Process for producing shaped polyurethane hydrogel articles

• US 4,209,605 A
• Filed: 10/19/1978
• Issued: 06/24/1980
• Est. Priority Date: 10/19/1978
• Status: Expired due to Term

• Current Assignee: Union Carbide Corporation (Dow, Inc.)
• Original Assignee: Union Carbide Corporation (Dow, Inc.)
• Inventors: Hoy, Kenneth L., Knopf, Robert J., Jones, Allen P.
• Primary Examiner(s): Cockeram, H. S.
• Application Number:
  US05/952,730
• Time in Patent Office: 614 Days
• Field of Search: 528/904, 528/44, 528/77, 528/58, 528/54, 528/59, 528/61, 528/46, 521/905
• US Class Current: 528/54
• CPC Class Codes: C08G 18/0895 Manufacture of polymers by continuous processes C08G18/0838 takes precedence
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/307 Atmospheric humidity
• CPC Class Codes: C08G 18/4833 Polyethers containing oxyethylene units
• CPC Class Codes: C08G 2210/00 Compositions for preparing hydrogels
• CPC Class Codes: Y10S 528/904 Isocyanate polymer having stated hydrophilic or hydrophobic property

Abstract

Continuous process for producing hydrogels by charging preselected feeds containing poly(oxyalkylene) polyols, organic diisocyanate and catalyst to a reaction zone followed by crosslinking by exposure to atmospheric humidity. Solvents are not used and the hydrogels are shaped in desired configuration as they exit the extruder.

Claims

1. A continuous, solventless process for producing water swellable, lightly crosslinked, hydrogel polymer comprising the steps of:

(a) preparing a plurality of at least two feed compositions consisting of poly(oxyalkylene)polyol, organic polyisocyanate and catalyst, with the provisos that the catalyst is not in the same composition in which both of the poly(oxyalkylene)polyol and organic polyisocyanate are present and that the feed compositions are devoid of organic solvents,

(b) feeding metered amounts of each of the feed compositions continuously through at least one in-line mixer to achieve uniform, homogeneous mixture,

(c) continuously feeding the said uniform, homogeneous mixture into the inlet end and through tubular reactor means and producing an isocyanato terminated prepolymer of high specific viscosity,

(d) extruding the said isocyanato terminated prepolymer through appropriate dies at the exit of said tubular reactor to form a shaped article,

(e) lightly crosslinking said shaped article as it exits said tubular reactor with an equivalent amount of a crosslinking agent of the group water or organic polyamine; and

(f) recovering the shaped polyurethane hydrogel polymer article produced;

wherein said isocyanato terminated prepolymer comprises the reaction product of;

(i) a poly(oxyalkylene) polyol having an average molecular weight up to about 25,000, wherein the alkyleneoxy group contains from 2 to 4 carbon atoms, and

(ii) an organic polyisocyanate, and, further, wherein said poly(alkyleneoxy) polyol is a mixture of a major amount of poly(ethyleneoxy)diol having an average molecular weight of from about 4,000 to about 25,000 and a minor amount of poly(alkyleneoxy) triol or poly(alkyleneoxy) tetrol or aliphatic polyhydroxyl compound of the formula C_n H_2n+2-m (OH)_m wherein n has a value of 3 to 6 and m has a value of 3 to 4, or mixtures thereof, said triol or tetrol having an average molecular weight of from about 92 to 5,000, wherein the mole ratio of diol to higher polyol in said mixture is from about 6;

1 to 40;

1; and

wherein the equivalents ratio of isocyanato groups to hydroxyl groups is from about 1.05;

1 to about 2;

1; and

wherein said polyamine is a primary or secondary diamine or triamine and wherein the equivalents of reactive crosslinking groups in said crosslinking agent used is equivalent to the number of equivalents of isocyanato groups present in said prepolymer.

2. A process as claimed in claim 1, wherein the temperature in the reaction zone of said tubular reactor means is from about 110°

C. to about 175°

C.

3. A process as claimed in claim 1, wherein the equivalents ratio of isocyanato groups to hydroxyl groups is from 1.15:

1 to 1.5;

1.

4. A process as claimed in claim 1, wherein said plurality of feed compositions consists of a first feed composition containing said poly(oxyalkylene) diol, said poly(oxyalkylene) triol and said catalyst and a second feed composition containing said poly(oxyalkylene) diol and said organic diisocyanate.

5. A process as claimed in claim 4, wherein said first feed composition contains poly(oxyethylene) diol having an average hydroxyl number of about 13, a poly(oxyethylene) triol having an average hydroxyl number of about 170 and triethylene diamine catalyst and said second feed composition contains poly(oxyethylene) diol having an average hydroxyl number of about 13 and methylenebis(4-phenylisocyanate).

6. A process as claimed in claim 1, wherein said plurality of feed compositions consists of a first feed composition containing said poly(oxyethylene) diol and said poly(oxyethylene) triol, a second feed composition containing said poly(oxyethylene) diol and said organic diisocyanate, and a third feed composition containing said poly(oxyethylene) diol and said catalyst.

7. A process as claimed in claim 6, wherein said first feed composition contains poly(oxyethylene) diol having an average hydroxyl number of about 15 and a poly(oxyethylene) triol having an average hydroxyl number of about 140, said second feed composition contains poly(oxyethylene) diol having an average hydroxyl number of about 15 and methylenebis(4-phenylisocyanate) and said third feed composition contains poly(oxyethylene) diol having an average hydroxyl number of about 15 and dibutyltin dilaurate.