US4176106A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Phenol/formaldehyde resoles and cellular products derived therefrom
Assignee: Union Carbide Corp
•
Filing: 1977-07-28
•
Granted: 1979-11-27
•
Expires: 1997-07-28
Abstract
Abstract The present invention provides particular phenol/formaldehyde resoles which are especially useful as foamable resins, and further provides cellular phenolic products having physical properties which are especially attractive for end-use application as construction foam. The resoles are characterized by a particular relationship between their viscosity and water content, expressed as the area bounded by certain points on a plot of resole viscosity on a logarithmic scale, as a function of water content of the resole, the particular area depending upon the mole ratio of formaldehyde-to-phenol at which the resole has been condensed. It has been found that phenol-formaldehyde resoles having the defined viscosity/water relationship are capable of providing phenolic foam having acceptable foam processability, a foam density from about 1.90 to about 3.70 pounds per cubic foot and, within this foam density range, a good balance of friability resistance and compressive strength, that is, a friability of less than 35 percent weight loss and a compressive strength of at least 20 pounds per square inch. Preferred resoles within the invention are foamable to phenolic foam having a reduced tendency to punk as well as the aforementioned desirable combination of foam processability and mechanical properties.
Inventors
- 👤 Wallace G. Reid
- 👤 Rakesh Saini
- 👤 Kenneth E. Atkins
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 06:54
CPC Classifications
C; C08; C08J; C08J9/00; C08J9/04; C08J9/12; C08J9/14; C08G; C08G8/00; C08G8/04; C08G8/08; C08G8/10; C08J2361/00; C08J2361/04; C08J2361/06; C08J2361/08; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31942
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
411 words
A phenolic resole capable of being foamed to a phenolic foam having a density from 1.90 to 3.70 pounds per cubic foot and, within said density range, a friability of less than 35 percent weight loss (after 10 minutes) and a compressive strength (parallel of at least 20 pounds per square inch which resole has been produced by the base-catalyzed condensation of formaldehyde and phenol at a formaldehyde-to-phenol mole ratio from about 1.6:1 to about 2.2:1, the aqueous alkaline condensate having been brought to a pH from about 5.0 to about 7.0 by the addition thereto of a salt-forming acidic compound, said resole being characterized by an average molecular weight such that a plot of log viscosity as a function of water content of the resole falls within the area defined by straight line interconnection in series of points (i)-(iv) where points (i)-(iv) are as follows for the indicated formaldehyde-to-phenol mole ratios: (a) at a formaldehyde-to-phenol mole ratio of at least 1.9:1 and no more than about 2.2:1, points (i)-(iv) are: (i) a viscosity of about 50,000 centipoise at a water content of about 1.7 weight percent; (ii) a viscosity of about 50,000 centipoise at a water content of about 9.5 weight percent; (iii) a viscosity of about 12,000 centipoise at a water content of about 15.0 weight percent; and (iv) a viscosity of about 1,000 centipoise at a water content of about 15.0 weight percent; (b) at a formaldehyde-to-phenol mole ratio of at least 1.7:1 and less than 1.9:1, points (i)-(iv) are: (i) a viscosity of about 50,000 centipoise at a water content of about 3.0 weight percent; (ii) a viscosity of about 50,000 centipoise at a water content of about 14.0 weight percent; (iii) a viscosity of about 25,000 centipoise at a water content of about 16.0 weight percent; and (iv) a viscosity of about 1,000 centipoise at a water content of about 16.0 weight percent; (c) at a formaldehyde-to-phenol mole ratio of at least about 1.6:1 and less than 1.7:1, points (i)-(iv) are: (i) a viscosity of about 50,000 centipoise at a water content of about 6.5 weight percent; (ii) a viscosity of about 50,000 centipoise at a water content of about 12.5 weight percent; (iii) a viscosity of about 25,000 centipoise at a water content of about 16.0 weight percent; and (iv) a viscosity of about 3,000 centipoise at a water content of about 16.0 weight percent; wherein the said viscosity values are Brookfield at 25° C.
Claim 2
Dependent Claim
411 words
A phenolic resole capable of being foamed to a phenolic foam having a density from 1.90 to 3.70 pounds per cubic foot and, within said density range, a friability of less than 35 percent weight loss (after 10 minutes) and a compressive strength (parallel of at least 20 pounds per square inch which resole has been produced by the base-catalyzed condensation of formaldehyde and phenol at a formaldehyde-to-phenol mole ratio from about 1.6:1 to about 2.2:1, the aqueous alkaline condensate having been brought to a pH from about 5.0 to about 7.0 by the addition thereto of a salt-forming acidic compound, said resole being characterized by an average molecular weight such that a plot of log viscosity as a function of water content of the resole falls within the area defined by straight line interconnection in series of points (i)-(iv) where points (i)-(iv) are as follows for the indicated formaldehyde-to-phenol mole ratios: (a) at a formaldehyde-to-phenol mole ratio of at least 1.9:1 and no more than about 2.2:1, points (i)-(iv) are: (i) a viscosity of about 50,000 centipoise at a water content of about 1.7 weight percent; (ii) a viscosity of about 50,000 centipoise at a water content of about 9.5 weight percent; (iii) a viscosity of about 12,000 centipoise at a water content of about 15.0 weight percent; and (iv) a viscosity of about 1,000 centipoise at a water content of about 15.0 weight percent; (b) at a formaldehyde-to-phenol mole ratio of at least 1.7:1 and less than 1.9:1, points (i)-(iv) are: (i) a viscosity of about 50,000 centipoise at a water content of about 3.0 weight percent; (ii) a viscosity of about 50,000 centipoise at a water content of about 14.0 weight percent; (iii) a viscosity of about 25,000 centipoise at a water content of about 16.0 weight percent; and (iv) a viscosity of about 1,000 centipoise at a water content of about 16.0 weight percent; (c) at a formaldehyde-to-phenol mole ratio of at least about 1.6:1 and less than 1.7:1, points (i)-(iv) are: (i) a viscosity of about 50,000 centipoise at a water content of about 6.5 weight percent; (ii) a viscosity of about 50,000 centipoise at a water content of about 12.5 weight percent; (iii) a viscosity of about 25,000 centipoise at a water content of about 16.0 weight percent; and (iv) a viscosity of about 3,000 centipoise at a water content of about 16.0 weight percent; wherein the said viscosity values are Brookfield at 25° C.
Claim 3
Dependent Claim
30 words
A phenolic resole as defined in claim 1 wherein the formaldehyde-to-phenol mole ratio at which the condensation reaction is affected is at least 1.9:1 and no more than about 2.2:1.
Claim 4
Dependent Claim
28 words
A phenolic resole as defined in claim 1 wherein the formaldehyde-to-phenol mole ratio at which the condensation reaction is effected is at least 1.7:1 and less than 1.9:1.
Claim 5
Dependent Claim
29 words
A phenolic resole as defined in claim 1 wherein the formaldehyde-to-phenol mole ratio at which the condensation reaction is effected is at least about 1.6:1 and less than 1.7:1.
Claim 6
Dependent Claim
27 words
A phenolic resole as defined in claim 1 in which the condensation reaction is effected in the presence of an alkali metal hydroxide as the condensation catalyst.
Claim 7
Dependent Claim
16 words
A phenolic resole as defined in claim 5 in which the condensation catalyst is sodium hydroxide.
Claim 8
Dependent Claim
16 words
A phenolic resole as defined in claim 5 in which the condensation catalyst is potassium hydroxide.
Claim 9
Dependent Claim
28 words
A phenolic resole as defined in claim 1 in which the condensation reaction is effected in the presence of an alkaline earth metal hydroxide as the condensation catalyst.
Claim 10
Dependent Claim
16 words
A phenolic resole as defined in claim 8 in which the condensation catalyst is barium hydroxide.
Claim 11
Dependent Claim
256 words
A phenolic resole capable of being foamed to a phenolic foam having a density from 1.90 to 3.70 pounds per cubic foot and, within said density range, a friability of less than 35 percent weight loss (after 10 minutes) and a compressive strength (parallel) of at least 20 pounds per square inch which resole has been produced by the base-catalyzed condensation of formaldehyde and phenol as the sole organic reactants fed to the condensation reaction, at a mole ratio of at least 1.9 and no more than about 2.2 moles of formaldehyde per mole of phenol, the aqueous alkaline condensate having been brought to a pH from about 5.0 to about 7.0 by the addition thereto of a salt-forming acidic compound, said resole being characterized by an average molecular weight such that a plot of log viscosity as a function of water content of the resole falls within the area defined by straight line interconnection in series of points (a)-(e) where points (a)-(e) are as follows: (a) a viscosity of about 50,000 centipoise at a water content of about 7.0 weight percent; (b) a viscosity of about 50,000 centipoise at a water content of about 9.5 weight percent; (c) a viscosity of about 26,000 centipoise at a water content of about 12.0 weight percent; (d) a viscosity of about 4,000 centipoise at a water content of about 12.0 weight percent; and (e) a viscosity of about 20,000 centipoise at a water content of about 7.0 weight percent; wherein the viscosity values are Brookfield at 25° C.
Claim 12
Dependent Claim
256 words
A phenolic resole capable of being foamed to a phenolic foam having a density from 1.90 to 3.70 pounds per cubic foot and, within said density range, a friability of less than 35 percent weight loss (after 10 minutes) and a compressive strength (parallel) of at least 20 pounds per square inch which resole has been produced by the base-catalyzed condensation of formaldehyde and phenol as the sole organic reactants fed to the condensation reaction, at a mole ratio of at least 1.9 and no more than about 2.2 moles of formaldehyde per mole of phenol, the aqueous alkaline condensate having been brought to a pH from about 5.0 to about 7.0 by the addition thereto of a salt-forming acidic compound, said resole being characterized by an average molecular weight such that a plot of log viscosity as a function of water content of the resole falls within the area defined by straight line interconnection in series of points (a)-(e) where points (a)-(e) are as follows: (a) a viscosity of about 50,000 centipoise at a water content of about 7.0 weight percent; (b) a viscosity of about 50,000 centipoise at a water content of about 9.5 weight percent; (c) a viscosity of about 26,000 centipoise at a water content of about 12.0 weight percent; (d) a viscosity of about 4,000 centipoise at a water content of about 12.0 weight percent; and (e) a viscosity of about 20,000 centipoise at a water content of about 7.0 weight percent; wherein the viscosity values are Brookfield at 25° C.
Claim 13
Dependent Claim
254 words
A phenolic resole capable of being foamed to a phenolic foam having a density from 1.90 to 3.70 pounds per cubic foot and, within said density range, a friability of less than 35 percent weight loss (after 10 minutes) and a compressive strength (parallel) of at least 20 pounds per square inch which resole has been produced by the base-catalyzed condensation of formaldehyde and phenol as the sole organic reactants fed to the condensation reaction, at a mole ratio of at least 1.7 and less than 1.9 moles of formaldehyde per mole of phenol, the aqueous alkaline condensate having been brought to a pH from about 5.0 to about 7.0 by the addition thereto of a salt-forming acidic compound, said resole being characterized by an average molecular weight such that a plot of log viscosity as a function of water content of the resole falls within the area defined by straight line interconnection in series of points (a)-(e) where points (a)-(e) are as follows: (a) a viscosity of about 50,000 centipoise at a water content of about 7.0 weight percent; (b) a viscosity of about 50,000 centipoise at a water content of about 9.5 weight percent; (c) a viscosity of about 25,000 centipoise at a water content of about 12.0 weight percent; (d) a viscosity of about 4,200 centipoise at a water content of about 12.0 weight percent; and (e) a viscosity of about 34,000 centipoise at a water content of about 7.0 weight percent; wherein the viscosity values are Brookfield at 25° C.
Claim 14
Dependent Claim
254 words
A phenolic resole capable of being foamed to a phenolic foam having a density from 1.90 to 3.70 pounds per cubic foot and, within said density range, a friability of less than 35 percent weight loss (after 10 minutes) and a compressive strength (parallel) of at least 20 pounds per square inch which resole has been produced by the base-catalyzed condensation of formaldehyde and phenol as the sole organic reactants fed to the condensation reaction, at a mole ratio of at least 1.7 and less than 1.9 moles of formaldehyde per mole of phenol, the aqueous alkaline condensate having been brought to a pH from about 5.0 to about 7.0 by the addition thereto of a salt-forming acidic compound, said resole being characterized by an average molecular weight such that a plot of log viscosity as a function of water content of the resole falls within the area defined by straight line interconnection in series of points (a)-(e) where points (a)-(e) are as follows: (a) a viscosity of about 50,000 centipoise at a water content of about 7.0 weight percent; (b) a viscosity of about 50,000 centipoise at a water content of about 9.5 weight percent; (c) a viscosity of about 25,000 centipoise at a water content of about 12.0 weight percent; (d) a viscosity of about 4,200 centipoise at a water content of about 12.0 weight percent; and (e) a viscosity of about 34,000 centipoise at a water content of about 7.0 weight percent; wherein the viscosity values are Brookfield at 25° C.
Claim 15
Dependent Claim
380 words
In a process for producing phenol/formaldehyde resoles by the base-catalyzed condensation of phenol and formaldehyde and wherein the aqueous alkaline condensate is brought to a pH from about 5.0 to about 7.0 by the addition thereto of salt-forming acidic compound, the improvement which comprises introducing formaldehyde and phenol to the condensation reaction at a mole ratio of from about 1.6 to about 2.2 moles of formaldehyde per mole of phenol and effecting the condensation reaction under conditions such that a plot of log viscosity as a function of water content of the resole product falls within the area defined by straight line interconnection in series of points (i)-(iv) where points (i)-(iv) are as follows for the formaldehyde-to-phenol mole ratios indicated below: (a) at a formaldehyde-to-phenol mole ratio of at least 1.9:1 and no more than about 2.2:1, points (i)-(iv) are: (i) a viscosity of about 50,000 centipoise at a water content of about 1.7 weight percent; (ii) a viscosity of about 50,000 centipoise at a water content of about 9.5 weight percent; (iii) a viscosity of about 12,000 centipoise at a water content of about 15.0 weight percent; and (iv) a viscosity of about 1,000 centipoise at a water content of about 15.0 weight percent; (b) at a formaldehyde-to-phenol mole ratio of at least 1.7:1 and less than 1.9:1, points (i)-(iv) are: (i) a viscosity of about 50,000 centipoise at a water content of about 3.0 weight percent; (ii) a viscosity of about 50,000 centipoise at a water content of about 14.0 weight percent; (iii) a viscosity of about 25,000 centipoise at a water content of about 16.0 weight percent; and (iv) a viscosity of about 1,000 centipoise at a water content of about 16.0 weight percent; (c) at a formaldehyde-to-phenol mole ratio of at least about 1.6:1 and less than 1.7:1, points (i)-(iv) are: (i) a viscosity of about 50,000 centipoise at a water content of about 6.5 weight percent; (ii) a viscosity of about 50,000 centipoise at a water content of about 12.5 weight percent; (iii) a viscosity of about 25,000 centipoise at a water content of about 16.0 weight percent; and (iv) a viscosity of about 3,000 centipoise at a water content of about 16.0 weight percent; wherein the said viscosity values are Brookfield at 25° C.
Claim 16
Dependent Claim
380 words
In a process for producing phenol/formaldehyde resoles by the base-catalyzed condensation of phenol and formaldehyde and wherein the aqueous alkaline condensate is brought to a pH from about 5.0 to about 7.0 by the addition thereto of salt-forming acidic compound, the improvement which comprises introducing formaldehyde and phenol to the condensation reaction at a mole ratio of from about 1.6 to about 2.2 moles of formaldehyde per mole of phenol and effecting the condensation reaction under conditions such that a plot of log viscosity as a function of water content of the resole product falls within the area defined by straight line interconnection in series of points (i)-(iv) where points (i)-(iv) are as follows for the formaldehyde-to-phenol mole ratios indicated below: (a) at a formaldehyde-to-phenol mole ratio of at least 1.9:1 and no more than about 2.2:1, points (i)-(iv) are: (i) a viscosity of about 50,000 centipoise at a water content of about 1.7 weight percent; (ii) a viscosity of about 50,000 centipoise at a water content of about 9.5 weight percent; (iii) a viscosity of about 12,000 centipoise at a water content of about 15.0 weight percent; and (iv) a viscosity of about 1,000 centipoise at a water content of about 15.0 weight percent; (b) at a formaldehyde-to-phenol mole ratio of at least 1.7:1 and less than 1.9:1, points (i)-(iv) are: (i) a viscosity of about 50,000 centipoise at a water content of about 3.0 weight percent; (ii) a viscosity of about 50,000 centipoise at a water content of about 14.0 weight percent; (iii) a viscosity of about 25,000 centipoise at a water content of about 16.0 weight percent; and (iv) a viscosity of about 1,000 centipoise at a water content of about 16.0 weight percent; (c) at a formaldehyde-to-phenol mole ratio of at least about 1.6:1 and less than 1.7:1, points (i)-(iv) are: (i) a viscosity of about 50,000 centipoise at a water content of about 6.5 weight percent; (ii) a viscosity of about 50,000 centipoise at a water content of about 12.5 weight percent; (iii) a viscosity of about 25,000 centipoise at a water content of about 16.0 weight percent; and (iv) a viscosity of about 3,000 centipoise at a water content of about 16.0 weight percent; wherein the said viscosity values are Brookfield at 25° C.
Claim 17
Dependent Claim
33 words
A process as defined in claim 12 in which the condensation reaction is effected in the presence of sodium hydroxide at a formaldehyde-to-phenol ratio of at least 1.9:1 and up to about 2.2:1.
References Cited (Backward Citations)
US2744875A
Cited
US3271331A
Cited
US3298973A
Cited
US3673130A
Cited
US3876620A
Cited
US3953645A
Cited
US4001148A
Cited
US4033909A
Cited
US3968300A
Cited
US4033910A
Cited
US4070313A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1982-11-26 | 1983-05-28 | 1983-11-27 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-11-26 | 1987-05-28 | 1987-11-27 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-11-26 | 1991-05-28 | 1991-11-27 | $7700.00 | Window Closed / Lapsed |