U.S. patent application number 10/622394 was filed with the patent office on 2004-03-18 for resins for lining surfaces.
Invention is credited to Nava, Hildeberto.
Application Number | 20040053062 10/622394 |
Document ID | / |
Family ID | 31190754 |
Filed Date | 2004-03-18 |
United States Patent
Application |
20040053062 |
Kind Code |
A1 |
Nava, Hildeberto |
March 18, 2004 |
Resins for lining surfaces
Abstract
A method of lining a surface of a substrate comprises providing
a reactive mixture which comprises (1) a resin containing active
hydrogens; (2) a polycarbodiimide; and (3) an organic diluent;
reacting the resin containing active hydrogens and the
polycarbodiimide to chemically bind the resin and the
polycarbodiimide; applying the chemically bound resin and
polycarbodiimide to the surface of the substrate; and curing the
chemically bound resin and polycarbodiimide in the presence of an
initiator to form a cured resin material which lines the surface of
the substrate.
Inventors: |
Nava, Hildeberto; (Cary,
NC) |
Correspondence
Address: |
MYERS BIGEL SIBLEY & SAJOVEC
PO BOX 37428
RALEIGH
NC
27627
US
|
Family ID: |
31190754 |
Appl. No.: |
10/622394 |
Filed: |
October 31, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10622394 |
Oct 31, 2003 |
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09519924 |
Mar 7, 2000 |
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09519924 |
Mar 7, 2000 |
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09261713 |
Mar 3, 1999 |
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09261713 |
Mar 3, 1999 |
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08919090 |
Aug 27, 1997 |
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5925409 |
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Current U.S.
Class: |
428/473.5 ;
427/239; 525/123; 525/457 |
Current CPC
Class: |
C08G 18/095 20130101;
B29C 63/34 20130101; Y10T 428/31721 20150401; C08G 18/68 20130101;
B29C 35/02 20130101; Y10T 428/1352 20150115; Y10T 428/1355
20150115; Y10S 525/907 20130101; Y10T 428/1372 20150115; C08G
18/797 20130101; C08G 18/683 20130101; C09D 201/02 20130101; F16L
55/162 20130101 |
Class at
Publication: |
428/473.5 ;
525/123; 525/457; 427/239 |
International
Class: |
C08F 002/00 |
Claims
That which is claimed:
1. A method of lining a surface of a substrate, said method
comprising: providing a reactive mixture which comprises (1) a
resin containing active hydrogens; (2) a polycarbodiimide; and (3)
an organic diluent; reacting the resin containing active hydrogens
and the polycarbodiimide to chemically bind the resin and the
polycarbodiimide; applying the chemically bound resin and
polycarbodiimide to the surface of the substrate; and curing the
chemically bound resin and polycarbodiimide in the presence of a
initiator to form a cured resin material which lines the surface of
the substrate.
2. The method according to claim 1, wherein the substrate is a
conduit.
3. The method according to claim 1, wherein the reactive mixture
comprises greater than about 5 percent by weight of
polycarbodiimide.
4. The method according to claim 1, wherein the resin containing
active hydrogens is selected from the group consisting of saturated
polyester resins, unsaturated polyester resins, vinyl ester resins,
polyurethane resins, and mixtures thereof.
5. The method according to claim 1, wherein the organic diluent is
selected from the group consisting of toluene, xylene,
chlorobenzene, chloroform, tetrahydrofuran, ethyl acetate,
isopropyl acetate, butyl acetate, butyl phthalate, acetone, methyl
cellosolve acetate, cellosolve acetate, butyl cellosolve, methyl
ethyl ketone, diethyl ketone, cyclohexanone, styrene,
alphamethylstyrene, p-methyl styrene, divinyl benzene, vinyl
toluene, divinyl toluene, ethyl styrene, tert-butyl styrene,
monochloro styrene, dichloro styrene, vinyl cyclohexane, vinyl
cyclopentane, vinyl toluene, vinyl anthracenes, 3-vinyl benzyl
chloride, 4-vinyl biphenyl, 4-vinyl-1-cuclohexene, vinyl
cyclooctane, 2-vinyl naphthalene, 5-vinyl-2-norbornene,
1-vinylimidazole, 2-vinyl pyridine, 4-vinyl pyridine,
1-vinyl-2-pyrroldinone, 9-vinyl carbazole, ethylene glycol
dimethacrylate, butanediol dimethacrylate, hexanediol
dimethacrylate, and mixtures thereof.
6. The method according to claim 1, wherein the organic diluent
comprises a polyfunctional acrylate component.
7. The method according to claim 1, wherein the polycarbodiimide is
formed from a reaction between an isocyanate-containing
intermediate and a diisocyante.
8. The method according to claim 7, wherein the
isocyanate-containing intermediate is formed from a reaction
between a component containing active hydrogens and a
diisocyanate.
9. The method according to claim 8, wherein the component
containing active hydrogens is selected from the group consisting
of alcohols, amines, thiols, phenols, silanol, --P--OH, --P--H, and
mixtures thereof.
10. The method according to claim 8, wherein the component
containing active hydrogens is an alcohol.
11. The method according to claim 1, wherein the initiator is an
organic peroxide selected from the group consisting of cumene
hydroperoxide; methyl ethyl ketone peroxide; benzoyl peroxide;
acetyl peroxide; 2,5-dimethylhexane-2,5-dihydroperoxide; tert-butyl
peroxybenzoate; di-tert-butyl perphthalate; dicumyl peroxide;
2,5-dimethyl-2,5-bix(tert-b- utylperoxide)hexane;
2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne;
bix(tert-butylperoxyisopropyl)benzene; ditert-butyl peroxide;
1,1-di(tert-amylperoxy)-cyclohexane;
1,1-di-(tert-butylperoxy)-3,3,5-trim- ethylcyclohexane;
1,1-di-(tert-butylperoxy)-cyclohexane;
2-di-(tert-butylperoxy)butane;
n-butyl-4,4-di(tert-butylperoxy)valerate;
ethyl-3,3-di-(tert-amylperoxy)butyrate;
ethyl-3,3-di(tert-butylperoxy)-bu- tyrate; t-butyl
peroxy-neodecanoate; di-(4-5-butyl-cyclohexyl)-peroxydicar- bonate;
lauryl peroxyde; 2,5-dimethyl-2,5-bis(2-ethyl-hexanoyl peroxy)
hexane; t-amyl peroxy-2-ethylhexanoate;
2,2'-azobis(2-methyl-propionitril- e);
2,2'-azobis(2,4-methlbutanenitrile); and mixtures thereof.
12. The method according to claim 1, wherein the initiator is a
photoinitiator.
13. The method according to claim 1, wherein said curing step is
carried out in the presence of a promoter.
14. The method according to claim 1, wherein said reactive mixture
further comprises fibrous reinforcement material.
15. The method according to claim 14, wherein the fibrous
reinforcement material is selected from the group consisting of
fiberglass, polyester, carbon, metal, organic fibers, and mixtures
thereof.
16. The method according to claim 1, wherein said reacting step is
carried out at a temperature ranging from about 5.degree. C. to
about 60.degree. C.
17. The method according to claim 1, wherein said curing step is
carried out at a temperature ranging from about 40.degree. C. to
about 150.degree. C.
18. A method of lining a surface of a conduit comprising: providing
a reactive mixture which comprises (1) a resin containing active
hydrogens; (2) a polycarbodiimide; and (3) an organic diluent;
inserting the reactive mixture into a tube, the tube being defined
by an inner membrane and an outer membrane; reacting the resin
containing active hydrogens and the polycarbodiimide to chemically
bind the resin and the polycarbodiimide; inserting the tube into a
conduit having an inner surface; applying pressure to the tube such
that the tube comes in contact with the inner surface of the
conduit; and curing the chemically bound resin and polycarbodiimide
in the presence of an initiator to form a cured resin material
which lines the surface of the conduit.
19. The method according to claim 18, wherein the reactive mixture
comprises greater than about 5 percent by weight of
polycarbodiimide.
20. The method according to claim 18, wherein the resin containing
active hydrogens is selected from the group consisting of saturated
polyester resins, unsaturated polyester resins, vinyl ester resins,
polyurethane resins, and mixtures thereof.
21. The method according to claim 18, wherein the organic diluent
is selected from the group consisting of toluene, xylene,
chlorobenzene, chloroform, tetrahydrofuran, ethyl acetate,
isopropyl acetate, butyl acetate, butyl phthalate, acetone, methyl
cellosolve acetate, cellosolve acetate, butyl cellosolve, methyl
ethyl ketone, diethyl ketone, cyclohexanone, styrene,
alphamethylstyrene, p-methyl styrene, divinyl benzene, vinyl
toluene, divinyl toluene, ethyl styrene, tert-butyl styrene,
monochloro styrene, dichloro styrene, vinyl cyclohexane, vinyl
cyclopentane, vinyl toluene, vinyl anthracenes, 3-vinyl benzyl
chloride, 4-vinyl biphenyl, 4-vinyl-1-cuclohexene, vinyl
cyclooctane, 2-vinyl naphthalene, 5-vinyl-2-norbornene,
1-vinylimidazole, 2-vinyl pyridine, 4-vinyl pyridine,
1-vinyl-2-pyrrolidinone, 9-vinyl carbazole, ethylene glycol,
dimethacrylate, butanediol dimethacrylate, hexanediol
dimethacrylate, and mixtures thereof.
22. The method according to claim 18, wherein the organic diluent
comprises a polyfunctional acrylate component.
23. The method according to claim 18, wherein the polycarbodiimide
is formed from a reaction between an isocyanate-containing
intermediate and a diisocyante.
24. The method according to claim 23, wherein the
isocyanate-containing intermediate is formed from a reaction
between a component containing active hydrogens and a
diisocyanate.
25. The method according to claim 24, wherein the component
containing active hydrogens is selected from the group consisting
of alcohols, amines, thiols, phenols, silanol, --P--OH, --P--H, and
mixtures thereof.
26. The method according to claim 24, wherein the component
containing active hydrogens is an alcohol.
27. The method according to claim 18, wherein the reactive mixture
further comprises fibrous reinforcement material.
28. The method according to claim 27, wherein the fibrous
reinforcement material is selected from the group consisting of
fiberglass, polyester, carbon, metal, organic fibers, and mixtures
thereof.
29. The method according to claim 18, wherein the initiator is an
organic peroxide initiator selected from the group consisting of
cumene hydroperoxide; methyl ethyl ketone peroxide; benzoyl
peroxide; acetyl peroxide; 2,5-dimethylhexane-2,5-dihydroperoxide;
tert-butyl peroxybenzoate; di-tert-butyl perphthalate; dicumyl
peroxide; 2,5-dimethyl-2,5-bix(tert-butylperoxide)hexane;
2,5-dimethyl-2,5-bis(tert- -butylperoxy)hexyne;
bix(tert-butylperoxyisopropyl)benzene; ditert-butyl peroxide;
1,1-di(tert-amylperoxy)-cyclohexane; 11-di-(tert-butylperoxy)-3-
,3,5-trimethylcyclohexane; 1,1-di-(tert-butylperoxy)-cyclohexane;
2,2-di-(tert-butylperoxy)butane;
n-butyl-4,4-di(tert-butylperoxy)valerate- ;
ethyl-3,3-di-(tert-amylperoxy)butyrate;
ethyl-3,3-di(tert-butylperoxy)-b- utyrate; t-butyl
peroxy-neodecanoate; di-(4-5-butyl-cyclohexyl)-peroxydica- rbonate;
lauryl peroxyde; 2,5-dimethyl-2,5-bis(2-ethyl-hexanoyl peroxy)
hexane; t-amyl peroxy-2-ethylhexanoate;
2,2'-azobis(2-methyl-propionitril- e);
2,2'-azobis(2,4-methlbutanenitrile); and mixtures thereof.
30. The method according to claim 18, wherein the initiator is a
photoinitiator.
31. The method according to claim 18, wherein the reaction mixture
further comprises a promoter.
32. The method according to claim 18, wherein said reacting step is
carried out at a temperature ranging from about about 5.degree. C.
to about 60.degree. C.
33. A lined substrate comprising: a cured resin material comprising
a resin chemically bound to a polycarbodiimide; and a surface of
said substrate which contains said cured resin material
thereon.
34. The lined substrate according to claim 33, wherein the resin
chemically bound to a polycarbodiimide is selected from the group
consisting of saturated polyester resins, unsaturated polyester
resins, vinyl ester resins, polyurethane resins, and mixtures
thereof.
35. The lined substrate according to claim 32, wherein said
substrate is a conduit.
36. The lined substrate according to claim 32, wherein said cured
resin material further comprises fibrous reinforcement material
selected from the group consisting of fiberglass, polyester,
carbon, metal, organic fibers, and mixtures.
Description
FIELD AND BACKGROUND OF THE INVENTION
[0001] The present invention relates to a method of utilizing
resins for lining substrate surfaces which are damaged or
cracked.
[0002] Substrates which are exposed to outdoor conditions are
utilized in, for example, sidewalks, roads, reservoirs, and the
like. These substrates are typically formed from concrete, metals,
and polymer composites. In addition to the above, the substrates
are employed underground and used in a number of applications
relating to the transport of petroleum, natural gas, chemicals,
municipal water, and the like. Due to exposure to a number of
influences over time such as, for example, temperature
fluctuations, ground movements, corrosive fluids, etc., the pipes
tend to crack and damage. As a result, the pipes often are unable
to successfully transport the above mentioned fluids and thus
become unsuitable for their intended use.
[0003] Various methods have been proposed to repair the pipes. One
approach is presented in U.S. Pat. No. 4,009,063 to Wood, and
involves lining the inside of the pipe with a tubular fibrous felt
impregnated with a thermosetting resin which contains a catalyst.
Wood teaches that the impregnated felt is inserted into the damaged
pipe and is inflated using hot air or water. The expansion of the
tubular felt molds it into the shape of the pipe. Heat from the hot
air or water activates the catalyst causing the resin to cure and
form a rigid liner.
[0004] Another approach involves utilizing glass fiber which is
woven into a tubular shape. The glass fiber is impregnated with a
thermosetting resin containing a catalyst, and the resin is then
cured. Carbon fiber may be interwoven with the glass fiber such
that curing may be accomplished by applying an electrical current
to the carbon fibers to generate heat. As a result, the catalyst is
activated and the resin cures forming a rigid pipe lining. In this
instance, hot air or hot water is not required.
[0005] The use of thermally activated catalysts which is described
above, however, present disadvantages. Since the catalysts
typically require temperatures well above ambient, the viscosity of
the impregnated resin decreases while in the pipe. As the viscosity
decreases, the resin tends to sag. The resulting pipe lining formed
from the resin is non-uniform in appearance and often possesses
non-uniform physical properties.
[0006] In order to address the above difficulties, agents such as
fumed silica have been added to the resins such that they become
thixotropic. A thixotropic material is advantageous in that its
flow at room temperature is limited in the absence of an applied
shear force. Nonetheless, using thixotropic materials is
problematic in that their viscosities are excessively high making
them difficult to pump. Also, heating thixotropic materials reduces
the resin viscosity such that the materials run off and are
difficult to contain.
[0007] It would be desirable to provide a method of lining damaged
surfaces such as those found in pipes or conduits which addresses
the problems mentioned above.
SUMMARY OF THE INVENTION
[0008] It is therefore an object of the present invention to
provide a method for lining a surface with a resin which may be
transported more easily to the surface and provide more uniform
physical properties to the surface.
[0009] To this end and others, the invention provides a method of
lining a surface. The method comprises providing a reactive mixture
which comprises (1) a resin containing active hydrogens; (2) a
polycarbodiimide; and (3) an organic diluent; reacting the resin
containing active hydrogens and the polycarbodiimide to chemically
bind the resin and the polycarbodiimide; applying the chemically
bound resin and polycarbodiimide to the surface of the substrate;
and curing the chemically bound resin and polycarbodiimide to form
a cured resin material which lines the surface of the
substrate.
[0010] To cure the chemically bound resin, an initiator is
employed. Additionally, in another embodiment, a promoter may be
used in conjunction with the initiator.
[0011] The invention also provides a method of lining a surface
which defines a conduit. The method comprises providing a reactive
mixture which comprises (1) a resin containing active hydrogens;
(2) a polycarbodiimide; and (3) an organic diluent; inserting the
reactive mixture into a tube, the tube being defined by an inner
membrane and an outer membrane; reacting the resin containing
active hydrogens and the polycarbodiimide to chemically bind the
resin and the polycarbodiimide; inserting the tube into a conduit
having an inner surface; applying pressure to the tube such that
the tube comes in contact with the inner surface of the conduit;
and curing the chemically bound resin and polycarbodiimide to form
a crosslinked resin material which lines the surface of the
conduit.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] In the drawings which form an original portion of the
disclosure as filed:
[0013] FIG. 1 illustrates a tube filled with a resin according to
the invention;
[0014] FIG. 2 illustrates a tube filled with a resin according to
the invention being present inside a conduit;
[0015] FIG. 3 illustrates a tube filled with a resin according to
the invention being urged by pressure against an inner surface of a
conduit; and
[0016] FIG. 4 illustrates a tube filled with a resin according to
the invention being urged by pressure against a tube previously
inserted and against an inner surface of a conduit.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0017] The present invention will now be described more fully
hereinafter, in which preferred embodiments of the invention are
shown. This invention may, however, be embodied in different forms
and should not be construed as limited to the embodiments set forth
herein. Rather, these embodiments are provided so that this
disclosure will be thorough and complete, and will fully convey the
scope of the invention to those skilled in the art.
[0018] In one aspect, the invention relates to a method for lining
a surface of a substrate with a resin, typically the surface of a
conduit such as a pipe. The method comprises providing a reactive
mixture which comprises (1) a resin containing active hydrogens,
(2) a polycarbodiimide, and (3) an organic diluent. The
polycarbodiimide is preferably dispersed or contained in the
organic diluent during the providing step. The reaction mixture
preferably contains greater than about 5 percent by weight of
polycarbodiimides. The resin containing active hydrogens and the
polycarbodiimide then react such that the resin and the
polycarbodiimide become chemically bound, namely the resin becomes
thickened. This step is preferably carried out at a temperature
between about 5.degree. C. and about 60.degree. C. The chemically
thickened resin preferably has a viscosity ranging from about
30,000 centipoise to about 50 million centipoise, and more
preferably from about 100,000 centipoise to about 20 million
centipoise.
[0019] The chemically bound resin and polycarbodiimide is then
applied to the surface of the substrate. Subsequently, chemically
bound resin and polycarbodiimide is cured to form a crosslinked
resin material which lines the surface of the substrate. The curing
step is preferably carried out at a temperature between about
40.degree. C. and about 150.degree. C., more preferably between
about 50.degree. C. and about 100.degree. C. The curing step is
performed in the presence of an initiator.
[0020] The invention is advantageous in that the glass transition
temperature (T.sub.g) of the cured resin material may be enhanced
by virtue of the method disclosed herein. Preferably, the T.sub.g
of the cured resin material increases from about 5 percent to about
600 percent, and more preferably from about 10 percent to about 300
percent. As a result of this elevation in T.sub.g, the physical
properties of the cured resin are believed to be enhanced.
[0021] As a result of this elevation in T.sub.g, it is believed
that the physical properties of the cured resin materials are
enhanced. Preferably, the cured resin material has a flexural
strength ranging from about 3000 psi to about 80,000 psi; a tensile
strength ranging from about 1000 psi to about 50,000 psi; and a
percent elongation ranging from about 1 to about 1000. In addition
to the above, it should be appreciated that various types of resins
may have differing preferred ranges of physical property values.
For example, cured unsaturated polyester resins preferably have
tensile strengths ranging from about 3000 psi to about 50,000 psi
and elongations ranging from about 1 to about 10 percent, while
cured polyurethanes preferably have tensile strengths ranging from
about 800 to about 5000 psi and elongations ranging from about 70
to about 1000.
[0022] Preferably, the reactive mixture contains between about 3 to
about 50 percent by weight of polycarbodiimide, more preferably
between about 3 and about 20 weight percent polycarbodiimide, and
most preferably between about 6 and about 12 weight percent
polycarbodiimide.
[0023] The resin which contains active hydrogens may be selected
from a number of resins well known to those skilled in the art. For
the purposes of the invention, the term "resin containing active
hydrogens" refers to any resin which contains functional groups
containing active hydrogens. Functional groups containing active
hydrogens can be defined as those which are capable of reacting
with polycarbodiimide repeating units (N.dbd.C.Arrow-up bold.N).
Suitable functional groups including, for example, hydroxyl,
carboxyl, amino, phenol, silanol, --P--OH, --P--H, as well as other
appropriate substituents. Resins containing active hydrogens
include, but are not limited to, saturated polyester resins (e.g.,
resins employed in hot melt adhesives and powder coatings),
unsaturated polyester resins (e.g., resins used in forming molded
articles), aliphatic and aromatic polyethers, vinyl ester resins
(e.g., resins used in filament winding and open and closed
molding), polyurethanes, and mixtures of any of the above.
[0024] For the purposes of the invention, unsaturated polyester
resins, saturated polyester resins, and vinyl ester resins are
preferably employed. An unsaturated polyester resin may be formed
from conventional methods. Typically, the resin is formed from the
reaction between a polyfunctional organic acid or anhydride and a
polyhydric alcohol under conditions known in the art. The
polyfunctional organic acid or anhydride which may be employed are
any of the numerous and known compounds. Suitable polyfunctional
acids or anhydrides thereof include, but are not limited to, maleic
acid, fumaric acid, citraconic acid, itaconic acid, glutaconic
acid, phthalic acid, isophthalic acid, terephthalic acid,
cyclohexane dicarboxylic acid, succinic anhydride, adipic acid,
sebacic acid, azealic acid, malonic acid, alkenyl succinic acids
such as n-dodecenylsuccinic acid, docecylsuccinic acid,
octadecenylsuccinic acid, and anhydrides thereof. Lower alkyl
esters of any of the above may also be employed. Mixtures of any of
the above are suitable.
[0025] Additionally, polybasic acids or anhydrides thereof having
not less than three carboxylic acid groups may be employed. Such
compounds include 1,2,4-benzenetricarboxylic acid, 1,3,5-benzene
tricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid,
2,5,7-naphthalene tricarboxylic acid, 1,2,4-naphthalene
tricarboxylic acid, 1,3,4-butane tricarboxylic acid, 1,2,5-hexane
tricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-carboxym-
ethylpropane, tetra(carboxymethyl)methane, 1,2,7,8-octane
tetracarboxylic acid, and mixtures thereof.
[0026] Suitable polyhydric alcohols which may be used in forming
the unsaturated polyester resin include, but are not limited to,
ethylene glycol, diethylene glycol, propylene glycol, dipropylene
glycol, 1,3-butanediol, 1,4-butanediol, 1,3 hexanediol, neopentyl
glycol, 2-methyl-1,3-propanediol, 1,3-butylene glycol,
1,6-hexanediol, hydrogeneated bisphenol "A", cyclohexane
dimethanol, 1,4-cyclohexanol, ethylene oxide adducts of bisphenols,
propylene oxide adducts of bisphenols, sorbitol,
1,2,3,6-hexatetrol, 1,4-sorbitan, pentaerythritol,
dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-butanetriol;
1,2,5-pentanetriol, glycerol, 2-methyl-propanetriol,
2-methyl-1,2,4-butanetriol, trimethylol ethane, trimethylol
propane, and 1,3,5-trihydroxyethyl benzene. Mixtures of the above
alcohols may be used.
[0027] The vinyl ester resins employed in the invention include the
reaction product of an unsaturated monocarboxylic acid or anhydride
with an epoxy resin. Exemplary acids and anhydrides include (meth)
acrylic acid or anhydride, .alpha.-phenylacrylic acid,
.alpha.-chloroacrylic acid, crotonic acid, mono-methyl and
mono-ethyl esters of maleic acid or fumaric acid, vinyl acetic
acid, sorbic acid, cinnamic acid, and the like, along with mixtures
thereof. Epoxy resins which may be employed are known and include
virtually any reaction product of a polyfunctional halohydrin, such
as epichlorohydrin, with a phenol or polyhydric phenol. Suitable
phenols or polyhydric phenols include, for example, resorcinol,
tetraphenol ethane, and various bisphenols such as Bisphenol "A",
4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydrohy byphenyl,
4,4'-dihydroxydiphenyl methane, 2,2'-dihydroxydiphenyloxide, and
the like. Novolac epoxy resins may also be used. Mixtures of any of
the above may be used. Additionally, the vinyl ester resins may
have pendant carboxyl groups formed from the reaction of esters and
anhydrides and the hydroxyl groups of the vinyl ester backbone.
[0028] The resins containing reactive hydrogens may be used alone
or in conjunction with other appropriate materials to help enhance
physical properties of the resin. Suitable materials include, for
example, fibrous reinforcements, fillers, flame retardants, woven
and nonwoven fibrous sheets and mats, and the like. Any
conventionally known fibrous reinforcement material may be used
including fiberglass, polyester, carbon, metal, graphite, high
modulus organic fibers (e.g., aromatic polyamides,
polybenzimidazoles, and aromatic polyimides), other organic fibers
(e.g., polyethylene, liquid crystals, and nylon), and natural
fibers. The fibrous materials may be incorporated into the resin in
accordance with techniques which are known in the art. Fillers may
include but are not limited to calcium carbonate, aluminum oxide,
aluminum hydroxide, silica gel, barite, graphite powder, and the
like. Mixtures of the above may also be used.
[0029] Saturated polyester resins and polyurethanes which are
thickened include, for example, those described in U.S. Pat. Nos.
4,871,811; 3,427,346; and 4,760,111; the disclosures of which are
incorporated herein by reference in their entirety. The saturated
polyester resins and polyurethanes are particularly useful in hot
melt adhesives and pressure sensitive adhesive applications.
Appropriate saturated polyester resins include, but are not limited
to, crystalline and amorphous resins. The resins may be formed by
any suitable technique. For example, the saturated polyester resin
may be formed by polycondensating an aromatic or aliphatic di-or
polycarboxylic acid and an aliphatic or alicyclic di- or polyol or
its prepolymer. Optionally, either the polyols may be added in
excess to obtain hydroxyl end groups or the dicarboxylic monomers
may be added in excess to form carboxylic end groups. Suitable
polyurethane resins may be formed by the reaction of diols or
polyols as described in U.S. Pat. No. 4,760,111 along with
diisocyanates. The diols are added in an excess to obtain hydroxyl
end groups at the chain ends of the polyurethane.
[0030] Polycarbodiimides which may be employed in the present
invention include those which are known in the art. Exemplary
polycarbodiimides are described in U.S. Patent Nos. 5,115,072;
5,081,173; 5,008,363; and 5,047,588; the disclosures of which are
incorporated herein by reference in their entirety. The
polycarbodiimides can include aliphatic, cycloaliphatic, or
aromatic polycarbodiimides.
[0031] The polycarbodiimides can be prepared by a number of known
reaction schemes. Preferably, the polycarbodiimides are synthesized
by reacting an isocyanate-containing intermediate and a diisocyante
under suitable reaction conditions. The isocyanate containing
intermediate is formed by the reaction between a component,
typically a monomer, containing active hydrogens and a
diisocyanate. Included are also polycarbodiimides prepared by the
polymerization of isocyanates to form a polycarbodiimide, which
subsequently react with a component containing active
hydrogens.
[0032] Components containing active hydrogens, which may be
employed are well known and numerous, with monomers being typically
utilized. Examples of such monomers include, but are not limited
to, acrylates, alcohols, amines, esters, polyesters, thiols,
phenols, aromatic and aliphatic polyethers, siloxanes,
phosphorus-containing materials, olefins, unsaturated aromatic
monomers, and mixtures thereof. Alcohols are typically used, with
monofunctional alcohols being preferably employed. Monofunctional
alcohols which may be used include, for example, ethanol, butanol,
propanol, hexanol, octanol, ethylhexyl alcohol, and longer-chain
alcohols (i.e., those alcohols containing up to 50 carbon atoms)
and their isomers.
[0033] Other monomers having active hydrogens which may be used
include, for example, acrylic acid, methacrylic acid, acetic acid,
phenylacetic acid, phenoxyacetic acid, propionic acid,
hydrocynnamic acid, and the like. Hydroxyalkyl acrylates or
methacrylates such as hydroxyethyl acrylate, hydroxyethyl
methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate,
hydroxybutyl acrylate, hydroxybutyl methacrylate, and the like may
also be employed. Polyols can be additionally be used including,
but not limited to, ethylene glycol; 1,2 and 1,3-propylene glycol;
1,4 and 2,3-butylene glycol; 1,5-pentanediol; 1,6-hexanediol;
1,8-octanediol; neopentyl glycol; 1,4-bis-hydroxymethyl
cyclohexane; 2-methyl-1,3-propanediol; glycerol;
trimethylolpropane; 1,2,6-hexanetriol; trimethylol ethane;
pentaerythritol; quinitol; mannitol; sorbitol; diethylene glycol;
triethylene glycol; tetraethylene glycol; 1,4-butanediol;
polyethylene glycols having a molecular weight of up to 400;
dipropylene glycol; ethoxylated and propoxylated bisphenol "A";
polybutylene glycols having a molecular weight of up to 400; methyl
glucoside; diethanolamino-N-methyl phosphonic acid esters; castor
oil; diethanolamine; N-methyl ethanolamine; and triethanolamine.
Mixtures of any of the above may be used. Any of the above
compounds may also include any one or a combination of halogens
such as chlorine, fluorine, bromine, or iodine; or phosphorus, or
silicon groups.
[0034] Diisocyanates which are used in the above reactions are well
known to the skilled artisan. For the purposes of the invention,
diisocyantes include aliphatic, cycloaliphatic, araliphatic,
aromatic and heterocyclic diisocyantes of the type described, for
example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562,
pages 75 to 136, (1949) for example, those corresponding to the
following formula:
OCN--R--NCO
[0035] wherein R represents a difunctional aliphatic,
cycloaliphatic, aromatic, or araliphatic radical having from about
4 to 25 carbon atoms, preferably 4 to 15 carbon atoms, and free of
any group which can react with isocyanate groups. Exemplary
diisocyantes include, but are not limited to, toluene diisocyanate;
1,4-tetramethylene diisocyanate; 1,4-hexamethylene diisocyanate;
1,6-hexamethylene diisocyanate; 1,12-dodecane diisocyante;
cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate;
cyclohexane-1,4-diisocyanate;
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane;
2,4-hexahydrotolylene diisocyanate; 2,6-hexahydrotolylene
diisocyanate; 2,6-hexahydro-1,3-phenylene diisocyanate;
2,6-hexahydro-1,4-phenylene diisocyanate; per-hydro-2,4'-diphenyl
methane diisocyanate; per-hydro-4,4'-diphenyl methane diisocyanate;
1,3-phenylene diisocyanate; 1,4-phenylene diisocyanate;
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanates; diphenyl
methane-2,4'-diisocyanate; diphenyl methane-4,4'-diisocyanate;
naphthalene-1,5-diisocyanate; 1,3-xylylene diisocyanate;
1,4-xylylene diisocyanate; 4,4'-methylene-bis(cyclohexyl
isocyanate); 4,4'-isopropyl-bis-(cyclohexyl isocyanate);
1,4-cyclohexyl diisocyanate;
3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI);
1-methyoxy-2,4-phenylene diisocyanate; 1-chloropyhenyl-2,4-diisoc-
yante; p-(1-isocyanatoethyl)-phenyl isocyanate;
m-(3-isocyanatobutyl)-phen- yl isocyanate; and
4-(2-isocyanate-cyclohexyl-methyl)-phenyl isocyanate. Mixtures of
any of the above may be employed. When deemed appropriate, a
diisocyante may be employed which contains other functional groups
such as hydroxy or amino functionality.
[0036] In the reaction involving the component containing active
hydrogens and the diisocyanate, it is preferred to employ a
catalyst. A number of catalysts known to the skilled artisan may be
used for this purpose. Such catalysts include, but are not limited
to, an organo tin catalyst such as dibutyl tin diacetate, dibutyl
tin di-2-ethylhexoate, dibutyl tin dilaurate, dibutyl tin oxide,
and the like. Tertiary amines, such as triethyl amine,
tributylamine, triethylene-diamine tripropylamine, and the like may
also be used. Mixtures of the above catalysts may be used. The
catalyst may be used in various suitable amounts, preferably
between about 0.005 and about 0.50 percent based on the weight of
the component containing active hydrogens and the diisocyanate.
[0037] The reaction between the component containing reactive
hydrogens and the diisocyanate forms a isocyanate-containing
intermediate. The isocyanate-containing intermediate is then
reacted with any of the diisocyantes described herein to form a
poly-carbodiimide. The latter reaction described above is
preferably carried out in the presence of a catalyst. Suitable
catalysts which may be used include, for example, those described
in U.S. Pat. No. 5,008,363; the disclosure of which is incorporated
herein by reference in its entirety. Particularly useful classes of
carbodiimide-forming catalysts are the phospholene-1-oxides and
phospholene-1-sulfides. Representative compounds within these
classes are triphenyl phosphine; 3-methyl-1-phenyl-3-phospholine
1-oxide; 1-ethyl-phenyl-3-phospholine 1-oxide;
3-(4-methyl-3-pentynyl)-1-phenyl-3-- phospholine 1-oxide;
3-chloro-1-phenyl-3-phospholine 1-oxide; 1,3-diphenyl-3-phospholine
1-oxide; 1-ethyl-3-phospholine 1-sulfide; 1-phenyl-3-phospholine
1-sulfide; and 2-phenyliso-phosphindoline 2-oxide;
1-phenyl-2-phospholene 1-oxide; 3-methyl-phenyl-2-phospholene
1-oxide; 1-phenyl-2-phospholene 1-sulfide; 1-ethyl-2-phospholene
1-oxide; 1-ethyl-3-methyl-2-phospholene 1-oxide; and
1-ethyl-3-methyl-2-phospholen- e 1-oxide. Other isomeric
phospholenes corresponding to all the above-named compounds also
can be used. Mixtures of any of the above may be used. The catalyst
may be used in various suitable amounts, preferably from about
0.005 to about 10 percent based on the weight of the reactants,
more preferably from about 0.02 to about 5 weight percent, and most
preferably from about 0.03 to about 2 weight percent.
[0038] A vinyl monomer may also be included as a diluent with the
polycarbodiimide and the unsaturated and saturated resins. Suitable
monomers may include those such as, for example, styrene and
styrene derivatives such as alpha-methyl styrene, p-methyl styrene,
divinyl benzene, divinyl toluene, ethyl styrene, vinyl toluene,
tert-butyl styrene, monochloro styrene, dichloro styrene, vinyl
benzyl chloride, fluorostyrene, and alkoxystyrenes (e.g.,
paramethoxy styrene). Also, toluene, xylene, chlorobenzene,
chloroform, tetrahydrofuran, ethyl acetate, isopropyl acetate,
butyl acetate, butyl phthalate, acetone, methyl cellosolve acetate,
cellosolve acetate, butyl cellosolve, methyl ethyl ketone, diethyl
ketone, and cyclohexanone may be used. Other monomers which may be
used include, for example, diallyl phthalate, hexyl acrylate, octyl
acrylate, octyl methacrylate, diallyl itaconate, diallyl maleate,
hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl
acrylate, hydroxypropyl methacrylate, and mixtures thereof.
[0039] Any suitable polyfunctional acrylate may be used in the
resin composition, including those described, for example, in U.S.
Pat. No. 4,916,023 to Kawabata et al., the disclosure of which is
incorporated by reference herein in its entirety. Such compounds
include ethylene glycol dimethacrylate, butanediol dimethacrylate,
hexanediol dimethacrylate, ethoxylated trimethylolpropane
triacrylate, trimethylolpropane tri(meth)acrylate,
trimethylolpropane triacrylate, trimethylolmethane
tetramethacrylate, pentaerythritol tetramethacrylate,
dipentaerythritol tetramethacrylate, dipentaerythritol
pentamethacrylate, dipentaerythritol hexamethacrylate, ethoxylated
polyhydric phenol diacrylates and dimethacrylates containing from 1
to 30 ethylene oxide units per OH group in the phenol, propoxylated
polyhyric phenol diacrylates and dimethacrylates containing from 1
to 30 propylene oxide groups per OH groups in the phenol. Examples
of some useful di-and polyhydric phenols include catechol;
resorcinol; hydroquinone; 4,4'-biphenol;
4,4'-ispropylidenebis(o-cresol); 4,4'-isopropylidenebis(2-phenyl
phenol); alkylidenediphenols such as bisphenol "A"; pyrogallol;
phloroglucinol; naphthalene diols; phenol; formaldehyde resins;
resorcinol/formaldehyde resins; and phenol/resorcinol formaldehyde
resins. Mixtures of the above di-and polyacrylates may also be
employed.
[0040] The vinyl monomers and polyfunctional acrylates may be used
in varying amounts, preferably from about 20 to 50 based on the
weight of the components which may be dissolved therein, and more
preferably from about 30 to 45 weight percent.
[0041] The method of thickening a resin may be carried out using
known equipment. Typically, for example, a resin containing active
hydrogens is placed in a vessel, mixing tank, or other reactor
along with a catalyst that will be mixed for a period lasting from
about 5 to about 20 minutes. Subsequently, a polycarbodiimide which
is present (typically dissolved) in an organic diluent is added to
the above resin and is allowed to mix therein for a period lasting
typically from about 3 to about 15 minutes. In general, the
reactive mixture of resin containing active hydrogens and
polycarbodiimide is applied to a surface of a substrate and the
resin containing active hydrogens and the polycarbodiimide become
chemically bound. An alternative way of mixing the resin containing
active hydrogens and the polycarbodiimide may be accomplished by
using a self balancing internal mix chopper system made
commercially available from Magnum Industries from Clearwater,
Fla.
[0042] The reactive mixture includes an initiator to facilitate
curing of the chemically bound resin and polycarbodiimide. The
initiator is typically added to the reactive mixture prior to the
thickening of the resin. An example of an initiator is an organic
peroxide compound. Exemplary organic peroxides that may be used
include, for example, cumene hydroperoxide; methyl ethyl ketone
peroxide; benzoyl peroxide; acetyl peroxide;
2,5-dimethylhexane-2,5-dihydroperoxide; tert-butyl peroxybenzoate;
di-tert-butyl perphthalate; dicumyl peroxide;
2,5-dimethyl-2,5-bix(tert-butylperoxide)hexane;
2,5-dimethyl-2,5-bis(tert- -butylperoxy)hexyne;
bix(tert-butylperoxyisopropyl)benzene; ditert-butyl peroxide;
1,1-di(tert-amylperoxy)-cyclohexane; 1,1-di-(tert-butylperoxy)--
3,3,5-trimethylcyclohexane; 1,1-di-(tert-butylperoxy)-cyclohexane;
2,2-di-(tert-butylperoxy)butane; n-butyl-4,4-di(tert-butylperoxy
butylperoxy)valerate; ethyl-3,3-di-(tert-amylperoxy)butyrate;
ethyl-3,3-di(tert-butylperoxy)-butyrate; t-butyl
peroxy-neodecanoate; di-(4-5-butyl-cyclohexyl)-peroxydicarbonate;
lauryl peroxyde; 2,5-dimethyl-2,5-bis(2-ethyl-hexanoyl peroxy)
hexane; t-amyl peroxy-2-ethylhexanoate;
2,2'-azobis(2-methylpropionitrile);
2,2'-azobis(2,4-methlbutanenitrile); and the like. Mixtures of any
of the above may be used. The initiator is preferably employed in
an amount from about 1 to 2.5 percent based on the weight of the
thickened resin, more preferably from about 1 to 1.5 percent by
weight, and most preferably from about 1 to 1.25 percent by
weight.
[0043] Suitable initiators used in curing the thickened resin may
also encompass photoinitiators which may be activated upon exposure
to a source of energy such as infrared, visible, or ultraviolet
radiation. Examples of suitable photoinitiators include, but are
not limited to, an aliphatic or aromatic diketone and a reducing
agent (e.g., benzil and dimethyl benzyl amine); vicinal
polyketaldonyl compounds (e.g., diacetyl benzil and benzil ketal);
a-carbonyl alcohols (e.g., benzoin); acyloin ethers (e.g., benzoin
methyl ether); polynuclear quinones (e.g., 9,10-antraquinone), and
benzophenone. Preferably, the amount of photoinitiator ranges from
about 0.005 to 5 percent based on the weight of the thickened
resin. Suitable commercial photoinitiators include those available
from Ciba-Geigy Corporation sold under the tradenames Irgacure 500,
Irgacure 369, Irgacure 1700, Darocur 4265, and Irgacure 819. It
should be appreciated that other commercial photoinitiators may be
used for the purposes of the invention.
[0044] Suitable curing accelerators or promoters may also be used
and include, for example, cobalt naphthanate, cobalt octoate,
N,N-dimethyl aniline, N,N-dimethyl acetamide, and N,Ndimethyl
p-toluidine. Mixtures of the above may be used. The curing
accelerators or promoters are preferably employed in amounts from
about 0.05 to about 1.0 percent by weight, more preferably from
about 0.1 to 0.5 percent by weight, and most preferably from about
0.1 to 0.3 percent by weight of the thickened resin.
[0045] Additional additives known by the skilled artisan may be
employed in the thickened resin composition of the present
invention including, for example, paraffins, fatty acids, fatty
acid derivatives, lubricants, and shrink-reducing additives.
Various percentages of these additives can be used in the resin
composition.
[0046] As recited herein, the invention relates to a method of
lining the surfaces of substrates. For the purposes of the
invention, the term "surfaces" is to be broadly construed and
includes, but is not limited to, those which are typically exposed
to conditions which may cause damage such as temperature
fluctuations, earth movement, and the like. The substrates may be
formed from a number of materials such as, but not limited to,
concrete, metals, polymeric composites, and mixtures thereof. Flat
and contoured surfaces may be encompassed within the scope of the
invention. In one embodiment, the invention relates to lining a
surface which forms a conduit. The term "conduit" is to be broadly
interpreted and includes, for example, pipes. One example involves
the lining of a surface which forms a conduit as described in U.S.
Pat. No. 4,009,063 to Wood, the disclosure of which is incorporated
herein by reference in its entirety.
[0047] In general, the resin may be applied to the conduit surface
using any of the known and accepted techniques. For the purposes of
the invention, the term "lining" substrate surfaces should be
construed broadly, and includes employing the resin alone or in
conjunction with other materials. For example, as illustrated in
FIG. 1, the resin may be inserted into a tube denoted by 10. The
tube depicted in this instance is defined by an outer membrane 30
and an inner membrane 40 which may contain conventional fibrous
reinforcement materials such as, but not limited to, fiberglass,
polyester, carbon, metal, high modulus organic fibers (e.g.,
aromatic polyamides, polybenzimidazoles, and aromatic polyimides),
other organic fibers (e.g., polyethylene, liquid crystals, and
nylon), and natural fibers. The tube 10 may be constructed out of
any of a number of appropriate materials known to one skilled in
the art including suitable polymeric materials, and is fabricated
by conventional methods. As discussed below, since the tube 10 is
made to conform to the shape and size of the conduit 20 as
illustrated in FIG. 2, it is desirable that the outer membrane 30
be formed from materials which possess a certain degree of
elasticity. Examples of suitable materials include, but are not
limited to, polyethylene, polyvinylchloride, rubber, cellophane
nitrate, neoprene, and polyester film. The dimensions of the tube
may be configured in a manner such that the tube fits within a
variety of conduits.
[0048] The reactive mixture may be inserted into the tube 10 using
known procedures, typically involving the impregnation of membrane
40. The insertion of the reactive mixture typically taking place
prior to placing the tube 10 in conduit 20. For example, the
reactive mixture may be pumped or injected into tube 10 through one
end or at puncture ports located at several intervals along the
tube 10. Additional materials may be present along with the
reactive mixture in tube 10. Specifically, tube 10 may include
those materials which are typically used in conjunction with resins
such as, for example, fibrous reinforcement material, woven and
nonwoven fibrous sheets or mats, fillers, fire retardants,
colorants, and the like. The selection of these materials is known
to one who is skilled in the art.
[0049] At this point, the reactive mixture is a viscous material in
tube 10, and it is allowed to thicken for 1 to 24 hours or longer
to become a gel-like substance which remains flexible. Preferably,
the process occurs between about 5.degree. C. and about 60.degree.
C., and more preferably between about 10.degree. C. and about
35.degree. C. Tube 10 remains flexible and can allow for good
control for its insertion into conduit 20.
[0050] The insertion of tube 10 into conduit 20 may be carried out
using various techniques. For example, as shown in FIG. 2, the tube
10 may be drawn into the conduit 20 and expanded or inflated by air
pressure such that it fills conduit channel 50 and conforms to the
shape of conduit 20. In another embodiment, illustrated in FIG. 3,
the tube 10 may be inverted during insertion into the conduit 20
using, for example, water pressure. As a result, the inner membrane
40 may contact the inner surface of conduit 20. Moreover, the tube
10 may be inserted by employing an approach which combines both of
the above methods. As shown in FIG. 4, a tube 10 is drawn into the
conduit 20. Next, a second tube 10' which contains a thin inner
membrane 40 is inverted into the first tube 10 which is drawn into
conduit 20 as described herein above.
[0051] The curing of the thickened resin which is present in tube
10 contained in conduit 20 may occur using known techniques. For
example, hot air, hot water, or other means such as electricity,
radiation, and the like may be employed. The temperature under
Which the curing takes place preferably ranges from about
40.degree. C. to about 150.degree. C. The cured crosslinked resin
material serves to line the conduit 20. In addition to the tube
described above, it should be noted that other tubes, membranes,
and the like may be utilized in conjunction with tube 10 to form a
multi-layer composite liner structure within conduit 20.
[0052] The following examples are provided to illustrate the
present invention, and should not be construed as limiting
thereof.
EXAMPLES 1-20
Polycarbodiimide Preparation Using a Neat Preparation
[0053] Examples 1-20 represent polycarbodiimides prepared by using
a neat preparation which is described herein below. Table 1 lists
the compositions for the polycarbodiimides.
[0054] Toluene diisocyanate is placed in a reactor and n-butanol is
added at a rate to maintain the reaction temperature below
120.degree. C. The temperature is then increased to 120.degree. C.
and maintained for thirty minutes to complete the first step of the
reaction. Next, a carbodiimide forming catalyst,
3-methyl-1-phenyl-2-phospholene-1-oxide, is added and the reaction
is continued at 140.degree. C. to complete the second step of the
reaction. Once a small amount of unreacted isocyanate groups
remain, as detected by infrared spectroscopy, a second charge of
n-butanol is added to the reaction mixture. After 15 to 60 minutes,
when no unreacted isocyanate groups are detected, the temperature
is decreased to 100.degree. C. Styrene containing an inhibitor is
then added. The reaction is cooled continuously until room
temperature is reached, thus completing the reaction.
[0055] Table 2 describes the resulting molecular weights (Mn and
Mw) and polydispersity (D) for these examples as measured by gel
permeation chromatography. Also listed are the viscosities
determined by a Brookfield viscometer (LVF #3 spindle at 30 rpm)
and percent solids.
EXAMPLES 21 THROUGH 27
Polycarbodiimide Preparation in the Presence of Styrene
[0056] Examples 21-27 are polycarbodiimides which are prepared in
the presence of styrene. Specifically, toluene diisocyanate,
styrene, and p-benzoquinone are placed in a reactor, and n-butanol
is added at a rate to maintain a reaction temperature below
120.degree. C. The temperature is then increased to 120.degree. C.
and maintained for thirty minutes to complete the first step of the
reaction. Next, a carbodiimide forming catalyst,
3-methyl-1-phenyl-2-phospholene-1-oxide, is added and the reaction
is continued at 140.degree. C. to complete the second step of the
reaction. Once a small amount of unreacted isocyanate groups
remain, as detected by infrared spectroscopy, a second charge of
n-butanol is added to the reaction. After 15 to 60 minutes, when no
more unreacted isocyanate groups are detected, the temperature is
decreased to 100.degree. C. and additional styrene is added to the
reaction. The reaction is cooled continuously until room
temperature is reached, and thus completing the reaction.
[0057] Table 3 describes the resulting molecular weights (Mn and
Mw) and polydispersity (D) as measured by gel permeation
chromatography. Also listed are the viscosities determined by a
Brookfield viscometer (LVF #3 spindle at 30 rpm) and percent
solids.
[0058] Resins Thickened Using Polycarbodiimides
[0059] Described below are resins which have been thickened using
the polycarbodiimides referred to above. All resins are available
from Reichhold Chemicals, Inc., Durham, N.C.
[0060] The resins are as follows. DION.RTM. 6694 is a corrosion
resistant modified bisphenol fumarate. Polylite.RTM. 31612 types
are unsaturated polyesters containing propylene glycol and maleic
anhydride. Polylite.RTM. 31013-00 contains
2-methyl-1,3-propanediol, ethylene glycol, terephthalic acid, and
maleic anhydride. Polylite.RTM. 31830-00 is an unsaturated
polyester containing diethylene glycol, adipic acid, isophthalic
acid and maleic anhydride. Polylite.RTM. 31506-00 is an unsaturated
polyester containing propylene glycol, isophthalic acid,
terephthalic acid, and maleic anhydride.
[0061] The following catalysts are used in the curing process.
Superox.RTM. 46744 is a pourable, pumpable BPO dispersion available
from Reichhold Chemicals, Inc., Durham, N.C. Trigonox.RTM. 21 is a
t-butyl peroxy-2-ethylhexanoate catalyst available from Akzo
Chemicals, Inc., Chicago, Ill.
[0062] The procedure for thickening a resin begins by placing an
unsaturated polyester in a container and mixing a catalyst with the
resin for five to ten minutes. The polycarbodiimide is then added
and mixed for one minute. The percentage of polycarbodiimide used
can be varied to achieve the desired viscosity at the required time
interval. Viscosities in the following tables are measured with a
Brookfield viscometer RVF#4 at 10 rpm if the reported viscosity is
below 20,000 cps and with a Brookfield viscometer HBT TC spindle at
1 rpm for viscosities exceeding 20,000 cps.
[0063] Description of Data
[0064] Table 4 illustrates the chemical thickening profile of
DION.RTM. 6694 using the polycarbodiimide described in Example 18.
A general procedure to line a pipe is described below. FIGS. 1 and
3 illustrate the lining of the pipe. In one embodiment, unsaturated
polyester resin Don.RTM. 6694 is mixed with Superox.RTM. 46744 for
about 10 minutes and then the polycarbodiimide described in Example
18 is added in the amount described in Table 4. The reactive
mixture is pumped into tube 10 through one end or at several
puncture ports located along tube 10. The reactive mixture is
allowed to thicken for 24 hours at room temperature to become a
gel-like substance that remains flexible to allow for good control
during insertion into conduit 20. As shown in FIG. 3, tube 10 is
inverted during insertion into conduit 20 by using water pressure.
As a result, inner membrane 40 is forced inside-out and contacts
the inner surface of conduit 20. After inversion of tube 10, one of
the ends is sealed so that water remains in the inner portion of
the tube. The temperature of the water is then gradually increased
to about 90.degree. C. for about 1 to about 4 hours. At the end of
this period, the impregnated tube 10 becomes a hardened material
lining conduit 20.
[0065] Table 5 illustrates the chemical thickening profiles of
Polylite.RTM. 31612 types using two different polycarbodiimide
concentrations: (1) 8 weight percent of Example 10 and (2) 10
weight percent of Example 26. Table 6 illustrates the chemical
thickening profiles of Polylite.RTM. 31013-000 at two different
polycarbodiimide concentrations: (1) 8 weight percent of Example 3
and (2) 10 weight percent of Example 9. Table 7 illustrates the
chemical thickening profiles for Polylite.RTM. 31013-00 and
Polylite.RTM. 31830-00 blend, 75/25 weight percent respectively,
using 8 weight percent of polycarbodiimides prepared in (1) Example
10 and (2) Example 18.
[0066] Table 8 illustrates two hour chemical thickening profiles
using Polylite.RTM. 31506-00 with polycarbodiimides described in
Examples 3, 4, 6, and 7. Table 9 illustrates chemical thickening
profiles using Polylite.RTM. 31506-00 with polycarbodiimides
described in Examples 3, 4, 5, 8, 9, 16, 17, 19, and 20. Table 10
illustrates chemical thickening profiles for Polylite.RTM. 31506-00
containing styrene-prepared polycarbodiimides described in Examples
21 and 25. Table 11 illustrates the effect of polycarbodiimide
concentration on the chemical thickening profile using
Polylite.RTM. 31506-00 with the polycarbodiimide prepared in
Example 9. Table 12 illustrates batch-to-batch variation with
polycarbodiimides prepared in Examples 7 and 18 and two batches of
Polylite.RTM. 31506-00: A and B. Table 13 details the effect of
temperature on the chemical thickening profile of Polylite.RTM.
31506-00 and the polycarbodiiumide prepared in Example 8.
[0067] Comparison of Chemical Thickening Processes
[0068] Table 14 compares four different chemical thickening
systems. The polycarbodiimide system according to the invention was
prepared by mixing 2 g of Superox.RTM. 46744 with 180 g of
Polylite.RTM. 31612-10 for two minutes. The polycarbodiimide
prepared in Example 18 was then added in the amount of 20 g and
mixed for one minute.
[0069] A magnesium oxide system was prepared by mixing 2 g of
Superox.RTM. 46744 with 200 g Polylite.RTM. 31612-10 for two
minutes. Maglite D.RTM. (C. P. Hall Company, Chicago, Ill.) in the
amount of 8 g was then added and mixed for one minute.
[0070] A combination magnesium oxide and polycarbodiimide system
was prepared by mixing 2 g of Superox.RTM. 46744 with 190 g of
Polylite.RTM. 31612-10 for two minutes. Maglite D.RTM. was then
added in the amount of 6 g as well as 10 g of Example 18. The
material was mixed for one minute.
[0071] A Rubinate M.RTM. (ICI, Sterling Heights, Mich.) system was
made by mixing 2 g of Superox.RTM. 46744 with 200 g of
Polylite.RTM. 31612-10 for two minutes. Rubinate M.RTM. in the
amount of 10 g and 1 g of dibutyl tin dilaurate were added and
mixed for one minute.
1TABLE 1 General Polycarbodiimide Production Total Charge Weight
Percent Raw Material Neat Preparation Sytrene Preparation Toluene
diisocyanate 48.78 48.78 Styrene 0 20.00 p-benzoquinone
0.0112-0.0300 0.0300 n-butanol 13.835 13.835 Phospholene oxide*
0.03-0.05 0.03-0.05 Sytrene 37.31-37.34 17.31-17.33
*3-methyl-1-phenyl-2-ph- ospholene-1-oxide
[0072]
2TBALE 2 Polycarbodiimide Production Neat Preparation Physical
Molecular Properties n-Butanol Charge Weight Data Viscosi- Percent
Percent Percent Example Mn Mw D ty cps Solids 1.sup.st Add 2.sup.nd
Add 1 1570 23600 15 260 58.1 86.7 13.3 2 1650 30300 18 310 57.6
86.7 13.3 3 1460 14400 10 364 57.1 86.7 13.3 4 1440 13100 9 324
57.5 86.7 13.3 5 1430 10500 7.4 204 56.2 86.7 13.3 6 1370 11500 8.4
420 57.4 95 5 7 1210 7240 6.0 224 57.2 97.5 2.5 8 1110 4280 3.8 180
58.6 98.5 1.5 9 1210 5780 4.8 228 59.2 97.5 2.5 10 1500 9200 6.1
320 59.2 97.5 2.5 11 1270 6310 5 328 59.6 97.5 2.5 12 1290 5960 4.6
284 59.5 97.5 2.5 13 1210 5070 4.2 260 59.8 97.5 2.5 14 1210 5040
4.2 280 59.2 97.5 2.5 15 1170 4370 3.7 240 59.5 97.5 2.5 16* 1190
5040 4.2 380 59.4 97.5 2.5 17 1420 9420 6.6 480 59.4 97.5 2.5 18
1440 9230 6.4 560 59.2 97.5 2.5 19 1200 4680 3.9 344 58.5 97.5 2.5
20 1200 5800 4.8 440 58.6 97.5 2.5 *Example 16 is a composite of
Examples 11 through 15.
[0073]
3TABLE 3 Polycarbodiimide Production Styrene Preparation Physical
Molecular Properties n-Butanol Charge Weight Data Viscosi- Percent
Percent Percent Example Mn Mw D ty cps Solids 1.sup.st Add 2.sup.nd
Add 21 1170 4630 3.9 268 60.2 90 10 22 1350 10400 7.7 344 61.6 90
10 23 1470 14500 9.9 400 61.4 90 10 24 1530 15600 10 432 60.4 90 10
25 1230 5490 4.5 392 60.9 100 0 26 1100 5620 5.1 336 59.8 98.5 1.5
27 1140 5640 5 480 61.3 98 2
[0074]
4TABLE 4 Chemical Thickening Profile DION .RTM. 6694 Blend
Component Weight Percent 6694 92 Example 18 8 Superox .RTM. 46744 1
g/100 g mix Viscosity Time from Mixing Minutes cps 0 1000 15 1660
30 3120 45 6640 60 14400 90 1.44 .times. 10.sup.6 120 2.08 .times.
10.sup.6 24 hours 3.86 .times. 10.sup.6 Gel Time Data Gel time at
90.degree. C. 29.5 min Peak exotherm 205.7.degree. C. Total time to
peak 47.4 min
[0075]
5TABLE 5 Chemical Thickening Profiles Polylite .RTM. 31612 Types
Blend Component Weight Percent 31612-10 92 Example 10 8 Trigonox
.RTM. 21 1 g/100 g mix Viscosity Time from Mixing Minutes cps 0
1200 15 2150 30 3300 45 4600 60 5700 90 7700 120 9100 150 10400 180
10800 24 hours 13140 Gel Time Data Gel time at 90.degree. C. 6.8
min Peak exotherm 221.0.degree. C. Total time to peak 9.0 min Blend
Component Weight Percent 31612-25 90 Example 26 10 Viscosity Time
from Mixing Minutes cps 0 3600 2 4480 4 5240 6 6310 8 7770 10 9620
15 19400 20 30000 25 70000 45 6.44 .times. 10.sup.6 120 6.72
.times. 10.sup.6
[0076]
6TABLE 6 Chemical Thickening Profiles Polylite .RTM. 31013-00 Blend
Component Weight Percent 31013-00 69 Styrene 23 Example 3 8
Viscosity Time from Mixing Minutes cps 0 500 2 540 4 600 6 660 8
720 10 800 15 1000 20 1200 25 1440 30 1640 45 2420 60 3280 70 3880
80 4500 90 5280 100 5940 110 6500 120 6920 270 12320 360 15660
Blend Component Weight Percent 31013-00 67.5 Styrene 22.5 Example 9
10 Viscosity Time from Mixing Minutes cps 0 740 15 1200 30 2000 45
2880 60 4560 90 8040 120 14300 20 hours 1.96 .times. 10.sup.6
[0077]
7TABLE 7 Chemical Thickening Profiles Polylite .RTM. 31013-00 and
Polylite .RTM. 31830-00 Blend Blend Component Weight Percent
31013-00 69 31830-00 23 Example 10 8 Trigonox .RTM. 21 1 g/100 g
mix Viscosity Time from Mixing Minutes cps 0 760 15 1100 30 1500 45
1960 60 2480 90 3340 120 4160 24 hours 8540 Gel Time Data Gel Time
at 90.degree. C. 6.3 min Peak exotherm 236.7.degree. C. Total time
to peak 15.7 min Blend Component Weight Percent 31013-00 69
31830-00 23 Example 18 8 Viscosity Time from Mixing Minutes cps 0
980 15 1540 30 2260 45 3280 60 4060 90 5580 120 6860 24 hours
13200
[0078]
8TABLE 8 Chemical Thickening Profiles Polylite .RTM. 31506-00
Weight Weight Weight Weight Blend Component Percent Percent Percent
Percent 31506-00 92 92 92 92 Polycarbodiimide 8 8 8 8
Polycarbodiimide Example 3 Example 4 Example 6 Example 7 Time from
Mixing Viscosity Viscosity Viscosity Viscosity Minutes cps cps cps
cps 0 900 850 700 700 2 980 920 800 800 4 1080 1020 850 800 6 1160
1060 900 800 8 1260 1200 1000 825 10 1360 1300 1000 850 15 1700
1600 1150 1100 20 2240 2120 1350 1200 25 3080 2600 1600 1400 30
4280 3450 18000 1600 40 7020 6300 -- -- 45 -- -- 300 2400 50 240000
50000 -- -- 60 1.12 .times. 10.sup.6 1.44 .times. 10.sup.6 5150
3650 70 1.96 .times. 10.sup.6 2.16 .times. 10.sup.6 7400 4800 80
2.48 .times. 10.sup.6 2.60 .times. 10.sup.6 10950 7200 90 3.08
.times. 10.sup.6 2.92 .times. 10.sup.6 >100000 8600 120 4.40
.times. 10.sup.6 4.12 .times. 10.sup.6 -- --
[0079]
9TABLE 9 Chemical Thickening Profiles Polylite .RTM. 31506-00
Weight Weight Weight Weight Weight Blend Component Percent Percent
Percent Percent Percent 31506-00 92 92 92 92 92 Polycarbodiimide 8
8 8 8 8 Polycarbodiimide Example 3 Example 4 Example 5 Example 8
Example 9 Time from Mixing Viscosity Viscosity Viscosity Viscosity
Viscosity Minutes cps cps cps cps cps 0 -- -- -- 700 700 15 1640
1686 1608 1080 1060 30 10 3390 2780 1760 1640 45 -- -- -- 2560 2620
60 100000 1.34 .times. 10.sup.6 42400 3660 4020 75 -- -- -- 5940
5800 90 2.40 .times. 10.sup.6 4.00 .times. 10.sup.6 2.40 .times.
10.sup.6 8720 11560 120 -- -- -- 40000 120000 150 4.00 .times.
10.sup.6 5.20 .times. 10.sup.6 4.08 .times. 10.sup.6 1.28 .times.
10.sup.6 1.80 .times. 10.sup.6 24 Hours 6.70 .times. 10.sup.6 6.20
.times. 10.sup.6 8.60 .times. 10.sup.6 4.84 .times. 10.sup.6 5.52
.times. 10.sup.6 Weight Weight Weight Weight Blend Component
Percent Percent Percent Percent 31506-00 92 92 92 92
Polycarbodiimide 8 8 8 8 Polycarbodiimide Example 16 Example 17
Example 19 Example 20 Time from Mixing Viscosity Viscosity
Viscosity Viscosity Minutes cps cps cps cps 0 780 720 750 700 15
1000 1040 1000 1000 30 1260 1460 1400 1500 45 1740 1940 1900 2000
60 2200 2600 2450 2800 90 3280 4320 4200 4100 120 4600 6300 5500
4800 150 -- 10780 -- -- 24 Hours 1.00 .times. 10.sup.6 1.48 .times.
10.sup.6 2.40 .times. 10.sup.6 2.88 .times. 10.sup.6
[0080]
10TABLE 10 Chemical Thickening Profiles: Styrene Preparations
Polylite .RTM. 31506-00 Blend Component Weight Percent Weight
Percent 31506-0 92 92 Polycarbodiimide 8 8 Polycarbodiimide Example
21 Example 25 Time from Mixing Minutes Viscosity cps Viscosity cps
0 760 860 2 840 900 4 880 940 6 920 980 8 1000 1020 10 1060 1060 15
1300 1200 20 1600 1380 25 1860 1520 30 2500 1720 45 4780 2460 60
12800 3240 70 0.48 .times. 10.sup.6 4740 80 2.84 .times. 10.sup.6
5620 90 4.16 .times. 10.sup.6 7540 120 -- 16000 240 6.64 .times.
10.sup.6 -- 24 Hours -- 3.76 .times. 10.sup.6
[0081]
11TABLE 11 Chemical Thickening Profiles: Effect of Polycarbodiimide
Concentration Weight Weight Weight Weight Blend Component Percent
Percent Percent Percent 31506-00 96 95 94 93 Example 9 4 5 6 7 Time
from Mixing Viscosity Viscosity Viscosity Viscosity Minutes cps cps
cps cps 0 700 640 660 700 15 900 940 1120 1300 30 1200 1440 2100
3000 45 1600 2420 4360 120000 60 1900 3440 -- 880000 90 2800 8260
1.12 .times. 10.sup.6 1.52 .times. 10.sup.6 120 3800 80000 1.24
.times. 10.sup.6 1.84 .times. 10.sup.6
[0082]
12TABLE 12 Chemical Thickening Profiles Batch to Batch Variation
Weight Weight Weight Weight Blend Component Percent Percent Percent
Percent 31506-00 92 92 92 92 Polycarbodiimide 8 8 8 8 Example 7
Example 18 31506-00 Batch A B A B Times from Mixing Viscosity
Viscosity Viscosity Viscosity Minutes cps cps cps cps 0 800 1400
700 1560 15 1100 2150 1000 2880 30 1640 3550 1300 5460 45 2460 5600
1900 10240 60 4120 9600 2500 20000 90 8020 80000 3900 2.04 .times.
10.sup.6 120 120000 2.04 .times. 10.sup.6 5800 3.28 .times.
10.sup.6 150 1.24 .times. 10.sup.6 -- 8200 -- 24 hours 4.96 .times.
10.sup.6 3.00 .times. 10.sup.6 3.44 .times. 10.sup.6 3.60 .times.
10.sup.6
[0083]
13TABLE 13 Chemical Thickening Profiles - Effect of Temperature
Weight Weight Weight Blend Component Percent Percent Percent
31506-00 92 92 92 Example 8 8 8 8 Viscosity Viscosity Viscosity cps
cps cps Time from Mixing minutes 50.degree. F. 77.degree. F.
90.degree. F. 0 600 600 600 15 1300 900 920 30 1700 1300 1400 45
2100 1900 2000 60 2600 2600 3700 90 3100 4000 6200 120 3800 5800
13600 150 4900 8600 80000 24 hours 1.16 .times. 10.sup.6 1.14
.times. 10.sup.6 0.68 .times. 10.sup.6
[0084]
14TABLE 14 Comparison of Chemical Thickening Processes Weight
Weight Weight Weight Blend Component Percent Percent Percent
Percent 31612-10 90 100 95 100 Example 18 10 -- 5 -- Maglite D -- 4
g/100 g 3 g/100 g -- resin mix Rubinate M -- -- -- 5 g/100 g resin
Dibutyl tin -- -- -- 0.5 g/100 g dilaurate resin Superox .RTM.
46744 1 g/100 g 1 g/100 g 1 g/100 g 1 g/100 g mix resin mix Time
from Mixing Viscosity Viscosity Viscosity Viscosity Minutes Cps Cps
Cps Cps 0 800 1140 900 620 15 1200 1140 1800 740 30 2400 1200 2500
980 45 4600 1200 3100 1300 60 5700 1460 41000 1920 60 5700 1460
4000 1920 90 7700 2480 6300 3720 120 9100 5200 10400 8380 24 hours
4.22 .times. 10.sup.6 3.84 .times. 10.sup.6 3.20 .times. 10.sup.6
7.60 .times. 10.sup.6 Gel Time Data Gel time at 90.degree. C. 18.1
min 14.6 min 13.2 min 15.0 min Peak exotherm 215.9.degree. C.
238.5.degree. C. 226.4.degree. C. 200.8.degree. C. Total time to
27.8 min 19.5 min 18.0 min 22.0 min peak
[0085] The invention has been described in detail with reference to
its preferred embodiments and its examples. However, it will be
apparent that numerous variations and modifications can be made
without departure from the spirit and scope of the invention as
described in the foregoing specification and claims.
* * * * *