amounts for tire tread applications. A typical amount of adhesive resins is about 0.2 parts to about 10 parts per 100 parts by weight of the natural and/or synthetic rubbers, usually about 1 part to about 5 parts.
Typical amounts of zinc oxide comprise about 2 parts to about 5 parts per 100 parts by weight of natural and/or synthetic rubbers. Typical amounts of waxes comprise about 1 part to about 5 parts per 100 parts by weight of natural and/or synthetic rubbers. Often microcrystalline waxes are used. Typical amounts of retarders range from about 0.05 parts to about 2 parts per 100 parts by weight of natural and/or synthetic rubbers. Typical amounts of peptizers comprise about 0.1 parts to about 1 part per 100 parts by weight of natural and/or synthetic rubbers. Typical peptizers may be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide. All additive percentages and amounts are based on the weight of natural and/or synthetic rubbers.
Vulcanization of the rubber composition described herein is generally carried out at conventional temperatures ranging from about 100° C. to about 200° C. Preferably, the vulcanization is conducted at temperatures ranging from about 110° C. to about 180° C. Any of the usual vulcanization processes may be used such as heating in a press or mold, heating with superheated steam or hot air, or in a salt bath.
Upon vulcanization of the rubber composition at a temperature ranging from about 100° C. to about 200° C., the rubber composition can be used for various purposes. For example, the vulcanized rubber composition may be in the form of a tire, belt, hose, motor mounts, gaskets and air springs. In the case of a tire, it can be used for various tire components. Such tires can be built, shaped, molded, and cured by various methods which are known and will be readily apparent to those having skill in such art. When the rubber composition is used in a tire, its use may be in a wire coat, bead coat, tread, apex, sidewall, and combination thereof. As can be appreciated, the tire may be a passenger tire, aircraft tire, truck tire, and the like. Preferably, the tire is a passenger tire. The tire may also be a radial or bias, with a radial tire being preferred.
The invention may be better understood by reference to the following examples in which parts and percentages are by weight unless otherwise indicated.
In the following examples, cyclic dimerate esters were applied to EPDM (Royalene 501 and Royalene 502), natural rubber, and neoprene. Previous work determined that conventional organic esters were either incompatible or too volatile for many elastomer applications.
The following Tables I-VI include original physical properties, processing and curing properties, compatibility, low temperature, and heat aging data for elastomeric compositions which have been plasticized with representative dimerate ester compositions or previously known plasticizers. The dimerate esters were evaluated at 30 parts per hundred parts by weight of natural and/or synthetic rubbers (phr) and compared to a conventional paraffinic oil at 60 phr (i.e., the conventional rubber plasticizer was added to an elastomer composition at twice the amount of the rubber plasticizers disclosed herein).
Results
Table I illustrates the use of dimerate esters and conventional plasticizers in an EPDM compound. The processing and curing properties show no major differences when compared with paraffinic oils except that since the dimerates are evaluated at lower phr they do produce higher viscosity compounds. Compatibility data (i.e., lack of roll spew) show all dimerate esters evaluated in Table I are compatible with EPDM. The dimerate esters provide higher tensile strength and hardness values than other plasticizers.
Table I shows the low temperature properties for elastomers plasticized with various compounds. The low temperature properties of the compositions plasticized with the dimerate esters are highly significant in comparison to elastomers plasticized with paraffinic oil. Elastomers plasticized with the dimerates possess better lower temperature properties than elastomers plasticized with paraffinic oil, even though the dimerates are at 30 phr and paraffinic oil is at 60 phr. Elastomers plasticized with dimerates exhibit an unexpected combination of high strength and hardness with excellent low temperature properties, and such properties can have importance in applications such as V-belts, radiator hoses, automotive insulation, seals and gaskets.
The air oven aging results show that the dimerates are essentially equal to the paraffinic oil in weight loss. The dimerate esters are significantly lower in volatility when compared to the tallate esters, RX-13577 and RX-13782.













TABLE I







Example
1
2
3
4
5
6












Royalene 501
100.00






 


N-550
60.00






 


Kadox 930
5.00






 


Stearic Acid
1.00






 













RX-13577
30.00
—
—
—
—
—


RX-13782
—
30.00
—
—
—
—


RX-13804
—
—
30.00
—
—
—


RX-13805
—
—
—
30.00
—
—


RX-13806
—
—
—
—
30.00
—


SUNPAR 2280
—
—
—
—
—
60.00


Subtotal
196.00
196.00
196.00
196.00
196.00
226.00









Mill Addition




Spider Sulfur
0.80






 


Premix MBT
0.9375






 


Premix TMTD
0.625






 


Premix DPTT
0.625






 


Premix TDEC
0.625






 













Total
199.61
199.61
199.61
199.61
199.61
229.61

















RX-
RX-
RX-
RX-
RX-
SUNPAR


Major Variable
13577
13782
13804
13805
13806
2280
















Processing Properties








Viscosity and Curing Properties


Mooney Viscosity at 135° C.(275° F.)


Minimum Viscosity
22
21.3
25.9
26.4
25.3
13


t5, minutes
7.9
7.8
5.9
5.9
5.9
9


t10, minutes
9.3
9.1
7.2
7.2
7.1
10.8


t35, minutes
18.3
20.3
9.6
9.9
9.7
14.7


Oscillating Disc Rheometer at


160°(320° F.)


ML
4.4
4.1
5.1
5.2
5
2.3


MH
17.9
15.9
28.1
28.7
28.2
17.4


ts2, minutes
2.7
2.8
2.3
2.3
2.2
3.3


t'c(90), minutes
7.3
6.8
5.7
6
5.5
7.8


1.25*t'c(90), minutes
9.2
8.5
7.1
7.5
6.9
9.8


Cure Rate Index
21.5
25
29.9
27.3
30
22.2













Vulcanizate Properties








Roll Spew


Temperature @ −40° C.


24 hours
NONE
NONE
NONE
NONE
NONE
NONE


48 hours
NONE
NONE
NONE
NONE
NONE
NONE


72 hours
NONE
NONE
NONE
NONE
NONE
NONE


96 hours
NONE
NONE
NONE
NONE
NONE
NONE


Temperature @ −3° C.


24 hours
NONE
NONE
NONE
NONE
NONE
NONE


48 hours
NONE
NONE
NONE
NONE
NONE
NONE


72 hours
NONE
NONE
NONE
NONE
NONE
NONE


96 hours
NONE
NONE
NONE
NONE
NONE
NONE


Temperature @ 25° C.


24 hours
NONE
NONE
NONE
NONE
NONE
NONE


48 hours
NONE
NONE
NONE
NONE
NONE
NONE


72 hours
NONE
NONE
NONE
NONE
NONE
NONE


96 hours
NONE
NONE
NONE
NONE
NONE
NONE





Example
1
2
3
4
5
6





Original Physical Properties













Stress @ 100% Elongation, MPa,
0.8
0.7
1.6
1.8
1.6
1.3


psi
114
101
236
256
234
188


Stress @ 200% Elongation, MPa
1.1
0.9
3.2
3.5
3.2
2.7


Stress @ 300% Elongation, MPa
1.6
1.2
4.8
5.2
4.8
4.2


Tensile Ultimate, MPa,
3.0
2.0
14.4
14.8
14.7
12.1


psi
435
288
2094
2148
2126
1751


Elongation @ Break, %
744
640
734
689
724
669


Hardness Duro A, pts.
51
50
57
58
57
49


Specific Gravity
1.062
1.062
1.067
1.070
1.067
1.038


Compression Set, % 22 hrs. @ 100° C.
92
92
69
71
75
68


Low Temperature Properties


Low Temperature Impact - Brittleness


Brittle Point, as molded, all pass, ° C.
<−75
<−75
<−75
−71
<−75
−72


After air oven aging, all pass, ° C.
<−75
−72
<−75
<−75
<−75
<−75


Low Temperature Torsion - Gehman


As molded, Relative Modulus


T2, ° C.
−4
−6
−21
−26
−13
−26


T5, ° C.
−39
−34
−51
−47
−33
−41


T10, ° C.
−55
−43
−55
−55
−44
−46


T100, ° C.
−67
−70
−66
−65
−61
−55


Apparent Modulus of Rigidity
83.3
90.5
128.8
149.8
131.9
95.5


Temperature at 500 psi, ° C.


  500 psi, ° C.
−47
−35
−43
−39
−28
−41


  5,000 psi, ° C.
−65
−59
−62
−59
−56
−53


10,000 psi ° C.
−68
−68
−65
−62
−59
−55


25,000 psi, ° C.
−72
−75
−68
−75
−75
−60


50,000 psi, ° C.
−75
<−75
−75
<−75
<−75
−70


Aged Vulcanizate Properties


Air Oven Aging, 70 h @ 150° C.


Stress @ 100% Elongation, MPa,
8.4
9.0
5.4
5.7
5.2
3.0


psi
1216
1307
777
823
749
433


Stress Change, %
970
1199
230
221
219
131


Tensile Ultimate, MPa,
10.5
11.6
7.9
9.8
8.9
7.6


psi
1520
1689
1151
1428
1290
1109


Tensile Change, %
250
486
−45
−34
−39
−37


Elongation @ Break, %
127
131
140
163
160
207


Elongation Change, %
−83
−80
−81
−76
−78
−67


Hardness Duro A, pts.
80
82
75
71
68
57


Hardness Change, pts.
29
32
18
13
11
8


Weight Change, %
−11
−12
−2.4
−2.3
−2.0
−1.5









The next experiments with dimerate esters were in an EPDM having a different ethylene/propylene ratio (Royalene 502). Again, dimerate esters were evaluated at 30 phr and compared to a conventional paraffinic oil at 60 phr.
Results
The processing and curing properties of the EPDM compositions plasticized with dimerates show no major differences when compared with elastomer compositions plasticized with paraffinic oils except that since the dimerates are evaluated at lower phr they do produce higher viscosity compounds. Compatibility data (i.e., lack of roll spew) show all esters evaluated in Table II are compatible with EPDM. The dimerate esters provide higher tensile strength and hardness values than other plasticizers.
Table II shows the low temperature properties for elastomers plasticized with various compounds. The low temperature properties of the compositions plasticized with the dimerate esters are highly significant in comparison to elastomers plasticized with paraffinic oil. Elastomers plasticized with the dimerates possess better lower temperature properties than elastomers plasticized with paraffinic oil, even though the dimerates are at 30 phr and paraffinic oil is at 60 phr. Elastomers plasticized with dimerates exhibit an unexpected combination of high strength and hardness with excellent low temperature properties, and such properties can have importance in applications such as V-belts, radiator hoses, automotive insulation, seals and gaskets.
The air oven aging results show that the dimerates are essentially equal to the paraffinic oil in weight loss, which is a significant improvement over conventional organic ester plasticizers and tallate compounds.













TABLE II







Example
7
8
9
10
11
12












Royalene 502
100.00






 


N-550
60.00






 


Kadox 930
5.0






 


Stearic Acid
1.0






 


RX-13577
30.00






 













RX-13782
—
30.00
—
—
—
—


RX-13804
—
—
30.00
—
—
—


RX-13805
—
—
—
30.00
—
—


RX-13806
—
—
—
—
30.00
—


SUNPAR 2280
—
—
—
—
—
60.00


Subtotal
196.00
196.00
196.00
196.00
196.00
226.00









Mill Addition




Spider Sulfur
0.80






 


Premix MBT
0.94






 


Premix TMTD
0.63






 


Premix DPTT
0.63






 


Premix TDEC
0.63

















Total
199.61
199.61
199.61
199.61
199.61
229.61

















RX-
RX-
RX-
RX-
RX-
SUNPAR22


Major Variable
13577
13782
13804
13805
13806
80
















Processing Properties








Viscosity and Curing Properties


Mooney Viscosity at 135° C.(275° F.)


Minimum Viscosity
41.7
40.1
48.4
49.3
48.6
26


t5, minutes
6.8
6.6
4.7
4.6
4.8
7.3


t10, minutes
7.9
7.5
5.6
5.4
5.7
8.8


t35, minutes
10.6
9.8
7.8
7.4
7.8
11.8


Oscillating Disc Rheometer at


160° C.(320° F.)


ML
9.8
9.4
11.1
10.8
11.1
5.5


MH
35
33
47.5
42.5
44.7
29.2


TS2, minutes
2.2
2.2
1.8
1.8
1.7
2.5


t'c(90), minutes
6.3
6
5.5
5.8
5.2
7.8


1.25*t'c(90), minutes
7.9
7.5
6.9
7.3
6.5
9.8


Cure Rate Index
24
26.1
27.3
25
28.6
18.8













Vulcanizate Properties








Roll Spew


Temperature @ −40° C.


24 hours
NONE
NONE
NONE
NONE
NONE
NONE


48 hours
NONE
NONE
NONE
NONE
NONE
NONE


72 hours
NONE
NONE
NONE
NONE
NONE
NONE


96 hours
NONE
NONE
NONE
NONE
NONE
NONE


Temperature @ −3° C.


24 hours
NONE
NONE
NONE
NONE
NONE
NONE


48 hours
NONE
NONE
NONE
NONE
NONE
NONE


72 hours
NONE
NONE
NONE
NONE
NONE
NONE


96 hours
NONE
NONE
NONE
NONE
NONE
NONE


Temperature @ 25° C.


24 hours
NONE
NONE
NONE
NONE
NONE
NONE


48 hours
NONE
NONE
NONE
NONE
NONE
NONE


72 hours
NONE
NONE
NONE
NONE
NONE
NONE


96 hours
NONE
NONE
NONE
NONE
NONE
NONE





Example
7
8
9
10
11
12
















Original Physical Properties








Stress @ 100% Elongation, MPa,
1.0
0.9
2.0
2.0
1.8
1.5


psi
150
137
290
287
259
215


Stress @ 200% Elongation, MPa
1.6
1.4
4.2
4.2
3.8
3.2


Stress @300%  Elongation, MPa
2.5
2.1
6.4
6.4
5.8
5


Tensile Ultimate, MPa,
11.2
9.0
15.3
15.3
14.7
12.1


psi
1629
1301
2216
2221
2126
1752


Elongation @ Break, %
1878
1867
580
576
606
573


Hardness Duro A, pts.
55
52
60
60
59
50


Specific Gravity
1.063
1.064
1.068
1.071
1.069
1.038


Compression Set, % 22 hrs. @
68
75
56
53
57
58


100° C.


Low Temperature Properties


Low Temperature Impact - Brittleness


Brittle Point, as molded, all pass,
<−75
<−75
−73
−73
<−75
−60


° C.


After Air Oven Aging, all pass,
<−75
<−75
<−75
<−75
<−75
<−75


° C.


Low Temperature Torsion - Gehman


As molded, Relative Modulus


T2, ° C.
−14
−12
−25
−25
−15
−21


T5, ° C.
−44
−33
−47
−46
−31
−39


T10, ° C.
−54
−44
−52
−52
−40
−46


T100, ° C.
−68
−60
−66
−66
−57
−54


Apparent Modulus of Rigidity
160.5
159.8
191.4
204.3
185.4
123.5


Temperature at


  500 psi, ° C.
−35
−29
−33
−30
−21
−38


  5,000 psi, ° C.
−63
−54
−57
−56
−49
−49


10,000 psi, ° C.
−66
−58
−60
−59
−52
−53


25,000 psi, ° C.
−70
−75
−66
−65
−70
−60


50,000 psi, ° C.
−75
<−75
−75
<−75
<−75
<−75


Aged Vulcanizate Properties


Air Oven Aging, 70 h @ 150° C.


Stress @ 100% Elongation, MPa,
9.1
9.6
5.8
5.9
5.7
3.3


psi
1321
1399
847
860
829
479


Stress Change, %
781
921
192
200
220
123


Tensile Ultimate, MPa,
11.1
13.5
10.6
12.4
11.7
9.3


psi
1612
1957
1532
1795
1699
1356


Tensile Change, %
−1
50
−31
−19
−20
−23


Elongation @ Break, %
125
148
169
194
184
227


Elongation Change, %
−93
−92
−71
−66
−70
−60


Hardness Duro A, pts.
82
83
73
72
71
61


Hardness Change, pts.
27
31
13
12
12
11


Weight Change, %
−11
−11.8
−2.3
−2.3
−2
−1.8









The data of Table III shows results from the evaluation of different dimerate esters in EPDM-Royalene 501. Again, the dimerate esters were evaluated at 30 phr and compared to a conventional paraffinic oil at 60 phr.
Results
The processing and curing properties show no major differences when compared with paraffinic oils except that since the dimerates are evaluated at lower phr they do produce higher viscosity compounds. The dimerate esters evaluated in Table III are compatible with the elastomers. The dimerate esters also provide higher tensile strength and hardness values than other plasticizers.
Table III shows the low temperature properties for elastomers plasticized with various compounds. The low temperature properties of the compositions plasticized with the dimerate esters are highly significant in comparison to elastomers plasticized with paraffinic oil. Elastomers plasticized with the dimerates possess better lower temperature properties than elastomers plasticized with paraffinic oil, even though the dimerates are at 30 phr and paraffinic oil is at 60 phr. Elastomers plasticized with dimerates exhibit an unexpected combination of high strength and hardness with excellent low temperature properties, and such properties can have importance in applications such as V-belts, radiator hoses, automotive insulation, seals and gaskets.
Additionally, the elastomeric composition of Example 15, which was plasticized with dioctyl sebacate shows roll spew at all temperatures tested, even at room temperature (25° C.). Thus, Example 15 indicates that conventional plasticizers, more specifically linear diesters, are not sufficiently compatible with elastomeric compositions so as to provide superior low temperature properties.
The air oven aging results show that the dimerates are essentially equal to the paraffinic oil in weight loss, but the air oven loss for the dimerate esters is significantly less than when conventional plasticizers such as dioctyl sebacate, and tallate compounds are used.
Glass transition data for the EPDM compositions plasticized with dimerate esters RX-13804 and RX-13824 further illustrate the efficacy of the disclosed plasticizers. For example, the disclosed plasticizers provide glass transition temperatures in EPDM which are comparable to those achieved with the conventional plasticizers, dioctyl sebacate and paraffinic oil (even though a significantly lower content of the dimerate plasticizer is used to plasticize the EPDM).












TABLE III







Example
3
13
14
15
16












Royalene 501
100.00






 


N-550
60.00






 


Kadox 930
5.00






 


Stearic Acid
1.00






 












RX-13804
30.00
—
—
—
—


 


RX-13824
—
30.00
—
—
—


RX-13853
—
—
30.00
—
—


Plasthall DOS
—
—
—
30.00
—


Sunpar 2280
—
—
—
—
60.00


Subtotal
196.00
196.00
196.00
196.00
226.00









Mill Addition




Sulfur
0.80






 


Premix MBT
0.94






 


Premix TMTD
0.63






 


Premix DPTT
0.63






 


Premix TDEC
0.63






 












Total
199.61
199.61
199.61
199.61
229.61
















RX-
RX-
RX-
Plasthall
Sunpar


Major Variable
13804
13824
13853
DOS
2280















Processing Properties







Viscosity and Curing Properties


Mooney Viscosity at 275° F.(135° C.)


Minimum Viscosity
27.2
29
24.5
27.5
15.4


t5, minutes
6.2
6.6
8.2
5.7
9


t10, minutes
7.4
7.8
9.3
6.8
10.8


t35, minutes
10.1
10.5
17.2
9.1
14.6


Oscillating Disc Rheometer at


320° F.(160° C.)


ML
4.9
6
4.4
5.2
2.5


MH
32.7
37.1
20.6
42.6
21


tS2, minutes
2.3
2.3
2.7
2.2
3


t'c(90), minutes
5.2
5.7
7
6.2
7.5


1.25*t'c(90), minutes
6.5
7.1
8.8
7.7
9.4


Cure Rate Index
35.2
29.9
23.1
25
22.2












Vulcanizate Properties







Roll Spew


Temperature @ −40° C.


24 hours
NONE
NONE
NONE
YES
NONE


48 hours
NONE
NONE
NONE
YES
NONE


72 hours
NONE
NONE
NONE
YES
NONE


96 hours
NONE
NONE
NONE
YES
NONE


Temperature @ −3° C.


24 hours
NONE
NONE
NONE
YES
NONE


48 hours
NONE
NONE
NONE
YES
NONE


72 hours
NONE
NONE
NONE
YES
NONE


96 hours
NONE
NONE
NONE
YES
NONE


Temperature @ 25° C.


24 hours
NONE
NONE
NONE
YES
NONE


48 hours
NONE
NONE
NONE
YES
NONE


72 hours
NONE
NONE
NONE
YES
NONE


96 hours
NONE
NONE
NONE
YES
NONE





Example
3
13
14
15
16















Original Physical Properties







Stress @ 100% Elongation, MPa,
1.6
1.7
0.8
2.2
1.2


psi
225
240
120
315
170


Stress @ 200% Elongation, MPa
2.9
3.1
1.2
4.3
2.2


Stress @ 300% Elongation, MPa
4.2
4.5
1.6
6.2
3.4


Tensile Ultimate, MPa,
14.8
14.6
4.2
11.3
13.8


psi
2150
2120
615
1645
2005


Elongation @ Break, %
825
785
1000
555
815


Hardness Duro A, pts.
57
57
51
59
48


Specific Gravity
1.068
1.068
1.060
1.070
1.038


Compression Set, % 22 hrs. @ 100° C.
67
64
85
58
70


Low Temperature Properties


Low Temperature Impact - Brittleness


Brittle Point, as molded, all pass, ° C.
>−75
>−75
>−75
>−75
−70


After Air Oven Aging @ 150° C., all
>−75
>−75
−70
>−75
−70


pass, ° C.


After Air Oven Aging @ 169° C., all
−60
−65
−70
>−75
−70


pass, ° C.


Low Temperature Torsion - Gehman


As molded, Relative Modulus


T2, ° C.
−29
−28
−6
−40
−25


T5, ° C.
−50
−47
−43
−53
−41


T10, ° C.
−54
−53
−55
−58
−47


T100, ° C.
−64
−62
−66
−70
−55


Apparent Modulus of Rigidity
142.6
152
86.8
185.9
90.2


Temperature at


500 psi, ° C.
−42
−39
−47
−46
−42


5,000 psi, ° C.
−60
−58
−64
−63
−53


10,000 psi, ° C.
−64
−61
−67
−66
−55


25,000 psi, ° C.
−67
−64
−69
−75
−64


50,000 psi, ° C.
−70
−70
>75
>−75
−70


Aged Vulcanizate Properties


Air Oven Aging,


70 h @ 150° C.(302° F.)


Stress TM 100% Elongation, MPa,
3.2
3.3
2.7
7.8
2.3


psi
465
475
390
1135
340


Stress Change, %
107
98
225
260
100


Tensile Ultimate, MPa,
11.1
12.5
10.7
14.6
10.7


psi
1610
1815
1550
2115
1555


Tensile Change, %
−25
−14
152
29
−22


Elongation @ Break, %
310
350
410
185
365


Elongation Change, %
−62
−55
−59
−67
−55


Hardness Duro A, pts.
65
65
64
81
56


Hardness Change, pts.
8
8
13
22
8


Weight Change, %
−1.8
−1.8
−3.5
−15
−1.5















Example
3
13
15
15 
16





Air Oven Aging,












70 h @ 169° C.(336° F.)







Stress @ 100% Elongation, MPa
4.8
5.1
7.2
11.9
2.6


psi
690
735
1040
1720
375


Stress Change, %
207
206
767
446
121


Tensile Ultimate, MPa
6.5
6.9
7.8
12.9
6.0


psi
940
1000
1130
1875
870


Tensile Change, %
−56
−53
84
14
−57


Elongation @ Break, %
130
130
110
110
190


Elongation Change, %
−84
−83
−89
−80
−77


Hardness Duro A, pts.
70
70
75
84
57


Hardness Change, pts.
13
13
24
25
9


Weight Change, %
−3.4
−3.2
−8.3
−15.4
−3.4


Glass Transition, Tg, ° C.
55.1
53.4
—
61.7
−50.3









Table IV compares the formulation of Example 3 to one containing UBS 020602, which has essentially the same molecular composition as RX-13804 (the ester additive in the formulation of Example 3), but is substantially hydrogenated. The study was done with the same elastomer used in Tables I and III (Royalene 501) and all tests were conducted the same as in Tables I–III. The main differences seen between the two formulations is the UBS 020602 provides moderately better heat aging properties, which could be significant for critical high temperature applications.









TABLE IV







Example
3
17





Royalene 501
100.00






 


N-550
60.00






 


Kadox 930
5.00






 


Stearic Acid
1.00






 


RX-13804
30.00
—


UBS 020602
—
30.00


Subtotal
196.00
196.00









Mill Addition




Spider Sulfur
0.80






 


Premix MBT
0.94






 


Premix TMTD
0.63






 


Premix DPTT
0.63






 


Premix TDEC
0.63






Total
199.61
199.61












Major Variable
RX-13804
UBS 020602












Processing Properties




Viscosity and Curing Properties


Mooney Viscosity at 135° C.(275° F.)


Minimum Viscosity
30
29.6


t5, minutes
5.8
5.4


t10, minutes
7
6.7


t35, minutes
9.7
9.8


Oscillating Disc Rheometer at


160° C.(320° F.)


ML
5.6
5.9


MH
34.1
36.9


tS2, minutes
2.2
2.2


t'c(90), minutes
4.8
6.5


1.25*t'c(90), minutes
6
8.1


Cure Rate Index
37.6
23.1









Vulcanizate Properties




Roll Spew


Temperature @ −40° C.


24 hours
NONE
NONE


48 hours
NONE
NONE


72 hours
NONE
NONE


96 hours
NONE
NONE


Temperature @ −3° C.


24 hours
NONE
NONE


48 hours
NONE
NONE


72 hours
NONE
NONE


96 hours
NONE
NONE


Temperature @25° C.


24 hours
NONE
NONE


48 hours
NONE
NONE


72 hours
NONE
NONE


96 hours
NONE
NONE





Example
3
17












Original Physical Properties




Stress @ 100% Elongation, MPa,
1.5
2.1


psi
220
300


Stress @ 200% Elongation, MPa
2.9
4.3


Stress @ 300% Elongation, MPa
4.3
6.1


Tensile Ultimate, MPa,
14.3
13.3


psi
2080
1930


Elongation @ Break, %
805
590


Hardness Duro A, pts.
57
60


Specific Gravity
1.067
1.068


Compression Set, % 22 hrs.
71
58


Low Temperature Properties


Low Temperature Impact - Brittleness


Brittle Point, as molded, all pass, ° C.
>−75
>−75


After Air Oven Aging @ 150° C.
>−75
>−75


After Air Oven Aging @169° C.
−70
−70


Low Temperature Torsion - Gehman


As molded, Relative Modulus


T2, ° C.
−34
−38


T5, ° C.
−49
−51


T10, ° C.
−55
−55


T100, ° C.
−65
−65


Apparent Modulus of Rigidity
172
198


Temperature at


  500 psi, ° C.
−41
−41


  5,000 psi, ° C.
−60
−59


10,000 psi, ° C.
−63
−62


25,000 psi, ° C.
−67
−65


50,000 psi, ° C.
−72
−75


Aged Vulcanizate Properties


Air Oven Aging, 70 h @ 150° C.


Stress @ 100% Elongation, MPa,
3.2
4.1


psi
470
595


Stress Change, %
114
98


Tensile Ultimate, MPa,
10.8
11.3


psi
1570
1640


Tensile Change, %
−25
−15


Elongation @ Break, %
280
220


Elongation Change, %
−65
−63


Hardness Duro A, pts.
67
67


Hardness Change, pts.
10
7


Weight Change, %
−1.9
−1.2












Example
3
17












Air Oven Aging, 70 h @ 169° C.




Stress @ 100% Elongation,
4.7
5.2


psi
680
760


Stress Change, %
209
153


Tensile Ultimate, MPa,
6.6
8.4


psi
955
1215


Tensile Change, %
−54
−37


Elongation @ Break, %
130
145


Elongation Change, %
−84
−75


Hardness Duro A, pts.
71
70


Hardness Change, pts.
14
10


Weight Change, %
−3.0
−1.6









In the following examples provided in Table V, cyclic dimerate esters were applied to Natural Rubber (SMR CV 60). The dimerate esters were evaluated at 15 phr and compared to a conventional napthenic oil at 30 phr (i.e., the conventional rubber plasticizer was added to the elastomer composition at twice the amount of the rubber plasticizers disclosed herein).
Results
The processing and curing properties show no major differences except that since the dimerates are evaluated at lower phr they do produce higher viscosity compounds. Compatibility data (i.e., lack of roll spew) show that the dimerate ester evaluated in Table V is compatible with natural rubber. The dimerate esters provide higher tensile strength and hardness values than other plasticizers.
Table V shows the low temperature properties for elastomers plasticized with various compounds. The low temperature properties of the compositions plasticized with dimerate esters are highly significant in comparison to elastomers plasticized with paraffinic oil. For example, even though the dimerates are at 15 phr and napthenic is at 30 phr, the dimerates provide substantially equal low temperature properties. The combination of high strength and hardness with excellent low temperature properties are important for applications such as hoses, automotive isolators, seals and gaskets.
Additionally, the dimerate esters are significantly lower in volatility when compared to napthenic oil.












TABLE V







Example
18
19
20
21
22












SMR CV 60
100.00






 


Kadox 930
5.00






 


Stearic Acid
2.00






 


N 330
35.00






 












Process Oil C-255-E
30.00
—
—
—
—


RX-13804
—
15.00
—
—
—


RX-13824
—
—
15.00
—
—


RX-13805
—
—
—
15.00
—


RX-13896
—
—
—
—
15.00









Mill Addition




Sulfur
2.25






 


Santocure TBBS
0.70






 












Total
174.95
159.95
159.95
159.95
159.95
















Process







Oil
RX-
RX-
RX-
RX


Major Variable
C-255-E
13804
13824
13805
13896















Processing Properties







Viscosity and Curing Properties


Mooney Viscosity at 168° C.(335° F.)


Minimum Viscosity
32.9
34.1
30.9
31.5
28.6


t5, minutes
3.4
1.8
2.4
2.2
2.6


t10, minutes
3.8
2.6
3
2.9
3


t35, minutes
4.3
3.5
3.8
3.6
3.6


Oscillating Disc Rheometer at


168° C.(335° F.)


ML
4.3
6.1
5.8
6.7
6.7


MH
4.5
6.1
5.8
6.7
6.7


tS2, minutes
2.5
2
2.3
2.2
2.2


t'c(90), minutes
3.6
3.1
3.4
3.3
3.4


1.25*t'c(90), minutes
4.5
3.9
4.3
4.1
4.3


Cure Rate Index
92.6
92.6
91.7
92.6
80















Example
18
19
20
21
22















Original Physical Properties







Stress @ 100% Elongation, MPa,
0.8
1.1
1.2
1.1
1.2


psi
115
160
170
160
170


Stress @ 200% Elongation, MPa
1.6
2.4
2.6
2.4
2.6


Stress @ 300% Elongation, MPa
3.1
4.7
5
4.7
5


Tensile Ultimate, MPa,
16.3
23.6
24.2
23.0
22.5


psi
2365
3420
3505
3330
3260


Elongation @ Break, %
695
700
705
700
670


Hardness Duro A, pts.
40
46
47
46
47


Specific Gravity
1.049
1.065
1.067
1.068
1.069


Low Temperature Properties


Low Temperature Impact - Brittleness


Brittle Point, as molded, all pass, ° C.
−55
−60
−55
−55
−55


Low Temperature Torsion - Gehman


As molded, Relative Modulus


T2, ° C.
−42
−47
−49
−48
−49


T5, ° C.
−54
−57
−57
−57
−58


T10, ° C.
−58
−59
−59
−59
−60


T100, ° C.
−64
−65
−65
−65
−65


Apparent Modulus of Rigidity
65
103
118
118
102


Temperature at


500 psi, ° C.
−57
−56
−56
−56
−57


5,000 psi, ° C.
−64
−64
−63
−63
−64


10,000 psi, ° C.
−65
−65
−64
−64
−65


25,000 psi, ° C.
−67
−68
−65
−65
−68


50,000 psi, ° C.
−69
−69
−69
−69
−69


Air Oven Aging, 70 h @ 100° C.


Stress @ 100% Elongation, MPa,
1.1
1.1
1.1
1.1
1.1


psi
165
160
165
160
160


Stress Change, %
43
0
−2.9
0.0
−5.9


Tensile Ultimate, MPa,
4.4
4.3
3.6
3.9
3.1


psi
635
630
520
570
450


Tensile Change, %
−73
−82
−85
−83
−86


Elongation @ Break, %
290
270
240
260
220


Elongation Change, %
−58
−61
−66
−63
−67


Hardness Duro A, pts
46
40
41
39
39


Hardness Change, pts.
6
−6
−6
−7
−8


Weight Change, %
−13
−0.90
−0.47
−0.48
−0.43









In the following examples provided in Table VI, cyclic dimerate esters were applied to Polychloroprene (Neoprene WRT). Again, the dimerate esters were evaluated at 15 phr and compared to a conventional napthenic oil at 30 phr (i.e., the conventional rubber plasticizer was added to the elastomer composition at twice the amount of the rubber plasticizers disclosed herein).
Results
The processing and curing properties show no major differences except that since the dimerates are evaluated at lower phr they do produce higher viscosity compounds. Compatibility data show that the dimerate ester evaluated in Table VI is compatible, as indicated by the lack of roll spew and low weight loss in air oven aging. The dimerate ester provides higher tensile strength and hardness values than other plasticizers.
Table VI shows the low temperature properties for elastomers plasticized with various compounds. The low temperature properties of the composition plasticized with the dimerate ester are highly significant in comparison to elastomers plasticized with paraffinic oil. For example, even though the dimerate is at 15 phr and the processing oil at 30 phr, the dimerate provides equal low temperature properties. The combination of high strength and hardness with excellent low temperature can have importance in applications such as V-belts, radiator hoses, automotive insulation, seals and gaskets.
Additionally, the dimerate ester is significantly lower in volatility when compared to the napthenic oil (air oven aging).









TABLE VI







Example
23
24












Neoprene WRT
100.00






 


Stearic Acid
2.00






 


Octamine
1.00






 


Mag Ox TN16
2.20






 


N 774
70.00






 


Premix TMTD
0.30






 


Process Oil C-255-E
30.00
—


RX-13804
—
15.00


Subtotal
205.50
190.50


Mill Addition




PB(ETU)75
0.80






 


Kadox 930
5.00






 


Total
211.30
196.30


Processing Properties


Viscosity and Curing Properties


Mooney Viscosity at 135° C.(275° F.)


Minimum Viscosity
16.6
36.2


t5, minutes
9.5
7.3


t10, minutes
10.8
8.2


t35, minutes
13.8
10.3


Oscillating Disc Rheometer at


160° C.(320° F.)


ML
3.1
8


MH
19.1
50.7


tS2, minutes
3.6
2.5


t'c(90), minutes
14.8
17.3


1.25*t'c(90), minutes
18.5
21.7


Cure Rate Index
8.9
6.7












Example
23
24












Original Physical Properties




Stress @ 100% Elongation, MPa
2.5
4.8


psi
360
690


Stress @ 200% Elongation, MPa
6.5
13.5


Stress @ 300% Elongation, MPa
12.3
—


Tensile Ultimate, MPa,
13.2
15.8


psi
1920
2295


Elongation @ Break, %
320
225


Hardness Duro A, pts.
56
69


Specific Gravity
1.342
1.394


Low Temperature Properties


Low Temperature Impact - Brittleness


Brittle Point, as molded, all pass, ° C.
−41
−40


Low Temperature Torsion - Gehman


As molded, Relative Modulus


T2, ° C.
−28
−22


T5, ° C.
−37
−34


T10, ° C.
−40
−39


T100, ° C.
−46
−45


Apparent Modulus of Rigidity
144
232


Temperature at


500 psi, ° C.
−40
−24


5,000 psi, ° C.
−44
−41


10,000 psi, ° C.
−45
−44


25,000 psi, ° C.
−48
−45


50,000 psi, ° C.
−50
−49


Air Oven Aging, 70 h @ 125° C.


Stress @ 100% Elongation, MPa,
9.9
6.7


psi
1430
970


Stress Change, %
297
41


Tensile Ultimate, MPa
14.9
16.4


psi
2160
2375


Tensile Change, %
13
3


Elongation @Break, %
165
205


Elongation Change, %
−48
−9


Hardness Duro A, pts
86
75


Hardness Change, pts.
30
6


Weight Change, %
−13
−0.48
















TABLE VII







Materials List for Tables I–VI









Material
Chemical Description
Supplier





Royalene 501
Ethylene-propylene
Uniroyal



ethylidene norbornene



rubber 57/43 EP Ratio


Royalene 502
ENB third monomer
Uniroyal



62/38 EP ratio


N-550
Carbon Black
Engineering Carbon


Kadox 930
Zinc Oxide
The C. P. Hall Company


Stearic Acid
Stearic Acid, Rubber
The C. P. Hall Company



Grade


RX-13577
Tridecyl tallate
The C. P. Hall Company


RX-13782
Capryl Tallate
The C. P. Hall Company


RX-13804
Di(2-ethylhexyl)dimerate
The C. P. Hall Company



(Empol 1016)


RX-13805
Di(2-ethylhexyl)dimerate
The C. P. Hall Company



(Empol 1018)


RX-13806
Didecyl dimerate
The C. P. Hall Company


RX-13824
Di-tridecyl dimerate
The C. P. Hall Company


RX-13853
Di-hexyldecyl tallate
The C. P. Hall Company


RX-13896
Di(2-ethylhexyl)dimerate
The C. P. Hall Company



(Unidyme 22)


SMR CV 60
Natural Rubber
The C. P. Hall Company


N-330
Carbon Black
Degussa


Process Oil C-255-E
Parraffinic Oil
The C. P. Hall Company


Sulfur
Sulfur
The C. P. Hall Company


Santocure TBBS
N-t-butyl-2-benzo-
Harwick Standard



thiazolesulfenamide


UBS 020602
Di(2-ethylhexyl)dimerate
The C. P. Hall Company



(Pripol 1006)


Plasthall DOS
Dioctyl Sebacate
The C. P. Hall Company


Sunpar 2280
Parraffinic Oil
Sun Refining


Spider Sulfur
Elemental Sulfur
The C. P. Hall Company


Premix MBT
2-mercaptobenzothiazole
The C. P. Hall Company


Premix TMTD
Tetramethyl thiuram
The C. P. Hall Company



disulfide


Premix DPTT
Dipentamethylene
The C. P. Hall Company



thiuram(tetra)sulfide


Premix TDEC
Tellurium
The C. P. Hall Company



diethyldithiocarbamate


Neoprene WRT
Polychloroprene
R. T. Vanderbilt


Octamine
Octylated diphenylamine
Uniroyal


Mag Oxide TN16
Magnesium Oxide
The C. P. Hall Company


N-774
Carbon Black
Degussa


PB(ETU)75
Ethylene Thiourea 75%
Rhein Chemie

## Claims

1. A plasticized elastomer composition comprising rubber selected from the group consisting of natural rubber, synthetic rubber, and a combination thereof, and a cyclic dimerate or trimerate ester plasticizer compound having formula I, II, or a mixture thereof:



wherein R5 and R7, same or different, are a C3–C24 hydrocarbon chain, straight chain or branched, either saturated or having 1 to 6 carbon-to-carbon double bonds;
R6 and R8, same or different, are a C3–C24 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and
R10 and R11, same or different, are a C3–C24, saturated hydrocarbon chain, straight chain or branched; or an unsaturated C3–C24, hydrocarbon chain, straight chain or branched, having 1 to 6 carbon-to-carbon double bonds;




wherein R12, R14 and R18, same or different, are a C3–C24 hydrocarbon chain, straight chain or branched, either saturated or having 1 to 6 carbon-to-carbon double bonds;
R13, R15 and R19, same or different, are a C3–C24 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and
R16, R17 and R20, same or different, are a C3–C24 saturated hydrocarbon chain, straight chain or branched; or unsaturated C3–C24 hydrocarbon chain, straight chain or branched, containing 1 to 6 carbon-to-carbon double bonds.

2. A composition in accordance with claim 1, wherein the plasticizer is selected from the group consisting of formula I, II, and a combination thereof:



wherein R5 and R7, are a C6–C24 hydrocarbon chain, straight chain or branched; either saturated or having 1 to 3 carbon-to-carbon double bonds;
R6 and R8, same or different, are a C3–C18 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds, and
R10 and R11, same or different, are C3–C18 saturated hydrocarbon chain, straight chain or branched; or an unsaturated hydrocarbon chain, straight chain or branched, containing 1 to 3 carbon-to-carbon double bonds;




wherein R12, R14 and R18, same or different, are a C6–C24 hydrocarbon chain, straight chain or branched, either saturated or containing 1 to 3 carbon-to-carbon double bonds;
R13, R15 and R19, same or different, are a C3–C18 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and
R16, R17 and R20, same or different, are a C3–C18 saturated hydrocarbon chain, straight chain or branched; or an unsaturated C3–C18 hydrocarbon-chain, straight chain or branched, containing 1 to 3 carbon-to-carbon double bonds.

3. A composition in accordance with claim 1, wherein the plasticizer compound having formula I, II, or a mixture thereof is present in an amount from about 0.1 parts to about 50 parts by weight per 100 parts of rubber.

4. A composition in accordance with claim 1, wherein the plasticizer compound having formula I, II, or a mixture thereof is present in an amount from about 2 parts to about 40 parts by weight per 100 parts of rubber.

5. A composition in accordance with claim 1, wherein the plasticizer compound having formula I, II, or a mixture thereof is present in an amount from about 10 parts to about 35 parts per 100 parts of rubber.

6. A composition in accordance with claim 1, wherein the plasticizer is an unsaturated diester formed by the reaction of a C36 dimer acid and a C3–C18 alcohol, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds.

7. A composition in accordance with claim 6, wherein the alcohol is 2-ethylhexyl alcohol.

8. A composition in accordance with claim 6, wherein the alcohol is tridecyl alcohol.

9. A composition in accordance with claim 6, wherein the alcohol is oleyl alcohol.

10. A composition in accordance with claim 6, wherein the alcohol is n-butyl alcohol.

11. A composition in accordance with claim 1, wherein the plasticizer comprises the following dimer acid reacted with a C3–C24 alcohol:

12. A composition in accordance with claim 1, wherein the plasticizer comprises the following dimer acid reacted with a C3–C24 alcohol:

13. A composition in accordance with claim 1, wherein the plasticizer comprises the following dimer acid reacted with a C3–C24 alcohol:

14. A composition in accordance with claim 1, wherein the plasticizer is the reaction product of a C3–C24 alcohol with a tricarboxylic acid, having the following formula:

15. A composition in accordance with claim 1, wherein the plasticizer is a combination of compounds represented by formula I and II.

16. A composition in accordance with claim 15, wherein the plasticizer is a reaction product of a C3–C24 alcohol straight chain or branched, saturated, or unsaturated having 1 to 3 carbon-to-carbon double bonds, with a dimer acid having CAS #61788-89-4.

17. A composition in accordance with claim 16, wherein the alcohol is 2-ethylhexyl alcohol.

18. A composition in accordance with claim 16, wherein the alcohol is tridecyl alcohol.

19. A rubber composition in accordance with claim 16, wherein the alcohol is oleyl alcohol.

20. A composition in accordance with claim 16, wherein the alcohol is n-butyl alcohol.

21. The composition in accordance with claim 1, wherein R5, R7, R12, R14 are fatty acid residues derived from animal or vegetable fatty acids.

22. The composition of claim 21, wherein the fatty acids are selected from the group consisting of butter; lard; tallow; grease; herring; menhaden; pilchard; sardine; babassu; castor; coconut; corn; cottonseed; jojoba; linseed; oiticia; olive; palm; palm kernel; peanut; rapeseed; safflower; soya; sunflower; tall; tung; and mixtures thereof.

23. The composition of claim 21, wherein the fatty acid residues are selected from the group consisting of hexanoic; octanoic; decanoic; dodecanoic; 9-dodecenoic; tetradecanoic; 9-tetradecenoic; hexadecanoic; 9-hexadecenoic; octadecanoic; 9-octadecenoic; 9-octadecenoic, 12-hydroxy; 9,12-octadecadienoic; 9,12,15-octadecatrienoic; 9,11,13-octadecatrienoic; 9,11,13-octadecatrienoic; 4-oxo; octadecatetrenoic; eicosanoic; 11-eicosenoic; eicosadienoic; eicosatrienoic; 5,8,11,14-eicosatetraenoic; eicosapentaenoic; docosanoic; 13-docosenoic; docosatetraenoic; 4,8,12,15,19-docosapentaenoic; docosahexaenoic; tetracosenoic; and 4,8,12,15,18,21-tetracosahexaenoic.

24. A method of plasticizing an elastomeric composition, said elastomeric composition including one or more natural or synthetic rubbers, and a rubber vulcanizing agent, comprising adding to said rubber composition, in an amount of about 0.1 parts to about 50 parts by weight per 100 parts of rubber in the composition, a cyclic ester plasticizer of formula I, II, or mixtures thereof:



wherein R5 and R7, same or different, are a C3–C24 hydrocarbon chain, straight chain or branched, either saturated or having 1 to 6 carbon-to-carbon double bonds;
R6 and R8, same or different, are a C3–C24 alkyl radical, straight chain or branched; and
R10 and R11, same or different, are a C3–C24, saturated hydrocarbon chain, straight chain or branched; or an unsaturated C3–C24, hydrocarbon chain, straight chain or branched, having 1 to 6 carbon-to-carbon double bonds;




wherein R12, R14 and R18, same or different, are a C3–C24 hydrocarbon chain, straight chain or branched, either saturated or having 1 to 6 carbon-to-carbon double bonds;
R13, R14 and R19, same or different, are a C3–C24 alkyl radical, straight chain or branched, saturated, or unsaturated containing 1 to 3 carbon-to-carbon double bonds; and
R16, R17 and R20, same or different, are a C3–C24 saturated hydrocarbon chain, straight chain or branched; or unsaturated C3–C24 hydrocarbon chain, straight chain or branched, containing 1 to 6 carbon-to-carbon double bonds.

25. The method of claim 24, wherein the cyclic ester plasticizer is added in an amount from about 2 parts to about 40 parts by weight per 100 parts of rubber.

26. The method of claim 24, wherein the cyclic ester plasticizer is added in an amount from about 10 parts to about 35 parts per 100 parts of rubber.