Syntactic polyurethane elastomer based on soft segment prepolymer and non-mercury catalyst for use in subsea pipeline insulation
Syntactic polyurethane elastomers are made using a non-mercury catalyst. The elastomer is made from a reaction mixture containing a prepolymer made from a polyether polyol and a polyisocyanate, a chain extender, a polyisocyanate and microspheres. The elastomer adheres well to itself, which makes it very useful as thermal insulation for pipelines and other structures that have a complex geometry.
1. A process for producing a substrate having an applied syntactic polyurethane elastomer, comprising
a) forming a section of a syntactic polyurethane elastomer on at least a portion of the substrate by (1) applying a first reaction mixture containing an alkylene glycol chain extender, 5 to 35 weight percent, based on the weight of the reaction mixture, of microspheres, an isocyanate-terminated prepolymer having an isocyanate content of 3 to 12% by weight, based on the weight of the isocyanate-terminated prepolymer, and a non-mercury catalyst, wherein (i) the prepolymer is the reaction product of at least one polyether polyol having a number average hydroxyl equivalent weight of at least 800 with an excess of an aromatic polyisocyanate, (ii) the amount of prepolymer provided to the reaction mixture is to provide an isocyanate index of 80 to 130, (iii) wherein the non-mercury catalyst is a zinc carboxylate or a mixture of 98-99.99 weight percent of one or more zinc carboxylates and 0.01 to 2 weight percent of one or more zirconium carboxylates and (iv) the reaction mixture is devoid of mercury compounds, to at least a portion of the substrate and (2) partially curing the first reaction mixture to maintain its shape to form the first section of syntactic polyurethane elastomer, and then
b) forming a second section of syntactic polyurethane elastomer on at least a portion of the substrate by (1) applying a second reaction mixture containing an alkylene glycol chain extender, 5 to 35 weight percent, based on the weight of the reaction mixture, of microspheres, an isocyanate-terminated prepolymer having an isocyanate content of 3 to 12% by weight, based on the weight of the isocyanate-terminated prepolymer, and a non-mercury catalyst, wherein (i) the prepolymer is the reaction product of at least one polyether polyol having a number average hydroxyl equivalent weight of at least 800 with an excess of an aromatic polyisocyanate, (ii) the amount of prepolymer provided to the reaction mixture is to provide an isocyanate index of 80 to 130, (iii) wherein the non-mercury catalyst is a zinc carboxylate or a mixture of 98-99.99 weight percent of one or more zinc carboxylates and 0.01 to 2 weight percent of one or more zirconium carboxylates and (iv) the reaction mixture is devoid of mercury compounds to at least a portion of the substrate and in contact with the first section of syntactic polyurethane elastomer to form at least one bondline between the first section of syntactic polyurethane elastomer and the second reaction mixture and (2) partially curing the second reaction mixture to form the second section of syntactic polyurethane elastomer adherent to the first section of syntactic polyurethane elastomer, wherein the bondline has a bond strength of at least 8.0 MPa, as measured according to ASTM D638.
2. The process of claim 1 wherein the substrate is an undersea pipe or undersea architecture.
3. The process of claim 2 wherein the undersea pipe or undersea architecture is branched, curved or has another non-linear configuration.
4. The process of claim 2 wherein the undersea pipe or undersea architecture has one or more external features that protrude partially or completely through the applied syntactic polyurethane elastomer.
5. The process of claim 1 , wherein the polyether polyol used to make the isocyanate-terminated prepolymer is prepared by (A) adding propylene oxide and ethylene oxide to a difunctional or trifunctional initiator to produce a polyol having a hydroxyl equivalent weight of 1500 to 2500 and containing 5 to 30% by weight polymerized ethylene oxide, based on total product weight, wherein the polymerized ethylene oxide is randomly polymerized with the propylene oxide, forms one or more internal blocks and/or forms terminal blocks that result in primary hydroxyl groups or (B) homopolymerizing propylene oxide or randomly copolymerizing 75-99.9 weight percent propylene oxide and 0.1 to 25 weight percent ethylene oxide onto a trifunctional initiator, and optionally capping the resulting polyether with up to 30% by weight, based on total product weight ethylene oxide to form a polyether polyol having an equivalent weight of 1500 to 2500.
6. The process of claim 5 , wherein the chain extender is 1,4-butanediol.
7. The process of claim 1 wherein each respective reaction mixture contains 15 to 25 weight percent microspheres.