Initiator mixture, composition, the use thereof, polyol polymer preparation method, and polyol polymer obtained by the method

Patent metadata

Field	Value
Publication number	US-10882941-B2
Application number	US-201615760261-A
Country	US
Kind code	B2
Filing date	Sep 16, 2016
Priority date	Sep 18, 2015
Publication date	Jan 5, 2021
Grant date	Jan 5, 2021

Abstract

The present invention relates to an initiator mixture, a composition, use thereof, a process of preparing polymer polyol, and a polymer polyol obtained by the process. The initiator mixture comprises: a first peroxide of formula (I) R1—O—O—R2, wherein R1 and R2 are independent an alkyl group or an alkanoyl group comprising 1 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 4 to 20 carbon atoms; and a second peroxide of formula (II) R3—O—O—R4—O—O—R5, wherein R3 and R5 are independently an alkyl group comprising 1 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 5 to 10 carbon atoms, and R4 is a cycloalkylene group comprising 3 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and more preferably 5 to 10 carbon atoms.

First claim

The invention claimed is:

1. An initiator mixture comprising a first peroxide of formula (I) and a second peroxide of formula (II):
R 1 —O—O—R 2 ,  (I)

wherein R 1 and R 2 are independently an alkyl group or an alkanoyl group comprising 1 to 30 carbon atoms, and
R 3 —O—O—R 4 —O—O—R 5 ,  (II)

wherein R 3 and R 5 are independently an alkyl group comprising 1 to 30 carbon atoms, and R 4 is a cycloalkylene group comprising 3 to 30 carbon atoms,
wherein the initiator mixture comprises 70 to 90 wt % of the first peroxide of formula (I) and 10 to 30 wt % of the second peroxide of formula (II), based on the total weight of the initiator mixture.

2. The initiator mixture according to claim 1 , wherein at least one of R 1 and R 2 is an alkanoyl group.

3. The initiator mixture according to claim 1 , wherein at least one of R 1 and R 2 is a t-amyl group.

4. The initiator mixture according to claim 1 , wherein at least one of R 1 is an alkanoyl group and R 2 is a t-amyl group.

5. The initiator mixture according to claim 1 , wherein R 1 is selected from the group consisting of formacyl, acetyl, propionyl, butyryl, valeryl, pivaloyl, caproyl, enanthyl, capryloyl, 2-ethylcaproyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, and eicosanoyl,
wherein R 2 , R 3 and R 5 are independently a tert-alkyl group comprising 4 to 30 carbon atoms, and
wherein R 4 is a 1,1-cycloalkylene group.

6. The initiator mixture according to claim 1 , wherein the first peroxide of formula (I) comprises t-amyl peroxy-2-ethylhexanoate, tertio-amyl peroxypivalate, tertio-butyl peroxy-2-ethylhexanoate, or tertio-amyl peroxyneodecanoate, and/or the second peroxide of formula (II) comprises 1,1-di(t-amylperoxy)-cyclohexane, 1,1-di(tertio-butylperoxy)-3,3,5-trimethylcyclohexane, or 1,1-di(tertio-butylperoxy)-cyclohexane.

7. An initiator mixture comprising a first peroxide of formula (I), a second peroxide of formula (II), and a third peroxide of formula (III):
R 1 —O—O—R 2 ,  (I)

wherein R 1 and R 2 are independently an alkyl group or an alkanoyl group comprising 1 to 30 carbon atoms, and
R 3 —O—O—R 4 —O—O—R 5 ,  (II)

wherein R 3 and R 5 are independently an alkyl group comprising 1 to 30 carbon atoms, and R 4 is a cycloalkylene group comprising 3 to 30 carbon atoms,
R 6 —O—O—C(═O)—O—R 7 ,  (III)

wherein R 6 and R 7 are independently an alkyl group comprising 1 to 30 carbon atoms.

8. The initiator mixture according to claim 7 , wherein R 6 is a tert-alkyl group comprising 4 to 30 carbon atoms, and wherein R 7 is selected from the group consisting of methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, cetyl, octadecyl, and eicosyl.

9. The initiator mixture according to claim 7 , wherein the third peroxide of formula (III) comprises OO-t-amyl-O-(2-ethylhexyl)-monoperoxycarbonate or OO-t-butyl-O-(2-ethylhexyl)-monoperoxycarbonate.

10. The initiator mixture according to claim 7 , wherein the initiator mixture comprises 50 to 90 wt % of the first peroxide of formula (I), 10 to 50 wt % of the second peroxide of formula (II), and greater than 0 and equal to or less than 30 wt % of the third peroxide of formula (III), based on the total weight of the initiator mixture.

11. A composition comprising the initiator mixture of claim 1 and a thiol-based chain transfer agent.

12. The composition of claim 11 , wherein the thiol-based chain transfer agent comprises a chain transfer agent of formula (IV):
SH—R 8 —C(═O)—O—R 9 ,  (IV)

wherein R 8 is an alkylene group comprising 1 to 30 carbon atoms and R 9 is an alkyl group comprising 1 to 30 carbon atoms.

13. The composition according to claim 12 , wherein R 8 is selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene, and wherein R 9 is selected from the group consisting of methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, cetyl, octadecyl, and eicosyl.

14. The composition according to claim 12 , wherein the chain transfer agent of formula (IV) is 2-ethylhexyl thioglycolate.

15. The composition according to claim 11 , wherein the composition comprises 30 to 70 wt % of the initiator mixture and 30 to 70 wt % of the thiol-based chain transfer agent, based on the total weight of the composition.

16. A process of preparing a polymer polyol comprising polymerizing a reaction mixture comprising a polyol, an ethylenically unsaturated monomer, and optionally a macromonomer, in the presence of the initiator mixture of claim 1 .

17. The process according to claim 16 , wherein the amount of the initiator mixture is 0.1 to 0.8 wt % based on the weight of the reaction mixture.

Assignees

• Arkema France

Inventors

• Ji Bin
• Zou Shenglin
• Dai Peng

Classifications

• C08F4/38

  Mixtures of peroxy-compounds · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F212/08

  Styrene · CPC title

• C08F2/44 Primary

  Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers · CPC title

• C08F283/06 Primary

  on to polyethers, polyoxymethylenes or polyacetals {(C08F283/004 takes precedence)} · CPC title