Search

EP-4735510-A1 - SILOXANE MODIFIED AND SILANE MODIFIED POLYMERS VIA DIRECT INSERTION OF SILYL VINYL GROUPS INTO METAL-CARBON BONDS

EP4735510A1EP 4735510 A1EP4735510 A1EP 4735510A1EP-4735510-A1

Abstract

Processes, and related compositions, to form a siloxane modified olefin-based polymer, a silane modified olefin-based polymer, or a silane, each process, as described herein. Each process forms an Si-C bond through insertion of silyl vinyl into a metal carbon bond. The silyl vinyl double bond directly inserts into the metal-carbon bond to form a new, for example, alkyl-Si linkage.

Inventors

  • SUN, LIXIN

Assignees

  • Dow Global Technologies LLC

Dates

Publication Date
20260506
Application Date
20240628

Claims (16)

  1. olefin-based polymer. 11. The process of claim 10, wherein the olefin-based polymer is an ethylene-based polymer. 12. A composition formed by the process of any one of claims 1-11. 13. The composition of claim 12, wherein the composition further comprises an olefin- based polymer. 14. The composition of claim 13, wherein the olefin-based polymer is an ethylene-based polymer. 15. The composition of any one of claims 12-14, wherein the siloxane modified olefin- based polymer comprises at least one chain comprising at least one structure selected from T5) through T8), and where each asterisk (*) independently represents the respective remainder of the chain: T6) , where m ≥ 2; x ≥ 1; y ≥ 1; each n is independently ≥ 1; y ≥ 1; n ≥ 1; or 16. comprises from 15 wt% to 95 wt% of the siloxane modified olefin-based polymer, based on the weight of the composition. 17. The composition of any one of claims 13-16, wherein the composition comprises polymer and the olefin- the siloxane modified olefin- of any one of claims 12-18. 20. An article comprising at least one component formed from the composition of any one of claims 12-19. ABS modified olefin-based pol ch process, as described her ilyl vinyl into a metal carbon bon l-carbon bond to form a new, for example, alkyl-Si linkage. each n is defined above, and each respective unit of R 1 , R 2 , R 3 , R 4 is defined above; and each of R, R’ and R” is independently a hydrocarbyl or a heterohydrocarbyl; and M is Al; and each asterisk (*) independently represents the respective remainder of the complex; ix) each n is defined above, and each respective unit of R 1 , R 2 , R 3 , R 4 is defined above; and each of R, R’ and R” is independently a hydrocarbyl or a heterohydrocarbyl; and M is Al; and each asterisk (*) independently represents the respective remainder of the complex; or x) any combination thereof; hydrolyzing the one or more polysiloxane-M polymer complexes (C) to form the siloxane modified olefin-based polymer.
  2. 2. The process of claim 1, wherein, independently, for i, Hi, v, vi, viii, ix, each of R and R’ is independently an alkyl group or a vinyl group.
  3. 3. The process of claim 1 or claim 2, wherein, independently, for i-ix, for each respective n value, each of R 1 , R 2 , R 3 , R 4 is independently H or an alkyl group.
  4. 4. The process of any one of claims 1-3, wherein, independently, for ii, iv, v, vii, viii, ix, each R” is independently an alkyl group or a vinyl group.
  5. 5. The process of any one of claims 1-4, wherein M is Al.
  6. 6. The process of any one of claims 1-5, wherein the siloxane modified olefin-based polymer comprises the following polymeric segments al and/or a2, and b as follows: al) -O-Si(R)(R’)-CH2-CH2-(CR 1 R 2 -CR 3 R 4 ) n -CH3, where n is defined herein; and each of R, R’ is defined herein; and each of R 1 , R 2 , R 3 , R 4 is defined herein; a2) -O-Si(R”)-CH2-CH2-((CR 1 R 2 -CR 3 R 4 ) n -CH3)-, where n is defined herein; and R” is defined herein; and each of R 1 , R 2 , R 3 , R 4 is defined herein; b) -(O-SiR”’(R””))m-, where m > 1, and for each value of m, each of R”’and R”” is independently an H or a hydrocarbyl. 45 SUBSTITUTE SHEET (RULE 26)
  7. 7. The process of claim 6, wherein, for segment Z>, each of R’” and R”” is independently an H or an alkyl group.
  8. 8. The process of any one of claims 1-7, wherein the process is a solution process.
  9. 9. The process of any one of claims 1-8, wherein the process further comprises isolating “the composition comprising the siloxane modified olefin-based polymer.”
  10. 10. The process of any one of claims 1-9, wherein the composition further comprises an olefin-based polymer.
  11. 11. The process of claim 10, wherein the olefin-based polymer is an ethylene-based polymer.
  12. 12. A composition formed by the process of any one of claims 1-11.
  13. 13. The composition of claim 12, wherein the composition further comprises an olefin- based polymer.
  14. 14. The composition of claim 13, wherein the olefin-based polymer is an ethylene-based polymer.
  15. 15. The composition of any one of claims 12-14, wherein the siloxane modified olefin- based polymer comprises at least one chain comprising at least one structure selected from T5) through T8), and where each asterisk (*) independently represents the respective remainder of the chain: T8) any combination thereof.
  16. 16. The composition of any one of claims 12-15, wherein the composition comprises from 15 wt% to 95 wt% of the siloxane modified olefin-based polymer, based on the weight of the composition. SUBSTITUTE SHEET (RULE 26)

Description

SILOXANE MODIFIED AND SILANE MODIFIED POLYMERS VIA DIRECT INSERTION OF SILYL VINYL GROUPS INTO METAL-CARBON BONDS BACKGROUND OF THE INVENTION Silicone/polyolefin (Si-POE) blends and grafted copolymers are utilized widely across many application areas, where the silicon character imparts modified surface properties (reduced coefficient of friction, or COF) or moisture cure functionality to the material. Silicones are blended into a variety of ethylene-based polymers to impart improved haptics. Silicone-modified low density polyethylene (LDPE) materials, formed by direct copolymerization of ethylene with silicon monomers, in a high pressure process, are used in wire and cable applications. Silicone functionality is also added to linear low density polyethylene (LLDPE) materials through reactive extrusion methods, using peroxide grafting of silane monomers, such as, for example, vinyltriethoxysilane. Although many examples of these physical blends and reactive extrusion grafting technologies are practiced today, these materials suffer from limitations in ultimate properties related to the blend nature of the materials. A true Si-POE hybrid material is hypothesized to bring several advantages, including enhanced surface modification, improved adhesion, alternative crosslinking mechanisms, as well as potential benefits from imparting controllable crystallinity to silicone products. In particular, there is a need for an efficient and economical process to make Si modified polymers, including random copolymers and block copolymers, with an olefin- based polymer and a silicone source. International Publication WO 2012/103080 discloses a process for preparing a polyolefin-polysiloxane block copolymer, the process comprising contacting under coupling effective conditions, a polyolefinyl-aluminum compound with an acyclic polysiloxane or cyclic siloxane monomer, in such a way, so as to give a polyolefin-polysiloxane block copolymer. Such a block copolymer comprises a polyolefin block directly covalently bonded to a polysiloxane block, wherein the polyolefin block comprises the polyolefinyl portion of the polyolefinyl-aluminum compound and the polysiloxane block comprises at least a portion of the acyclic polysiloxane. See claim 1. The coupling reaction involves the chain scission of the polysiloxane or cyclic polysiloxane, and is a relatively slow reaction. U.S. Publication 2022/0073658 discloses telechelic polyolefins of the formula (I), A1L1L2 A2, and processes for preparing the same. This reference discloses a process for preparing a telechelic polyolefin, the process comprising: 1) combining starting materials comprising (A) a monomer component, (B) a chain transfer agent component, and (C) a catalyst component comprising a procatalyst, to form a solution, and polymerizing from greater than 10 mol% to less than, or equal to, 99 mol% of the (A) monomer component in the solution; 2) heating the solution; and 3) recovering a product comprising the telechelic polyolefin. The (B) chain transfer agent component comprises an organoaluminum compound of the formula Al(CH2CH(Y2)A2)3, where Y2 at each occurrence, independently, is hydrogen or a C1 to C30 hydrocarbyl group; and A2 at each occurrence, independently, is a hydrocarbyl group comprising a hindered double bond. See claim 12. The telechelic polyolefins can be chemically modified, such as by grafting (for example by use of maleic anhydride (MAH), silanes, glycidyl methacrylate, or other grafting agent), halogenation, amination, sulfonation, or other chemical modification. See paragraph [0497]. J. J. Eisch et al., Stereospecific Reductive Alkylation of Acetylenes by Successive Hydralumination and Carbodemetalation, J. Org. Chem., 1976, 41, 2214 -2215, discloses the stereospecific cis hydralumination of acetylenes and the alkylation of the aluminate complexes of the resulting vinylalanes. See page 2214. The direct hydralumination of mono- or disubstituted acetylenes is disclosed as providing a convenient and direct route to stereoregular di- and trisubstituted olefins, respectively. Drawbacks lie in the following features: (1) the slow rate with which certain disubstituted acetylenes hydraluminate; (2) the regioisomeric mixtures resulting when R does not equal R’ and (3) the contamination of RHC=CR’Al(i-C4H9)2 with small amounts of R—C=C—A1R2' formed from the metalation of terminal alkynes by aluminum alkyls. Trimethylsilyl derivatives of monosubstituted acetylenes can also be hyraluminated. See page 2214. P. R. Jones et al., Silaethylene Intermediates from alpha-Lithiosilanes.2. Reactions with Chlorosilanes and 1,3-Butadiene, 1977, J. Am. Chem. Soc., 99(26), 8447-8451, discloses the formation of silaethylene intermediates by the elimination of lithium chloride from alpha-lithiochlorosilanes, under appropriate experimental conditions. The reaction tert- butyllithium with vinyldimethylchlorosilane at low temperatures, in hydrocarbon solvents, is disclosed as resulting