Curable compositions of ionic silicones
View Patent ↗A curable composition of ionic silicones includes a silicone having the formula M 1 a M 2 b M 3 c D 1 d D 2 e D 3 f T 1 g T 2 h T 3 i Q j having ionic groups and crosslinking functional groups. The composition can further include polyorganosiloxane having the average compositional formula R 26 n R 27 o (OH) p SiO (4-n-o-p)/2 , organohydrogenoligosiloxane or organohydrogenpolysiloxane that has the average compositional formula H q R 28 r SiO (4-q-r)/2 a transition metal catalyst and other components such as UV stabilizer, cure accelerator, pigment, dye, antimicrobial agent, biocide, surfactant, functional or non-functional filler, conductive filler, finely divided surface treated/untreated metal oxides, clay, plasticizers, tackifiers, mold release agents, adhesion promoters, compatibilizers, pharmaceutical excipients, surfactants or antistatic agents.
1. A curable composition containing an ionic silicone of the following formula (I):
M 1 a M 2 b M 3 c D 1 d D 2 e D 3 f T 1 g T 2 h T 3 i Q j (I)
wherein:
M 1 =R 1 R 2 R 3 SiO 1/2
M 2 =R 4 R 5 R 6 SiO 1/2
M 3 =R 7 R 8 R 9 SiO 1/2
D 1 =R 10 R 11 SiO 2/2
D 2 =R 12 R 13 SiO 2/2
D 3 =R 14 R 15 SiO 2/2
T 1 =R 16 SiO 3/2
T 2 =R 17 SiO 3/2
T 3 =R 18 SiO 3/2
Q=SiO 4/2.
wherein R 1 , R 2 , R 5 , R 6 , R 8 , R 9 , R 11 , R 13 , and R 15 are aliphatic, aromatic or fluoro monovalent hydrocarbons having from 1 to 60 carbon atoms,
R 3 , R 10 , R 16 are independently chosen from —CH 2 CH(R′)(C n H 2n )—O—(C 2 H 4 O) o —(C 3 H 6 O) p —(C 4 H 8 O) q —R′, wherein subscript n is zero or positive and has a value in the range of 0 to 6, subscripts o, p and q are zero or positive and independently selected from a value in the range of 0 to 100, subject to the limitation of o+p+q greater than or equal to 1, wherein R′ is hydrogen or an aliphatic, aromatic or fluoro hydrocarbon having from 1 to 60 carbon atoms,
R 4 , R 12 , R 17 are monovalent radical-bearing ion-pairs having the formula (II) or zwitterions having formula (III), wherein formula (II) is as follows,
-A-I x− M n y+ (II);
where
A is a spacing group having at least one spacing atoms selected from a divalent hydrocarbon or hydrocarbonoxy group,
I is an ionic group selected from sulfonate —SO 3 − , sulfate —OSO 3 − , carboxylate —COO − , phosphonate —PO 3 2− and phosphate —OPO 3 2− groups,
M is hydrogen or a cation independently selected from alkali metals, alkaline earth metals, transition metals, metal complexes, quaternary ammonium and phosphonium groups, cationic hydrocarbons, organic cations, alkyl cations, cationic biopolymers, and the zwitterions have the formula (III):
—R′—NR″ 2 + —R′″—I (III)
where
R′ is a divalent hydrocarbon radical containing from 1 to about 60 carbon atoms,
R″ is monovalent hydrocarbon radical containing from 1 to about 60 carbon atoms,
R′″ is divalent hydrocarbon radical containing from 2 to about 20 carbon atoms, specifically from 2 to about 8 carbon atoms and more specifically from 2 to about 4 carbon atoms; and,
I is an ionic group selected from sulfonate —SO 3 − , sulfate —OSO 3 − , carboxylate —COO − , phosphonate —PO 3 2− and phosphate —OPO 3 2− groups,
where R 7 , R 14 , and R 18 are independently selected from hydrogen, or unsaturated monovalent radicals or epoxy group containing radicals,
where
the subscript a, b, c, d, e, f, g, h, i, j are zero or positive 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, b+e+h is greater than zero, and c+f+i is greater than zero, a+d+g is greater than zero, and a+b+c is greater than zero with the proviso that h+I is greater than zero.
2. The composition of claim 1 wherein R 4 , R 12 , R 17 are monovalent radical-bearing ion-pairs having the formula (II) and the divalent group of A in formula (II) is an arylene group selected from the group consisting of —(CH 2 ) l C 6 H 4 (CH 2 ) k —, —CH 2 CH(CH 3 )(CH 2 ) k C 6 H 4 —, and —CH 2 CH(R 1 )(CH 2 ) 1 C 6 H 3 R 19 where R 1 is as defined,
R 19 is a monovalent radical of from about 1 to about 20 carbon atoms, a sulfur atom(s), nitrogen atom(s), oxygen atom(s) or a radical containing combinations of the above atoms, where 1 has a value of 0 to 20, and k has a value of 0 to 20.
3. The composition of claim 1 wherein R 4 , R 12 , R 17 are monovalent radical-bearing ion-pairs having the formula (II) and the divalent group of A in formula (II) is an alkylene group of the formula —(CHR 20 ) m — where m has a value of 1 to 20 and R 20 is hydrogen or R 1 .
4. The composition of claim 1 wherein R 4 , R 12 , R 17 are monovalent radical-bearing ion-pairs having the formula (II) and the divalent group of A in formula (II) is a hydrocarbonoxy group selected from (CHR 20 ) m —(O—CH(R 20 )(CH 2 ) p —O—(CH 2 ) 1 — where 1 has a value of from 0 to 20, m has a value of 0 to 50 and p has the value from 1 to 50.
5. The composition of claim 1 wherein R 4 , R 12 , R 17 are monovalent radical-bearing ion-pairs having the formula (II) and M is a cation independently selected from Li, Na, K, Cs, Mg, Ca, Ba, Zn, Cu, Fe, Ni, Ga, Al, Mn, Cr, Ag, Au, Pt, Pd, Pb, Sb, Ru, Sn Rh, Co, Ce, Eu, Gd and La and R 7 , R 14 , R 18 are curable functional groups independently selected from hydrogen or the monovalent radical containing the group of the general formulae
wherein R 21 to R 25 are independently selected from hydrogen aliphatic/aromatic monovalent hydrocarbon having from 1 to 60 carbon atoms,
X is a divalent hydrocarbon linkage consisting of 1 to 60 carbon atoms and 0 to 20 heteroatoms selected from oxygen, nitrogen and sulfur.
6. The composition of claim 1 wherein R 1 , R 2 , R 5 , R 6 , R 8 , R 9 , R 11 , R 13 , and R 15 are selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, 2,2,4-trimethylpentyl group, n-nonyl group, n-decyl group, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, phenyl, naphthyl; o-, m- and p-tolyl, xylyl, ethylphenyl and benzyl.
7. The composition of claim 1 further including 0-99 parts by weight, based on total composition weight, of reinforcing filler or non-reinforcing filler selected from silica, fumed silica, nano silica, functionalized or unfuctionalized silicone resins, natural and synthetic fibers, polysaccharides, cork, graphite and carbon black, graphene, clay, boron nitride, finely divided metal and metal oxides with and without surface treatments.
8. A curable composition containing an ionic silicone of the following formula (I):
M 1 a M 2 b M 3 c D 1 d D 2 e D 3 f T 1 g T 2 h T 3 i Q j (I)
wherein:
M 1 =R 1 R 2 R 3 SiO 1/2
M 2 =R 4 R 5 R 6 SiO 1/2
M 3 =R 7 R 8 R 9 SiO 1/2
D 1 =R 10 R 11 SiO 2/2
D 2 =R 12 R 13 SiO 2/2
D 3 =R 14 R 15 SiO 2/2
T 1 =R 16 SiO 3/2
T 2 =R 17 SiO 3/2
T 3 =R 18 SiO 3/2
Q=SiO 4/2.
wherein R 1 , R 2 , R 5 , R 6 , R 8 , R 9 , R 11 , R 13 , and R 15 are aliphatic, aromatic or fluoro monovalent hydrocarbons having from 1 to 60 carbon atoms,
R 3 ,R 10 , R 16 are independently chosen from —CH 2 CH(R′)(C n H 2n )—O—(C 2 H 4 O) o —(C 3 H 6 O) p —(C 4 H 8 O) q —R′, wherein subscript n is zero or positive and has a value in the range of 0 to 6, subscripts o, p and q are zero or positive and independently selected from a value in the range of 0 to 100, subject to the limitation of o+p+q greater than or equal to 1, wherein R′ is hydrogen or an aliphatic, aromatic or fluoro hydrocarbon having from 1 to 60 carbon atoms,
R 4 , R 12 , R 17 are monovalent radical-bearing ion-pairs having the formula (II) or zwitterions having formula (III), wherein formula (II) is as follows,
-A-I x− M n y+ (II);
where
A is a spacing group having at least one spacing atoms selected from a divalent hydrocarbon or hydrocarbonoxy group,
I is an ionic group selected from sulfonate —SO 3 − , sulfate —OSO 3 − , carboxylate —COO − , phosphonate —PO 3 2− and phosphate —OPO 3 2− groups,
M is hydrogen or a cation independently selected from alkali metals, alkaline earth metals, transition metals, metal complexes, quaternary ammonium and phosphonium groups, cationic hydrocarbons, organic cations, alkyl cations, cationic biopolymers, and the zwitterions have the formula (III):
—R′—NR″ 2 + —R′″—I (III)
where
R′ is a divalent hydrocarbon radical containing from 1 to about 60 carbon atoms,
R″ is monovalent hydrocarbon radical containing from 1 to about 60 carbon atoms,
R′″ is divalent hydrocarbon radical containing from 2 to about 20 carbon atoms, specifically from 2 to about 8 carbon atoms and more specifically from 2 to about 4 carbon atoms; and,
I is an ionic group selected from sulfonate —SO 3 − , sulfate —OSO 3 − , carboxylate —COO − , phosphonate —PO 3 2− and phosphate —OPO 3 2− groups,
where R 7 , R 14 , and R 18 are independently selected from hydrogen, or unsaturated monovalent radicals or epoxy group containing radicals,
where
the subscript a, b, c, d, e, f, g, h, i, j are zero or positive 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, b+e+h is greater than zero, and c+f+i is greater than zero, the composition further including a polyorganosiloxane having the average compositional formula:
R 26 n R 27 o (OH) p SiO (4-n-o-p)/2
where R 26 is C 2-20 alkenyl that is directly bonded to silicone, R 27 is a group selected from unsubstituted or substituted monovalent hydrocarbyl other than alkenyl, alkoxy, cylcloalkyl, epoxy, cycloepoxy and aryl, and n, o, and p are positive numbers with n+o+p=1 to 2, n is greater than or equal to zero, p is greater than or equal to zero.
9. The composition of claim 8 wherein R 26 is vinyl, allyl, butenyl, hexenyl or decenyl.
10. The composition of claim 9 wherein R 27 is a group selected from methyl, ethyl, propyl, cyclohexyl, phenyl, tolyl, napthyl, 3-chloropropyl, 3,3,3,-trifluoropropyl, 2-(nonafluorobutyl)ethyl, ethylbenzyl, 1-phenylethyl, methoxy, ethoxy, n-propoxy and iso-propoxy, epoxy and cycloepoxy.
11. The composition of claim 1 further including organohydrogenoligosiloxane or organohydrogenpolysiloxane that has the average compositional formula
H q R 28 r SiO (4-q-r)/2
where R 28 is a group selected from unsubstituted or substituted monovalent hydrocarbyl (excluding alkenyl) selected from alkyl radicals of 1 to 60 carbon atoms, q is greater than zero, r is greater than or equal to zero, and q+r is less than or equal to 3.
12. The composition of claim 11 wherein R 28 is selected from the group consisting of methyl, ethyl, propyl, butylpentyl, n-pentyl, isopentyl, hexyl, octyl, phenyl, methylphenyl, cyclohexyl and haloalkyl radicals.
13. The composition of claim 1 further comprising a catalyst.
14. The composition of claim 13 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(PPh 3 ) 2 O 2 , iron, palladium and rhodium complexes.
15. The composition of claim 1 further including one or more components selected from UV stabilizer, chain extenders, cure accelerator, cure initiator, cure inhibitor, pigment, dye, antimicrobial agent, antifungal agent, drug, biocide, surfactant, conductive filler, finely divided surface treated/untreated metal oxides, nanofillers, clay, plasticizers, tackifiers, mold release agents, adhesion promoters, compatibilizers, pharmaceutical excipients, surfactants, compatibilizing agents, radio-opaque substances and antistatic agents.
16. A transparent to translucent silicone rubber composition comprising the curable ionic silicone of claim 1 .
17. A silicone rubber composition prepared by thermally curing the composition of claim 16 in the presence of a platinum catalyst.
18. A silicone rubber composition prepared by UV curing of the composition of claim 16 in the presence of a platinum catalyst.
19. A silicone rubber composition prepared by thermally curing the composition of claim 16 in the presence of a peroxide initiator.
20. The silicone rubber composition of claim 16 optionally comprising silver, copper, zinc, chlorhexidine, benzalkonium chloride, biguanide, polyquaternary ammonium compounds, quaternary phosphonium compounds, chitosan and its derivatives, antimicrobial peptides selected from nisin, pediocin, gomesin, pleuricidin and derivatives thereof as antimicrobial agents.
21. A transparent to translucent, silicone gel composition comprising the curable ionic silicone of claim 1 .
22. A silicone gel composition prepared by thermally curing the composition of claim 21 in the presence of a platinum catalyst.
23. A silicone gel composition prepared by UV curing of the composition of claim 21 in the presence of a UV catalyst.
24. An adhesive composition containing the silicone gel composition of claim 21 .
25. The silicone gel composition of claim 21 optionally comprising silver, copper, zinc, chlorhexidine, benzalkonium chloride, biguanide, polyquaternary ammonium compounds, polyquaternary phosphonium compounds, chitosan and its derivatives, antimicrobial peptides selected from nisin, pediocin, gomesin, pleuricidin and their derivatives and recombinant forms as antimicrobial agents.
26. A product for healthcare, personal care, automobile coatings, household paints, laundry detergents, textiles, electronics/electrical, aerospace, membranes, adhesives, fuel cells, construction, apparel, sporting goods, production of domestic appliances, machine and instrument construction and consumer goods said product comprising the composition of claim 1 .
27. The healthcare product of claim 26 comprising one or more additional agents selected from the group consisting of metals, metal ions, bioactives, anti-acne agents, anti-ageing agents, anti-caries agents, anti-fungal agents, anti-microbial agents, anti-oxidants, anti-cancer, anti-viral, anti-inflammatory, anti-coagulants, hemostatic agents, exfoliants, hormones, enzymes, medicinal compounds, biocides, external analgesics, oral care agents, oral care drugs, oxidizing agents, reducing agents, skin protectants, essential oils, insect repellents, UV light absorbing agents, solar filters, pigments, hydrating agents, vitamins and combinations thereof.
28. A product selected from wound dressings, dressings for scar reduction, drug delivery devices, medical tubing, clinical surfaces, pacemaker leads, pressure sensitive adhesives, wound healing patches, wound management device, medical adhesives, catheters, shunts, valves, stents, transdermal iontophoresis patches, scaffold for tissue engineering, anti-microbial devices, ophthalmic devices, bioinserts, surgical devices, plugs, medical devices, devices for medical storage, childcare products, assisted breathing apparatus, ophthalmic devices, prostheses, reconstructive devices and body implants, wherein said product comprises a rubber or gel adhesive derived from the composition of claim 1 .
29. The personal care product of claim 26 wherein said personal care component includes one or more deodorants, antiperspirants, antiperspirant/deodorants, sticks and roll-on products, skin lotions, moisturizers, toners, cleansing products, styling gels, hair dyes, hair color products, hair straighteners, nail polish, nail polish remover, sunscreen, anti-aging products, lipsticks, foundations, face powders, eye liners, eye shadows, blushes, makeup, mascaras, moisturizing preparations, foundations, body and hand preparations, skin care preparations, face and neck preparations, fragrance preparations, soft focus applications, night and day skin care preparations, tanning preparations, hand liquids, non-woven applications for personal care, baby lotions facial cleansing products, hair cuticle coats, personal care rinse-off products, gels, foam baths, scrubbing cleansers, controlled-release personal care products, hair conditioning mists, skin care moisturizing mists, skin wipes, pore skin wipes, pore cleaners, blemish reducers, skin exfoliators, skin desquamation enhancers, skin towelettes and cloths, depilatory preparations, personal care lubricants, nail coloring preparations, drug delivery systems for topical application of medicinal compositions that are to be applied to the skin and combinations thereof.