# Patent

## Title
Oxirane (ethylene oxide) polyurethane coatings

## Abstract

The present invention relates to hydrophilic, i.e., water loving coatings (hereafter referred to as “WLC”). Polyurethane epoxy alkylene oxide coatings usable as coatings on for example, medical devices are a preferred WLC.

## Background
BACKGROUND OF THE INVENTION
Hydrophilic, i.e., water loving coatings (hereafter referred to as “WLC”) are a utilitarian chemistry that may be used for hydrophilic and hydrophobic polyurethane epoxies as a replacement of isocyanate-based coatings on, for example, medical devices. WLC chemistry is attractive since prior art isocyanates-based coating compositions and coatings that may be used present possible health concerns. Another concern, with isocyanates, is the isocyanate sensitivity to water which reacts therewith to evolve carbon dioxide. That side reaction produces a very rough coating due to micro roughness when carbon dioxide exits the coating forming small pin holes. However, once the isocyanate is end capped to form polyurethane epoxy (glycidyl carbamate) in accordance with this invention, reactions with water and off gassing are no longer a concern and health concerns are significantly reduced. The use of WLC chemistry, in medical devices, and other coating areas, is thusly very attractive particularly for medical device applications.
SUMMARY OF THE INVENTION
WLC synthesis reactions can be optimized generally by running at lower temperatures which tends to reduce side reactions. Reaction order is also a very important consideration in WLC development. In the case of oxirane polyurethane-based WLC's the methylenebisdiisocyanate (MDI) should be either a liquid or a melted solid before polyol additions and that adipic acid dihydrazide is fully reacted before adding dibutyltin dilaurate catalyst and glycidol. Adding glycidol too early may result in amine reactions with glycidol, and addition of catalyst too early may alter the chain extending network and form a less desirable coating. WLC glycidyl(oxirane functionality) termination has shown an increase in coating adhesive and cohesive strength.




In the above formulae:

“n1”, relating to PEO, falls in the range of about 500 to about 45,000 or higher;

“n2”, relating to polyTHF, falls in the range of about 3 to about 600 or higher;

“n3”, relating to PDEGA, falls in the range of about 2 to about 60,000 or higher; and

“n4” is lower alkylene, n4 falling in the range of 1 to about 4.

Note that the n4 alkylene group optionally couples other isocyanate moieties as is noted below.

    1. Glycidol, PEO (polyethylene oxide), dimethylol propionic acid (DMPA), polytetrahydrofuran (polyTHF), and poly[di(ethylene glycol)adipate] (PDEGA hydroxyl) can react with methylenebisdiisocyanate for chain extension.
    2. Adipic acid dihydrazide (AAD) reacts with isocyanate for chain extension.
    3. End group is terminated with glycidol for glycidyl functionality.
    4. Reaction kinetics are faster with an aromatic group next to isocyanate.
    
        The monomers and oligomers (including the genericized polymer constituents) and synthetic route noted about was used to produce coatings/compositions of this invention.
    
    


Side reaction free reaction scheme to terminate with epoxy end groups and minimize side reactions.
The terminal oxirane polyurethane chemistry coatings of this invention primary reactions that make up the polyurethane coatings of this invention are listed below:
1. Terminal Oxirane Polyurethane Reactive Coating Compositions are an extremely lubricious durable coating that contains both hard and soft segments. This structure contains polyurethane and epoxy groups. This is a modified aqueous and solvent soluble material to increase physical crosslinks via hydrogen bonding. This structure relies on physical crosslinks for strength through hard segment domains. The hard segments contain aromatic groups, which also stack by pi-bond interactions. “Hard segments” as the term is used herein means substantially crystalline.




2. Terminal a Composition Comprising Epoxy Urethane Ester Carboxylic Acid Alkylene Oxide Reactive Coating Compositions
This example describes the preparation of an inventive water-loving coating (WLC) Epoxy urethane ester carboxylic acid alkylene oxide reactive coating compositions. A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 16.8 g of methylenebisdiisocyanate (MDI)>99.0% was charged to the reactor. The temperature was held at 40 degree C. for 40 minutes for solid softening. Next, 62.5 g of Poly[di(ethylene glycol)adipate] average Mn ̃2,500, 72.5 g of Poly(tetrahydrofuran) average Mn ̃2,900, and 3.35 g of 2,2-Bis(hydroxymethyl)propionic acid 98% was added, in the following order and homogenized by stirring for 5 minutes at 40.degree. C. To this homogenized mixture 150 grams of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 40 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40 degrees C. for one hour. After one hour 3.7 grams glycidol were added and the temperature was held overnight until reaction completion.




3. Terminal Oxirane Polyurethane Urea Chain Extender/(No Addition of Water).
Reactive Coating Compositions are an extremely lubricious durable coating that contains both hard and soft segments. The structure contains polyurethane, urea and epoxy groups. This is a modified aqueous and solvent soluble material that employs urea formation to increase physical crosslinks via hydrogen bonding. Carboxylic acid functionality in the polymer backbone and glycidol end groups add crosslinking. The epoxy end groups help with adhesion and cohesive strength. This structure relies on crosslinks much like the polyurethane epoxy but contains a chain extender based off adipic acid dihydrazide.




4. Terminal Oxirane Polyurethane Urea Chain Extender/(Water Excess).
Reactive Coating Compositions are an extremely lubricious durable coating that contains both hard and soft segments i.e., crystalline and amorphous segments. This structure contains polyurethane, urea and epoxy groups. This is a modified aqueous and solvent soluble material employs urea formation to increase physical crosslinks via hydrogen bonding. Carboxylic acid functionality in the polymer backbone and glycidol end groups add crosslinking, the reaction of isocyanate forms an unstable carbamic acid that forms an amine. The amine quickly reacts with isocyanate functionality to form a urea.
Water functionality reacts with excess MDI isocyanate to release CO2 and form an amine. The amine functionality reacts with excess isocyanate to form additional urea linkages. The water/amine reaction is highly, physically crosslink the system and enhance its mechanical properties. The active hydrogen of the secondary amine can further react with excess isocyanate to slightly crosslink the system. The combination of urea, and polyurethane hard segments and glycidol functionalities lead to a superior crosslinking system.




Water reactions with isocyanate to form urea

5. Terminal Oxirane Polyurethane Amide/Amide Urea/(No Addition of Water).
Reactive Coating Compositions are an extremely lubricious durable coating that contains both hard and soft segments. This is structure contains polyurethane, urea, amide (amide to form urea) and epoxy groups. This is a modified aqueous and solvent soluble material employs amide formation that may undergo additional reactions to form urea. Urea and hard segments yield an increase in hydrogen bonding for physical crosslinks, carboxylic acid functionality in the polymer backbone and glycidol end groups add crosslinking. Amide functionality can continue to react with isocyanate to form urea. This crosslinking system helps increase durability of the basecoat.
Isocyanate Reaction with Amide to Form Crosslinked Urea
For example, DMPA was used to construct the polymer backbone for the introducing carboxylic acid functionality. This functionality reacts with excess MDI isocyanate around 80 C to form an amide bond. The amide reaction is to slightly cross-link the system and increase its mechanical properties. The active hydrogen of the amide functionally can further react with excess isocyanate to form urea. The combination of amide, urea, and polyurethane hard segments and glycidol functionalities lead to a superior crosslinking system.







Isocyanate Reaction with Amide to Form Crosslinked Urea

Examples 46-48 illustrate this aspect of the invention.

For example, DMPA was used to construct the polymer backbone for the introducing carboxylic acid functionality. This functionality reacts with excess MDI isocyanate around 80 C to form an amide bond. The amide reaction is to slightly crosslink the system and increase mechanical properties. The active hydrogen of amide can further react with excess isocyanate to form urea. The combination of amide, urea, and polyurethane hard segments and glycidol functionalities lead to a superior crosslinking system.
The following references, patents, and patent applications are incorporated by reference herein in their entireties.













5,576,072
Hostettler et al., Process for producing slippery,



tenaciously adhering hydrogel coatings . . .


4,990,357
Karakelle et al., Elastomeric segmented hydrophilic



polyetherurethane. based lubricious coatings


6,706,025
Engelson et al., Lubricous catheters


7,776,956
Webster et al., Elastomeric segmented hydrophilic



polyurethane based coatings


4,119,094
Micklus et al., Coated substrate having a low coefficient



of friction hydrophilic coating and a method of making



the same


4,495,229
Wolf et al., One component heat curing polyurethane



coatings . . .


4,638,017
Larson et al., Hydrophilic polyurethane polyuria sponge


4,713,448
Balazs et al., Chemically modified hyaluronic acid



preparation . . .


5,041,100
Rowland et al., Catheter and hydrophilic friction-reducing



coating thereon


5,749,837
Palermo et al., Enhanced lubricity guidewire


5,912,314
Wolf, Reaction product of mixed uretdiones and a



disecondary diamine


5,919,570
Hostettler et al., Slippery, tenaciously adhering hydrogel



coatings . . .


7,193,011
Kim et al., Method of preparing water dispersible 



poly(urethane urea) having aromatic-alphatic isocyanate


7,226,972
Zhao et al., Process for crosslinking hyaluronic acid to



polymers


7,652,166
Haubennestel et al., Biuret compounds . . .


5,104,930
Rinde et al., Polyurea gel compositions . . .


5,175,229
Braatz et al., Biocompatible polyuria urethane hydrated



polymers


5,576,072
Hostettler et al., Medical device having hydrophilic



coatings . . .


5,688,855
Stoy et al., Thin film hydrophilic coatings


5,776,611
Elton et al., Crosslinked hydrogel coatings


20110015724
Kocher et al., Medical device having hydrophilic coatings


20110021657
Kocher, Hydrophilic polyurethane solutions


20110021696
Kocher et al., Hydrophilic polyurethane dispersions









Also, specifically incorporated by reference herein in its entirety is applicant's in concurrently filed patent application Ser. No. 13/834,810, entitled “Modified Hyaluronate Hydrophilic Compositions, Coatings and Methods.”


DETAILED DESCRIPTION
Examples of Composition 1
Example 1
This example describes the preparation of an inventive water loving coating (WLC) glycidyl carbamate dispersion (E-1). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 9.375 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 4.925 g of Poly[di(ethylene glycol)adipate] average Mn ̃500, 27.25 g of Poly(tetrahydrofuran) average Mn ̃2,900, was added, in the following order and homogenized by stirring for 5 minutes at 40° C. To this homogenized mixture 53.57 g of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 100 g of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 40 minutes. One drop Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40° C. for one hour. After one hour 2.8 grams glycidol were added and the temperature was held overnight until reaction completion.















eg.



Example 1 (E-1)
grams
Wt
moles


















4,4′-Methylenebis(phenyl isocyanate)
9.375
125
0.075


Poly [di(ethylene glycol)
4.925
250
0.0197


adipate] average Mn ~500





Poly(tetrahydrofuran) average Mn ~2,900
27.25
1450
0.018793


Poly (ethylene oxide) average Mv 100,000
53.57
50000
0.001071


glycidol
2.8
74
0.037838





0.077402









Example 2
This example describes the preparation of an inventive water loving coating (WLC) glycidyl carbamate dispersion (E-2). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 4.787 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 27.423 g of Poly(tetrahydrofuran) average Mn ̃2,900, was added, in the following order and homogenized by stirring for 5 minutes at 40° C. To this homogenized mixture 53.57 g of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 50 g of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 40 minutes. One drop of Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40° C. for one hour. After one hour 1.8 grams glycidol were added and the temperature was held overnight until reaction completion.















eg.



Example 2 (E-2)
grams
Wt
moles


















4,4′-Methylenebis(phenyl isocyanate)
4.787
125
0.038296


Poly(tetrahydrofuran) average Mn ~2,900
27.423
1450
0.018912


Poly (ethylene oxide) average Mv 100,000
53.57
50000
0.001071


glycidol
1.8
74
0.024324





1.044308









Example 3
This example describes the preparation of an inventive water loving coating (WLC) glycidyl carbamate dispersion (E-3). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 18.964 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 109.99 g of Poly(tetrahydrofuran) average Mn ̃2,900 was added and homogenized by stirring for 45 minutes at 40° C. To this homogenized mixture of 290 g of 1-Methyl-2-pyrrolidinone anhydrous, 99.5% was added. The solution homogenized by mixing thoroughly for 40 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40° C. for one hour. After one hour 5.5051 grams glycidol were added and the temperature was held overnight until reaction completion.













Example 3 (E-3)
grams
eg. Wt
moles


















4,4′-Methylenebis(phenyl isocyanate)
19.694
125
0.157552


Poly(tetrahydrofuran) average Mn ~2,900
109.99
1450
0.075855


glycidol
5.5051
74
0.074393





0.150248









Example 4
This example describes the preparation of an inventive water loving coating (WLC) glycidyl carbamate dispersion (E-4). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 18.964 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 19.464 g of Poly[di(ethylene glycol)adipate] average Mn ̃2500, 47.23 g of Poly(tetrahydrofuran) average Mn ̃2,900 was added, in the following order and homogenized by stirring for 45 minutes at 40° C. To this homogenized mixture 108.28 g of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 200 g of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 250 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40° C. for one hour. After one hour 4.048 grams glycidol were added and the temperature was held overnight until reaction completion













Example 4 (E-4)
grams
eg. Wt
moles


















4,4′-Methylenebis(phenyl isocyanate)
18.964
125
0.151712


Poly [di(ethylene glycol) adipate] average
19.464
1250
0.015571


Mn ~2,500





Poly(tetrahydrofuran) average Mn ~2,900
47.23
1450
0.032572


Poly (ethylene oxide) average Mv 100,000
108.28
50000
0.002166


glycidol
4.048
74
0.054703





0.105012









Examples for Composition 2
Example 5
This example describes the preparation of an inventive water loving coating (WLC) glycidyl carbamate dispersion (E-5). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 6.562 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 14.4 g of Poly[di(ethylene glycol)adipate] average Mn ̃2,500, 16.28 g of Poly(tetrahydrofuran) average Mn ̃2,900, and 0.6903 g of 2,2-Bis(hydroxymethyl) propionic acid 98% was added, in the following order and homogenized by stirring for 5 minutes at 40° C. To this homogenized mixture 50.0 of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 100 g of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 40 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40° C. for one hour. After one hour 0.3129 grams glycidol were added then 0.0741 grams of water were added after 45 minutes and the temperature was held overnight until reaction completion.













Example 5 (E-5)
grams
eg. Wt
moles


















4,4′-Methylenebis(phenyl isocyanate)
6.562
125
0.052496


Poly [di(ethylene glycol) adipate] average
14.4
1250
0.01152


Mn ~2500





Poly(tetrahydrofuran) average Mn ~2,900
16.28
1450
0.011228


2,2-Bis(hydroxymethyl)propionic acid
0.693
67.5
0.010267


Poly (ethylene oxide) average Mv 100,000
50
50000
0.001


glycidol
0.3129
74
0.004228





0.038243









Example 6
This example describes the preparation of an inventive water loving coating (WLC) glycidyl carbamate dispersion (E-6). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 10.33 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 25.82 g of Poly[di(ethylene glycol)adipate] average Mn ̃2,500, 29.95 g of Poly(tetrahydrofuran) average Mn ̃2,900, and 1.38 g of 2,2-Bis(hydroxymethyl) propionic acid 98% was added, in the following order and homogenized by stirring for 5 minutes at 40° C. To this homogenized mixture 30.98 g of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 40 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40° C. for one hour. After one hour 1.52 grams glycidol were added and the temperature was held overnight until reaction completion.













Example 6 (E-6)
grams
eg. Wt
moles


















4,4′-Methylenebis(phenyl isocyanate)
10.33
125
0.08264


Poly [di(ethylene glycol) adipate] average
25.82
1250
0.020656


Mn ~2500





Poly(tetrahydrofuran) average Mn ~2,900
29.95
1450
0.020655


2,2-Bis(hydroxymethyl)propionic acid
1.38
67.5
0.020444


Poly (ethylene oxide) average Mv 100,000
30.98
50000
0.00062


glycidol
1.52
74
0.020541





0.082916









Example 7
This example describes the preparation of an inventive water loving coating (WLC) glycidyl carbamate dispersion (E-7). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 16.8 g of 1,6-Diisocyanatohexane>99.0% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 62.5 g of Poly[di(ethylene glycol)adipate] average Mn ̃2,500, 72.5 g of Poly(tetrahydrofuran) average Mn ̃2,900, and 3.35 g of 2,2-Bis(hydroxymethyl)propionic acid 98% was added, in the following order and homogenized by stirring for 5 minutes at 40° C. To this homogenized mixture 1-Methyl-2-pyrrolidinone anhydrous, 99.5% was added. The solution homogenized by mixing thoroughly for 40 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40° C. for one hour. After one hour 3.7 grams glycidol were added and the temperature was held overnight until reaction completion.













Example 7 (E-7)
grams
eg. Wt
moles


















1,6-Diisocyanatohexane
16.8
84
0.2


Poly [di(ethylene glycol) adipate] average
62.5
1250
0.05


Mn ~2,500





Poly(tetrahydrofuran) average Mn ~2,900
72.5
1450
0.05


2,2-Bis(hydroxymethyl)propionic acid
3.35
67.5
0.04963


Poly (ethylene oxide) average Mv 100,000
72.5
50000
0.00145


glycidol
3.7
74
0.05





0.20108









Examples for Composition 3
Example 8
This example describes the preparation of an inventive water loving coating (WLC) glycidyl carbamate dispersion (E-8). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 20.14 g of 4,4′-Methylenebis(cyclohexyl isocyanate), mixture of isomers 90% was charged to the reactor. The temperature was held at 40 degree C. for 40 minutes for solid softening. Next, 62.16 g of Poly(tetrahydrofuran) average Mn ̃2,900, and 3.061 g of 2,2-Bis(hydroxymethyl)propionic acid 98% was added, in the following order and homogenized by stirring for 5 minutes at 40° C. To this homogenized mixture 43.34 g of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 300 g of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 40 minutes. Six drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40° C. for one hour. After one hour 3.2192 g of Adipic acid dihydrazide≧98% were added and mixed for two hours. To this homogenized mixture 7.5 grams glycidol were added and the temperature was held overnight until reaction completion.















eg.



Example 8 (E-8)
Grams
Wt
moles


















of 4,4′-
20.14
131
0.153740458


Methylenebis(cyclohexyl





isocyanate)





Poly(tetrahydrofuran)
43.34
1450
0.029889655


average Mn ~2,900





2,2-Bis(hydroxy-
3.061
67.5
0.045348148


methyl)propionic





acid





Poly (ethylene oxide)
62.16
50000
0.0012432


average Mv 100,000





Adipic acid dihydrazide
3.2192
87.1
0.036959816


glycidol
7.5
74
0.101351351





0.214792171









Example 9
This example describes the preparation of an inventive water loving coating (WLC) glycidyl carbamate dispersion (E-9). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 18.964 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 134.85 g of Poly(tetrahydrofuran) average Mn ̃2,900, was added and homogenized by stirring for 40 minutes at 40° C. To this homogenized mixture 216.75 g of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 290 g of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 40 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40° C. for one hour. After one hour 1.956 g of Adipic acid dihydrazide≧98% were added and mixed for two hours. To this homogenized mixture 0.33 grams glycidol were added and the temperature was held overnight until reaction completion.















eg.



Example 9 (E-9)
grams
Wt
moles


















4,4′-Methylenebis(phenyl isocyanate)
134.85
125
1.0788


Poly (ethylene oxide) average Mv 100,000
216.75
50000
0.004335


Adipic acid dihydrazide
1.956
87.1
0.0225028


glycidol
0.33
74
0.004459


Poly(tetrahydrofuran) average Mn ~2,900
134.85
1450
0.093





0.1242968









Example 10
This example describes the preparation of an inventive water loving coating (WLC) glycidyl carbamate dispersion (E-10). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 18.964 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 33.379 g of Poly[di(ethylene glycol)adipate] average Mn ̃2,500, 47.255 g of Poly(tetrahydrofuran) average Mn ̃2,900, and 2.000 g of 2,2-Bis(hydroxymethyl)propionic acid 98% was added, in the following order and homogenized by stirring for 5 minutes at 40° C. To this homogenized mixture 216.748 g of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 40 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40° C. for one hour. After one hour 1.956 g of Adipic acid dihydrazide≧98% were added and mixed for two hours. To this homogenized mixture 0.33 grams glycidol were added and the temperature was held overnight until reaction completion













Example 10 (E-10)
grams
eg. Wt
moles


















4,4′-Methylenebis(phenyl isocyanate)
18.964
125
0.151712


Poly [di(ethylene glycol) adipate]
33.379
1250
0.0267032


average Mn 2500





Poly(tetrahydrofuran) average
47.255
1450
0.03258


Mn ~2,900,





2,2-Bis(hydroxymethyl)propionic acid
2.000 g
67.5
0.029629


Poly (ethylene oxide) average
216.748
50000
0.04335


Mv 100,000





Adipic acid dihydrazide
1.956
87.1
0.02245569


glycidol
0.33
74
0.00445





0.15916789









Example 11
This example describes the preparation of an inventive water loving coating (WLC) glycidyl carbamate dispersion (E-11). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 18.972 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 33.29 g of Poly[di(ethylene glycol)adipate] average Mn ̃2,500, 47.92 g of Poly(tetrahydro-furan) average Mn ̃2,900, and 1.994 g of 2,2-Bis(hydroxymethyl)propionic acid 98% was added, in the following order and homogenized by stirring for 5 minutes at 40° C. To this homogenized mixture 43.349 g of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 290 g of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 40 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40° C. for one hour. After one hour 1.958 g of Adipic acid dihydrazide≧98% were added and mixed for two hours. To this homogenized mixture 2.426 grams glycidol were added and the temperature was held overnight until reaction completion.













Example 11 (E-11)
grams
eg. Wt
moles


















4,4′-Methylenebis(phenyl isocyanate)
18.792
125
0.150336


Poly [di(ethylene glycol) adipate]
33.29
1250
0.026632


average Mn ~2,500





Poly(tetrahydrofuran) average
47.92
1450
0.03304828


Mn ~2,900





2,2-Bis(hydroxymethyl)propionic acid
1.994
67.5
0.02954074


Poly (ethylene oxide) average
43.349
50000
0.00086698


Mv 100,000





Adipic acid dihydrazide
1.958
87.1
0.02247991


glycidol
2.426
74
0.03278378





0.14535169









Examples for Composition 4
Example 12
This example describes the preparation of an inventive water loving coating (WLC) glycidyl carbamate dispersion (E-12). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 18.964 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 40.456 g of Poly[di(ethylene glycol)adipate] average Mn ̃2,500, 45.911 g of Poly(tetrahydrofuran) average Mn ̃2,900, and 1.939 g of 2,2-Bis(hydroxymethyl)propionic acid 98% was added, in the following order and homogenized by stirring for 5 minutes at 40° C. To this homogenized mixture 210.0 g of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 290 g of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 250 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40° C. for one hour. After one hour 1.37 g of Adipic acid dihydrazide≧98% were added and mixed for two hours. To this homogenized mixture 1.436 grams glycidol were added and the temperature was held overnight until reaction completion. The final addition involved 0.3533 grams water to form a urea.















eg.



Example 12 (E-12)
grams
Wt
moles


















4,4′-Methylenebis(phenyl isocyanate)
18.964
125
0.151712


Poly [di(ethylene glycol) adipate]
40.456
1250
0.0323648


average Mn ~2,500





Poly(tetrahydrofuran) average
45.911
1450
0.031662759


Mn ~2,900





2,2-Bis(hydroxymethyl)propionic
1.939
67.5
0.028725926


acid





Poly (ethylene oxide) average
210
50000
0.0042


Mv 100,000





Adipic acid dihydrazide
1.37
87.1
0.015729047


glycidol
1.436
74
0.019405405





0.132087937


WATER
0.3533
18
0.01963









Example 13
This example describes the preparation of an inventive water loving coating (WLC) glycidyl carbamate dispersion (E-13). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 18.964 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 33.38 g of Poly[di(ethylene glycol)adipate] average Mn ̃2500, 47.23 g of Poly(tetrahydrofuran) average Mn ̃2,900 was added, and 1.99 g of 2,2-Bis(hydroxymethyl)propionic acid 98% was added, in the following order and homogenized by stirring for 45 minutes at 40° C. To this homogenized mixture 53.57 g of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 200 g of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 250 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40° C. for one hour. After one hour 1.354 g of Adipic acid dihydrazide≧98% were added and mixed for two hours. To this homogenized mixture 2.427 grams glycidol were added and the temperature was held overnight until reaction completion. The final addition involved 0.2409 grams water to form a urea.















eg.



Example 13 (E-13)
grams
Wt
moles


















4,4′-Methylenebis(phenyl isocyanate)
18.964
125
0.151712


Poly [di(ethylene glycol) adipate]
33.38
1250
0.026704


average Mn ~2,500





Poly(tetrahydrofuran) average
47.25
1450
0.032586207


Mn ~2,900





2,2-Bis(hydroxymethyl)propionic acid
1.9999
67.5
0.029628148


Poly (ethylene oxide) average
53.57
50000
0.0010714


Mv 100,000





Adipic acid dihydrazide
1.354
87.1
0.01554535


glycidol
2.427
74
0.032797297





0.138332403


WATER
0.2409
18
0.013382









Examples for Composition 5
Example 14
This example describes the preparation of an inventive water-loving coating (WLC) glycidyl carbamate dispersion (E-14). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 18.964 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 40.457 g of Poly[di(ethylene glycol)adipate] average Mn ̃2,500, 45.911 g of Poly(tetrahydrofuran) average Mn ̃2,900, and 1.939 g of 2,2-Bis(hydroxymethyl)propionic acid 98% was added, in the following order and homogenized by stirring for 5 minutes at 40° C. To this homogenized mixture 210.71 g of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 290 g of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 40 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40° C. for one hour. After one hour 1.3789 g of Adipic acid dihydrazide≧98% were added and mixed for two hours. To this homogenized mixture 1.436 grams glycidol were added and the temperature was held overnight until reaction completion.













Example 14 (E-14) POLYURETHANE

eg.



UREA W/EXCESS NCO
grams
Wt
moles


















4,4′-Methylenebis(phenyl isocyanate)
18.964
125
0.151712


Poly [di(ethylene glycol) adipate]
40.457
1250
0.0323656


average Mn ~2,500





Poly(tetrahydrofuran) average
45.911
1450
0.031662759


Mn ~2,900





2,2-Bis(hydroxymethyl)propionic acid
1.939
67.5
0.028725926


98%





Adipic acid dihydrazide
1.3789
87.1
0.015831228


glycidol
1.436
74
0.019405405





0.127990918









Examples for the Cross-Linking Reaction
Example 15
This example describes the preparation of an inventive water loving coating (WLC) glycidyl carbamate dispersion (E-15). A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 10.33 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 25.82 g of Poly[di(ethylene glycol)adipate] average Mn ̃2,500, 29.95 g of Poly(tetrahydrofuran) average Mn ̃2,900, and 1.38 g of 2,2-Bis(hydroxymethyl) propionic acid 98% was added, in the following order and homogenized by stirring for 5 minutes at 40° C. To this homogenized mixture 30.98 g of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 40 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 60° C. for one hour for homopolymerization. After one hour 1.52 grams glycidol were added and the temperature was held for 72 hours.













Example 15 (E-15)
grams
eg. Wt
moles


















4,4′-Methylenebis(phenyl isocyanate)
8.264
125
.066112


Poly [di(ethylene glycol) adipate]
20.656
1250
.0165248


average Mn ~2500





Poly(tetrahydrofuran) average
23.96
1450
.016524


Mn ~2,900





2,2-Bis(hydroxymethyl)propionic acid
1.104
67.5
.0163552


Poly (ethylene oxide) average Mv 100,000
24.78
50000
.000496


glycidol
1.21
74
.016432





.0663328









Example 16
This example describes the preparation of an inventive water-loving coating (WLC) Epoxy urethane alkylene oxide reactive coating compositions. A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 18.964 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40 degree C. for 40 minutes for solid softening. Next, 109.99 g of Poly(tetrahydrofuran) average Mn ̃2,900 was added and homogenized by stirring for 45 minutes at 40.degree. C. To this homogenized mixture of 290 g of 1-Methyl-2-pyrrolidinone anhydrous, 99.5% was added. The solution homogenized by mixing thoroughly for 40 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40 degrees C. for one hour. After one hour 5.5051 grams glycidol were added and the temperature was held overnight until reaction completion.
Example 17
This example describes the preparation of an inventive water-loving coating (WLC) Epoxy urethane ester carboxylic acid alkylene oxide reactive coating compositions. A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 16.8 g of 1,6-Diisocyanatohexane>99.0% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 62.5 g of Poly[di(ethylene glycol)adipate] average Mn ̃2,500, 72.5 g of Poly(tetrahydrofuran) average Mn ̃2,900, and 3.35 g of 2,2-Bis(hydroxymethyl)propionic acid 98% was added, in the following order and homogenized by stirring for 5 minutes at 40° C. To this homogenized mixture 150 grams of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 40 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at ° C. for one hour. After one hour 3.7 grams glycidol were added and the temperature was held overnight until reaction completion.
Example 18
This example describes the preparation of an inventive water-loving coating (WLC) Epoxy urethane urea carboxylic acid alkylene oxide reactive coating compositions. A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 18.964 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 33.379 g of Poly[di(ethylene glycol)adipate] average Mn ̃2,500, 47.255 g of Poly(tetrahydrofuran) average Mn ̃2,900, and 2.000 g of 2,2-Bis(hydroxymethyl)propionic acid 98% was added, in the following order and homogenized by stirring for 5 minutes at 40° C. To this homogenized mixture 216.748 g of Poly(ethylene oxide) average 100,000, powder was added immediately following the addition of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 40 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40 degrees C. for one hour. After one hour 1.956 g of Adipic acid dihydrazide≧98% were added and mixed for two hours. To this homogenized mixture 0.33 grams glycidol were added and the temperature was held overnight until reaction completion.
Example 19
This example describes the preparation of an inventive water loving coating (WLC) Epoxy urethane urea carboxylic acid alkylene oxide reactive coating compositions. A 500 mL four neck reaction kettle with condenser, nitrogen inlet and model Gemini J-KEM temperature controller, mechanical stirrer, and heating mantel was used for resin synthesis. 18.964 g of 4,4′-Methylenebis(phenyl isocyanate) 98% was charged to the reactor. The temperature was held at 40° C. for 40 minutes for solid softening. Next, 40.456 g of Poly[di(ethylene glycol)adipate] average Mn ̃2,500, 45.911 g of Poly(tetrahydrofuran) average Mn ̃2,900, and 1.939 g of 2,2-Bis(hydroxymethyl)propionic acid 98% was added, in the following order and homogenized by stirring for 5 minutes at 40° C. To this homogenized mixture 210.0 g of Poly(ethylene oxide) average Mv 100,000, powder was added immediately following the addition of 290 g of 1-Methyl-2-pyrrolidinone anhydrous, 99.5%. The solution homogenized by mixing thoroughly for 250 minutes. Four drops Dibutyltin dilaurate 95% were added drop wise and the reaction mixture was held at 40 degrees C. for one hour. After one hour 1.37 g of Adipic acid dihydrazide≧98% were added and mixed for two hours. To this homogenized mixture 1.436 grams glycidol were added and the temperature was held overnight until reaction completion. The final addition involved 0.3533 grams water to form a urea.
SUMMARY OF WLC CONNECTIVITY
Basecoat terminal epoxy groups react with top coat epoxy groups through ARM amine functionality which increase adhesive strength. Basecoat chemistry contains Easaqua XM-502, which is added during the base coat mixing step. This aqueous isocyanate contains mpeg for use in water based applications. When this material is added to basecoat the isocyanate reacts with the carboxylic acid and open epoxide hydroxyl groups for basecoat cohesive strength. Easaqua XM-502 also reacts with top coat ARM and open hydroxyl groups for adhesive strength.
Once crosslinked, with Easaqua XM-502, then the base coat becomes a hydrogel. The hydrogel crosslinks take in water and swell via soft segments (Terethane, PEO and PEDGA) to render the coating water loving with high lubricity. Crosslink chemistry allows water to become retained within the walls of the soft segment without going into solution. This chemical and physical process leads to an extremely durable and lubricious coating.







WLC Oxirane Connections

A resin sample of an aqueous polyurethane polymer was submitted to NSL Analytical Laboratories on Nov. 2, 2009 for characterization of the polymer. Various Mass Spectrometry techniques were utilized in this characterization, including Electro-Spray Ionization (ESI), Matrix Assisted Laser Desorption Ionization (MALDI) and Chemical Ionization (CI). The following are abbreviations are used to describe findings:















GA
glycidol alcohol



DEG
diethylene glycol



DMPA
dimethylolpropionic acid



DEGA
diethyleneglycol adipate



MDI
methylene-diiscocyanate



PEG
polyethylene glycol



PDEGA
polydiethyleneglycol adipate









Abbreviations Used to Describe Findings

The sample was analyzed by 1H NMR with the sample dissolved in TCE. This was able to provide the monomer ratios listed below.
















MDI
1
mol



Adipic
2.875
mol



DEG
3.075
mol



PTMEG (poly THF)
11
mol of THF



PEG (i.e. PEO)
24
moles of EO



Glycidolcarbonate
0.5
mol



DMPA
0.27
mol









Monomer Ratios Determined by Proton NMR

Coating Example Composition 1

Materials as synthesized above were then applied to substrates noted below in the following fashion:
Coating Polyurethane Tungsten Loaded Jacket

    
    
        a. An aqueous and or solvent dispersion basecoat was prepared from 8.8 g of composition 1 AND 0.2 Easaqua XM-502 were then added to the formulation and stirred at 900 rpm for 15 minutes.
        b. Basecoat (of this invention) was applied to the polyurethane jacketed wire, by dip coating, at a set speed for a desired film thickness
        c. The basecoat was then cured either at ambient or thermally until no longer-tacky
        d. An aqueous dispersion topcoat was prepared with crosslinker in the following order: (1) 0.005 grams Poly(ethylene oxide), 4-arm, amine terminated average Mn ̃10,000 was added to a one ounce bottle then (2) 0.02 '956 patent. To this crosslinker 11.576 grams of modified hyaluronan top coat formulated resin was added and crosslinker was stirred at 1800 rpm for 5 minutes
        e. Topcoat of the concurrently filed application noted above was then applied at a set speed for desired film thickness
        f. The coating was then cured at ambient or thermally until fully cured
        g. The final cured product resulted in a highly lubricious coating
    
    


Coating Metal Wire Substrate with Adhesion Promoter
Preparation of Adhesion Promoter

    
    
        i. 100 mL ETOH (ETOH anhydrous) provided by Sigma
        ii. Add 5.0 gram water
        iii. Stir 10 minutes
        iv. Add 3.84 grams 3-aminopropyltriethoxysilane (Provided by Gelest)
        v. Mix 5 minutes
        a. Coating wire with adhesion promoter
        vi. Pour adhesion promoter into 100 mL burette (use shaker to mix)
        vii. Place wire in graduated cylinder solution for 10 minutes
        viii. Take wire out of solution and place in 125 C oven for 10 minutes
    
    


Polyurethane tungsten loaded jacket

    
    
        b. An aqueous and or solvent dispersion basecoat was prepared from 8.8 g of composition 1 AND 0.015 Easaqua XM-502 were then added to the formulation and stirred at 900 rpm for 15 minutes.
        c. The wire from step a-viii was taken out of the 125 C oven for coating
        d. Basecoat was applied to the metal wire substrate with adhesion promoter, by dip coating, at a set speed for a desired film thickness
        e. The basecoat was then cured either at ambient or thermally until no longer-tacky
        f. An aqueous dispersion intermediate layer was prepared with Easaqua XM-502 (0.015) crosslinker, '956 patent and adipic acid dihydrazide (0.02). To this crosslinker 8.8 grams composition 1 plus water were formulated and stirred at 1800 RPM for 5 minutes. The intermediate layer contained 0.01 TPP catalyst.
        g. Intermediate layer was then applied at a set speed for desired film thickness
        h. The intermediate layer was then cured either at ambient or thermally until no longer-tacky
        i. An aqueous dispersion topcoat was prepared with crosslinker in the following order: (1) 0.01 grams adipic acid dihydrazide was added to a one ounce bottle then (2) 0.01 grams PZ-28 To this crosslinker 11.576 grams composition 2 was added to the crosslinker, which was stirred at 1800 rpm for 5 minutes
        j. Topcoat was then applied at a set speed for desired film thickness
        k. The coating was then cured at ambient or thermally until fully cured
        l. The final cured product resulted in a highly lubricious coating
    
    


Coating Example Composition 3
Materials were then applied to substrates noted below in the following fashion:
Coating Polyurethane Tungsten Loaded Jacket

    
    
        h. An aqueous and or solvent dispersion basecoat was prepared from 8.8 g of composition 3 AND 0.2 Polyaziridine PZ-28 were then added to the formulation and stirred at 900 rpm for 15 minutes.
        i. Basecoat was applied to the polyurethane jacketed wire, by dip coating, at a set speed for a desired film thickness
        j. The basecoat was then cured either at ambient or thermally until no longer-tacky
        k. An aqueous dispersion topcoat was prepared with crosslinker in the following order: (1) 0.002 grams Poly(ethylene oxide), 4-arm, amine terminated average Mn ̃10,000 was added to a one ounce bottle then (2) 0.0252 grams '956 patent. To this crosslinker 11.576 grams of modified hyaluronan top coat formulated resin was added and crosslinker was stirred at 1800 rpm for 5 minutes
        l. Topcoat was then applied at a set speed for desired film thickness
        m. The coating was then cured at ambient or thermally until fully cured
        n. The final cured product resulted in a highly lubricious coating
    
    


Coating Metal Wire Substrate with Adhesion Promoter
Preparation of Adhesion Promoter

    
    
        i. 100 mL ETOH (ETOH anhydrous) provided by Sigma
        ii. Add 5.0 gram water
        iii. Stir 10 minutes
        1. Add 3.84 grams 3-aminoethyltriethoxysilane (Provided by Gelest)
        iv.
        v. Mix 5 minutes
        m. Coating wire with adhesion promoter
        vi. Pour adhesion promoter into 100 mL burette (use shaker to mix)
        vii. Place wire in graduated cylinder solution for 10 minutes
        viii. Take wire out of solution and place in 125 C oven for 10 minutes
    
    


Polyurethane tungsten loaded jacket

    
    
        n. An aqueous and or solvent dispersion basecoat was prepared from 8.8 g of composition 3 AND 0.2 Polyaziridine PZ-28 were then added to the formulation and stirred at 900 rpm for 15 minutes.
        o. The wire from step viii was taken out of the 125 C oven for coating
        p. Basecoat was applied to the metal wire substrate with adhesion promoter, by dip coating, at a set speed for a desired film thickness
        q. The basecoat was then cured either at ambient or thermally until no longer-tacky
        r. An aqueous dispersion topcoat was prepared with crosslinker in the following order: (1) 0.002 grams Poly(ethylene oxide), 4-arm, amine terminated average Mn ̃10,000 was added to a one ounce bottle then (2) 0.0252 grams '956 patent. To this crosslinker 11.576 grams of modified hyaluronan top coat formulated resin was added and crosslinker was stirred at 1800 rpm for 5 minutes
        s. Topcoat was then applied at a set speed for desired film thickness
        t. The coating was then cured at ambient or thermally until fully cured
        u. The final cured product resulted in a highly lubricious coating
    
    


Coating Example Composition 5
Materials were then applied to substrates noted below in the following fashion:
Coating Polyurethane Tungsten Loaded Jacket

    
    
        o. An aqueous and or solvent dispersion basecoat was prepared from 8.8 g of composition 5 and stirred at 900 rpm for 15 minutes.
        p. Basecoat was applied to the polyurethane jacketed wire, by dip coating, at a set speed for a desired film thickness
        q. The basecoat was then cured either at ambient or thermally until no longer-tacky
        r. An aqueous dispersion topcoat was prepared with crosslinker in the following order: (1) 0.0005 grams Poly(ethylene oxide), 4-arm, amine terminated average Mn ̃10,000 was added to a one ounce bottle then (2) 0.0000271 grams '956 patent. To this crosslinker 11.576 grams of modified hyaluronan top coat formulated resin was added and crosslinker was stirred at 1800 rpm for 5 minutes
        s. Topcoat was then applied at a set speed for desired film thickness
        t. The coating was then cured at ambient or thermally until fully cured
        u. The final cured product resulted in a highly lubricious coating
    
    


Coating Metal Wire Substrate with Adhesion Promoter
Preparation of Adhesion Promoter

    
    
        i. 100 mL ETOH (ETOH anhydrous) provided by Sigma
        ii. Add 5.0 gram water
        iii. Stir 10 minutes
        iv. Add 3.84 grams 3-aminopropyltriethoxysilane (Provided by Gelest)
        v. Mix 5 minutes
        v. Coating wire with adhesion promoter
        vi. Pour adhesion promoter into 100 mL burette (use shaker to mix)
        vii. Place wire in graduated cylinder solution for 10 minutes
        viii. Take wire out of solution and place in 125 C oven for 10 minutes
    
    


Polyurethane tungsten loaded jacket

    
    
        v. An aqueous and or solvent dispersion basecoat was prepared from 8.8 g of composition 5 and stirred at 900 rpm for 15 minutes.
        w. Basecoat was applied to the polyurethane jacketed wire, by dip coating, at a set speed for a desired film thickness
        x. The basecoat was then cured either at ambient or thermally until no longer-tacky
        y. An aqueous dispersion topcoat was prepared with crosslinker in the following order: (1) 0.0005 grams Poly(ethylene oxide), 4-arm, amine terminated average Mn ̃10,000 was added to a one ounce bottle then (2) 0.0000271 grams '956 patent. To this crosslinker 11.576 grams of modified hyaluronan top coat formulated resin was added and crosslinker was stirred at 1800 rpm for 5 minutes
        z. Topcoat was then applied at a set speed for desired film thickness
        aa. The coating was then cured at ambient or thermally until fully cured
        w. The final cured product resulted in a highly lubricious coating
    
    


Coating Example Composition 7
Materials were then applied to substrates noted below in the following fashion:
Coating Polyurethane Tungsten Loaded Jacket

    
    
        bb. An aqueous and or solvent dispersion basecoat was prepared from 8.8 g of composition 7 AND 0.2 Easaqua XM-502 were then added to the formulation and stirred at 900 rpm for 15 minutes Basecoat was applied to the polyurethane jacketed wire, by dip coating, at a set speed for a desired film thickness
        cc. The basecoat was then cured either at ambient or thermally until no longer-tacky
        dd. An aqueous dispersion topcoat was prepared with crosslinker in the following order: (1) 0.02 grams Poly(ethylene oxide), 4-arm, amine terminated average Mn ̃10,000 was added to a one ounce bottle then (2) 0.015 grams '956 patent. To this crosslinker 11.576 grams of modified hyaluronan top coat formulated resin was added and crosslinker was stirred at 1800 rpm for 5 minutes
        ee. Topcoat was then applied at a set speed for desired film thickness
        ff. The coating was then cured at ambient or thermally until fully cured
        gg. The final cured product resulted in a highly lubricious coating
    
    


Coating Metal Wire Substrate with Adhesion Promoter
Preparation of Adhesion Promoter

    
    
        i. 100 mL ETOH (ETOH anhydrous) provided by Sigma
        ii. Add 5.0 gram water
        iii. Stir 10 minutes
        iv. Add 3.84 grams 3-aminopropyltriethoxysilane
        v. Mix 5 minutes
        x. Coating wire with adhesion promoter
        vi. Pour adhesion promoter into 100 mL burette (use shaker to mix)
        vii. Place wire in graduated cylinder solution for 10 minutes
        viii. Take wire out of solution and place in 125 C oven for 10 minutes
    
    


Polyurethane tungsten loaded jacket

    
    
        hh. An aqueous and or solvent dispersion basecoat was prepared from 8.8 g of composition 7 AND 0.2 Easaqua XM-502 were then added to the formulation and stirred at 900 rpm for 15 minutes Basecoat was applied to the polyurethane jacketed wire, by dip coating, at a set speed for a desired film thickness
        ii. The basecoat was then cured either at ambient or thermally until no longer-tacky
        jj. An aqueous dispersion topcoat was prepared with crosslinker in the following order: (1) 0.005 grams Poly(ethylene oxide), 4-arm, amine terminated average Mn ̃10,000 was added to a one ounce bottle then (2) 0.01 grams '956 patent. To this crosslinker 11.576 grams of modified hyaluronan top coat formulated resin was added and crosslinker was stirred at 1800 rpm for 5 minutes
        kk. Topcoat was then applied at a set speed for desired film thickness
        ll. The coating was then cured at ambient or thermally until fully cured
        y. The final cured product resulted in a highly lubricious and durable coating
    
    


Coating Example Composition 9
Materials were then applied to substrates noted below in the following fashion:
Coating Polyurethane Tungsten Loaded Jacket

    
    
        mm. An aqueous and or solvent dispersion basecoat was prepared from 8.8 g of composition 9 AND 0.02 Easaqua XM-502 were then added to the formulation and stirred at 900 rpm for 15 minutes Basecoat was applied to the polyurethane jacketed wire, by dip coating, at a set speed for a desired film thickness
        nn. The basecoat was then cured either at ambient or thermally until no longer-tacky
        oo. An aqueous dispersion topcoat was prepared with crosslinker in the following order: (1) 0.002 grams Poly(ethylene oxide), 4-arm, amine terminated average Mn ̃10,000 was added to a one ounce bottle then (2) 0.002 grams '956 patent. To this crosslinker 11.576 grams of modified hyaluronan top coat formulated resin was added and crosslinker was stirred at 1800 rpm for 5 minutes
        pp. Topcoat was then applied at a set speed for desired film thickness
        qq. The coating was then cured at ambient or thermally until fully cured
        rr. The final cured product resulted in a highly lubricious coating
    
    


Coating Metal Wire Substrate with Adhesion Promoter
Preparation of Adhesion Promoter

    
    
        i. 100 mL ETOH (ETOH anhydrous) provided by Sigma
        ii. Add 5.0 gram water
        iii. Stir 10 minutes
        2. Add 3.84 grams 3-trimethoxysilylpropyl-diethylenetriamine (Provided by Gelest)
        iv.
        v. Mix 5 minutes
        z. Coating wire with adhesion promoter
        vi. Pour adhesion promoter into 100 mL burette (use shaker to mix)
        vii. Place wire in graduated cylinder solution for 10 minutes
        viii. Take wire out of solution and place in 125 C oven for 10 minutes
    
    


Polyurethane tungsten loaded jacket

    
    
        ss. An aqueous and or solvent dispersion basecoat was prepared from 8.8 g of composition 9 AND 0.02 Easaqua XM-502 were then added to the formulation and stirred at 900 rpm for 15 minutes Basecoat was applied to the polyurethane jacketed wire, by dip coating, at a set speed for a desired film thickness
        tt. The basecoat was then cured either at ambient or thermally until no longer-tacky
        uu. An aqueous dispersion topcoat was prepared with crosslinker in the following order: (1) 0.002 grams Poly(ethylene oxide), 4-arm, amine terminated average Mn ̃10,000 was added to a one ounce bottle then (2) 0.002 grams '956 patent. To this crosslinker 11.576 grams of modified hyaluronan top coat formulated resin was added and crosslinker was stirred at 1800 rpm for 5 minutes
        vv. Topcoat was then applied at a set speed for desired film thickness
        ww. The coating was then cured at ambient or thermally until fully cured
        xx. The final cured product resulted in a highly lubricious and durable coating
    
    
    1. A composition comprising epoxy urethane alkylene oxide reactive coating compositions of the structure of formula (I).






    2. The composition of paragraph 1, wherein the epoxy urethane alkylene oxide reactive coating compositions are
    
        (a) Polytrimethylene ether glycol, with n having a number average molecular weight in the range of about 1,000 to about 4,000,000 where n=11 to about 46.
        (b) Optional Polyethylene oxide, with m having a number average molecular weight in the range of about 18,000 to about 2,000,000 where n=375 to about 41,667
        (c) Optional Poly[di(ethylene glycol)adipate, with o having a number average molecular weight in the range of about 400 to about 10,000.00 where n=2 to about 50
        (d) Glycidyl moieties are represented by the addition of glycidol
    
    
    3. A composition comprising epoxy urethane ester carboxylic acid alkylene oxide reactive coating compositions of the following structure (II):






    4. The composition of paragraph 3, wherein the epoxy urethane ester carboxylic acid alkylene oxide reactive coating compositions are
    
        (a) Poly[di(ethylene glycol) adipate having a number average molecular weight in the range of about 400 to about 10,000.00 where n=2 to about 50
        (b) Optional Polytrimethylene ether glycol having a number average molecular weight in the range of about 1,000 to about 4,000,000 where n=11 to about 46.
        (c) Optional Polyethylene oxide having a number average molecular weight in the range of about 18,000 to about 2,000,000 where n=375 to about 41,667
        (d) Acid moieties are represented by the addition of dimethylol propionic acid
        (e) Glycidyl moieties are represented by the addition of glycidol
        (f) Excess isocyanate can react with dimethylol propionic acid to form an amide resulting in a urea
    
    
    5. A composition comprising epoxy urethane urea carboxylic acid alkylene oxide reactive coating compositions of the following structure (III):






    6. The composition of paragraph 5, wherein the epoxy urethane urea carboxylic acid alkylene oxide reactive coating compositions are:
    
        (a) Poly[di(ethylene glycol) adipate having a number average molecular weight in the range of about 400 to about 10,000.00 where n=2 to about 50
        (b) Optional Polytrimethylene ether glycol having a number average molecular weight in the range of about 1,000 to about 4,000,000 where n=11 to about 46.
        (c) Optional Polyethylene oxide having a number average molecular weight in the range of about 18,000 to about 2,000,000 where n=375 to about 41,667
        (d) Acid moieties are represented by the addition of dimethylol propionic acid
        (e) Glycidyl moieties are represented by the addition of glycidol
        (f) Urea moieties are represented by the addition of adipic acid dihydrazide
        (g) Excess isocyanate can react with dimethylol propionic acid to form an amide resulting in a urea
    
    
    7. A composition comprising epoxy urethane urea (based off water addition) carboxylic acid alkylene oxide reactive coating compositions of the following structure (IV):






    8. The composition of paragraph 7, wherein the epoxy urethane urea carboxylic acid alkylene oxide reactive coating compositions are:
    
        (a) Poly[di(ethylene glycol) adipate having a number average molecular weight in the range of about 400 to about 10,000.00 where n=2 to about 50
        (b) Optional Polytrimethylene ether glycol having a number average molecular weight in the range of about 1,000 to about 4,000,000 where n=11 to about 46.
        (c) Optional Polyethylene oxide having a number average molecular weight in the range of about 18,000 to about 2,000,000 where n=375 to about 41,667
        (d) Acid moieties are represented by the addition of dimethylol propionic acid
        (e) Glycidyl moieties are represented by the addition of glycidol
        (f) Urea moieties are represented by the addition of reduced isocyanate system then adding water
    
    
    9. A composition comprising epoxy urethane urea (based off excess iscoyanate) carboxylic acid alkylene oxide reactive coating compositions of the following structure (V):









    10. The composition of paragraph 9, wherein the epoxy urethane urea carboxylic acid alkylene oxide reactive coating compositions are:
    
        (a) Poly[di(ethylene glycol) adipate having a number average molecular weight in the range of about 400 to about 10,000.00 where n=2 to about 50
        (b) Optional Polytrimethylene ether glycol having a number average molecular weight in the range of about 1,000 to about 4,000,000 where n=11 to about 46.
        (c) Optional Polyethylene oxide having a number average molecular weight in the range of about 18,000 to about 2,000,000 where n=375 to about 41,667
        (d) Acid moieties are represented by the addition of dimethylol propionic acid
        (e) Glycidyl moieties are represented by the addition of glycidol
        (f) Urea moieties are represented by the addition of excess isocyanate, in the system, to adipic acid dihydrazide
    
    
    11. An aqueous soluble or solvent soluble or mixture comprising claims paragraphs 1-10.
    12. A composition of paragraph 11, where an aqueous soluble solvent is water and solvent soluble solvents are aprotic.
    13. A composition of paragraph 12, where the aprotic solvents are NMP, DMSO or DMF.
    14. A composition of paragraph 11, where the solvent can be a polar non-reactive solvent
    15. A composition of paragraph 14, where the solvent can be PMA, Acetone or MEK.
    16. A composition of paragraphs 1-10 where a chain extender is added.
    17. A composition of paragraphs 1-10 where the curing agent is a self-crosslinking reaction via homopolymerization or polyetherification.






    18. A composition of paragraph 17, where kinetics of the reaction are improved with temperature
    19. A composition comprising a mixture compounds with structures (I), (II), (III), (IV) and (V)
    20. A coating composition of paragraphs 1-10 further comprising a curing agent
    21. A coating composition of paragraphs 3-10, wherein the curing agent is an aziridine curing agent
    22. A composition of paragraph 21, where basecoat carboxylic acid groups can react with polyaziridine (PZ-28 or PZ-33):






    
    
        a) Polyaziridine PZ-28 reaction with basecoat (paragraph 22):
        b) Polyaziridine PZ-28 or PZ-33, added to basecoat (paragraphs 3-10), reacts with carboxylic acid in modified Hyaluronic Acid topcoat:
    
    






    
    
        c) Polyaziridine PZ-28 or PZ-33 (paragraph 22), connecting basecoat to modified Hyaluronic Acid topcoat:
    
    






    23. A composition of paragraphs 1-10, where epoxy groups can react with an amine cross-linking agents (Figure below).






    24. The coating composition of paragraph 23, wherein the amine curing agent is Poly(ethylene oxide), 4-arm, amine terminated
    25. Basecoat epoxy groups can react with Poly(ethylene oxide), 4-arm, amine terminated found in topcoat.
    
        a. The '956 patent epoxy groups can react with Poly(ethylene oxide), 4-arm, amine terminated and Poly(ethylene oxide), 4-arm, amine terminated can react with basecoat to increase adhesive strength.
    
    






    26. A composition of paragraphs 1-10, where open hydroxyl groups from epoxy group ring opening can react with isocyanate cross-linking agents (Figure below).
    27. The coating composition of paragraph 26, wherein the isocyanate curing agent is Easaqua XM-502
    
        a) Easaqua XM-502 added to the basecoat reacts with basecoat carboxylic acid:
    
    






    
    
        b. Easaqua XM-502 added to the basecoat reacts with Poly(ethylene oxide), 4-arm, amine added as a crosslinker to the top-coat:
    
    






    
    
        c. Easaqua XM-502 added to the basecoat reacts with open hydroxyls when the base-coat epoxy ring opens:
    
    






    
    
        d. Easaqua XM-502 added to the basecoat reacts with open hydroxyls when the '956 patent ring opens:
    
    






    
    
        e. Easaqua XM-502 reacts with hydroxyl groups found in Hyaluronic acid:
    
    






    
    
        f. Easaqua XM-502 reacts with carboxylic groups found in Hyaluronic acid:
    
    






    28. A composition of paragraphs 1-10, where epoxy groups can be end-capped with mono-functional amines:






    29. A composition of paragraphs 3-10 where adding dimethylpropionic acid (DMPA) can lead to cross-linking sites and also help with water dispersion by forming water reducible epoxy polyurethanes.
    30. A composition of paragraph 29, where acid groups of DMPA can be neutralized with an amine then dispersed in water.
    31. A composition of paragraphs 1-10, where linear polyurethane epoxy polymers are elastomeric and can elongate.
    32. A composition of paragraphs 1-10, where hydration forms a hydrogel via physical cross-links; or, slight cross-linking can cause a swelling (hydrogel formation) or plasticization effect resulting in a lubricious polyurethane end capped glycidyl based polymers.
    33. Epoxy termination of paragraphs 1-10 may crosslink by amines, amides, carboxylic acids and hydroxyl functionality.
    34. A coating composition of paragraph 33, where open hydroxyl functionality, from epoxy ring group opening, can undergo hydroxyl reactions.
    35. A composition of paragraphs 1-10, are affected by diisocyanate type.
    36. The coating composition of paragraphs 1-10, wherein the diisocyanate is selected from 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 3,3′-dimethyl-4,4′-biphenyl diisocyanate, 4,4′methylene diphenyl diisocyanate, polymeric MDI, naphthalene diisocyanate, 4,4′-diisocynatodicyclohexylmethane, 1,4-benzene diisocyanate, trans-cyclohexane-1,4-diisocyanate, 1,5-naphthalene diisocyanate, 1,6-hexamethylene diisocyanate, 4,6-xylene diisocyanate, isophorone diisocyanate, with combinations and isomers thereof.
    37. A composition of paragraphs 1-10, are reacted with polyol cross-linkers.
    38. A composition of paragraphs 1-10, are reacted with amine cross-linkers.
    39. A composition of paragraphs 5-10, where a diol or amine chain extender is added.
    40. The coating composition of paragraph 20, wherein the diol chain extender is selected from hydroquinone-bis-(hydroxymethyl)ether, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,5-pentanediol, 2-methyl-2-ethyl-1,3-propanediol, 1,4-bis(hydroxyethoxy)benzene, bis(hydroxyethylene)terephthalate, hydroquinone bis(2-hydroxyethyl)ether, and combinations and isomers thereof.
    41. The coating composition of paragraph 20, wherein the amine chain extender is selected from 2,4 and 2,6 diethtltoluene diamine, methylene-bis-orthochloroaniline, unilink (UOP LLC), 4,4′-methylene-bis(3-chloro-2,6-diethylaniline), 1,2-ethylenediamine, 1,6-hexanediamine, 1,2-propanediamine, 4,4′-methylene-bis(3-chloroaniline), dimethylthiotoluenediamine, 4,4′diaminodiphenylmethane, 1,3-diaminobenzene, 1,4-diaminobenzene, 3,3′dimethoxy-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diamino biphenyl, and combinations and isomers thereof.
    42. Paragraph 36 isocyanate selection, and isomers, affect physical crosslinks of the final epoxy terminated polyurethane polymer.
    43. A coating composition of paragraph 42, where 4-4′MDI terminated epoxy polyurethanes provides excellent hard block domains due to linearity and aromatic groups.
    44. A coating composition of paragraph 42, where isocyanate isomers of 2-4-TDI and 2,6-TDI react differently and impart different resin properties of the terminated polyurethane epoxy.
    45. A coating composition of paragraph 36, where isocyanate crosslinkers can react with open hydroxyl functional groups (epoxy ring opening) to improve durability.
    46. A composition of paragraphs 1-10, where pre-polymers can be made first then terminated with glycidol.
    47. A composition of paragraphs 1-10, where a one shot synthesis can be used with all monomers, including glycidol, are added all at once.
    48. A composition of paragraph 47, where monomers can be added to the reaction non-sequentially at any time during the reaction.

## Claims

1. A composition comprising epoxy urethane alkylene oxide reactive coating compositions of the structure of formula (I)

2. A composition comprising epoxy urethane ester carboxylic acid alkylene oxide reactive coating compositions of the following structure (II):

3. A composition comprising epoxy urethane urea carboxylic acid alkylene oxide reactive coating compositions of the following structure (III):

4. The product of the following reaction sequence (IV):

5. A composition comprising epoxy urethane urea amide carboxylic acid alkylene oxide reactive coating compositions of the following structure (V):

6. A composition prepared according to the following reaction sequence: