SILICONE ADHESIVE COMPOSITIONS

• US 20140031734A1
• Filed: 12/20/2012
• Published: 01/30/2014
• Est. Priority Date: 01/04/2012
• Status: Active Grant

• Current Assignee: Momentive Performance Materials Incorporated (Momentive Performance Materials Holdings LLC)
• Original Assignee: Momentive Performance Materials Incorporated (Momentive Performance Materials Holdings LLC)
• Inventors: Saxena, Anubhav, Joshi, Pranav Ramchandra
• Granted Patent: US 9,399,123 B2
• Time in Patent Office: Days
• US Class Current: 602/48
• CPC Class Codes: A61F 13/0253 characterized by the adhesive material
• CPC Class Codes: A61K 9/7069 obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. polysiloxane, polyesters, polyurethane, polyethylene oxide
• CPC Class Codes: C08G 77/22 containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/28 sulfur-containing groups
• CPC Class Codes: C08G 77/30 phosphorus-containing groups
• CPC Class Codes: C08G 77/38 Polysiloxanes modified by chemical after-treatment C08G77/045 takes precedence
• CPC Class Codes: C08G 77/392 containing sulfur
• CPC Class Codes: C08G 77/395 containing phosphorus
• CPC Class Codes: C08L 83/06 containing silicon bound to oxygen-containing groups C08L83/12 takes precedence
• CPC Class Codes: C08L 83/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
• CPC Class Codes: C09J 183/06 containing silicon bound to oxygen-containing groups C09J183/12 takes precedence
• CPC Class Codes: C09J 183/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Abstract

A silicone adhesive composition including an ionic silicone and useful for healthcare applications such as wound care and drug delivery.

Claims

1. A silicone adhesive composition comprising an ionic silicone wherein the ionic silicone is a functionalized ionic silicone having the formula:

M¹_aM²_bM³_cD¹_dD²_eD³_fT¹_gT²_hT³_iQ_j 

 

(I)

wherein;

M¹=R¹R²R³SiO_1/2

M²=R⁴R⁵R⁶SiO_1/2

M³=R⁷R⁸R⁹SiO_1/2

D¹=R¹⁰R¹¹SiO_2/2

D²=R¹²R¹³SiO_2/2

D³=R¹⁴R¹⁵SiO_2/2

T¹=R¹⁶SiO_3/2

T²=R¹⁷SiO_3/2

T³=R¹⁸SiO_3/2

Q=SiO_4/2

where R¹, R², R³, R⁵, R⁶, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁵ and R¹⁶ are aliphatic, aromatic or fluoro containing monovalent hydrocarbon radicals containing from 1 to about 60 carbon atoms,

where R⁴, R¹² and R¹⁷ are monovalent radical bearing ion-pairs having the formula (II);

-A-I^x−

M_n^y+ 

 

(II)

where A is a spacing group having at least one spacing atom selected from a divalent hydrocarbon or hydrocarbonoxy group,

where I is an ionic group selected from sulfonate —

SO₃⁻

, sulfate —

OSO₃⁻

′

, carboxylate —

COO⁻

, phosphonate —

PO₃²⁻

and phosphate —

OPO₃²⁻

,

where M is hydrogen or a cation independently selected from alkali metals, alkali earth metals, transition metals, metal complexes, quaternary ammonium and phosphonium groups, organic cations, alkyl cations, cationic hydrocarbons and cationic polymers;

or, zwitterions having the formula (III);

—

R′

—

NR″

₂⁺—

R′

″

—

I 

 

(III)

where R′

is a divalent hydrocarbon radical containing from 1 to about 20 carbon atoms,

where R″

is a monovalent hydrocarbon radical containing from 1 to about 20 carbon atoms,

where R′

″

is a divalent hydrocarbon radical containing from 2 to about 20 carbon atoms,

where I is an ionic group selected from sulfonate —

SO₃⁻

, sulfate —

OSO₃⁻

′

, carboxylate —

COO⁻

, phosphonate —

PO₃²⁻

and phosphate —

OPO₃²⁻

,

where R⁷, R¹⁴ and R¹⁸ are independently selected from hydrogen or monovalent hydrocarbon radicals selected from —

OR²⁰, unsaturated monovalent radicals, monovalent epoxy group-containing radicals, monovalent sulfur atom-containing radicals, monovalent organosilane groups and monovalent hydroxyl group containing radicals, and a monovalent hydrocarbon group containing one or more of a halogen moiety, a carboxylate moiety, an imine moiety, an isocyanate moiety, an amide moiety, a nitrile moiety, or a tertiary amine moiety containing other than alkyl groups moiety,

where R²⁰ is hydrogen or a monovalent hydrocarbon radical containing from 2 to about 60 carbon atoms.

where superscripts x and y are independently selected from 1 to 6, and x is a multiply of n and y, and

where the subscripts a, b, c, d, e, f, g, h, I and j are zero or positive and subject to the following limitations;

the sum a+b+c+d+e+f+g+h+i+j is greater than or equal to 2 and less than or equal to 6000, and b+e+h is greater than zero.

2. The silicone adhesive composition of claim 1 wherein the monovalent hydrocarbon radical is independently selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2,2,4-trimethylpentyl, nonyl, decyl, cycloalkyl radicals and aryl radicals groups.

3. The silicone adhesive composition of claim 2, wherein the cycloalkyl radicals are independently selected from the group consisting of cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals.

4. The silicone adhesive composition of claim 2 wherein the aryl radicals are independently selected from the group consisting of phenyl, naphthyl;

o-, m- and p-tolyl, xylyl, ethylphenyl, and benzyl.

5. The silicone adhesive composition of claim 1 wherein the divalent hydrocarbon group is an arylene group selected from the group consisting of —

(CHR′

)_kC₆H₄(CH₂)_l—

, —

CH₂CH(R′

)(CH₂)_kC₆H₄—

, —

CH₂CH(R′

)(CH₂)_lC₆H₃R″

— and

—

CH₂CH(R′

)(CH₂)_lC₆H₂R¹R″

—

where R′

is a hydrogen or defined by R¹, R″

is a monovalent radical specifically from about 1 to about 20 carbon atoms, sulfur atom(s), nitrogen atom(s), oxygen atom(s) or a radical containing combinations of the above atoms, where l has a value of 0 to 20, and k has a value of 0 to 20.

6. The silicone adhesive composition of claim 1 wherein the divalent hydrocarbon group is an alkylene group of the formula —

(CHR¹⁹)_m—

where m has a value of 1 to about 20 and R¹⁹ is hydrogen or R¹.

7. The silicone adhesive composition of claim 1 wherein the divalent hydrocarbonoxy group is selected from the group consisting of —

(CHR¹⁹)_m—

(O—

CHR¹⁹CH₂)_m′

—

O—

(CH₂)_l where R¹⁹ is hydrogen or R¹, l has a value of from 1 to 20, m has a value from 0 to 20 and m′

has a value from 0 to 50.

8. The silicone adhesive composition of claim 1 wherein each of R⁷, R¹⁴ and R¹⁸ are a monovalent hydrocarbon radical selected from the group of the formulae (IV) to (XIV)

9. The silicone adhesive composition of claim 1 wherein the subscripts a, b, d, e, g and h are subject to the limitations a+b≧

2, d+e≧

0, g+h≧

0 and b+e+h>

0.

10. The silicone adhesive composition of claim 1, including a silicone compound having the formula:

A′

_a′

A″

_b′

(OH)_c′

SiO<sub>(4-a′

-b′

-c′

)/2</sub> 

 

(XV)

where A′

is an alkenyl group bonded directly to the silicon atom, A″

is a group selected from unsubstituted or substituted monovalent hydrocarbyl epoxy or alkoxy, but excluding alkenyl, and a′

, b′ and

c′

are positive numbers.

11. The silicone adhesive composition of claim 10 wherein A′

is vinyl, allyl, butenyl, hexenyl or decenyl.

12. The silicone adhesive composition of claim 10 wherein A″

is directly bonded to the silicon atom and is selected from unsubstituted or substituted monovalent hydrocarbyl, excluding alkenyl, and alkoxy, wherein the hydrocarbyl group is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl and tert-pentyl;

hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl and cycloheptyl, methylcyclohexyl radicals, phenyl, naphthyl;

o-, m- and p-tolyl, xylyl, ethylphenyl, benzyl, 3-chloropropyl, 3,3,3-trifluoropropyl, 2-(nonafluorobutyl)ethyl, ethylbenzyl, 1-phenethyl methoxy, ethoxy, n-propoxy, and i-propoxy, and wherein the OH is directly bonded to the silicon.

13. The silicone adhesive composition of claim 1, including the organohydrogen functional silicone compound of the formula:

H_d′

A*_e′

SiO<sub>(4-d′

-e′

)/2</sub> 

 

(XVI)

wherein A* is directly bonded to the silicon atom and is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl and tert-pentyl;

hexyl;

heptyl;

n-octyl, isooctyl, 2,2,4-trimethylpentyl group, nonyl, decyl, cyclopentyl, cyclohexyl and cycloheptyl, methylcyclohexyl radicals, phenyl, naphthyl;

o-, m- and p-tolyl, xylyl, ethylphenyl, benzyl, 3-chloropropyl, 3,3,3-trifluoropropyl, 2-(nonafluorobutyl)ethyl, ethylbenzyl, 1-phenethyl methoxy, ethoxy, n-propoxy, and i-propoxy,

where d′

is a positive number, and e′

is 0 or a positive number.

14. The silicone adhesive composition of claim 1 wherein the adhesive is in form of a polymer composite.

15. The silicone adhesive composition of claim 14 wherein the composition further comprises one or more polymerizable monomer(s) or prepolymer(s) or polymer(s) or combinations thereof.

16. The silicone adhesive composition of claim 14 wherein the polymer composite is obtained via polymerization of the silicone ionomer in presence of the polymer(s).

17. The silicone adhesive composition of claim 14 wherein the polymer composite is obtained via simultaneous or sequential polymerization of the silicone ionomer and the monomer(s) or prepolymer(s) or their mixtures.

18. The silicone adhesive composition of claim 14 wherein the polymer composite is obtained by physical or reactive blending of the silicone ionomer with suitable polymers.

19. The silicone adhesive composition of claim 15 wherein the monomers and prepolymers are selected from one or more of free-radical polymerization effective monomers or prepolymers.

20. The silicone adhesive compositions of claim 19 wherein the monomers and prepolymer comprise of at least one free-radical polymerization effective group selected from methacrylate, butylacrylate, propylacrylate, N,N-dimethylacrylamide, methacrylic acid, N-isopropyl acrylamide, 2-hydroxy-ethyl-methacrylate (HEMA) and methacrylic acid, 3-[tris(trimethylsiloxy)silyl]propyl methacrylate, acrylate and methacrylate functional carbosilane molecules, hexafunctional urethane acrylates, dipentaerythritol pentaacrylate, ethoxylated pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, butanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane trimethacrylate, oligofunctional urethane acrylates, tetraacrylate monomer, polyester acrylate oligomers, and combinations thereof.

21. The silicone adhesive composition of claim 15 wherein the monomers or prepolymers are selected from two or more addition polymerizable compounds.

22. The silicone adhesive composition of claim 21 wherein the monomer or prepolymers comprise compounds selected from hydride functional silicones, olefenically unsaturated organic moieties or organomodified silicones, compounds selected from epoxy, amino, hydroxyl or carboxyl moieties, compounds selected from isocyanates, hydroxyls or amine.

23. The silicone adhesive composition of claim 15 wherein the monomers or prepolymers are selected from one or more condensation curable compounds.

24. The silicone adhesive composition of claim 23 wherein the monomer or prepolymer comprises of two or more condensation polymerisable moieties selected from silanol, alkoxy silanes, silicates, silicic acids, and acyloxy silanes.

25. The silicone adhesive composition of claim 23 wherein the monomer or prepolymer comprises of the compounds forming poly esters, polyamides, polyimides, polyanhydrides, polysulfones, polycarbonates and polyetheretherketones.

26. The silicone adhesive composition of claim 23 wherein the monomer or prepolymer comprises two or more condensation polymerisable moieties selected from silanol, alkoxy silanes, silicates, silicic acids, acyloxy silanes and one or more of compounds forming polyesters, polyamides, polyimides, polyanhydrides, polysulfones, polycarbonates and polyetheretherketones.

27. The silicone adhesive composition of claim 15 wherein the monomer or prepolymer comprise of one or more ring opening polymerisable moieties selected from lactides or glycolides.

28. The silicone adhesive composition of claim 15 comprising at least one of the polymers selected from sulfonated polystyrene, polyelectrolytes, sulfonated polyesters, polyacrylates, polyacrylamides, polyurethanes, polyethers, polyesters, polylactones, polylactides, polyglycolides, polyacids, polyamides, polyamines, polyethylene, polypropylene, poly(alkylene oxides) selected from polyethylene oxide, polypropylene oxide, polybutadiene, polybutylene, polyacrylonitrile, polyvinyl chloride, polyvinyl acetate, polystyrene, polysulfone, PEEK, polycarbonate, polyepoxides, fluoropolymers selected from PTFE, polyvinylenedifluoride, synthetic and natural rubber, phenol formaldehyde, melamine formaldehyde, urea formaldehyde, polymers of natural or semi-synthetic origin selected from polysaccharides, cellulose, proteins, polypeptides, poly(amino acids), organosilicon polymers selected from polysiloxanes, polysilicates, polysilsesquioxanes, polysilanes, ionically modified versions of the above, and isomers and co-polymers of the above polymers.

29. The silicone adhesive composition of claim 15 wherein the silicone ionomer and the polymer interact with each other.

30. The silicone adhesive composition of claim 29 wherein the silicone ionomer and the polymer interact via ionic interactions between similar or dissimilar ionic groups.

31. The silicone adhesive composition of claim 30 wherein the interaction is via hydrophobic interactions, crystalline phases, acid-base interactions, co-ordination complexes, π

-interactions or hydrogen bonding.

32. The silicone adhesive composition of claim 14 wherein the silicone ionomer and the polymer are covalently linked through condensation reactions via multiple functional groups in their structures, and involving the liberation of small molecules.

33. The silicone adhesive composition of claim 1 further comprising a catalyst.

34. The silicone adhesive composition of claim 33 wherein the catalyst is a condensation catalyst selected from dibutyl tin dilaurate, tin octanoate and other alkyltin compounds;

acid-base salts of other metals selected from titanium, iron, zinc, aluminum, and organic ammonium compounds and silanolate salts.

35. The silicone adhesive composition of claim 33 wherein the catalyst is a transition metal based catalyst and selected from platinic chloride, chloroplatinic acid, bis(acetylacetonato)platinum, (η

⁵-cyclopentadienyl)trialkylplatinum complexes, Pt triazenido complex, Pt(PPh₃)₂Cl₂, iron, palladium and rhodium complexes.

36. The silicone adhesive composition of claim 1 further comprising an initiator.

37. The silicone adhesive composition of claim 36 wherein the initiator is a thermal or photoinitiator and is selected from benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzil, benzophenone, para methoxybenzophenone, 2,2-diethoxyacetophenone, alpha-alpha-dimethoxy-alpha-phenylacetophenone, methylphenyl glyoxylate, ethyphenyl glyoxylate, 4,4′

-bis-(dimethylaminobenzophenone), propiophenone, acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,2-diethoxyacetophenone, ethlphenylpyloxylate, phenanthraquinone, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, benzoyl peroxide, di-tert-butyl peroxide, 7-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acylophosphine oxide photoinitiators and combinations thereof.

38. The silicone adhesive composition of claim 36 wherein the initiator is a cationic photoinitiator and is selected from the group consisting of diaryliodonium salts, triarylsulfonium salts, triarylselenonium salts, tetraarylphosphonium salts and aryldiazonium salts, respectively represented by the formulas R²⁹₂I⁺Y⁻

, R²⁹₃S⁺Y⁻

, R²⁹₃Se⁺Y⁻

, R²⁹₄P⁺Y⁻

and R²⁹N₄⁺Y⁻

, wherein, R²⁹ represents an aryl group, and Y⁻

represents an anion selected from SbF₆⁻

, AsF₆⁻

, PF₆⁻

, BF₄⁻

, HSO₄⁻

and ClO₄⁻

.

39. The silicone adhesive composition of claim 1 further including one or more functional additives selected from fillers, solvents, surfactants, pigments, colorants, mold release agents, adhesion promoters, plasticizers, tackifiers, excipients, UV absorbers, photosensitizers, flattening agents, crosslinkers, chain terminators, rheology modifiers, thickeners, foam suppressers, antioxidants, drugs, fillers, bioactives, exfoliants, enzymes, proteins and peptides, medicinal compounds, biocides, oral care agents, oxidizing agents, reducing agents, skin protectants, essential oils, insect repellents, UV light absorbing agents, solar filters, pigments, hydrating agents, vitamins and their combinations thereof.

40. The silicone adhesive composition of claim 39 wherein the fillers are selected from re-enforcing or non-reinforcing fillers, conductive or non-conductive fillers, and are selected from selected from particulate forms of oxides of titanium, cerium, aluminum, zirconium and other metals and metalloids, metal or metal oxide nanoparticles with and without surface modification, carbon black, carbon nanotubes, graphite, graphene, glass fibers, talc, carborundum, mica, boron nitride, clay, inorganic fillers, polysaccharides, natural and synthetic fibers, and suitable combinations thereof.

41. A hydrophilic, moisture permeable woundcare article comprising the silicone adhesive composition of claim 1.

42. The woundcare article of claim 41 comprising antimicrobial agents selected from silver, copper, chlorhexidine, biguanide, zinc, benzalkonium chloride, polyquaternary ammonium compounds, chitosan and its derivatives, antimicrobial peptides selected from nisin, pediocin, and pleuricidin and their derivatives and recombinant forms and possessing antimicrobial property.

43. A transdermal drug delivery article comprising the silicone adhesive composition of claim 1 comprising at least one drug.

44. The transdermal drug delivery article of claim 43 wherein the drugs are selected from drugs that act upon the central nervous system selected from clozapine, risperidone, chordiazepoxide, buspirone, desipramine, maprotiline, timolol, selegiline;

drugs affecting renal and cardiovascular function selected from acetazolamide, isosorbide, furosemide, chlorothiazide, amiloride, captopril, enalapril, lisinopril, nifedipine, verapamil, lidocaine, propranolol, amiodarone, pravastatin, probucol, oxycontin;

drugs affecting gastrointestinal function selected from cimetidine, omeprazole and ranitidine;

drugs for treatment of helminthiasis selected from thiabendazole and mebendazole;

drugs for the treatment of microbial diseases selected from trimethoprim, norfloxacin, ciprofloxacin, penicillin, kanamycin, fluconazole, acyclovir, ritonavir, and ganciclovir;

drugs for the treatment of neoplastic diseases selected from dacarbazine, busulfan, and triazenes;

drugs for treatment of nutrient deficiency selected from folic acid, niacinamide, ascorbic acid and thiamine;

drugs for hormonal replacement therapy selected from testosterone and other androgenic steroids, progestational drugs, estradiol and their analogues and norethindrone;

drugs for inhibition of adrenocortical hormones selected from cortisol, cortisone and prednisone;

drugs used in dermatology selected from betamethasone, dipropionate, hydrocortisone, dexamethasone sodium phosphate, retinal, tretinoin, isotretinoin, dapsone, calipotriene, ketoconazole, clotrimazole itraconazole and arotinoid;

anti-inflammatory agents selected from ibuprofen, ketoprofen, diclofenac;

anti-histamines selected from azelastine, hydroxyzine, desloratadine, carbinoxamine, fexofenadine and brompheniramine;

respiratory agents selected from tadalafil, laronidase, ciclesonide and indacaterol maleate;

sympathomimetics selected from catecholamines, epinephrine and dopamine;

miotics;

cholinergic agonists selected from alvameline, muscarine, nicotine and pilocarpine;

humoral agents;

anti-spasmodics selected from baclofen, tizanidine and dantrolene;

anti-depressant drugs;

anti-diabetic drugs;

anti-anorectic drugs;

tranquilizers;

antipsychotics selected from olanzapine, risperidone, quetiapine, ziprasidone and amisulpride;

anti-pyretics selected from paracetamol, nabumetone;

drugs for Parkinson'"'"'s disease, anti-malarials, anti-ulcerative agents, therapeutic agents and combinations thereof.

45. The transdermal drug delivery article of claim 43 comprising an excipient wherein the excipient is selected from sugars and sugar derivatives selected from acacia, dextrin, dextrose, fructose, lactose, maltodextrin, mannitol, sorbitol, sucrose and xylitol;

starch and derivatives;

cellulosic materials selected from sodium carboxymethylcellulose, microcrystalline cellulose, cellulose acetate phthalate, sodium croscarmellose, methyl cellulose, ethyl cellulose, HPMC, hydroxypropyl cellulose;

polysaccharides selected from xanthan gum, guar gum;

polyethers selected from poloxamers, and polyoxyalkylene ethers;

polyvinyl alcohols and acetates;

acrylic acid and methacrylic acid polymers selected from Carbopol, Carbomer, Covacryl, polacrilin potassium;

pyrrolidone derivatives selected from povidone, crosspovidone and Kollidon;

glycouran polymers selected from hyaluronic acid, alginic acid, alginate, agar; and

other excipients selected from cholesterol, lecithin, gelatin and mallic acid.