Alkoxylates of S-vinylthioalkanols

Patent metadata

Field	Value
Publication number	US-10323107-B2
Application number	US-201415032916-A
Country	US
Kind code	B2
Filing date	Oct 30, 2014
Priority date	Oct 30, 2013
Publication date	Jun 18, 2019
Grant date	Jun 18, 2019

Abstract

Unsaturated compounds of formula (I):

wherein: R 1 , R 2 , and R 3 are each independently H or CH 3 ; R 4 is a linear or branched C 1 -C 30 -alkylene; R 5 and R 6 are each independently H, C 1 -C 20 -alkyl, C 3 -C 15 -cycloalkyl, aryl, —CH 2 —O—C 1 -C 20 -alkyl, or —CH 2 —O—C 2 -C 20 -alkenyl, where R 5 and R 6 may together form a C 3 -C 6 -alkylene; R 7 is independently H,C 1 -C 4 -alkyl, or

where R 8 is C 1 -C 22 -alkyl or C 2 -C 22 -alkenyl; and n is an integer from 2 to 200. Mixtures and polymers including the unsaturated compounds of formula (I). A method for preparing polymers by free-radical polymerization of monomers including the unsaturated compounds of formula (I). A process for preparing polymers including polymer-analogous reactions. And polymers including compounds (I) as cement additives, grinding aids, hydraulic binder additives, concrete plasticizers, reactive plasticizers for preparing plastics, rubber, or latex, associative thickeners and antioxidants, or for preparing polyether siloxanes.

First claim

The invention claimed is:

1. An unsaturated compound of formula (I)

wherein
R 1 , R 2 , and R 3 are the same or different and are each independently H or CH 3 ,
R 4 is a linear or branched C 1 -C 30 -alkylene,
R 5 and R 6 are the same or different and are each independently selected from the group consisting of H, C 1 -C 20 -alkyl, C 3 -C 15 -cycloalkyl, aryl, —CH 2 —O—CH 1 -C 20 -alkyl, and CH 2 —O—C 2 -C 20 -alkenyl, where R 5 and R 6 may together form a C 3 -C 6 -alkylene,
R 7 is the same or different and is independently H, C 1 -C 4 -alkyl, or

R 8 is C 1 -C 22 -alkyl or C 2 -C 22 -alkenyl, and
n is an integer from 21 to 200.

2. The unsaturated compound according to claim 1 , wherein, in formula (I):
R 4 is a C 2 -C 4 -alkylene group,
R 5 and R 6 are the same or different and are each independently selected from the group consisting of H, —CH 3 , —CH 2 —CH 3 , —C 3 -C 11 -alkyl, C 12 -C 22 -alkyl, phenyl, —CH 2 —O—C 1 -C 10 -alkyl, and CH 2 —O—C 2 -C 10 -alkenyl,
R 7 is or C 1 -C 4 -alkyl, and
n is 21 to 140.

3. The unsaturated compound according to claim 1 , wherein the compound of formula (I) is an unsaturated compound of formula (Ia):

wherein:
R 3 is 1or methyl,
R 4 is a linear or branched C 2 -C 10 -alkylene group,
R 5 and R 6 are each independently H, methyl, or ethyl, with the proviso that the sum total of carbon atoms in the R 5 and R 6 residues per alkoxy group is in each case 0 to 2, and
n is 21 to 160.

4. The unsaturated compound according to claim 1 , wherein the compound of formula (I) is an unsaturated compound of formula (Ib):

wherein n is 21 to 140.

5. The unsaturated compound according to claim 4 , wherein, in formula (Ib), n is 21 to 30.

6. A mixture comprising the unsaturated compounds of formula (I) according to claim 1 .

7. A polymer comprising the unsaturated compounds of formula (I) according to claim 1 as monomers.

8. A polymer comprising the unsaturated compounds of formula (Ia) according to claim 3 as monomers.

9. A polymer comprising the unsaturated compounds of formula (Ib) according to claim 4 as monomers.

10. The polymer according to claim 7 , wherein at least one further monomer different from the unsaturated compounds of formula (I)is present in the polymer.

11. The polymer according to claim 10 , wherein the at least one further monomer is at least one monoethylenically unsaturated monomer.

12. The polymer according to claim 11 , wherein the monoethylenically unsaturated monomers are monomers comprising acid groups, where the acid groups may also be completely or partly neutralized.

13. The polymer according to claim 12 , wherein the acid groups are selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and phosphonic acid groups.

14. The polymer according to claim 13 , wherein the polymer comprises at least one monomer having carboxylic acid groups selected from the group consisting of acrylic acid, methacrylic acid, (meth)acrylic anhydride, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylene malonic acid and salts thereof.

15. The polymer according to claim 13 , wherein the polymer comprises at least one monomer having phosphoric acid groups or phosphonic acid groups selected from the group consisting of vinylphosphonic acid, an ester of hydroxyethyl (meth)acrylate with (poly)phosphoric acid, an ester of hydroxypropyl (meth)acrylate with (poly)phosphoric acid, an ester of hvdroxybutyl (meth)acrylate with (poly)phosphoric acid, monovinyl phosphate, allylphosphonic acid, monoallyl phosphate, 3-butenylphosphonic acid, mono-3-butenyl phosphate, mono(4-vinyloxybutyl) phosphate, mono(2-hydroxy-3-vinyloxypropyl) phosphate, mono(1-phosphonoxymethyl-2-vinyloxyethyl)phosphate, mono(3-allyloxy-2-hydroxypropyl) phosphate, mono [2-(allyloxy-1-phosphonoxymethylethyl)]phosphate, 2-hydroxy-4-vinyloxymethyl-1,3,2-dioxaphosphole, 2-hydroxy-4-allyloxymethyl-1,3,2-dioxaphosphole and salts thereof.

16. The polymer according to claim 13 , wherein the polymer comprises at least one monomer having sulfonic acid groups selected from the group consisting of vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamidomethyldodecylsulfonic acid, 2-(meth)acryloxyethanesulfonic acid, 3-(meth)acryloxypropanesulfonic acid, allyloxybenzenesulfonic acid, vinylbenzenesulfonic acid, vinyltoluenesulfonic acid, allylsulfonic acid, methallylsulfonic acid and salts thereof.

17. The polymer according to claim 11 , wherein the at least one monoethylenically unsaturated monomer present is at least one selected from the group consisting of styrene, butadiene, methyl methacrylate, (meth)acrylate, ethyl acrylate, dibutyl maleate, methyl alpha-cyanoacrylate, acrylonitrile, acrylic acid, methacrylic acid, maleic acid (anhydride), itaconic acid, vinvlphosphonic acid, N-vinylpyrrolidone, N,N-dimethyl-N,N-diallylammonium chloride, acrylamide, vinylimidazole, vinyl alcohol, vinyl acetate, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, (iso)prenyl alkoxylate, (meth)allyl alkoxylate, and hydroxybutyl vinyl ether alkoxylate.

18. The polymer according to claim 17 , wherein the at least one monoethylenically unsaturated monomer present is at least one selected from the group consisting of acrylic acid, methacrylic acid, (meth)acrylate, maleic acid (anhydride), (iso)prenyl alkoxylate, (meth)allyl alkoxylate, and hydroxybutyl vinyl ether alkoxylate.

19. The polymer according to claim 18 , wherein the polymer consists of the unsaturated compounds of formula (I) and at least one monoethylenically unsaturated monomer selected from the group consisting of acid, methacrylic acid, (meth) acrylate, maleic acid (anhydride, (iso)prenyl alkoxylate, (meth)allyl alkoxylate, and hydroxybutyl vinyl ether alkoxylate as monomers.

20. The polymer according to claim 17 , wherein the polymer consists of the unsaturated compounds of formula (I) and at least one monoethylenically unsaturated monomer selected from the group consisting of acrylic acid, methacrylic acid, and maleic acid (anhydride) as monomers.

21. The polymer according to claim 20 , wherein the polymer consists of the unsaturated compounds of formula (I), acrylic acid, methacrylic acid, and maleic acid (anhydride) as monomers.

22. The polymer according to claim 7 , wherein from 5 to 99.9% by weight of the unsaturated compounds of formula (I) are present in the polymer, based on the total amount of monomers.

23. The polymer according to claim 11 , comprising, in each case based on a total amount of monomers:
from 5 to 99.9% by weight of the unsaturated compounds of formula (I); and
from 95 to 0.1% by weight of the at least one monoethylenically unsaturated monomer.

24. The polymer according to claim 18 , comprising, in each case based on a total amount of monomers:
from 5 to 99.9% by weight of the unsaturated compounds o

Assignees

• Basf Se

Inventors

• Maitro-Vogel Sophie
• Ernst Martin
• Schade Christian
• Tuzina Pavel
• Tran-Thien Hoang Trang
• Reis-Walther Eva-Maria
• Shabelina Natalia
• Hillesheim Nina Susanne
• Scholz Christian

Classifications

• C07C323/14

  the carbon skeleton being acyclic and unsaturated · CPC title

• C04B24/165

  containing polyether side chains · CPC title

• C08F228/02

  by a bond to sulfur · CPC title

• C08F28/04 Primary

  Thioethers · CPC title

• C04B2103/52

  Grinding aids; Additives added during grinding · CPC title