US5281644A
Expired / Lapsed
US
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Ambient temperature hardening binder compositions
Assignee: Hexion Inc
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Filing: 1992-11-04
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Granted: 1994-01-25
•
Expires: 2012-11-04
Abstract
Abstract There are disclosed methods and compositions for retarding the ambient temperature hardening of a phenolic resole resin alone or with an aggregate when such resin is contacted with a nitroalkane and a hardening agent such as lightburned magnesium oxide, an organic ester functional hardening agent, and mixtures of lightburned magnesium oxide and an organic ester functional hardening agent in an alkaline medium. There is also disclosed a hardener composition for phenolic resole resins wherein the hardener composition consists essentially of a solution of a nitroalkane in an organic ester functional hardening agent.
Inventors
- 👤 S. Raja Iyer
- 👤 David R. Armbruster
- 👤 Arthur H. Gerber
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-07 19:58
CPC Classifications
C; C08; C08L; C08L61/00; C08L61/04; C08L61/06; C08L61/12; C08K; C08K5/00; C08K5/16; C08K5/32; C08G; C08G8/00; C08G8/04; C08G8/08; C08G8/20; C08G8/22; C08K3/00; C08K3/18; C08K3/20; C08K3/22; C08K3/28; C08K3/34; C08K3/36; C08K3/38; C08K5/04; C08K5/10
Claims Analysis
Total Claims: 43
Claim 1
Independent Claim
128 words
A method for retarding the ambient temperature hardening of a phenolic resole resin and a hardening agent which hardens the resin at ambient temperature under alkaline conditions which comprises contacting said resin and hardening agent with a nitroalkane and permitting the resin to harden under alkaline conditions wherein the nitroalkane is in a amount sufficient to retard the hardening, said nitroalkane having the formula: ##STR3## wherein each of R 1 and R 2 is a member selected from the group consisting of hydrogen, alkyl group having from 1 to 5 carbon atoms and wherein R 1 and R 2 taken together with the carbon to which they are attached is a cycloaliphatic group and wherein the total number of carbon atoms in the nitroalkane does not exceed 6.
Claim 2
Independent Claim
128 words
A method for retarding the ambient temperature hardening of a phenolic resole resin and a hardening agent which hardens the resin at ambient temperature under alkaline conditions which comprises contacting said resin and hardening agent with a nitroalkane and permitting the resin to harden under alkaline conditions wherein the nitroalkane is in a amount sufficient to retard the hardening, said nitroalkane having the formula: ##STR3## wherein each of R 1 and R 2 is a member selected from the group consisting of hydrogen, alkyl group having from 1 to 5 carbon atoms and wherein R 1 and R 2 taken together with the carbon to which they are attached is a cycloaliphatic group and wherein the total number of carbon atoms in the nitroalkane does not exceed 6.
Claim 3
Dependent Claim
19 words
The method of claim 1 wherein the total number of carbon atoms in the nitroalkane does not exceed 4.
Claim 4
Dependent Claim
16 words
The method of claim 1 wherein the temperature is from about 65° F. to 100° F.
Claim 5
Dependent Claim
41 words
The method of claim 2 wherein the hardening agent is a member selected from the group consisting of: lightburned magnesium oxide; an organic ester functional hardening agent; and a mixture of lightburned magnesium oxide and an organic ester functional hardening agent.
Claim 6
Dependent Claim
33 words
The method of claim 4 wherein the resin is the reaction product of phenol and formaldehyde having a pH of at least 11 and the hardener is an organic ester functional hardening agent.
Claim 7
Dependent Claim
51 words
The method of claim 4 wherein the resin is the reaction product of phenol and formaldehyde having a pH of about 4.5 to 9.5 and the hardener is member selected from the group consisting of lightburned magnesium oxide and a mixture of lightburned magnesium oxide and organic ester functional hardening agent.
Claim 8
Dependent Claim
12 words
The method of claim 6 wherein the hardener is lightburned magnesium oxide.
Claim 9
Independent Claim
214 words
A method for retarding the ambient temperature hardening of a phenolic resole resin and a hardening agent which hardens the resin at ambient temperature under alkaline conditions which comprises contacting said resin with a hardening agent in sufficient quantity to harden the resin, said hardening agent selected from the group consisting of lightburned magnesium oxide, gamma-butyrolactone, gamma-caprolactone, gamma-valerolactone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, ethylene glycol diacetate, glycerol triacetate, dimethyl adipate, dimethyl glutarate, dimethyl succinate, an esterified phenol having at least one phenolic hydroxyl group and/or esterified phenolic hydroxyl group and further having at least one esterified methylol group ortho- and/or para- to a phenolic hydroxyl group or esterified phenolic hydroxyl group wherein the acid component of the ester has from 1 to 3 carbon atoms, and mixtures of said hardening agents with a nitroalkane in an amount sufficient to retard the hardening, said nitroalkane having the formula: ##STR4## wherein each of R 1 and R 2 is a member selected from the group consisting of hydrogen, alkyl group having from 1 to 5 carbon atoms and wherein R 1 and R 2 taken together with the carbon to which they are attached is a cycloaliphatic group and wherein the total number of carbon atoms in the nitroalkane does not exceed 6.
Claim 10
Independent Claim
214 words
A method for retarding the ambient temperature hardening of a phenolic resole resin and a hardening agent which hardens the resin at ambient temperature under alkaline conditions which comprises contacting said resin with a hardening agent in sufficient quantity to harden the resin, said hardening agent selected from the group consisting of lightburned magnesium oxide, gamma-butyrolactone, gamma-caprolactone, gamma-valerolactone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, ethylene glycol diacetate, glycerol triacetate, dimethyl adipate, dimethyl glutarate, dimethyl succinate, an esterified phenol having at least one phenolic hydroxyl group and/or esterified phenolic hydroxyl group and further having at least one esterified methylol group ortho- and/or para- to a phenolic hydroxyl group or esterified phenolic hydroxyl group wherein the acid component of the ester has from 1 to 3 carbon atoms, and mixtures of said hardening agents with a nitroalkane in an amount sufficient to retard the hardening, said nitroalkane having the formula: ##STR4## wherein each of R 1 and R 2 is a member selected from the group consisting of hydrogen, alkyl group having from 1 to 5 carbon atoms and wherein R 1 and R 2 taken together with the carbon to which they are attached is a cycloaliphatic group and wherein the total number of carbon atoms in the nitroalkane does not exceed 6.
Claim 11
Dependent Claim
11 words
The method of claim 8 wherein the hardening agent is gamma-butyrolactone.
Claim 12
Dependent Claim
12 words
The method of claim 8 wherein the hardening agent is ethylene carbonate.
Claim 13
Dependent Claim
12 words
The method of claim 8 wherein the hardening agent is propylene carbonate.
Claim 14
Dependent Claim
12 words
The method of claim 8 wherein the hardening agent is methyl lactate.
Claim 15
Dependent Claim
12 words
The method of claim 8 wherein the hardening agent is ethyl lactate.
Claim 16
Dependent Claim
13 words
The method of claim 8 wherein the hardening agent is ethylene glycol diacetate.
Claim 17
Dependent Claim
12 words
The method of claim 8 wherein the hardening agent is glycerol triacetate.
Claim 18
Dependent Claim
19 words
The method of claim 8 wherein the hardening agent is dimethyl adipate, dimethyl glutarate, dimethyl succinate or mixtures thereof.
Claim 19
Dependent Claim
40 words
The method of claim 8 wherein the total number of carbon atoms in the nitroalkane does not exceed 4, the temperature is from about 65° F. to 100° F., and the alkaline conditions have a pH of at least 11.
Claim 20
Dependent Claim
24 words
The method of claim 8 wherein the alkaline conditions are at a pH of at least 11 and the hardening agent is an ester.
Claim 21
Dependent Claim
40 words
The method of claim 8 wherein the total number of carbon atoms in the nitroalkane does not exceed 4, the temperature is from about 65° F. to 100° F., the alkaline conditions are at a pH of less than 10.
Claim 22
Dependent Claim
13 words
The method of claim 19 wherein the hardening agent is lightburned magnesium oxide.
Claim 23
Independent Claim
195 words
A method for retarding the hardening of a composition comprising a phenolic resole resin which comprises contacting at a temperature of about 50° F. to 120° F.: A. a hardenable, alkaline phenolic resole resin having a solids content of from about 40% to about 75% by weight thereof, an aldehyde to phenol molar ratio of from about 1.2:1 to about 2.6:1; an alkali to phenol molar ratio of from about 0.2:1 to about 1.2:1; and a pH above 11; B. an organic ester functional hardening agent selected from the group consisting of an organic carbonate, a lactone, a carboxylic acid ester, and mixtures thereof in an amount sufficient to harden the resin; and C. a nitroalkane in an amount sufficient to retard the hardening of the resin, said nitroalkane having the formula: ##STR5## wherein each of R 1 and R 2 is a member selected from the group consisting of hydrogen, alkyl having from 1 to 5 carbon atoms and wherein R 1 and R 2 taken together with the carbon to which they are attached is a cycloaliphatic group and wherein the total number of carbon atoms in the nitroalkane does not exceed 6.
Claim 24
Independent Claim
195 words
A method for retarding the hardening of a composition comprising a phenolic resole resin which comprises contacting at a temperature of about 50° F. to 120° F.: A. a hardenable, alkaline phenolic resole resin having a solids content of from about 40% to about 75% by weight thereof, an aldehyde to phenol molar ratio of from about 1.2:1 to about 2.6:1; an alkali to phenol molar ratio of from about 0.2:1 to about 1.2:1; and a pH above 11; B. an organic ester functional hardening agent selected from the group consisting of an organic carbonate, a lactone, a carboxylic acid ester, and mixtures thereof in an amount sufficient to harden the resin; and C. a nitroalkane in an amount sufficient to retard the hardening of the resin, said nitroalkane having the formula: ##STR5## wherein each of R 1 and R 2 is a member selected from the group consisting of hydrogen, alkyl having from 1 to 5 carbon atoms and wherein R 1 and R 2 taken together with the carbon to which they are attached is a cycloaliphatic group and wherein the total number of carbon atoms in the nitroalkane does not exceed 6.
Claim 25
Dependent Claim
25 words
The method of claim 21 wherein: the temperature is from 65° F. to 110° F.; and the nitroalkane has from 1 to 4 carbon atoms.
Claim 26
Dependent Claim
95 words
The method of claim 21 wherein the hardening agent is selected from the group consisting of gamma-butyrolactone, gamma-caprolactone, gamma-valerolactone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, ethylene glycol diacetate, glycerol triacetate, dimethyl adipate, dimethyl glutarate, dimethyl succinate, an esterified phenol having at least one phenolic hydroxyl group and/or esterified phenolic hydroxyl group and further having at least one esterified methylol group ortho- and/or para- to a phenolic hydroxyl group or esterified phenolic hydroxyl group wherein the acid component of the ester has from 1 to 3 carbon atoms, and mixtures of said hardening agents.
Claim 27
Dependent Claim
11 words
The method of claim 21 wherein the ester is a lactone.
Claim 28
Dependent Claim
13 words
The method of claim 21 wherein the ester is a cyclic organic carbonate.
Claim 29
Dependent Claim
11 words
The method of claim 21 wherein the ester is glycerol triacetate.
Claim 30
Independent Claim
112 words
A method for retarding the hardening of a composition comprising a phenolic resole resin which comprises contacting at a temperature of about 50° F. to 120° F.: A. a hardenable, phenolic resole resin having a pH of about 4.5 to 9.5; B. a hardening agent selected from the group consisting of lightburned magnesium oxide and lightburned magnesium oxide together with an organic ester functional hardening agent is an amount sufficient to harden the resin at said temperature at an alkaline pH of less than 10; and C. a primary or secondary nitroalkane having one nitro-group and 1 to 6 carbon atoms in an amount sufficient to retard the hardening of the resin.
Claim 31
Independent Claim
112 words
A method for retarding the hardening of a composition comprising a phenolic resole resin which comprises contacting at a temperature of about 50° F. to 120° F.: A. a hardenable, phenolic resole resin having a pH of about 4.5 to 9.5; B. a hardening agent selected from the group consisting of lightburned magnesium oxide and lightburned magnesium oxide together with an organic ester functional hardening agent is an amount sufficient to harden the resin at said temperature at an alkaline pH of less than 10; and C. a primary or secondary nitroalkane having one nitro-group and 1 to 6 carbon atoms in an amount sufficient to retard the hardening of the resin.
Claim 32
Dependent Claim
28 words
The method of claim 27 wherein the hardening agent is lightburned magnesium oxide together with an organic ester functional hardening agent and wherein said ester is a lactone.
Claim 33
Dependent Claim
29 words
The method of claim 27 wherein the hardening agent is lightburned magnesium oxide together with an organic ester functional hardening agent and the ester is a cyclic organic carbonate.
Claim 34
Dependent Claim
13 words
The method of claim 27 wherein the hardening agent is lightburned magnesium oxide.
Claim 35
Dependent Claim
10 words
The method of claim 27 wherein the ester is gamma-butyroilactone.
Claim 36
Independent Claim
146 words
A method for retarding the hardening of a phenolformaldehyde resole resin and an organic ester functional hardening agent at ambient temperature which comprises mixing: A. a hardenable, alkaline phenol-formaldehyde resole resin having a solids content of from about 40% to about 75% by weight thereof, a formaldehyde to phenol molar ratio of from about 1.2:1 to about 2.6:1; an alkali to phenol molar ratio of from about 0.2:1 to about 1.2:1; and a pH above 11; B. an organic ester functional hardening agent selected from the group consisting of an organic carbonate, a lactone, a carboxylic acid ester, and mixtures thereof in an amount sufficient to harden the resin; C. a primary or secondary nitroalkane having one nitro group and 1 to 6 carbon atoms in an amount sufficient to retard the hardening of the resin; and then permitting the resin to cure to a solid.
Claim 37
Independent Claim
146 words
A method for retarding the hardening of a phenolformaldehyde resole resin and an organic ester functional hardening agent at ambient temperature which comprises mixing: A. a hardenable, alkaline phenol-formaldehyde resole resin having a solids content of from about 40% to about 75% by weight thereof, a formaldehyde to phenol molar ratio of from about 1.2:1 to about 2.6:1; an alkali to phenol molar ratio of from about 0.2:1 to about 1.2:1; and a pH above 11; B. an organic ester functional hardening agent selected from the group consisting of an organic carbonate, a lactone, a carboxylic acid ester, and mixtures thereof in an amount sufficient to harden the resin; C. a primary or secondary nitroalkane having one nitro group and 1 to 6 carbon atoms in an amount sufficient to retard the hardening of the resin; and then permitting the resin to cure to a solid.
Claim 38
Dependent Claim
15 words
The method of claim 32 wherein the nitroalkane has from 1 to 4 carbon atoms.
Claim 39
Dependent Claim
12 words
The method of claim 33 wherein the ester is an aliphatic ester.
Claim 40
Independent Claim
109 words
A method for retarding the hardening of a phenolformaldehyde resole resin at ambient temperature which comprises mixing: A. a hardenable, phenol-formaldehyde resole resin having a pH of about 4.5 to 9.5; B. a hardening agent selected from the group consisting of lightburned magnesium oxide and lightburned magnesium oxide together with an organic ester functional hardening agent in an amount sufficient to harden the resin at an alkaline pH of less than 10; C. a primary or secondary nitroalkane having one nitro group and 1 to 6 carbon atoms in an amount sufficient to retard the hardening of the resin; and then permitting the resin to cure to a solid.
Claim 41
Independent Claim
109 words
A method for retarding the hardening of a phenolformaldehyde resole resin at ambient temperature which comprises mixing: A. a hardenable, phenol-formaldehyde resole resin having a pH of about 4.5 to 9.5; B. a hardening agent selected from the group consisting of lightburned magnesium oxide and lightburned magnesium oxide together with an organic ester functional hardening agent in an amount sufficient to harden the resin at an alkaline pH of less than 10; C. a primary or secondary nitroalkane having one nitro group and 1 to 6 carbon atoms in an amount sufficient to retard the hardening of the resin; and then permitting the resin to cure to a solid.
Claim 42
Dependent Claim
42 words
The method of claim 35 wherein the molar ratio of formaldehyde to phenol is from about 1.2 to 2.6 moles of formaldehyde per mole of phenol and wherein the hardening agent is lightburned magnesium oxide together with an ester functional hardening agent.
Claim 43
Dependent Claim
12 words
The method of claim 36 wherein the ester is an aliphatic ester.
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1997-01-24 | 1997-07-26 | 1998-01-25 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2001-01-24 | 2001-07-26 | 2002-01-25 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2005-01-24 | 2005-07-26 | 2006-01-25 | $7700.00 | Window Closed / Lapsed |