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Publication numberCA1090026 A
Publication typeGrant
Application numberCA 282839
Publication date18 Nov 1980
Filing date15 Jul 1977
Priority date22 Jul 1976
Also published asCA1090026A1
Publication numberCA 1090026 A, CA 1090026A, CA 282839, CA-A-1090026, CA1090026 A, CA1090026A
InventorsJohn P. Gibbons, Lawrence Wondolowski
ApplicantJohn P. Gibbons, Lawrence Wondolowski, Cpc International Inc.
Export CitationBiBTeX, EndNote, RefMan
External Links: CIPO, Espacenet
Carbohydrate-phenol based condensation resins incorporating nitrogen-containing compounds
CA 1090026 A
Abstract
ABSTRACT OF THE DISCLOSURE

A carbohydrate-phenolic resin and a process for production of same wherein an aldose saccharide, preferably a hexose, is reacted with a phenolic compound and urea in the presence of an acid catalyst to form a resin which is curable with amine crosslinking agents, such as hexamethylenetetramine.
Instead of urea, use can also be made of diamines, such as toluene diamines and alkylene diamines. The resin formed may be a solid fusible resin or a liquid resin; when a liquid resin is formed it may be reacted with a lower aliphatic alde-hyde in the presence of a basic catalyst to form a resol resin.
Claims(38)
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A process for producing a carbohydrate-phenolic resin comprising reacting in the presence of an acid catalyst (1) an aldose saccharide;

(2) a phenolic compound having the formula wherein R is selected from the group consisting of C1 to C3 alkyl, C1 to C3 alkoxy, halogen, hydroxy and hydrogen; and (3) urea or a diamine to form a resin.
2. A process as defined in claim 1, wherein the saccharide is a hexose.
3. A process as defined in claim 1, wherein the phenolic compound is phenol.
4. A process as defined in claim 1, wherein the aldose saccharide is a starch.
5. A process as defined in claim 1, wherein the phenolic compound is employed in an amount within the range of 0.1 to 10 moles of phenolic compound for each mole of anhydroglucose unit.
6. A process as defined in claim 1, wherein component (3) is urea employed in an amount ranging from 0.1 to 5 moles of urea for each mole of anhydroglucose unit.
7. A process as defined in claim 1, wherein the catalyst is a strong mineral acid.
8. A process as defined in claim 1, including the step of separating the resin, as a solid, fusible resin, from the reaction mixture.
9. A process as defined in claim 8, which includes the step of curing the solid, fusible resin with a cross-linking agent to render the resin thermosetting.
10. A process as defined in claim 1, wherein the aldose saccharide is reacted with urea prior to contact with the phenolic compound.
11. A process as defined in claim 1, 8 or 9, wherein reactant (3) is urea.
12. A carbohydrate-phenolic resin produced by the process defined in claim 1, 8 or 9.
13. A process for producing a carbohydrate-phenolic resin comprising reacting in the presence of an acid catalyst:
(1) an aldose saccharide;
(2) a phenolic compound having the formula wherein R is selected from the group consisting of C1 to C3 alkyl, C1 to C3 alkoxy, halogen, hydroxy and hydrogen, and (3) a polyfunctional amine having the formula:

wherein R is a divalent organic group;
to form a solid, fusible resin, and separating the resin from the reaction mixture.
14. A process as defined in claim 13, wherein the saccharide is a hexose.
15. A process as defined in claim 13, wherein the phenolic compound is phenol.
16. A process as defined in claim 13, wherein the aldose saccharide is a starch.
17. A process as defined in claim 13, wherein the phenolic compound is employed in an amount within the range of 0.1 to 10 moles of phenolic compound for each mole of aldose saccharide.
18. A process as defined in claim 13, wherein the poly-functional amine is employed in an amount ranging from 0.1 to 5 moles for each mole of aldose saccharide.
19. A process as defined in claim 13, wherein the catalyst is a strong mineral acid.
20. A process as defined in claim 13, which includes the step of curing the solid, fusible resin with a cross-linking agent to render the resin thermosetting.
21. A process as defined in claim 13, wherein R is selected from the group consisting of phenylene and substituted phenylene.
22. A process as defined in claim 13, wherein R is a C2 to C10 alkylene group.
23. A process as defined in claim 13, wherein the aldose saccharide is reacted with urea prior to contact with the phenolic compound.
24. A carbohydrate-phenolic resin produced by the process defined in claim 13, 18 or 20.
25. A process for producing a carbohydrate-phenolic resol resin which comprises the steps of:
a) reacting in the presence of an acid catalyst the following ingredients:
1) an aldose saccharide 2) a phenolic compound having the formula wherein R is selected from the group consisting of C1 to C3 alkyl, C1 to C3 alkoxy, halogen, hydroxy and hydrogen, and 3) urea to form a liquid resin wherein the water produced in condensation is less than about 5 moles per mole of aldose; and b) reacting said liquid resin with a lower aliphatic aldehyde in the presence of a basic catalyst to form said resol resin.
26. A process as defined in claim 25, wherein the aldose saccharide is a hexose.
27. A process as defined in claim 25, wherein the phenolic compound is phenol.
28. A process as defined in claim 25, wherein the aldose saccharide is derived from starch.
29. A process as defined in claim 25, 26 or 27, wherein the phenolic compound is employed in an amount within the range of 0.1 to 1.5 moles of phenolic compound for each mole of aldose unit.
30. A process as defined in claim 25, 26 or 27, wherein the urea is employed in an amount ranging from 0.1 to 5 moles of urea for each mole of aldose unit.
31. A process as defined in claim 25, 26 or 27, wherein the aliphatic aldehyde is employed in an amount ranging from about 2 moles to about 4 moles for each mole of phenol.
32. A process as defined in claim 25, 26 or 27, wherein the acid catalyst is a strong mineral acid.
33. A process as defined in claim 25, 26 or 27, wherein the alkaline catalyst is calcium hydroxide.
34. A process as defined in claim 25, 26 or 27, wherein the aliphatic aldehyde is formaldehyde.
35. A process as defined in claim 25, 26 or 27, wherein the aldose saccharide is reacted with urea prior to contact with the phenolic compound.
36. A carbohydrate-phenolic resol resin produced by the process defined in claim 25, 26 or 27.
37. A process for producing a carbohydrate-phenolic resin which comprises:
i) reacting in the presence of an acid catalyst (1) an aldose saccharide;
(2) a phenolic compound having the formula wherein R is selected from the group consisting of C1 to C3 alkyl, C1 to C3 alkoxy, halogen, hydroxy and hydrogen;
and (3) urea or a diamine to form the resin, or ii) a) reacting in the presence of an acid catalyst the following ingredients:
1) an aldose saccharide 2) a phenolic compound having the formula wherein R is selected from the group consisting of C1 to C3 alkyl, C1 to C3 alkoxy, halogen, hydroxy and hydrogen, and 3) urea to form a liquid resin wherein the water produced in condensation is less than about 5 moles per mole of aldose; and b) reacting said liquid resin with a lower aliphatic aldehyde in the presence of a basic catalyst to form the resin.
38. A carbohydrate-phenolic resin produced by a process defined in claim 37.
Description  (OCR text may contain errors)

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This invention relates to carbohydrate-based conden-sation resol resin and a process for producing same, and more particularly to carbohydrate-phenol liquid condensation resins and solid, fusible resins incorporating polyfunctional nitrogen-containing compounds as coupling agents, and to reaction of the liquid resin with a lower aliphatic aldehyde to produce resol resins.
Condensation resins based upon phenol and aliphatic aldehydes and based upon urea and aliphatic aldehydes have been used for many years in the plastics industry. As is now well , , .
established, the aldehyde, usually formaldehyde, is reacted with phenol or urea in the presence of an acid or ba~ic catalyst to form a condensation resin. The formaldehyde serves as a `~ coupling agent, interconnecting the phenol or urea molecules.
For example, in a phenol-formaldehyde resin, the poly-meric matrix includes the followlng groups:

OH OH OH

CH2 ~ CH2 ~ Hz - OH ;~

The formaldehyde ~erveA a ~imilar coupling function `~ ~
`~ in urea formaldehyde re~in which contains group~ of the following type:

i~ [CH2 - NH - C - ~H - CH2 - NH - I - ~H l ~

n `
.

, wherein n is related to the molecular weight of the resin, ~, . . .

, .: .

- , . ,, ~ ..
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: :
: : . ' ; . : : ' ~1~90~?;~;
he basic raw material for conden~ation resins of the type described above is petroleum. As is now well known, supplies of petroleum are becoming increasingly limited, and prices have increased significantly. There is thus a need to re-, place at least a portion of the petroleu~based components of condensation resins of the type described above with a less expensive, more abundant material. Carbohydrates, readily avail-able from plant sources, are thus one type of renewable resource ideally suited for use in the manufacture of plastics.
It has been proposed, as described in U.S. Patent NosO 1,593,342; 1,753,030; 1,801,053; 1,868,216 and 1,923,321 to ~ employ carbohydrates such as dextrose, starch and the like, in - phenol condensation resins whereby the carbohydrate, in effect, is substituted for a portion of the petroleum-based material, usually phenol. However, resins of the sort described in the fore-going patents are, for the most part, prepared by reaction of the carbohydrate with phenol, occasionally in the presence of an aldehyde or a nitrogen-containing compound, such as aniline and amino phenol. The result is that the amount of carbohydrate which can be used in the resin is limited by the somewhat lower reactivity of the carbohydrate.
It is accordingly an object of the present invention to produce and provide a method for producing a low cost resin system incorporating a carbohydrate with relatively high levels of substitution.
It is a more specific object of the present invention to produce a carbohydrate-phenol resin in which the phenol is partiall~ replaced by the carbohydrate material to produce a soluble liquid resin and to provide a method for producing a carbohydrate-urelde-phenol resol resin.

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The concepts of the present invention reside in a carbohydrate-phenolic resin produced by reaction of an aldose saccharide, a phenolic compound and urea or a diamine in the presence of an acid catalyst. When the reaction o~ the present ; invention is stopped at a liquid stage, this resin can then be reacted with an aldehyde to form a resol resin. Nevertheless, r, .
- a solid fusible resin may be produced by allowing the first stage reaction to continue, In accordance with the concepts of this invention, the resins can ambody relatively high levels of carbohydrate without sacrificing the physical properties of the reslllting resin. The solid fusible resin systems of the , .
, invention are characterized by good water resistance and improved ~ strength properties. The resol resins of the present invention -~ are excellent adhesives for plywood and the like.
Unlike the prior art efforts to react a phenolic compound with a carbohydrate, the present invention utilizes urea or a diamine as a coupling agent which is believed to link the carbohydrate component with the phenol, thereby minimizing the amount of the most expensive reagent, phenol, necessary to produce a ~olid fusible resin. Without limiting the present invention as to theory, it is believed that, in the case of urea, using dextrose as illustrative of the carbo-hydrate, the carbohydrate forms a diureide which is then reacted with the phenol. This postulated mechanism may be illustrated by way of the following reaction in which the dextrose is dehydrated to hydroxymethyl furfural, and then the hydroxy-methyl furfural is reacted with urea to form a diureide:

.'' ' , ~ ~ _ 3 _ "' ~ '' ` '".' :
' , 1, ~ 1 '. ' ' .

109~0Zfi ,. CH20H

~,~ H~ ~ _~HO - CH2 - h~ - C - H
"~ HO~I 1, ~

O
, ~' 11 ' .

OH o OH ~
-. HO - CH2 _ ~ -CH -- NH - C -- NH - CH - ~ - CH2 - OH

. and/or `;i, O :
i HO ~ --CH = N - C - N = CH -- ~ - CH2 - OH

' . The resulting diureide is then capable of reaction ,~,. . .
, with phenol to yield a resin believed to contain the following ... .
:1 groups:
.: OH OH

~H2~ CH = 17 ~ 1 = CH - ~ CH2 [~ 2 " ~ CH=~-C - N = CH ~ _ CH2 - ~

:~ 10 rrhe foregoing postulated structure shows that, using , urea as a coupling agent in accordance with the concepts of this . invention, use can be made of 1 mole of dextrose for every mole ::. of phenol employed. rrhat permits the amount of phenol employed ",.:
in the resin to be cut in half, if desired, with a concomitant ~- reduction in the cost of the resin, or without sacrificing . . ...
physical properties of the resin.
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; In the practice of this invention, the preferred car-bohydrate is dextrose, although a variety of other carbohydrates can be used as desired~ In general, use can be made of aldose saccharides containing 1 to 106 saccharide units per molecule, with the preferred aldoses beinghexoses and pentoses Included ` are dextrose, maltose, maltotriose, lactose, sucrose, glycogen, ' glucosides, corn syrup, low D,E. hydrolyzed cereal solids and the like.
Also included as the carbohydrate useful in the ; 10 practice of this invention are the various starches containing as many as 106 repeating units. Such starches can be repre-sented by the structure:
r~
- CH20H 1 CH~OH I CH2H
H ~ I H ~ H ~ H ~ H

HO ~ l ~ O ~ OH

H OHI H H I H OH
., I I '.
:...................... I I , , ~ I I .:
L _ _ _ _ ~ n ... .
wherein n, designating the number of repeating units, can range from up to 106. Starches suitable for use in the practice of this invention include all varieties of starch, such as corn starch, tapioca starch, wheat starch, grain sorghum, potato starch, rice starch, sago, etc., as well as types and grades thereof including waxy starches, high amylose starches, chemically modified starches, dextrins, thin boiling starches and pregelatinized starches~ Also included are crude starches, such as mill starch, corn flour, wheat flour, brewers grits, broken rice, etc.

:.

:........ .. .. ,, ~ .

i ~
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As ~he phenolic compound used in the practice of this invention, preferred are the phenolic compounds having the formula:
OH

~R

wherein R is a group selected from Cl to C3 to alkyl, Cl to C3 ~' alkoxy, halogen, hydroxy and hydrogen. The preferred phenolic ~ compound is phenol, but other phenolic compounds include cresol, -- chlorophenol, bromophenol, resorcinol and the like, The relative proportions of reactants em~loyed in the practice of this invention can be varied within relatively wide limits. One of the advantages of the present invention stems from the fact that use can be made of one mole of the carbo-` hydrate for every mole of phenol employed, although it will be ;~ understood that, if desired, use can also be made of greater ~`~ amounts of phenol. In general, the amount of phenol employed ranges from 0.1 to 10 moles of phenolic compound for each mole ,1 of carbohydrate employed, and preferably 0.1 to 1.5 moles of .~:
~ phenolic compound per mole of carbohydrate. As will likewise be ~, appreciated by those skilled in the art, the proportions of urea employed depend upon the proportions of phenolic compound based on the carbohydrate. In general, use can be made of 0.1 to 5 , moles of urea for each mole of carbohydrate, and preferably 0.2 to 0.8 moles of urea per mole of carbohydrate.
For producing a resol resin according to this ,; .
~ invention, we prefer to use a liquid resin wherein the phenol, t: carbohydrate and urea components are maintained within the aforementioned range.
The acid catalysts used in the practice of this invention are typical of those acid catalysts employed in the condensation of aldehydes with phenols and urea.

`

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... . . .

~090~3;2~
Included are the strong mineral acids such as sulfuric acid, hydrochloric acid, etc., sulfonics include paratoluene sulfonic acid, naphthalene sulfonic acid, etc.' sulfur tri-chloride, antimony chloride, as well as a number of others, all of which are well known to those skilled in the art~
In carrying out the reaction in the practice of this invention, it is possible to form the diureide prior to reaction with the phenolic compound, although it has been found that there is frequently no advantage in doing so. It is sufficient to simply place the reactants in a reaction vessel in the presence of an acid catalyst and then heat the reaction mixture to a temperature sufficient to cause the condensation reaction to occur. In general, use can be made of reaction temperatures ranging from 70 to 200C. with the length of time of the reaction depending upon the reaction temperature.
The resulting solid-fusible resin is a brittle mate-rial which can be thermoset by the addition of a suitable cross . , linking agent, preferably hexamethylenetetramine. The resins ~- thus producted are thermosetting and find widespread use as mold-,~i;
ing and foundry resins. They are characterized by excellent water resistance and improved properties, particularly tensile strengths.
The liquid resin used for production of resol resin~ is easy to handle and provides a desirable viscosity for mixing and `~ adding the aldehyde reactant and the alkaline catalyst for pro-duction of the resol resin. Moreover, it has been found that the liquid state of the resin or the dextrose-diureide-phenol resin ,, can be controlled by monitoring the amount of water produced. We ; prefer to control the water produced by condensation to below about 5.0 moles water in the reaction. Attempts to resolubilize the solid-fusible resins by reaction with formaldehyde proved difficult to impossible since viscosity remained at impractical levels.

. ~ .. , . : . ... .. . . . ...
... . . ~, . , . : .
. , , , ~... . .. .. .

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While not equivalent to urea in the practice of this invention, use can also be made of polyfunctional amines as the coupling agent in place of urea. Such amines in~lude amines of the formula:

wherein R is a divalent organic group, preferably an alkylene group containing 2 to 10 carbon atoms (e.g., dimethylene, tri-methylene, tetramethylene, etc.) or an arylene group such as phenylene and phenylene-substituted with a Cl to C3 alkyl group, Cl to C3 alkoxy group, etc.
It will also be appreciated by those skilled in the art that various additives can be incorporated into the reaction mixture. For example, it has been found that~the addition of fatty acid amines, preferably containing 12 to 22 carbon atoms, can be added to the reaction vessel during the reaction to further increase water resistance and final thermoset resin mold-ability. For this purpose, use can be made of a variety of fatty acid amines commercially available, including, for example, ARMEEN T-Tallow amine, a long chain fatty acid amine from Armak.
For the production of the resol resin of this invention, it has been found that best results can be obtained when the amount of aliphatic aldehyde (i.e., formaldehyde, acetaldehyde or propionaldehyde) ranges from about 2 moles to about 4 moles for each mole of phenol.
:
The use of a basic catalyst in the reaction of the liquid resin to form a resol resin is an important concept of the invention. Any of a number of basic catalysts can be used in the practice of this invention, all of which are well known to those skilled in the art. Included are the alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide, etc.), alkaline earth .

: ~o9(~oz~;
metal oxides and hydroxides (e.g. calcium oxide, barium oxide, magnesium oxide, etc.) as well as ammonia and like bases. In - general, the basic catalyst should be used in an amount suf-ficient to adjust the pH of the second stage reaction medium to at least 8
;;~ This invention is further illustrated by the following ~ examples, which, however, are not to be taken as limiting in any - respect. All parts and percentages, unless expressly stated to be otherwise, are by weight.

This example illustrates the practice of this in~ention --using dextrose, urea and phenol as the reactants.
:~ A 1000 ml reaction flask equipped with a condenser, stirrer and thermometer is charged with 360 g. of dextrose, 60 g.
of urea and 208 g. of 9~/0 phenol, corresponding to a mole ratio ., .
of dextrose-urea-phenol of 1:0.5:1.

2,5 ml of 5N sulfuric acid catalyst are added to the reaction flask, and the flask heated to a temperature varying , ........................................................................ . .
-i between 123 and 182C. for about 8.6 hours. During that time, ~ -171 ml of water are collected from the reaction vessel.

The resulting resin, a solid black material at room temperature, is recovered from the reaction vessel.

;j:.
~' This example illustrates the use of starch as the car-.:
bohydrate in the preparation of a carbohydrate-phenol con-densation resin.
A 500 ml reaction flask is charged with 184 g. of starch (Argo Code 3005), 104 g~ of 9~/O phenol, 100 g. of water and 14 g. of 5N H2S04.
The resulting mixture is stirred initially at 95 to 114C. to hydrolyze the starch and thereby form a black soiution from which 105 ml of water are collected.

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' . ', . : ' ' . . ' , ' ' . ~ . . .

10900Z~
At this stage, 30 g. of urea is added to the flask, and the condensation reaction proceeds at a temperature varying from 114 to 183 C. over a period of 6,4 hours. During the ` latter period, an additional 101 ml of water are recovered from the reaction vessel.
The resulting resin weighs 210 g. and is a brittle solid at room temperature.

: .
~ EXAMPLE 3 ;~ Using the apparatus and procedure described in Example .
- 10 2, 360 g. of dextrose, 60 g. urea, 204 g. 9~/O phenol and 9.6 g, of 5N H2SO4 are charged to the reaction vessel, Water of con-densation, totalling 206 ml is collected over a period of 9 1 hours while the reaction temperature of the vessel varies between 118 and 185C, Recovered from the reaction vessel are 380 g, of a black rasin, brittle at room temperature.

This example illustrates the practice of this invention ,., wherein the resin is prepared in the presence of a fatty acid ,r, 20 amine to improve the water resistance of the resin and the final thermoset resin moldability.
Into a 500 ml flask, there is charged 180 g. of dextrose 30 g. of urea, 104 g. of 90~/0 phenol, 9 g, of ARMEE~ T-Tallow amine and 1.4 g. of 5N H2SO4. The reactants are cooked in the reaction vessel at a temperature from 129 to 189C. for a period of 4.9 hours; during that time, 97.5 ml of water of condensation are collectedO

The resulting resin is separated from the reaction vessel, and is a black material, brittle at room temperature, -- 10 _ ':
,~
, :
.~, . .

lV900~;

This example illustrates the effect of varying the dextrose-urea-phenol molar ratios on physical properties, namely - water resistance and resin moldability.
(a) In the first test, a 1:1:1 molar ratio of dextrose-urea-phenol is made by adding 180 g. of dextrose, 60 g~ of urea, 104 g.
of 90/O phenol and 2.8 g. of 5~ H2SO4 to ` the reaction flask. The reaction tempera-ture varies from 127 to 194C. and 112 ml . ,',. . .
` of water of condensation is recovered in 6.1 hours~

(b) In the next test, the molar ratio of dextrose-urea-phenol is 1:0.75:1, with 180 g. of ` dextrose, 45 g. of urea, 104 g. of 9~/O
. -~ i phenol, and 1.4 g. of 5N H2S04 being added to the reaction vessel, The condensation reaction ;~ is run for 4.7 hours at 130 to 180C. while - collecting 98.5 ml water of condensation.
` 20 (c) In this test, the mole ratio is 1:0.25:1 obtained by using 180 g. of dextrose, 15 g.
of urea, 104 g. of 9~/0 phenol, 9 g.of ARMEEN
T* and 1.4 g. of 5N H2S04. The temperature ~ ~' ranges from 129 to 180C. for 4.8 hours, ' with 91 mL water of condensation being col-lected.
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This example illustrates the use of toluene diamine as the nitrogen-containing coupling agent.
~` Using the procedure described in Example 1, there is charged to a 500 ml flask, 180 g. of dextrose, 61.1 g. of toluene diamine, 104 g. of 9C/0 phenol and 1~4 g. of 5N H2S04.
The reactants are maintained at 113 to 186C. for 4.2 hours ; during which 79 ml water of condensation are obtained.
` The black resin, weighing 260 g. was obtained, and brittle at room temperature.
~`~

_ ~; This example illustrates the use of ethylene diamine as the polyfunctional amine coupling agent in the practice of , 'r this invention.
Using the procedure described in Example 6, a reaction mixture is formed of 180 g. of dextrose, 30 g. of ethylene di-amine, 104 g. of 90/O phenol, and 1.4 g. of 5~ H2S04 as a ~, catalystO The reaction occurs over 5 hours, while the temperature varies from 111 to 178C. A total of 96 ml water of condensation are recovered.
The resulting resin is a black material, brittle at room temperature.

. .
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. . , , .' .

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; EXAMPLE 8 This example illustrates the use of the resins pre-;; pared in accordance with the concepts of this invention in moldingapplications, indicating the physical properties obtain-able in the practice of the invention.
, Each of the resins from Example 1 through 4, 5(a), - 5(b), 5(c), 6 and 7 is compounded in accordance with the ; following recipe:
Resin 46 g.

Hexamethylenetetramine Varied quantities as indicated Calcium stearate 2.0 g.
Calcium oxide 2.0 g.
Wood flour 46 g.
Each of the re~ins are compounded with the above recipe and milled at 200F. for two minutes. The recipe is then formed into bars (5" x 0,5" x 1/8") by molding at 350F. for five minutes, - The resulting test bars are then tested to determine their water resistance, first by contacting the test bars with boiling water for two hours, and in another test, by immersion in water for 24 hours in accordance with ASTM D570-63 t6a).
The bars are also tested to determine their flexural modulus.
The results of those tests are set forth in the following Table:

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~ EXAMPLE 9 i~, This example is provided for comparative purposes ', , !
and illustrates the use of a monofunctional amine compound, aniline, in accordance with the practice of the prior art.
a) A 1000 ml reaction flask of the type utilized in Example 1 is charged with 183 g. of dextrose, 93 g. of aniline 103 g. of 9~/O phenol and 1.5 g. of 5N H2S04. The condensation reaction continues for 145 minutes at tempera-tures varying from 109 to 183C. A
total of 95 ml of water of condensa-tion is collected.
b) Using the same procedure as described ; above, 180 g, of dextrose, 53 g. of 90/O
. . , phenol, 94 g. of aniline and 1.3 g. of 5N H2S04 are charged to a reaction vessel. The reaction occurs over 4.7 . .
~; hours at reaction temperatures ranging ; 20 from 113 to 168C. A total of 83 ml of water of condensation is collected .... .
during the reaction.
c) Using the same procedure as described in Example 8, ~he resin is compounded, milled and molded into bars as described in that example. The bars are subjected to the same physical tests described in Example 7 with the following results:
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As can be seen from the foregoing data using aniline as in the prior art, the resulting test bars have excellent ~..
d`` water resistance, but have a strength, expressed as flexural modulus, less than that achieved using urea as the coupling agent.
:-, This example illustrates the use of corn flour as the carbohydrate employed in the pratice of this invention.
A 500 ml.reaction flask was charged with the following ingredients: 184 g. starch (yellow corn flour), 104 g. phenol (9C/O d.b.), 30 g. urea, and 40 g. 5~ H2S04.
The starch was added to the flask in two increment~ and hydrolysis allowed to proceed over a period of 3 hours whereby the urea was then added. The condensation reaction occurred over a period of 8.2 hours at a temperature of 112 - 186C. while collecting 118 ml of water. A-black, brittle solid (yield 223 g.) at room temperature was obtained.
The product was compounded, milled and tested for water resis-tance and strength properties as given below:

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Water Resistance 2 Hr. Boi in~ Water 24 Hr Immersion Flexural ; % H20 /O Weight % H20 % Weight Modulus Hexa, Example /O Absorbed Loss Abs_rbed Los _ psi x 105 ' 7 7.00 0.62 2.03 0.05 12.0 , 10 10 6.10 0.80 2.37+0.19 11 4 ; 20 7.28 3.92 4.25 1.20 10 4 `: :

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`- As will be appreciated by those skilled in the art, - it is possible, and sometimes de~sirable, in the practice of this invention, to form the diureide prior to the reaction with the phenolic compound. This concept of the invention may be illustrated by reference to the following example.
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Diglucose ureide was prepared according to the directions in U.S. Patent 2,967,859.
The reaction of Example 3 was repeated using di-glucose ureide in place of dextrose and urea. Water volu-tion was slower requiring 20 hours for completion. From 110 g. of the diglucose ureide was obtained 133 g. of black product.
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When resins were prepared from the product in the usual manner, they showed the following properties:
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This example illustrates the preparation of t~e resol resin of this invention by reacting the dextrose-diureide phenol liquid resin and formaldehyde to form a resol resin.
270 g. dextrose, 45 g. of urea, and 156 g. of - phenol (9~/~ by weight) was added to a reaction flask and 13.5 g. of 5.0 Normal H2S04 was added to serve as a catalyst Reaction was allowed to proceed at 125C. to 153C. for

4 hours during which time 112 g. of water was collected using a water cooled condenser. This resin was a dark - liquid product.
The liquid resin was cooled to about 90C. and the ~ water of condensation returned to the reaction flask. At '' this pointl3.0 g. of calcium hydroxide was added to neutra-~;~ lize the acid and to provide a basic catalyst system.
- Reactlon temperature was cooled to about 70C. and 450 g.
of aqueous 35% (by weight) formaldehyde was added.

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The reaction was held with stirring until the exo-therm subsided. The reaction mixture was then held for about 1 ` hour at about 80C. The resol resin was then cooled to room temperature and was a liquid product having a viscosity of :
about 500 centipoise. Final sol;ids content was 49.4% by weight.
As can be seen, the molar ratio of reactants in this .: .
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~, A resol resin prepared as shown in Example 12 was used as a plywood adhesive wherein the adhesive formulation ,....
was prepared in the following order:

- Distilled Water 86.3 g.

' Hard Wheat Flour 9.0 Norparfil* (a filler) 27.0 i:
'; Resol Resin (49.4% d.b.) 34.8

5~/O NaOH 9,4 Sodium Carbonate 3.6 Resol Resin '~ (49.4% d.b.) 121~9 , Final adhesive viscosity is about 3,100 centipoise.
The adhesive was then applied to three 12" x 12 sheets of ,- Douglas Fir or Southern Pine veneer at a level of 63 lb/1000 ft.2 per glue line. The plies were stacked together and cured ~, in a preheated press (285F.) at 175 psi for the minimum time to cure the adhesive (usually about 4 1/2 minutes~
~ The laminates prepared using the novel resol resins of the example showed excellent water resistance in boiling , water for 18 hours without delamination.
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This example illustrates the preparation of the ~ resol resin of this invention starting with starch hydrolysate or corn syrup.
332 g. of starch hydrolysate at about 81% dry sub-, stance by weight was placed in a reaction flask at about 85C.
and 8.1 g. of 5 Normal H2S04 acicl was added. The reaction was held for 2 hours to begin breakdown to dextrose and then ~5 g.
- of urea, and 156 g. of phenol (9~/0 by weight) was added~ The ` 10 reaction was allowed to proceed at 112 - 163C. for about 6 hours during which time 152 g. of water was collected using a water cooled condenser. This resin was a dark liquid product.
- This liquid resin was cooled to about 90~C. and the , water of condensation returned to the reaction flask. At this !~ point 13.0 g. of calcium hydroxide was added to neutralize the . ,.
acid and to provide a basic catalyst system, Reaction temperature was cooled to about 70C. and 375 g. of aqueous .;
35% (by weight) formaldehyde was added.
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The reaction was held with stirring,until the exo-therm subsided. The reaction was then held for about 1 hour at about 80C. The resol resin was then cooled to room temperature and was a liquid product having a viscosity of about 500 centi-poise. Final solids content was 51.4% by weight.
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Plywood adhesive formulations were prepared as shown in Example 13. The resulting finished laminates prepared using j~ this resol resin showed good water resistance in boiling water for about 2 hours without delamination.
; EXAMPLE 15 This example further illustrates the preparation of resol resins of this invention wherein formaldehyde is added to a dextrose-diureide-phenol liquid resin. Moreover, this example shows other molar ratios for reactantq and the results - -- 22 _ ~ , . . .... . . . . . .

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obtained in pl~wood laminates prepared using the novel resol ' resins of this invention.
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US94936037 May 201115 Nov 2016Knauf Insulation SprlCarbohydrate binders and materials made therewith
US95058838 May 201429 Nov 2016Knauf Insulation SprlCarbohydrate polyamine binders and materials made therewith
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Classifications
International ClassificationC08G83/00, C07H7/04, C08G
Legal Events
DateCodeEventDescription
18 Nov 1997MKEXExpiry