US 3,935,133 AGrant
High Resilience Polyurethane Foam Stabilized With a Silicate-Based Surfactant Composition
Issue Date:1976-01-27
•16 Claims
Abstract
High resilience polyether polyurethane foam is prepared from a reaction mixture comprising a silicate-based surfactant composition.
Metadata
Assignee
- Olin Corporation
Inventors
- Bruce G. VAN Leuwen
- Ralph A. Colafati, III
Application Information
Application Number:US 5355494
Filing Date:1974-12-23
Priority Date:1973-12-26
Art Unit:141
Classifications
IPC:
C08G 1814C08K 554
Field of Search:
2602.5 AH;2.5 AP
Patent Drawings
This patent does not have any drawings.
Description
The following examples are provided to illustrate the invention. In these examples, all parts and percentages are by weight unless otherwise specified.
Example 1
A 5 liter 3-neck flask fitted with a magnetic stirrer, a thermometer and a gas outlet was charged with 849.5 grams (5 moles) of silicon tetrachloride and cooled to 0.degree.C with an ice-water bath. A solution of 81 mls. (4.5 moles) of H.sub.2 O in 2 kgs. (33.3 moles) of isopropanol was then added with stirring over a period of 2.5 hours. Rapid HCl evolution during the early stages of the aqueous isopropanol addition helped to cool the reaction mixture making it relatively easy to maintain a temperature between 4.degree. and 10.degree.C. After about half the isopropanol was added, HCl evolution slowed considerably resulting in an apparent exotherm, and frequent stirring of the ice bath was required to maintain the temperature of the reaction mixture below 20.degree.C. During the latter stages of the addition, the reaction mixture became cloudy with ultimate formation of two phases. After addition of aqueous isopropanol was complete, the mixture was heated to 82.degree.C under reflux for 3 hours, at which point it was homogeneous.
The product thus formed was then stripped of volatiles up to a bottoms temperature of 100.degree.C and 20 m.m. of mercury pressure. The over-head fractions, mainly excess unreacted isopropanol and by-product hydrochloric acid, were discarded, leaving a viscous liquid residual intermediate weighing 662 grams and having a viscosity of 60 c.s. at 100.degree.F.
The amount of 215 grams of the intermediate prepared above was used to prepare a silicate-based surfactant composition following this procedure. A 1-liter, 3-neck flask equipped with a mechanical stirrer, a nitrogen inlet, a dry ice-cooled Dewar condenser and a Dean-Stark trap was charged with 350 g of a butanol initiated, oxyethylated, oxypropylated polyether having a molecular weight of 1,800 and a 1:1 weight ratio of ethylene oxide:propylene oxide. To this there were added 215 grams of the intermediate obtained above and 0.3 gram of tetrabutyl titanate catalyst. The flask was then immersed in a 130.degree.C oil bath. With a nitrogen sweep of 550 cc/min. and rapid stirring (375 rpm), the oil bath was rapidly heated (10-15 min.) to 195.degree.C and maintained at this temperature for 4 hours. The product was cooled under nitrogen and the volatile distillate (15 g. isopropanol) was discarded leaving a final product of 524 grams which was a homogeneous liquid surfactant composition having a kinematic viscosity of 407 cs. at 100.degree.F. The components of this composition could not be identified by available methods, e.g., gas chromatography, mass spectrometry, nuclear magnetic resonance, and infrared analysis. However, its over-all content of silicon, carbon, hydrogen and oxygen was determined by gravimetric analysis to be as follows:
silicon: 7.25%
carbon: 50.24%
hydrogen: 8.8%
oxygen: 33.7%
A flexible high resilience polyurethane foam was prepared from a reaction mixture comprised of 0.3 parts of the surfactant composition prepared above and the following ingredients.
The above mixture was hand mixed at room temperature and immediately poured into a cake box. Using a stop-watch, the "cream time", "rise time" and "gel time" were measured, all being from the moment the mixture is placed in the mold. The cream time was 8 seconds and this is the time elapsed, up to the point when foaming commences, during which time the mixture is transformed from a liquid to a cream or emulsion. The rise time was 120 seconds and this is the time elapsed for completion of the foaming reaction or expansion of the foam. This is usually evidenced by appearance of gas bubbles on the surface of the foam. The gel time was 130 seconds and this is the time elapsed for the resulting foam to become a self-supporting body as evidenced by the foam exhibiting resistance to being penetrated by a dull instrument.
The product produced was a good, open-celled, stable foam.
Example 2
The exact procedure of Example 1 was followed with one exception. This is that the intermediate product obtained by the reaction of carbon tetrachloride with water and isopropanol was subjected to further purification by distillation. To this end, it was placed in a 1-liter, 3-neck flask equipped with a magnetic stirrer, a 5 inch vacuum jacketed Virgreux column, a vacuum take-off head, a fraction cutter, and an immersed pot thermometer. Distillation was carried out up to a bottoms temperature of 210.degree.C and 15 m.m. of mercury pressure. The bottoms fraction thus obtained weighed 538 grams which represented 75% yield based on SiCl.sub.4 charged. This fraction which had a kinematic viscosity at 100.degree.F of 139.0 cs was then transesterified exactly as described in Example 1. After removal of liberated isopropanol, a liquid surfactant composition was obtained which had a viscosity of about 390 cs at 100.degree.F. The overall silicon, carbon, hydrogen and oxygen content in this composition was determined by gravimetric analysis to be as follows: 7.94% silicon, 50.56% carbon, 9.3% hydrogen and 32.47% oxygen.
The product of this example was found to be effective as a stabilizer, when used exactly as described in Example 1, in the preparation of polyurethane foam.
Example 3
The identical procedure of Example 2 was followed with the following exceptions. In carrying out the transesterification reaction, 62 grams of the butanol-initiated polyether and 38 grams of the bottoms fraction, of the product of the reaction of SiCl.sub.4 with water and isopropyl alcohol, were used. In addition, the catalyst used to promote transesterification was metallic sodium (0.05 gram) instead of the tetrabutyl titanate. Finally the transesterification reaction was effected at 165.degree.C.
After transesterification and removal of evolved isopropanol, a homogeneous, viscous liquid product was obtained with weighed 96 grams. This product was found to be equally effective as a stabilizer when used in preparing polyurethane foam as described in Example 1.
Example 4
The identical procedure of Example 3 was followed except that 0.05 gram of sodium hydride was used as the transesterification catalyst instead of the metallic sodium. Again the product of transesterification, after removal of liberated isopropanol, was found to be an effective stabilizer in the production of a high resilience polyurethane foam based on the formulation used in Example 1.
Example 5
The identical procedure of Example 3 was followed with one exception. This is that in carrying out the first reaction, instead of 33.3 moles, 20 moles of isopropanol were used. The final product, after being freed of liberated isopropanol, was found to be an effective stabilizer in preparing high resilience polyurethane foam per Example 1.
Example 6
The procedure of Example 5 was followed except that instead of the 20 moles of isopropanol used in the first reaction, 33 moles of butanol-2 were employed. The final product, after removal of liberated butanol, was a viscous liquid. Its over-all content of silicon, carbon, hydrogen and oxygen was determined by gravimetric analysis to be as follows:
silicon : 7.58%
carbon : 54.14%
hydrogen: 9.49%
oxygen : 28.79%
The product of this example was found to be an effective stabilizer in the production of high resilience polyurethane foam based on the formulation of Example 1.
Claims
What is claimed is:
1. A flexible polyurethane foam prepared from a reaction mixture which is comprised of: a. an organic polyisocyanate, b. a polyether polyol having in its structure the nucleus of an aliphatic alcohol having 2-8 reactive hydrogens and polyoxyalkylene chain segments attached through one end thereof to said nucleus at the site of the reactive hydrogens, said polyether polyol being further characterized by (1) a molecular weight of at least about 4,000 and (2) a ratio of primary to secondary hydroxyl end groups ranging from about 1.5:1 to about 6:1, c. a foaming agent, d. a reaction catalyst, and e. a silicate-based surfactant composition which is prepared by a process that comprises 1. reacting together, at a temperature of about 40.degree.-200.degree.C, (a) a silicon tetrahalide selected from the group consisting of silicon tetrachloride, silicon tetrabromide, and silicon tetraiodide, and, per every mole of said silicon tetrahalide (b) about 0.2-2.0 moles of water and (c) at least about one mole of an alcohol represented by the formula R.sub.1 OH wherein R.sub.1 is alkyl of 2-20 carbon atoms or aromatic hydrocarbon of 6-14 carbon atoms, the reaction yielding a product made up of a volatile portion, which has a boiling point no greater than about 125.degree.C at 10 mm of mercury pressure, and a non-volatile portion, and 2. removing said volatile portion, and 3. at a temperature of about 65.degree.-320.degree.C in the substantial absence of moisture and in the presence of a transesterification catalyst, reacting the non-volatile portion of the product of step (1) with a polyether alcohol having a molecular weight of about 500-5,000 and represented by the formula R.sub.2 --C.sub.n H.sub.2n O--H wherein R.sub.2 is alkyl of 1-10 carbon atoms and the moiety --C.sub.n H.sub.2n O-- represents a polyoxyalkylene chain consisting of from about 10 to 100 percent by weight of oxyethylene units, and, correspondingly, about 90-0 percent of oxypropylene units, oxybutylene units or a mixture of oxypropylene and oxybutylene units, said polyether alcohol being employed in a molar proportion ranging from about 0.006 to about 1.1 moles per every mole of said silicon tetrahalide which is used in step (1), with the proviso that the molar proportion of said polyether alcohol is no more than about 55% of the molar proportion of alcohol reacted in thre reaction of step (1).
2. The polyurethane foam of claim 1 wherein said polyether polyol is an oxypropylated, oxyethylated aliphatic triol having a molecular weight of about 5,800-6,600 and a ratio of primary to secondary hydroxyl groups ranging from about 2.2:1 to about 4.5:1.
3. The polyurethane foam of claim 2 wherein said organic polyisocyanate is a mixture of (1) toluene diisocyanate and (2) polymethylene polyphenylisocyanate in a weight ratio, (1):(2), ranging from about 75:25 to about 94:6.
4. The polyurethane foam of claim 1 wherein the process of preparing said surfactant composition includes the added step of removing alcohol of said formula R.sub.1 OH which is liberated during the reaction of step (3).
5. The polyurethane foam of claim 4 wherein said R.sub.1 is alkyl of 3-8 carbon atoms, said R.sub.2 contains 1-6 carbon atoms and said transesterification catalyst is selected from the group consisting of a Lewis acid, an alkali metal and an alkali metal hydride.
6. The polyurethane foam of claim 5 wherein said polyether poly-1 is an oxypropylated, oxyethylated triol having a molecular weight of about 5,700-7,000.
7. The polyurethane foam of claim 6 wherein said silicon tetrahalide is silicon tetrachloride and said polyether alcohol has a molecular weight of about 1,500-4,000 and in which said (C.sub.n H.sub.2n O) moiety represents a polyoxyethylene chain or a polyoxyethylene-oxypropylene chain having a weight ratio of oxyethylene to oxypropylene units ranging from about 2:1 to about 1:2.
8. The polyurethane foam of claim 7 wherein the reaction of step (1) is carried out at about 55.degree.-110.degree.C, under reflux, and using, per every mole of said silicon tetrachloride, about 2-12 moles of said alcohol and about 0.4-1.7 moles of said water.
9. The polyurethane foam of claim 8 wherein the reaction of step (3) is carried out at about 80.degree.-260.degree.C, and using about 0.06-0.8 moles of said polyether alcohol per every mole of said silicon tetrachloride which is used in step (1).
10. The polyurethane foam of claim 9 wherein said polyether triol has a ratio, of primary to secondary hydroxy groups, ranging from about 2:1 to about 5:1.
11. The polyurethane foam of claim 10 wherein organic polyisocyanate is toluene diisocyanate or a mixture thereof with polymethylene polyphenylisocyanate.
12. The polyurethane foam of claim 11 wherein said reaction catalyst is selected from the group consisting of a tertiary amine, an organo-tin salt and mixture thereof.
13. The polyurethane foam of claim 12 wherein said organic polyisocyanate is a mixture of (1) toluene diisocyanate and (2) polymethylene polyphenylisocyanate in a weight ratio, (1):(2), ranging from about 75:25 to about 94:6.
14. A polyurethane foam as claimed in claim 13 wherein said silicate-based surfactant composition is the product of the process which comprises the following steps: 1. at a temperature from about -30.degree.C to about 20.degree.C, mixing together silicon tetrachloride and, per every mole of said silicon tetrachloride, about 0.7-1.4 moles of water and about 3-8 moles of isopropyl alcohol, 2. allowing said mixture to react at a temperature of about 60.degree.-100.degree.C and under reflux conditions, thereby forming a reaction product made up of hydrochloric acid, unreacted isopropyl alcohol and a non-volatile mixture comprised of silicate-based materials, 3. stripping off said hydrochloric acid and unreacted isopropyl alcohol, 4. reacting said non-volatile mixture with a polyether alcohol having a molecular weight of about 1,200-1,500 and represented by the formula C.sub.4 H.sub.9 (C.sub.n H.sub.2n O) H wherein the moiety (C.sub.n H.sub.2n O) represents a polyoxyethylene-oxypropylene chain having a weight ratio, of oxyethylene to oxypropylene units, ranging from about 6:4 to about 4:6, the reaction being carried out. a. using about 0.1-0.7 mole of said polyether alcohol per each mole of said silicon tetrachloride used in step (a), b. at a temperature of about 140.degree.-220.degree.C, c. in the substantial absence of moisture, and d. in the presence of a transesterification catalyst selected from the group consisting of a Lewis acid, an alkali metal and an alkali metal hydride, thereby forming a product comprised of a silicate-based surfactant composition and liberated isopropyl alcohol, and 5. removing said liberated isopropyl alcohol and recovering said silicate-based surfactant composition.
15. The polyurethane foam of claim 14 wherein said foaming agent is water.
16. The polyurethane foam of claim 15 wherein said polyether triol is oxypropylated, oxyethylated glycerin.
Patent Citations (2)
| Patent | Date | Inventor | Cited By |
|---|---|---|---|
| US3795636 | 1974-03-01 | Huffman | |
| US3821130 | 1974-06-01 | Barron |