U.S. patent application number 13/931268 was filed with the patent office on 2013-10-31 for polyurethane.
This patent application is currently assigned to MICHELIN RECHERCHE ET TECHNIQUE S.A.. The applicant listed for this patent is Michael Edward Dotson. Invention is credited to Michael Edward Dotson.
Application Number | 20130287982 13/931268 |
Document ID | / |
Family ID | 39536758 |
Filed Date | 2013-10-31 |
United States Patent
Application |
20130287982 |
Kind Code |
A1 |
Dotson; Michael Edward |
October 31, 2013 |
POLYURETHANE
Abstract
A polyurethane that is a reaction product of reaction
components, the reaction components comprising (a) a polyol; (b) a
polyisocyanate selected from an aromatic, alicyclic or aliphatic
polyisocyanate or combinations thereof; (c) a mixture of chain
extenders that includes (i) a chain extender having a sulfur bridge
in an amount of between 1 and 30 weight percent of the total
mixture of claim extenders and (ii) a main chain extender, wherein
the chain extender having a sulfur bridge. The chain extender
having a sulfur bridge may be characterized as
R.sub.1-A-S.sub.x--B--R.sub.2 wherein R.sub.1 and R.sub.2 are
selected from an OH, an NH.sub.2 or combinations thereof, A and B
are selected from a divalent aliphatic, alicyclic or aromatic
organic group or combinations thereof, A and B may be the same or
different and x is an integer of between 2 and 10.
Inventors: |
Dotson; Michael Edward;
(Greenville, SC) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Dotson; Michael Edward |
Greenville |
SC |
US |
|
|
Assignee: |
; MICHELIN RECHERCHE ET TECHNIQUE
S.A.
Granges-Paccot
CH
COMPAGNIE GENERALE DES ESTABLISSEMENTS MICHELIN
Clermont-Ferrand
FR
|
Family ID: |
39536758 |
Appl. No.: |
13/931268 |
Filed: |
June 28, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12520285 |
Jun 19, 2009 |
8512834 |
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PCT/US07/88476 |
Dec 20, 2007 |
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13931268 |
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60875948 |
Dec 20, 2006 |
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Current U.S.
Class: |
428/35.8 ;
425/470; 428/425.8; 528/48; 528/52 |
Current CPC
Class: |
C08G 18/7614 20130101;
C08G 18/10 20130101; Y10T 428/31605 20150401; C08G 18/10 20130101;
Y10T 428/1355 20150115; Y10T 428/1352 20150115; C08G 18/10
20130101; C08G 18/3865 20130101; C08G 18/3206 20130101; C08G
18/3857 20130101; C08G 18/10 20130101; C08K 3/06 20130101; Y10T
428/2938 20150115 |
Class at
Publication: |
428/35.8 ;
528/48; 528/52; 428/425.8; 425/470 |
International
Class: |
C08G 18/76 20060101
C08G018/76 |
Claims
1. A polyurethane that is a reaction product of reaction
components, the reaction components comprising: (a) a polyol; (b) a
polyisocyanate selected from an aromatic, alicyclic or aliphatic
polyisocyanate or combinations thereof; (c) a mixture of chain
extenders that includes (i) a chain extender having a sulfur bridge
in an amount of between 1 and 30 weight percent of the total
mixture of claim extenders and (ii) a main chain extender, wherein
the chain extender having a sulfur bridge is characterized as
R.sub.1-A-S.sub.x--B--R.sub.2 wherein R.sub.1 and R.sub.2 are
selected from an OH, an NH.sub.2 or combinations thereof, wherein A
and B are selected from a divalent aliphatic, alicyclic or aromatic
organic group or combinations thereof, wherein A and B may be the
same or different and wherein x is an integer of between 2 and 10;
and (d) an enhancer selected from free sulfur, a rubber curing
accelerator or combinations thereof.
2. The polyurethane of claim 1, wherein the enhancer is the rubber
curing accelerator.
3. The polyurethane of claim 2, wherein the rubber curing
accelerator is diphenyl guanidine.
4. The polyurethane of claim 2, wherein the reaction components
comprise between 90 and 110 mole percent of the sulfur bridge chain
extender moles.
5. The polyurethane of claim 2, wherein the reaction components
comprise between 0.5 and 10 weight percent of the polyol.
6. The polyurethane of claim 1, wherein the enhancer is the free
sulfur.
7. The polyurethane of claim 1, wherein the main chain extender
carries no cationic group.
8. The polyurethane of claim 1, wherein the main chain extender is
a short-chained chain extender.
9. The polyurethane of claim 1, wherein the main chain extender is
selected from 1,2, ethanediol, 1,2 propanediol, 1,2 butanediol,
ethylene diamine, 1,2 propane diamine, propylene diamine,
propylenediol, 4,4'-methylene bis-(3-chloro-2,6-diethylaniline)
(MCDEA), 4,4'-methylene bis(2-chloroaniline) (MOCA),
diethylthiotoluenediamine (DETDA) and dimethylthiotoluenediamine
(DMTDA) or combinations thereof.
10. The polyurethane of claim 1, wherein the main chain extender is
selected from a dialcohol, a diamine or combinations thereof.
11. The polyurethane of claim 1, wherein the mixture of chain
extenders includes the chain extender having a sulfur bridge in an
amount of between 2 and 25 weight percent of the total mixture of
claim extenders.
12. The polyurethane of claim 1, wherein the mixture of chain
extenders includes the chain extender having a sulfur bridge in an
amount of between 5 and 15 weight percent of the total mixture of
claim extenders.
13. The polyurethane of claim 1, wherein the polyisocyanate is a
diisocyanate.
14. The polyurethane of claim 1, wherein the chain extender having
a sulfur bridge is selected from 2,2 dithiodiethanol,
4,4-dithiodianiline or combinations thereof.
15. The polyurethane of claim 1, wherein x is an integer between 2
and 5.
16. The polyurethane of claim 1, wherein the polyurethane is
moldable.
17. An apparatus, comprising: the polyurethane of claim 1 disposed
on at least one surface of a metal substrate.
18. The apparatus of claim 17, wherein the polyurethane is of claim
2.
19. The apparatus of claim 18, wherein the metal substrate is a
metal reinforcement element.
20. The apparatus of claim 17, wherein the metal substrate is a
metal reinforcement element.
21. The apparatus of claim 17, wherein the apparatus is a conduit,
wherein one or more walls of the conduit comprise the polyurethane
elastomer of claim 1 and the one or more walls are reinforced with
the metal substrate embedded therein.
22. The apparatus of claim 17, wherein the apparatus is a conveyer
belt.
23. The apparatus of claim 17, wherein the apparatus is a caster.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates generally to polyurethane and more
specifically, to polyurethane formed from reactants that include a
dithiodiol and/or a dithiodiamine.
[0003] 2. Description of the Related Art
[0004] Polyurethane is a specialty polymer that is used in a wide
variety of commercial applications including, for example, rigid or
flexible foams, elastomers, coatings, adhesives and sealants. The
chemistry of polyurethane makes use of the reaction of an
isocyanate (--N.dbd.C.dbd.O) with an active hydrogen compound
(R--OH) or (R--NH.sub.2) to produce the class of polymers known as
polyurethane, which includes the group of polyurethane-urea
polymers that are produced by the reaction of R--NH.sub.2 with the
isocyanate.
SUMMARY OF THE INVENTION
[0005] Particular embodiments of the present invention include a
polyurethane that is a reaction product of reaction components, the
reaction components comprising (a) a polyol; (b) a polyisocyanate
selected from an aromatic, alicyclic or aliphatic polyisocyanate or
combinations thereof; (c) a mixture of chain extenders that
includes (i) a chain extender having a sulfur bridge in an amount
of between 1 and 30 weight percent of the total mixture of claim
extenders and (ii) a main chain extender, wherein the chain
extender having a sulfur bridge. The chain extender having a sulfur
bridge may be characterized as
R.sub.1-A-S.sub.x--B--R.sub.2
wherein R.sub.1 and R.sub.2 are selected from an OH, an NH.sub.2 or
combinations thereof, wherein A and B are selected from a divalent
aliphatic, alicyclic or aromatic organic group or combinations
thereof, wherein A and B may be the same or different and wherein x
is an integer of between 2 and 10.
[0006] Particular embodiments of the polyurethane may further
include free sulfur and/or a rubber-curing accelerator as reaction
components.
[0007] Particular embodiments of the polyurethane include foamed
polyurethane, coatings, sealants, moldable and/or castable
polyurethane.
[0008] Particular embodiments further include apparatus comprise
any of the polyurethane disclosed herein. Particular embodiments
include the polyurethane disposed on at least one surface of a
metal substrate. The metal substrate may be a metal reinforcement
element selected, for example, from metal wire, metal cord, a metal
tire cord, a metal cable, a metal strand, a metal rod, a metal
plate, a metal filament or combinations thereof.
[0009] In some embodiments, the apparatus may be a conduit, wherein
one or more walls of the conduit comprise the polyurethane
elastomer of claim 1 and the one or more walls are reinforced with
the metal substrate embedded therein. As such, the apparatus may
be, for example, a pipe or a hose or even a conveyor belt.
[0010] The foregoing and other objects, features and advantages of
the invention will be apparent from the following more particular
description of a preferred embodiment of the invention, as
illustrated in the accompanying drawing wherein like reference
numbers represent like parts of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a perspective view of a cast polyester caster
having a metal substrate.
DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS
[0012] The present invention provides a polyurethane, methods for
making the polyurethane and articles made therefrom as well as
methods for making such articles. Particular embodiments of the
present invention include a polyurethane that creates strong bonds
with metal substrates disposed within or on the surface of the
polyurethane. Therefore, particular embodiments of the present
invention include articles having a metal substrate with the
polyurethane disposed on a surface of the metal substrate.
Particular embodiments of such articles include a metal substrate
that provides structural support and/or reinforcement of the
polyurethane. Particular embodiments of the present invention are
also not soluble in water and/or do not easily form an emulsion
with water.
[0013] Elastomers are a class of polymeric materials that have a
high degree of reversible deformation, i.e., a material that can
return to its original shape when a deforming or stretching load is
removed. Elastomers comprising polymeric materials may typically
possess viscoelastic properties. Particular embodiments of the
polyurethane have elastomeric properties.
[0014] Embodiments of the polyurethane may be used as a coating, as
a sealant or as an adhesive. Because the polyurethane bonds well to
other materials, the polyurethane is useful in particular
embodiments as a sealant, coating and/or adhesive. If a blowing
agent is added to particular embodiments of the polyurethane, then
articles may be manufactured from the foamed polyurethane.
Embodiments further include a polyurethane that is moldable and/or
castable.
[0015] Embodiments of the polyurethane may be obtained by reacting
components that include (1) a polyol, (2) an aromatic, alicyclic or
aliphatic polyisocyanate or combinations thereof and (3) a mixture
of chain extenders that includes a main chain extender and a sulfur
bridge chain extender. The sulfur bridge chain extender may be
characterized as a dialcohol having a sulfur bridge, a diamine
having a sulfur bridge and/or an amino alcohol having a sulfur
bridge. An amino alcohol as used herein is a compound that includes
both one alcohol functional group and one amine functional group.
The main chain extender makes up the majority of the mixture of
chain extenders by weight. In particular embodiments the main chain
extender may carry no anionic and/or cationic group and/or may also
include no sulfur bridge. The quantity of reaction components added
to the reactive mass are, unless otherwise noted, expressed as
weight percent based upon the total weight of the polyol reaction
component.
[0016] A suitable polyol reaction component contains at least two
isocyanate-reacting groups that are attached to a single molecule.
The molecule may be, for example, a polyester, a polyether, a
polycaprolactone, a polypropylene glycol or combinations thereof.
In particular embodiments, the polyol may be a hydroxyl-terminated
polyol, an amino-terminated polyol or combinations thereof.
[0017] A suitable polyol reaction component may be selected, for
example, from the polyols that are adequately known in the
polyurethane chemistry or combinations thereof. The polyol reaction
component of particular embodiments may be characterized as having,
for example, a number-average molecular weight of between about 500
and about 20,000 g/mol, between about 600 and about 20,000 g/mol,
between about 600 and about 10,000 g/mol, between about 600 and
about 7,000 g/mol or between about 600 and about 4000 g/mol.
[0018] Examples of a suitable polyol reaction component include
polyether polyols, amine-terminated polyols, polyester polyols,
polyester ether polyols, castor oil polyols, polycyclic polyols and
polycarbonate polyols. Polyether polyols include polytetramethylene
ether glycol (PTMEG), polypropylene oxide glycol (PPO) and
polybutylene oxide glycol (PBO). Amine-terminated polyols are based
on polyether glycols that have had the terminal hydroxyl groups
replaced by primary or secondary amino functionalities. The
polyester polyols include, for example, polyethylene adipates,
polyethyleneglycol adipates, polycaprolactone diols, and
polycaprolactone-polyadipate copolymer diols. Many other polyols
are available and may be used as known to those skilled in the art.
A suitable polyol reaction component may include mixtures of two or
more polyols.
[0019] A suitable aromatic, alicyclic and/or aliphatic
polyisocyanate reaction component may be characterized as a
polyisocyanate having two or more aliphatically, alicyclically or
aromatically bound isocyanate groups. Suitable polyisocyanates
include, for example, the polyisocyanates that are known in
polyurethane chemistry or combinations thereof. Suitable aliphatic
and alicyclic polyisocyanates include, for example,
1,6-diisocyanatohexane (HDI),
1-isocyanato-5-isocyanatomethyl-3,3,5-trimethylcyclo-hexane (IPDI),
bis(4-iso-cyanatocyclohexyl)methane (H.sub.12MDI),
1,3-bis-(1-isocyanato-1-methyl-ethyl)benzene (m-TMXDI), mixtures
thereof or industrial isomer mixtures of individual aliphatic
polyisocyanates.
[0020] Suitable aromatic polyisocyanates include, for example,
2,4-toluene diisocyanate (TDI), 4,4'-diphenyl-methane diisocyanate
(MDI) and, if appropriate, its higher homologues (polymeric MDI),
naphthalene diisocyanate (NDI), polymeric methylene diphenyl
diisocyanate (PMDI), mixtures thereof or industrial isomer mixtures
of individual aromatic polyisocyanates.
[0021] A suitable polyisocyanate reaction component may also
include, for example, modified compounds of the polyisocyanate in
the form of an allophanate, a biuret, a carbodiimide as well as an
oligomer of the isocyanate. Many other polyisocyanates are
available and any useful polyisocyanate may be used as known to one
having ordinary skill in the art.
[0022] The polyisocyanate reaction component may be added to the
reaction mass in an amount, for example, of between 10 and 200
weight percent based upon the total weight of the polyol.
Particular embodiments may include an amount of polyisocyanate, for
example, of between 20 and 150 weight percent, between 35 and 110
weight percent or even between 40 and 100 weight percent based upon
the total weight of the polyol.
[0023] Particular embodiments of methods for making the
polyurethane may include combining the polyol and the
polyisocyanate reaction components first to form a prepolymer as
known to one having ordinary skill in the art. The prepolymer may
then be reacted with the mixture of chain extenders as known to
those having ordinary skill in the art. The prepolymer may be made
with any polyol or polyisocyanate as disclosed above and may, in
particular embodiments, be characterized as having an NCO content
of between 1 and 50 percent, between 3 and 40 percent, between 7
and 15 percent or even between 6 and 20 percent.
[0024] In addition to the polyol and polyisocyanate reaction
components, the reaction mass further includes a mixture of chain
extenders that includes a main chain extender and a sulfur bridge
chain extender. The main chain extender makes up a majority of the
mixture of chain extenders by weight. The mixture of chain
extenders may be added in the reaction mass in an amount, for
example, of between 1 and 40 weight percent based upon the total
weight of the polyol. Particular embodiments may include an amount
of the mixture of chain extenders, for example, of between 2 and 30
weight percent, between 4 and 20 weight percent or even between 5
and 15 weight percent based upon the total weight of the
polyol.
[0025] A suitable sulfur bridge chain extender reaction component
is a dialcohol having a sulfur bridge, a diamine having a sulfur
bridge and/or an amino alcohol having a sulfur bridge characterized
by the following formula (I):
R.sub.1-A-S.sub.x--B--R.sub.2 (1)
wherein R.sub.1 and R.sub.2 are selected from an OH, an NH.sub.2 or
a combination thereof (as in the case of an amino alcohol), wherein
A and B are selected from a divalent aliphatic, alicyclic or
aromatic organic group or combinations thereof and wherein x is an
integer between about 2 and 10. In particular embodiments, x is an
integer between 2 and 10, between 2 and 8 or between 2 and 5. A and
B may be the same or different.
[0026] The sulfur bridge chain extender may be added to the
reaction mass in an amount, for example, of at least 0.5 weight
percent but no more than 30 weight percent based upon the total
weight of the mixture of chain extenders. Particular embodiments
may include an amount of the sulfur bridge chain extender, for
example, of between 1 and 30 weight percent, of between 2 and 25
weight percent, of between 3 and 23 weight percent, of between 4
and 20 weight percent or even between 5 and 15 weight percent based
on the total weight of the mixture of chain extenders.
[0027] Particular embodiments of the present invention may include
the dialcohol 2,2'-dithiodiethanol or the diamine
4,4-dithiodianiline as the sulfur bridge chain extender. Both of
these compounds conform to the general formula (1) above with A and
B both being C.sub.2H.sub.4 or C.sub.6H.sub.4 respectively and x
being 2. Particular embodiments of the polyurethane include both A
and B of formula (1) being straight-chained alkyl groups. Other
embodiments include both A and B of formula (1) being alicyclic
and/or aromatic moieties and/or straight-chained alkyl moieties
and/or wherein A and B may be the same or different.
[0028] Other examples of compounds having the general formula (1)
include hydroxyalkyldi(tri, tetra, or penta)sulfides such as
bis(hydroxymethyl)disulfide, bis(hydroxymethyl)trisulfide,
bis(hydroxymethyl) tetrasulfide, bis(hydroxymethyl)-pentasulfide,
bis(2-hydroxyethyl)disulfide, bis(2-hydroxyethyl)trisulfide,
bis(2-hydroxyethyl)tetrasulfide, bis(2-hydroxyethyl)pentasulfide,
bis(3-hydroxypropyl)disulfide, bis(3-hydroxy-propyl)trisulfide,
bis(3-hydroxypropyl)tetrasulfide, bis(2-hydroxypropyl)disulfide,
bis(2-hydroxypropyl)trisulfide, bis(2-hydroxypropyl)tetrasulfide,
bis(4-hydroxybutyl)disulfide, bis(4-hydroxybutyl)trisulfide,
bis(4-hydroxybutyl)tetrasulfide, bis(8-hydroxyoctyl)disulfide,
bis(8-hydroxyoctyl)trisulfide, bis(8-hydroxyoctyl)tetrasulfide and
the like, and ethylene oxide or propylene oxide adducts of the
aforementioned hydroxyalkyldi(tri, tetra, or penta)sulfides;
di(2-hydroxyethyl)esters (ethylene oxide adducts) or
di(hydroxypropyl)esters (propylene oxide adducts) or the like of
di(tri or tetra)sulfidodicarboxylic acids such as
2,2'-dithiodiglycolic acid, 2,2'-trithiodiglycolic acid,
2,2'-tetrathiodiglycolic acid, 3,3'-dithio-dipropionic acid,
3,3'-trithiodipropionic acid, 3,3'-tetrathiodipropionic acid,
3,3'-pentathio-dipropionic acid, 4,4'-dithiodibutanoic acid,
4'-trithiodibutanoic acid, 4,4'-tetrathiodibutanoic acid,
8,8'-dithiodioctanoic acid, 8,8'-trithiodioctanoic acid,
8,8'-tetrathiodioctanoic acid, 3,3' dihydroxydiphenyl disulfide,
3,3' dihydroxydiphenyl trisulfide, 3,3' dihydroxydiphenyl
disulfide, 3,3' dihydroxydiphenyl tetrasulfide and the like.
[0029] Other examples of compounds having the general formula (1)
wherein R.sub.1 and R.sub.2 are an NH.sub.2 moiety include 4,4'
dianiline disulfide, 4,4' dianiline trisulfide, 4,4' dianiline
tetrasulfide, 2,2' dianiline disulfide, 2,2' dianiline trisulfide,
2,2' dianiline tetrasulfide and the like.
[0030] Examples of compounds having the general formula (1) wherein
R.sub.1 and R.sub.2 are different include the amino alcohols 1,2
aminoethanol, 1,3 amino propanol and 1,4 amino butanol.
[0031] The main chain extender of the mixture of chain extenders
does not contain a sulfur bridge as characterized in formula (1)
above. The main chain extender does make up the majority of the
mixture of chain extenders by weight. A suitable main chain
extender reaction component may be selected from the curatives that
are known in the polyurethane chemistry or combinations thereof. In
particular embodiments, the main chain extender may be
characterized as carrying no anionic and/or cationic group.
[0032] In particular embodiments, the main chain extender may be an
aliphatic, alicyclic and/or aromatic selected from a polyalcohol, a
polyamine or combinations thereof. Furthermore, in some embodiments
the main chain extender may be characterized as being a
short-chained dialcohol, a short-chained diamine or combinations
thereof. Embodiments of the polyurethane may include a di-, tri-,
and/or tetra-alcohol and/or amine but typically a diol or a diamine
is selected as the second chain extender.
[0033] Examples of suitable short-chained chain extenders include,
for example, 1,2, ethanediol, 1,2 propanediol, 1,2 butanediol,
ethylene diamine, 1,2 propane diamine, propylene diamine,
propylenediol, 4,4'-methylene bis-(3-chloro-2,6-diethylaniline)
(MCDEA), 4,4'-methylene bis(2-chloroaniline) (MOCA),
diethylthiotoluenediamine (DETDA) and dimethylthiotoluenediamine
(DMTDA). A suitable second chain extender reaction component is
available commercially from Albermarle Corporation as ETHACURE 300,
which comprises DMTDA and has a reported molecular weight of 214
g/mol. However, any chain extender that is known to those having
ordinary skill in the polyurethane art may be used if the second
chain extender provides a polyurethane composition having the
properties desired for a given application. A short-chained chain
extender has a number-average molecular weight of between 60 and
600 g/mol.
[0034] Particular embodiments of the present invention may further
include sulfur and/or a curing accelerator. Adding sulfur and/or a
curing accelerator increases the bonding strength of the
polyurethane to a metal substrate in particular embodiments.
[0035] Suitable sulfur includes pulverized sulfur, rubber maker's
sulfur, commercial sulfur and insoluble sulfur. In particular
embodiments, the sulfur may be added to the reactant mass in an
amount of between 0.5 and 10 weight percent of the polyol or in an
amount such that the number of moles of sulfur added is between 90
and 110 mole percent of the total number of moles of the sulfur
bridge chain extender.
[0036] Suitable curing accelerators may be selected from those that
are known as curing accelerators for rubber. In particular
embodiments, the curing accelerator may be added to the reactant
mass in an amount of between 0.5 and 10 weight percent of the
polyol or in an amount such that the number of moles of the curing
accelerator added is between 90 and 110 mole percent of the total
number of moles of the sulfur bridge chain extender.
[0037] One classification of rubber-curing accelerators is as
follows:
TABLE-US-00001 TABLE 1 Rubber-Curing Accelerator Classification
Type Time at 284.degree. F. Examples Moderately fast Circa 60 min
Diphenylguanidine Hexamethylene tetramine Fast Circa 30 min
Mercaptobenzothiazole Benzothiazyl disulfide Ultra-accelerators
Several minutes Thiurams Dithiocarbamates Xanthates H. L. Stephans
in "The Compounding and Vulcanization of Rubber", Chapter 2, Rubber
Technology 3.sup.rd edition, edited by Maurice Morton, 1987,
incorporated herein by reference.
[0038] Examples of dithiocarbamate accelerators include zinc
dibenzyl dithiocarbamate (ZBEC-CAS No. 14726-36-4),
zinc-N-dimethyl-dithiocarbamate (ZDMC),
zinc-N-diethyldithiocarbamate (ZDEC-CAS No. 14323-55-1),
zinc-N-dibutyl-dithiocarbamate (ZDBC-CAS No. 35884-05-0),
zinc-N-ethylphenyl-dithiocarbamate (ZEBC-(CAS No. 14364-93-6),
zinc-N-pentamethylene dithiocarbamate (ZPMC-CAS No. 13878-54-1),
piperidinium pentamethylene dithiocarbamate (CAS No. 98-77-1),
sodium diethyl dithiocarbamate (CAS No. 148-18-5); bismuth dimethyl
dithiocarbamate (CAS No. 21260-46-8); cadmium diethyl
dithiocarbamate (CAS No. 14239-68-0); copper dibutyl
dithiocarbamate (CAS No. 13927-71-4); copper dimethyl
dithiocarbamate (CAS No. 137-29-1); cyclohexylethylammonium
cyclohexyl ethyl dithiocarbamate; dimethylammonium dimethyl
dithiocarbamate (CAS No. 598-64-1); dimethylcyclohexylammonium
dibutyl dithiocarbamate (CAS No. 149-82-6); lead diamyl
dithiocarbamate (36501-84-5); lead dimethyl dithiocarbamate (CAS
No. 19010-66-3); CAS No. 72146-43-1; CAS 72146-41-9; CAS No.
72146-42-0; nickel di-isobutyl dithiocarbamate (CAS No.
15317-78-9); nickel dibutyl dithiocarbamate (CAS No. 13927-77-0);
nickel di-methyl dithiocarbamate (CAS No. 15521-65-0);
N-oxydiethylenethiocarbamyl-N'oxydiethylenesulfenamide (CAS No.
13752-51-7); potassium di-methyl dithiocarbamate (CAS No.
128-03-0); selenium diethyl dithiocarbamate (CAS No. 5456-28-0);
selenium dimethyl dithiocarbamate (CAS No. 144-34-3); sodium
cylclohexylethyl dithiocarbamate; sodium dibenzyl dithiocarbamate
(CAS No. 55310-46-8); sodium dibutyl dithiocarbamate (CAS No.
136-30-1); sodium dimethyl dithiocarbamate (CAS No. 128-04-1);
disodium ethylene-bis-dithiocarbamate; sodium diisobutyl
dithiocarbamate (CAS No. 2219-18-3); tellurium
diethyldithiocarbamate (CAS No. 20941-65-5); zinc diamyl
dithiocarbamate (CAS No. 15337-18-5); zinc dibutyl dithiocarbamate
(CAS No. 136-23-2); zinc diisobutyl dithiocarbamate (CAS No.
36190-62-2); zinc dimethyl dithiocarbamate (CAS No. 137-30-4); N, N
dimethyl cyclohexyl ammonium dithiocarbamate;
2,2'-dithiodo(ethylammonium)bis(dibenzyl dithiocarbamate).
[0039] Examples of thiuram accelerators include tetramethylthiuram
monosulphide (TMTM), tetramethylthiuram disulphide,
tetraethylthiuram disulfide (TETD), tetrabenzylthiuram disulfide
(TBzTD). Examples of xanthate accelerators include zinc isopropyl
xanthate (ZIX), sodium isopropyl xanthate (SIX), zinc butyl
xanthate (ZBX), dibutyl xanthogen disulfide, diethyl xanthogenate,
diisopropyl xanthogen disulfide, diisobutyl xanthogen
disulfide.
[0040] Examples of dithiophosphate accelerators include copper
diisopropyl dithiophosphate, zinc-O--,
O-di-n-butylphosphorodithioate.
[0041] Examples of other suitable accelerators include thiazoles,
sulphenamides, guanidines, thiourea derivatives, amine derivatives,
and combinations thereof. These include, but are not limited to a
zinc or sodium salt of 2-mercaptobenzothiazole (ZMBT), diphenyl
guanidine (DPG), triphenyl guanidine (TPG), diorthotolyl guanidine
(DOTG), o-tolylbigaunide (OTBG), ethylene thiourea (ETU),
diethylthiourea (DETU), diphenyl thiourea (DPTU), benzothiazole
disulfide (MBTS) and hexamethylene tetramine (HMT).
[0042] Selection of the reaction components used to produce
particular embodiments of the polyurethane composition of the
present invention are dependent upon the particular application and
desired characteristics of the polyurethane. Each of the reaction
components affects the physical properties of the resulting
polyurethane composition as well as, for example, reaction times
that affect the process of making the polyurethane. Such selections
are made by methods well known to those having ordinary skill in
the art and are not a part of the present invention.
[0043] Particular embodiments of the present invention may include
other components as known to those having ordinary skill in the
art. Such components may include, for example, catalysts,
colorants, stabilizers against heat and/or UV radiation,
antioxidants and combinations thereof.
[0044] Particular embodiments of the present invention are not
soluble in water. "Not soluble" is used herein as one having
ordinary skill in the art would interpret the phrase; i.e.,
difficult or incapable of being dissolved in water. Therefore,
particular embodiments of the present invention include a second
chain extender that carries no anionic and/or no cationic
group.
[0045] Particular embodiments of the present invention further
provide articles made of polyurethanes obtained by reaction of
reaction components that include a polyisocyanate selected from an
aromatic, alicyclic or aliphatic polyisocyanate or combinations
thereof as well as a polyol and a dialcohol having a sulfur bridge
as described above in formula (I). Particular embodiments may
further provide articles made by reaction of an additional reaction
component that is a curative. The curative may further be
characterized in some embodiments as carrying no anionic and/or
cationic group. Particular embodiments further include a metal
substrate having at least one surface on which the polyurethane
adheres. Such substrates may be for decorative purposes but are
more typically useful as structural support and/or reinforcement of
the polyurethane article.
[0046] Polyurethane articles can be reinforced with a metal
substrate. The metal substrate may be on the surface of the
polyurethane but typically the metal substrate is embedded in the
polyurethane. While not limiting the invention, metals that are
useful as metal substrates include, for example, steel, copper,
tin, brass, nickel, vanadium, aluminum and alloys thereof. The
metal substrates may also be coated with other metals such as, for
example, brass-coated steel.
[0047] Many terms are used to describe metal substrates used to
decorate, strengthen, support and/or reinforce polyurethane
articles. The terms cord, tire cord, cable, strand, wire, rod,
plate and filament can all be used to describe metal reinforcing
elements used to strengthen polyurethane articles. The term metal
reinforcement as used herein is generic to all articles for
reinforcing polyurethane articles including those listed above.
Thus, without being limited thereto, a metal reinforcement can be
metal wire, metal cord, a metal tire cord, a metal cable, a metal
strand, a metal rod, a metal plate, a metal filament or
combinations thereof. Likewise, decorative metal substrates may
include, without limitation, a metal rod, a metal strand, a metal
plate, a metal sphere or combinations thereof.
[0048] One such polyurethane article having a metal substrate
support is a caster suitable for support and movement of, for
example, furniture, trucks, and portable equipment. FIG. 1 is a
perspective view of an exemplary caster in accordance to the
present invention. The caster 10 is made of polyurethane obtained
from reaction components that include a dialcohol having a sulfur
bridge and other reactants as described above. The caster 10
includes spokes 14 and a rim 12 that are molded around a hub 22.
The hub 22 includes a hearings housing 16. The caster 10 further
includes metal reinforcing wires 24 embedded in the rim 12. The
caster 10 is molded around the reinforcing wires 24 by methods well
known to one having ordinary skill in the art.
[0049] Methods for making the polyurethane are well known by one
having ordinary skill and include both one shot methods and the
prepolymer methods as known to one having ordinary skill in the
art. The methods further include foaming for the production of a
foamed polyurethane. Foaming agents may be added as known to one
having ordinary skill in the art to produce a foamed polyurethane,
such foaming agents including
[0050] The invention is further illustrated by the following
examples, which are to be regarded only as illustrations and not
delimitative of the invention in any way.
Example 1
[0051] The prepolymer method was used to produce several samples of
the polyurethane. The quantities and ingredients are shown in Table
2. The quantity of each reaction component added is expressed as
weight percent based upon the total weight of the prepolymer.
[0052] The prepolymer was VIBRATHANE B-836, a prepolymer based on a
polyether and MDI and available from Chemtura. The titanium
catalyst was available from VERTEC. The COCURE 55 is an
organomercurial catalyst available from Rutherford Chemicals of New
Jersey. The DABCO catalyst is known as trimethylene diamine
catalyst. CONAP 1146 is commercially available from Cytec
Industries as a high strength adhesive for bonding liquid urethanes
to a substrate during the curing process.
TABLE-US-00002 TABLE 2 Polyurethane Mixes 1 2 3 4 5 6 7 VIBRATHANE
B-836 (PP) 100 100 100 100 100 100 100 1,4 Butanediol (BDO) 9.39
9.51 9.04 9.04 9.04 9.04 8.53 2,2'-dithiodiethanol 0.81 0.81 0.81
0.81 4,4' Dithiodianiline 2.62 sulfur 1.36 1.36 2.70 diphenyl
guanidine (DPG) 0.06 0.06 0.12 Titanium Catalyst (mg/100 g PP) 1 1
1 1 1 1 CoCure 55 (mg/100 g PP) 110 mg DABCO Catalyst (mg/100 g PP)
22 0.3 0.3 0.3 0.3 0.3 0.3 Adhesive applied to cables Y N N N N N N
Pullout Test Results - Maximum Pullout Force, N Brass Cables 352
678 543 787 566 501 Steel Cables 374 443 433 305 805 680 543
[0053] The 1,4 Butanediol (BDO) was the main chain extender while
the 2,2'-dithiodiethanol and the 4,4' dithiodianiline were sulfur
bridge chain extenders.
[0054] If used for the particular mix, the titanium and DABCO
catalysts were added to the BDO before mixing with the prepolymer.
If used, the DPG and the sulfur bridge chain extenders were added
to the BDO before mixing with the prepolymer.
[0055] The prepolymer was heated to about 70.degree. C. and
degassed for approximately 10 minutes under reduced pressure. The
elemental sulfur, if used, was added and mixed under the reduced
pressure until a majority of the sulfur was dissolved. The BDO
mixture was then added to the prepolymer and mixed together for
15-60 seconds. The mixture was then poured into a mold.
[0056] The mold cavity dimensions were 12.5 mm.times.12.5
mm.times.200 mm. The pullout mold had 15 slots and approximately
6.25 mm in depth. The slots were orthogonal to the mold cavity.
Metal cables were placed in the slots before the polyurethane
mixture was poured into the molds.
[0057] The polyurethane was cured in the molds as the mold was
heated for 30 minutes at 150.degree. C. The composite was demolded,
placed in an oven and post cured overnight at 100.degree. C.
Preferably, the polyurethane block should be allowed to post cure
at room temperature for a minimum of 7 days.
Example 2
[0058] Metallic cables were prepared for placing in the mold slots
as described in Example 1. The cables that were used were standard
tire cables approximately 1 mm in diameter. One set of cables was
coated with brass and the second set of cables had the brass
coating removed to expose the steel underneath.
[0059] The cables were cleaned with ethyl acetate to remove oil
from the surface. Using the manufacturer's recommendation, the
CONAP 1146 adhesive was applied to the cable surface and heated if
applicable for the witness test above in Example 1.
Example 3
[0060] The cured samples of Example 1 were tested using a pullout
procedure similar to the ASTM D 2229 method for testing rubber/tire
cable adhesion. An INSTRON 5500R with a 5 kN load cell was used to
pull the cables out of the cured polyurethane block. Standard
INSTRON clamps (catalogue no. 2712-017) were used to grip the
metallic cables. For all tests, a 50 mm gage length and
displacement rate of 100 mm/min was used. The pullout forces are
reported in Table 1 in Newtons (N).
[0061] The terms "comprising," "including," and "having," as used
in the claims and specification herein, shall be considered as
indicating an open group that may include other elements not
specified. The term "consisting essentially of," as used in the
claims and specification herein, shall be considered as indicating
a partially open group that may include other elements not
specified, so long as those other elements do not materially alter
the basic and novel characteristics of the claimed invention. The
terms "a," "an," and the singular forms of words shall be taken to
include the plural form of the same words, such that the terms mean
that one or more of something is provided. The terms "at least one"
and "one or more" are used interchangeably. The term "one" or
"single" shall be used to indicate that one and only one of
something is intended. Similarly, other specific integer values,
such as "two," are used when a specific number of things is
intended. The terms "preferably," "preferred," "prefer,"
"optionally," "may," and similar terms are used to indicate that an
item, condition or step being referred to is an optional (not
required) feature of the invention. Ranges that are described as
being "between a and b" are inclusive of the values for "a" and
"b."
[0062] It should be understood from the foregoing description that
various modifications and changes may be made in the preferred
embodiments of the present invention without departing from its
true spirit. The foregoing description is provided for the purpose
of illustration only and should not be construed in a limiting
sense. Only the language of the following claims should limit the
scope of this invention.
* * * * *