CA1101416A - Compounds useful as curing agents and processes for their preparation - Google Patents
Compounds useful as curing agents and processes for their preparationInfo
- Publication number
- CA1101416A CA1101416A CA276,500A CA276500A CA1101416A CA 1101416 A CA1101416 A CA 1101416A CA 276500 A CA276500 A CA 276500A CA 1101416 A CA1101416 A CA 1101416A
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- Prior art keywords
- integer
- molecular weight
- bonded
- carbon atoms
- terminal carbon
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyethers (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE INVENTION
Novel compounds typified by N,N'-polyoxyalkylene bis (pyrrolidinone-3-carboxylic acid) are disclosed as useful as epoxy curing accelerators. Alkali metal salts thereof are curing agents for isocyanurate foams.
Novel compounds typified by N,N'-polyoxyalkylene bis (pyrrolidinone-3-carboxylic acid) are disclosed as useful as epoxy curing accelerators. Alkali metal salts thereof are curing agents for isocyanurate foams.
Description
~01~16 This invention relates to novel products particularly characteri~ed by their use as curing agents for epoxy resins or isocyanurate foams or as accelerators for curable epoxy resins.
As is well known to those skilled in the art, epoxy resins may be cured by the use of aromatic amines such as (i) methylene dianiline, (ii) the polymeric condensation produc~ of aniline and formaldehyde, etc.
Typical prior art curing, at elevated temperatures of 80C or higherJ yields products which are resistant to attack by chemicals, solvents, etc. Curing of epoxy resins at ambient temperature however yields product coatings which are undercured, brittle, without strength, and readily attacked by many chemicals and solvents.
It is an object of this invention to provide novel products which may be used in curing systems. Other objects will be apparent to those skilled in the art.
In accordance with certain of its aspects, this invention is directed to novel products ] ~ C - C - C00M ) ~' a wherein x is an integer 0-2, a is an integer at least 2, preferably 2-3, M is hydrogen or a cation derived from a strong base R"' is a polyoxyalkylene chain having terminal carbon atoms to which the nitrogen atoms are bonded, .^~.
11~31~16 and the molecular weight of R" ' is 200 to about 2000 except that the molecular weight of R I I is 300 to about 2000 when _ is 0 and M is hydrogen and to the process for preparing these products which comprises adding to a reaction mixture a moles of unsaturated carboxylic acid HOOC - C = C
Cx C - COH
o adding to said reaction mixture about one mole of a polyoxyalkylene polyamine r 1 :
L R I~ (NH2)a maintaining said unsaturated carboxylic acid and said polyoxyalkylene polyamine at ring-forming conditions ~hereby forming said product; and recovering said product .
The salts, in which M is a cation derived from a base~ may be prepared either by reacting the charge acid in the form of its salt or by reacting the acid product with a base.
In accordance with certain of its more specific aspects, this invention is directed to novel products HOOC - C - C C - C - COOH
C - C / { ~ ` C -- C
O O
wherein x is an integer 0-2, and -R"- is a polyoxyalkalene chain of molecular weight of about 200-2000 having terminal carbon atoms to which the nitrogen atoms are bonded~ and to : ~ - 2 -a process for preparing these products which comprises adding to a reaction mixture two moles of unsaturated carboxylic acid HOOC - C = C
., C
x C~COH
O
adding to said reaction mixture about one mole of a polyoxyalkalene diamine X2N ~ R ~ NH2 maintaining said unsaturated carboxylic acid and said polyoxyalkylene diamine at ring-forming conditions thereby forming said product;
and recovering said product.
i, 11~1416 DESCRIPTION OF THE INVENTION
The charge unsaturated carboxylic acids which may be used in prac-tice of the process of this invention are characterized by the formula:
HOOC - C = C
,C
: C - C - OH
o wherein x is an integer 0-2. Valence bonds in this structure, or in others in this specification, may be filled with hydrogen or with inert substituents which do not interfere with the reaction.
When x is 2~ the acid may be represented by the formula (typified by alpha-methylene adipic acid):
HOOC - C = C
C
C
C - C - OH
When x is 1, the acid may be represented by the formula (typified by alpha-methylene glutaric acid):
HOOC - C - C
C
C - C - OH
o When x is 0, the acid may be represented by the formula (typified 15 by itaconic acid):
HOOC - C = C
C - C - OH
o .:
In the preferred acid, x is zero. The preferred acid is thus ` itaconic acid.
The polyoxyalkylene polyamines which may be used in practice of - the process of this invention are characterized by the formula r ~ O
L
wherein a is an integer preferably 2-3 and R "' is a polyoxyalkylene chain of molecular weight 200-2000 havlng a terminal carbon atoms to which the nitrogen atoms are bonded. When a is 3, an illustrative compound of molec-ular weight of about 400 may be CH2 ~ OCX2CH(CH3) ~ 2 CH3CH2 ~ C-CH _ ~ OCH CH(CH ~ NH2 g CH2 ~ L 0CH2CH(CH3 ~ 2 wherein f plus ~ plus h is 5.3 typically as available under the trademark Jeffamine T-403 of Jefferson Chemical Company.
The preferred amines which may be used in practice of the process of this invention are polyoxyalkylene diamines characterized by the formula:
H2N ~ R 3 NH2 wherein R" is a polyoxyalkylene chain of molecular weight of about 200-2000 having terminal carbon atoms to which the nitrogen atoms are bonded. R" is derived from an oxyalkylene group, typified by oxyethylene -CH2CH20-, oxy-propylene -OCH2CH(CH3)- etc. R" may also be a polyoxyethylene bearing an added polyoxypropylene (as in the compositions marketed by Jefferson Chemical Co. under the trademark Jeffamine ED-series) typified by C,H3 ,CH3 ,CH3 ,CH3 NH2 CHCH2 (OCH2CH)n (OCH2CH2)m (OCH2CH)k OCH2CHNH2 l4~6 Typical of the polyoxyalkylene diamines which may be used in practice of the process of this invention may be those lis-ted in the table:
TABLE
a. The diterminal diamine of polyoxypropylene of molecular weight 427;
b. The diterminal diamine of polyoxypropylene of molecular weight 235;
c. The diterminal diamine of polyoxypropylene of molecular weight 2000;
d. The diterminal diamine of polyoxyethylene of molecular weight 600; etc.
It will be apparent to those skilled in the art that many of the suitable polyoxyalkylene polyamines may be available as and used as commercial mixtures of several components. Useful commercial materials include those available under the trademarks Jeffamine D-, T-, and ED- etc. as marketed by Jefferson Chemical Company.
In practice of the process of this invention, according to certain of its aspects, an equivalent amount of unsaturated carboxylic acid is added to a reaction mixture together with one mole of polyoxyalkylene polya~ine.
The reaction may be carried out in the absence of added solvent-diluent, but the latter may be present if desired -including water, toluene, etc. Water is preferably added in amount of 50 w%-200 w%, say about 100 W% of the amine.
`` 11~14~6 During the reaction, the reaction mixture is main-tained at temperature of 80C-200C, say 100 C for 4-12 hours~ say 8 hours. During this period, the following reaction occurs:
HOOC - C = C
a C + ~R~ 3 ~ NH ~ >
: C - C - OH
o C - C - COOH
~R ~ ] N \ C
C - C
o In the case of the preferred diamines, the reaction may be:
XOOC - C = C + H2N ~ R~ 3 NH2 >
As is well known to those skilled in the art, epoxy resins may be cured by the use of aromatic amines such as (i) methylene dianiline, (ii) the polymeric condensation produc~ of aniline and formaldehyde, etc.
Typical prior art curing, at elevated temperatures of 80C or higherJ yields products which are resistant to attack by chemicals, solvents, etc. Curing of epoxy resins at ambient temperature however yields product coatings which are undercured, brittle, without strength, and readily attacked by many chemicals and solvents.
It is an object of this invention to provide novel products which may be used in curing systems. Other objects will be apparent to those skilled in the art.
In accordance with certain of its aspects, this invention is directed to novel products ] ~ C - C - C00M ) ~' a wherein x is an integer 0-2, a is an integer at least 2, preferably 2-3, M is hydrogen or a cation derived from a strong base R"' is a polyoxyalkylene chain having terminal carbon atoms to which the nitrogen atoms are bonded, .^~.
11~31~16 and the molecular weight of R" ' is 200 to about 2000 except that the molecular weight of R I I is 300 to about 2000 when _ is 0 and M is hydrogen and to the process for preparing these products which comprises adding to a reaction mixture a moles of unsaturated carboxylic acid HOOC - C = C
Cx C - COH
o adding to said reaction mixture about one mole of a polyoxyalkylene polyamine r 1 :
L R I~ (NH2)a maintaining said unsaturated carboxylic acid and said polyoxyalkylene polyamine at ring-forming conditions ~hereby forming said product; and recovering said product .
The salts, in which M is a cation derived from a base~ may be prepared either by reacting the charge acid in the form of its salt or by reacting the acid product with a base.
In accordance with certain of its more specific aspects, this invention is directed to novel products HOOC - C - C C - C - COOH
C - C / { ~ ` C -- C
O O
wherein x is an integer 0-2, and -R"- is a polyoxyalkalene chain of molecular weight of about 200-2000 having terminal carbon atoms to which the nitrogen atoms are bonded~ and to : ~ - 2 -a process for preparing these products which comprises adding to a reaction mixture two moles of unsaturated carboxylic acid HOOC - C = C
., C
x C~COH
O
adding to said reaction mixture about one mole of a polyoxyalkalene diamine X2N ~ R ~ NH2 maintaining said unsaturated carboxylic acid and said polyoxyalkylene diamine at ring-forming conditions thereby forming said product;
and recovering said product.
i, 11~1416 DESCRIPTION OF THE INVENTION
The charge unsaturated carboxylic acids which may be used in prac-tice of the process of this invention are characterized by the formula:
HOOC - C = C
,C
: C - C - OH
o wherein x is an integer 0-2. Valence bonds in this structure, or in others in this specification, may be filled with hydrogen or with inert substituents which do not interfere with the reaction.
When x is 2~ the acid may be represented by the formula (typified by alpha-methylene adipic acid):
HOOC - C = C
C
C
C - C - OH
When x is 1, the acid may be represented by the formula (typified by alpha-methylene glutaric acid):
HOOC - C - C
C
C - C - OH
o When x is 0, the acid may be represented by the formula (typified 15 by itaconic acid):
HOOC - C = C
C - C - OH
o .:
In the preferred acid, x is zero. The preferred acid is thus ` itaconic acid.
The polyoxyalkylene polyamines which may be used in practice of - the process of this invention are characterized by the formula r ~ O
L
wherein a is an integer preferably 2-3 and R "' is a polyoxyalkylene chain of molecular weight 200-2000 havlng a terminal carbon atoms to which the nitrogen atoms are bonded. When a is 3, an illustrative compound of molec-ular weight of about 400 may be CH2 ~ OCX2CH(CH3) ~ 2 CH3CH2 ~ C-CH _ ~ OCH CH(CH ~ NH2 g CH2 ~ L 0CH2CH(CH3 ~ 2 wherein f plus ~ plus h is 5.3 typically as available under the trademark Jeffamine T-403 of Jefferson Chemical Company.
The preferred amines which may be used in practice of the process of this invention are polyoxyalkylene diamines characterized by the formula:
H2N ~ R 3 NH2 wherein R" is a polyoxyalkylene chain of molecular weight of about 200-2000 having terminal carbon atoms to which the nitrogen atoms are bonded. R" is derived from an oxyalkylene group, typified by oxyethylene -CH2CH20-, oxy-propylene -OCH2CH(CH3)- etc. R" may also be a polyoxyethylene bearing an added polyoxypropylene (as in the compositions marketed by Jefferson Chemical Co. under the trademark Jeffamine ED-series) typified by C,H3 ,CH3 ,CH3 ,CH3 NH2 CHCH2 (OCH2CH)n (OCH2CH2)m (OCH2CH)k OCH2CHNH2 l4~6 Typical of the polyoxyalkylene diamines which may be used in practice of the process of this invention may be those lis-ted in the table:
TABLE
a. The diterminal diamine of polyoxypropylene of molecular weight 427;
b. The diterminal diamine of polyoxypropylene of molecular weight 235;
c. The diterminal diamine of polyoxypropylene of molecular weight 2000;
d. The diterminal diamine of polyoxyethylene of molecular weight 600; etc.
It will be apparent to those skilled in the art that many of the suitable polyoxyalkylene polyamines may be available as and used as commercial mixtures of several components. Useful commercial materials include those available under the trademarks Jeffamine D-, T-, and ED- etc. as marketed by Jefferson Chemical Company.
In practice of the process of this invention, according to certain of its aspects, an equivalent amount of unsaturated carboxylic acid is added to a reaction mixture together with one mole of polyoxyalkylene polya~ine.
The reaction may be carried out in the absence of added solvent-diluent, but the latter may be present if desired -including water, toluene, etc. Water is preferably added in amount of 50 w%-200 w%, say about 100 W% of the amine.
`` 11~14~6 During the reaction, the reaction mixture is main-tained at temperature of 80C-200C, say 100 C for 4-12 hours~ say 8 hours. During this period, the following reaction occurs:
HOOC - C = C
a C + ~R~ 3 ~ NH ~ >
: C - C - OH
o C - C - COOH
~R ~ ] N \ C
C - C
o In the case of the preferred diamines, the reaction may be:
XOOC - C = C + H2N ~ R~ 3 NH2 >
2 C
._ C - COH
o HOOC - C - C
. \ - ~ / C - C - COOH
Cx N - - R~ ~ N Cx C - C C - C
O O
In the case of one preferred embodiment, itaconic acid -10 polyoxyethylene di-primary amine, the reacti.on may be:
1~1416 HOOC - C = C ~_ + H2N~-- CH2CH20-- 2CH2 NH2 C - COH ~ 15 O
,C - C - COOH
HOOC - C - C ~ _ _ / - CH2CH20 _ 2 2 O O
In the case of another preferred embodiment a specific reaction may be as follows:
HOOC - C = C _ _ l 2 2 ~ CH CH20 _ _ CH2-CH- NH2 >
C - COH
.. _ CH3 - 15 CH3 o HOOC - C - C \ _ _ C-C-COOH
C - C / l CH CH20 ~ - CH2-CH N /
" CH3 15 CH3 C-C
O
As reaction continues, the water produced by the reaction (in amount of one mole per mole of acid reacted) may be distilled off. If desired, the water may be removed during refluxing by azeotropic distil-lation with eg toluene. Typically at the end of the reaction period, the reaction mixture may be recovered and filtered, preferably in the IO presence of added filter aid such as Supercell* brand.
~Trademark - ~ -The product so obtained is preferably worked up by stripping, as in a rotary evaporator at ~0C-200C, say 95C. Stripping may typically be carried out under vacuum of 0.1-50 mm. Hg, say 0.5 mm. Hg.
Yield is about stoichiometric.
Typical product is recovered as composition which ~depending on the components from which it is prepared and its molecular weight) may generally be characterized as a clear viscous liquid, a light brown viscous liquid, a tacky resin, etc.
These products are generally characterized by their solubility in alcohols (eg benzyl alcohol, ethanol, hexanols, etc). They are particularly characterized by solubility in polymer systems in which they may find use.
These products may be used as recovered or in the form of solutions in eg benzyl alcohol. They are characterized when they are in the form of their salts, eg alkali-metal salts ~preferably potassium K, but also sodium Na, etc) by their ability to serve as accelerators for curing epoxy resins. Although they may be used as the mono-alkali-metal salt, it is preferred to use them in the form of their di-alkali metal, eg di-potassium, salt.
It is a particular feature of the novel products of this inven~ion, that when they are present as acids they serve as curing agents for isocyanurate foamed compositions.
~14~6 The dialkali metal salt iB preferably prepared by adding to the recovered reaction mixture an equivalent amount of eg potassium hydroxide in 5%-30%, say 20%
aqueous solution at 20 C-80C, say 50 C. After 10-20 minutes, say 15 minutes agitation, the reaction mixture may be filtered through a bed of filter aid and the resulting solution may be used as recovered, eg as a 10%-80%, say 50% solution. If desired the salt may be recovered as by evaporation. Both the mono-alkali and the di-alkali metal salts may be recovered.
In practice of certain of its aspects, this invention includes the method of preparing a cured epoxy resin characterized by the fact that when cured at ambient temperature of 20C-50C, say 30C, it is found to possess outstanding properties particularly with respect to strength and retention of strength after immersion in solvents. Curing agents falling outside the scope of this invention (such as eg the reaction product of itaconic acid and eg p-phenylene diamine -as disclosed in Paytash et al J. A. C. S. 72, 1415-6 (1950) - are not satisfactory as curing accelerators for - epoxy resins because they are generally high-melting solid compositions which do not readily blend in with the viscous epoxy formulation. The novel products of this invention are particularly characterized by their high compatibility with the components of the epoxy resins. The fact that they are generally liquids provides a substantial advantage to the processor.
An epoxy resin which may be cured by the process of this invention may typically be one prepared for example by the reaction of bisphenol-A with epichlorohydrin C ~ - CHCH2 Cl in the presence of a base - preferably O
sodium hydroxide. After the condensation is complete, the crude resin is freed of residual epichlorohydrin, washed well to remove salt and soluble by-products, and recovered.
Curing of 100 parts of such a resin is effected in the presence of 20-40 parts, say 30 parts of an aromatic polyamine curing agent and 1-15 parts of the accelerator of this invention in eg 10-30 parts, say 20 parts of a solution containing 10-50% of the accelerator of this invention.
Typical aromatic polyamine curing agent which may be employed is a condensation product of formaldehyde and aniline. (as marketed under the trademark JEFFAMI~E
AP-22). Illustrative curing agents may include:
TABLE
methylene dianiline diamino-diphenyl ether meta-phenylene diamine tolylene diamine ~' ` 11(;~141~
The accelerator of this invention, preferably in the form of the free acid, is mixed with the liquid epoxy resin and curing agent; and the mixture is degassed, poured into aluminum molds, and cured typically for seven days at ambient temperature.
The product epoxy resin is particularly characterized by increased strength and by increased resistance to the deteriorative action of a wide range of liquids.
In practice of certain of its other aspects, this invention includes the method of preparing cured isocyanurate foams particularly characterized by their desirably longer cream time which desirably allows more latitude during preparation - i.e. the formulation is more mobile and handleable during a longer period of time.
An isocyanurate foam which may be cured by the process of this invention may be one prepared by reacting an isocyanate typified by a phosgenated condensation product of aniline and formaldehyde having an NC0 equivalent weight of 134 and a functionality of 2.7.
~ ` 11(~1416 The isocyanate is preferably reacted with a polyol which has two or more active hydrogen atoms as determined by the Zerewitinoff method e.g. the polyoxyalkylene polyols which may be employed in practice of this invention will be organic compounds having two or more reactive hydrogen atoms which will react with organic polyfunctional isocyanates to give urethane polymers. These polyoxyalkylene polyols typically having a hydroxyl number of 100-800 preferably 200-300, say 200, may include polyesters, polyethers, polyisocyanate modified polyesters, polyisocyanate modified polyester amides, alkylene glycols, polyamines, polyiso-cyanate modified alkylene glycols, etc. It will be understood that these polyols may have active primary or secondary hydroxyl groups. The polyol may be a hydroxyl-containing polyether or polyester including fatty acid glycerides. Polyesters, which are a preferred type of polyol, may be obtained by esterification condensation reaction of e.g. an aliphatic dibasic carboxylic acid with a glycol or a triol or mixture thereof in proportion such that the resultant polyesters may contain predominantly terminal hydroxyl groups. Dibasic carboxylic acids suitable for preparing polyesters may include aliphatic and aromatic acids such as adipic acid, fumaric acid, sebacic acid, phthalic acid; suitable alcohols include ethylene glycol, diethylene glycol, trimethylol propane, etc. The fatty acid glycerides may include those having a hydroxyl number of at least about 50 such as castor oils, hydrogenated castor oil, or blown natural oils.
Polyethers, another preferred type of polyol, may include polyalkylene glycols, e.g. polyethylene glycols and polypropylene glycols preferably having a molecular weight of at least 60. For convenience, the term "polyol" or "polyoxyalkylene polyol" may be employed to designate the substances having two or more active hydrogen atoms as determined by the Zerewitinoff method, which may be employed in practice of this invention.
In one aspect of the process of this invention, the isocyanurate foam may be prepared by reacting (i) an organic composition having at least two Zerewitinof~
active hydrogen atoms i.e. a "polyol", (ii) an organic polyfunctional isocyanate, (iii) a cell modifying agent such as the Dow Corning DC-193 brand trimethyl-end-blocked dimethyl polysiloxane, (iv) a blowing agent such as the Kaiser R-ll-B fluorocarbon, trifluoro~ch]oro-methane;
and (v) a di~alkali metal salt of the composition of this invention.
Formation of product by practice of the process of this in~ention may be effected by using isocyanate and polyol in amount to provide an isocyanate index in the reaction medium of 1-10, preferably 3-6, say 5. Blowing agent is present in amount of 5-20 parts, preferably 10-14 parts, say 12 parts. Cell modifying agent is present in amount of 0.1-15 parts, preferably 0.3-0.8 parts, say 0.5 parts. Catalyst of this invention is present in amount of 0.5-10 parts, preferably 1-4 parts, say 2 parts. (all parts are parts by weightper 100 parts of total formula-tion).
" 1101416 The foamed isocyanurate product is found to be desirably characterized by cream times in excess of about 10 seconds and typically about 15 seconds, by increased heat distortion, and by substantially better dimensional stability at low temperature eg minus 20 F/dry.
DESCRIPTIO~ OF PREFERRED EMBODIMENTS
Practice of the novel process of this invention may be apparent from the following description of preferred embodiments wherein, as elsewhere in this specification, all parts are parts by weight unless otherwise specifically noted.
EXA~PLE I
In this example which represents practice of the process of this invention, 393 grams (3 moles) of itaconic acid, 600 grams of water, and 6~o.5 grams of the di-terminal diamine of polyoxy-propylene (molecular weight about 427, and containing 4.69 milli-equivalents of primary amine per gram~ are heated to reflux for 8.5 hours. Supercell* filter aid is added and the reaction mixture is filtered hot and then stripped at 0.5 mm Hg in a rotary drum drier with a bath temperature of 95C.
On cooling, a clear viscous liquid is recovered having an acidity of 3.26 milliequivalents per gram and corresponding to the following formula:
HOOC-C-C \ r ~ /C-C-COOH
¦ N t R~ ~ N
C-C C-C
.. ..
O O
R" is a polyoxypropylene residue (of molecular weight of about 400) having terminal carbon atoms to which the nitrogen atoms are bonded.
*Trademark - 15 -i -`~ llJJ1~16 EXAMPLE II
In this example which represents practice of the process of this invention, 526 grams (4.03 moles) of itaconic acid, 600 grams of water, and 470 grams (2 moles) of the diterminal diamine of poly-oxypropylene (molecular weight about 235, and containing 8.53 milli-equivalents of primary amine per gram) are heated to reflux for 8 hours. Suepercell* filter aid is added and the reaction mixture is filtered hot and then stripped at 0.5 mm Hg in a rotary drum drier with a bath temperature of 95 C.
: 10 On cooling, a light, tacky flowable, viscous resin is re-covered having an acidity of 4.74 milliequivalents per gram, a nitro-gen content of 6.35% and corresponding to the following formula:
HOOC-C-C~ C-C-COOH
I > - [ R" ~ ~ ~
C-C C-C
O O
R" is a polyoxypropylene residue (of molecular weight of about 200) having terminal carbon atoms to which the nitrogen atoms are bonded.
EXAMPLE III
In this example which represents practice of the process of this invention, 131 grams (1 mole) of itaconic acid, 100 grams of water, and 1030 grams (0.5 mole) of the di-terminal di-amine of poly-oxypropylene (molecular weight about 2060, and containing 0.97 milli-equivalents of primary amine per gram) are heated to reflux of *Trademark - 16 -'~
" 11~1~16 98C-100C for 19 hours. Water is removed by azeotropic distillation with 500 ml of toluene, which is added during the course of the reac-tion. Supercell* filter aid is added and the reaction mixture is fil-tered hot and then stripped at 0.5 mm Hg in a rotary drum drier with a bath temperature of 138C.
On cooling, a light brown viscous liquid is recovered having an acidity of 0.82 milliequivalents per gram and corresponding to the following formula XOOC-C-C / C-C-COOH
¦ ~ ~ R" ~ N
--C C-C
.. ..
O O
R" is a polyoxypropylene residue (of molecular weight of about 2030) having terminal carbon atoms to which the nitrogen atoms are bonded.
Results comparable to those of Examples I-III are achieved if the amine is as follows:
Example Amine IV tri-terminal tri-primary amine of polyoxypropylene of m. wt.
of 400 (as marketed under the trademark Jeffamine T-403) V di-terminal di-primary amine of polyoxyethylene-polyoxypropylene of m. wt. of 600 (as marketed under the trademark Jeffamine ED-600) etc.
*Trademark - 17 -Similarly results comparable to those of Examples I-III
are achieved if the acid is Example Acid VI alpha-methylene glutaric acid VII alpha-methylene adipic acid In certain of the Examples which follow, the following properties are measured:
Cream time (seconds) - the time interval beginning with mix-ing of the isocyanate and the B-component (a standard mixture con-taining the polyol, catalys-t, blowing agent, surfactan-t, and fire retardant) and ending when the composition changes color from dark brown to cream color;
Rise time (seconds) - the time interval beginning with mix--ing of the isocyanate and the B-component and ending when the foam has stopped rising;
Tack-free time (seconds) - The time interval beginning with mixing of the isocyanate and the B-component and ending when the surface of the foam ceases to be tacky when touched;
Density (pounds per cubic foot) - the weight of a given rolume of the productj 4~i K-factor (watt-inches/C)- as measured by ASTM test : C 177-63 using Dupont modified guarded hot plate;
lon~ation at Break (%) - as measured by ASTM test D-638;
Tensile strength (psi) - as measured by ASTM test D-638;
T ile Modulus (psi) - as measured by ASTM test D-638;
Flexura~ Stren~th (psi) - as measured by ASTM test D-790;
F~exural Mod lus (psi) - as measured by ASTM test D-790i Shore D-Hardness 0-10 seconds - as measured -by ASTM
test D-2240;
HTD (C, 264 psi/66 psi.) - as measured by ASTM test D-648;
Izod Impact Strength (~t lbs/in) - as measured by ASTM test D-256;
Compressive Strength (PSi) - as measured by- ASTM
test D-1625-73;
Heat Distortion (C) - as measured by the temperature at which a standard sample is depressed 0.1 inches at a load corresponding to 10~ of its Compressive Strength with Rise;
Closed Cells (%) - as measured by ASTM Test D-2856-70;
Dimensional Stability (%) ~ as measured by ASTM test D-2126-75 - modified in that the sample actually used had di-mension of 2" x 2" x 2" instead of 4" x 4" x 4";
14~6 Fla~mability - as measu-red by the Butler Chimney Test -ASTM test D-3019-73. Preferred practice based upon the inherent dangers due to possible flammability of various compositions includ-ing urethanes, suggest that -the reader be advised that numerical or other data from this test are not intended to reflect ha~ards pre-sented by this or any other material under actual fire conditions.
The data represent the behavior of the tested material under specific controlled test conditions.
EXAMPLE VIII
In this example which represents practice of the process of this invention, the preparation of a cured isocyanurate foam is carried out.
A B-component is first prepared containing the following:
(i) 159 grams of polyol - a polyoxyethylene adduct of a novalak resin of hydroxyl number 187, and an average functionality of 2-5;
(ii) 3 grams of silicone surfacted - the Dow Corning DC-193 brand of trimethyl and blocked dimethyl polysiloxane;
(iii) 72 grams of fluorocarbon - the Kaiser R-ll-B
brand of trifluoro-chloro-methane;
(iv) 12 grams of a 50% (in polyethylene glycol of molecular weight 300) solution of the dipotassium salt of the product of Example I - prepared by addition to the product of Example I, of an equivalent amount of potassium hydroxide (i.e.
two moles of potassium hydroxide per mole of said product) and of polyethylene glycol.
_ 20 -11(~14~6 .
To this B-component is added ~54 grams of a phosgenated aniline-formaldehyde condensate of functionality 2.7 and an NC0 equivalent weight of 134.
The mixture is vigorously stirred and then poured into a box mold and allowed to rise.
Property Time (seconds) Cream Time 15 Rise Time 140 Tack-free Time 150 The properties of the product foam are listed in the table which follows Example IX*.
EXAMPLE IX*
In this control example, the procedure of Example VIII was followed except that (i) 160.8 grams of polyol was used;
(ii) 6 grams of a 50% solution (in polyoxyethylene triol ha~ing average molecular weight of 700) of potassium octoate, a prior art curing agent, was used in place of the 12 grams of the dipotassium salt solution of Example VIII.
( iY) 358.2 grams of isocyanate was used in place of 354 grams as in Example VIII.
Property Time (Seconds) Cream Time 5-6 Rise Time 65 Tack-free Time 100 This control foam is less satisfactory than is the experimental foam. The cream time and the rise time in particular are much too low to be satisfactory in commer-cial practice. Eor proper commercial use, the minimum cream time in a panel-line formulation ~or example, should be about 12 seconds and preferably 15-20 seconds as is the case with Example VIII.
s~l O ~
~ ~D
~ ++ l *
H
~\ ~ N
a~ o ~ o ~ ~ . ~ c~
~1ClJ ~ O ~ .. . .. ,~
. . ~ ~ ~ ~y ~ ~r c~ L~ o o N O ~ r~ l C~ I I I ~ H ~ 15 r~
i ~)J
ol + ~1 a) .~ ++~
H
H
H
C~~1 ~ ~
G) U~ ~ ~ ' ~ ~ ~ ~O
~1 Q~ ~ ~ O O~:: C'l ~1 ~1 O . . .
~ +~
~ ,_ Cq C~ O
~1 a .D c~ o ~1 ~
~ h co O--~ h ~ ~ rl ~rl ~ `--:~ ~ O ~ ~j\~c~ ~ ~ ~
'Q ~ ~ ~4 ~ ~ ~ ~ CD ,n ~ ~ ~ ~ o ~ o o $~
a) ~ c) 5~ o o O ~ d O
~ a) I o a) ,~
P~ 1~ ~ V
~1~14~6 The clear superiority o~ the foam of Example ~III
over that of Example IX* is apparent. In addition to the above comments, particular attention is directed to the generally superior properties including (i) improved heat distortion, (ii) ~olume and linear dimensional stability at low temperature, (iii) weight stability, etc.
EXAMPLE X
In this example which represents practice o~
the process of this invention, the preparation of a cured epoxy resin is carried out.
The uncured epoxy resin (100 grams) which is used as charge is identified as a liquid diglyc1dylether glycol ester of bisphenol A epoxy resin Eq. Wt. 190.
Curing ol the so-prepared epoxy resin (100 g) is effected by addition thereto of (i) 30 parts of a condensation product o~
formaldehyde and aniline o~ equivalent weight 50, a polyaromatic polyamine curing agent, (marketed under the trademark JEFFAMINE AP-22).
-24_ (ii) 20 parts of a 20 w % solution in benzyl alcohol of the accelerator composition prepared by the process of Example I.
This mixture of components was mixed thorough'~, degassed, poured into aluminum molds, and cured for seven days at ambient conditions ca 25C.
The properties of the Formulation were determined on samples cut from the castings, Pro,nerties o~ cured 1/8" casting Value Izod impact strength (ft-lbs/in.) 0.61 Tensile strength (psi) 9,300 Tensile mod~tlus (psi) 404,ooo Elongation at break ~) 5.1 Flexural strength ()si) 15 000 Flexural modulus (psi) 42~ OGO
Shore D ~ardness ~0-10 sec.) 86-~4 HDT (C, 264 psi/~6 psi) 44/48 Fle~ral samples were cut and immersed in several chemicals for 28 days. All tests were conducted at ambient temperature of ca 25C except that in distilled water which was carried out at 40C. After remo~al from the chemicals, flexural strength of the immersed samples was determined.
Pertinent retention of flexural strength T;Jas then computed with the ~ollowing results:
~ Retention of Sample immersed in Flexural Strength Isopropanol 104 Xylene 104 Acetic acid (25~o) 89 Sodium Hydroxi~e (50%) 115 Sulfuric acid (3C~o) 102 Distilled ~ater 88 ?141~
It will be apparent from inspection oP the above properties that the cured epoxy formulations are outstanding with respect to strength and retention of strength after immersion in various chemicals.
EXAMPLE XI*
In this control example, the procedure of Bxample X is duplicated except that curing is carried out in the absence of the accelerator.
After seven days cure at ambient temperature, the formulations were so brittle and undercured that it was not possible to cut samples for the tests from the castings. It was apparent that the formulations were totally unsatisfactory and of low strength.
EXAMPLES XII-XIII*
A liquid accelerating mixture for use in conJunction with aromatic amine curatives is prepared by dlssolving 20 g. polyoxypropylene-alpha, omega Bls (pyrrolidinone-3-carboxylic acid) in 80 g benzyl alcohol.
The above mixture is combined into an epoxy system as follows Formulation:
Liquid DGEEA epoxy resin (Equivalent weight 190) 100 parts Aromatic polyamine Jeffamine AP 22 brand 33 parts of the condensation product of formaldehyde and aniline Accelerator mixture described above 20 parts The formulation is mixed thoroughly degassed and poured into aluminum molds and cured ~or seven days under ambient conditions. The castings are then cut into samples and tested with the following results:
~1416 Properties of cured 1/8" casting:
IZOD-impact strength ft.-lbs./in. 0.61 Tensile strength, psi 9300 Tensile modulus, psi 404000 Elongation at break, ~ 5.1 Flexural strength, psi 15000 Flexural modulus, psi. 424000 Shore D hardness, 0-10 sec. 86.84 HDT, C 264 psi/66 psi 44/48 Flexural samples were cut and immersed in several chemicals for 28 days. After removal from the chemicals, flexural strength of the immersion samples was determined. Percent retention of flexural strength was then computed with the following results -Sample immersed in Percent Retention, Flex. strength Isopropanol, R.T. 104 Xylene, RT. 104 Acetic acid, 25% R.T. 89 Sodium hydroxide 50~, R.T. 115 Sulfuric acid, 30%, R.T. 102 Distilled water, 40C 88 Castings cured without the accelerator mixture (Example XIII*) were brittle and undercured after 7 days curin; at ambient temperatures. Samples could not be cut from such castings. In contrast the castings cured with the accelerator mixture (Example XII) were properly cured, not brittle and readily cuttable.
R.T. means Room Temperature lla~4l6 Although this invention has been illustrated by reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modi~ications may be made which clearly fall within the scope of this invention.
-28_
._ C - COH
o HOOC - C - C
. \ - ~ / C - C - COOH
Cx N - - R~ ~ N Cx C - C C - C
O O
In the case of one preferred embodiment, itaconic acid -10 polyoxyethylene di-primary amine, the reacti.on may be:
1~1416 HOOC - C = C ~_ + H2N~-- CH2CH20-- 2CH2 NH2 C - COH ~ 15 O
,C - C - COOH
HOOC - C - C ~ _ _ / - CH2CH20 _ 2 2 O O
In the case of another preferred embodiment a specific reaction may be as follows:
HOOC - C = C _ _ l 2 2 ~ CH CH20 _ _ CH2-CH- NH2 >
C - COH
.. _ CH3 - 15 CH3 o HOOC - C - C \ _ _ C-C-COOH
C - C / l CH CH20 ~ - CH2-CH N /
" CH3 15 CH3 C-C
O
As reaction continues, the water produced by the reaction (in amount of one mole per mole of acid reacted) may be distilled off. If desired, the water may be removed during refluxing by azeotropic distil-lation with eg toluene. Typically at the end of the reaction period, the reaction mixture may be recovered and filtered, preferably in the IO presence of added filter aid such as Supercell* brand.
~Trademark - ~ -The product so obtained is preferably worked up by stripping, as in a rotary evaporator at ~0C-200C, say 95C. Stripping may typically be carried out under vacuum of 0.1-50 mm. Hg, say 0.5 mm. Hg.
Yield is about stoichiometric.
Typical product is recovered as composition which ~depending on the components from which it is prepared and its molecular weight) may generally be characterized as a clear viscous liquid, a light brown viscous liquid, a tacky resin, etc.
These products are generally characterized by their solubility in alcohols (eg benzyl alcohol, ethanol, hexanols, etc). They are particularly characterized by solubility in polymer systems in which they may find use.
These products may be used as recovered or in the form of solutions in eg benzyl alcohol. They are characterized when they are in the form of their salts, eg alkali-metal salts ~preferably potassium K, but also sodium Na, etc) by their ability to serve as accelerators for curing epoxy resins. Although they may be used as the mono-alkali-metal salt, it is preferred to use them in the form of their di-alkali metal, eg di-potassium, salt.
It is a particular feature of the novel products of this inven~ion, that when they are present as acids they serve as curing agents for isocyanurate foamed compositions.
~14~6 The dialkali metal salt iB preferably prepared by adding to the recovered reaction mixture an equivalent amount of eg potassium hydroxide in 5%-30%, say 20%
aqueous solution at 20 C-80C, say 50 C. After 10-20 minutes, say 15 minutes agitation, the reaction mixture may be filtered through a bed of filter aid and the resulting solution may be used as recovered, eg as a 10%-80%, say 50% solution. If desired the salt may be recovered as by evaporation. Both the mono-alkali and the di-alkali metal salts may be recovered.
In practice of certain of its aspects, this invention includes the method of preparing a cured epoxy resin characterized by the fact that when cured at ambient temperature of 20C-50C, say 30C, it is found to possess outstanding properties particularly with respect to strength and retention of strength after immersion in solvents. Curing agents falling outside the scope of this invention (such as eg the reaction product of itaconic acid and eg p-phenylene diamine -as disclosed in Paytash et al J. A. C. S. 72, 1415-6 (1950) - are not satisfactory as curing accelerators for - epoxy resins because they are generally high-melting solid compositions which do not readily blend in with the viscous epoxy formulation. The novel products of this invention are particularly characterized by their high compatibility with the components of the epoxy resins. The fact that they are generally liquids provides a substantial advantage to the processor.
An epoxy resin which may be cured by the process of this invention may typically be one prepared for example by the reaction of bisphenol-A with epichlorohydrin C ~ - CHCH2 Cl in the presence of a base - preferably O
sodium hydroxide. After the condensation is complete, the crude resin is freed of residual epichlorohydrin, washed well to remove salt and soluble by-products, and recovered.
Curing of 100 parts of such a resin is effected in the presence of 20-40 parts, say 30 parts of an aromatic polyamine curing agent and 1-15 parts of the accelerator of this invention in eg 10-30 parts, say 20 parts of a solution containing 10-50% of the accelerator of this invention.
Typical aromatic polyamine curing agent which may be employed is a condensation product of formaldehyde and aniline. (as marketed under the trademark JEFFAMI~E
AP-22). Illustrative curing agents may include:
TABLE
methylene dianiline diamino-diphenyl ether meta-phenylene diamine tolylene diamine ~' ` 11(;~141~
The accelerator of this invention, preferably in the form of the free acid, is mixed with the liquid epoxy resin and curing agent; and the mixture is degassed, poured into aluminum molds, and cured typically for seven days at ambient temperature.
The product epoxy resin is particularly characterized by increased strength and by increased resistance to the deteriorative action of a wide range of liquids.
In practice of certain of its other aspects, this invention includes the method of preparing cured isocyanurate foams particularly characterized by their desirably longer cream time which desirably allows more latitude during preparation - i.e. the formulation is more mobile and handleable during a longer period of time.
An isocyanurate foam which may be cured by the process of this invention may be one prepared by reacting an isocyanate typified by a phosgenated condensation product of aniline and formaldehyde having an NC0 equivalent weight of 134 and a functionality of 2.7.
~ ` 11(~1416 The isocyanate is preferably reacted with a polyol which has two or more active hydrogen atoms as determined by the Zerewitinoff method e.g. the polyoxyalkylene polyols which may be employed in practice of this invention will be organic compounds having two or more reactive hydrogen atoms which will react with organic polyfunctional isocyanates to give urethane polymers. These polyoxyalkylene polyols typically having a hydroxyl number of 100-800 preferably 200-300, say 200, may include polyesters, polyethers, polyisocyanate modified polyesters, polyisocyanate modified polyester amides, alkylene glycols, polyamines, polyiso-cyanate modified alkylene glycols, etc. It will be understood that these polyols may have active primary or secondary hydroxyl groups. The polyol may be a hydroxyl-containing polyether or polyester including fatty acid glycerides. Polyesters, which are a preferred type of polyol, may be obtained by esterification condensation reaction of e.g. an aliphatic dibasic carboxylic acid with a glycol or a triol or mixture thereof in proportion such that the resultant polyesters may contain predominantly terminal hydroxyl groups. Dibasic carboxylic acids suitable for preparing polyesters may include aliphatic and aromatic acids such as adipic acid, fumaric acid, sebacic acid, phthalic acid; suitable alcohols include ethylene glycol, diethylene glycol, trimethylol propane, etc. The fatty acid glycerides may include those having a hydroxyl number of at least about 50 such as castor oils, hydrogenated castor oil, or blown natural oils.
Polyethers, another preferred type of polyol, may include polyalkylene glycols, e.g. polyethylene glycols and polypropylene glycols preferably having a molecular weight of at least 60. For convenience, the term "polyol" or "polyoxyalkylene polyol" may be employed to designate the substances having two or more active hydrogen atoms as determined by the Zerewitinoff method, which may be employed in practice of this invention.
In one aspect of the process of this invention, the isocyanurate foam may be prepared by reacting (i) an organic composition having at least two Zerewitinof~
active hydrogen atoms i.e. a "polyol", (ii) an organic polyfunctional isocyanate, (iii) a cell modifying agent such as the Dow Corning DC-193 brand trimethyl-end-blocked dimethyl polysiloxane, (iv) a blowing agent such as the Kaiser R-ll-B fluorocarbon, trifluoro~ch]oro-methane;
and (v) a di~alkali metal salt of the composition of this invention.
Formation of product by practice of the process of this in~ention may be effected by using isocyanate and polyol in amount to provide an isocyanate index in the reaction medium of 1-10, preferably 3-6, say 5. Blowing agent is present in amount of 5-20 parts, preferably 10-14 parts, say 12 parts. Cell modifying agent is present in amount of 0.1-15 parts, preferably 0.3-0.8 parts, say 0.5 parts. Catalyst of this invention is present in amount of 0.5-10 parts, preferably 1-4 parts, say 2 parts. (all parts are parts by weightper 100 parts of total formula-tion).
" 1101416 The foamed isocyanurate product is found to be desirably characterized by cream times in excess of about 10 seconds and typically about 15 seconds, by increased heat distortion, and by substantially better dimensional stability at low temperature eg minus 20 F/dry.
DESCRIPTIO~ OF PREFERRED EMBODIMENTS
Practice of the novel process of this invention may be apparent from the following description of preferred embodiments wherein, as elsewhere in this specification, all parts are parts by weight unless otherwise specifically noted.
EXA~PLE I
In this example which represents practice of the process of this invention, 393 grams (3 moles) of itaconic acid, 600 grams of water, and 6~o.5 grams of the di-terminal diamine of polyoxy-propylene (molecular weight about 427, and containing 4.69 milli-equivalents of primary amine per gram~ are heated to reflux for 8.5 hours. Supercell* filter aid is added and the reaction mixture is filtered hot and then stripped at 0.5 mm Hg in a rotary drum drier with a bath temperature of 95C.
On cooling, a clear viscous liquid is recovered having an acidity of 3.26 milliequivalents per gram and corresponding to the following formula:
HOOC-C-C \ r ~ /C-C-COOH
¦ N t R~ ~ N
C-C C-C
.. ..
O O
R" is a polyoxypropylene residue (of molecular weight of about 400) having terminal carbon atoms to which the nitrogen atoms are bonded.
*Trademark - 15 -i -`~ llJJ1~16 EXAMPLE II
In this example which represents practice of the process of this invention, 526 grams (4.03 moles) of itaconic acid, 600 grams of water, and 470 grams (2 moles) of the diterminal diamine of poly-oxypropylene (molecular weight about 235, and containing 8.53 milli-equivalents of primary amine per gram) are heated to reflux for 8 hours. Suepercell* filter aid is added and the reaction mixture is filtered hot and then stripped at 0.5 mm Hg in a rotary drum drier with a bath temperature of 95 C.
: 10 On cooling, a light, tacky flowable, viscous resin is re-covered having an acidity of 4.74 milliequivalents per gram, a nitro-gen content of 6.35% and corresponding to the following formula:
HOOC-C-C~ C-C-COOH
I > - [ R" ~ ~ ~
C-C C-C
O O
R" is a polyoxypropylene residue (of molecular weight of about 200) having terminal carbon atoms to which the nitrogen atoms are bonded.
EXAMPLE III
In this example which represents practice of the process of this invention, 131 grams (1 mole) of itaconic acid, 100 grams of water, and 1030 grams (0.5 mole) of the di-terminal di-amine of poly-oxypropylene (molecular weight about 2060, and containing 0.97 milli-equivalents of primary amine per gram) are heated to reflux of *Trademark - 16 -'~
" 11~1~16 98C-100C for 19 hours. Water is removed by azeotropic distillation with 500 ml of toluene, which is added during the course of the reac-tion. Supercell* filter aid is added and the reaction mixture is fil-tered hot and then stripped at 0.5 mm Hg in a rotary drum drier with a bath temperature of 138C.
On cooling, a light brown viscous liquid is recovered having an acidity of 0.82 milliequivalents per gram and corresponding to the following formula XOOC-C-C / C-C-COOH
¦ ~ ~ R" ~ N
--C C-C
.. ..
O O
R" is a polyoxypropylene residue (of molecular weight of about 2030) having terminal carbon atoms to which the nitrogen atoms are bonded.
Results comparable to those of Examples I-III are achieved if the amine is as follows:
Example Amine IV tri-terminal tri-primary amine of polyoxypropylene of m. wt.
of 400 (as marketed under the trademark Jeffamine T-403) V di-terminal di-primary amine of polyoxyethylene-polyoxypropylene of m. wt. of 600 (as marketed under the trademark Jeffamine ED-600) etc.
*Trademark - 17 -Similarly results comparable to those of Examples I-III
are achieved if the acid is Example Acid VI alpha-methylene glutaric acid VII alpha-methylene adipic acid In certain of the Examples which follow, the following properties are measured:
Cream time (seconds) - the time interval beginning with mix-ing of the isocyanate and the B-component (a standard mixture con-taining the polyol, catalys-t, blowing agent, surfactan-t, and fire retardant) and ending when the composition changes color from dark brown to cream color;
Rise time (seconds) - the time interval beginning with mix--ing of the isocyanate and the B-component and ending when the foam has stopped rising;
Tack-free time (seconds) - The time interval beginning with mixing of the isocyanate and the B-component and ending when the surface of the foam ceases to be tacky when touched;
Density (pounds per cubic foot) - the weight of a given rolume of the productj 4~i K-factor (watt-inches/C)- as measured by ASTM test : C 177-63 using Dupont modified guarded hot plate;
lon~ation at Break (%) - as measured by ASTM test D-638;
Tensile strength (psi) - as measured by ASTM test D-638;
T ile Modulus (psi) - as measured by ASTM test D-638;
Flexura~ Stren~th (psi) - as measured by ASTM test D-790;
F~exural Mod lus (psi) - as measured by ASTM test D-790i Shore D-Hardness 0-10 seconds - as measured -by ASTM
test D-2240;
HTD (C, 264 psi/66 psi.) - as measured by ASTM test D-648;
Izod Impact Strength (~t lbs/in) - as measured by ASTM test D-256;
Compressive Strength (PSi) - as measured by- ASTM
test D-1625-73;
Heat Distortion (C) - as measured by the temperature at which a standard sample is depressed 0.1 inches at a load corresponding to 10~ of its Compressive Strength with Rise;
Closed Cells (%) - as measured by ASTM Test D-2856-70;
Dimensional Stability (%) ~ as measured by ASTM test D-2126-75 - modified in that the sample actually used had di-mension of 2" x 2" x 2" instead of 4" x 4" x 4";
14~6 Fla~mability - as measu-red by the Butler Chimney Test -ASTM test D-3019-73. Preferred practice based upon the inherent dangers due to possible flammability of various compositions includ-ing urethanes, suggest that -the reader be advised that numerical or other data from this test are not intended to reflect ha~ards pre-sented by this or any other material under actual fire conditions.
The data represent the behavior of the tested material under specific controlled test conditions.
EXAMPLE VIII
In this example which represents practice of the process of this invention, the preparation of a cured isocyanurate foam is carried out.
A B-component is first prepared containing the following:
(i) 159 grams of polyol - a polyoxyethylene adduct of a novalak resin of hydroxyl number 187, and an average functionality of 2-5;
(ii) 3 grams of silicone surfacted - the Dow Corning DC-193 brand of trimethyl and blocked dimethyl polysiloxane;
(iii) 72 grams of fluorocarbon - the Kaiser R-ll-B
brand of trifluoro-chloro-methane;
(iv) 12 grams of a 50% (in polyethylene glycol of molecular weight 300) solution of the dipotassium salt of the product of Example I - prepared by addition to the product of Example I, of an equivalent amount of potassium hydroxide (i.e.
two moles of potassium hydroxide per mole of said product) and of polyethylene glycol.
_ 20 -11(~14~6 .
To this B-component is added ~54 grams of a phosgenated aniline-formaldehyde condensate of functionality 2.7 and an NC0 equivalent weight of 134.
The mixture is vigorously stirred and then poured into a box mold and allowed to rise.
Property Time (seconds) Cream Time 15 Rise Time 140 Tack-free Time 150 The properties of the product foam are listed in the table which follows Example IX*.
EXAMPLE IX*
In this control example, the procedure of Example VIII was followed except that (i) 160.8 grams of polyol was used;
(ii) 6 grams of a 50% solution (in polyoxyethylene triol ha~ing average molecular weight of 700) of potassium octoate, a prior art curing agent, was used in place of the 12 grams of the dipotassium salt solution of Example VIII.
( iY) 358.2 grams of isocyanate was used in place of 354 grams as in Example VIII.
Property Time (Seconds) Cream Time 5-6 Rise Time 65 Tack-free Time 100 This control foam is less satisfactory than is the experimental foam. The cream time and the rise time in particular are much too low to be satisfactory in commer-cial practice. Eor proper commercial use, the minimum cream time in a panel-line formulation ~or example, should be about 12 seconds and preferably 15-20 seconds as is the case with Example VIII.
s~l O ~
~ ~D
~ ++ l *
H
~\ ~ N
a~ o ~ o ~ ~ . ~ c~
~1ClJ ~ O ~ .. . .. ,~
. . ~ ~ ~ ~y ~ ~r c~ L~ o o N O ~ r~ l C~ I I I ~ H ~ 15 r~
i ~)J
ol + ~1 a) .~ ++~
H
H
H
C~~1 ~ ~
G) U~ ~ ~ ' ~ ~ ~ ~O
~1 Q~ ~ ~ O O~:: C'l ~1 ~1 O . . .
~ +~
~ ,_ Cq C~ O
~1 a .D c~ o ~1 ~
~ h co O--~ h ~ ~ rl ~rl ~ `--:~ ~ O ~ ~j\~c~ ~ ~ ~
'Q ~ ~ ~4 ~ ~ ~ ~ CD ,n ~ ~ ~ ~ o ~ o o $~
a) ~ c) 5~ o o O ~ d O
~ a) I o a) ,~
P~ 1~ ~ V
~1~14~6 The clear superiority o~ the foam of Example ~III
over that of Example IX* is apparent. In addition to the above comments, particular attention is directed to the generally superior properties including (i) improved heat distortion, (ii) ~olume and linear dimensional stability at low temperature, (iii) weight stability, etc.
EXAMPLE X
In this example which represents practice o~
the process of this invention, the preparation of a cured epoxy resin is carried out.
The uncured epoxy resin (100 grams) which is used as charge is identified as a liquid diglyc1dylether glycol ester of bisphenol A epoxy resin Eq. Wt. 190.
Curing ol the so-prepared epoxy resin (100 g) is effected by addition thereto of (i) 30 parts of a condensation product o~
formaldehyde and aniline o~ equivalent weight 50, a polyaromatic polyamine curing agent, (marketed under the trademark JEFFAMINE AP-22).
-24_ (ii) 20 parts of a 20 w % solution in benzyl alcohol of the accelerator composition prepared by the process of Example I.
This mixture of components was mixed thorough'~, degassed, poured into aluminum molds, and cured for seven days at ambient conditions ca 25C.
The properties of the Formulation were determined on samples cut from the castings, Pro,nerties o~ cured 1/8" casting Value Izod impact strength (ft-lbs/in.) 0.61 Tensile strength (psi) 9,300 Tensile mod~tlus (psi) 404,ooo Elongation at break ~) 5.1 Flexural strength ()si) 15 000 Flexural modulus (psi) 42~ OGO
Shore D ~ardness ~0-10 sec.) 86-~4 HDT (C, 264 psi/~6 psi) 44/48 Fle~ral samples were cut and immersed in several chemicals for 28 days. All tests were conducted at ambient temperature of ca 25C except that in distilled water which was carried out at 40C. After remo~al from the chemicals, flexural strength of the immersed samples was determined.
Pertinent retention of flexural strength T;Jas then computed with the ~ollowing results:
~ Retention of Sample immersed in Flexural Strength Isopropanol 104 Xylene 104 Acetic acid (25~o) 89 Sodium Hydroxi~e (50%) 115 Sulfuric acid (3C~o) 102 Distilled ~ater 88 ?141~
It will be apparent from inspection oP the above properties that the cured epoxy formulations are outstanding with respect to strength and retention of strength after immersion in various chemicals.
EXAMPLE XI*
In this control example, the procedure of Bxample X is duplicated except that curing is carried out in the absence of the accelerator.
After seven days cure at ambient temperature, the formulations were so brittle and undercured that it was not possible to cut samples for the tests from the castings. It was apparent that the formulations were totally unsatisfactory and of low strength.
EXAMPLES XII-XIII*
A liquid accelerating mixture for use in conJunction with aromatic amine curatives is prepared by dlssolving 20 g. polyoxypropylene-alpha, omega Bls (pyrrolidinone-3-carboxylic acid) in 80 g benzyl alcohol.
The above mixture is combined into an epoxy system as follows Formulation:
Liquid DGEEA epoxy resin (Equivalent weight 190) 100 parts Aromatic polyamine Jeffamine AP 22 brand 33 parts of the condensation product of formaldehyde and aniline Accelerator mixture described above 20 parts The formulation is mixed thoroughly degassed and poured into aluminum molds and cured ~or seven days under ambient conditions. The castings are then cut into samples and tested with the following results:
~1416 Properties of cured 1/8" casting:
IZOD-impact strength ft.-lbs./in. 0.61 Tensile strength, psi 9300 Tensile modulus, psi 404000 Elongation at break, ~ 5.1 Flexural strength, psi 15000 Flexural modulus, psi. 424000 Shore D hardness, 0-10 sec. 86.84 HDT, C 264 psi/66 psi 44/48 Flexural samples were cut and immersed in several chemicals for 28 days. After removal from the chemicals, flexural strength of the immersion samples was determined. Percent retention of flexural strength was then computed with the following results -Sample immersed in Percent Retention, Flex. strength Isopropanol, R.T. 104 Xylene, RT. 104 Acetic acid, 25% R.T. 89 Sodium hydroxide 50~, R.T. 115 Sulfuric acid, 30%, R.T. 102 Distilled water, 40C 88 Castings cured without the accelerator mixture (Example XIII*) were brittle and undercured after 7 days curin; at ambient temperatures. Samples could not be cut from such castings. In contrast the castings cured with the accelerator mixture (Example XII) were properly cured, not brittle and readily cuttable.
R.T. means Room Temperature lla~4l6 Although this invention has been illustrated by reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modi~ications may be made which clearly fall within the scope of this invention.
-28_
Claims (34)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of formula (R ''') wherein x is an integer 0-2; a is an integer of at least 2; M is hydrogen or a cation derived from a strong base; R''' is a polyoxyalkylene chain having terminal carbon atoms to which the nitrogen atoms are bonded; and the molecular weight of R''' is 200 to about 2000, except that the molecular weight of R''' is 300 to about 2000 when x is 0 and M is hydrogen.
2. A compound claimed in claim 1 of formula ( R ''' ) wherein x is an integer 0-2; a is an integer of at least 2; R''' is a polyoxyalkylene chain having terminal carbon atoms to which the nitrogen atoms are bonded; and the molecular weight of R ''' is 300 to about 2000.
3. A compound claimed in claim 2 wherein the molecular weight of R''' is 400 to about 2000.
4. A compound claimed in claim 1 of formula (R''') wherein a is an integer of at least 2; R''' is a polyoxyalkylene chain having terminal carbon atoms to which the nitrogen atoms are bonded; and the molecular weight of R''' is 300 to about 2000.
5. A compound claimed in claim 1 of formula ( R''' ) wherein a is an integer of at least 2; R''' is a polyoxyalkylene chain having terminal carbon atoms to which the nitrogen atoms are bonded; and the molecular weight of R''' is 200 to about 2000.
6. A compound claimed in claim 1 of formula ( R''' ) wherein a is an integer of at least 2; R''' is a polyoxyalkylene chain having terminal carbon atoms to which the nitrogen atoms are bonded; and the molecular weight of R''' is 200 to about 2000.
7. A compound claimed in claim 1 of formula ( R''' ) wherein a is an integer of at least 2; R"' is a polyoxyalkylene chain having terminal carbon atoms to which the nitrogen atoms are bonded;
and the molecular weight of R''' is about 200-2000; and M is an alkali metal.
and the molecular weight of R''' is about 200-2000; and M is an alkali metal.
8. A compound claimed in claim 1 of formula ( R''' ) wherein a is an integer of at least 2; R''' is a polyoxyalkylene chain having terminal carbon atoms to which the nitrogen atoms are bonded; and the molecular weight of R''' is 200 to about 2000; and M is an alkali metal.
9. A compound claimed in claim 1 of formula ( R ''' ) wherein a is an integer of at least 2; R''' is a polyoxyalkylene chain having terminal carbon atoms to which the nitrogen atoms are bonded; and the molecular weight of R''' is 200 to about 2000; and M is an alkali metal.
10. A compound claimed in claim 1 of formula wherein x is an integer of 0-2; R" is a polyoxyalkylene chain having terminal carbon atoms to which the nitrogen atoms are bonded; and the molecular weight of R" is 300 to about 2000.
11. Alkali metal N,N'-polyoxyalkylene bis (pyrrolidinone-3-carboxy-late) as claimed in claim 1.
12. N,N'-polyoxyalkylene bis (pyrrolidinone-3-carboxylic acid) wherein said polyoxyalkylene has a molecular weight of 300-2100 as claimed in claim 1.
13. The method of preparing product ( R''' ) wherein x is an integer of 0-2; a is an integer of at least 2; and R''' is a polyoxyalkylene chain of a molecular weight of about 200 to about 2000 having terminal carbon atoms to which the nitrogen atoms are bonded which comprises the steps of adding to a reaction mixture a moles of unsaturated carboxylic acid adding to said reaction mixture about one mole of a polyoxyalkylene poly-amine ( R''' ) - ( NH2 )a maintaining said unsaturated carboxylic acid and said polyoxyalkylene polyamine at ring-forming conditions including temperature of 80°C.-200°C.
thereby forming said product; and recovering said product.
thereby forming said product; and recovering said product.
14. The method according to claim 13 of preparing product wherein x is an integer of 0-2; R" is a polyoxyalkylene chain of molecular weight of about 200 to about 2000 having terminal carbon atoms to which the nitrogen atoms are bonded, which comprises the steps of adding to a reaction mixture two moles of unsaturated carboxylic acid adding to said reaction mixture about one mole of a polyoxyalkylene diamine H2N - ( R'' ) - NH2 maintaining said unsaturated carboxylic acid and said polyoxyalkylene diamine at ring-forming conditions including temperature of 80°C.-200°C. thereby forming said product; and recovering said product.
15. The method of claim 14 wherein said R" chain is a polyoxyethylene chain having terminal carbon atoms to which the nitrogen atoms are bonded.
16 The method of claim 14 wherein said R" chain is a polyoxypropylene chain having terminal carbon atoms to which the nitrogen atoms are bonded.
17. The method of claim 14 wherein said acid is itaconic acid.
18. The method of claim 14 wherein said acid is alpha-methylene glutaric acid.
19. The method of claim 14 wherein said acid is alpha-methylene adipic acid.
20. The method of curing an uncured epoxy resin which comprises curing 100 parts of said uncured epoxy resin in the presence of aromatic curing agent and 1-15 parts of an accelerator ( R''' ) wherein x is an integer of 0-2; a is an integer of at least 2; R''' is a polyoxyalkylene chain having terminal carbon atoms to which the nitrogen atoms are bonded; and the molecular weight of R''' is 200 to about 2000.
21. The method according to claim 20 of curing an uncured epoxy resin which comprises curing 100 parts of said uncured epoxy resin in the presence of 20-40 parts of aromatic curing agent and 1-15 parts of an accelerator wherein x is an integer of 0-2, and R" is a polyoxyalkylene chain of molecu-lar weight of about 200 to about 2000 having terminal carbon atoms to which the nitrogen atoms are bonded.
22. The method of curing an uncured epoxy resin as claimed in claim 21 wherein x is zero.
23. The method of curing an uncured epoxy resin as claimed in claim 21 wherein R" is polyoxyethylene.
24. The method of curing an uncured epoxy resin as claimed in claim 21 wherein said accelerator is the reaction product of two moles of itaconic acid and about one mole of polyoxyethylene diamine.
25. The method of preparing a cured isocyanurate foam which comprises reacting an isocyanate with a polyol having at least two active Zerewitinoff-active hydrogen atoms in the presence of a blowing agent thereby forming a polyisocyanurate foam; and conducting said reaction in the presence of 0.5-10 parts (per 100 parts of total formulation) of a curing agent ( R''' ) wherein x is an integer 0-2; a is an integer at least 2; M is a cation of a strong base; R''' is a polyoxyalkylene chain, of a molecular weight of about 200 to about 2000, having terminal carbon atoms to which the nitrogen atoms are bonded.
26. The method according to claim 25 of preparing cured isocyanuarate foam which comprises reacting an isocyanate with a polyol having at least two active Zerewitinoff-active hydrogen atoms in the presence of a blowing agent thereby forming a polyisocyanurate foam; and conducting said reaction in the presence of 0.5-10 parts (per 100 parts of total formulation) of a curing agent wherein x is an integer 0-2, M is a cation of a strong base, and R" is a polyoxyalkylene chain of molecular weight of about 200 to about 2000 having terminal carbon atoms to which the nitrogen atoms are bonded.
27. The method of preparing a cured isocyanurate foam as claimed in claim 26 wherein, in said curing agent, x is zero.
28. The method of preparing a cured isocyanurate foam as claimed in claim 26 wherein, in said curing agent, R" is polyoxyethylene.
29. The method of preparing a cured isocyanurate foam as claimed in claim 26 wherein said curing agent is the reaction product of two moles of itaconic acid and about one mole of polyoxyethylene diamine.
30. The method of preparing a cured isocyanurate foam as claimed in claim 26 wherein said curing agent is present as its di-alkali metal salt.
31. The method of preparing a cured isocyanurate foam as claimed in claim 26 wherein said curing agent is present as its di-potassium salt.
32. The method of preparing a cured isocyanurate foam as claimed in claim 26 wherein said curing agent is present as its di-quanternary ammonium salt.
33. A compound claimed in claim 1 of formula ( R''' ) wherein x is an integer 0-2; a is an integer of at least 3; M is hydrogen, or a cation of a strong base; and R''' is a polyalkylene chain, of molecular weight 200 to about 2000, having terminal carbon atoms to which the nitrogen atoms are bonded.
34. A compound claimed in claim 33 wherein M is an alkali metal.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68940976A | 1976-05-24 | 1976-05-24 | |
| US689,409 | 1976-05-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1101416A true CA1101416A (en) | 1981-05-19 |
Family
ID=24768326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA276,500A Expired CA1101416A (en) | 1976-05-24 | 1977-04-19 | Compounds useful as curing agents and processes for their preparation |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS537799A (en) |
| BE (1) | BE853555A (en) |
| CA (1) | CA1101416A (en) |
| DE (1) | DE2721626A1 (en) |
| FR (1) | FR2352850A1 (en) |
| GB (1) | GB1578821A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4235811A (en) * | 1979-04-02 | 1980-11-25 | Texaco Development Corp. | Compounds from aminated alkoxylated aliphatic alcohol |
| EP0020293B1 (en) * | 1979-04-27 | 1984-05-23 | Ciba-Geigy Ag | Stabilising compounds, process for their preparation and compositions containing them |
| JPS56152470U (en) * | 1980-04-15 | 1981-11-14 | ||
| JPS5725316A (en) * | 1980-07-22 | 1982-02-10 | Inoue Mtp Co Ltd | Production of organic polyisocyanate polymer |
| JPS5736115A (en) * | 1980-08-12 | 1982-02-26 | Mitsui Tekisako Chem Kk | Curing agent composition for polyurethane |
| JPS5766477A (en) * | 1980-10-13 | 1982-04-22 | Tokyo Shibaura Electric Co | Video display unit |
| JPS5789380A (en) * | 1980-11-25 | 1982-06-03 | Olympus Optical Co Ltd | Television picture photographic device |
| CA1256092A (en) * | 1985-12-20 | 1989-06-20 | Borg-Warner Chemicals, Inc. | Aminocarboxylic acid-terminated polyoxyaklylenes and process for the preparation thereof |
| DE102009030412A1 (en) * | 2009-06-25 | 2010-12-30 | Clariant International Ltd. | Polyalkylene glycol based Etherpyrrolidoncarbonsäuren and concentrates for the production of synthetic coolants containing them |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2993021A (en) * | 1955-12-12 | 1961-07-18 | Pfizer & Co C | Plastic composition comprising a vinyl resin and a bis-nu-substituted pyrrolidinone |
-
1977
- 1977-03-04 GB GB9137/77A patent/GB1578821A/en not_active Expired
- 1977-04-08 FR FR7710724A patent/FR2352850A1/en not_active Withdrawn
- 1977-04-13 BE BE176684A patent/BE853555A/en unknown
- 1977-04-19 CA CA276,500A patent/CA1101416A/en not_active Expired
- 1977-05-13 DE DE19772721626 patent/DE2721626A1/en not_active Withdrawn
- 1977-05-20 JP JP5776777A patent/JPS537799A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FR2352850A1 (en) | 1977-12-23 |
| JPS537799A (en) | 1978-01-24 |
| BE853555A (en) | 1977-10-13 |
| DE2721626A1 (en) | 1977-12-15 |
| GB1578821A (en) | 1980-11-12 |
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