TWI681994B - Polyolefin composition - Google Patents

Abstract

A polyolefin composition comprising a polyolefin polymer, an alkenyl-functional monocyclic organosiloxane, and an organic peroxide; products made therefrom; methods of making and using same; and articles containing same.

Description

Polyolefin composition

Fields include polyolefin compositions, products made from them, methods of making and using them, and products containing them.

Insulated electrical conductors usually include a conductive core covered by an insulating layer. The conductive core may be solid or stranded (for example, a wire harness). Some insulated electrical conductors may also contain one or more other elements, such as one or more semi-conductive layers and/or protective sleeves (eg, wound wires, tapes, or jackets). Examples are coated metal wires and power cables, including for low voltage (“LV”,> 0 to <5 kilovolts (kV)), medium voltage (“MV”, 5 to <69 kV), high voltage (“ HV", 69 to 230 kV) and ultra-high voltage ("EHV",> 230 kV) electrical transmission/distribution applications. The evaluation of power cables can use AEIC/ICEA standards and/or IEC test methods.

US Pat. No. 4,005,254 granted to B. T. MacKenzie, Jr. ("MacKenzie") regarding a pressureless curing system for chemically crosslinking ethylene-containing polymers and products formed therefrom. The curable composition includes an ethylene-containing polymer, a curing agent, and an inorganic filler treated with tetramethyltetravinylcyclotetrasiloxane. In the preparation of the composition, the polymer, inorganic filler, tetramethyltetravinylcyclotetrasiloxane and other additives are finely blended as in Banbury. During this compounding operation, it is said that tetramethyltetravinylcyclotetrasiloxane interacts with or coats the filler, and the product is called a filler treated with silicone. If necessary, the inorganic filler can be pre-treated with tetramethyltetravinylcyclotetrasiloxane in a separate operation, and then the filler treated with silicone is blended with the polymer and other additives. The data of the toluene extract (compound %) of MacKenzie of Example 1 (0.0 weight percent (wt%) tetramethyltetravinylcyclotetrasiloxane) was 11.6% and for Examples 2 and 3 (by weight of the total composition , Each 0.97 wt% tetramethyltetravinylcyclotetrasiloxane) were 9.6% and 11.8%, respectively (Table I). In view of the percentage of extractables in Comparative Example 1 (relative to those of Example 2 and Example 3), those skilled in the art should recognize that the tetramethyltetravinylcyclotetrasiloxane in Example 2 and Example 3 is It does not contribute to the crosslinking of ethylene-containing polymers. Conversely, tetramethyltetravinylcyclotetrasiloxane coated aluminum silicate fillers, as taught by MacKenzie.

US 8,426,519 B2 granted to J. M. Cogen et al. relates to polysiloxane thermoplastic polymer reactive blends and copolymer products prepared using low-cost post-reactor reactive mixing (eg extrusion). The procedure is based on the ring-opening polymerization of cyclic silicone in a thermoplastic polymer matrix. In a preferred mode, the thermoplastic polymer is a polyolefin, optionally containing silane groups that can be used to react with the polysiloxane polymer formed in situ. The resulting material provides mixing capabilities that can extend the range of applications beyond those achieved only by thermoplastic polymers or polysiloxanes or their physical blends.

CN104277182A and the article "Crosslinking of low density polyethylene with Octavinyl polyhedral oligomeric silsesquioxane as the crosslinker" granted to Zl Wu et al. , J. Wu. et al., "RSC Advances", 2014, Volume 4, page 44030, concerning the preparation of low crosslinking using octavinyl polyhedron oligomeric silsesquioxane as crosslinking agent Method of density polyethylene.

We recognize a problem that compromises the cross-linking and performance of previous polyolefins. Auxiliaries can be blended with polyolefins to obtain polyolefin compositions with increased crosslinking capabilities, but conventional additives have their limitations. For example, conventional adjuvants generally have limited solubility or miscibility in polyolefin compositions. This limits the maximum loading of additives in the composition. It also causes improper migration of the additives to the surface of the composition (such as the surface of pellets), which limits the shelf life of the composition. Conventional additives can also cause other problems. For example, it may produce a cross-linked product with insufficient cross-linking during curing. Or the composition may cure too slowly to be used in certain manufacturing operations (such as power cable manufacturing, injection molding, and film extrusion). Or the composition may cure prematurely (ie, there is a tendency to scorch during cable extrusion, injection molding, and film extrusion). Unexpectedly, these problems limit the structure of conventional additives used with polyolefins. Generally, conventional adjuvants include conventional substructure groups bonded to two or more olefin crosslinking groups. The conventional sub-structure group is a non-cyclic or cyclic multivalent group including a main structure or a ring, respectively. The main structure or ring contains carbon atoms and optionally nitrogen and/or oxygen atoms, but no silicon atoms.

The problems described impair the effectiveness of power cables operating at higher voltages. The insulating layer may scorch during extrusion and eventually cause damage to it. The time to such damage can be extended by using a more elastic material in the insulating layer, and thereby improve the reliability of power transmission and reduce maintenance costs.

The technical solution to this problem is not obvious from the prior art. Therefore, the problem to be solved by creativity is to find a new polyolefin composition, which contains a polyolefin polymer and an improved auxiliary agent, wherein the polyolefin composition and the cured cross-linked product thereof can be applied at a higher voltage It is used as an insulation layer in power cables (HV or EHV power cables). Our analysis indicates that the new adjuvant should ideally be a cyclic molecule that does not contain carbon or nitrogen atoms in its ring.

Our technical solutions to this problem include a polyolefin composition comprising a polyolefin polymer and an alkenyl functional monocyclic organosiloxane; a cross-linked polyolefin product made therefrom; methods of making and using the same ; And products containing it.

The polyolefin compositions and products of the present invention can be used in any applications where polyolefins (including crosslinked polyolefins) are used, including extruded articles, coatings, films, sheets, and injection molded articles, as well as electrical transmission applications and other Related applications (such as containers or carrier parts).

The summary and abstract of the invention are incorporated herein by reference.

The polyolefin composition of the present invention containing a polyolefin polymer and an alkenyl functional monocyclic organosiloxane can be cured (crosslinked) by irradiation or organic peroxide without the opening of an alkenyl functional monocyclic organosiloxane ring. The curing reaction is carried out in such a way that the alkenyl functional monocyclic organosiloxane does not form a polymerized siloxane (polysiloxane polymer). Without being bound by theory, Xinxin chooses the components of the polyolefin composition so that the alkenyl-functional monocyclic organosiloxane does not ring-open during the curing of the polyolefin composition to form a ring-opening silanol (S-OH) function Organic siloxane oligomers (straight chain or branched chain), and therefore do not form polymeric siloxanes (polysiloxane polymers) in situ within polyolefin polymers. The alkenyl functional monocyclic organosiloxane cannot undergo ring opening at least in part because the polyolefin composition does not contain a ring opening catalyst, and therefore proceeds in the absence of a ring opening catalyst due to the curing reaction. Ring opening catalysts not included are known and include phosphazene bases. Phosphazene bases have a core structure P=N, where N free valency is connected to hydrogen, a hydrocarbon group, -P=N or =P-N, and P free valence is connected to =N or -N. Examples of phosphazene bases are found in US 8,426,519 B2, column 9, line 29 to column 10, line 31. Other types of ring-opening catalysts are known, which are not included in the polyolefin composition and therefore are not included in the crosslinked polyolefin products prepared therefrom. For example, see F.O. Stark et al., "Silicones", "Comprehensive Organometallic Chemistry", Volume 2, 305, Pergamon Press (1982). Examples are strong acids such as trifluoromethanesulfonic acid and its metal salts, sulfuric acid, perchloric acid and hydrochloric acid; cationic ring-opening catalysts such as metal halides; and anionic ring-opening catalysts such as organolithium, alkali metal oxides and alkali metals hydroxide. In the absence of a ring-opening catalyst, the polyolefin composition of the present invention undergoes cross-linking of the polyolefin polymer with an alkenyl functional monocyclic organosiloxane, and forms a cross-linked polyolefin product via free radical curing. The crosslinking of the present invention can be advantageously carried out even in the presence of environmental moisture without the ring opening of the alkenyl functional monocyclic organosiloxane. The cross-linking embodiments of the present invention avoid one or more harmful effects of the phosphazene base on the cross-linking level (degree of cross-linking).

Unpredictably, the functionality is halved relative to homopolymers (oligomers) containing linear vinyl methoxysiloxane (oligomers), homopolymers (oligomers) of vinylmethylsiloxane (oligomers) or cage vinyl The comparative polyolefin composition of silicone or a product prepared therefrom respectively, the polyolefin composition of the present invention containing an alkenyl functional monocyclic organosiloxane or the crosslinked polyolefin product of the present invention prepared therefrom has at least one Improved properties. The improved property may be that the time period for achieving 90% crosslinking ("T90") in the crosslinked polyolefin product is shorter, as measured by the T90 crosslinking time test method described below, which shows that the curing rate is advantageously more Fast; higher maximum torque value ("MH"), as measured by the T90 cross-linking time test method, which indicates that the degree of cross-linking in the cross-linked polyolefin product is advantageously higher; coking is achieved at 140°C The increase in time ("ts1"), as measured by the coking time test method described below, indicates that the resistance to premature curing of the polyolefin composition during extrusion is advantageously increased (eg, in an extruder Curing instead of curing in post-extruder operation); and/or alkenyl functional monocyclic organosiloxane loaded into polyolefin polymer at a higher concentration without self-alkenyl functional monocyclic organosiloxane The ability to "bleed out" is possible compared to the case where conventional additives are loaded into the polyolefin polymer. The "bleed-out" during storage of the polyolefin composition over a period of time as determined by the migration measurement test method or surface migration test method described below, which indicates the alkenyl functionality in the polyolefin polymer of the polyolefin composition High compatibility and/or solubility of monocyclic organosiloxane (as a silicon additive).

The polyolefin composition of the present invention contains an organic peroxide as a curing agent, as compared to a comparative polyolefin composition containing polyolefin and organic peroxide but not containing alkenyl functional monocyclic organosiloxane by curing Among the comparative cross-linked polyolefin products that can be achieved, the cross-linked polyolefin product of the present invention obtained by curing it can be characterized by a higher degree of cross-linking (higher number of cross-links). Compared with what can be achieved by using conventional additives instead of alkenyl functional monocyclic organosiloxane, the resulting crosslinked polyolefin product of the present invention can have a higher degree of crosslinking. Polyolefin compositions can have a longer storage life without experiencing "bleed-out", possibly due to the polymerization of alkenyl-functional monocyclic organosiloxanes in polyolefins compared to the solubility of conventional additives in polyolefin polymers The solubility is higher. The polyolefin composition of the present invention can have a shorter T90 crosslinking time (faster crosslinking) than what can be achieved using conventional additives instead of alkenyl functional monocyclic organosiloxanes. When the comparative cross-linked polyolefin product is formulated to have the same number of cross-links as the cross-linked polyolefin product of the present invention, the cross-linked polyolefin product of the present invention may have higher scorch resistance (eg, ts1 at 140°C).

The following describes some embodiments of the present invention in a numbered form for ease of cross-reference. Other embodiments are described elsewhere herein.

Aspect 1. A polyolefin composition comprising (A) a polyolefin polymer, which contains 50 to 100% by weight (wt%) ethylenic monomer units and 50 to 0% by weight (C ₃ -C ₂₀ )α -Low-density polyethylene (LDPE) polymers derived from olefin-derived comonomer units and 20 to 0 wt% diene comonomer units, of which the total weight percentage is 100.00 wt%; the effective amount of crosslinking is (B) formula ( I) Monocyclic organosiloxane: [R ¹ ,R ² SiO _2/2 ] _n (I), where the subscript n is an integer greater than or equal to 3; each R ^{1 is} independently (C ₂ -C ₄ ) Alkenyl or H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -where R ^1a is H or methyl and the subscript m is an integer from 1 to 4; and each Each R ^{2 is} independently H, (C ₁ -C ₄ )alkyl, phenyl or R ¹ ; and (C) an organic peroxide; its limitation is that the polyolefin composition does not contain (ie does not have ) Phosphazene base. In some aspects, the polyolefin composition does not contain any ring-opening catalyst. In some aspects, when the subscript n is 4, the polyolefin composition does not contain 24 wt% or more, alternatively does not contain 22 wt% or more, alternatively does not contain 20.0 wt% or more, alternatively does not Contains 15 wt% or more, alternatively does not contain 10 wt% or more, alternatively does not contain selected from the group consisting of aluminum oxide, aluminum silicate, calcium silicate, magnesium silicate, silica, titanium dioxide and mixtures thereof Group of inorganic fillers; in some aspects, n is 3, 4, 5 or 6; alternatively 3, 4 or 5; alternatively 5 or 6; alternatively 3 or 4; alternatively 3; alternatively 4; Alternately 5; Alternately 6.

Aspect 2. A polyolefin composition comprising (A) a polyolefin polymer, which contains 50 to 100% by weight (wt%) of ethylenic monomer units, and 50 to 0% by weight (C ₃ -C ₂₀ ) α -Low-density polyethylene (LDPE) polymers of olefin-derived comonomer units and 20 to 0 wt% diene comonomer units, of which the total weight percentage is 100.00 wt%; (B) monocyclic ring of formula (I) Organosiloxane: [R ¹ ,R ² SiO _2/2 ] _n (I), where the subscript n is an integer greater than or equal to 3; each R1 is independently (C ₂ -C ₄ )alkenyl or H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -where R ^1a is H or methyl and the subscript m is an integer from 1 to 4; and each R ^{2 is} independently H, (C ₁ -C ₄ )alkyl, phenyl or R ¹ ; and (C) organic peroxides; the limitation is that when the subscript n is 4, the polyolefin composition does not contain 24 wt% or more , Instead does not contain 22 wt% or more, alternatively does not contain 20.0 wt% or more, alternatively does not contain 15 wt% or more, alternatively does not contain 10 wt% or more, alternatively does not contain selection Free from inorganic fillers of the following groups: alumina, aluminum silicate, calcium silicate, magnesium silicate, silica, titanium dioxide, and mixtures thereof; and the restriction is that the polyolefin composition does not contain phosphazene base. In some aspects, the polyolefin composition does not contain any ring-opening catalyst. In some aspects, n is 3, 4, 5 or 6; alternatively 3, 4 or 5; alternatively 5 or 6; alternatively 3 or 4; alternatively 3; alternatively 4; alternatively 5; alternatively 6.

Aspect 3. The polyolefin composition as described in Aspect 1 or Aspect 2, wherein the subscript n is 3 and (B) the alkenyl functional monocyclic organosiloxane of formula (I) is limited by (i) Description to any of (x): (i) each R ^{1 is} independently (C ₂ -C ₃ )alkenyl; and each R ^{2 is} independently H, (C ₁ -C ₂ )alkyl Or (C ₂ -C ₃ )alkenyl; (ii) each R ¹ is vinyl; and each R ^{2 is} independently (C ₁ -C ₂ )alkyl; (iii) each R ¹ is vinyl ; And each R ² is methyl; (iv) each R ¹ is allyl; and each R ^{2 is} independently (C ₁ -C ₂ ) alkyl; (v) each R ¹ is allyl Radical; and each R ² is methyl; (vi) each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -where R ^1a is H Or methyl and the subscript m is an integer from 1 to 4; and each R ^{2 is} independently H, (C ₁ -C ₂ )alkyl, or (C ₂ -C ₃ )alkenyl; (vii) each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -where R ^1a is H and the subscript m is 3; and each R ^{2 is} independently ( C ₁ -C ₂ )alkyl; (viii) each R ^{1a is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -where R ^1a is methyl and The subscript m is 3; and each R ^{2 is} independently (C ₁ -C ₂ ) alkyl; (ix) the polyolefin composition does not contain 24 wt% or more, alternatively does not contain 22 wt% or more , Instead of not containing 20.0 wt% or more, alternatively not containing 15 wt% or more, alternatively not containing 10 wt% or more, alternatively not containing an inorganic filler selected from the group consisting of: oxidation Aluminum, aluminum silicate, calcium silicate, magnesium silicate, silicon dioxide, titanium dioxide, and mixtures thereof; and (x) a combination of restrictions (ix) and any of restrictions (i) to (viii).

Aspect 4. The polyolefin composition as described in Aspect 1 or Aspect 2, wherein the subscript n is 4 and (B) the alkenyl functional monocyclic organosiloxane of formula (I) is limited by (i) Description to any of (x): (i) each R ^{1 is} independently (C ₂ -C ₃ )alkenyl; and each R ^{2 is} independently H, (C ₁ -C ₂ )alkyl Or (C ₂ -C ₃ )alkenyl; (ii) each R ¹ is vinyl; and each R ^{2 is} independently (C ₁ -C ₂ )alkyl; (iii) each R ¹ is vinyl ; And each R ² is methyl; (iv) each R ¹ is allyl; and each R ^{2 is} independently (C ₁ -C ₂ ) alkyl; (v) each R ¹ is allyl Radical; and each R ² is methyl; (vi) each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a is H or methyl and the subscript m is an integer from 1 to 4; and each R ^{2 is} independently H, (C ₁ -C ₂ )alkyl or (C ₂ -C ₃ )alkenyl; (vii) each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a is H and the subscript m is 3; and each R ^{2 is} independently (C ₁ -C ₂ )alkyl; (viii) each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a is A And the subscript m is 3; and each R ^{2 is} independently (C ₁ -C ₂ ) alkyl; (ix) the polyolefin composition does not contain 24 wt% or more, alternatively does not contain 22 wt % Or more, alternatively not containing 20.0 wt% or more, alternatively not containing 15 wt% or more, alternatively not containing 10 wt% or more, alternatively not containing any inorganic filler; and (x ) The combination of restriction (ix) and any of restrictions (i) to (viii).

Aspect 5. The polyolefin composition as described in Aspect 1 or Aspect 2, wherein the subscript n is 5 or 6 and (B) the alkenyl functional monocyclic organosiloxane of formula (I) is limited by ( i) Any one of (x) description: (i) each R ^{1 is} independently (C ₂ -C ₃ )alkenyl; and each R ^{2 is} independently H, (C ₁ -C ₂ ) Alkyl or (C ₂ -C ₃ )alkenyl; (ii) each R ¹ is vinyl; and each R ^{2 is} independently (C ₁ -C ₂ ) alkyl; (iii) each R ¹ is Vinyl; and each R ² is methyl; (iv) each R ¹ is allyl; and each R ^{2 is} independently (C ₁ -C ₂ ) alkyl; (v) each R ¹ is Allyl; and each R ² is methyl; (vi) each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -where R ^1a Is H or methyl and the subscript m is an integer from 1 to 4; and each R ^{2 is} independently H, (C ₁ -C ₂ )alkyl, or (C ₂ -C ₃ )alkenyl; (vii) Each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -where R ^1a is H and the subscript m is 3; and each R ^{2 is} independently Is (C ₁ -C ₂ )alkyl; (viii) each R ^{1a is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -where R ^1a is A And the subscript m is 3; and each R ^{2 is} independently (C ₁ -C ₂ ) alkyl; (ix) the polyolefin composition does not contain 24 wt% or more, alternatively does not contain 22 wt% or More, alternatively not containing 20.0 wt% or more, alternatively not containing 15 wt% or more, alternatively not containing 10 wt% or more, alternatively not containing an inorganic filler selected from the group consisting of : Alumina, aluminum silicate, calcium silicate, magnesium silicate, silica, titania, and mixtures thereof; and (x) a combination of restrictions (ix) and any of restrictions (i) to (viii).

Aspect 6. The polyolefin composition as described in any one of aspects 1 to 5 is described by any one of the restrictions (i) to (vii): (i) (A) Characteristics of the polyolefin polymer Because as measured by ASTM D792-13, Method B, in 2-propanol, the density is 0.86 to 0.97 g/cm3 (g/cm ³ ); (ii) (A) The polyolefin polymer is poly 80 to 99.89% by weight (wt%) of the weight of the olefin composition; (iii) the monocyclic organosiloxane of formula (I) described in (B) is 0.1 to 3% by weight of the polyolefin composition; and (C ) The organic peroxide is 0.01 to 4.5 wt% of the polyolefin composition; (iv) (i) and (ii) both; (v) (i) and (iii) both; (vi) (ii) and (Iii) both; and (vii) (i), (ii) and (iii) each.

Aspect 7. The polyolefin composition according to any one of aspects 1 to 6, further comprising at least one additive selected from the group consisting of: (D) conventional auxiliary agents; (E) antioxidants; (F) Filler; (G) flame retardant; (H) hindered amine stabilizer; (I) tree retardant; (J) methyl radical scavenger; (K) scorch inhibitor, (L) Core agent, and (M) carbon black; the limitation is that the total amount of at least one additive is> 0 to 70 wt% of the polyolefin composition, alternatively> 0 to 60 wt%, alternatively> 0 to 40 wt% , Instead> 0 to 20 wt% and the limitation is that (F) the filler does not include any omitted filler. In some aspects, the polyolefin composition further includes (E) an antioxidant; alternatively (E) an antioxidant and (H) a hindered amine stabilizer.

Aspect 8. A method of manufacturing a polyolefin composition, the method comprising (A) a polyolefin polymer, which is composed of 50 to 100% by weight (wt%) of ethylenic monomer units, 50 to 0 wt% ( C ₃ -C ₂₀ ) Low-density polyethylene (LDPE) polymers derived from comonomer units derived from α-olefins and 20 to 0 wt% diene comonomer units, of which the total weight percentage is 100.00 wt%; (B) The monocyclic organosiloxane of formula (I): [R ¹ ,R ² SiO _2/2 ]n(I) are mixed together to produce the polyolefin composition of any one of aspects 1 to 6. The subscript n and the groups R ¹ and R ² are as defined in any one of aspects 1 to 5. (A) The polyolefin polymer is as defined in any one of aspects 1, 2 and 6. The method may further include mixing at least one of the additives defined in aspect 7 with components (A), (B), and (C) to prepare the polyolefin composition of aspect 7.

Aspect 9. A method of radically curing the polyolefin composition of any one of Aspects 1 to 7 to produce a crosslinked polyolefin product, the method comprising heating the polyolefin composition at a curing effective temperature in this manner The (A) polyolefin polymer is reacted with the (B) monocyclic organosiloxane of formula (I), thereby producing a crosslinked polyolefin product. In some aspects, the polyolefin composition and the cross-linked polyolefin product do not contain a phosphazene base, instead any ring-opening catalyst. In some aspects, the polyolefin composition is the polyolefin composition of any one of aspects 1 to 6. Under the conditions of effective curing temperature and any other required reaction conditions (for example, pressure or inert gas atmosphere), the effective amount of crosslinking (B) and (C) organic peroxide combination is sufficient to cure the polyolefin composition and Manufacture of cross-linked polyolefin products in the environment described above.

Aspect 10. A crosslinked polyolefin product prepared by the curing method of Aspect 9.

Aspect 11. A manufactured article comprising the shaped form of the polyolefin composition of any one of aspects 1 to 7 or the crosslinked polyolefin product of aspect 10. In some aspects, the manufactured article is selected from: coatings, films, sheets, extruded articles, and injection molded articles. For example, coated conductors, coatings for wires and cables used to transmit power or telecommunications, agricultural films, food packaging, clothing bags, grocery bags, heavy duty bags, industrial sheets, pallets and shrinkage Wraps, bags, barrels, refrigerator containers, lids, toys.

Aspect 12. A coated conductor comprising a conductive core and an insulating layer at least partially covering the conductive core, wherein at least a portion of the insulating layer comprises the polyolefin composition or aspect of any one of aspects 1 to 7. The crosslinked polyolefin product of sample 10. An embodiment of the conductive core may be a wire having a proximal end and a distal end, at least one of the ends may be free of an insulating layer.

Aspect 13. A method of transmitting electricity, the method comprising applying a voltage across the conductive core of the coated conductor as in aspect 12, so as to generate a current through the conductive core. The conductive core may be a wire having a proximal end and a distal end and electricity may flow from one end of the wire to the other end.

The term "auxiliaries" means compounds that enhance cross-linking, that is, curing aids. "Conventional additives" are non-cyclic or cyclic compounds that enhance cross-linking and contain carbon atoms in their corresponding main structures or ring sub-structures. Therefore, the main structure or ring substructure of conventional additives is based on carbon (carbon substructure). In contrast, silicon-based additives mean non-cyclic or cyclic compounds that enhance crosslinking and contain silicon atoms in their corresponding main structures or ring substructures. (B) The monocyclic organosiloxane of formula (I) is a cyclic silicone additive.

The terms "curing" and "crosslinking" are used interchangeably herein to mean that a crosslinked product (network polymer) is formed without ring-opening polymerization.

The expression "curing effective temperature" is the degree of thermal energy sufficient to initiate the decomposition of (C) the organic peroxide to become (free radical) reactant between components (A) and (B).

The term "ethylene-containing polymer" means a macromolecule containing repeating units derived from H ₂ C=CH ₂ .

The term "(meth)acrylate" includes acrylate, methacrylate and combinations thereof. The (meth)acrylate may be unsubstituted.

The term "ring-opening catalyst" as used herein means a substance that initiates the ring-opening polymerization reaction of cyclic siloxane monomers and/or promotes the rate of ring-opening polymerization reaction of cyclic siloxane monomers.

The term "ring-opening polymerization" as used herein is a type of chain-growth polymerization in which the reactive ends of the polymer chain open the ring of cyclic monomers to produce a longer polymer chain.

Polyolefin composition: single-phase or multi-phase, homogeneous or non-uniform, continuous phase or discontinuous phase containing macromolecules and alkenyl groups composed of repeating units derived from one or more monomers containing carbon-carbon double bonds A crosslinkable substance of a functional monocyclic organosiloxane molecule. In some aspects, the polyolefin composition may further contain one, two, or more optional ingredients or additives. The total weight of the polyolefin composition is 100.00 wt%.

Polyolefin compositions can be prepared in many different ways. In some aspects, the polyolefin composition can be prepared by: (A) a melt of a polyolefin polymer and (B) a monocyclic organosiloxane of formula (I) and (C) an organic peroxide Materials and any optional components (for example, any zero, one or more components (D) to (M)) are mixed to obtain as components (A), (B), (C) and any The mixing of the optionally present polyolefin composition of the components may include compounding, kneading or extrusion. To facilitate mixing, one or more components (eg, (B), additives (C), (D), (E), etc.) may be provided in the form of an additive masterbatch contained in a part of (A).

In another aspect, the polyolefin composition can be prepared by: combining (B) the monocyclic organosiloxane of formula (I) and optionally zero, one or more components that are optionally present (E.g. (D) Antioxidant) Contact with (A) polyolefin polymer in unmelted form to obtain a polyolefin combination as a blend of components (A), (B) and any optional components Thing. Contacting may include soaking, aspiration or injection. The component (B) and any one or more optional components can be independently combined by compounding, extruding, sucking, injecting, kneading or soaking. The mixing or contacting may be performed at a temperature of about 20°C to 100°C for 0.1 to 100 hours, for example, 60°C to 80°C for 0.1 to 24 hours. Higher temperatures can be used for mixing or contacting, with the restriction that (C) the organic peroxide is not subjected to said temperature. If necessary, the blend can be cooled to a temperature below the decomposition temperature of the peroxide before being mixed or contacted with the (C) organic peroxide. If necessary, the polyolefin composition may be cooled to a storage temperature (for example, 23° C.) and stored for a period of 1 hour, 1 week, 1 month, or longer.

The polyolefin composition can be prepared as a one-part formulation, alternatively a multi-part formulation, such as a two-part formulation, or alternatively a three-part formulation. There is no inherent reason why any combination of components cannot be included in the parts of these formulations.

Component (A) polyolefin polymer: a crosslinkable macromolecule composed of an olefin monomer and optionally repeating units made of one or more olefin functional comonomers, wherein the macromolecule has substantially the following A main structure consisting of or consisting of carbon atoms or a collection of such cross-linkable macromolecules, which produces a network structure when cross-linked with component (B). (A) may be a homopolymer containing repeating units derived from the same monomer; or an interpolymer (also known as a copolymer) containing monomers and repeating units derived from comonomers derived from different monomers The derived repeat unit. Interpolymers include dimers, trimers, and the like. In some aspects, (A) does not contain silicon atoms.

(A) The polyolefin polymer may be a polyethylene homopolymer containing 99 to 100 wt% of ethylene monomer units. The polyethylene homopolymer may be a high-density polyethylene (HDPE) homopolymer made by coordination polymerization or a low-density polyethylene (LDPE) homopolymer made by free radical polymerization.

Alternatively, (A) the polyolefin polymer may be an ethylene/α-olefin copolymer containing 50 to <100 wt% ethylenic monomer units and 50 to 0 wt% (C ₃ -C ₂₀ ) α-olefin derivative Of comonomer units. (A) Examples of ethylene/α-olefin copolymers of ethylene/α-olefin copolymers may be linear low density polyethylene (LLDPE), medium density polyethylene (MDPE) or high density polyethylene (HDPE). Alternatively, the polyolefin polymer may be low density polyethylene (LDPE). The ethylene/α-olefin (“α-olefin”) interpolymer has an α-olefin content of at least 1 wt%, at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20, based on the total interpolymer weight wt%, or at least 25 wt%. The α-olefin content of these interpolymers may be less than 50 wt%, less than 45 wt%, less than 40 wt%, or less than 35 wt% based on the weight of all interpolymers. Illustrative ethylene/α-olefin interpolymers are ethylene/propylene, ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene, ethylene containing 20 to 1 wt% of diene comonomer units /Diene, ethylene/propylene/1-octene, ethylene/propylene/1-butene, ethylene/1-butene/1-octene; containing 50 to 100 wt% ethylene monomer units, 49 to> 0 wt % Ethylene/propylene/diene (EPDM) of propylene comonomer units and 20 to 1 wt% of diene comonomer units. The diene used to prepare the diene comonomer unit in the ethylene/diene copolymer or EPDM can independently be 1,3-butadiene, 1,5-hexadiene, 1,7-octadiene, Ethylene norbornene, dicyclopentadiene, vinyl norbornene, or any combination of two or more thereof.

(A) Ethylene/α-olefin copolymer and poly((C ₃ -C ₂₀ ) α-olefin polymer of polyolefin polymer (C ₃ -C ₂₀ ) α-olefin can be of formula (I) Compound: H ₂ C=C(H)-R (I), where R is a linear (C ₁ -C ₁₈ )alkyl. (C ₁ -C ₁₈ )alkyl is a monovalent having 1 to 18 carbon atoms Unsubstituted saturated hydrocarbons. Examples of R are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl , Fourteen, fifteen, sixteen, seventeen and eighteen. In some embodiments, (C ₃ -C ₂₀ ) α-olefin is 1-propene, 1-butene, 1-hexyl Ene or 1-octene; alternatively 1-butene, 1-hexene or 1-octene; alternatively 1-butene or 1-hexene; alternatively 1-butene or 1-octene; alternatively 1-hexene or 1-octene; alternatively 1-butene; alternatively 1-hexene; alternatively 1-octene; alternatively 1-butene, 1-hexene and 1-octene A combination of the two. Alternatively, the alpha-olefin may have a cyclic structure, such as cyclohexane or cyclopentane, resulting in compounds such as 3-cyclohexyl-1-propene (allyl cyclohexane) and vinyl cyclohexane Α-olefin. (C ₃ -C ₂₀ ) α-olefin can be used as comonomer with ethylene monomer.

Alternatively, (A) the polyolefin polymer may be a polyolefin having at least one graft functional group selected from acrylate, methacrylate, and trialkoxysilane.

(A) The polyolefin polymer may be a blend or combination of two or more of the foregoing polymers and copolymers.

(A) The polyolefin polymer may be a blend of two or more different polyolefin polymers or the reactor product of a polymerization reaction by two or more different catalysts. (A) Polyolefin polymers can be made in two or more reactors, such as the ELITE™ polymer from The Dow Chemical Company.

(A) Polyolefin polymers can be prepared by any suitable method, many of which are well known in the art. (A) can be prepared by any conventional method for preparing polyolefin polymers or production methods found below. Usually the production method includes one or more polymerization reactions. For example, LDPE can be prepared using high-pressure polymerization methods. Alternatively, LDPE can be prepared using a coordination polymerization method that uses one or more polymerization catalysts such as Ziegler-Natta, chromium oxide, metallocene, post-metallocene catalysts . A suitable temperature is 0°C to 250°C, or 30°C or 200°C. Suitable pressure is atmospheric pressure (101 kPa) to 10,000 atmospheres (approximately 1,013 megapascals (“MPa”)). In most polymerizations, the molar ratio of the catalyst to the polymerizable olefin (monomer/comonomer) is ^10-12 : 1 to ^10-1 : 1, or ^10-9 : 1 to ^10-5 :1.

The amount of (A) polyolefin polymer in the polyolefin composition may be 40 to 99.99 wt%, alternatively 55 to 99.00 wt%, alternatively 70 to 98 wt%, alternatively 80 to 97 wt%; The total weight of the olefin composition.

Component (B) monocyclic organosiloxane of formula (I): a molecule containing the following: a single ring substructure composed of silicon and oxygen atoms arranged in an alternating arrangement; and unsaturated organic groups; and optionally H , Saturated or aromatic substituents; where there are at least two unsaturated organic groups and each of the at least two silicon atoms in the ring substructure has at least one unsaturated organic group bonded to it, and wherein After considering unsaturated organic groups and oxygen atoms, any remaining valence states of silicon atoms are bonded to H, saturated or aromatic substituents; or a collection of such molecules. Component (B) can be a single-ring organosilicon composed of 6-membered ring (n=3), 8-membered ring (n=4), 10-membered ring (n=5) or 12-membered ring (n=6) alkyl. The ring substructure is composed of units of formula (I): [R ¹ , R ² SiO _2/2 ] _n (I), where the subscripts n, R ¹ and R ^{2 are} as defined above. In each [R ¹ ,R ² SiO _2/2 ] unit, its R ¹ and R ² groups are bonded to its silicon atom. The unit can be simply designated as D ^{R1, R2} using the conventional abbreviation of organosiloxane, so that formula (I) becomes [D ^{R1, R2} ] _n . R ¹ and R ² may be the same instead of different.

In some aspects of (B) the monocyclic organosiloxane of formula (I), R ¹ is vinyl and R ² is ethyl and (B) is D ^{Vi, Et} , where Vi is vinyl and Et is Ethyl; alternatively R ¹ is allyl and R ² is ethyl and (B) is D ^{allyl , Et} ; alternatively R ¹ is butenyl (H ₂ C=C(H)CH ₂ CH ₂ -) and R ² is ethyl and (B) is D ^{butenyl , Et} . In some aspects, R ¹ is vinyl and R ² is vinyl and (B) is D ^Vi,Vi ; alternatively R ¹ is allyl and R ² is allyl and (B) is D ^{allyl group, an allyl group;} alternatively, R ¹ is a butenyl group _{(H 2 C = C (H} ) CH 2 CH 2 -) and R ² is a butenyl group and (B) is ^{D-butenyl, butenyl.} In some aspects R ¹ is vinyl and R ² is phenyl and (B) is D ^Vi,Ph , where Ph is phenyl; alternatively R ¹ is allyl and R ² is phenyl and (B) Is D ^{allyl , Ph} ; alternatively R ¹ is butenyl (H ₂ C=C(H)CH ₂ CH ₂ -) and R ² is phenyl and (B) is D ^{butenyl , Ph} . When R ² is a methyl group (CH ₃ ), the unit can be more simply designated as D ^R1 , so that formula (I) becomes [D ^R1 ] _n . In some aspects, R ¹ is vinyl and R ² is methyl and (B) is D ^Vi ; alternatively R ¹ is allyl and R ² is methyl and (B) is D ^allyl ; instead R ¹ is butenyl (H ₂ C=C(H)CH ₂ CH ₂ -) and R ² is methyl and (B) is D ^butenyl . In some embodiments, (B) is 2,4,6-trimethyl-2,4,6-trivinyl-cyclotrisiloxane, "(D ^Vi ) ₃ "(CAS number 3901-77- 7); 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl-cyclotetrasiloxane, "(D ^Vi ) ₄ "(CAS No. 2554-06-5); Or a combination thereof.

In some aspects of the monocyclic organosiloxane of (B) formula (I), each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a and the subscript m are as defined above. In some aspects R ^1a is H, alternatively R ^1a is methyl. In some aspects, the subscript m is 1, 2 or 3; alternatively m is 2, 3 or 4; alternatively m is 2 or 3; alternatively m is 1; alternatively m is 2; alternatively m is 3 ; Alternatively m is 4. In some aspects, each R ^{2 is} independently (C ₁ -C ₂ )alkyl or (C ₂ -C ₃ )alkenyl; alternatively each R ^{2 is} independently (C ₁ -C ₂ )alkyl Radical; alternatively each R ^{2 is} independently methyl.

The amount of the monocyclic organosiloxane of component (B) formula (I) in the polyolefin composition may be 0.01 to 50 wt%, alternatively 0.1 to 25 wt%, alternatively 1.00 to 20 wt%, alternatively 1.05 to 15 wt%, alternatively 0.01 to 5 wt%, alternatively 0.05 to 4.0 wt%, alternatively 0.1 to 3 wt%, alternatively 0.10 to 2.0 wt%, alternatively 0.20 to 1.0 wt%; all based on polyolefin The weight of the composition.

The amount of component (B) monocyclic organosiloxane of formula (I) in the polyolefin composition can be an effective amount of crosslinking. The term "crosslinking effective amount" means an amount sufficient to achieve crosslinking of polyene macromolecules via the multivalent crosslinking agent group derived from (B) under the environment (wt% described above). The environment may include (B) loading level (wt%), (C) organic peroxide loading level (wt%). Compared with the comparative composition without (B) monocyclic organosiloxane of formula (I), the effective amount of crosslinking formula (B) at the specific loading level (wt%) of (C) organic peroxide (I) The monocyclic organosiloxane produces a higher degree of crosslinking. The environment can also be determined (if present) by the total amount of any optional additives present in the polyolefin composition, such as (E) antioxidants, (F) fillers and/or (G) flame retardants. In order to determine the effective amount of crosslinking used in a specific embodiment of the polyolefin composition, the amount of monocyclic organosiloxane (B) of formula (I) in the polyolefin composition may initially be less than the effective amount of crosslinking. Thereafter, the amount of (B) is increased by increasing (for example, doubling with each increase) until the effective amount of crosslinking under the environment is reached.

The effective amount of the cross-linking monocyclic organosiloxane of component (B) formula (I) in the polyolefin composition may be 0.01 to 50 wt%, alternatively 0.1 to 25 wt%, alternatively 1.00 to 20 wt% , Alternatively 1.05 to 15 wt%, alternatively 0.01 to 5 wt%, alternatively 0.050 to 4.0 wt%, alternatively 0.10 to 2.0 wt%, alternatively 0.20 to 1.0 wt%; Weight meter. The effective amount of the cross-linking monocyclic organosiloxane of component (B) formula (I) in the polyolefin composition can vary depending on the environment described above. For example, the effective amount of crosslinking (B) may be higher in the embodiment of the polyolefin composition containing (F) filler than in the embodiment of the polyolefin composition without (F) filler. .

Regarding the determination of the effective amount of crosslinking of component (B), a moving die rheometer (MDR) can be used to detect the presence of crosslinking by torque increase. In some aspects, the presence of cross-linking can be detected in the form of solvent extraction percentage (Ext%). Ext% = W1/Wo*100%, where W1 is the weight after extraction, Wo is the initial weight before extraction, / indicates division by, and * indicates multiplication. In the cross-linked polyolefin product, the (B) unsaturated organic group (for example, R ¹ ) carbon-carbon double bond is missing or reduced (due to coupling with (A) polyolefin polymer) by carbon 13 or Silicon 29 nuclear magnetic resonance ( ¹³ C-NMR spectroscopy and/or ²⁹ Si-NMR) spectroscopy.

Component (C) Organic peroxides: molecules containing carbon atoms, hydrogen atoms and two or more oxygen atoms and having at least one -OO- group, with the restriction that when there is more than one -OO- group In the case of groups, each -OO- group is indirectly bonded to another -OO- group via one or more carbon atoms, or a batch of such molecules. (C) The organic peroxide may be added to the polyolefin composition for curing, the curing comprising heating the polyolefin composition comprising components (A), (B), and (C) to be at or above ( C) The temperature of the decomposition temperature of organic peroxides. (C) The organic peroxide may be a single peroxide of the formula R ^O -OOR ^O , where each R ^{O is} independently (C ₁ -C ₂₀ )alkyl or (C ₆ -C ₂₀ )aryl. Each (C ₁ -C ₂₀ )alkyl group is independently unsubstituted or substituted with 1 or 2 (C ₆ -C ₁₂ )aryl groups. Each (C ₆ -C ₂₀ )aryl group is unsubstituted or substituted with 1 to 4 (C ₁ -C ₁₀ )alkyl groups. Alternatively, (C) may be a diperoxide of the formula R ^O -OOROOR ^O , where R is a divalent hydrocarbon group, such as (C ₂ -C ₁₀ ) alkylene, (C ₃ -C ₁₀ ) cycloalkyl Or phenylene, and each R ^{O is} as defined above. (C) The organic peroxide may be bis(1,1-dimethylethyl) peroxide; bis(1,1-dimethylpropyl) peroxide; 2,5-dimethyl-2 ,5-bis(1,1-dimethylethylperoxy)hexane; 2,5-dimethyl-2,5-bis(1,1-dimethylethylperoxy)hexyne ; 4,4-bis(1,1-dimethylethylperoxy)valeric acid; butyl ester; 1,1-bis(1,1-dimethylethylperoxy)-3,3, 5-trimethylcyclohexane; benzoyl peroxide; third butyl peroxybenzoate; di-third pentyl peroxide ("DTAP"); bis(α-third butyl-peroxy) Isopropyl)benzene ("BIPB"); isopropyl cumyl tertiary butyl peroxide; tertiary butyl cumene peroxide; di-tertiary butyl peroxide; 2,5- Bis(tert-butylperoxy)-2,5-dimethylhexane; 2,5-bis(tert-butylperoxy)-2,5-dimethylhexyne-3,1, 1-bis(third butylperoxy)-3,3,5-trimethylcyclohexane; cumene cumene peroxide cumene peroxide; 4,4-bis(third butyl peroxide Oxygen) butyl valerate; or bis(isopropyl cumyl) peroxide; or dicumyl peroxide. (C) The organic peroxide may be dicumyl peroxide. In some aspects, only a blend of two or more (C) organic peroxides is used, for example, tert-butyl cumene peroxide and bis(tert-butylperoxyisopropyl)benzene Of 20:80 (wt/wt) blend (for example LUPEROX D446B, which can be purchased from Arkema). In some aspects, at least one, alternatively each (C) organic peroxide contains a -OO- group. If present, (C) the organic peroxide may be 0.01 to 4.5 wt% of the polyolefin composition, alternatively 0.05 to 2 wt%, alternatively 0.10 to 2.0 wt%, alternatively 0.2 to 0.8 wt%.

The optional component (D) conventional auxiliary agent: a molecule containing the main structure or the ring substructure and one or two, or two or more acryl, acrylate and/or vinyl groups bonded thereto, wherein The sub-structure consists of carbon atoms and optionally nitrogen atoms, or a collection of such molecules. (D) The conventional additives do not contain silicon atoms. (D) The conventional auxiliaries may be propylene-based functional conventional auxiliaries as described by any one of restrictions (i) to (v): (i) (D) is 2-allylbenzene Allyl ether; 4-isopropenyl-2,6-dimethylphenyl allyl ether; 2,6-dimethyl-4-allylphenyl allyl ether; 2-methoxy-4 -Allyl phenyl allyl ether; 2,2'-diallyl bisphenol A; O,O'-diallyl bisphenol A; or tetramethyldiallyl bisphenol A; (ii ) (D) is 2,4-diphenyl-4-methyl-1-hexene or 1,3-diisopropenylbenzene; (iii) (D) is triallyl isocyanurate ("TAIC ""; triallyl cyanurate ("TAC"); triallyl trimellitate ("TATM");N,N,N',N',N'',N''-hexaallyl Yl-1,3,5-triazine-2,4,6-triamine (“HATATA”; also known as N ² ,N ² ,N ⁴ ,N ⁴ ,N ⁶ ,N ⁶ -hexaallyl- 1,3,5-triazine-2,4,6-triamine); triallyl orthoformate; pentaerythritol triallyl ether; triallyl citrate; or triallyl aconiate; (iv ) (D) is a mixture of any two of the propylene-based functional additives in (i). Alternatively, (D) may be an acrylate functional conventional additive selected from the group consisting of trimethylolpropane triacrylate ("TMPTA"), trimethylolpropane trimethacrylate ("TMPTMA") , Ethoxylated bisphenol A dimethacrylate, 1,6-hexanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, tris (2-hydroxyethyl) isocyanurate tri Acrylate and propoxylated glyceryl triacrylate. Alternatively, (D) may be a vinyl functional conventional aid selected from polybutadiene having at least 50 wt% 1,2-vinyl content and trivinylcyclohexane ("TVCH"). Alternatively, (D) may be a conventional adjuvant described in US 5,346,961 or US 4,018,852. Alternatively, (D) may be any two or more or a combination of the aforementioned conventional auxiliary agents. In some aspects, the polyolefin composition and the cross-linked polyolefin product do not contain (D). If present, (D) the conventional auxiliary agent may be 0.01 to 4.5 wt% of the polyolefin composition, alternatively 0.05 to 2 wt%, alternatively 0.1 to 1 wt%, alternatively 0.2 to 0.5 wt%.

The optional component (E) antioxidant: organic molecules that inhibit oxidation, or a collection of such molecules. (E) Antioxidants are used to provide antioxidant properties to polyolefin compositions and/or crosslinked polyolefin products. Examples of suitable (E) are bis(4-(1-methyl-1-phenylethyl)phenyl)amine (for example, NAUGARD 445); 2,2'-methylene-bis(4-methyl -6-tert-butylphenol) (for example, VANOX MBPC); 2,2'-thiobis(2-tert-butyl-5-methylphenol (CAS number 90-66-4; 4,4 '-Thiobis(2-third butyl-5-methylphenol) (also known as 4,4'-thiobis(6-third butyl m-cresol), CAS number 96-69-5 , Commercially available LOWINOX TBM-6); 2,2'-thiobis(6-tert-butyl-4-methylphenol (CAS No. 90-66-4, commercially available LOWINOX TBP-6); three [( 4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2,4,6-trione (for example, CYANOX 1790); pentaerythritol Tetrakis(3-(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl) propionate (for example, IRGANOX 1010, CAS number 6683-19-8); 3,5- 2,2'-thiodiethylenediyl bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate (for example, IRGANOX 1035, CAS number 41484-35-9); thiodipropylene Octadecyl acid ester ("DSTDP"); dilauryl thiodipropionate (for example, IRGANOX PS 800); 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propane Octadecyl acid ester (for example, IRGANOX 1076); 2,4-bis(dodecylthiomethyl)-6-methylphenol (IRGANOX 1726); 4,6-bis(octylthiomethyl) ) O-cresol (eg IRGANOX 1520); and 2',3-bis[[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyl]]propionylhydrazine (IRGANOX 1024) In some aspects, (E) is 4,4'-thiobis(2-third butyl-5-methylphenol) (also known as 4,4'-thiobis(6-third Butyl m-cresol); 2,2'-thiobis(6-tert-butyl-4-methylphenol; tri[(4-tert-butyl-3-hydroxy-2,6-dimethyl Phenyl)methyl]-1,3,5-triazine-2,4,6-trione; octadecyl thiodipropionate; or dilauryl thiodipropionate; or Any combination of two or more. The combination may be tri[(4-thirdbutyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine- 2,4,6-Trione and octadecyl thiodipropionate. In some aspects, the polyolefin composition and cross-linked polyolefin product do not contain (E). If present, then (E) The antioxidant may be 0.01 to 1.5 wt% of the polyolefin composition, alternatively 0.05 to 1.2 wt%, alternatively 0.1 to 1.0 wt%.

The optional component (F) filler: finely divided particulate solids or gels that occupy the space in the host material and affect the function of the host material as appropriate. (F) The filler may be calcined clay, organic clay, or hydrophobized fumed silica, such as those commercially available from Cabot Corporation under the trade name CAB-O-SIL. (F) The filler may have a flame retardant effect. In some aspects, the polyolefin composition and the cross-linked polyolefin product do not contain (F). If present, the (F) filler may be 1 to 40 wt% of the polyolefin composition, alternatively 2 to 30 wt%, and alternatively 5 to 20 wt%.

Regarding the filler (F), in some aspects, the polyolefin composition does not contain 20 wt% or more, alternatively does not contain 15 wt% or more, alternatively does not contain 10 wt% or more, and alternatively Free of inorganic fillers selected from the group consisting of alumina, aluminum silicate, calcium silicate, magnesium silicate, silica, titania, and mixtures thereof. In some aspects, the polyolefin composition does not contain 20 wt% or more, alternatively does not contain 15 wt% or more, alternatively does not contain 10 wt% or more, alternatively does not contain a member selected from the group consisting of Group of inorganic fillers: Al-containing solids, Ca-containing solids, Mg-containing solids, Si-containing solids, Ti-containing solids and mixtures thereof. In some aspects, the polyolefin composition does not contain silsesquioxanes, but instead does not contain any silicones other than component (B). In some aspects, the polyolefin composition does not contain any of the groups of silsesquioxane and the above inorganic filler. For the avoidance of doubt, the term "inorganic filler" does not include carbon black.

The component (G) flame retardant as the case may be: a molecule or substance that inhibits combustion, or a collection of such molecules. (G) may be halogenated or halogen-free compounds. (G) Halogenated (G) flame retardants are examples of organic chlorides and organic bromides, and examples of organic chlorides are chlorobridge acid derivatives and chlorinated paraffins. Examples of organic bromides are decabromodiphenyl ether, decabromodiphenylethane, polymeric brominated compounds such as brominated polystyrene, brominated carbonate oligomers, brominated epoxy oligomers, Tetrabromophthalic anhydride, tetrabromobisphenol A and hexabromocyclododecane. Generally, halogenated (G) flame retardants are used in conjunction with synergists to increase their efficiency. The synergist may be antimony trioxide. Examples of halogen-free (G) flame retardants are inorganic minerals, organic nitrogen-swelling compounds, and phosphorus-swelling compounds. Examples of inorganic minerals are aluminum hydroxide and magnesium hydroxide. Examples of phosphorus-based swelling compounds are organic phosphonic acids, phosphonates, phosphonites, phosphonite diesters, phosphinates, phosphine oxides, phosphines, phosphites, phosphates, phosphazene chloride, phosphorus esters Acetamide, amide phosphate, amide phosphonate, amide phosphinate, melamine and melamine derivatives, including melamine polyphosphoric acid, melamine pyrophosphate and melamine cyanuric acid, and two of these materials Or a mixture of more. Examples include phenyl dodecyl phosphate, phenyl di neopentyl phosphate, phenyl ethylene hydrogen phosphate, phenyl-bis(3,5,5'trimethylhexyl) phosphate, ethyl diphenyl phosphate , 2-ethylhexyl di(p-tolyl) phosphate, diphenyl phosphate, bis(2-ethyl-hexyl) p-tolyl phosphate, tricresyl phosphate, bis(2-ethylhexyl) phosphate- Phenyl ester, tris(nonylphenyl) phosphate, phenyl methyl phosphate, bis(dodecyl) p-tolyl phosphate, tricresyl phosphate, triphenyl phosphate, triphenyl phosphate, dibutylbenzene phosphate Ester, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate and diphenyl hydrogen phosphate. Phosphate esters of the type described in US Patent No. 6,404,971 are examples of phosphorus-based flame retardants. Other examples include liquid phosphates, such as bisphenol A diphosphate (BAPP) (Adeka Palmarole) and/or resorcinol bis(diphenyl phosphate) (Fyroflex RDP) (Supresta, ICI); solid phosphorus, such as Ammonium phosphate (APP); piperazine pyrophosphate and piperazine polyphosphate. Ammonium polyphosphate is commonly used with flame retardant auxiliary additives such as melamine derivatives. Melafine (DSM) (2,4,6-triamine-1,3,5-triazine; finely ground melamine) can also be used. In some aspects, the polyolefin composition and the cross-linked polyolefin product do not contain (G). If present, the concentration of (G) may be 0.01 to 70 wt% of the polyolefin composition, alternatively 0.05 to 40 wt%, and alternatively 1 to 20 wt%.

The optionally present component (H) hindered amine stabilizer: a molecule containing an alkali nitrogen atom bonded to at least one sterically large organic group and acting as an inhibitor of degradation or decomposition, or a collection of such molecules. (H) is a compound having a sterically hindered amine functional group and inhibiting oxidative degradation, and it can also increase the storage life of the embodiment of the polyolefin composition containing (C) organic peroxide. Examples of suitable (H) are dimethyl succinate, polymers with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine-ethanol (CAS No. 65447-77-0, Commercially available LOWILITE 62); and N,N'-bismethylformyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-hexanediamine (CAS number 124172 -53-8, commercially available Uvinul 4050 H). In some aspects, the polyolefin composition and the cross-linked polyolefin product do not contain (H). If present, the (H) hindered amine stabilizer may be 0.001 to 1.5 wt% of the polyolefin composition, alternatively 0.002 to 1.2 wt%, alternatively 0.002 to 1.0 wt%, alternatively 0.005 to 0.5 wt%, alternatively 0.01 to 0.2 wt%, alternatively 0.05 to 0.1 wt%.

The optional component (I) anti-tree agent: molecules that inhibit water and/or electrical treeing, or a collection of such molecules. The anti-tree agent may be a water tree retardant or an electrical tree retardant. Water resistant tree agent is a compound that inhibits water tree. Water tree is a process of polyolefin degradation when exposed to the combination of electric field and moisture or moisture. Anti-electric tree agent, also known as voltage stabilizer, is a compound that suppresses the electric tree. The electric tree is an electric pre-decomposition process in solid electrical insulation caused by partial discharge. Electric trees can occur in the absence of water. Water trees and electric trees are problems with cables that contain coated conductors (where the coating contains polyolefin). The (I) may be poly(ethylene glycol) (PEG). In some aspects, the polyolefin composition and the cross-linked polyolefin product do not contain (I). If present, (I) the anti-tree agent may be 0.01 to 1.5 wt% of the polyolefin composition, alternatively 0.05 to 1.2 wt%, alternatively 0.1 to 1.0 wt%.

The component (J) methyl radical scavenger, as the case may be: molecules that can react with methyl radicals, or a collection of such molecules. (J) Reacts with methyl radicals in polyolefin compositions or cross-linked polyolefin products. (J) may be a "TEMPO" derivative of 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl or 1,1-diarylethylene. An example of a TEMPO derivative is 4-propenyloxy-2,2,6,6-tetramethyl-1-piperidinyl-N-hydrocarbyloxy (CAS number 21270-85-9, "acrylate TEMPO" ), 4-allyloxy-2,2,6,6-tetramethyl-1-piperidinyl-N-hydrocarbyloxy (CAS No. 217496-13-4, "allyl TEMPO"); double (2,2,6,6-tetramethyl-1-piperidinyl-N-hydrocarbyloxy) sebacate (CAS No. 2516-92-9, "Double TEMPO"); N, N-bis ( Acryloyl-4-amino)-2,2,6,6-tetramethyl-1-piperidinyl-N-hydrocarbyloxy (CAS No. 1692896-32-4, "Diacrylamido TEMPO") ; And N-propenyl-4-amino-2,2,6,6-tetramethyl-1-piperidinyl-N-hydrocarbyloxy (CAS No. 21270-88-2, "monopropenylamide TEMPO"). Examples of 1,1-diarylethylene are 1,1-stilbene and α-methylstyrene. In some aspects, the polyolefin composition and the cross-linked polyolefin product do not contain (J). If present, the (J) methyl radical scavenger may be 0.01 to 1.5 wt% of the polyolefin composition, alternatively 0.05 to 1.2 wt%, alternatively 0.1 to 1.0 wt%.

The optional component (K) scorch inhibitor: molecules that inhibit premature curing, or a collection of such molecules. Examples of scorch inhibitors are hindered phenols; semi- hindered phenols; TEMPO; TEMPO derivatives; 1,1-stilbene; 2,4-diphenyl-4-methyl-1-hexene (also known as α- Methyl styrene dimer or AMSD); and allyl-containing compounds described in US 6277925B1, row 2, column 62 to row 3, column 46. In some aspects, the polyolefin composition and the cross-linked polyolefin product do not contain (K). If present, the (K) scorch inhibitor may be 0.01 to 1.5 wt% of the polyolefin composition, alternatively 0.05 to 1.2 wt%, alternatively 0.1 to 1.0 wt%.

Component (L) nucleating agent as the case may be: organic or inorganic additives that promote the crystallization rate of polyolefin polymers. Examples of (L) are calcium carbonate, titanium dioxide, barium sulfate, ultra-high molecular weight polyethylene, potassium hydrogen phthalate, benzoic acid compounds, sodium benzoate compounds, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid Disodium, zinc monoglycerate and 1,2-cyclohexane dicarboxylic acid calcium salt: zinc stearate. In some aspects, the polyolefin composition and the cross-linked polyolefin product do not contain (L). If present, the concentration of (L) may be 0.01 to 1.5 wt% of the polyolefin composition, alternatively 0.05 to 1.2 wt%, alternatively 0.1 to 1.0 wt%.

The optional component (M) carbon black: finely divided form of the same crystalline carbon with a high surface area to volume ratio (but lower than the surface area to volume ratio of activated carbon). Examples of (M) are furnace carbon black, acetylene carbon black, and conductive carbon (such as carbon fiber, carbon nanotubes, graphene, graphite, and expanded graphite platelets). In some aspects, the polyolefin composition and the cross-linked polyolefin product do not contain (M). If present, the concentration of (M) may be 0.01 to 40 wt% of the polyolefin composition, alternatively 0.05 to 35 wt%, alternatively 0.1 to 20 wt%, alternatively 0.5 to 10 wt%, alternatively 1 to 5 wt%.

In addition, the polyolefin composition may independently further comprise 0.001 to 50 wt%, alternatively 0.05 to 30 wt%, alternatively 0.1 to 20 wt%, alternatively 0.5 to 10 wt%, alternatively 1 to 5 wt% One or more of the following additives as appropriate: carrier resin, lubricant, processing aid, slip aid, plasticizer, surfactant, filler oil, acid scavenger, and metal deactivator. For example, the filling oil can be up to 50 wt% of the polyolefin composition. In some aspects, the polyolefin composition and the cross-linked polyolefin product do not contain any of the aforementioned additives.

The aforementioned components of the Xianxin polyolefin composition do not act as a ring-opening catalyst in which the cyclic silicone is used. However, if any one or more of the aforementioned components of the polyolefin composition unexpectedly acts as a ring-opening catalyst for cyclic silicone, such one or more components will be excluded from the polyolefin composition.

Crosslinked polyolefin product: a reaction product containing a reticulated polyolefin resin containing CC bonds formed during curing (crosslinking) of the polyolefin composition. The reticulated polyolefin resin may include a macromolecule coupling (A) a polyolefin polymer and a (B) monocyclic organosiloxane molecule of formula (I) to generate a reaction product of a network structure, the network structure Contains via the reaction between two or more macromolecules of (A) polyolefin polymer and one or more R ¹ groups of (B) monocyclic organosiloxane molecules of formula (I) Two or more macromolecular polyvalent monocyclic organosiloxane crosslinker groups from (A) polyolefin polymer. In some aspects, two (A) macromolecules can be added across the same carbon-carbon double bond of one R ¹ . For example, when two or more R ¹ is vinyl and zero, one or more R ² is vinyl, the network structure of the crosslinked polyolefin product may contain two or more formulas ( II) [-CH ₂ CH ₂ (R ² )SiO _2/2 ] (II) and/or formula (III) [CH ₃ C(-)(H),(R ² )SiO _2/2 ] (III) Multivalent monocyclic organosiloxane crosslinker group and n-2 or less (eg n-3) unreacted units of formula (I) (if present), where the subscript n is for formula (I ) Is defined and "-" indicates one of the polyvalent numbers. When each R ² in formula (I) is independently H, (C ₁ -C ₄ )alkyl or phenyl, each R ^{2 in} formula (II) and formula (III) is independently H, (C ₁ -C ₄ )alkyl or phenyl.

The crosslinked polyolefin product may also contain curing by-products, such as (C) alcohol and ketone by-products of the reaction of organic peroxides. When the polyolefin composition further contains any optional additives such as (E) antioxidants or one or more of the components, the crosslinked polyolefin product may also contain optional additives such as (E) or Any one or more of the components, or one or more reaction products formed therefrom during curing of the polyolefin composition. The crosslinked polyolefin product can be in the form of a dispersed solid or continuous form. The dispersed solid form may contain granules, pellets, powder, or any combination of two or more of them. The continuous form may be a molded part (eg, injection molded part) or an extruded part (eg, coated conductor or cable).

The cross-linked polyolefin product may be free of ring-opening catalysts and/or silicone polymer molecules (polysiloxane, which is prepared by ring-opening polymerization of (B)).

Coated conductor. The coated conductor may be an insulated electrical conductor. Insulated electrical conductors may be coated metal wires or cables, including for low voltage (“LV”,> 0 to <5 kilovolts (kV)), medium voltage (“MV”, 5 to <69 kV) , High-voltage (“HV”, 69 to 230 kV) or ultra-high-voltage (“EHV”,> 230 kV) power cables for data transmission and electrical transmission/distribution applications. "Wire" means a single-strand or single-wire conductive material, such as a conductive metal, such as copper or aluminum. "Cable" and "power cable" are synonymous and mean an insulated electrical conductor that includes at least one wire placed within a sheath, sheath (protective outer sheath), or coating. Insulated electrical conductors can be designed and constructed for medium, high or ultra-high voltage applications. Examples of suitable cable designs are shown in US 5,246,783; US 6,496,629; and US 6,714,707.

The insulated electrical conductor may contain a conductor/transmitter core and an outer single-layer covering or an outer multi-layer covering placed around it in order to protect the conductor/transmitter core and isolate the conductor core from the external environment. The conductor/transmitter core may be composed of one or more metal wires. When the conductor/transmitter core contains two or more metal wires, the metal wires can be subdivided into discrete wire bundles. Each wire or fiber in the conductor/transmitter core, whether bundled or not, may be individually coated with an insulating layer and/or the discrete bundles may be coated with an insulating layer. Single-layer coverings or multi-layer coverings (for example, single-layer or multi-layer coatings or sheaths) are mainly used to protect the conductor/transmitter core from the external environment (such as sunlight, water, heat, oxygen, other conductive materials) (Eg to prevent short circuits) and/or other corrosive materials (eg chemical fumes) to isolate.

The single-layer or multi-layer covering from one insulated electrical conductor to the next can be configured in different ways, depending on its corresponding intended use. For example, looking at the cross-section, the multilayer covering of the insulated electrical conductor can be sequentially configured with the following components from its innermost layer to its outermost layer: inner semiconductor layer, containing crosslinked polyolefin product (crosslinked product of the invention) Cross-linked polyolefin insulation layer, outer semiconductor layer, metal shield, and protective sheath. The layer and sheath are continuous in the circumferential direction and coaxial (longitudinal). The metal shield (grounding) is coaxial and continuous, and is continuous (layer) or discontinuous (band or line) along the circumferential direction. Depending on the intended application, the multi-layer covering for the insulated optical fiber may omit the semiconductive layer and/or the metal shield. The outer semiconducting layer (if present) can be composed of peroxide-crosslinked semiconducting products, which can be combined with the crosslinked polyolefin layer or can be stripped from the crosslinked polyolefin layer.

In some aspects is a method of manufacturing a coated conductor, the method comprising extruding a coating comprising a layer of polyolefin composition onto a conductor/transmitter core to obtain a coated core, and allowing the coated The core passes through a continuous vulcanization (CV) equipment, which is equipped with suitable CV conditions for curing the polyolefin composition, resulting in a coated conductor. CV conditions include temperature, atmosphere (eg, nitrogen), and linear velocity or the time period of passage through the CV equipment. Appropriate CV conditions can provide a coated conductor leaving the CV equipment, where the coated conductor contains a cross-linked polyolefin The layer by layer is cured to form a crosslinked polyolefin layer.

Conductive method. The conductive method of the present invention may use the coated conductor of the present invention including an insulated electrical conductor embodiment. The method of transmitting data using the coated conductor of the present invention including insulated electrical conductors is also covered.

Density according to ASTM D792-13, Standard Test Methods for Density and Specific Gravity (Relative Density) of Plastics by Displacement, method B (used in water removal Measurement of solid plastics in other liquids (such as liquid 2-propanol). Report the results in units of grams per cubic centimeter (g/cm ³ or g/cc).

Melt index (I ₂ ) according to ASTM D1238-04 (190°C, 2.16 kg), Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Platometer ) Measurement, using condition 190℃/2.16 kilograms (kg), previously known as "Condition E" and also known as I ₂ . The results are reported in units of dissolved grams per 10 minutes (g/10 min.) or equivalents in grams per minute per 1.0 minutes (dg/1 min.). 10.0 dg = 1.00 g.

Migration measurement test method. The migration additive can be observed by placing 5 grams (g) pellets in an unused transparent self-sealing polyethylene bag and pressing the pellets 5 times to observe whether there are any marks (oil marks) imprinted on the bag. If a trace is observed, it is recorded as "Yes", and if no trace is observed, it is recorded as "No".

Test method of coking time. The coking time of sample "X" or the time to reach coking (ts1) is measured by MDR at 140°C and is abbreviated as ts1@140°C. The coking time was measured according to ISO 6502 on the Alpha Technologies rheometer MDR 2000E as follows. Put 5 to 6 g of test material (pellet) into the MDR 200E instrument. The torque is measured at 100 cycles per minute (cpm) for 0.5 radian oscillation deformation, and changes from time 0 (initial) to 120 minutes at 140°C with time, and a torque curve is plotted against time. ts1 is the length of time required from the beginning of the test (0 minutes) to the observed increase in torque from the minimum value in the torque curve by 1 minute Newton-meter (dNm). Use ts1@140°C to characterize scorch resistance during melt processing methods such as melt compounding or extrusion.

T90 cross-linking time test method: ASTM D5289-12, standard test method for rubber properties- vulcanization using Rotorless curing meter. Use the following procedure to measure the torque of the test sample. The test sample was heated in a dynamic mode rheometer (MDR) instrument MDR2000 (Alpha Technologies) at 180°C for 20 minutes, while monitoring the change of the moment of oscillation deformation of 0.5 radians at 100 cpm. The measured minimum torque value is expressed as "ML", expressed in minutes Newton-meter (dN-m). As the curing or crosslinking progresses, the measured torque value increases and eventually reaches the maximum torque value. The measured maximum or maximum torque value is expressed as "MH", expressed as dN-m. Under the condition that all other factors are the same, the higher the MH torque value, the greater the degree of crosslinking. The T90 crosslinking time is determined as the number of minutes required to achieve a torque value equal to 90% of the difference between MH minus ML (MH-ML), which is 90% from ML to MH. The shorter the T90 crosslinking time, that is, the earlier the torque value becomes 90% from ML to MH, the faster the curing rate of the test sample. Conversely, the longer the T90 cross-linking time, that is, the torque value becomes 90% from ML to MH, the more time it takes, the slower the curing rate of the test sample.

The following data predicts how the composition of the present invention will behave when extruded and crosslinked (for example, in CV equipment) to form the insulation layer of a cable. Examples

LDPE (A1): By combining LDPE (A2) with 0.12 wt% antioxidant (E1), 0.24 wt% antioxidant (E2) and 50 parts per million (wt) hindered amine stabilizer (H1) (Yes A2), (E1), (E2) and (H1) are described below) mixed to prepare low density polyethylene (LDPE) with a density of 0.92 g/cm ³ and a melt index (I ₂ ) of 2 g/10 min.

LDPE (A2): Low-density polyethylene (LDPE) product produced by a high-pressure reactor, having an average of more than 0.3 carbon-carbon double bonds per 1,000 carbon atoms, a density of 0.92 g/cm ^3, and a melt index (I ₂ ) Is 2 g/10 min (190°C, 2.16 kg) and is obtained from The Dow Chemical Company, Midland, Michigan, USA. LDPE (A2) is made in a tubular high-pressure reactor and the type of method is described in "Introduction to Polymer Chemistry ", Stille, Wiley and Sons, New York, 1962, pages 149 to 151. The method is free radical initiation and is carried out at a pressure of 170 to 310 megapascals (MPa, that is, 25,000 to 45,000 pounds per square inch (psi)) and a temperature of 200°C to 350°C.

LDPE (A3): Low-density polyethylene (LDPE) is prepared by Brabender single screw extruder at 120°C. A known amount of LDPE (A2) is blended into LDPE (A1) to obtain LDPE (A3), which It is loaded with 0.06 wt% antioxidant (E1), 0.09 wt% antioxidant (E2) and 19 ppm hindered amine stabilizer (H1), and has a density of 2.0 g/cm ³ and a melt index (I ₂ ) of 0.92 g/ 10 min.

Monocyclic organosiloxane (B1): 2,4,6-trimethyl-2,4,6-trivinyl-cyclotrisiloxane obtained from Gelest, "(D ^Vi ) ₃ "(CAS number 3901-77-7).

Monocyclic organosiloxane (B2): 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl-cyclotetrasiloxane obtained from Dow Chemical Company, "(D ^Vi ) ₄ " (CAS No. 2554-06-5).

Monocyclic organosiloxane (B3): 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentavinyl-cyclopentasiloxane obtained from Gelest, "( D ^Vi ) ₅ ”(CAS No. 17704-22-2).

Organic peroxide (C1): Dicumyl peroxide ("DCP") obtained from Fangruida.

Conventional additives (D1): Triallyl isocyanurate (TAIC) obtained from Fangruida, People's Republic of China.

Antioxidant (E1): Cyanox 1790, available from Cytec Industries Inc.

Antioxidant (E2): DSTDP, available from Reagens.

Hindered amine stabilizer (H1): Uvinul 4050 from BASF.

Octavinyl polyhedral oligomeric silsesquioxane (OV-POSS): To a 500 mL three-necked flask, add anhydrous methanol (200 mL), deionized water (9 mL) and concentrated hydrochloric acid (36 wt%, 2 mL) . The resulting first mixture was stirred at 40°C for about 10 minutes. Then a solution of vinyltrimethoxysilane (20 mL, H ₂ C=C(H)Si(OCH ₃ ) ₃ ) in methanol (50 mL) was added dropwise to the first mixture over 4 hours. After the vinyl trimethoxysilane solution was added, an additional portion of methanol (30 mL) was added at once. The resulting combined mixture was stirred at 40°C for 5 days. An OV-POSS precipitate formed and it was filtered off. The resulting filter cake was dissolved in a minimum amount of tetrahydrofuran, and ethanol was added to the resulting solution to reprecipitate OV-POSS. The reprecipitated OV-POSS was filtered and dried under reduced pressure to produce 1 g (11% yield) of OV-POSS as a white solid.

Phosphazene base ("P4-t-Bu"): 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphine Amino]-25,45-diphenyl(phosphazene) in 0.4 mol solution in hexane, obtained from Sigma-Aldrich.

Comparative Examples 1 and 2 (CE1 and CE2): OV-POSS was added to the melt of LDPE (A3) in a separate operation at 40 revolutions per minute (rpm) for 5 minutes at 120°C in a Brabender closed mixer To obtain an intermediate product composition. The intermediate product composition was pressed at 120°C for 2 minutes to form a thin plate. The sheet was cut into pellets, and the pellets were soaked with organic peroxide (C1) at 80°C for 6 hours to obtain CE1 and CE2. See Tables 1 and 3.

Comparative Examples 3 and 4 (CE3 and CE4): In a separate operation, the LDPE (A2) was melted in the HAAKE internal mixture at 50 revolutions per minute (rpm) at 120°C for 5 minutes. Subsequently, monocyclic organosiloxane (B3) and phosphazene base P4-t-Bu (different amounts) were added, and the resulting combination was mixed for 30 seconds. Subsequently, the organic peroxide (C1) was added, and the resulting combination was mixed for 30 seconds to obtain an intermediate product composition. The intermediate product composition was pressed at 120 ℃ under a pressure of 10 megapascals (MPa) for 30 seconds to obtain CE3 and C4 in the form of thin plates, respectively. See Tables 1 and 3.

Comparative Examples 5 and 6: LDPE (A3) pellets were immersed in organic peroxide (C1) at 80°C for 6 hours to obtain compositions CE5 and CE6. See Tables 1 and 3. Table 1: Composition of CE1 to CE6 (0=0.00)

Examples 1 to 6 of the present invention (IE1 to IE6): In a separate operation, the monocyclic organosiloxane (B1), (B2) or (B3) and optionally triallyl isocyanurate (TAIC) are made in an oven ) And the organic peroxide (C1) are immersed in LDPE (A3) or (A2) at 80°C for 6 hours to obtain compositions IE1 to IE6 of the present invention in the form of pellets. See Tables 2 and 4. Table 2: Composition of IE1 to IE6. (0=0.00)

*初始遷移在17小時之後測定。 表4：IE1至IE6之表徵。

*初始遷移在17小時之後測定。According to one or more of the T90 crosslinking time test method, the coking time test method and the migration measurement test method, this is a test sample that characterizes the pellets of the compositions CE1 to CE6 and IE1 to IE6 composition. See Tables 3 and 4. Table 3: Characterization of CE1 to CE6.

*Initial migration is measured after 17 hours. Table 4: Characterization of IE1 to IE6.

*Initial migration is measured after 17 hours.

As indicated by comparing the data of CE1 with the data of CE5, OV-POSS impairs coking resistance to achieve the same curing level, such as by the shorter coking of CE5 at 140°C (min.) compared to the value of CE1 Time indicated by ts1 value. As indicated by comparing the data of CE6 with the data of IE1, in order to achieve the same curing level, (B) monocyclic organosiloxane improves the scorch resistance. For example, by comparing the value of CE6 with IE1 at 140℃ The telephoto time is indicated by the ts1 value. As indicated by comparing the data of CE2 with the data of CE5, in the presence of another auxiliary, triallyl isocyanurate, by comparing the value of CE2 with the comparable scorch time ts1 of CE5 at 140°C ( min.) The value indicates that OV-POSS does not impair the coking resistance. As indicated by comparing the data of CE6 with the data of IE4, in the presence of another auxiliary agent triallyl isocyanurate, (B) the monocyclic organosiloxane still improves the scorch resistance. The value is indicated by the longer coking time ts1 (min.) value of IE4 at 140°C. As indicated by comparing the data of CE3 and CE4 with the data of IE6, the phosphazene base (P4-t-Bu) in CE3 and CE4 does not contribute to crosslinking and actually damages (reduces) the level of crosslinking, such as It is indicated by the highest torque MH at 180°C. The values of CE3 and CE4 are significantly lower than the values of IE6 maximum torque MH at 180°C. The harmful effect of phosphazene base on the cross-linking level gradually increases with the concentration of phosphazene base (CE3 vs. CE4).

The following patent application ranges are incorporated here by reference, such as the numbered version, the difference is that the "formation" is used instead of "patent application range".

Claims (13)

A polyolefin composition comprising (A) a polyolefin polymer, which is a copolymer containing 50 to 100% by weight (wt%) of ethylenic monomer units and 50 to 0% by weight (C ₃ -C ₂₀ ) α-olefin-derived copolymer Low-density polyethylene (LDPE) polymers with monomer units and 20 to 0 wt% diene comonomer units, of which the total weight percentage is 100.00 wt%; crosslinking effective amount of (B) monocyclic organic compounds of formula (I) Siloxane: [R ¹ ,R ² SiO _2/2 ] _n (I), where the subscript n is an integer greater than or equal to 3; each R ^{1 is} independently (C ₂ -C ₄ )alkenyl or H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a is H or methyl and the subscript m is an integer from 1 to 4; and each R ^{2 is} independently Is H, (C ₁ -C ₄ )alkyl, phenyl or R ¹ ; and (C) an organic peroxide; the limitation is that the polyolefin composition does not contain a phosphazene base. A polyolefin composition comprising (A) a polyolefin polymer, which is a copolymer containing 50 to 100% by weight (wt%) of ethylenic monomer units and 50 to 0% by weight (C ₃ -C ₂₀ ) α-olefin-derived copolymer Low-density polyethylene (LDPE) polymers with monomer units and 20 to 0 wt% diene comonomer units, of which the total weight percentage is 100.00 wt%; (B) monocyclic organosiloxane of formula (I): [ R ¹ ,R ² SiO _2/2 ] _n (I), where the subscript n is an integer greater than or equal to 3; each R ^{1 is} independently (C ₂ -C ₄ )alkenyl or H ₂ C=C( R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a is H or methyl and the subscript m is an integer from 1 to 4; and each R ^{2 is} independently H, (C ₁ -C ₄ ) alkyl, phenyl or R ¹ ; and (C) organic peroxide; the limitation is that the polyolefin composition does not contain phosphazene base; and the limitation is when the subscript n is 4 , The (A) polyolefin composition does not contain 24wt% or more of inorganic fillers selected from the group consisting of alumina, aluminum silicate, calcium silicate, magnesium silicate, silica, titanium dioxide and mixtures thereof . The polyolefin composition as described in item 1 or 2 of the patent application scope, wherein the subscript n is 3 and the monocyclic organosiloxane of (B) formula (I) is restricted by (i) to ( Description of any of x): (i) each R ^{1 is} independently (C ₂ -C ₃ )alkenyl; and each R ^{2 is} independently H, (C ₁ -C ₂ )alkyl or ( C ₂ -C ₃ )alkenyl; (ii) each R ¹ is vinyl; and each R ^{2 is} independently (C ₁ -C ₂ )alkyl; (iii) each R ¹ is vinyl; and Each R ² is methyl; (iv) each R ¹ is allyl; and each R ^{2 is} independently (C ₁ -C ₂ ) alkyl; (v) each R ¹ is allyl; And each R ² is methyl; (vi) each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a is H or Methyl and the subscript m is an integer from 1 to 4; and each R ^{2 is} independently H, (C ₁ -C ₂ )alkyl or (C ₂ -C ₃ )alkenyl; (vii) each R ¹ Independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a is H and the subscript m is 3; and each R ^{2 is} independently (C ₁ -C ₂ )alkyl; (viii) each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a is methyl and The subscript m is 3; and each R ^{2 is} independently (C ₁ -C ₂ ) alkyl; (ix) the polyolefin composition does not contain 24 wt% or more selected from aluminum oxide, aluminum silicate, Inorganic fillers of the group consisting of calcium silicate, magnesium silicate, silica, titanium dioxide, and mixtures thereof; and (x) the combination of restrictions (ix) and any of restrictions (i) to (viii). The polyolefin composition as described in item 1 or item 2 of the patent application, wherein the subscript n is 4 and the monocyclic organosiloxane of (B) formula (I) is restricted by (i) to ( Description of any of x): (i) each R ^{1 is} independently (C ₂ -C ₃ )alkenyl; and each R ^{2 is} independently H, (C ₁ -C ₂ )alkyl or ( C ₂ -C ₃ )alkenyl; (ii) each R ¹ is vinyl; and each R ^{2 is} independently (C ₁ -C ₂ )alkyl; (iii) each R ¹ is vinyl; and Each R ² is methyl; (iv) each R ¹ is allyl; and each R ^{2 is} independently (C ₁ -C ₂ ) alkyl; (v) each R ¹ is allyl; And each R ² is methyl; (vi) each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a is H or Methyl and the subscript m is an integer from 1 to 4; and each R ^{2 is} independently H, (C ₁ -C ₂ )alkyl, or (C ₂ -C ₃ )alkenyl; (vii) each R ¹ Independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a is H and the subscript m is 3; and each R ^{2 is} independently (C ₁ -C ₂ )alkyl; (viii) each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a is methyl and The subscript m is 3; and each R ^{2 is} independently (C ₁ -C ₂ ) alkyl; (ix) the polyolefin composition does not contain any inorganic filler of 24 wt% or more; and (x) The combination of restriction (ix) and any of restrictions (i) to (viii). The polyolefin composition as described in item 1 or item 2 of the patent application, wherein the subscript n is 5 or 6 and the monocyclic organosiloxane of (B) formula (I) is limited by (i) Description to any of (x): (i) each R ^{1 is} independently (C ₂ -C ₃ )alkenyl; and each R ^{2 is} independently H, (C ₁ -C ₂ )alkyl Or (C ₂ -C ₃ )alkenyl; (ii) each R ¹ is vinyl; and each R ^{2 is} independently (C ₁ -C ₂ )alkyl; (iii) each R ¹ is vinyl ; And each R ² is methyl; (iv) each R ¹ is allyl; and each R ^{2 is} independently (C ₁ -C ₂ ) alkyl; (v) each R ¹ is allyl Radical; and each R ² is methyl; (vi) each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a is H or methyl and the subscript m is an integer from 1 to 4; and each R ^{2 is} independently H, (C ₁ -C ₂ )alkyl or (C ₂ -C ₃ )alkenyl; (vii) each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a is H and the subscript m is 3; and each R ^{2 is} independently (C ₁ -C ₂ )alkyl; (viii) each R ^{1 is} independently H ₂ C=C(R ^1a )-C(=O)-O-(CH ₂ ) _m -, where R ^1a is A And the subscript m is 3; and each R ^{2 is} independently (C ₁ -C ₂ ) alkyl; (ix) the polyolefin composition does not contain 24wt% or more selected from alumina, silicic acid Inorganic fillers consisting of aluminum, calcium silicate, magnesium silicate, silica, titanium dioxide, and mixtures thereof; and (x) limit (ix) and any combination of limits (i) to (viii). The polyolefin composition as described in item 1 or 2 of the patent application scope is described by any one of the restrictions (i) to (vii): (i) The (A) polyolefin polymer is characterized by As measured by ASTM D792-13, Method B, in 2-propanol, the density is 0.86 to 0.97 g/cm3 (g/cm ³ ); (ii) the (A) polyolefin polymer is 80 to 99.89% by weight (wt%) of the weight of the polyolefin composition; (iii) the monocyclic organosiloxane of (B) formula (I) is 0.1 to 3% by weight of the polyolefin composition ; And the (C) organic peroxide is 0.01 to 4.5 wt% of the polyolefin composition; (iv) (i) and (ii) both; (v) (i) and (iii) both ; (Vi) both (ii) and (iii); and (vii) (i), (ii) and (iii) each. The polyolefin composition as described in item 1 or item 2 of the patent application scope, further includes Contains at least one additive selected from the group consisting of: (D) conventional additives; (E) antioxidants; (F) fillers; (G) flame retardants; (H) hindered amine stabilizers; (I) Tree retardant; (J) methyl radical scavenger; (K) scorch inhibitor, (L) nucleating agent and (M) carbon black; the limiting condition is the total amount of the at least one additive It is >0 to 70 wt% of the polyolefin composition, and the limitation is that the (F) filler does not include any omitted filler. A method for manufacturing a polyolefin composition, the method comprising (A) a polyolefin polymer and (B) a monocyclic organosiloxane of formula (I): [R ¹ ,R ² SiO _2/2 ] _n ( I) Mix together to produce the polyolefin composition as described in any one of claims 1 to 6. A method for free radical curing the polyolefin composition as described in any one of patent application items 1 to 7 to produce a crosslinked polyolefin product, the method comprising combining with (C) organic at a curing effective temperature The peroxide heats the polyolefin composition together, in this way allowing (A) the polyolefin polymer to react with (B) the monocyclic organosiloxane of formula (I), thereby producing a crosslinked polyolefin product. A cross-linked polyolefin product produced by the curing method described in item 9 of the patent application. A manufactured article comprising the polyolefin composition as described in any one of patent application items 1 to 7, or the polyolefin composition prepared by the method as described in patent application item 8, Or the shaped form of the cross-linked polyolefin product as described in item 10 of the patent application. A coated conductor comprising a conductive core and an insulating layer at least partially covering the conductive core, wherein at least a part of the insulating layer comprises the polymer as described in any one of claims 1 to 7 An olefin composition or a crosslinked polyolefin product as described in item 10 of the patent application. A method of transmitting electricity, the method comprising applying a voltage across a conductive core of a coated conductor as described in item 12 of the patent application, so as to generate a current through the conductive core.