High viscosity polyoxyalkylene glycol block copolymers and method of making the same

• US 4,481,367 A
• Filed: 11/22/1983
• Issued: 11/06/1984
• Est. Priority Date: 12/26/1979
• Status: Expired due to Fees

• Current Assignee: Union Carbide Corporation (Dow, Inc.)
• Original Assignee: Union Carbide Corporation (Dow, Inc.)
• Inventors: Knopf, Robert J.
• Primary Examiner(s): Helfin, Bernard
• Application Number:
  US06/553,880
• Time in Patent Office: 350 Days
• Field of Search: 560/158, 560/26, 560/115
• US Class Current: 560/26
• CPC Class Codes: C08G 18/4837 and other oxyalkylene units
• CPC Class Codes: C10M 107/44 Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C10M 2217/042 between the nitrogen-containing monomer and an aldehyde or ketone
• CPC Class Codes: C10M 2217/043 Mannich bases
• CPC Class Codes: C10N 2040/06 Instruments or other precision apparatus, e.g. damping fluids
• CPC Class Codes: C10N 2040/08 Hydraulic fluids, e.g. brake-fluids

Abstract

A high molecular weight, high viscosity liquid, water soluble polyoxyalkylene block copolymer suitable as a functional fluid is provided having the formula ##STR1## wherein Q is the organic residue from an organic diisocyanate; x is an integer in the range of about 1 to 10; R¹ and R² are hydrogen, methyl, ethyl, or mixtures thereof with the proviso that the overall content of species wherein R¹ and R² are hydrogen must be at least 50 percent by weight; R³ and R⁴ are organic residues resulting from the removal of terminal hydrogen atoms from difunctional polyols; y and z are integers representing the polyether blocks in said copolymer and the sum of which must be from about 1.05 to 2.0 times the value of x; and n, m, r, and s are integers wherein n=m and r=s and the sums n+m and r+s are each in the range of 8 to 250.

Claims

1. A high molecular weight, high viscosity, liquid, water-soluble, random polyoxyalkylene glycol block copolymer having the formula:

##STR3## wherein Q is the organic residue from an aliphatic or aromatic diisocyanate selected from the group consisting of 4,4'"'"'-methylenebis (4-phenylisocyanate), tolylene diisocyanate, phenylene diisocyanate, 4,4'"'"'-methylenebis (cyclohexylisocyanate) and trimethylhexamethylene diisocyanate, or prepolymers derived therefrom having a molecular weight up to about 1500 and essentially free of monofunctional species capable of cross-linking;

x is an integer representing the average number of polyurethane blocks in said copolymer and is about 1 to about 10;

R¹ and R², are mixtures of hydrogen, methyl, or ethyl, with the proviso that the overall content of species wherein R¹ and R² are hydrogen must be at least 60 percent by weight;

R³ and R⁴, which can be the same or different, are organic residues resulting from the removal of terminal hydrogen atoms from difunctional polyols selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, bisphenol A and mixtures thereof;

y and z represent the average number of polyether blocks in said copolymer with the proviso that the sum of y and z must be from about 1.15 to 1.50 times the value of x;

n, m, r, and s, which can be the same or different, are integers wherein n=m and r=s and the sums of n+m and r+s, which can be the same or different, are each in the range wherein each of the polyether blocks in said copolymer has a molecular weight within the range of about 1500 to about 6000;

wherein each of said polyether blocks is the residue of a liquid, watersoluble diol of molecular weight from about 1500 to about 6,000 and having a random molecular structure comprising a random copolymer of mixed alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide wherein about 65 to 85 percent by weight of the total weight of the diol is ethylene oxide, and wherein said block copolymer is water-soluble and suitable for use as a functional fluid in an aqueous medium.

2. The block copolymer of claim 1 wherein R¹ and R² are mixtures of hydrogen and methyl.

3. The block copolymer of claim 1 wherein Q is an organic residue from an aromatic diisocyanate.

4. The block copolymer of claim 1 wherein R³ and R⁴ are alkylene, arylene, alkarylene, aralkylene radicals or mixtures thereof.

5. The block copolymer of claim 2 wherein Q is an organic residue from an aromatic diisocyanate.

6. The block copolymer of claim 5 wherein R³ and R⁴ are alkylene radicals.

7. The block copolymer of claim 5 wherein R₃ and R₄ are alkarylene radicals.

8. The block copolymer of claim 6 wherein R³ and R⁴ are short chain alkylene radicals of 2 to 6 carbon atoms.

9. A method of preparing the water-soluble, high molecular weight polyoxyalkylene glycol block copolymers of claim 1 which comprises reacting with vigorous agitation and for the time necessary to prepare a hydroxyl-terminated block copolymer a stoichiometric excess of a polyoxyalkylene diol containing at least 60 percent by weight of oxyethylene groups with an organic diisocyanate having molecular weight up to about 1500 wherein the total equivalent of hydroxyl functionality of said diol exceeds the equivalents of isocyanate functionality by a factor of from about 1.15 to 1.50:

1.

10. The method of claim 9 in which said polyoxyalkylene diol has the formula:

space="preserve" listing-type="equation">R--O--CH.sub.2 CHR.sup.1 O).sub.n H].sub.2

wherein R is an organic residue resulting from the removal of terminal hydrogen atoms from diols and are alkylene, arylene, alkarylene, aralkylene, cycloalkylene, heterocycloarylene radicals or mixtures thereof, R¹ is hydrogen, methyl, ethyl or mixtures thereof, and n is an integer in the range of 4 to about 125.

11. The method of claim 9 in which said polyoxyalkylene diol is essentially free of alkalinity.

12. The method of claim 9 in which said polyoxyalkylene diol is essentially free of water.

13. The method of claim 11 in which said polyoxyalkylene diol is essentially free of water.

14. The method of claim 9 in which said organic diisocyanate is an aromatic diisocyanate.

15. The method of claim 11 in which said organic diisocyanate is an aromatic diisocyanate.

16. The method of claim 14 wherein R³ and R⁴ are short chain alkylene radicals of 2 to 6 carbon atoms.