Polyolefin-polydiorganosiloxane block copolymer and method for the synthesis thereof

Patent metadata

Field	Value
Publication number	US-12037462-B2
Application number	US-201916975736-A
Country	US
Kind code	B2
Filing date	Feb 22, 2019
Priority date	Mar 19, 2018
Publication date	Jul 16, 2024
Grant date	Jul 16, 2024

Abstract

A polyolefin-polydiorganosiloxane block copolymer may be prepared by Piers-Rubinsztajn reaction.

First claim

The invention claimed is:

1. A method for preparing a polyolefin-polydiorganosiloxane block comprising:
optionally pre-1) preparing a silyl terminated polyolefin having 1 to 2 terminal silyl groups per molecule, where the terminal silyl group has formula

where each R 1 is an independently selected monovalent hydrocarbyl group and subscript a is 1 or 2,
by a process comprising
i) combining starting materials comprising
a polymeryl-metal,
optionally b) a nitrogen containing heterocycle, and
c) a halosilane, and
optionally d) a solvent; thereby forming a product comprising the silyl-terminated polyolefin;

optionally ii) washing the product with water, thereby removing unwanted materials comprising starting material b); and
optionally iii) recovering the silyl terminated polyolefin, wherein A) the silyl terminated polyolefin, has unit formula (A 3 ):

where subscript f is 0 to 1, and subscripts t and u have relative values such that 0<t≤1, 0≤u≤1, subscript g is 1 or more, and each R 7 is independently a monovalent hydrocarbyl group of 2 to 20 carbon atoms; and
1) combining starting materials comprising:
A) the silyl terminated polyolefin,
B) a substantially linear polydiorganosiloxane having 1 to 2 hydrolyzable substituents capable of undergoing reaction with a silicon bonded hydrogen atom; and
C) a Lewis Acid catalyst;
optionally D) a solvent; and

optionally E) an alkoxysilyl-functional organosilicon compound having at least one silicon bonded hydrogen atom.

2. The method of claim 1 , where B) the polydiorganosiloxane has formula (B1):

where each R 2 is independently a hydrolyzable substituent, each R 3 is independently a hydrogen atom or a monovalent organic group free of hydrolyzable functionality, R 4 is selected from R 2 and R 3 , and subscript b is 0 or a positive number.

3. The method of claim 2 , where each R 2 is a hydroxyl group, each R 3 is an alkyl or an aryl group, and subscript b is 2 to 2,000.

4. The method of claim 1 , where C) the Lewis Acid catalyst is selected from the group consisting of (C 5 F 4 )(C 6 F 5 ) 2 B; (C 5 F 4 ) 3 B; (C 6 F 5 )BF 2 ;
BF(C 6 F 5 ) 2 ; B(C 6 F 5 ) 3 ; BCl 2 (C 6 F 5 ); BCl(C 6 F 5 ) 2 ; B(C 6 H 5 )(C 6 F 5 ) 2 ;
B(C 6 H 5 ) 2 (C 6 F 5 ); [C 6 H 4 (mCF 3 )] 3 B; [C 6 H 4 (pOCF 3 )] 3 B; (C 6 F 5 )B(OH) 2 ;
(C 6 F 5 ) 2 BOH; (C 6 F 5 ) 2 BH; (C 6 F 5 )BH 2 ; (C 7 H 11 )B(C 6 F 5 ) 2 ; (C 8 H 14 )B(C 6 F 5 );
(C 6 F 5 ) 2 B(OC 2 H 5 ); and (C 6 F 5 ) 2 B—CH 2 CH 2 Si(CH 3 ).

5. The method of claim 4 , where C) is tris(pentafluorophenyl)borane.

6. The method of claim 1 , where any one of conditions A) to D) is met, where:
Condition A) is that the silyl terminated polyolefin has one terminal silyl group per molecule,
Condition B) is that the silyl terminated polyolefin has two terminal silyl groups per molecule,
Condition C) is that the polyorganosiloxane has one hydrolyzable substituent per molecule, and,
Condition D) is that the polyorganosiloxane has two hydrolyzable substituents per molecule.

7. The method of claim 6 , where one of conditions E) to I) is met, where
Condition E) means both condition A) and condition C),
Condition F) means both condition A) and condition D),
Condition G) means both condition B) and condition C),
Condition H) means all three of A), B), and D), and
Condition I) means all three of B), C), and D).

8. The method of claim 1 , where the copolymer has unit formula

where each R 1 is an independently selected monovalent hydrocarbyl group, each R 3 is independently selected from a hydrogen atom and a monovalent organic group free of hydrolyzable functionality, each R 5 is an independently selected hydrogen terminated polyolefin, each R 6 is an independently selected divalent polyolefin, each R 10 is independently selected from R 3 and an alkoxysilyl functional hydrocarbylene containing group each subscript a is independently 1 or 2, each subscript b is independently 0 or a positive number; subscript w is 0 to 2, subscript x is 0 or a positive number, subscript y is 0 or a positive number, subscript z is 0 to 2, a quantity (w+y)≥1, a quantity (x+z) ≥1, with the proviso that when subscript w is 0, subscript z is >0 and when subscript z=0, subscript w>0.

9. The method of claim 8 , where x=0, y=0, w=1 and z=1, and the copolymer has formula:

10. The method of claim 8 , where w=2, z=0, x≥1, and y≥1, and the copolymer has formula:

where subscript c≥0.

11. The method of claim 8 , where subscript w=2, subscript x=1, subscript y=0 and subscript z=0, and the copolymer formula:

12. The method of claim 8 , where z=2, w=0, x≥1, and y≥1, and the copolymer has formula:

where subscript d≥0.

13. The method of claim 8 , where subscript w=0, subscript x=1, subscript y=0 and subscript z=2, and the copolymer has formula:

14. The method of claim 8 , where the copolymer has at least one instance of R 10 representing an alkoxysilyl functional hydrocarbylene containing group with a formula selected from:

one or both of

where each R L is an oxygen atom, each R D is independently a divalent hydrocarbyl group of 2 to 18 carbon atoms; each subscript aa is independently 0, 1, or 2; subscript D is 0 to 20; E is 0 or more, subscript F is 1 or more, and subscript G is 1 or more and 4≤(E+F+G)≤50.

15. The method of claim 1 , further comprising, forming A) the polyolefin having the silyl terminal group before step 1) by a method comprising:
a) combining starting materials comprising i) an olefin monomer, ii) a catalyst, and iii) a chain shuttling agent to prepare a polymeryl-metal;
b) combining iii) the polymeryl-metal and iv) a halosilane;
where steps a) and b) are performed in a solution in a continuous reactor, thereby forming a mixture comprising A) the polyolefin having the silyl terminal group of formula (A1), unreacted i) olefin monomer, and v) solvent; and
c) using the mixture to deliver starting material A) in step 1).

16. The method of claim 1 , where C) the Lewis Acid catalyst contains boron.

17. A method for preparing a polyolefin-polydiorganosiloxane block copolymer comprising:
optionally pre-1) preparing a silyl terminated polyolefin having 1 to 2 terminal silyl groups per molecule, where the terminal silyl group has formula

where each R 1 is an independently selected monovalent h

Assignees

• Dow Silicones Corp
• Dow Global Technologies Llc

Inventors

• Swier Steven
• Hustad Phillip
• Devore David
• Kean Zachary
• Spencer Liam
• Reddel Jordan
• Neilson Bethany
• Horstman John Bernard
• Kawamoto Ken

Classifications

• C08G77/12

  containing silicon bound to hydrogen · CPC title

• C08G77/08

  characterised by the catalysts used · CPC title

• C08F2810/40

  taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains · CPC title

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F110/02

  Ethene · CPC title