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Патент USA US3049526

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_
rates
#1 ite It
hit
3,049,515
Patented Aug. 14, 1952
1
2
,
about two molar proportions of the selected polyether
3,049,516
- ORDERED
polyol (b).
ETHER-BASED URE
‘
POLY
The ordered hydroxy-terminated urethane compositions
COMPOSITIGNS
of the present invention have certain advantages over
HYDROXY-TERIVIINATED
Adolfas Damusis, Detroit, Mich, assignor to Wyandotte 5 ordinary hydroxyl-bearing materials such as polyesters
{Chemicals Corporation, Wyandotte, Mich, a corpora
tion of lviichigan
No Drawing. Filed Mar. 26, 1959, Ser. No. 802,018
18 Claims.
(Cl. 260-775)
-
The present invention relates to novel ordered hydroxy
terminated polyether-based methane compositions which
are especially useful as hydroXy-terminated-urethane com
ponents for two-component polyurethane coatings or cor
responding single component systems which employ as
the other, or diisocyanate ingredient, a blocked isocyanate,
and which are also of special utility as bodying agents
for urethane coatings, particularly when it is not desired
tov employ thermoplastic resins for such purpose.
It is an object of the present invention to provide novel
bodying agents for urethane coatings. It is a further ob
ject to provide novel and valuable ordered hydroxy-termi
nated urethane components for polyurethane coatings sys
tems. A further object is the provision of such composi
and regular polyols. Polyurethane coatings prepared
thereform by reaction with an isocyanate-terminated com
ponent dry to touch upon evaporation of solvent, and
have considerably less sagging tendency than polyurethane
coating formulations incorporating regular polyols.~ When
the ordered hydroXy-terminated urethane compositions of the present invention are reacted with ‘an isocyanate-termi
nated component, the resulting polyurethane surface coat
ings are characterized by properties which are superior to
those obtained from the same isocyanate component and
previously known polyhydroxy components. The same is
true when they are employed as one ingredient of a single
component surface coating composition together with a
blocked isocyanate as the other ingredient (for example,
in baking enamels or wire coatings). This is also true
for polyurethane surface coatings prepared‘ from the
ordered hydroxy-terminated urethane compositions of the
invention as opposed to those prepared from random hy
?ons which are poly-ether-based urethanes. Another ob—
droxy-terminated urethane reaction products, compared
ject is the provision of such ordered urethane composi
tions which lend advantageous properties to polyurethane
to which latter a higher solid content at lower viscosity
can be attained in surface coatings embodying the ordered
coatings in which they are employed as the hydroxy
terminated component or ingredient. .Still another ob
ject of the invention is the provision of a process for the
production of such ordered urethane compositions sequentially by the reaction of about one mol of polypropyl
eneether glycol with about two mols of a selected arylene
diisocyanate, and reaction of the thus-produced iso
cyanate-terminated urethane with about two mols of a se
lected polyether polyol, and the products thereby pro
duced. Other objects of the invention will become ap
parent hereinafter.
The foregoing and ‘additional objects are accomplished
by the provision of ordered urethane compositions of
the following idealized formula:
hydroxy-terminated urethane compositions of the inven
tion.
'
The ordered hydroxy-terminated urethane compositions
of the present invention are prepared by reacting about
one molar proportion of extending polypropyleneether
glycol (a) of selected molecular weight between about
134 and 1000 and about two molar proportions of an
appropriate arylene diisocyanate (0), selected from
phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6
tolylene diisocyanate, including mixtures of 2,4-and 2,6
tolylene diisocyanates, and diphenylmethane-4,4'-diiso
cyanate, to produce a diisocyanate-terminated urethane
having a tree NCO group at each end of the molecule.
If desired, about one molar proportion of one diisocyanate
0
Q-QINH
O '
O
R
wherein R is selected from hydrogen and methyl, wherein
-—O——G--O-~ is the radical of a polypropyleneether
II
NEG-Q
R
and about one molar proportion of another diisocyanate
may be used. One molar proportion of this isocyanate
glycol (a) having a molecular weight between about 134 50 terminated urethane adduct is then reacted with about two
molar proportions of the selected polyether polyol (b) to
and 1000, wherein T1 is
produce an ordered hydroxy-terminated urethane com
position in which the terminal hydroxy groups are
and T2 is
furnished by the polyether polyol molecule.
The polyether polyol (b) used in the ?nal stage of the
sequential reaction is a propylene oxide addition product
of a lower \alkanol, containing up to and including ten
carbon atoms and containing at least three and not more
than six hydroxy groups per molecule, and may be rep
wherein y is a number from zero to one, inclusive, and
wherein Q is the same in both occurrences and is the 60 resented by the formula:
radical of a branched polyether polyol (b) which is a
propylene oxide addition product of a lower alkanol
containing at least three ‘and not more than six hydroxy
groups per molecule, said urethane composition being
prepared sequentially by the reaction of about one molar 65 wherein R' with attached oxygen atoms represents a lower
proportion of polypropylene ether glycol (a) with about
two molar proportions of arylene diisocyanate (0) se
lected from the group consisting of phenylene diiso
alkanol radical; x is a number from zero to one; z is a
number from zero to threepand n is a number from zero
to three, provided that when 1:0, at least one n is at
cyanate, tolylene diisocyanate, and diphenylmethane-4,4'
least one; when z=l, at least two n’s are at least one;
diisocyanate, to produce‘lan isocyanate-terminated poly 70 when z=2, at least three n’s are at least one; and when
propyleneether glycol urethane (I), and subsequent re
action of the isocyanate-terminated urethane (I) with
z=3, at least four n’s are at least one. It will be under
stood that x, z and n may be the same or different in each
8,049,516
A
occurrence. Representative polyether polyols encom
tive surface surface coating solvent. Many such solvents
passed by this formula include the addition products of
suitable in general for urethane coatings and components 7
glycerine, hexanetriol, ‘and trimethylolpropane with from
thereof are known in the ‘art, for example, toluene, xylene,
one to nine mols of propylene oxide, the addition products
ethyl acetate, butyl acetate, amyl acetate, other similar‘
of such polyols further reacted with one mol of ethylene 5 esters, 2-ethoxyethyl-, 2-methoxyethyl- or 2-butyoxyethyl
oxide, the addition product of pentaerythritol with from
acetate, dioxane, ketones, chlorinated solvents, nitro-ali
two to twelve mols of propylene oxide, the addition prod
phatic solvents, and the like. In some instances no sol
ucts of such polyols further reacted with one mol of
vent is required during any stage of the reaction.
ethylene oxide, the addition products of dipentaerythritol
Polyether polyols used in‘ the reaction are preferably
‘and sorbitol with from four to eighteen mols of propylene 10 stripped of water by azeotropic distillation with toluene.
oxide, the addition products of such polyols further re
In this manner, the amount of Water can be decreased
acted with one mol of ethylene oxide, and the like. The
from 0.08-0.15 to 0.02% or even less. ' A clean, dry,
terminal ethylene oxide unit, when added to the polyoxy
three-necked ?ve-liter ?ask was used as a reaction vessel,
propylene chain or unit, provides a primary hydroxy
and a nitrogen blanket was maintained over the reactants.
group of relatively high reactivity for de?nite direction 15
and precedence of reaction with NCO groups in preparing
Example 1 (OH-2)
the ?nal OH-terminated urethane from the intermediate
3
A
NCO-terminated urethane.
Reactants
Mols
Parts
Weight,
In practice, the molecular weights of the ordered
hydroxy-terminated urethane compositions of the inven 20
tion, prepared in this sequential manner, have been found
Polypropyleneether
to be very close to the molecular weight of a composition
having an ‘idealized structure, since very little polymeri
P410 (M.W. 420) _____________________ __
2
s40
21. 1
Tolylene diisoeyanate, TDI; 80/20; 2,4/2,6_
Polyoxypropylene derivative of trimeth
4
696‘
. 17. 5
Percent
ylolpropaue-Pluracol TP-440 (M.W.
411) ................................. __
zation occurs using predetermined molar proportions and
the sequential addition under moderate reaction condi
tions, viz., exclusion of moisture and initial reaction tem
perature not exceeding about 60° ‘C. Also, in practice, a
chain length of not greater than about 750, and prefer
a'bly about 400, molecular weight has been found most
advantageous for the starting polypropyleneether glycol,
and a polyol having no more than an average of about
glycol - Pluracol
'
4
1, 644
41.4
398
10. O
25 Z-ethoxyethyl acetate or Z-butox thyl
acetate _______________________________________ __
Xylene
‘
398
10.0
,3, 976
100.0
‘ Norn.—Ratio of reactivegroups: N CO/OH=4/8=1/2.
3O
PROCEDURE
,
Stage 1: Add to the S-liter reaction vessel—--
two propylene oxide units added per individual chain of
7
‘Parts
starting polyol is usually preferred. When the polyol (b)
‘employed has four hydroxy groups, the polyether glycol
TDI
(a) preferably has a molecular weight greater than 400. 35
~
Polypropyleneether glycol,
As for the isocyanate employed, tolylene diisocyanate,
696
Pluracol 'P-140
‘(M.W. 420) __________ __' _____________ __ 840
usually a mixture of about 80% / 20% of the 2,4 and 2,6
By gradual addition of polypropyleneether glycol, Plura
isomers, is preferred for reasons of economy. Other var
col ‘13-410, the temperature of the exothermic reaction is
iations in the starting materials to procure variations in
maintained below 60° C. If necessary, cooling is ap
'the substituents of the ordered hydroxy-terminated ure ‘10 plied. 'Ihe reactants are stirred for 2 hours at 60° C.
thane compositions may be usefully made to obtain poly
and then diluted with:
urethane surface coatings of varying types and character
>
istics upon reaction with a selected diisocyanate ‘compo
chains shown in the above formulae results in a polyure
thane coating having a longer pot life, greater ?exibility,
.
Parts
2-ethoxyethyl acetate _______________________ _.. 177
nent. For example, lengthening of the polyoxypropylene
Xylene
177
45
Stage 2:
Parts
Add to the prepared adduct polyoxypropylene
and lower solvent resistance, while shortening of these
polyoxypropylene chains has just the oposite effect.
Flexibility of such coatings can, for example, be readily
‘derivative of trimethylolpropane-—Pluracol
'I‘P-440 (M.W. 411) _________ -2 ______ __ 1644
adjusted by changing the length of the polyoxypropylene
chain or chains, either in the starting polypropyleneether 50 Increase the temperature to 80° C. and stir the reactants
for 3 hours. Measure the viscosity after each, hour with
glycol (a) or in the polyether polyol (b), or both if de
the Gardner Bubble Viscosimeter. When the viscosity
sired, and in general employment of products of the in
rises over Z6, dilute the content of the vessel to 80%
vention introduce a trend toward ?exibility in coating
solids with:
compositions embodying same. The preferred equivalent
weight of the hydroxy-terminated urethanes of the present
invention is between about 200 and 400.
'
60 and cap it tightly in order to exclude moisture.
Properties of 01-1-2:
NCO/OH
to‘ form a hydroxy-terminated intermediate with free OH
groups on both ends of the molecule. The addition of
1/2
Average molecular weight ______________ _.. 1590
Average equivalent weight ____.; _________ __ 398
propyleneether glycol and the selected diisocyanate is pre
- are added to one molar proportion of the adduct in order
Parts
Xylene
221
Pour the resulting OH-2 solution into a clean, dry bottle
The following examples are given to illustrate the pres
ent invention but are not to be construed as limiting.
pared in the ?rst stage at a ratio of NCO/ OH of about
2/1 and contains two free NCO groups. In the second
stage, two molar proportions of polyether triol or tetraol
7
2-ethoxyethyl acetate ________________________ __ 221
'
GENERAL PROCEDURE
Hydroxy-terminated‘urethanes, such as OH-2 of Ex
ample 1, are prepared in two stages. The adduct of poly
'
55
65
Hydroxyl number ______________________ __ 14-1
Percent hydroxyl _________________ __,__.___ 4.27
Properties of 01-1-2 solution:
.
Non-volatile, percent __________________ __
80
Weight per gallon, lb. __________________ __ 8.84
Viscosity at 25° C., cps. ________ __12,000-15,000
two polyether triol molecules to the adduct changes the 70
OH-2 IN URETHANE COATINGS
NCO/ OH ratio to 1/2.0; two polyether tetraols to l/2.5;
two polyether pentols to 1/ 3.0; and two polyether hexols
Two ‘typical urethane coating formulations are pre
'to 1/3'.5. Dilution of the NCO-terminated intermediate
sented with hydroxy-terminated intermediate OH-2 as the
at'the end of stage 1 may be with any suitable non-reac 75 second component.
A
3,049,516
6
TWO COMPONENT URETHANE COATINGS
Properties .of OH-ZA: '
NCO/0H
Average
Formulation
Composition
1
lsocyfvvangte-terminated intermediate _________ __
21
2 N (30-1
8 N C 08%
_
OH-2
OH-Z
_
100
NCO/0H ___________________________________ __
1. 2/1
Parts _________________ __V_,._____
_ _ _ .._
Average equivalent weight ; _ _ _ _
_ _ _ .._
212
Hydroxyl
_ _ _ __
265
Percent hydroxyl ______________________ __
8.17
_ _ _ _ _ _ _ __
Non-volatile, percent ________ _'_ __________ __
10
Formulation
adduct of trimethylolpropane 0r hexanetriol, the phenylure
thanes of any of the foregoing, TDI, MDI, and the like.
2NC0—1 is the NCO-terminated reaction product of three
moles of TDI with one mol of TP 440 polyol (propylene oxide
Composition
.
‘
-
agdittio?oproduct of trimethylolpropane having a M.W. of
on
i
Isocyanate-terminated intermediate
.
a
,4
' 1U-1688-1
Pa
3NCO—3 is the NCO-terminated reaction product of two
mols of NCO-1 with one mol of P410 polyol (propyleneether
.
glycol, LLW. about 410).
2
150
OH-2A
100
2/1
2/1
dusocyanate, and one mol of polypropyleneether glycol
25 ene
glilliaéifl P-élO. (2 mols of U-168S-1 reacted with one of
Curing time:
Dust free, hr ____________________________ __
l. 2
Dry to touch, hr
3.0
Pot life, hr ________ -_
56
64
40-52
12-38
Sward hardness__-__
Elongation, percent
40-70
Tensile strength, p.s. ____
3, 600-5, 000
Impact test-Gard11er, in
ct
1. 4
4. 2
1, 600-4, 000 30
(1)
Tnlnene
3
4
>30
>30
46
.
Formulation
Properties
200-360
>30
>30
Solvent resistance, hr.: -
60
(1)
>4
>4
2-Ethoxyethyl acetate ___________________ __
4
2
Methyl isohutyl ketone _________________ -_
3
2
1. 0
1. 2
24
1. 0
1. 2
28
60-72
6-8
58-70
8-10
16
4
20
4
>4
>4
4
>3
Water resistance:
Immersion 24 hr., 25° C-_' _______________ _Immersion 96 hr., 100° C; _______ __
Weatherometer (Twin Arc) test, 500 hr.
1 Excellent.
2 No effect.
(i)
(i)
(I)
(1)
(1)
(l)
40
3 No loss of gloss.
Toluene
Methyl isobutyl ketone _______________ -_
Example 3 (OH-2B)
Reactants
Example 2 (‘OH-2A)
Reactants
Mols
Parts
Weight,
45
'
Moles
Parts
Weight,
percent
Polypropyleneether glycol P-4i0 (M.W.
Percent
ylolpropane (TMP + 3 mols of pro
Polypropyleneether glycol-Piuracol P
410 (M.W. 42
=U-1ess-2
90
011-2».
100
1_U—1‘688—1 consists of 1 mol of P3680? .polyoxypropylene
der1vat1ve_0f pentaerythritol (M.W. 368) and four mols of
tolylene diisocyanate.
2_U—1'688—2 consists of 2 mols of P3681‘ polyoxypropylene
derivative of pentaerythritol (M.W. 368), eight mols of tolyl
Formulation
Properties
1
60
Viscosity at 25° C.,'cps. ...._..__ _____ __ 5000-8000
‘OH-2A IN URETHANE COATINGS
1Numerous other organic polyisocyanates can be used as
well as NCO-1 and NCO-3, such as, for example, tri TDI
a
‘1272
Weight per gallon, lb. _______________ ___ 8.95
10
1. 2/1
_ __ _ _
number
weight
Properties of OH-2A solution:
or s ____________________________ _
Hydroxyl-terminated intcrmediate-_
1/2.5
molecular
_______________________ __
2
840
19. 8
Tolylene diisocyanate, T131, 80/20; 24/26
Polyoxypropylene derivative of penta
4
696
16. 4
erythritol-PE P-252’l‘ (M.W. 252) .... __
4
1,008
23. 8
2-ethoxyethyl acetate ___________________________ __
848
20. 0
Xylene
848
20.0
4, 240
100. 0
pylene oxide)-TP-116 (M.W. 308) _____ __
5
1, 540
2-Ethoxyethy1 acetate __________________________ ..
Xylene
31. 2
740
-
740
4,940
15.0
.
15.0
100.0
N0'rn.—NCO/OH ratio:10/20=1/2.
PROCEDURE
55
Nora-Ratio of reactive groups: NCO/OH=4/10=1/2.5.
PROCEDURE
-
870 parts of TDI are reacted in a 5-liter vessel with
1050 parts of polypropyleneether glycol P-410 at a tem
perature not over 60° C. for at least 2 hours. The con
tents are diluted with 200 parts 2-ethoxyethyl acetate and _
200 parts xylene. In this stage, the adduct with two
696 parts of TDI are reacted with 840 parts of poly 60 free NCO groups is formed.
In the second stage this vadduc’t is. combined with two
propyleneether glycol, Pluracol P-410, in a 5—liter reactor
mols
0f polyoxypropylene derivative of trimethylolpro
at a temperature not .over 60° C.’ for at leastv 2 hours.
pane TP-1l6. 1540 parts of polyol TP-116 are added
. The contents of the reactor are diluted with 142 parts of
in one portion with the solvents: 540 parts of Z-ethoxy
Z-ethoxyethyl acetate and 142 parts of xylene. In this
ethyl acetate and 540 parts, xylene. ' The reactants are
65
?rst stage, an adduct with free NCO groups is produced.
stirred at 70° C. for 3 hours.
'In the second stage the preparation, 1008 parts of
Properties of OH-2B:
polyoxypropylene derivative of pentaerythritol, PE
Average molecular weight ______________ __ 1384
P-252T, are dispersed in 706 parts of 2-ethoxyethyl ace
Average equivalent weight _____________ __ 346
tate and added at once to the adduct. The temperature
is raised to 70° C. and the reactants heated for 2, hours. 70
The contents are then diluted with 706 parts of xylene
and heated for one additional hour. The viscosity is
pmeasnred periodically; when it comes to a stillstand the
product is bottled and capped tightly.
Hydroxyl number _____________________ _._
Percent hydroxyl __; ___________________ __
163
4.92
Properties of OH-2B solution:
Non-volatile, percent ___________________ __
70
Weight per gallon, lb. __________________ __ 9.00
Viscosity at 25° rc., cps. ____- ____ __ 2s,ooo-3o,0oo
3,049,516
_
..
.
.
'
$
ample 1, OH-ZY gives urethane ?lmsiwhich. are less
?exible but which have greater ?lm hardness than the
?lms of Example 1. Chemical resistance and Water im
OH-2B IN URETHANE COATINGS
Formulation
Composition -
mersion resistance are excellent.
-
'
5
'
'
6
Example 6 (OH-ZZ) '
Isocyanate-terminated intermediate ‘_
vPa
NCO-1
s _________________________ _-
r
Hydroxyl-terminated intermediate.
_
Parts _________________________ ..
232
011-213
'
NCO/OH ................................... _-
NC 0-1
140
011-218
10
~
Reactants
Mols "
Parts -
100
1.2/1.0
2.0/1.0
10
Dipropylene glycol .... -_
TDI (30/20; 2,4/2,e) _____ _; ____ _;___‘_; _________ __~__-_.= --
~
Addition
mol of glycerine
product of
(M.W.
8 mols550)
of propylene
.....................
oxide to one-_ ,
Properties
2-ethoxyethyl acetate
-
I
'
1,
134
2
34s
2
1,g100
>
339
Xylenel
Curing time:
Dust tree, hr ____________________________ __
1.0
Dry to touch, hr_
1. 2
2. 5
2. 1 15
28
Pot life, hr _________ __
_
24
Sward hardness ____ __
_
40-56
48-64
Elongation, percent
_
40-00
20-40
Tensile strength _____________________________ -_ 4,000—6,000
Procedure’: Same as in Examples 1-3.
Properties:
5,000—7,00
Impact test-Gardner:
Direct, in.-lbs_--Indirect, in.-1bs_
16-20
12-16
4-6
2-4
50
40
,
Abrasion resistance, In ./1,000 cycles
Solvent resistance:
339
~
‘
'
"
>4
>4
_ _ . __
>4
>4
Methyl isobutyl ketone _________________ __
Tnlnenp
‘
"
3
>4
2-Eth0xyethyl acetate ___________ __' .
7.
j .
NCO/ OH
1/ 2.0
Average molecular Weight ______________ __
Average equivalent weight ___ "
1592
39-8
Hydroxyl number _____________________ __
141
Percent hydroxyl _____________________ _;__
4.27
OH-2Z IN URE’I‘lEl'ANElv SURFACE COATINGS
When employed as the second component together with
Chemical resistance and water immersion resistance 25 NCO-l or NCO-3 in the NCO/OHyproportions of ,Ex
ample 1, 01-1-22 gives urethane ?lms which are less ?ex
are excellent. The OH-ZB .of Example 3 vgives a faster
ible but which have slightly greater solventresistance than
curing and a harder, more solvent resistant coating than
the ?lms of Exampleflg Chemicalqresistance andwater
the 01-1-2 of Example 1.
immersion resistance are good. _ r
‘
Example 4 (OH-2X)
30
Reactants
Mols
.
Example-7-(QH-2-P)
Parts
Reaétaxits V
Polypropyleneether glycol, M.W. 600 l q
Phenylene diisocyanate ___________________________ __
1
2
600
320
Dipropylene glycol.-.
Monoethylene oxide addition product of TP-116, a
pane of M.W. 308 ............................... -_
2
Procedure: Same as in Examples 1-3.
‘
1i‘
NCO/0H
'
'
-
'
V
134
-
2
>
Xylene
348
,
2-etl10xyetl1yl acetate
1, 680
'
285
'
285
‘
40 ‘Procedure: Same as in Examples 1-3.
Properties:
'
'
re
mol of pentaerythritol (M.W. 840) _.‘ _____________ __ p.
704
329
329
'
'2
Addition product of 12 in
2-eth0xyethyl acetate
Xylene
Parts
' 1
TDI (80/20; 2,4/2,6) ____ ._
polyoxypropylene derivative of .trimethylolproé
Properties:
Mols
‘
.
NCO/OH
‘
'
'
1/ 2.5
1/2.0
Average molecular weight _____________ ___
1620
Average. eschew Weight ---.-,
.7 V
Hydroxyl number _A____ _..,_.._1__,_‘_ ‘_,______'_'V
Percent-hydroxyl _;_..._..‘...._'_____________ -4
405
139
4.22
Average molecular weight "___" _________ __
Average equivalent Weight ___;
2160
_
360
Hydroxyl number ___- ________ __
45,
156
' Percent 'hydroxyl ___________ __' ______ __'__
4.73
OH-ZP IN URETHANE SURFACE, QoArrNos
0H-2X IN URETHANETSURFACE comma. .
I)
_When employed as the second component together'with
When employed as ._the.'second component together
with NCO-lfor NICO-12in the"I_\l(_2O(Q_I-I7 proportions of
NCO-1 or NCO-3 in the NCO/OHproportions ofrEx
Example-1, OH-2X gives hard urethane ?lms which are 50 ‘ample 1, OH-2P give urethane ?lms which are more ?ex- ‘
ible but'which, have slightly less solvent resistance than
the ?lms of Example}. Chemical resistance and water
more flexible but which have slightly less solvent re
sistance than the ?lms .of_ vExample 1. ~Chemical re
immersion resistance are excellent.
sistance and Water immersion resistance are excellent.
'
Reactants
Mols
V Polypropyleneether glycol, M.W. 420 _______ __-__l____
1
Diphenylmethane-4,4’-diisocyanate ________________ __
2
Reactants
. Parts 1'
420
V
mol of pentaerythritol (P—368-TM.W. 368) ______ __
'
2
I
. 550
‘
5750
7
1
TDI
2
_-
-
»
2ethoxyethyl acetate
Xylene ‘V
65.
V
Properties:
.
NCO/OH
V
I’
342
'
'
276
Hydroxyl number,’
203 70
r¢icenthydroxy1'___,__.. ______________ _'_V_’. ‘6.16
»- ole-2r» IN \URETHZANE sURFAcE'coATmq's'
7
342
‘
~
~
Average equivalent weight: __
,
’
.
Average equivalent weight ___.
r
498
-,
Average’molec'ular weight ___
_
348
2
'
1/2.5
r
V
-
l
Average. 9191mm?" Weight ----.--, -------- -- ‘ 1656
Noo/oH
- 750
‘
Procedure: Same as in Examples 1‘-3‘. '
Procedure: Same as in Examples 1-3. 7
Properties:
~
Parts
Polypropyleneether glycol, M.W. 750 _____________ __
propyleneoxide adduct of glycerine (M.W. 249)____ -
736
7
‘
Mols
Addition product of one mol of ethylene oxide to di-
496
Addition product of 4 mols of propylene oxide to one
Z-ethoxyethyl acetate
.
Example 8-(OH-2D) '
. ’ Example 5 (OH-ZY)
Xylene
-
~
-
.. 1/2.0
__
1596
__
399
,Hydroxyl number ______ __-_ ________ __‘___..
141
w
Percent hydroxyl __________ ..; __________ __‘ 4.27
.ion-zn m
suRrAcn oon'rnics
When employed as the second component together with
. :Wh'eni employed as the‘ second component together with
NCO-1 or NCO-Sin the NCO/OH proportions of Ex
NCO-1 or NCO-3 in the‘ NCO/OH'proportions of Ex 75 ample 1, OH-ZD‘giVe urethane ?lms which'are more ?ex
3,049,516
9
19
ible but which have less solvent resistance than the ?lms
of Example 1. Chemical resistance and water immersion
resistance are good.
?exible but which have greater solvent resistance than
the ?lms of Example 1. Chemical resistance and water
Example 9 (OH-2Q)
then one mol of ethylene oxide to one mol of hexanetriol (M.W. 300).
2-eth0ryethy1acetqto
immersion resistance are excellent.
Example 12 (OH-2N)
5
2
Xylene
600
257
lene oxide units and one ethyleneom'de unit (M.W.
292 _
2-ethoxyethyl aceta te
257
Xylene
Procedure: Same as in Examples l-3.
2
584
646
V
646
15 Procedure: Same as in Examples 1-3.
Properties:
P
NCO/OH ____________________________ __ 1/20
Average molecular Weight ““““““““““ "‘
1224
Average equwelem welght ______________ __
306
Hydroxyl number --------------------- "'
183
Percent hydrexyl ______________________ __
5-55
.
ro erties.
'
pNCO/OH
U25
Average molecular weight ______________ __ 1944
Average equivalent Weight _____________ __
20
OH'L’Q IN URETHANE SURFACE COATINGS
When employed as. the second component together
with
.
324
Hydroxyl number _'_ _____ __‘ _____________ __
173
Percent hydroxyl _____________________ __
524 e
OBI-2N IN URETHANE SURFACE COATINGS;
Wh en employed as the second. component together wlth
.
Nco'l "1 NCO‘? “1 the NCO/OH PF°P°m°ns 0f .EX‘
NCO-1 or NCO-3 in the NCO/OH proportions of Ex
ample l, OH-ZQ give urethane ?lms which are less ?exible 25 amp1e 1’ OH_2N gives urethane ?lms which are more
but which have greater solvent resistance than the ?lms of
?exible ‘but which have greater ?lm hardness than the
Example 1.
?lms ‘of Example L Chemical resistance and Water im_
Chemical resistance and Water immersion
resistance are excellent’
mersion resistance are excellent.
EmmP’e 1” (OH-2L)
Beactants
Polypropyleneether glycol, M.W. 420 _____________ __
TDIWWA/ZIQ --------------------------- --
Addition product of 4 mols of propylene oxlde to one
30
Mols
Parts
1
2
2
zg?llo‘ggeltlg?il?-w- 360) '
Xylene
Procedure: Same as in Examples 1-3.
Example 13 (OH-ZNX)
Reactants
Properties:
NCO/OH
348 35 Addition
i‘iiil’éi’il’elieieil?eéfiii‘il:ELYLE‘EIIII:3:3:
product of 4 mols of propylene om'de to one
720
mol of hexanetriol (M.W. 350) ___________________ __
32%
' 2
700
Pro erties'
pNCOiOH
Average moiecular welfgm """""""""" " 1532
Average eqmv'f?ent ‘Welght """"""""" "
Hydroxyl number """""""""""""" "'
--------------------- """
5
319 '40 2X£SEII£IEYBWY1
Procedure: 9mm")
Same as in Examples 1__3_
1””
Percent
Parts
420
319
*
Mols
l1/2.0
Average molecular weight ______________ __ 1516
Average equivalent weight _____________ _.._ 379
45
4‘4
OH'ZL IN URETHANE SURFACE COATINGS
lI-lydroxyl number _____________________ __r
148
Percent
4.5
_____________________ __
OH-2NX IN URETHANE SURFACE COATINGS
When employed as
With
. the second component together
.
when em 10yed as the second com onent to ether with
.
N004 °I “305 .m the NCO/OH Pmlfm‘ms 0? EX‘
NCO-1 or 12100-3 in the NCo/oHpproportigns of Ex
ample 1.’ OH'ZL gl‘fes Nathan‘? ?lms which are slightly 50 ample 1, OH-ZNX gives urethane ?lms which are less
kiss ?exlble but whlch have Shgh?y greater solYent re?exible ‘but which have greater solvent resistance than
slstance than the films of. Example 1‘ Chemlcal Te‘
the ?lms of Example 1. Chemical resistance and Water
sistance and water immersion resistance are good.
immersion resistance are excellent.
Example 11 (OH'ZM)
Bantams
g\%§p(lé%?g)l.egegfheé)glycol’ M‘W' 420 "" "-"""" "
55
M015
Parts
Reactants
é
Addition pi‘oduot’of 113161"; 815565512111? Billie-EH61}?
mol of trimethylolpropane (M.W. 360).
2
Example 14 (OH-2EX)
Mols
Parts
Polypropyleneether glycol, P-410 (M.W. 420)._._-__
1
420
60 TDI. (W20; 2’ 4/2, 6) --------------------- --.--~-'------
2
348
2
2500
720
A‘lfgflgllsgigil?t&fll%vmggsg§Propylene ‘M10 to one
2x'etggiyethyl acemm
2~ethoxyethyl acetate -
Y
_____________________ n
1091
Xylene
procedlfrez Same as m Examples 1_3'
Propiigegion
65 Procedure: Same as in Examples 1-3.
1/2 0
Average molecularweight ______________ __
15218
Average equivalent Weight _____________ __
382
Hydroxyl number _____________________ __
122
Percent hydroxyl
3.7
_____________________ __
1091
ProPer?es'
NCO/ OH
‘
70
7
1/3-5
Hvgrage leqmvijlent Welght ————————————— -—
y roxy
When employed as the secondcomponent together with
340
Hum‘ er —————————————————————— —>
Percent hydroxyl ______________________ __
OH-2M IN URETHANE SURFACE COATINGS
‘ NCO-1 or NCO-3 in the NCO/OH proportions of EX-
_
gverage molecular we1_ght —————————————— -— 3400
165
e
5.0
OH'2EX IN URETHANE SURFACE COATING$
7
When employed as the second component together With
ample l, OH-2M gives urethane ?lms which are lessv 75 NCO-1 or NCO-3 in the NCO/OH proportions of Ex
3,049,516
11
12
,
tion according to claim 2 wherein the arylene diisocyanate
ample 1, OH-ZEX gives urethane ?lms which are slightly
(c) is tolylene diisocyanate and the polyether polyol (b)
more ?exible but which have slightly less solvent resistance
than the ?lms o£.Example 1. Chemical ‘resistance and
is a pentaerythritol alkylene oxide addition product.
5. An ordered hydroxy-terminated urethane composi
tion according to claim 2 wherein the arylene diisocyanate
' water immersion resistance are excellent.
Example 15 ,(OH-2ET)
(c) is tolylene diisocyanate and the polyether‘polyol (b)
' Reactants
Mols
is a hexanetriol alkylene oxide addition product.
6. An ordered hydroxy-terminated urethane composi
tion according to claim 2~wherein the arylene diisocyanate
Parts
Tetrapropylene glycol-.-.V__.V_--.;--__;_;_; _________ __
1
250
TDI (80/20; 2,4/2,6) ___________________ -_
2
348
Addition product of 12 mols of propylene
.
mol of dipentaerythritol (M.W. 970)_____-.'-_'.' ____ __
2-ethoxyethy1 acetate
Xylene
‘
'
>
'
'
'
'
2
1, 940
'
'
845
e
-
a
a
845
Properties:
-NCO/ OH
1/ 3.5
Average molecular weight ______________ __ 2600
Average equivalent weight ______________ __
260
*Hydroxyl number ___________ a. ________ __
216
Percent hydroxyl _______ __'_ ____________ __'
5.58
o'H-2ET IN URETHANE SURFACE COATINGS
10
(c) is tolylene vdiisocyanate and the polyether polyol (b)
is a glycerine alkylene oxide addition product.
7. An ordered hydroxy-terminated urethane composi
tion according to claimil wherein the average equivalent
weight is between about 200 and about 400.
8. A solution of an ordered hydroxy-terminated ure
thane composition according to claim 1 in a surface coat
ing solvent which is non~reactive therewith.
9. A urethane coating composition including as one
component an ordered'hydroxy-terminated urethane com
20 position according to claim 1 and including an organic
polyisocyanate as a second component.
10. A coating composition according to claim 9_ in
cluding an organic surface coating solvent which is non
When employed as the second component together with
reactive with both the components of the coating com
NCO-l or NCO-3 in the NCO/ OH proportions of ‘Exam
pie 1, OH-ZET gives urethane ?lms which are less ?exible 25 position and their polyurethane reaction product.
11. A process for producing an ordered .hydroxy-teru
but which have slightly’ greater solvent resistance than
minated urethane composition according to claim 18,
the ?lms of Example 1. Chemical resistance and water
wherein the polypropyleneether glycol (a) has a molecu
immersion resistance are excellent.
_
V
7
g I
lar weight not greater than about 750, 11 does not exceed
It is to be understood that the invention is not limited
to the exact details of operation or exact compounds 30 an average of two,‘ and n has a value of at least one in
each occurrence.
"
shown and described, as obvious modi?cations and equiva
12. A process for producing an ordered hydroxy-ter
lents will be‘ apparent to one skilled in the art, and the
minated urethane composition according to claim 11,
invention is therefore to be limited only by thescope of
the appended claims.
I
claim:
~
'
wherein the arylene diisocyanate (c) is tolylene diisocya
'
'
-
"
35 nate and the polyether polyol (b) is an alkylene oxide ad
-
1. An orderedhydroxy-terminated urethane composi
tion prepared sequentially by ?rstmixing and reacting
dition product of trimethylolpropane.
together ‘about one molar proportion of'pdlypropylene
13. A process for producing'an orderedhydroxy-ter
‘minated urethane composition according to claim 11,
ether glycol (a) having a molecular weight between about
wherein the arylene‘ diisocyanate (c) is tolylene diisocya
isocyanate-terminated polypropyleneether glycol urethane,
wherein the arylene'diisocyanate '(c) is tolylene diisocya
and then mixing and reacting. about one molar proportion
of the thus-formed isocyanate-terminated urethane with.
abouttwo molar proportions of polyether polyol (b) have
oxide addition product.
134 and 1000, with about two molar proportions of 40 nate and the polyether polyol (b) is a pentaerythritol
alkylene oxide addition product.
arylene diisocyanate (c) selected from the group con
sisting of phenylenediisocyanate, tolylene diisocyanate,
14. A process for producing an ordered hydroxy-ter
minated urethane composition according to claim 11,
and diphenylmethane-4,4'-diisocyanate, to produce an
the formula:
.
a
.
nate and the polyether polyol (b) is a hexanetriol alkylene
15. A process for producing an ordered ‘hydroxy-ter
minated urethane composition according to claim 11,
wherein the arylene diisocyanate (c) is tolylene diisocya
nate and the polyether polyol (b) is a ‘glycerine alkylene
oxide addition product.
'
zero to one; z is a number from zero to three; and n is
16. A novel ordered hydroxy-terminated polyether
based urethane composition produced by mixing and re
acting together about one molar proportion of a poly
propyleneether glycol (a), having a molecular weight be
a number from zero to three, provided that when z=0,
tween about 134 and 1000, and about two molar propor
atleast one n is at least one; when z: 1, at least two n’s
tions of an arylene diisocyanate (c) selected from the
wherein R’ with attached oxygen atoms represents a poly
hydric lower-aliphatic alcohol radical; x is a number from
group consisting of tolylene diisocyanate, phenylene di
isocyanate, and' diphenylmethane-4,4’-diisocyanate, to
produce the desired order hydroxy-terminated urethane 6 produce a polyether-based isocyanate-terminated urethane
intermediate adduct, and then mixing and reacting to
composition, the initial reaction temperature in the ?rst
gether about one molar proportion of the thus-produced
step "of the reaction being not greater than about sixty
adduct with about two molar proportionsof a polyol (b)
which is a propylene oxide addition product of a poly
2. An ordered hydroxy-terminated urethane composi
tion according to claim 1 wherein the polypropyleneether 65 hydric lower-aliphatic alcohol having at least three and
notmore than six hydroxy groups in the molecule.
glycol (a) has a molecular weight not greater thanabout
are at least one; when z=2, at least three n’s are at least
one; and’ when z=3, at least four n’s are at least one; to
degrees
centigrade.
~
.-
a
a
7
~
750, It does not exceed an average of two, and n has a
value of at least one in each occurrence.
3. An ordered hydroxy-terminated urethane composi
tion according to claim 2, wherein the arylene diisocyanate
(c) is" tolylene diisocyanate and the polyether polyol (b)
17. A process for the production of a novel ordered
hydroxy-terminated ‘polyether-based urethane composi
tion, which includes the step of mixing and reacting to
gether about one molar proportion of a polypropylene
ether glycol (a), having a molecular weight between about
is an alkylene oxide addition product of trimethylol
134 and 1000, and about two molar proportions of an
propane.
arylene diisocyanate (0) ‘selected from the group consist
'
>
g
,4. An ordered hydroxy-terminated urethane composi 75 ing of tolylene diisocyanate, phenylene diisocyanate, and
3,049,516
13
wherein R’ with attached oxygen atoms represents the ’
diphenylmethane-4,4’-diisocyanate, to produce a polyether
based isocyanate-terminated urethane intermediate ad
duct, and then mixing and reacting together about one
molar proportion of the thus-produced adduct with about
radical of a polyhydric lower-aliphatic alcohol; x is a
number from zero to one; z is a number from zero to
three; and n is a number from zero to three, provided
that when z=0, at least one n is at least one;vwhen z= 1,
at least two n’s are at least one; when z=2, at least three
n’s are at least one; and when z=3, at least four n’s are
at least one; to produce the desired ordered hydroxy
two molar proportions of a polyol (b) which is a pro
pylene oxide addition product of a polyhydric lower-ali
phatic alcohol having at least three and not more than
six hydroxy groups in the molecule.
terminated urethane composition, the initial reaction tem
perature in the ?rst step of the reaction being not greater
18. A process for the sequential production of an or
dered hydroxy-terminated urethane composition which in
cludes the steps of ?rst mixing and reacting together
than about sixty degrees Centigrade.
about one molar proportion of a polypropyleneether gly
col (a) having a molecular weight between about 134
and 1000 with about two molar proportions of arylene
References Cited in the ?le of this patent
diisocyanate (c) selected from the group consisting of 15
phenylene diisocyanate, tolylene diisocyanate, and di
phenylmethane-4,4’-diisocyanate, to produce an isocya
nate~terminated polypropyleneether glycol urethane and
then mixing and reacting about one molar proportion of
the thus-produced isocyanate-terminated urethane with
about two molar proportions of polyether polyol (b)
having the formula:
UNITED STATES PATENTS
2,814,605
2,866,774
2,871,226
2,897,181
Stilmar ______________ .._. Nov.
Price ________________ __ Dec.
McShane ___________ ____.. Jan.
Wendemuth ___________ __ July
26,
30,
27,
28,
1957
1958
1959
1959
FOREIGN PATENTS
>
25
206,295
205,456
Australia _____________ ____ Feb. 10, 1955
Australia ______________ __ Jan. 4, 1957
769,091
Great Britain ___________ __ Feb. 27, 1957
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3vO49v516
August 14, 1962
Adolfas Damusis
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
Column 1, line 24, for "poly—ether—based" read
—— polyether-based —--; column 3, line 25, after "addition"
insert —- procedure —-—; column 4, line 35.0 for "P-lélO" read
—- P~41O —--; column ll,I after the table in Example 15, insert
-- Procedure: Same as in Examples 1-3. -—; line 6OI for
"order"
read
-- ordered
--.
Signed and sealed this 16th day of April 1963.,
(SEAL)
Attest:
ERNEST w. SWIDER
Attesting Officer
DAVID L. LADD
Commissioner of Patents
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