Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Cellular products or processes of preparing a cellular...
Reexamination Certificate
1998-03-16
2001-07-17
Cooney, Jr., John M. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Cellular products or processes of preparing a cellular...
C521S131000, C521S170000, C521S172000, C521S173000, C521S174000, C528S059000, C528S067000, C528S076000, C560S026000, C560S334000, C560S359000, C560S360000
Reexamination Certificate
active
06262139
ABSTRACT:
BACKGROUND OF THE INVENTION
The invention provides an isocyanate prepolymer composition, a method of preparing the isocyanate prepolymer composition, a method of using the composition in the manufacture of polyurethane foams and the resultant foams.
The reactions of polyisocyanates with compounds containing at least two isocyanate-reactive hydrogen atoms are well known. When conducted in the presence of a catalyst and blowing agent, such reactions are used to manufacture both rigid and flexible polyurethane foams. Flexible polyurethane foams are distinct from rigid foams and have a limited resistance to an applied load, are open-celled, permeable to air and are reversibly deformable. See G. Hauptman, H.-A. Freitog and A. Volland,
Polyurethane Handbook
, Chapter 5, Sections 5.0 and 5.3-5.3.3 (Ed. G. Oertal 1985), the disclosure of which is hereby incorporated by reference.
Flexible foams are generally produced via a continuous slabstock process or a discontinuous molding process. Molding processes are advantageous because articles may be produced fairly easily and without waste. Flexible polyurethane molded foams are particularly suitable for use in seating applications in the home, office and automobile markets.
However, the production of flexible polyurethane molded foams having optimum performance properties can be challenging, particularly where the mold is relatively large and includes a complicated shape or configuration. In particular, if the viscosity of the foaming mixture increases to a certain point before the mixture reaches all portions of the mold, the mold will not become fully filled. Foam formulations which gel before the mold is adequately filled are said to have inadequate flow.
When the foam formulation has inadequate flow, the resultant molded foams are of suspect quality. They are often prone to instability and collapse and exhibit impaired performance characteristics. Inadequate flowability characteristics can also be manifest as voids and other physical imperfections.
Several prior art attempts to address this problem have focused on the isocyanate component. Particular attempts have used combinations of toluene diisocyanate (TDI), and diphenylmethane diisocyanate (MDI) and/or (polymeric-MDI or polyphenyl-polymethylene polyisocyanates PMDI). For example, U.S. Pat. No. 3,492,251 discloses a mixture of polyisocyanates having 50 to 65 percent PMDI and 30 to 50 percent TDI. However, the foams produced were rigid foams lacking the performance characteristics desired in automotive seating.
U.S. Pat. No. 4,256,849 discloses a process for the production of cold setting, flexible foams containing urethane groups wherein the isocyanate component was a mixture of diphenylmethane diisocyanates and polyphenyl-polymethylene polyisocyanates, both substantially free of carbodiimide groups, the mixture having an isocyanate content of greater than 30 percent. The mixture contained from 60 to 90 percent by weight of 4,4′-diphenylmethane diisocyanate, 3 to 30 percent by weight of 2,4′-diphenylmethane diisocyanate, and up to 20 percent by weight of other polyisocyanates including toluene diisocyanate isomers.
In U.S. Pat. No 4,803,229 a molded flexible polyurethane foam was prepared by reacting a polyol with a urea-biuret modified polyisocyanate mixture composed of toluene diisocyanate and polymeric diphenylmethane diisocyanate. The disclosure required that either or both of the TDI and PMDI be modified with urea-biuret structures. The patent was directed toward obtaining molded flexible polyurethane foams with improved air flow and compression set.
Finally, U.S. Pat. No. 5,132,334 discloses a polyisocyanate mixture having 21 to 95 percent by weight of toluene diisocyanate and 5 to 79 percent by weight of a mixture of diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates containing (1) 55 to 87 percent by weight of 4,4′-diphenylmethane diisocyanate, (2) 8 to 30 percent by weight of 2,4′-diphenylmethane diisocyanate, (3) 0 to 4 percent by weight of 2,2′-diphenylmethane diisocyanate, and (4) 5 to 35 percent by weight of polyphenylpolymethylene polyisocyanates. While the '334 patent discloses a relatively high toluene diisocyanate content, the present invention is distinguishable in that the prepolymer is incorporated in the isocyanate portion of the prepolymer.
Since the prior art has failed to provide an adequate solution to the above problem, it is an object of this invention to provide an isocyanate component which has flowability characteristics such that large molds having complicated configurations may be adequately filled to produce flexible polyurethane molded foams having an optimum balance of performance properties.
More particularly, it is an object of the instant invention to provide an isocyanate prepolymer composition, capable of functioning as the isocyanate component in a flexible polyurethane foam formulation which exhibits improved flowability characteristics.
It is yet another object of the present invention to provide for flexible foam formulations including a relatively high quantity of toluene diisocyanate and average densities of below about 40.0 kg/m
3
.
SUMMARY OF THE INVENTION
These objects and more are satisfied with the isocyanate prepolymer composition of the invention. The isocyanate prepolymer composition provides improved flowability such that relatively large molds, having complicated shapes and configurations, can be adequately filled to produce flexible polyurethane molded foams having an optimum balance of performance properties.
The isocyanate prepolymer composition of the invention is obtained by combining: about 50.0 to about 90.0% by weight of an isocyanate blend (a.) having 55.0 to about 75.0 percent by weight of 4,4′-diphenylmethane diisocyanate, 17.0 to about 27.0 percent by weight of 2,4′-diphenylmethane diisocyanate, 1.0 to about 10.0 percent by weight of 3-ring oligomers of polymethylene polyphenyl polyisocyanate and 1.0 to about 15.0 percent by weight of n-ring oligomers of polymethylene polyphenyl polyisocyanate (n being greater than 3); about 5.0 to about 30.0 percent by weight of a polyhydroxy containing polyol (b.) having a molecular weight of from 700 to about 6000; and about 15.0 to about 75.0 percent by weight of a toluene diisocyanate (c.) wherein the total of a)-c) is 100.0 percent by weight.
The resulting isocyanate prepolymer composition has a free NCO content of from about 35.0 to about 45.0 percent by weight and is characterized as having from 12.0 to about 45.0 percent by weight 4,4′-diphenylmethane diisocyanate, 6.0 to about 15.0 percent by weight 2,4′-diphenylmethane diisocyanate, 4.0 to about 10.0 percent by weight of a prepolymer which is the reaction product of PMDI and the polyhydroxy containing polyol, 1.0 to about 5.0 percent by weight 3-ring MDI oligomer, 2.0 to about 6.0 percent by weight n-ring MDI oligomers (n being greater than 3), 4.0 to about 8.0 percent by weight of 2,6-toluene diisocyanate, and 30.0 to about 60.0 percent by weight 2,4-toluene diisocyanate.
The invention also provides a method of preparing the isocyanate prepolymer composition, a method of making a polyurethane foam utilizing the composition of the invention, as well as polyurethane foams produced by said process.
The isocyanate prepolymer composition of the invention is believed to have the advantages of MDI-based systems and the flowability characteristics typically exhibited by TDI-based isocyanate blends. Use of the composition will ideally provide the ability to obtain a wider hardness range at a particular index as compared with TDI-based systems, as well as the ability to obtain a greater percentage of open cells as compared to those typically obtained with TDI-based systems. The composition allows for a processing latitude typically exhibited with MDI-based systems and allows the use of lower mold temperatures.
Finally, the isocyanate prepolymer composition provides the advantages of decreased surface defects and decreased potential for shrinkage
Lovell David J.
Narayan Thirumurti
Shimazaki Alejandro
BASF Corporation
Borrego Fernando A.
Cooney Jr. John M.
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