# US 10,865,333 B2 · Polyurethane adhesives for reverse osmosis modules

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- Number: US 10,865,333 B2
- Document ID: US10865333B2
- Status: Granted
- Kind: B2
- Application number: 15/092,892
- Filed: 2016-04-07
- Published: 2016-10-13
- Granted: 2020-12-15
- Earliest claimed: 2015-04-09
- Assignees: Elantas PDG, Inc.
- Applicants: Elantas Pdg, Inc.
- Inventors: Tanmoy Dey; Richard D. Jordan, Jr.; Michael Causer
- Web page: https://patentgrep.com/patent/US10865333B2

## CPC

- C09J 175/08: from polyethers
- B01D 65/003: {Membrane bonding or sealing}
- C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G 18/246: {containing also tin-carbon bonds}
- C08G 18/3206: {aliphatic}
- C08G 18/36: Hydroxylated esters of higher fatty acids
- C08G 18/48: Polyethers
- C08G 18/4825: {Polyethers containing two hydroxy groups (C08G18/4833 - C08G18/5096 take precedence)}
- C08G 18/4829: {Polyethers containing at least three hydroxy groups (C08G18/4833 - C08G18/5096 take precedence)}
- C08G 18/4837: {and other oxyalkylene units}
- C08G 18/6208: {Hydrogenated polymers of conjugated dienes}
- C08G 18/6677: {having at least three hydroxy groups}
- C08G 18/73: acyclic
- C08G 18/7642: {containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring}
- C08G 18/7671: {containing only one alkylene bisphenyl group}
- C08G 18/797: {containing carbodiimide and/or uretone-imine groups}
- C08G 18/8019: {Masked aromatic polyisocyanates}
- C09J 5/00: Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J 175/04: Polyurethanes
- B01D 61/025: {Reverse osmosis; Hyperfiltration}
- B01D 2313/042: Adhesives or glues
- C09J 2475/00: Presence of polyurethane
- Y02A 20/131: Reverse-osmosis
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- Y02A: TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE

## Abstract

An adhesive composition is made from a first part containing an isocyanate group-containing prepolymer that is a reaction product of a first isocyanate and at least one polyol; and a second isocyanate that is essentially unreacted with the first isocyanate, the at least one polyol, and the isocyanate group containing prepolymer; and a second part containing at least two polyols; wherein the adhesive composition is essentially free of diluent oils and solvents. A polyurethane adhesive is made by mixing the first part and the second part in a 1:1 to 1.2:1 weight ratio of the first part to the second part to form a mixture, and curing the mixture. The polyurethane adhesive can be used in articles, including semipermeable membranes and reverse osmosis modules. When a solvent is filtered through the semipermeable membranes by reverse osmosis, the polyurethane adhesive prevents or reduces osmotic blistering.

## Claims

### Claim 1

An adhesive composition comprising:
a first part comprising:
an isocyanate group-containing prepolymer comprising a reaction product of a first isocyanate and at least one polyol; and
a second isocyanate that is essentially unreacted with the first isocyanate, the at least one polyol, and the isocyanate group containing prepolymer, wherein said second isocyanate may be the same or different than the first isocyanate;
a second part comprising at least two polyols; and
from 0.5 to 35 weight percent of a plasticizer, based on the total weight of the adhesive composition, wherein the plasticizer is selected from the group consisting of dicarboxylate esters, tricarboxylate esters, benzoates, dibenzoates, epoxidized vegetable oils, esters of soybean oils, phthalates, phosphate esters and combinations of thereof;
wherein the adhesive composition is essentially free of diluent oils and solvents, wherein the first part of the composition has a total NCO content of 10 to 35 weight percent, based on the total weight of the first part, as measured in accordance with ASTM D2572.

### Claim 2 (depends on 1)

The adhesive composition of claim 1, wherein the second isocyanate is the same as the first isocyanate.

### Claim 3 (depends on 1)

The adhesive composition of claim 1, wherein polybutadiene diols and polyisobutylene diols are absent from the first part.

### Claim 4 (depends on 1)

The adhesive composition of claim 1, wherein the first isocyanate and the second isocyanate are independently 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3-diisocyanate and cyclohexane-1,4-diisocyanate, 1-isocyanato-2-isocyanatomethyl cyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, 2,4′-dicyclohexylmethane diisocyanate, 1,3-bis(cyclohexyl) diisocyanate, 1,4-bis-(isocyanatomethyl)-cyclohexane, bis(4-isocyanato-3-methyl-cyclohexyl)methane, 1-isocyanato-1-methyl-4(3)-isocyanatomethyl cyclohexane, alpha,alpha,alpha′,alpha′-tetramethyl-1,3-xylylene diisocyanate, alpha,alpha,alpha′,alpha′-tetramethyl-1,4-xylylene diisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-diphenylmethane diisocyanate, 1,5-diisocyanato naphthalene, 4,4′-diphenylmethane diisocyanate, a chemical modification of at least one of the foregoing isocyanates, a prepolymer derived from reaction of at least one of the foregoing isocyanates with a diol or a diamine, or combinations comprising at least one of the foregoing isocyanates.

### Claim 5 (depends on 1)

The adhesive composition of claim 1, wherein the first isocyanate and second isocyanate are independently monomeric diphenylmethane diisocyanate, a modified diphenylmethane diisocyanate having an average of greater than 2 and less than or equal to 4 isocyanate groups per molecule, or a combination comprising at least one of the foregoing isocyanates.

### Claim 6 (depends on 1)

The adhesive composition of claim 1, wherein the first isocyanate and second isocyanate are independently a modified diphenylmethane diisocyanate selected from a carbodiimide-modified diphenylmethane diisocyanate, a prepolymer derived from reaction of diphenylmethane diisocyanate with a diol or diamine, or a combination comprising at least one of the foregoing isocyanates.

### Claim 7 (depends on 1)

The adhesive composition of claim 1, wherein the at least two polyols of the second part comprise castor oil, a castor oil derivative, an ester of ricinoleic acid, a polyether polyol, a polyol derived from natural oils, a polyol derived from fats, a polyether polyol, a polylactone, a polyester polyol, a polybutadiene polyol, a polyisobutylene diol, a polyol having amine functionality, or a combination comprising at least one of the foregoing polyols.

### Claim 8 (depends on 1)

The adhesive composition of claim 1, wherein the at least two polyols of the second part comprise a polyether polyol, castor oil, a castor oil derivative, an ester of ricinoleic acid, a polyol having amine functionality, or combinations comprising at least two of the foregoing polyols.

### Claim 9 (depends on 1)

The adhesive composition of claim 1, wherein the at least one polyol of the first part comprises castor oil, a castor oil derivative, an ester of ricinoleic acid, a polyether polyol, a polyol derived from natural oil, a polyol derived from fats, a polyether polyol, a polylactone, a polyester polyol, a polybutadiene polyol, a polyisobutylene diol, a polyol having amine functionality, or a combination comprising at least one of the foregoing polyols.

### Claim 10 (depends on 1)

The adhesive composition of claim 1, wherein the at least one polyol of the first part comprises castor oil, a castor oil derivative, an ester of ricinoleic acid, a polyether polyol, a polybutadiene polyol, a polyisobutylene diol, or a combination comprising at least one of the foregoing polyols.

### Claim 11 (depends on 8)

The adhesive composition of claim 8, wherein the at least one polyol of the first part consists of castor oil or a castor oil derivative.

### Claim 12 (depends on 8)

The adhesive composition of claim 8, wherein the at least one polyol of the first part comprises castor oil or a castor oil derivative, and a polyether diol.

### Claim 13 (depends on 8)

The adhesive composition of claim 8, wherein the at least one polyol of the first part consists of a tetrol.

### Claim 14 (depends on 8)

The adhesive composition of claim 8, wherein the at least one polyol of the first part consists of polybutadiene polyol.

### Claim 15 (depends on 10)

The adhesive composition of claim 10, wherein the at least two polyols of the second part comprise castor oil, a castor oil derivative, an ester of ricinoleic acid, a polyol derived from natural oils, a polyether polyol, or a combination comprising at least two of the foregoing polyols.

### Claim 16 (depends on 10)

The adhesive composition of claim 10, wherein the at least two polyols of the second part comprise a transesterification product of castor oil with pentaerythritol, and a polyether triol.

### Claim 17 (depends on 10)

The adhesive composition of claim 10, wherein the at least two polyols of the second part comprise castor oil, a transesterification product of castor oil with pentaerythritol, a polyol derived from natural oils, a polyether tetrol, or a combination comprising at least one of the foregoing polyols.

### Claim 18 (depends on 10)

The adhesive composition of claim 10, wherein the at least two polyols of the second part comprise castor oil, a polyether tetrol, a polyol having amine functionality, or a combination comprising at least two of the foregoing polyols.

### Claim 19 (depends on 1)

The adhesive composition of claim 1, wherein the first isocyanate comprises an aromatic isocyanate and the second isocyanate comprises an aliphatic isocyanate.

### Claim 20 (depends on 1)

The adhesive composition of claim 1, wherein the first isocyanate comprises an aromatic isocyanate and the second isocyanate comprises 1 to 50 weight percent aliphatic isocyanate and 49 to 50 weight percent of aromatic isocyanate, based on the total weight of the second isocyanate.

### Claim 21 (depends on 1)

The adhesive composition of claim 1, further comprising a desiccant.

### Claim 22 (depends on 1)

A polyurethane adhesive made by mixing the first part and the second part of the adhesive composition of claim 1 in a 1:1 to 1.2:1 weight ratio of the first part to the second part to form a mixture, and curing the mixture.

### Claim 23 (depends on 22)

An article comprising the polyurethane adhesive of claim 22.

### Claim 24 (depends on 23)

The article of claim 23, wherein the article further comprises a semipermeable membrane, wherein the polyurethane adhesive adheres to the semipermeable membrane.

### Claim 25 (depends on 24)

The article of claim 24, wherein the article is a reverse osmosis module.

### Claim 26 (depends on 1)

A method for preventing or reducing osmotic blistering of a semipermeable membrane otherwise subject thereto, the method comprising:
forming the adhesive composition of claim 1;
mixing the first part and second part of the adhesive composition to form a mixture;
applying the mixture to a semipermeable membrane in an amount sufficient to secure the semipermeable membrane to a porous support;
curing the mixture to form a polyurethane adhesive; and
filtering a solvent through the semipermeable membrane by reverse osmosis;
wherein the polyurethane adhesive prevents or reduces osmotic blistering of the semipermeable membrane.