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Patent 1090026 Summary

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(12) Patent: (11) CA 1090026
(21) Application Number: 282839
(54) English Title: CARBOHYDRATE-PHENOL BASED CONDENSATION RESINS INCORPORATING NITROGEN-CONTAINING COMPOUNDS
(54) French Title: RESINES DE CONDENSATION A BASE DE GLUCIDES ET DE PHENOLS ET COMPRENANT DES COMPOSES CONTENANT DE L'AZOTE
Status: Expired
Bibliographic Data
(52) Canadian Patent Classification (CPC):
  • 402/45
(51) International Patent Classification (IPC):
  • C07H 7/04 (2006.01)
  • C08G 83/00 (2006.01)
(72) Inventors :
  • GIBBONS, JOHN P. (United States of America)
  • WONDOLOWSKI, LAWRENCE (United States of America)
(73) Owners :
  • CPC INTERNATIONAL INC. (Not Available)
(71) Applicants :
(74) Agent: SHERMAN
(74) Associate agent:
(45) Issued: 1980-11-18
(22) Filed Date: 1977-07-15
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data:
Application No. Country/Territory Date
808,580 United States of America 1977-06-22
707,600 United States of America 1976-07-22

Abstracts

English 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

Note: Claims are shown in the official language in which they were submitted.


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


Image


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.

26

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

Image

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:
H2N - R - NH2
wherein R is a divalent organic group;
to form a solid, fusible resin, and separating the resin from
the reaction mixture.


27

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.

28

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




Image

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.


29

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




Image





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




Image


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.


31

Description

Note: Descriptions are shown in the official language in which they were submitted.


z~
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,
~, . . .


- 1 -

,
.: .

- , . ,, ~ ..
. . :. : .
: :
: : . ' ; . : : '

~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.



, .
-- 2 --

~o~oo~4;
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 ' .
H2N - C - NH2
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.
. .

... .

,,~, . .

~: ,
i, .
~' ' 4
"

.

:~09f)Q2~
; 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 ~
1~91)02~
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.

`
-- 6 --

"i ' ' :
... . . .

~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.
-- 7 --

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

90Q;~
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:
H2N - R - NH
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



-- 8 --


.

: ~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 8Ø
;;~ 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.
EXAMPLE 1
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.

EXAMPLE 2
;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.

. .
:, .
,, _ g _

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

. ~ . . .

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.
EXAMPLE 4
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~;
EXAMPLE 5
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.
' ,' '.
~ *trademark

:::
. . '
.,
,, -- 11 --


. .
.. . . . . .
.. . ..
., .

lO90~
EXAMPLE 6
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.
~`~
EXAMPLE 7
_
~; 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.




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

9CIUZ~
; 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.
:-,
EXAMPLE 10
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:


.' ,.
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.
.',~ .~
EXAMPLE 11
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 évolu-
tion was slower requiring 20 hours for completion. From
110 g. of the diglucose ureide was obtained 133 g. of black
product.
i .
When resins were prepared from the product in the
usual manner, they showed the following properties:
., " ' .
Water Resistance
. . ,
2 Hr. Boilinq Water 24 Hr. Immersion
Flexural
% 2 % Weight % H2O % Weight Modulus
,, Hexa,
~ ExamPle % Absorbed Loss Absorbed Loss psi x 105
,"
7.0 3.70 0.0 0.77 0.05 10.4
1110.0 2.95 0.0 0.91 0.0 10.5
, 20.0 3.32 0.68 1.2 0.0 10.1

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EXAMPLE 12
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
.: .
example for the preparation of the intermediate resin is about

1 mole dextrose : 0.5 mole urea : 1 mole phenol and for the

resol stage about 3.5 mole formaldehyde per mole phenol.

- EXAMPLE 13

~, 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.
~, *trade mark
, .
- 21 -
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: . . . . : . . ..
: . ' ' ' , . .

,- lOgOVZ~
EXAMPLE 14
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.
:;
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.
. .: .
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 _


~ , . . .... . . . . . .

1090(1 Z6
:`
obtained in pl~wood laminates prepared using the novel resol
' resins of this invention.
~ ~ .
. The liquid resin and resol resin formation as
shown in the procedures of Example 12 were used with the
`~ exception of different molar rati.os with the results
.~ summarized in the following table:
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: While the invention has been described in connection
with specific embodiments thereof, it will be understood that
.,~ it is capable of further modification, and this application is
intended to cover any variation, uses, or adaptions of the
invention following, in general the principles of the
invention and including such departures from the present
~ disclosure as come within known or customary practice in
- the art to which the invention pertains and as may be applied
~:: to the essential features hereinbefore set forth, as fall
within the scope of the invention.



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Representative Drawing

Sorry, the representative drawing for patent document number 1090026 was not found.

Administrative Status

For a clearer understanding of the status of the application/patent presented on this page, the site Disclaimer , as well as the definitions for Patent , Administrative Status , Maintenance Fee  and Payment History  should be consulted.

Administrative Status

Title Date
Forecasted Issue Date 1980-11-18
(22) Filed 1977-07-15
(45) Issued 1980-11-18
Expired 1997-11-18

Abandonment History

There is no abandonment history.

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $0.00 1977-07-15
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
CPC INTERNATIONAL INC.
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Drawings 1994-04-12 1 13
Claims 1994-04-12 6 199
Abstract 1994-04-12 1 26
Cover Page 1994-04-12 1 24
Description 1994-04-12 25 911