阅读说明：本技术 聚烯烃组合物 (Polyolefin compositions ) 是由 孙亚斌 张楷男 J·M·柯吉恩 T·J·珀森 于 2017-06-29 设计创作，主要内容包括：一种聚烯烃组合物,其包含聚烯烃聚合物和烯基官能性单环有机硅氧烷；由其制得的产物；制备和使用其的方法；和含有其的制品。(A polyolefin composition comprising a polyolefin polymer and an alkenyl-functional monocyclic organosiloxane; products made therefrom; methods of making and using the same; and articles comprising the same.)

1. A polyolefin composition comprising (a) a polyolefin polymer and a crosslinking effective amount of (B) a monocyclic organosiloxane of formula (I): [ R ]¹,R²SiO_2/2]_n(I) Wherein subscript n is an integer greater than or equal to 3; each R¹Independently is (C)₂-C₄) Alkenyl or H₂C＝C(R^1a)-C(＝O)-O-(CH₂)_m-, wherein R^1aIs H or methyl and subscript m is an integer of 1 to 4; and each R²Independently H, (C)₁-C₄) Alkyl, phenyl or R¹(ii) a With the proviso that the polyolefin composition does not contain a phosphazene base.

2. A polyolefin composition comprising (a) a polyolefin polymer and (B) a monocyclic organosiloxane of formula (I): [ R ]¹,R²SiO_2/2]_n(I) Wherein subscript n is an integer greater than or equal to 3; each R¹Independently is (C)₂-C₄) Alkenyl or H₂C＝C(R^1a)-C(＝O)-O-(CH₂)_m-, wherein R^1aIs H or methyl and subscript m is an integer of 1 to 4; and each R²Independently H, (C)₁-C₄) Alkyl, phenyl or R¹(ii) a With the proviso that the polyolefin composition is free of phosphazene base; and with the proviso that when the polyolefin polymer is an ethylene-containing polymer and subscript n is 4, the (a) polyolefin composition does not contain 24 wt% or more of an inorganic filler selected from the group consisting of: alumina, aluminum silicate, calcium silicate, magnesium silicate, silicon dioxide, titanium dioxide, and mixtures thereof.

3. The polyolefin composition according to claim 1 or 2 wherein subscript n is 3 and the (B) monocyclic organosiloxane of formula (I) is described by any one of the limitations (I) to (x): (i) each R¹Independently is (C)₂-C₃) An alkenyl group; and each R²Independently H, (C)₁-C₂) Alkyl or (C)₂-C₃) An alkenyl group; (ii) each R¹Is a vinyl group; and each R²Independently is (C)₁-C₂) An alkyl group; (iii) each R¹Is a vinyl group; and each R²Is methyl; (iv) each R¹Is an allyl group; and each R²Independently is (C)₁-C₂) An alkyl group; (v) each R¹Is an allyl group; and each R²Is methyl; (vi) each R¹Independently is H₂C＝C(R^1a)-C(＝O)-O-(CH₂)_m-, wherein R^1aIs H or methyl and subscript m is an integer of 1 to 4; and each R²Independently H, (C)₁-C₂) Alkyl or (C)₂-C₃) An alkenyl group; (vii) each R¹Independently is H₂C＝C(R^1a)-C(＝O)-O-(CH₂)_m-, wherein R^1aIs H and subscript m is 3; and each R²Independently is (C)₁-C₂) An alkyl group; (viii) each R¹Independently is H₂C＝C(R^1a)-C(＝O)-O-(CH₂)_m-, wherein R^1aIs methyl and subscript m is 3; and each R²Independently is (C)₁-C₂) An alkyl group; (ix) the polyolefin composition does not contain 24 wt% or more of an inorganic filler selected from the group consisting of: alumina, aluminum silicate, calcium silicate, magnesium silicate, silicon dioxide, titanium dioxide, and mixtures thereof; and (x) a combination of limit (ix) and any one of limits (i) to (viii).

4. The polyolefin composition according to claim 1 or 2 wherein subscript n is 4 and the (B) monocyclic organosiloxane of formula (I) is described by any one of the limitations (I) to (x): (i) each R¹Independently is (C)₂-C₃) An alkenyl group; and each R²Independently H, (C)₁-C₂) Alkyl or (C)₂-C₃) An alkenyl group; (ii) each R¹Is a vinyl group; and each R²Independently is (C)₁-C₂) An alkyl group; (iii) each R¹Is a vinyl group; and each R²Is methyl; (iv) each R¹Is an allyl group; and each R²Independently is (C)₁-C₂) An alkyl group; (v) each R¹Is an allyl group; and each R²Is methyl; (vi) each R¹Independently is H₂C＝C(R^1a)-C(＝O)-O-(CH₂)_m-, wherein R^1aIs H or methyl and subscript m is an integer of 1 to 4; and each R²Independently H, (C)₁-C₂) Alkyl or (C)₂-C₃) An alkenyl group; (vii) each R¹Independently is H₂C＝C(R^1a)-C(＝O)-O-(CH₂)_m-, wherein R^1aIs H and subscript m is 3; and each R²Independently is (C)₁-C₂) An alkyl group; (viii) each R¹Independently is H₂C＝C(R^1a)-C(＝O)-O-(CH₂)_m-, wherein R^1aIs methyl and subscript m is 3; and each R²Independently is (C)₁-C₂) An alkyl group; (ix) the polyolefin composition does not contain 24 wt% or more of any inorganic filler; and (x) a combination of limit (ix) and any one of limits (i) to (viii).

5. The polyolefin composition of claim 1 or 2 wherein subscript n is 5 or 6 and the (B) monocyclic organosiloxane of formula (I) is described by limiting any one of (I) to (x): (i) each R¹Independently is (C)₂-C₃) An alkenyl group; and each R²Independently H, (C)₁-C₂) Alkyl or (C)₂-C₃) An alkenyl group; (ii) each R¹Is a vinyl group; and each R²Independently is (C)₁-C₂) An alkyl group; (iii) each R¹Is a vinyl group; and each R²Is methyl; (iv) each R¹Is an allyl group; and each R²Independently is (C)₁-C₂) An alkyl group; (v) each R¹Is an allyl group; and each R²Is methyl; (vi) each R¹Independently is H₂C＝C(R^1a)-C(＝O)-O-(CH₂)_m-, wherein R^1aIs H or methyl and subscript m is an integer of 1 to 4; and each R²Independently H, (C)₁-C₂) Alkyl or (C)₂-C₃) An alkenyl group; (vii) each R¹Independently is H₂C＝C(R^1a)-C(＝O)-O-(CH₂)_m-, wherein R^1aIs H and subscript m is 3; and each R²Independently is (C)₁-C₂) An alkyl group; (viii) each R¹Independently is H₂C＝C(R^1a)-C(＝O)-O-(CH₂)_m-, wherein R^1aIs methyl and subscript m is 3; and each R²Independently is (C)₁-C₂) An alkyl group; (ix) the polyolefin composition does not contain 24 wt% or more of an inorganic filler selected from the group consisting of: alumina, aluminum silicate, calcium silicate, magnesium silicate, silicon dioxide, titanium dioxide, and mixtures thereof; and (x) a combination of limit (ix) and any one of limits (i) to (viii).

6. The polyolefin composition of any of claims 1 to 5, wherein the (A) polyolefin polymer is described by limiting any of (i) the (A) polyolefin polymer is a polyethylene polymer comprising from 50 to 100 weight percent (wt%) ethylene monomer units, from 50 to 0 wt% (C3-C20) α -olefin derived comonomer units and from 20 to 0 wt% diene comonomer units, wherein the total weight percent is 100.00 wt%, (ii) the (A) polyolefin polymer is a polypropylene polymer comprising from 50 to 100 weight percent (wt%) propylene monomer units and from 50 to 0 wt% ethylene or (C4-C20) α -olefin derived comonomer units and optionally from 20 to 0 wt% diene comonomer units, (iii) the (A) polyolefin polymer is an ethylene/vinyl acetate (EVA) copolymer comprising from 50 to <100 wt% ethylene monomer units and from 50 to <100 wt% ethylene/vinyl acetate (EVA) copolymer, and from 50 to 50 wt% ethylene/vinyl acetate (A) copolymer, and from (A) the (A) copolymer is a copolymer comprising from 50 to 50 wt% ethylene/vinyl acetate, the (A) ethylene/vinyl acetate (A) copolymer and from at least 50 wt% ethylene/vinyl acetate (A) ethylene/vinyl acrylate (A) copolymer, and from (A) ethylene/vinyl acetate (A) copolymer, wherein the (A) copolymer is a copolymer and from 50 to (V) the polyolefin copolymer comprises from at least one of ethylene/vinyl acrylate (A) ethylene-monomer units, wherein the copolymer and from the copolymer, the copolymer is a copolymer, the copolymer.

7. The polyolefin composition of claim 6, wherein the (C3-C20) α -olefin derived comonomer units and/or (C4-C20) α -olefin derived comonomer units are derived from 1-butene, 1-hexene, 1-octene, or a combination of any two thereof.

8. The polyolefin composition according to any of claims 1 to 7, further comprising at least one additive selected from the group consisting of: (C) an organic peroxide; (D) conventional auxiliaries; (E) an antioxidant; (F) a filler; (G) a flame retardant; (H) a hindered amine stabilizer; (I) an anti-tree agent; (J) a methyl radical scavenger; (K) a scorch retarder; (L) a nucleating agent; and (M) carbon black; with the proviso that the total amount of the at least one additive is >0 to 70 wt% of the polyolefin composition and with the proviso that the (F) filler does not comprise any omitted filler.

9. A method of preparing a polyolefin composition, the method comprising reacting (a) a polyolefin polymer with (B) a monocyclic organosiloxane of formula (I): [ R ]¹,R²SiO_2/2]_n(I) Mixed together to produce the polyolefin composition according to any one of claims 1 to 7.

10. A process for free radically curing a polyolefin composition to produce a crosslinked polyolefin product, the polyolefin composition comprising (a) a polyolefin polymer and a crosslinking effective amount of (B) a monocyclic organosiloxane of formula (I): [ R ]¹,R²SiO_2/2]_n(I) Wherein subscript n is 3, 4, 5, or 6; each R¹Independently is (C)₂-C₄) An alkenyl group; and each R²Independently H, (C)₁-C₄) Alkyl, (C)₂-C₄) Alkenyl or phenyl, said process comprising irradiating said polyolefin composition with (C) an organic peroxide using a cure effective dose of irradiation and/or heating said polyolefin composition with (C) an organic peroxide at a cure effective temperature in a manner that reacts said (a) polyolefin polymer with said (B) mono-ring organosiloxane of formula (I), thereby producing a crosslinked polyolefin product.

11. A crosslinked polyolefin product made by the curing process of claim 10.

12. An article of manufacture comprising the shaped polyolefin composition of any of claims 1 to 8 or the crosslinked polyolefin product of claim 11.

Technical Field

The field includes polyolefin compositions, products made therefrom, methods of making and using the same, and articles comprising the same.

Background

Polyolefins are used in a variety of commercial applications. These include coatings, films, sheets and injection molded articles. The coatings are useful for wires and cables for power transmission and telecommunications applications. Films and sheets are used in both packaging and non-packaging applications. Examples are films for agriculture, food packaging, bags for clothing, bags for groceries, heavy duty bags, sheets for industry, pallets and shrink wraps and bags. LLDPE injection molded articles include pails, refrigerator containers, lids, toys.

US 4,005,254 to b.t. MacKenzie, Jr. ("MacKenzie") pertains to pressureless curing systems for chemically crosslinking ethylene-containing polymers and products formed therefrom. The curable composition comprises an ethylene-containing polymer, a curing agent, and an inorganic filler treated with tetramethyltetravinylcyclotetrasiloxane. In the preparation of the compositions, the polymer, inorganic filler, tetramethyltetravinylcyclotetrasiloxane and other additives are finely blended, for example, in Banbury (Banbury). During this compounding operation, the tetramethyltetravinylcyclotetrasiloxane is said to interact with or coat the filler, and the product is referred to as the siloxane-treated filler. If desired, the inorganic filler may be pretreated with tetramethyltetravinylcyclotetrasiloxane in a separate operation, and the siloxane-treated filler is subsequently blended with the polymer and other additives. MacKenzie's example 1 data on toluene extraction (compound%) 0.0 weight percent (wt%) tetramethyltetravinylcyclotetrasiloxane was 11.6% and examples 2 and 3 data on 0.97 wt% tetramethyltetravinylcyclotetrasiloxane by total composition weight were 9.6% and 11.8%, respectively (table I). In view of the percent extractables of comparative example 1 (relative to those of examples 2 and 3), one skilled in the art will recognize that the tetramethyltetravinylcyclotetrasiloxane of examples 2 and 3 does not contribute to the crosslinking of the ethylene-containing polymer. In contrast, tetramethyltetravinylcyclotetrasiloxane coats aluminum silicate fillers, as taught, for example, by MacKenzie.

US 8,426,519B2 to j.m. cogen et al is concerned with silicone thermoplastic polymer reactive blends and copolymer products prepared using low cost post reactor reactive mixing such as extrusion. The procedure is based on the ring-opening polymerization of cyclic siloxanes within a thermoplastic polymer matrix. In a preferred mode, the thermoplastic polymer is a polyolefin, optionally containing silane groups available for reaction with the in situ-formed silicone polymer. The resulting materials provide mixing properties that enable the range of applications to be extended beyond those achieved with thermoplastic polymers or silicones alone or physical blends thereof.

CN104277182A to Z-l Wu et al and article Cross-linking of Low Density polyethylene Using octavinyl polyhedral oligomeric silsesquioxane as a cross-linker J.Wu et al RSC Advances (RSC Advances), 2014, Vol.4, p.44030, relate to a process for preparing cross-linked low Density polyethylene using octavinyl polyhedral oligomeric silsesquioxane as a cross-linker.

Disclosure of Invention

We have recognized a problem of compromising the crosslinking and performance of previous polyolefins. The coagent may be blended with the polyolefin to obtain a polyolefin composition with increased crosslinking capability, but conventional coagents have their limitations. For example, conventional adjuvants typically have limited solubility or miscibility in polyolefin compositions. This limits the maximum loading of adjuvant in the composition. It also causes the adjuvants to improperly migrate to the surface of the composition (e.g., the surface of the pellets), limiting the shelf life of the composition. Conventional adjuvants can also cause other problems. For example, it may produce a crosslinked product that is not crosslinked to an adequate degree upon curing. Or the composition may cure too slowly for certain manufacturing operations (e.g., power cable manufacturing, injection molding, and film extrusion). Or the composition may cure prematurely (i.e., may have a tendency to scorch during cable extrusion, injection molding, and film extrusion). These problems limit the structure of conventional adjuvants used with polyolefins. Typically, conventional coagents comprise a conventional substructure group bonded to two or more olefinic crosslinking groups. Conventional substructure groups are acyclic or cyclic multivalent groups containing the main structure or ring, respectively, containing carbon atoms and optionally nitrogen and/or oxygen atoms, but no silicon atoms in the main structure or ring.

Detailed Description