Method and compositions for spray molding polyurethane three dimensional objects

• US 6,362,302 B1
• Filed: 11/29/1999
• Issued: 03/26/2002
• Est. Priority Date: 11/29/1999
• Status: Active Grant

• Current Assignee: Carl E. Boddie
• Original Assignee: Carl E. Boddie
• Inventors: Boddie, Carl E.
• Primary Examiner(s): GORR, RACHEL F
• Application Number:
  US09/449,871
• Time in Patent Office: 848 Days
• Field of Search: 528/73, 528/76, 521/158, 521/163, 264/309, 264/337, 524/789
• US Class Current: 528/73
• CPC Class Codes: C08G 18/0885 using additives, e.g. absorbing agents
• CPC Class Codes: C08G 18/222 metal compounds not provided for in groups C08G18/225 - C08G18/26
• CPC Class Codes: C08G 18/3256 Reaction products of polyamines with aldehydes or ketones
• CPC Class Codes: C08G 18/4816 mixtures of two or more polyetherpolyols having at least three hydroxy groups
• CPC Class Codes: C08G 18/6685 with compounds of group C08G18/3225 or polyamines of C08G18/38
• CPC Class Codes: C08G 18/7671 containing only one alkylene bisphenyl group

Abstract

A method of producing three dimensional polyurethane shapes by spray molding a quasi-gel like polymer precursor composition that is first mixed and then sprayed by a spray gun. The spray coating of quasi-gel polymer precursor composition subsequently cures to form a molded polyurethane polymer shape. Such artificial three dimensional shapes may include rocks, rock walls or faces, tree stumps or limbs, animals, architectural features or settings in which a certain visual appearance is desired. The method includes: creating a mold and supporting cradle having a mold cavity conforming to the exterior of shape desired, the mold having a substantial degree of flexibility; spraying a quasi-gel polymer precursor composition into the mold cavity, the quasi-gel polymer precursor composition comprising a mixture of an isocyanate portion and a curative portion and being mixed prior to introduction into a spray gun, carrying out the spraying to build up the molded three dimensional shape to a desired thickness and stripping the cradle and mold from the molded polyurethane three dimensional shape after the curing of the quasi-gel polymer precursor.

Claims

1. A method of making a molded polyurethane three dimensional shape, the method comprising

creating a mold and supporting cradle having a mold cavity conforming to the exterior of shape desired, said mold having a substantial degree of flexibility;

spraying a quasi-gel polymer precursor composition into the mold cavity, said quasi-gel polymer precursor composition comprising a mixture of an isocyanate portion and a curative portion and being mixed prior to introduction into a spray gun,

carrying out said spraying to build up the molded three dimensional shape to a desired thickness and

stippling said cradle and mold from the molded polyurethane three dimensional shape after the curing of said quasi-gel polymer precursor,

wherein the curative portions of the quasi-gel polymer precursor includes a rigid polymer resin, a gelling agent, a flexible polymer resin, a molecular sieve drying agent, a crosslinking agent, a suspension agent and a polymerization co-catalyst, and

wherein the rigid polymer resin is a combination of penta erythritol base quadra functional polyol and a polyether base triol,

the gelling agent is a aromatic diamine

the flexible polymer resin is a polyether base triol,

the molecular sieve drying agent is an aluminosilicate,

the crosslinking agent is selected from aldimines, ketimines and oxazolidines,

the suspension agent is a mixture of salts from alkylamides and esters, and

the polymerization co-catalyst is phenyl mercuric neodecanoate.

2. The method of claim 1, wherein the isocyanate portion of the quasi-gel polymer precursor includes a isocyanate polymer resin and a molecular sieve drying agent.

3. The method of claim 1, wherein the isocyanate polymer resin is a mixture of 2,4 and 2,6 diphenyldiisocyanate and the molecular sieve drying agent is an aluminosilicate.

4. The method of claim 1, wherein

the aldimine is the reaction product of isophorone diamine and isobutyraldehyde

the ketimine is the condensation reaction of para-phenylenediamine reacted with methyl amyl ketone; and

the oxazolidine is selected from oxazolidines having the formula;

wherein X is selected to be hydrogen, C₁ to C₈ alkyls or C₁ to C₈ alkylol and R′ and

R″

are independently selectable from hydrogen, C₁ to C₈ alkyl.

5. The method of claim 1, wherein the mixture of the isocyanate portion and the curative portion of the quasi-gel polymer precursor is in a ratio from about 0.75:

1.0 to about 1.25;

1.00.

6. The method of claim 5, wherein the ratio of the isocyanate portion and the curative portion is about 1.14:

1.00.

7. The method of claim 1, wherein the quasi-gel polymer precursor includes an additive selected from the group consisting of sand, carbon fibers, glass fibers, glass fiber cloth, metal fibers or metal cloth, synthetic fiber, natural fiber, colorants, pigments and combinations thereof.

8. A method of spray coating a three dimensional object with a polyurethane polymer coating, said method comprising;

forming a premixed quasi-gel polymer precursor composition by combining an isocyanate portion and a curative portion to form said quasi-gel polymer precursor;

spraying said quasi-gel polymer precursor composition onto said three dimensional object to be coated with the polyurethane polymer coating carrying out said spraying to build up the coating to a desired thickness and

allowing said quasi-gel polymer precursor composition to cure thereby becoming said polyurethane polymer coating,

wherein the curative portion includes

a rigid polymer resin which is a combination of penta erythritol base quadra functional polyol and a polyether base triol,

a gelling agent which is an aromatic diamine,

a flexible polymer resin which is a polyether base triol,

a molecular sieve drying agent which is an aluminosilicate,

a crosslinking agent which is selected from aldimines, ketimines and oxazolidines,

a suspension agent which is a mixture of salts from alkylamides and esters, and

a polymerization co-catalyst which is a phenyl mercuric neodecanoate salt.

9. The method of claim 8, wherein the isocyanate portion includes an isocyanate polymer resin which is a mixture of 2,4 and 2,6 diphenyldiisocyanate and a molecular sieve drying agent which is an aluminosilicate.

10. The method of claim 8, wherein

the aldimine is the reaction product of isophorone diamine and isobutyraldehyde

the ketimine is the condensation reaction of para-phenylenediamine reacted with methyl amyl ketone; and

the oxazolidine is selected from oxazolidines having the formula;

wherein X is selected to be hydrogen, C₁ to C₈ alkyls or C₁ to C₈ alkylol and R′ and

R″

are independently selectable from hydrogen, C₁ to C₈ alkyl.

11. The method of claim 8, wherein the mixture of the isocyanate portion and the curative portion of the quasi-gel polymer precursor is in a ratio from about 0.75:

1.0 to about 1.25;

1.00.

12. A method of spray forming a polyurethane polymer foam, said method comprising:

forming a premixed quasi-gel polymer precursor composition by combining an isocyanate portion and a curative portion to form said quasi-gel polymer precursor;

spraying said quasi-gel polymer precursor composition in combination with a sufficient amount of water so as to cause the quasi-get polymer precursor composition to form a foam of quasi-gel polymer precursor composition upon contact with a surface,

allowing said foam of quasi-gel polymer precursor composition to cure thereby becoming said polyurethane polymer foam wherein the isocyanate portion includes an isocyanate polymer resin which is a mixture of 2,4 and 2,6 diphenyldiisocyanate, and

wherein the curative portion includes

a rigid polymer resin which is a combination of penta erythritol base quadra functional polyol and a polyester base triol,

a gelling agent which is an aromatic diamine,

a flexible polymer resin which is a polyether base triol,

a crosslinking agent which is selected from aldimines, ketimines and oxazolidines,

a suspension agent which is a mixture of salts from alkylamides and esters, and

a polymerization co-catalyst which is a phenyl mercuric neodecanoate salt.

13. The method of claim 12, wherein

the aldimine is the reaction product of isophorone diamine and isobutyraldehyde

the ketimine is the condensation reaction of para-phenylenediamine reacted with methyl amyl ketone; and

the oxazolidine is selected from oxazolidines having the formula;

wherein X is selected to he hydrogen, C₁ to C₈ alkyls or C₁ to C₈ alkylol and R′ and

R″

are independently selectable from hydrogen, C₁ to C₈ alkyl.

14. The method of claim 12, wherein the mixture of the isocyanate portion and the curative portion of the quasi-gel polymer precursor is in a ratio from about 0.75:

1.0 to about 1.25;

1.00.