Language selection

Search

Patent 1087800 Summary

Third-party information liability

Some of the information on this Web page has been provided by external sources. The Government of Canada is not responsible for the accuracy, reliability or currency of the information supplied by external sources. Users wishing to rely upon this information should consult directly with the source of the information. Content provided by external sources is not subject to official languages, privacy and accessibility requirements.

Claims and Abstract availability

Any discrepancies in the text and image of the Claims and Abstract are due to differing posting times. Text of the Claims and Abstract are posted:

  • At the time the application is open to public inspection;
  • At the time of issue of the patent (grant).
(12) Patent: (11) CA 1087800
(21) Application Number: 247028
(54) English Title: BIODEGRADABLE HYDROPHILIC POLYURETHANE FOAMS AND METHOD
(54) French Title: OBTENTION DE MOUSSES DE POLYURETHANNE HYDROPHILE ET BIODEGRADABLE
Status: Expired
Bibliographic Data
(52) Canadian Patent Classification (CPC):
  • 403/40
(51) International Patent Classification (IPC):
  • C08G 18/10 (2006.01)
  • A61L 15/42 (2006.01)
  • C08G 18/32 (2006.01)
  • C08G 18/42 (2006.01)
  • C08G 18/48 (2006.01)
(72) Inventors :
  • MARANS, NELSON S. (United States of America)
  • POLLACK, ALLAN R. (United States of America)
(73) Owners :
  • W. R. GRACE CO. (Not Available)
(71) Applicants :
(74) Agent: GOWLING LAFLEUR HENDERSON LLP
(74) Associate agent:
(45) Issued: 1980-10-14
(22) Filed Date: 1976-03-03
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data:
Application No. Country/Territory Date
597,258 United States of America 1975-07-18

Abstracts

English Abstract




Abstract of the Disclosure
The invention disclosed is directed to biodegradable
hydrophilic polyurethane structures prepared by using an
isocyanate capped hydroxyester polyol reactant with large
amounts of aqueous reactant. The resultant foam has
economy in handling, and upon contact with liquids or
body fluids, the foam is highly absorptive while being
readily biodegradable after use.


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 method for forming a biodegradable polyurethane
foam having a 3-dimensional network comprising reacting a
first component comprising an isocyanate-capped, ester
containing polyol mixture having an isocyanate functionally
of at least 2, said ester-containing polyol mixture prior to
capping comprising a member of the group consisting of:
(a) an essentially linear, hydroxy terminated poly-
ether having a molecular weight not exceeding about
4,000 and a reaction product formed by reacting an
aliphatic alcohol having from 3 to 8 hydroxyl
groups per mole and a molecular weight of less than
about 1,000 with a monobasic hydroxy carboxylic acid
to esterify the hydroxyl groups of said aliphatic
alcohol;
(b) an aliphatic alcohol having from 3 to 8 hydroxyl
groups per mole and a molecular weight of less than
about 1,000 and an essentially linear hydroxy terminated
polyether having a molecular weight not exceeding
about 4,000, wherein the hydroxyl groups of the poly-
ether are esterified by reaction with a monobasic
hydroxy carboxylic acid; and
(c) the esterification products of an
aliphatic hydroxy carboxylic acid with the hydroxyl
groups of (1) a hydroxy terminated essentially linear
polyether and (2) a monomeric low molecular weight
aliphatic alcohol containing from 3 to 8 hydroxyl groups
per mole , with a second component comprising an aqueous
reactant wherein the H2O Index Value is about 1,300
to 78,000.

17






2. The method of Claim 1 wherein the isocyanate-
capped hydroxyester polyol is present in the first component
in an amount from about 3% by weight up to 100% by weight,
wherein an isocyanate-capped polyoxyethylene polyol having a
terminal member with an isocyanate functionality of two is
present in an amount from 0% up to about 97% by weight.
3. The method of Claim 1 wherein the polyol moiety of
the isocyanate-capped member has a weight average molecular
weight of about 200 to 4,000, and a hydroxyl functionality
of about 2 to about 8.
4. The method of Claim 3 wherein the weight average
molecular weight is about 600 to 3,500.
5. The method of Claim 3 wherein the H2O Index Value
is from about 4,000 to about 40,000.
6. A biodegradable polyurethane foam having a 3-
dimensional network comprising the reaction product of an
isocyanate-capped, ester-containing polyol mixture having an
isocyanate functionality of at least 2, said ester-containing
polyol mixture prior to capping comprising a member of the
group consisting of:
(a) an essentially linear, hydroxy terminated polyether
having a molecular weight not exceeding about 4,000
and a reaction product formed by reacting an aliphatic
alcohol having from 3 to 8 hydroxyl groups per mole and
a molecular weight of less than about 1,000 with a
monobasic hydroxy carboxylic acid to esterify the
hydroxyl groups of said aliphatic alcohol;
(b) an aliphatic alcohol having from 3 to 8 hydroxyl
groups per mole and a molecular weight of less than
about 1,000 and an essentially linear hydroxy terminated
polyether having a molecular weight not exceeding about
4,000, wherein the hydroxyl groups of the poly-

18





ether are esterified by reaction with a monobasic
hydroxy carboxylic acid; and
(c) the esterification products of an aliphatic hydroxy
carboxylic acid with the hydroxyl groups of (1)
a hydroxy terminated essentially linear polyether
and (2) a monomeric low molecular weight aliphatic
alcohol containing from 3 to 8 hydroxyl groups per
mole,
and an aqueous reactant wherein the H2O Index Value is about
1,300 to 78,000. .
7. A biodegradable polyurethane foam-forming composition
upon the addition of an aqueous reactant wherein the H2O Index
Value is about 1,300 to 78,000 comprising an isocyanate-capped
ester-containing polyol mixture having an isocyanate function-
ality of at least 2, said ester-containing polyol mixture prior
to capping comprising a member of the group consisting of

(a) an essentially linear, hydroxy terminated polyether
having a molecular weight not exceeding about 4,000 and
a reaction product formed by reacting an aliphatic alcohol
having from 3 to 8 hydroxyl groups per mole and a
molecular weight of less than about 1,000 with a mono-
basic hydroxy carboxylic acid to esterify the hydroxyl
groups of said aliphatic alcohol;
(b) an aliphatic alcohol having from 3 to 8 hydroxyl
groups per mole and a molecular weight of less than
about 1,000 and an essentially linear hydroxy terminated
polyether having a molecular weight not exceeding about
4,000, wherein the hydroxyl groups of the polyether
are esterified by reaction with a monobasic hydroxy car-
boxylic acid; and
(c) the esterification products of an aliphatic hydroxy
carboxylic acid with the hydroxyl groups of (1) a

19


-


hydroxy terminated essentially linear polyether
and (2) a monomeric low molecular weight aliphatic
alcohol containing from 3 to 8 hydroxyl groups per
mole.
8. A foam as in Claim 6 or 7 wherein the
polyether is a polyoxyalkylene copolymer containing at least
% by weight of oxyethylene units.
9. A foam as in Claim 6 or 7 wherein the hydroxy
acid is lactic acid.
10. A foam as in Claim 6 or 7 wherein component (b)
is the trilactate ester formed by reacting trimethylolpropane
and lactic acid.
11. A foam as in Claim 6 or 7 wherein the polyether
has a molecular weight of less than about 4,000.





Description

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


7~

Thls invention relates to a me-thod for preparing
new biodegradeable Eoams. More particularly, the present
invention provides ne~ dental and b~iomed~cal foams usiny
a hydrophilic polyurethane foam having a biodegradable
moiety.
Numerous devices have been proposed in the prior
art for use as dental and biomedical foams for absorbing
or removing body fluids. Typically, the prior art appro- -
aches have relied upon natural materials such as cotton,
which is now becoming relatively expensive while providing
a resultant structure which is generally fragile in use.
Also, the amount of adsorption by natural materials is
relatively low.
Various polyurethanes have been used as dentàl
and biomeaical foams but suffer a disadvantage in that such
foams are not readily biodegradable. It has now been found,
however, that by practice of the present invention, there
is provided a method for preparing new simple and highly ;
efficient dental and biomedical foams which are readily
biodegradable after use, and which are characterized by
high adsorptive ability of body fluids in use.
Various attempts have also been made in the
prior art to prepare foams of organic substances for use
in cavities of the human body. However, such organic sub-
stances typically require, for example, catalysts or the
like during the foaming reaction. These additives remain
in the foam after foaming and are readily leached into the
human body when in contact with body fluids. Thus, although
artificial foams, especially those o polyurethane, of the
prior art possess the capacity of high absorptivity of body -


- 2 - ~

~; '


8~

fluids, usage within the human body typicall~ invites
disadvantayes beyond advantages ~ealiæed b~ low cost and
high absorptivity. Thus, artificial foams such as
polyurethanes of the prior art have received limited
practical acceptance by the medical, dental and government
regulatory agencies when proposed ~or internal usage in
the human body. There is especia~ly a disadvantage of such
foams.
By the present method, new biodegradable foams may
be prepared having utility dental and biomedical foam
structures, using hydrophilic crosslinked polyurethane ;
foams by reacting a particular isocyanate capped poly-
hydroxyester polyol with large amounts of an aqueous
reactant. The thus generated forms may be configurated
to handy size as desired. Such structures may be readily
used in the oral cavity and while in the oral cavity, the
structure absorbs oral fluids, and thereafter may be discarded
since it is biodeyradable.
Thus, in accordance with the present teachings, a
method is provided for forming a biodegradable polyurethane
foam which has a three-dimensional network and comprises
reacting a first component comprising an isocyanate-capped,
ester containing polyol mixture which has an isocyanate
functionality of at least two, the ester-containing polyol
mixture prior to capping comprises a member o~ the group
consisting of: ;
(a) an essentially linear, hydroxy terminated poly-
ether which has a molecular weight not exceeding about 4,000
and a reaction product which is formed by reacting an aliphatic
alcohol having from 3 to 8 hydroxyl groups per mole and a
molecular weight of less than about 1,000 with a monobasic

hydroxy carboxylic acid to esterify the hydroxyl groups of


E~ - -

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

- 1~87~

the aliphatic alcohols;
(b) an aliphatic alcohol which has ~rom 3 to 8 hydroxyl
groups per mole and a molecular weight o~ less than about 1,000
and an essentially linear hydroxy terminated polyether which
has a molecular weight not exceeding about 4,000 and wherein
the hydroxyl groups of the polyether are esterified by
reaction with a monobasic hydroxy carboxylic acîd; and
(c) the esterification products of an aliphatic
hydroxy carboxylic acid with the hydroxyl groups of 1) a
hydroxy terminated essentially linear polyether and 2) a
monomeric low molecular weight aliphatic alcohol containing
from 3 to 8 hydroxyl groups per mole,
with a second component comprising an a~ueous reactant
wherein the H2O index value is about 1,300 to 78,000.
In accordance with a further embodiment of the present
teachings there is provided a biodegradable polyurethane foam-
forming composition upon the addition of an aqueous reactant
wherein the H2O index value is about 1,300 to 78,000 and :
comprises an isocyanate-capped, ester-containing polyol mixture
which has an isocyanate functionality of at least two, the
ester-containing polyol mixture prior to capping comprises
a member of the group consisting of
ta) an essentially linear, hydroxy terminated polyether
which has a molecular weight nok exceeding about 4,000 and a
reaction product which is ormed by reacting an aliphatic :
alcohol which has from 3 to 8 hydroxyl groups per mole and a .
molecular weight of less than about 1,000 with a monobasic
hydroxy carboxylic acid to esteriy the hydroxyl groups o~
the aliphatic alcohol;
(b) an aliphatic alcohol which has from 3 to 8 hydroxyl
groups per mole and a molecular weight of less than 1,000 and
an essentially linear hydroxy terminated polyether which has a


',

~(~8~
molecular weigh-t not exceeding about 4,000, and wherein the
hydroxyl groups o the polyether are esterified by reaction
with a monobasic hydroxy carboxylic actd; and
(c) the esterification product of an aliphatic
hydroxy carboxylic acid with the hydroxyl groups o 1) a
hydroxy terminated essentially linear polyether and 2) a
monomeric low molecular weight aliphatic alcohol containing
f`rom 3 to 8 hydroxyl groups per mole. ;
The present foams have utility as handy expandable
sponges for personal use. The sponges are easily carried
and may be readily prepared with detergents, lotions,
perfumes, biostats and the like and upon contact with
water, the sponges are found to be very soft, very .
hydrophilic and biodegradable. The sponges may be used
for washing, wiping, cleaning, etc. for external body
cleaning; or alternatively for internal body usage `~
such as is necessary in dental and medical applications.
The present sponges also have utility as intimate absorptive
products, such as diapers, sanitary napkins, incontinent
pads and the like.




' ~

-3b-

E!

~87~0

Polyurethane foam structures prepared herein with
hydroxye~ter polyisocyanates, ~ater and certain surfact-
ants, have an exceptionally Eine, uniform, soft, hydro-
philic cell structure.
The following condi-tions seem to be important
to obtaining foams of the above mentioned desirable proper-
ties.
One mole of a polyoxyethylene diol of molecular
weight less than 4,000 containing about 0.1 to about 4.0 ~ `
mole, preferably about 0.2 to about 2.5 moles of polyols
with 3 or greater hydroxyl groups per molecule, preferably
tri- or polyhydroxy ester crosslinking agent such as
trimethylolpropane trilactate or the like.
The prepolymer is next capped with diisocyanates.
The useful range of polyisocyanates is about 0.60 to about
1.3 moles of diisocyanate per equivalent group in the
polyol mixture. The preferred range of diisocyanate is about
0.95 to about 1.15 moles of diisocyanate per equivalent of
the polyol mixture.

.. . . .
The resultant polyester polyisocyanate prepoly-
mers are foamed by reacting with about 10 to about 200 parts
of water, preferred range of about 50 to about 160 part.s
of water, to 100 parts of prepolymer in the presence of about
Q.05 to about 30 parts surfackant, preferred range of about
0.1 to about 15 parts surfactant, per 100 parts of prepolymer.
The suractants can be added either to the prepolymer or
the water. Surfactants which are soluble in water and/or ` `~
in their own right are hydrophilic, are preferred.
The polyurethane foams made in the manner described

above are exceptionally soft, hydrophilic and biodegradable



r
~ 4 ~

1tl87~(~0

as compared to conventional polyurethane Eoams. The foams
described above can be dried to form so~t dense materials
which, upon exposure to water, almost instantly absorb the
water.
A l~w density foam is thus prepared for ease and
economy in handling and shipping, but is readily biodegrad- ~ `
able after usage. When warm and/or wet the foam is useful ~
for its flexibility, softness and hydrophilicity. ~-
The original foam is biodegradable within about 7
days by contacting the foam with certain enzymes. The foam
is soft and flexible when wet and~or warm and rigid or soft
when cold and/or dry.
The present foams may be characterized as low
density polyurethane foam (1 to 6 lbs/ft3) which is easily
biodegradable.
Preparation of the present foam structures will be-
come more apparent from the following detailed description. ~-
During capping, it is desirable that the polyiso-
cyanate be reacted such that the reaction product, i.e.,
the capped product, is substantially void of reactive hydroxy
groups while containing more than two reactive isocyanate
sites per average molecule. Another route for achieving
this de~ired result is to react a polyisocyanate having
two reactive active isocyante sites per average molecule,
in a rea~tion system during foaming having a polyfunctional
reactive component such as one having from three up to
about eight or m~re reac~ive amine, hydroxy, thiol, or
carboxylate sites per average molecule. These latter
sites are highly reactive with the two reactive isocya-
nate sites and thereby form a three dimensional product.


-- 5 --


~, . , , ~

1(11*7 !3(~0

Polyoxyethylene polyol used as a reactant in pre-
paring the capped product to be foamed may have a weight
average molecular weight of about 200 to about 4,0Q0, and
pre~erably between about 600 to 3500, with a hydroxyl ~unc-
tionality o~ 2 or greater, preferably from about 3 -to about
8.
The polyoxyethylene polyol is combined with a cross-
linking agent for the prepolymer.
Trimethylolpropane trilactate or the like can be
used in combination with other polyols or trimethlolpropane
trilactate can be oxyethylated or oxypropylated to yield
the appropriate polyol. Other hydroxy acids may be used
for the crosslinking agent esterification. These include
but are not limited to hydroxyacetic acid and other
y, ~, etc., hydroxy acids.
The polyoxyethylene polyol ester mixture is term-
inated or capped by reaction with a polyisocyanate. The
reaction may be carried out according to conventional prac-
tice. The polyisocyanates used for capping the polyoxyethylene
polyol include polyisocyanates which are PAPI (polyaryl poly-
isocyanate as de~ined in the United States Patent No.
2,683,730), tolylene diisocyanate, triphenylmethane-4, 4',
4", triisocyanate~ benzene-1,3,5-triisocyanate, toluene-
2,4,6-toluene-2,4,6-triisocyanate, diphenyl-2,4,4'-triiso-
cyanate, hexamethylene diisocyanate, xylene diisocyanate,
chlorophenylene diisocyanate, diphenylmethane-4,4'-
diisocyanate, naphthalene-l, 5-diisocyanate, xylene-
alpha, alpha'-diisothiocyanate, 3,3'-dimethyl-4,4l-biphenyl~
lene diisocyanate, 4,4'-methylenebis (phenylisocyanate),
4,4'-sulfonylbis (phenylisocyanate), 4,4'-methylene
bis(orthotolylisocyanate), ethylene diisocyanate, ethylene

,,~ ,`. :'


,, . , . ., . ,. " .. ,,. ., . . , . , ~ .

~871~

diisothiocyanate, trimethylenediisocyanate and the like.
Mixtures of any one or more of the above mentioned organic
isothiocyanates or isocyanates may be used as desired.
The aromatic diisocyanates and polyisocyanates or mixtures
thereof which are especially suitable are those which are
readily commercially available, have a high degree of
reactivity and a relatively low cost.
Capping of the polyoxyethylene polyol may be ef-
fected using stoichiometric amounts of reactants. Desir-

ably, however, an excess of isocyanate is used to insure
complete capping of ~he polyol. Thus, the ratio of iso-
cyanate groups to the hydroxyl groups used for capping is
between about 1 to about 4 isocyanate to hydroxyl, and pre-
ferably about 2 to about 3 isocyanate to hydroxyl molar ratio.
In order to achieve an infinite crosslinked network for-
mation on foaming, the reactive components may be formu-
lated in one of the following by way of example. First,
when water is the sole reactant with the isocyanate groups
leading to chain growth during the foaming-process, the
isocyanate capped reaction product must have an average
isocyanate functionality greater than 2 and up to about 6
or more depending upon the composition of the polyol and
capping agent components. Secondly, when the isocyanate
capped reaction product has an isocyanate functionality of
only about two, then the aqueous reactant, may contain a
dissolved or dispersed isocyanate-reactive crosslinking agent
having an effective functionality greater than two. In
this case, the reactive crosslinking agent is reacted with
the capped resin when admixed during and after the foaming
process has been initiated. Thirdly, when the isocyanate
" `'




, . ; . . ... .. . .

-
7~3~0

capped resin has an isocyanate functionality of only about
two, then a polyisocyanate crosslinking agent when an
isocyanate functionality greater than two may be incor-
porated therein, either preformed or formed in situ, and
the resultant mixture may -then be reacted with the aqueous
reactant, optionally containing dissolved or dispersed
reactive isocyanate-reactive crosslinking agent, leading
to a crosslinked, infinite network hydrophilic polyurethane
foam.
Water soluble or water dispersible crosslinking
agents operable in this invention desirably should be poly-
- functional and reactive with isocyanate groups and include
t but are not limited to materials such as diethylenetriamine,
'::
`~ triethylenetetramine, tetraethylenepentamine, polyethylenei-
mine, glycerol, trimethylolpropane, pentaerythritol,
tolylene 2,~ r 6-triamine, ethylenediamine, aminoethanol,
trimethylenediamine, tetramethylenediamine, pentamethylene-
diamine, hexamethylenediamine, ethanolamine, diethanola-
amine, hydrazine, triethanolamine, benzene-1,2,~-tricarboxy-
. .
~ 20 lic acid, nitrolotriacetic acid, citric acid, 4,4'-methy
r, lenebis (o-chloroaniline), and the like. The water soluble
or water dispersible crosslinking agents chosen are those
which cause a crosslinked network to form during or after
~; the foaming process begins to take place.
It has also been found that the capped resin having
an isocyanate functionality greater than two used to prepare
~ a three dimensional network polymer must be present in an
; amount sufficient to insure formation of the dimensional
,.j :. ~
network. Thus, amounts of the capped polyoxyethylene
polyol having an isocyanate ~unctionality greater than 2 ~;



", '

~ .. .. . . . : ~

J878C~0

in the component to be foamed range from about 3~ by weight
of this component up to 100~ by weiyht. Thus, it is possible ,
to include a capped polyoxyethylene polyol having a terminal
member with an isocyanate functionality of two ite., a
diisocyanate in an amount from 0% by weight up to about
97~ by weight of the component to be foamed. The maximum
amounts of diisocyanate used are limited to that necessary
to permit crosslinking to take place during foaming, as ;~
contrasted to formation of a linear polymeric structure, -
and the properties desired in the finally prepared foam.
``~1
To effect foaming and preparation of the crosslink-
~ ed network polymer, the component including the isocyanate
- capped polyoxyethylene polyol having a functionality about
2 or greater is simply combined with the aqueous component.
For simplicity, this isocyanate capped reaction component
will herein be referred to as resin reactant.
The aqueous component, i.e., water slurry or sus-
,.~ .
`, pension, may include various additives such as detergents,
:~1
biostats, perfumes or the~like as desired for use in a given
20~ produc~. Obviously, additives are avoided ar carefully
selected for specific purposes for foam structures intended
for internal body usage. `~
,
! The dramatic way in which additions of water in-~j fluences practice of the present invention is by considera-
tion of the following water index value,
.
1 equivalents of H2O `~
;~ Water Index Value = X 100
I equivalents of NCO
~i ,

! 30
~i
~ 9 ~
"

"

..~'

1~37~

Thus, because one-half mole of water is equal to one
equivalent of isocyanate, where O.S m H2O is used with
1 eq. NCO, the water index value is 100.
An Index of 100 indicates that both equi~alents are
equal or "balanced". An Index of 95 indicates that there
is a ~ shortage of water while an Index of 105 indicates
a 5% surplus of water. A slight theoretical excess of
isocyanate, usually 3 S~, is common pr~ctice, in tha prior
art particularly with flexible foams.
Vsing the present resin xeactant and water in amounts
from about H2O Index Value of 100 up to about H2O Index
Value of 200, poor foaming results unless materials such
:`
as surfactants or the like are includ~. Amounts up to
about H2O Index Value of 200 require a catalyst. When
using about H2O Index Value 78,000, surprisingly good
foams result which improve in characteristics with added
amounts of molar water. Thus, the available water content
in the aqueous reactant is ffom about an H2O Index Value
of about 1300 to about 78,000 and desirably from about
i 20 4,000 to about 40,000.
`,i
"Available water" in the aqueous reactant is that
water accessible for reaction with the resin reactant, and
which is exclusive of water which may layer during reaction,
or supplemental water which may be necessary because of
addi~ives present in and forming the a~ueous reactant.
~ecause large amounts of water are in the aqueous
reactant during reaction, i.e., the present system is not
dependent upon a lar NCO-water type reaction, it is possi-
ble to combine a great variety of materials in the aqueous
:`
reactant which are otherwisa not p~ssi~ie ~ith`l-imited


water reacting system6.

~ 10 --
::~

1~1!8'78~)

The aqueous reactant may be used at temperatures from
about 2C. to about 100C. as desired.
Al-though foaming of the present resin reactant, i.e., -;
prepolymer, is effected simply, it is also possible to add,
although not necessary, supplemental foaming materials such
as those well known to the artifical sponge foaming art.
After foaming has been effected, the foam may be
dried, if desired, under vacuum from 1 to 760 Torr at a tem-
perature of about 0 to about 150C. When used internally,
the foams may be heat or chemically sterilized prior to use.
The following examples will aid in explaining, but
should not be deemed as limiting, practice of the present
invention. In all cases, unless otherwise noted, all parts

~: .
i~, and percentages are by weight.
: ~
Example 1

Polyethyleneglycol PEG 1000 (actual M.W. 1064) and

trimethylolpropane trilactate (361g and 60g respectively)

~^ were dried for 2.5 hours at 103C. and 4 Torr. This mixture
:
was added to 225g of toluenediisocyanate and 0.2g of Metal
and Thermit ~ T-9 catalyst, a catalyst containing stannous
octoate, over a period o~ 80 minutes at a temperature of 60C.
After completion of addition, the reaction mixture was
maintained at 60C. for an additional hour. To the reaction
mixture there was then added an additional 12g of tolylene-
` diisocyanate and heating continued for another hour at 60C.
The final viscosity was 24,500 cp at 25C. and the NCO was 2.38

1 meq/g (theory 2.33 meq/g).
From the above reaction mixture, a foam was prepared
~i using lOOg of prepolymer, lOg of Union Carbide Silicone surfactant
L-520 ~ and lOOg of water. Aqueous solutions of enzymes, 1%,
J! were prepared and tested on this foam. Maxa-tase, ~ H.T.
.~.; .

, . :
.

.:

~7~

proteolytic concen-trate, and protease amylase, gave essentially
comple-te degrada-tion after seven days at 25C. Several
others, such as mucinase, trypsin and some experimental enzyme
broths, showed some evidence oE degradation. A standard
polyurethane foam prepared from 100 pts of prepolymer, iso-
cyanate capped polyoxyethylene polyol, 1 pt 1-520 and 100 pts
of water gave no change over the same period of time with . .
these enzymes. ~
The oam was buried in a compost heap for three months. ~:
. 10 On removal from the compost heap, the foam had started to
:~ fragment and could not be washed without falling apart.
The foam was then compared with a foam made in a . .
5 jmilar manner with trimethylolpropane instead of the tri-
methylolpropane trilactate. The trimethylolpropane lactate
based foam in ten minutes at 250F. turned tacky and begun to
degrade. The trimethylolpropane based oam showed no change
i.n 20 minutes at 250F. Conventional polyoxypropylene based
polyurethanes show no change in three hours. ~:
. A similar comparison at 100C. in boiling water gave
.: .
.. : 20 breakdown into viscous lumps in 240 minutes after becoming
.
: tacky in 30 minutes for the trimethylolpropane trilactate

:; biodegradable polymeric foam. The trimethylolpropane based

- foam showed no change in 240 minutes at 100C.

Example 2

` The procedure of Example 1 was repeated for foam ;;


generation. Next a synthetic sewage sludge was allowed to

. react with the foam for one week. The trimethylolpropane ~

.`.......... trilactate based foam had completely disintegrated. The ;~ :

~ . standard polyurethane foam was intact.

: 30 Example 3

` The trimethylolpropane trilactate that had been pre-
'
- 12 -
,.
., .

~8~7~ao

pared was used with a different polyol. ~ mixture of one mole
each of trimethylolpropane trilactate and Pluronic ~ lO-R-5
(a Wyandotte polyol with a molecular weight of 1970, an
equivalent weight of 985 and end-capped with oxypropylene on
an oxyethylene backbone with approximately 50% by weight of
oxypropylene and 50% by weigh~ of oxyethylene) was dried at
110Co and 3 torr for three hours. The mixture was then added
to 4.75 moles of the standard 80-20 mixture of 2,4 and 2,6-
tolylenediisocyanate over a period of one hour maintaining the
temperature at 60C. The reaction was completed by heating
~ for an addi~ional three hours at 60C. with the addition of
- Metal and Thermits' T-9 stannous octoate catalyst (5 drops).
To the final prepolymer was added 0.75 moles of tolylenediiso-
cyanate to give a prepolymer with a viscosity of 17,250 cp.
The prepolymer was converted to a foam by the addition of l
part of silicon surfactant L-520 to the prepolymer (lO0 parts)
and then adding lO0 parts water to the prepolymer phase. The
polymeric foam when placed in a synthekic sewer sludge dis-
~` integrated within one week.
Example 4
The trimethylolpropane trilactate was prepared as
above in Example 3. A mixture was prepared from one mole of
trimethylolpropane lactate and 0.5 mole Pluronic P-65 supplied
~; by Wyandotte (this polyol has a molecular weight of 3500 and has
a polyoxypropylene base, end-capped with oxyethylene units,
being 50% oxyethylene and 50% oxypxopylene by weight) and
was dried by heating for a period of three hours at 115C and
5 torr. This mixture was added to 3.8 moles of commercial TDI ~;
`~i over a period of one hour with the temperature maintained at
60C. After completion of the addition, 10 drops of Metal and
Thermit catalyst T-9 was added and the reaction mixture was
.~

,,

r ~ 13

- .

o

heated for an additional -three hours at 65C. to force the pre-
polymer formation. Then 0.6 mole of TDI was added to the
reaction mixture and the reaction heated for an additional
two hours to give a prepolymer with a viscosity of 16,000 cp
; at 25C. A foam was prepared from this prepolymer using 100
parts of prepolymer, 1.0 part of Plurafac ~ B-26, 1.7 parts
of tertiary amine of Thancat ~ DD catalyst by Jefferson
Chemicals, and 50 parts of water (the latter three all being
in the aqueous phase). The foam that was formed decomposed in
a compost heap in two months. The conventional polyoxypropyl-
ene polyurethane foam showed no change.
Example 5
Trimethylolpropane hydroxyacetate (glycolate) is
- prepared by simple esterification using one mole trimethylol-
propane and 3.12 moles glycolic acid (hydroxylacetic acid).
The mixture was heated for four hours at reflux and then strip-
i ?
; ped at 125C. and 12 Torr.
~l The prepolymer was prepared by adding a dried mixture
of 2.0 moles o~ PEG-1000 (molecular weight 1064) and 1.0 mole
of trimethylolpropane triglycolate to 6.7 moles of tolylene-
diisocyanate over a period of one hour at a reaction flask
temperature of 60C. The reaction was continued at 60C. for ~ `
an additional three hours and the measured NCO content in
meq/g. was 1.82 meq/g(theory 1.78 meq/g.). To the reaction
mixture was then added an additional 1.0 mole of TDI with '~
heating and stirring continued for an additional two hours
at 60C. The NCO was 2.18 meq/g(theory 2~23 meq/q.), viscosity
' at 25C. 19,000 cp.
,,
A foam was prepared from this prepolymer by using 100
g. of prepolymer and 100 parts of 5~ so-ution of Pluratac B-26
~By Wyandotte) in water. The generated foam was found to de~
:,; ''
.
,.
`''."'. ' ' ''
: . , . , .. . . . , , . ,, . ,, .. ~ . ~ .

-
~7B(~O

grade with Mexatase enzyme in six days at 25C. while the foam ,~
prepared from trimethylolpropane was intact. In boiling water,
decomposition occurred in 200 minutes with -the trimethylol-
propane glycolate based material. With the trimethylolpropane
based prepolymer, no change was noted in the same time period.
Example 6
Instead of preparing the hydroxyacid ester of the
crosslinking agent as in the previous example, the hydroxy~
acid ester of polyoxyalkylene glycol was prepared. To 1 mole
of polyethylene glycol having a molecular weight of 1064 (PEG-
1000) there was added 2.22 moles of 88~ lactic acid. The
mixture was refluxed for four hours after which the resi~ual
lactic acid was stripped at 130C. and 4 Torr.
The product weighing 1215 g., mainly polyethylene
glycol dilactate, was combined with 67 g. o trimethylolpropane
and stripped of residual water at 105C. and 3 Torr for four
hours. This mixture was then added at 60C. flask temperature
to 574 g. of tolylenediisocyanate over a period of two hours.
The reaction mixture was then heated for an additional four

,.~", :
20 hours at 60C. To the reaction mixture was then added an

` additional 87 g. of tolylenediisocyanate in thirty minutes at

60C. and the reaction mixture heated for an addltional two

hours at 60C. The NCO content was 2.06 meq/g.(theory 2.11
: . .
meq/g.); the viscosity was 18,000 cp at 25C.
., ,

` A foam was prepared from the prepolymer of this ex- ~
.:,
~' ample using 100 parts of prepolymer and 100 parts of 5% solution
. .
;~ of Pluronic P-75 in water. The final foam was dried and on
;
treatment with a synthetic sewer sludge, disintegrated within
. , .~ .
ten days. A similar sample was prepared from a prepolymer
30 containing polyethylene glycol 1000 and trimethylolpropane
showed no signs of decomposition in the same period of time.
''' .
;, .

- 15 -
~, .

~, 8~1~

It is understood that the foregoing detailed descrip-
tion is given merely by way of illustration and that many
variations may be made therein without departing from ~he spirit
of this invention.




~ 10 ''



:,




. .
.



. ~



,.
", .
.~,

~ .
,.' '' '' .~' ::,
- 16 -

:'

Representative Drawing

Sorry, the representative drawing for patent document number 1087800 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 1980-10-14
(22) Filed 1976-03-03
(45) Issued 1980-10-14
Expired 1997-10-14

Abandonment History

There is no abandonment history.

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $0.00 1976-03-03
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
W. R. GRACE CO.
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.
Documents

To view selected files, please enter reCAPTCHA code :



To view images, click a link in the Document Description column. To download the documents, select one or more checkboxes in the first column and then click the "Download Selected in PDF format (Zip Archive)" or the "Download Selected as Single PDF" button.

List of published and non-published patent-specific documents on the CPD .

If you have any difficulty accessing content, you can call the Client Service Centre at 1-866-997-1936 or send them an e-mail at CIPO Client Service Centre.


Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Drawings 1994-04-11 1 15
Claims 1994-04-11 4 184
Abstract 1994-04-11 1 32
Cover Page 1994-04-11 1 32
Description 1994-04-11 17 822