Ethylene-Based Polymer Composition Containing a Triorganoaminophosphine
20220282073 · 2022-09-08
Inventors
- Bharat I. Chaudhary (Collegeville, PA)
- Jeffrey M. Cogen (Collegeville, PA)
- Charles Liotta (Sandy Springs, GA, US)
- Sarath Chand Sarngadharan (Kollam, IN)
- Pamela Pollet (Atlanta, GA, US)
Cpc classification
International classification
Abstract
The present disclosure provides a composition. The composition includes (i) an ethylene-based polymer; (ii) an organic peroxide, (iii) a triorganoaminophosphine, and (iv) a protic acid-source compound (“PASC”) selected from a protic acid, a protic acid-generator compound (“PAGC”), and combinations thereof. The present disclosure also provides a coated conductor. The coated conductor includes a conductor and a coating on the conductor, the coating containing a composition including (i) an ethylene-based polymer; (ii) an organic peroxide, (iii) a triorganoaminophosphine, and (iv) a protic acid-source compound (“PASC”) selected from a protic acid, a protic acid-generator compound (“PAGC”), and combinations thereof.
Claims
1. A composition comprising: (i) an ethylene-based polymer; (ii) an organic peroxide; (iii) a triorganoaminophosphine of Structure (1) ##STR00015## (iv) a protic acid-source compound (“PASC”) selected from the group consisting of a protic acid, a protic acid-generator compound (“PAGC”), and combinations thereof; wherein R.sup.1 and R.sup.2 each is independently selected from the group consisting of a C.sub.1-C.sub.40 hydrocarbyl group, a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group; and wherein R.sup.3 is selected from the group consisting of a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group.
2. The composition of claim 1, wherein the PASC is the protic acid; and the composition has a Retained Peroxide Percentage from 12% to 100% after the composition has been heated at 100° C. for 2 hours in an air atmosphere, and the peroxide content of the resulting headed composition is measured using liquid chromatography.
3. The composition of claim 1, wherein the PASC is the protic acid, and the protic acid is selected from the group consisting of a sulfonic acid, a sulfenic acid, a sulfinic acid, a carboxylic acid, a phosphorus-based acid, and a combination thereof.
4. The composition of claim 1 wherein the PASC is the PAGC, and the PAGC is an antioxidant.
5. The composition of claim 4 wherein the antioxidant is a sulfur-based antioxidant.
6. The composition of claim 1, wherein R.sup.1 and R.sup.2 each is independently selected from the group consisting of a phenyl group, a N,N-diethylamino group, a pyrrolidinyl group, a 4-(N,N-dimethylamino)phenyl group, and a cyclohexyl group; and R.sup.3 is selected from the group consisting of a N,N-diethylamino group, a pyrrolidinyl group, and a 4-(N,N-dimethylamino)phenyl group.
7. The composition of 6, wherein at least two of R.sup.1, R.sup.2, and R.sup.3 are the same.
8. The composition of claim 1, wherein the organic peroxide is dicumyl peroxide.
9. The composition of claim 1, wherein the composition comprises from 0.001 to 1.0 wt % of the triorganoaminophosphine having the Structure (1), based on the total weight of the composition; R.sup.1 is a phenyl group; and R.sup.2 and R.sup.3 each is a N,N-diethylamino group.
10. The composition of claim 1, wherein the composition comprises from 0.001 to 1.0 wt % of the triorganoaminophosphine having the Structure (1), based on the total weight of the composition; and R.sup.1, R.sup.2, and R.sup.3 each is a pyrrolidinyl group.
11. The composition of claim 1, wherein the composition comprises from 0.001 to 1.0 wt % of the triorganoaminophosphine having the Structure (1), based on the total weight of the composition; R.sup.1 and R.sup.2 each is a phenyl group; and R.sup.3 is a 4-(N,N-dimethylamino)phenyl group.
12. The composition of claim 1, wherein the composition comprises from 0.001 to 1.0 wt % of the triorganoaminophosphine having the Structure (1), based on the total weight of the composition; R.sup.1 and R.sup.2 each is a cyclohexyl group; and R.sup.3 is a 4-(N,N-dimethylamino)phenyl group.
13. A crosslinked product made by heating the composition of claim 1 to a temperature sufficient to crosslink the composition.
14. A coated conductor comprising: a conductor; and a coating on the conductor, the coating comprising, a composition comprising: (i) an ethylene-based polymer; (ii) an organic peroxide; (iii) a triorganoaminophosphine of Structure (1) ##STR00016## (iv) a protic acid-source compound (“PASC”) selected from the group consisting of a protic acid, a protic acid-generator compound (“PAGC”), and combinations thereof; wherein R.sup.1 and R.sup.2 each is independently selected from the group consisting of a C.sub.1-C.sub.40 hydrocarbyl group, a C.sub.7-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group; and wherein R.sup.3 is selected from the group consisting of a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N dialkyl)aminoaryl group.
15. The coated conductor of claim 14 wherein the composition has a Retained Peroxide Percentage of greater than 12%, after heating at 100° C. for 2 hours.
16. The coated conductor of claim 15 where the composition is crosslinked.
Description
DETAILED DESCRIPTION
[0053] The present disclosure provides a composition suitable for wire and cable applications. The composition includes: (i) an ethylene-based polymer; (ii) an organic peroxide, (iii) a triorganoaminophosphine, and (iv) a protic acid-source compound (“PASC”) selected from a protic acid, a protic acid-generator compound (“PAGC”), and combinations thereof. The triorganoaminophosphine has the Structure (1):
##STR00003##
[0054] wherein R.sup.1 and R.sup.2 each is independently selected from the group consisting of a C.sub.1-C.sub.40 hydrocarbyl group, a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group; and
[0055] wherein R.sup.3 is selected from the group consisting of a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group.
[0056] In an embodiment, the composition includes (i) an ethylene-based polymer; (ii) an organic peroxide, (iii) a triorganoaminophosphine, and (iv) a PASC selected from the group consisting of a protic acid, a PAGC, and combinations thereof; and (v) optionally, an additive. The triorganoaminophosphine has the Structure (1):
##STR00004##
[0057] wherein R.sup.1 and R.sup.2 each is independently selected from the group consisting of a C.sub.1-C.sub.40 hydrocarbyl group, a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group; and
[0058] wherein R.sup.3 is selected from the group consisting of a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group.
[0059] i. Ethylene-Based Polymer
[0060] The present composition includes an ethylene-based polymer.
[0061] The ethylene-based polymer may be any ethylene-based polymer disclosed herein.
[0062] The ethylene-based polymer may be an ethylene homopolymer or an ethylene interpolymer. Examples of ethylene-based polymer include LDPE and linear polyethylene. Examples of linear polyethylene include LLDPE, ULDPE, VLDPE, multi-component ethylene-based copolymer (EPE), ethylene/α-olefin multi-block copolymers (also known as olefin block copolymer (OBC)), single-site catalyzed linear low density polyethylene (m-LLDPE), substantially linear, or linear, plastomers/elastomers, MDPE, and HDPE. In an embodiment, the ethylene-based polymer is selected from LDPE, LLDPE, ULDPE, VLDPE, EPE, OBC, m-LLDPE, substantially linear, or linear, plastomers/elastomers, MDPE, HDPE, and combinations thereof.
[0063] In an embodiment, the ethylene-based polymer is an ethylene/α-olefin copolymer. In a further embodiment, the ethylene/α-olefin copolymer is an ethylene/C.sub.3-C.sub.20 α-olefin, or an ethylene/C.sub.3-C.sub.10 α-olefin, or an ethylene/C.sub.4-C.sub.10 α-olefin, or an ethylene/C.sub.4-C.sub.8 α-olefin. Examples of suitable α-olefins include 1-butene, 1-hexene, and 1-octene.
[0064] In an embodiment, the ethylene-based polymer is void of, or substantially void of, styrene.
[0065] In an embodiment, the ethylene/α-olefin copolymer consists of the ethylene, and a C.sub.4-C.sub.8 α-olefin comonomer. In other words, the ethylene/C.sub.4-C.sub.8 α-olefin copolymer contains the ethylene and C.sub.4-C.sub.8 α-olefin comonomer as the only monomeric units.
[0066] The ethylene-based polymer may or may not be functionalized. A “functionalized ethylene-based polymer” includes a functional group. In an embodiment, the functional group is grafted pendant to the polymer chain. The functional group may also be incorporated through copolymerization of a suitable monomer containing the desired functional group. Examples of suitable functional groups include halo, particularly chloro and bromo, hydroxyl, carboxyl, carbonyl, phosphono, acid anhydride, amino, amine, imide, epoxy, mercapto, sulfate, sulfonate, amido, and ester groups. Examples of unsaturated carboxylic acid and acid anhydride compounds that can be grafted onto the preformed ethylene-based polymer include maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, and itaconic anhydride. In an embodiment, the functionalized ethylene-based polymer is a maleic-anhydride functionalized ethylene/α-olefin interpolymer. In a further embodiment, the functionalized ethylene-based polymer is a maleic-anhydride functionalized ethylene/octene interpolymer. The ethylene-based polymer may include one or more of ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-vinyl trimethoxysilane copolymer, or other copolymers made in a high pressure reactor and containing from 0.2 wt % to less than 50 wt %, or 50 wt % comonomer.
[0067] In an embodiment, the ethylene-based polymer is not functionalized.
[0068] The ethylene-based polymer contains from 50 wt %, or 55 wt %, or 60 wt %, or 65 wt %, or 70 wt %, or 75 wt % to 80 wt %, or 85 wt %, or 90 wt %, or 95 wt %, or 100 wt % ethylene, based on the total weight of the ethylene-based polymer.
[0069] In an embodiment, the ethylene-based polymer contains from 55 wt %, or 60 wt %, or 65 wt %, or 70 wt %, or 75 wt % to 80 wt %, or 85 wt %, or 90 wt %, or 95 wt % ethylene; and a reciprocal amount of α-olefin comonomer, or from 5 wt %, or 10 wt %, or 15 wt %, or 20 wt % to 25 wt %, or 30 wt %, or 35 wt %, or 40 wt %, or 45 wt % α-olefin comonomer, based on the total weight of the ethylene-based polymer.
[0070] The ethylene-based polymer may comprise two or more embodiments disclosed herein.
[0071] ii. Organic Peroxide
[0072] The present composition includes an organic peroxide. An “organic peroxide” is a compound containing at least one carbon atom having the following Structure (2):
R.sup.4—O—O—R.sup.5 Structure (2)
wherein R.sup.4 and R.sup.5 each is independently selected from a C.sub.1-C.sub.40 hydrocarbyl group, a C.sub.1-C.sub.40 heterohydrocarbyl group, hydrogen, and combinations thereof; with the proviso that at least one of R.sup.4 and R.sup.5 is a C.sub.1-C.sub.40 hydrocarbyl group or a C.sub.1-C.sub.40 heterohydrocarbyl group.
[0073] Examples of suitable organic peroxides include dicumyl peroxide (DCP), lauryl peroxide, benzoyl peroxide, tertiary butyl perbenzoate, di(tertiary-butyl) peroxide, cumene hydroperoxide, 2,5-dimethyl-2,5-di(t-butyl-peroxy)hexyne-3,2,5-di-methyl-2,5-di(t-butyl-peroxy)hexane, tertiary butyl hydroperoxide, isopropyl percarbonate, alpha,alpha′-bis(tertiary-butylperoxy)diisopropylbenzene, t-butylperoxy-2-ethylhexyl-monocarbonate, 1,1-bis(t-butylperoxy)-3,5,5-trimethyl cyclohexane, 2,5-dimethyl-2,5-dihydroxyperoxide, t-butylcumylperoxide, alpha,alpha′-bis(t-butylperoxy)-p-diisopropyl benzene, di-(tert-butylperoxyisopropyl)benzene, tert-butyl cumyl peroxide, di-tert-butyl peroxide, and combinations thereof.
[0074] Non-limiting examples of suitable commercially available organic peroxides include TRIGONOX™ from AkzoNobel and LUPEROX™ from ARKEMA.
[0075] In an embodiment, the organic peroxide is selected from dicumyl peroxide (DCP); 2,5-di-methyl-2,5-di(t-butyl-peroxy)hexane; di-(tert-butylperoxyisopropyl)benzene; tert-butyl cumyl peroxide; di-tert-butyl peroxide; and combinations thereof.
[0076] In an embodiment, the organic peroxide is dicumyl peroxide (DCP).
[0077] In an embodiment, the peroxide is a dialkylperoxide. A “dialkylperoxide” is a compound having the following Structure (2A):
R.sup.4—O—O—R.sup.5 Structure (2A)
wherein R.sup.4 and R.sup.5 each is an alkyl group.
[0078] In an embodiment, R.sup.4 and R.sup.5 of Structure (2A) each is a C.sub.1-C.sub.20 alkyl group, or a C.sub.1-C.sub.10 alkyl group.
[0079] Organic peroxide excludes organic hydroperoxide, which contains an —OOH group.
[0080] Organic peroxide excludes hydrogen peroxide, which has the formula H.sub.2O.sub.2, because hydrogen peroxide lacks carbon.
[0081] The organic peroxide may comprise two or more embodiments disclosed herein.
[0082] iii. Triorganoaminophosphine
[0083] The present composition includes a triorganoaminophosphine.
[0084] A “triorganoaminophosphine” is a compound having the following Structure (1):
##STR00005##
[0085] wherein R.sup.1 and R.sup.2 each is independently selected from the group consisting of a C.sub.1-C.sub.40 hydrocarbyl group, a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group; and
[0086] wherein R.sup.3 is selected from the group consisting of a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group.
[0087] In an embodiment, the triorganoaminophosphine is a compound having the following Structure (1′):
##STR00006##
wherein R.sup.1′, R.sup.2, and R.sup.3′ each is independently selected from a C.sub.1-C.sub.40 hydrocarbyl group, a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group, and combinations thereof; with the proviso that at least one of R.sup.1′, R.sup.2, and R.sup.3′ contains at least one nitrogen atom; and the nitrogen atom is (i) bonded directly to the phosphorus atom or (ii) bonded to an alkyl group or an aryl group that is bonded directly to the phosphorus atom.
[0088] The triorganoaminophosphine includes a phosphorous atom bonded to three carbon atoms, or a phosphorous atom bonded to from one, or two to three nitrogen atoms.
[0089] The descriptions described herein with respect to Structure (1), R.sup.1, R.sup.2, and R.sup.3 also apply to Structure (1′), R.sup.1′, R.sup.2, and R.sup.3′, respectively.
[0090] In an embodiment, the triorganoaminophosphine includes a phosphorous atom bonded to three carbon atoms. At least one of R.sup.1, R.sup.2, and R.sup.3 of Structure (1) contains at least one nitrogen atom, and the nitrogen atom is bonded to a C.sub.1-C.sub.20, or a C.sub.2-C.sub.10, or a C.sub.4-C.sub.8 alkyl group or a C.sub.5-C.sub.20, or a C.sub.6-C.sub.10, or a C.sub.4-C.sub.8 aryl group that is bonded directly to the phosphorus atom.
[0091] In an embodiment, the triorganoaminophosphine includes a phosphorous atom directly bonded to from one, or two to three nitrogen atoms. In another embodiment, the triorganoaminophosphine includes a phosphorous atom directly bonded to three nitrogen atoms.
[0092] In an embodiment, the hydrocarbyl group of Structure (1) is a C.sub.1-C.sub.20 hydrocarbyl group, or a C.sub.1-C.sub.10 hydrocarbyl group, or a C.sub.2-C.sub.8 hydrocarbyl group, or a C.sub.6-C.sub.8 hydrocarbyl group. Examples of suitable C.sub.1-C.sub.40 hydrocarbyl groups include phenyl groups, p-tolyl groups, cyclohexyl groups, n-octyl groups.
[0093] In an embodiment, R.sup.1 and R.sup.2 each is a C.sub.1-C.sub.40, or C.sub.1-C.sub.20, or C.sub.2-C.sub.10, or C.sub.4-C.sub.8, or C.sub.6 hydrocarbyl group; and R.sup.3 is a C.sub.8-C.sub.40, or C.sub.8-C.sub.20, or C.sub.8-C.sub.10 (N,N-dialkyl)aminoaryl group. An example of a suitable (N,N-dialkyl)aminoaryl group is a 4-(N,N-dimethylamino)phenyl group.
[0094] In an embodiment, R.sup.1 is selected from a C.sub.1-C.sub.40 hydrocarbyl group, a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group; and R.sup.2 and R.sup.3 each is independently selected from a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group, and combinations thereof. The phosphorous atom is directly bonded to two, or three, nitrogen atoms.
[0095] In Structure (1), R.sup.1, R.sup.2, and R.sup.3 may be the same or different. In an embodiment, R.sup.1, R.sup.2, and R.sup.3 are the same. In another embodiment, at least two, or each of R.sup.1, R.sup.2, and R.sup.3 are different.
[0096] In an embodiment, in Structure (1), at least two of R.sup.1, R.sup.2, and R.sup.3 are the same.
[0097] In an embodiment, R.sup.1, R.sup.2, and R.sup.3 each is independently selected from a phenyl group, a N,N-diethylamino group, a pyrrolidinyl group, a 4-(N,N-dimethylamino)phenyl group, a cyclohexyl group, and combinations thereof; with the proviso that at least one of R.sup.1, R.sup.2, and R.sup.3 contains at least one nitrogen atom.
[0098] In an embodiment, R.sup.1 is a phenyl group; and R.sup.2 and R.sup.3 each is a N,N-diethylamino group. The triorganoaminophosphine is bis(diethylamino)phenyl phosphine.
[0099] In an embodiment, R.sup.1, R.sup.2, and R.sup.3 each is a pyrrolidinyl group. The triorganoaminophosphine is tris-(1-pyrrolyidinyl)phosphine.
[0100] In an embodiment, R.sup.1 and R.sup.2 each is a phenyl group; and R.sup.3 is a 4-(N,N-dimethylamino)phenyl group. The triorganoaminophosphine is (dimethylamino)phenyldiphenylphosphine.
[0101] In an embodiment, R.sup.1 and R.sup.2 each is a cyclohexyl group; and R.sup.3 is a 4-(N,N-dimethylamino)phenyl group. The triorganoaminophosphine is dicyclohexyl-4-(N,N-dimethylamino)phenyl phosphine.
[0102] In an embodiment, the triorganoaminophosphine is selected from bis(diethylamino)phenyl phosphine, tris-(1-pyrrolyidinyl)phosphine, (dimethylamino)phenyldiphenylphosphine, dicyclohexyl-4-(N,N-dimethylamino)phenyl phosphine, and combinations thereof.
[0103] In an embodiment, the triorganoaminophosphine is selected from bis(diethylamino)phenyl phosphine, tris-(1-pyrrolyidinyl)phosphine, and combinations thereof.
[0104] In an embodiment, the triorganoaminophosphine is selected from (dimethylamino)phenyldiphenylphosphine, dicyclohexyl-4-(N,N-dimethylamino)phenyl phosphine, and combinations thereof.
[0105] The triorganoaminophosphine may comprise two or more embodiments disclosed herein.
[0106] iv. Protic Acid-Source Compound
[0107] The present composition includes a protic acid-source compound.
[0108] A “protic acid source compound” (or “PASO”) is a protic acid, or a protic acid-generator compound (“PAGC”).
A. Protic Acid
[0109] A “protic acid” is a substance that yields hydrogen ions (H+) under polyolefin melt extrusion or other conditions and is capable of causing ionic decomposition of organic peroxides instead of free radical decomposition. Protic acids exclude polyolefin-based radicals. Protic acids can act as proton donors, and can accept a pair of electrons to form a covalent bond. Examples of suitable protic acid include sulfur-based acid, carboxylic acid, phosphorus-based acid, and combinations thereof.
[0110] A “sulfur-based acid” is an organic acid containing a sulfur atom. Examples of suitable sulfur-based acids include sulfonic acid, sulfenic acid, sulfinic acid, and combinations thereof.
[0111] A “sulfonic acid” is an organic acid containing a group of the following Structure (3):
##STR00007##
[0112] An example of a suitable sulfonic acid is dodecylbenzene sulfonic acid (DBSA).
[0113] A “sulfenic acid” is an organic acid containing a group of the following Structure (4):
—S—O—H Structure (4)
[0114] An example of a suitable sulfenic acid is methanesulfenic acid.
[0115] A “sulfinic acid” is an organic acid containing a group of the following Structure (5):
##STR00008##
[0116] An example of a suitable sulfinic acid is phenylsulfinic acid.
[0117] A “phosphorus-based acid” is an organic acid containing a phosphorous atom. Examples of suitable phosphorous-based acid include phosphorous acid, phosphoric acid, and combinations thereof.
[0118] In an embodiment, the protic acid is selected from sulfonic acid, sulfenic acid, sulfinic acid, carboxylic acid, and combinations thereof. In a further embodiment, the protic acid is selected from sulfonic acid, sulfenic acid, sulfinic acid, and combinations thereof.
[0119] The protic acid may comprise two or more embodiments disclosed herein.
B. Protic Acid-Generator Compound
[0120] A “protic acid-generator compound” (or “PAGC”) is a substance that is not a protic acid, but contains a functional group that reacts with oxygen and/or oxidation products (such as hydroperoxides) so as to be converted to or to generate a protic acid during the formation, storage, processing, and/or extrusion of the present composition. The PAGC is a latent protic acid. During the formation (e.g., melt blending), storage, processing, and/or extrusion of the composition, the PAGC undergoes a reaction or a series of reactions that yields a protic acid.
[0121] Examples of suitable PAGC include antioxidants (AO), additives, fillers, and combinations thereof. Examples of suitable antioxidants include phosphite antioxidants and sulfur-based antioxidants.
[0122] In an embodiment, the PAGC is a phosphite antioxidant. Phosphite antioxidants and their oxidation products (phosphates) undergo hydrolysis in use (as an antioxidant) and/or during processing to yield a phosphorus-based acid. Oxidation may occur before or after hydrolysis. An example of a suitable phosphite antioxidant is tris(2,4-di-tert-butylphenyl)phosphite, commercially available as IRGAFOS™ 168 from BASF Inc.
[0123] In an embodiment, the PAGC is a sulfur-based antioxidant. Sulfur-based antioxidants oxidize during formation, storage, processing, and/or extrusion of the present composition. The oxidation product undergoes thermal cleavage to form a sulfur-based acid, such as sulfonic acid, sulfenic acid, sulfinic acid, and combinations thereof. The sulfur-based acid may undergo further oxidation to form a sulfur-based acid with a higher oxidation state. Examples of sulfur-based antioxidants include distearyl thiodipropionate (DSTDP); 4,4′-thiobis(2-t-butyl-5-methylphenol) (e.g., LOWINOX™ TBM-6, available from Addivant Corporation); 2,2′-thiobis(6-t-butyl-4-methylphenol) (e.g., LOWINOX™ TBP-6, available from Addivant Corporation); and combinations thereof.
[0124] In an embodiment, the PAGC is an ester additive. Esters can hydrolyze during use, processing, and/or storage to form carboxylic acids. Examples of suitable ester additive include pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g., IRGANOX™ 1010 available from BASF); octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate (e.g., IRGANOX™ 1076, available from Ciba Inc.); and combinations thereof.
[0125] In an embodiment, the PAGC is selected from a sulfur-based antioxidant, a phosphite antioxidant, an ester additive, and combinations thereof.
[0126] In an embodiment, the PAGC is selected from a sulfur-based antioxidant, a phosphite antioxidant, and combinations thereof.
[0127] The PAGC may comprise two or more embodiments disclosed herein.
[0128] The present composition may include a PAGC (such as a sulfur-based antioxidant) when the composition is formed, and will then include a protic acid once the PAGC undergoes a reaction (such as oxidation) that yields a protic acid (such as sulfonic acid, sulfenic acid, and/or sulfinic acid). At a single point in time, the composition may include (i) only the PAGC (and not the protic acid), (ii) a combination of both the PAGC and the protic acid, or (iii) only the protic acid (and not the PAGC).
[0129] The PASC, and further the PAGC, is different than the ethylene-based polymer. In other words, the PASC, and further the PAGC, excludes ethylene-based polymer and any oxidation reaction products from the ethylene-based polymer.
[0130] The PASC may comprise two or more embodiments disclosed herein.
[0131] v. Optional Additive
[0132] The present composition may include one or more additives. Examples of suitable additives include antioxidants, colorants, corrosion inhibitors, lubricants, ultra violet (UV) absorbers or stabilizers, anti-blocking agents, coupling agents, compatibilizers, plasticizers, fillers, processing aids, moisture scavengers, scorch retardants, metal deactivators, and combinations thereof.
[0133] The additive may comprise two or more embodiments disclosed herein.
[0134] vi. Composition
[0135] The present composition includes: (i) the ethylene-based polymer; (ii) the organic peroxide; (iii) the triorganoaminophosphine; (iv) the PASC selected from a protic acid, a PAGC, and combinations thereof; and (v) optionally, an additive. The triorganoaminophosphine has the Structure (1):
##STR00009##
[0136] wherein R.sup.1 and R.sup.2 each is independently selected from the group consisting of a C.sub.1-C.sub.40 hydrocarbyl group, a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group; and
[0137] wherein R.sup.3 is selected from the group consisting of a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group.
[0138] In an embodiment, the triorganoaminophosphine has the Structure (1′).
[0139] In an embodiment, the composition includes from 45 wt %, or 50 wt %, or 55 wt %, or 60 wt %, or 65 wt %, or 70 wt % to 75 wt %, or 80 wt %, or 85 wt %, or 90 wt %, or 95 wt %, or 98 wt %, or 99 wt %, or 99.96 wt % ethylene-based polymer, based on the total weight of the composition.
[0140] In an embodiment, the composition includes from 0.02 wt %, or 0.05 wt %, or 0.1 wt %, or 0.5 wt %, or 1 wt % to 2 wt %, or 3 wt %, or 4 wt %, or 5 wt % organic peroxide, based on the total weight of the composition.
[0141] In an embodiment, the composition includes from 0.001 wt %, or 0.01 wt %, or 0.02 wt %, or 0.04 wt %, or 0.05 wt % to 0.10 wt %, or 0.20 wt %, or 0.30 wt %, or 0.40 wt %, or 0.50 wt %, or 0.60 wt %, or 0.70 wt %, or 0.80 wt %, or 0.90 wt %, or 1.00 wt % triorganoaminophosphine, based on the total weight of the composition. In an embodiment, the composition incudes from 0.001 wt % to 1.00 wt %, or from 0.01 wt % to 1.00 wt %, or from or from 0.01 wt % to 0.50 wt %, or from 0.01 wt % to 0.10 wt %, or from 0.02 wt % to 1.00 wt %, or from 0.02 wt % to 0.60 wt %, or from 0.02 wt % to 0.60 wt %, or from 0.04 wt % to 0.60 wt %, or from 0.04 wt % to 0.60 wt % triorganoaminophosphine, based on the total weight of the composition.
[0142] In an embodiment, the composition includes from 0.001 mol %, or 0.01 mol %, or 0.02 mol %, or 0.04 mol %, or 0.1 mol % to 0.4 mol %, or 0.5 mol %, or 1.0 mol %, or2.0 mol %, or 5.0 mol %, or 10 mol %, or 15 mol %, or 20 mol %, or 25 mol % triorganoaminophosphine, based on the total composition.
[0143] In an embodiment, the composition includes from 0.0001 wt %, or 0.001 wt %, or 0.01 wt %, or 0.05 wt %, or 0.1 wt %, or 0.5 wt %, or 1.0 wt %, or 5 wt %, or 10 wt %, or 15 wt % to 20 wt %, or 25 wt %, or 30 wt %, or 35 wt %, or 40 wt %, or 45 wt %, or 50 wt % PASC, based on the total weight of the composition.
[0144] In an embodiment, the composition includes from 0 wt %, or greater than 0 wt %, or 0.001 wt %, or 0.002 wt %, or 0.005 wt %, or 0.006 wt % to 0.007 wt %, or 0.008 wt %, or 0.009 wt %, or 0.01 wt %, or 0.1 wt %, or 0.2 wt %, or 0.3 wt %, or 0.4 wt %, or 0.5 wt %, or 1.0 wt %, or 2.0 wt %, or 2.5 wt %, or 3.0 wt %, or 4.0 wt %, or 5.0 wt % to 6.0 wt %, or 7.0 wt %, or 8.0 wt %, or 9.0 wt %, or 10.0 wt %, or 15.0 wt %, or 20.0 wt % additive, based on the total weight of the composition.
[0145] In an embodiment, the composition has a Retained Peroxide Percentage from 5%, or 7%, or 10%, or 12%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 2 hours. In a further embodiment the composition has a Retained Peroxide Percentage from 5% to 100%, or from 10% to 100%, or from 12% to 100%, or from 15% to 100%, or from 20% to 100%, or from 50% to 100%, or from 70% to 100%, or from 75% to 100%, or from 90% to 100%, or from 95% to 100%, or from 98% to 100% after heating at 100° C. for 2 hours. Not wishing to be bound by any particular theory, it is believed that the inclusion of the triorganoaminophosphine in the present composition prevents, or slows, the decomposition of the organic peroxide conventionally caused by the presence of protic acid in the composition. By stopping, or slowing the decomposition of the organic peroxide during the formation, storage, processing, and/or extrusion of the present composition, the triorganoaminophosphine advantageously enables the retention of the organic peroxide such that the organic peroxide is present and available for free-radical crosslinking after extrusion of the present composition onto a conductor. Without sufficient retention of the organic peroxide during the formation, storage, processing, and/or extrusion of the present composition, a coating formed from the present composition would not crosslink after being extruded onto a conductor.
[0146] In an embodiment, the composition has a Retained Peroxide Percentage from 10%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 1.5 hours.
[0147] In an embodiment, the composition has a Retained Peroxide Percentage from 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 1.0 hours.
[0148] In an embodiment, the composition has a Retained Peroxide Percentage from 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 0.5 hours.
[0149] In an embodiment, the composition contains: (i) from 45 wt %, or 50 wt %, or 55 wt %, or 60 wt %, or 65 wt %, or 70 wt % to 75 wt %, or 80 wt %, or 85 wt %, or 90 wt %, or 95 wt %, or 98 wt %, or 99 wt %, or 99.96 wt % ethylene-based polymer; (ii) from 0.02 wt %, or 0.05 wt %, or 0.1 wt %, or 0.5 wt %, or 1 wt % to 2 wt %, or 3 wt %, or 4 wt %, or 5 wt % organic peroxide; (iii) from 0.001 wt %, or 0.01 wt %, or 0.02 wt %, or 0.04 wt %, or 0.05 wt % to 0.10 wt %, or 0.20 wt %, or 0.30 wt %, or 0.40 wt %, or 0.50 wt %, or 0.60 wt %, or 0.70 wt %, or 0.80 wt %, or 0.90 wt %, or 1.00 wt % triorganoaminophosphine; (iv) from 0.0001 wt %, or 0.001 wt %, or 0.01 wt %, or 0.05 wt %, or 0.1 wt %, or 0.5 wt %, or 1.0 wt %, or 5 wt %, or 10 wt %, or 15 wt % to 20 wt %, or 25 wt %, or 30 wt %, or 35 wt %, or 40 wt %, or 45 wt %, or 50 wt % PASC; (v) from 0 wt %, or greater than 0 wt %, or 0.001 wt %, 0.005 wt %, or 0.01 wt %, or 0.1 wt %, or 0.5 wt %, or 1.0 wt %, or 2.0 wt %, or 3.0 wt %, or 4.0 wt %, or 5.0 wt % to 6.0 wt %, or 7.0 wt %, or 8.0 wt %, or 9.0 wt %, or 10.0 wt %, or 15.0 wt %, or 20.0 wt % additive, based on the total weight of the composition; and the composition has one, some, or all, of the following properties: (a) a Retained Peroxide Percentage from 5%, or 7%, or 10%, or 12%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 2 hours; and/or (b) a Retained Peroxide Percentage from 10%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 1.5 hours; and/or (c) a Retained Peroxide Percentage from 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 1.0 hours; and/or (d) a Retained Peroxide Percentage from 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 0.5 hours.
[0150] In an embodiment, the composition contains: (i) from 45 wt %, or 50 wt %, or 55 wt %, or 60 wt %, or 65 wt %, or 70 wt % to 75 wt %, or 80 wt %, or 85 wt %, or 90 wt %, or 95 wt %, or 98 wt %, or 99 wt %, or 99.96 wt % ethylene-based polymer; (ii) from 0.02 wt %, or 0.05 wt %, or 0.1 wt %, or 0.5 wt %, or 1 wt % to 2 wt %, or 3 wt %, or 4 wt %, or 5 wt % organic peroxide; (iii) from 0.001 wt %, or 0.01 wt %, or 0.02 wt %, or 0.04 wt %, or 0.05 wt % to 0.10 wt %, or 0.20 wt %, or 0.30 wt %, or 0.40 wt %, or 0.50 wt %, or 0.60 wt %, or 0.70 wt %, or 0.80 wt %, or 0.90 wt %, or 1.00 wt % triorganoaminophosphine; (iv) from 0.0001 wt %, or 0.001 wt %, or 0.01 wt %, or 0.05 wt %, or 0.1 wt %, or 0.5 wt %, or 1.0 wt %, or 5 wt %, or 10 wt %, or 15 wt % to 20 wt %, or 25 wt %, or 30 wt %, or 35 wt %, or 40 wt %, or 45 wt %, or 50 wt % PASC selected from a sulfonic acid, a sulfenic acid, a sulfinic acid, a sulfur-based antioxidant, and combinations thereof; (v) from 0 wt %, or greater than 0 wt %, or 0.001 wt %, 0.005 wt %, or 0.01 wt %, or 0.1 wt %, or 0.5 wt %, or 1.0 wt %, or 2.0 wt %, or 3.0 wt %, or 4.0 wt %, or 5.0 wt % to 6.0 wt %, or 7.0 wt %, or 8.0 wt %, or 9.0 wt %, or 10.0 wt %, or 15.0 wt %, or 20.0 wt % additive, based on the total weight of the composition; and the composition has one, some, or all, of the following properties: (a) a Retained Peroxide Percentage from 5%, or 7%, or 10%, or 12%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 2 hours; and/or (b) a Retained Peroxide Percentage from 10%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 1.5 hours; and/or (c) a Retained Peroxide Percentage from 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 1.0 hours; and/or (d) a Retained Peroxide Percentage from 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 0.5 hours.
[0151] In an embodiment, the composition contains from 0.001 wt %, or 0.01 wt %, or 0.02 wt %, or 0.04 wt %, or 0.10 wt % to 0.60 wt %, or 1.0 wt % triorganoaminophosphine, based on the total weight of the composition, and, in Structure (1), R.sup.1 is a phenyl group; and R.sup.2 and R.sup.3 each is a N,N-diethylamino group. In an embodiment, the composition has a Retained Peroxide Percentage from 5%, or 10%, or 12%, or 20%, or 50%, or 55%, or 70%, or 80%, or 90%, or 95%, or 97%, or 98%, or 99% to 100% after heating at 100° C. for 2 hours.
[0152] In an embodiment, the composition contains from 0.001 wt %, or 0.01 wt %, or 0.02 wt %, or 0.04 wt %, or 0.10 wt % to 0.60 wt %, or 1.0 wt % triorganoaminophosphine, based on the total weight of the composition, and, in Structure (1), R.sup.1, R.sup.2, and R.sup.3 each is a pyrrolidinyl group. In an embodiment, the composition has a Retained Peroxide Percentage from 5%, or 10%, or 12%, or 20%, or 50%, or 55%, or 70%, or 80%, or 90%, or 95%, or 97%, or 98%, or 99% to 100% after heating at 100° C. for 2 hours.
[0153] In an embodiment, the composition contains from 0.001 wt %, or 0.01 wt %, or 0.02 wt %, or 0.04 wt %, or 0.10 wt % to 0.60 wt %, or 1.0 wt % triorganoaminophosphine, based on the total weight of the composition, and, in Structure (1), R.sup.1 and R.sup.2 each is a phenyl group; and R.sup.3 is a 4-(N,N-dimethylamino)phenyl group. In an embodiment, the composition has a Retained Peroxide Percentage from 5%, or 10%, or 12%, or 20%, or 50%, or 55%, or 70%, or 80%, or 90%, or 95%, or 97%, or 98%, or 99% to 100% after heating at 100° C. for 2 hours.
[0154] In an embodiment, the composition contains from 0.001 wt %, or 0.01 wt %, or 0.02 wt %, or 0.04 wt %, or 0.10 wt % to 0.60 wt %, or 1.0 wt % triorganoaminophosphine, based on the total weight of the composition, and, in Structure (1), R.sup.1 and R.sup.2 each is a cyclohexyl group; and R.sup.3 is a 4-(N,N-dimethylamino)phenyl group. In an embodiment, the composition has a Retained Peroxide Percentage from 5%, or 10%, or 12%, or 20%, or 50%, or 55%, or 70%, or 80%, or 90%, or 95%, or 97%, or 98%, or 99% to 100% after heating at 100° C. for 2 hours.
[0155] The sum of the components in each of the compositions disclosed herein, including the foregoing compositions, yields 100 weight percent (wt %).
[0156] The composition may be formed by melt blending (such as by extrusion) all, or some, of the components. In an embodiment, the ethylene-based polymer, the triorganoaminophosphine, the PASC, and the optional additive are extruded and pelletized. Then, the organic peroxide is imbibed in the pellets in a soaking step. The pellets containing all of the components may be stored in bags, barrels, boxes, or railcars for a period of time. The pellets may be added to an extruder and extruded onto a surface of a conductor.
[0157] In an alternate embodiment, all of the components of the composition are combined in an extruder, and the composition is extruded onto a surface of a conductor.
[0158] The composition may comprise two or more embodiments disclosed herein.
[0159] In an embodiment, the composition is crosslinked.
[0160] The composition may comprise two or more embodiments disclosed herein.
[0161] The present disclosure also provides a crosslinked product made by heating the composition to a temperature sufficient to crosslink the composition. The crosslinked product may be a coating on a conductor.
[0162] vii. Coated Conductor
[0163] The present disclosure also provides a coated conductor. The coated conductor includes a conductor and a coating on the conductor, the coating including a composition. The composition includes: (i) the ethylene-based polymer; (ii) the organic peroxide; (iii) the triorganoaminophosphine; (iv) the PASC selected from a protic acid, a PAGC, and combinations thereof; and (v) optionally, an additive. The triorganoaminophosphine has the Structure (1):
##STR00010##
[0164] wherein R.sup.1 and R.sup.2 each is independently selected from the group consisting of a C.sub.1-C.sub.40 hydrocarbyl group, a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group; and
[0165] wherein R.sup.3 is selected from the group consisting of a C.sub.2-C.sub.40 N,N-dialkylamino group, a C.sub.4-C.sub.6 N-heterocycloalkyl, a C.sub.8-C.sub.40 (N,N-dialkyl)arylamino group, and a C.sub.8-C.sub.40 (N,N-dialkyl)aminoaryl group.
[0166] In an embodiment, the triorganoaminophosphine has the Structure (1′).
[0167] The composition, ethylene-based polymer, organic peroxide, triorganoaminophosphine, PASC, and optional additive may be any respective ethylene-based polymer, organic peroxide, triorganoaminophosphine, PASC, and optional additive disclosed herein.
[0168] In an embodiment, the coating includes a composition having a Retained Peroxide Percentage from 5%, or 10%, or 12%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 2 hours. In a further embodiment the coating includes a composition having a Retained Peroxide Percentage from 5% to 100%, or from 10% to 100%, or from 12% to 100%, or from 15% to 100%, or from 20% to 100%, or from 50% to 100%, or from 70% to 100%, or from 80% to 100%, or from 90% to 100% after heating at 100° C. for 2 hours. Not wishing to be bound by any particular theory, it is believed that the inclusion of the triorganoaminophosphine in the composition prevents, or slows, the ionic decomposition of the organic peroxide conventionally caused by the presence of protic acid in the composition. By stopping, or slowing the ionic decomposition of the organic peroxide during the formation, storage, processing, and/or extrusion of the composition, the triorganoaminophosphine advantageously enables the retention of the organic peroxide such that the organic peroxide is present and available for free-radical crosslinking after extrusion of the present composition onto a conductor. Without sufficient retention of the organic peroxide during the formation, storage, processing, and/or extrusion of the present composition, a coating formed from the present composition would not crosslink after being extruded onto a conductor.
[0169] In an embodiment, the coating includes a composition having a Retained Peroxide Percentage from 10%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 1.5 hours.
[0170] In an embodiment, the coating includes a composition having a Retained Peroxide Percentage from 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100%
[0171] In an embodiment, the coating includes a composition having a Retained Peroxide Percentage from 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100%.
[0172] In an embodiment, the coating is an insulation sheath for a conductor. In another embodiment, the coating is a jacket for a conductor.
[0173] The process for producing a coated conductor includes heating the present composition to at least the melting temperature of the ethylene-based polymer, and then extruding the polymeric melt blend onto the conductor. The term “onto” includes direct contact or indirect contact between the polymeric melt blend and the conductor. The polymeric melt blend is in an extrudable state.
[0174] The coating is located on the conductor. The coating may be one or more inner layers such as an insulating layer. The coating may wholly or partially cover or otherwise surround or encase the conductor. The coating may be the sole component surrounding the conductor. When the coating is the sole component surrounding the conductor, the coating may serve as a jacket and/or an insulation. In an embodiment, the coating is the outermost layer on the coated conductor. Alternatively, the coating may be one layer of a multilayer jacket or sheath encasing the metal conductor. In an embodiment, the coating directly contacts the conductor. In another embodiment, the coating directly contacts an insulation layer surrounding the conductor.
[0175] In an embodiment, the coating directly contacts the conductor. The term “directly contacts,” as used herein, is a coating configuration whereby the coating is located immediately adjacent to the conductor, the coating touches the conductor, and no intervening layers, no intervening coatings, and/or no intervening structures, are present between the coating and the conductor.
[0176] In another embodiment, the coating indirectly contacts the conductor. The term “indirectly contacts,” as used herein, is a coating configuration whereby an intervening layer, an intervening coating, or an intervening structure, is present between the coating and the conductor. Examples of suitable intervening layers, intervening coatings, and intervening structures include insulation layers, moisture barrier layers, buffer tubes, and combinations thereof. Examples of suitable insulation layers include foamed insulation layers, thermoplastic insulation layers, crosslinked insulation layers, and combinations thereof.
[0177] In an embodiment, the coating is an insulation layer of a high voltage power transmission cable or an extra high voltage power transmission cable.
[0178] The coating is crosslinked. In an embodiment, crosslinking of the present coating begins in the extruder, but only to a minimal extent. In another embodiment, crosslinking is delayed until the coating is extruded upon the conductor. Crosslinking of the present coating can be initiated and/or accelerated through the application of heat or radiation. In an embodiment, after extrusion, the coated conductor is conditioned at a temperature from 160° C., or 180° C. to 200° C., or 400° C. in a continuous vulcanization tube.
[0179] In an embodiment, the coated conductor incudes, consists essentially of, or consists of a conductor and a coating on the conductor. The coating incudes, consists essentially of, or consists of a composition. The composition incudes, consists essentially of, or consists of: (i) from 45 wt %, or 50 wt %, or 55 wt %, or 60 wt %, or 65 wt %, or 70 wt % to 75 wt %, or 80 wt %, or 85 wt %, or 90 wt %, or 95 wt %, or 98 wt %, or 99 wt %, or 99.96 wt % ethylene-based polymer; (ii) from 0.02 wt %, or 0.05 wt %, or 0.1 wt %, or 0.5 wt %, or 1 wt % to 2 wt %, or 3 wt %, or 4 wt %, or 5 wt % organic peroxide; (iii) from 0.001 wt %, or 0.003 wt %, or 0.005 wt %, or 0.007 wt %, or 0.01 wt %, or 0.02 wt %, or 0.04 wt %, or 0.05 wt % to 0.10 wt %, or 0.20 wt %, or 0.30 wt %, or 0.40 wt %, or 0.50 wt %, or 0.60 wt %, or 0.70 wt %, or 0.80 wt %, or 0.90 wt %, or 1.00 wt % triorganoaminophosphine; (iv) from 0.0001 wt %, or 0.001 wt %, or 0.01 wt %, or 0.05 wt %, or 0.1 wt %, or 0.5 wt %, or 1.0 wt %, or 5 wt %, or 10 wt %, or 15 wt % to 20 wt %, or 25 wt %, or 30 wt %, or 35 wt %, or 40 wt %, or 45 wt %, or 50 wt % PASC; (v) from 0 wt %, or greater than 0 wt %, or 0.001 wt %, 0.005 wt %, or 0.01 wt %, or 0.1 wt %, or 0.5 wt %, or 1.0 wt %, or 2.0 wt %, or 3.0 wt %, or 4.0 wt %, or 5.0 wt % to 6.0 wt %, or 7.0 wt %, or 8.0 wt %, or 9.0 wt %, or 10.0 wt %, or 15.0 wt %, or 20.0 wt % additive, based on the total weight of the composition; and the composition has one, some, or all, of the following properties: (a) a Retained Peroxide Percentage from 5%, or 7%, or 10%, or 12%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 2 hours; and/or (b) a Retained Peroxide Percentage from 10%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 1.5 hours; and/or (c) a Retained Peroxide Percentage from 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 1.0 hours; and/or (d) a Retained Peroxide Percentage from 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 0.5 hours.
[0180] In an embodiment, the coated conductor incudes, consists essentially of, or consists of a conductor and a coating on the conductor. The coating incudes, consists essentially of, or consists of a composition. The composition incudes, consists essentially of, or consists of: (i) from 45 wt %, or 50 wt %, or 55 wt %, or 60 wt %, or 65 wt %, or 70 wt % to 75 wt %, or 80 wt %, or 85 wt %, or 90 wt %, or 95 wt %, or 98 wt %, or 99 wt %, or 99.96 wt % ethylene-based polymer; (ii) from 0.02 wt %, or 0.05 wt %, or 0.1 wt %, or 0.5 wt %, or 1 wt % to 2 wt %, or 3 wt %, or 4 wt %, or 5 wt % organic peroxide; (iii) from 0.001 wt %, or 0.003 wt %, or 0.005 wt %, or 0.007 wt %, or 0.01 wt %, or 0.02 wt %, or 0.04 wt %, or 0.05 wt % to 0.10 wt %, or 0.20 wt %, or 0.30 wt %, or 0.40 wt %, or 0.50 wt %, or 0.60 wt %, or 0.70 wt %, or 0.80 wt %, or 0.90 wt %, or 1.00 wt % triorganoaminophosphine; (iv) from 0.0001 wt %, or 0.001 wt %, or 0.01 wt %, or 0.05 wt %, or 0.1 wt %, or 0.5 wt %, or 1.0 wt %, or 5 wt %, or 10 wt %, or 15 wt % to 20 wt %, or 25 wt %, or 30 wt %, or 35 wt %, or 40 wt %, or 45 wt %, or 50 wt % PASC selected from a sulfonic acid, a sulfenic acid, a sulfinic acid, a sulfur-based antioxidant, and combinations thereof; (v) from 0 wt %, or greater than 0 wt %, or 0.001 wt %, 0.005 wt %, or 0.01 wt %, or 0.1 wt %, or 0.5 wt %, or 1.0 wt %, or 2.0 wt %, or 3.0 wt %, or 4.0 wt %, or 5.0 wt % to 6.0 wt %, or 7.0 wt %, or 8.0 wt %, or 9.0 wt %, or 10.0 wt %, or 15.0 wt %, or 20.0 wt % additive, based on the total weight of the composition; and the composition has one, some, or all, of the following properties: (a) a Retained Peroxide Percentage from 5%, or 7%, or 10%, or 12%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 2 hours; and/or (b) a Retained Peroxide Percentage from 10%, or 15%, or 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 1.5 hours; and/or (c) a Retained Peroxide Percentage from 20%, or 25%, or 30%, or 35%, or 40%, or 45%, or 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 1.0 hours; and/or (d) a Retained Peroxide Percentage from 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%, or 97%, or 98% to 100% after heating at 100° C. for 0.5 hours.
[0181] In an embodiment, the coating includes a composition containing from 0.001 wt %, or 0.01 wt %, or 0.02 wt %, or 0.04 wt %, or 0.10 wt % to 0.60 wt %, or 1.0 wt % triorganoaminophosphine, based on the total weight of the composition, and, in Structure (1), R.sup.1 is a phenyl group; and R.sup.2 and R.sup.3 each is a N,N-diethylamino group. In an embodiment, the composition has a Retained Peroxide Percentage from 5%, or 10%, or 12%, or 20%, or 50%, or 55%, or 70%, or 80%, or 90%, or 95%, or 97%, or 98%, or 99% to 100% after heating at 100° C. for 2 hours.
[0182] In an embodiment, the coating includes a composition containing from 0.001 wt %, or 0.01 wt %, or 0.02 wt %, or 0.04 wt %, or 0.10 wt % to 0.60 wt %, or 1.0 wt % triorganoaminophosphine, based on the total weight of the composition, and, in Structure (1), R.sup.1, R.sup.2, and R.sup.3 each is a pyrrolidinyl group. In an embodiment, the composition has a Retained Peroxide Percentage from 5%, or 10%, or 12%, or 20%, or 50%, or 55%, or 70%, or 80%, or 90%, or 95%, or 97%, or 98%, or 99% to 100% after heating at 100° C. for 2 hours.
[0183] In an embodiment, the coating includes a composition containing from 0.001 wt %, or 0.01 wt %, or 0.02 wt %, or 0.04 wt %, or 0.10 wt % to 0.60 wt %, or 1.0 wt % triorganoaminophosphine, based on the total weight of the composition, and, in Structure (1), R.sup.1 and R.sup.2 each is a phenyl group; and R.sup.3 is a 4-(N,N-dimethylamino)phenyl group. In an embodiment, the composition has a Retained Peroxide Percentage from 5%, or 10%, or 12%, or 20%, or 50%, or 55%, or 70%, or 80%, or 90%, or 95%, or 97%, or 98%, or 99% to 100% after heating at 100° C. for 2 hours.
[0184] In an embodiment, the coating includes a composition containing from 0.001 wt %, or 0.01 wt %, or 0.02 wt %, or 0.04 wt %, or 0.10 wt % to 0.60 wt %, or 1.0 wt % triorganoaminophosphine, based on the total weight of the composition, and, in Structure (1), R.sup.1 and R.sup.2 each is a cyclohexyl group; and R.sup.3 is a 4-(N,N-dimethylamino)phenyl group. In an embodiment, the composition has a Retained Peroxide Percentage from 5%, or 10%, or 12%, or 20%, or 50%, or 55%, or 70%, or 80%, or 90%, or 95%, or 97%, or 98%, or 99% to 100% after heating at 100° C. for 2 hours.
[0185] In an embodiment, the coated conductor is selected from a fiber optic cable, a communications cable (such as a telephone cable or a local area network (LAN) cable), a power cable, wiring for consumer electronics, a power cable, a power charger wire for cell phones and/or computers, computer data cords, power cords, appliance wiring material, home interior wiring material, consumer electronic accessory cords, and any combination thereof.
[0186] In another embodiment, the present composition is melt-shaped into an article other than a coating on a conductor, e.g., an electrical connector or a component of an electrical connector.
[0187] The coated conductor may comprise two or more embodiments disclosed herein.
[0188] By way of example, and not limitation, some embodiments of the present disclosure will now be described in detail in the following Examples.
EXAMPLES
[0189] The materials used in the examples are provided in Table 1 below.
TABLE-US-00001 TABLE 1 Materials Component Specification Source bis(diethylamino) phenyl phosphine
[0190] The following three types of Stock Solutions are prepared and used for making Sample Solutions: (i) a solution of dicumyl peroxide (DCP) in dodecane at 0.1154 M (Stock Solution A); (ii) a solution of dodecylbenzene sulfonic acid (DBSA) in dodecane at 0.00346 M (Stock Solution B); and (iii) a solution containing 0.1 wt % of a triorganoaminophosphine in 0.1154 M DCP solution in dodecane (Stock Solution C). Stock Solution C is stirred in an oil bath set at 80° C. (for 1-2 minutes) to ensure complete dissolution of the triorganoaminophosphine.
[0191] The Sample Solutions and Comparative Solutions are formed in 6 dram glass vials. Dodecane simulates the properties of (that is, serves as a model for) the ethylene-based polymer. The solutions are stirred with a magnetic stir bar. The composition of each solution is provided in Table 2 below.
[0192] Comparative Solution 1 (CS 1) is prepared by adding 2 mL of Stock Solution A, and 2 mL of Stock Solution B to a glass vial and mixing with a magnetic stir bar at room temperature. The total volume of CS 1 is 4 mL. CS 1 contains 0.0577 M DCP (equivalent to 2 wt % DCP) and 0.00173 M DBSA. CS 1 contains no triorganoaminophosphine. The composition of CS 1 is provided in Table 2 below.
[0193] Comparative Solution 2 (CS 2) is prepared by adding 2 mL of Stock Solution A and 2 mL dodecane to a glass vial and mixing with a magnetic stir bar at room temperature. The total volume of CS 2 is 4 mL. CS 2 contains 0.0577 M DCP (equivalent to 2 wt % DCP). CS 2 contains no triorganoaminophosphine and no DBSA. The composition of CS 2 is provided in Table 2 below.
[0194] Sample Solutions 1-7 and 9-20 each is prepared by adding 2 mL of Stock Solution B, X mL of Stock Solution C, and (2-X) mL of Stock Solution A to a glass vial and mixing with a magnetic stir bar at room temperature, wherein X is equal to 10 multiplied by the weight percent concentration of triorganoaminophosphine. For example, to prepare a Sample Solution containing 0.05 wt % triorganoaminophosphine, 2 mL of Stock Solution B is mixed with 1.5 mL of Stock Solution A and 0.5 mL of Stock Solution C. The composition of Sample Solutions 1-7 and 9-20 is provided in Table 2 below.
[0195] Sample Solution 8 is prepared by adding 2 mL of Stock Solution A and 2 mL of Stock Solution B to a glass vial and mixing with a magnetic stir bar at room temperature. Triorganoaminophosphine is added to the contents of the glass vial. The composition of Sample Solution 8 is provided in Table 2 below.
[0196] Then, the glass vials are immersed in a well-stirred (500 rpm) bath of silicon oil maintained at a temperature of 100° C. on a Corning™ PC-420D stirring hot plate. The Comparative Solutions and Sample Solutions each is heated to a temperature of 100° C., and maintained at 100° C., while mixing, and 600 μl aliquots are taken after a period of 2 minutes (at which point there is complete dissolution of the triorganoaminophosphine in the solution), 0.5 hours, 1.0 hours, 1.5 hours, and 2.0 hours. The Comparative Solutions and Sample Solutions each is heated in the glass vial without a cap or lid (in other words, the solution is exposed to the atmosphere while heating).
[0197] Each 600 μl aliquot taken from a glass vial is placed in a 1.5 mL mini centrifuge tube, cooled in an ice bath for 7-10 minutes, and centrifuged in a VWR Galaxy Mini Centrifuge, Model C.sub.1413, at an rpm of 6,000. Then, a 350 μl clear fraction is taken from each aliquot and combined with 700 μl of i-propanol and analyzed with liquid chromatography to determine the concentration of DCP present in the fraction (Shimadzu LC-20AD Liquid Chromatograph with SPD-20A UV Visible detector set at 210 nm; the column is a Waters SunFire C18 2.1 mm×50 mm column with a 3.5 μm particle size; the mobile phase is 75% methanol/25% water at a flow rate of 0.25 mL/minute). The amount of DCP in the sample solution measured after 2 minutes at 100° C. is referred to as the initial DCP amount.
[0198] The Retained Dicumyl Peroxide (DCP) Percentage is calculated in accordance with the following Equation (2):
wherein t=0.5 hours, 1.0 hours, 1.5 hours, or 2.0 hours.
[0199] For example, after heating at 100° C. for 2 hours, Solution 1 contains 1.0209 wt % DCP. The initial amount of DCP (i.e., after 2 minutes at 100° C.) in Solution 1 is 1.9630 wt %. Thus, the Retained DCP Percentage of Solution 1 after heating at 100° C. for 2 hours is calculated in accordance with the following Equation (2A):
[0200] The Retained DCP Percentage of Solution 1 after heating at 100° C. for 2 hours is 52.01%.
[0201] The properties of the Sample Solutions and Comparative Solutions are provided in Table 2 below.
TABLE-US-00002 TABLE 2 dicyclo- hexyl- bis (dimethyl- 4-(N,N- dodecyl- (diethyl- tris-(1- amino) dimethyl- benzene amino) pyrrolyi- phenyl amino) dicumyl sulfonic Retained DCP Percentage (%) phenyl dinyl) diphenyl- phenyl peroxide acid 0.5 1.0 1.5 2.0 phosphine phosphine phosphine phosphine (DCP) (DBSA) Dodecane Total hours hours hours hours wt % wt % wt % wt % wt % wt % wt % wt % @ @ @ @ (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) (mol %) 100° C. 100° C. 100° C. 100° C. CS 1 — — — — 2.0080 0.0738 97.9182 100 50.43 18.64 5.70 0.44 (1.2950) (0.0388) (98.6861) (100) CS 2 — — — — 1.9511 — 98.0489 100 100 100 100 100 (1.2382) (98.7618) (100) Solution 1 0.0025 — — — 1.9630 0.0739 97.9606 100 85.97 72.26 59.22 52.01 (0.0017) (1.2463) (0.0388) (98.7132) (100) Solution 2 0.0050 — — — 1.9863 0.0739 97.9349 100 97.39 93.59 87.52 84.51 (0.0034) (1.2611) (0.0388) (98.6966) (100) Solution 3 0.0075 — — — 1.9541 0.0739 97.9646 100 99.47 99.59 98.85 95.24 (0.0051) (1.2406) (0.0388) (98.7155) (100) Solution 4 0.0100 — — — 2.0185 0.0738 97.8977 100 100 100 100 100 (0.0068) (1.2818) (0.0388) (98.6726) (100) Solution 5 0.0200 — — — 1.9745 0.0739 97.9316 100 100 100 100 100 (0.0136) (1.2536) (0.0388) (98.6939) (100) Solution 6 0.0300 — — — 1.9655 0.0739 97.9306 100 100 100 100 100 (0.0204) (1.2480) (0.0388) (98.6928) (100) Solution 7 0.0501 — — — 1.9187 0.0739 97.9573 100 100 100 100 100 (0.0341) (1.2181) (0.0388) (98.7090) (100) Solution 8 0.1000 — — — 1.9270 0.0738 97.8912 100 100 100 100 100 (0.0680) (1.2236) (0.0388) (98.6654) (100) Solution 9 — 0.0025 — — 1.7936 0.0740 98.1300 100 73.42 57.37 41.35 37.50 (0.0018) (1.1380) (0.0389) (98.8214) (100) Solution 10 — 0.0050 — — 1.8326 0.0740 98.0884 100 97.41 92.76 83.91 82.51 (0.0036) (1.1629) (0.0389) (98.7946) (100) Solution 11 — 0.0100 — — 2.0652 0.0738 97.8510 100 99.53 97.34 94.32 99.45 (0.0071) (1.3116) (0.0388) (98.6424) (100) Solution 12 — 0.0500 — — 2.0307 0.0738 97.8455 100 100 100 100 100 (0.0356) (1.2897) (0.0388) (98.6359) (100) Solution 13 — — 0.0025 — 1.9782 0.0739 97.9454 100 74.36 44.38 28.21 19.34 (0.0014) (1.2559) (0.0388) (98.7038) (100) Solution 14 — — 0.0051 — 1.9688 0.0739 97.9522 100 83.22 59.09 43.12 32.90 (0.0028 (1.2500) (0.0388) (98.7083) (100) Solution 15 — — 0.0101 — 1.8682 0.0739 98.0477 100 97.48 94.39 92.18 88.68 (0.0057) (1.1857) (0.0388) (98.7698) (100) Solution 16 — — 0.0507 — 1.8609 0.0739 98.0145 100 98.28 96.07 96.96 99.08 (0.0285) (1.1812) (0.0388) (98.7514) (100) Solution 17 — — — 0.0025 1.9795 0.0739 97.9442 100 66.46 34.85 20.38 12.43 (0.0014) (1.2568) (0.0388) (98.7030) (100) Solution 18 — — — 0.0050 1.9728 0.0739 97.9483 100 75.36 49.78 34.46 26.41 (0.0027) (1.2525) (0.0388) (98.7059) (100) Solution 19 — — — 0.0101 1.9307 0.0739 97.9853 100 95.28 88.47 80.89 76.59 (0.0054) (1.2256) (0.0388) (98.7301) (100) Solution 20 — — — 0.0502 2.0105 0.0738 97.8654 100 100 100 90.28 97.27 (0.0272) (1.2769) (0.0388) (98.6571) (100)
[0202] CS 1 is a comparative solution containing (i) dodecane (to simulate the ethylene-based polymer); (ii) dicumyl peroxide (DCP); and (iii) dodecylbenzene sulfonic acid (DBSA)—and no triorganoaminophosphine. As shown in Table 2, CS 1 exhibits a Retained Peroxide (here, DCP) Percentage of only 0.44% after heating at 100° C. for 2 hours. Thus, CS 1 does not retain a suitable concentration of organic peroxide after heating at 100° C. for 2 hours to enable crosslinking of the composition. Consequently, CS 1 is representative of a peroxide-containing polymer composition that is not suitable for wire and cable applications, as well as other applications.
[0203] CS 2 is a comparative composition containing (i) dodecane (to simulate the ethylene-based polymer) and (ii) dicumyl peroxide (DCP)—and no triorganoaminophosphine or DBSA. Thus, CS 2 lacks a protic acid-source compound (PASC) that causes ionic decomposition of the DCP.
[0204] Applicant unexpectedly found that a composition (Solutions 1-20) containing (i) dodecane (to simulate the ethylene-based polymer); (ii) dicumyl peroxide (DCP); (iii) a triorganoaminophosphine (bis(diethylamino)phenyl phosphine, tris-(1-pyrrolyidinyl)phosphine, (dimethylamino)phenyldiphenylphosphine, or dicyclohexyl-4-(N,N-dimethylamino)phenyl phosphine); and (iv) dodecylbenzene sulfonic acid (DBSA) advantageously exhibits a Retained Peroxide (here, DCP) Percentage of at greater than 12%, and in some cases, greater than 97%, after heating at 100° C. for 2 hours. Consequently, Solutions 1-20 are representative of peroxide-containing polymer compositions that are suitable for wire and cable applications, as well as other applications.
[0205] It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.