SULFONATED POLYMERS AND COMPOSITIONS THEREOF

Abstract

A composition is disclosed comprising a sulfonated styrenic block copolymer (SSBC) having an ion exchange capacity (IEC) of at least 0.5 meq/g; and at least one compound which reacts with the SSBC forming a cross-linked SSBC. The compound is selected from: (i) a cross-linking agent, (ii) a metal cation, and (iii) a non-sulfonated polymer. A film prepared from the composition containing the cross-linked SSBC has a toughness in wet state measured after 1 week of 1.2 to 8 MJ/m.sup.3; and a tensile stress in wet state measured after 1 week of 3.2 to 8 MPa, according to ASTM D412. The film can be used as a water 10 purification membrane or an antimicrobial protection layer.

Claims

1. A composition comprising: (a) a sulfonated styrenic block copolymer having an ion exchange capacity (IEC) of at least 0.5 meq/g, wherein the sulfonated styrenic block copolymer is obtained by sulfonation of a styrenic block copolymer precursor; and (b) a sufficient amount of at least one compound which reacts with the sulfonated styrenic block copolymer to form a cross-linked sulfonated styrenic block copolymer, the compound is selected from: (i) a cross-linking agent selected from the group consisting of: multi-functional acrylates, compounds having at least two vinyl groups, di-isocyanates, polyisocyanates, polyester diols, and mixtures thereof, (ii) a metal cation selected from the group consisting of: Zn acetate, Fe(II) oxolate, Cu(II) i-butyrate, Ca stearate, Al 2-ethylhexanoate, Ti(IV) 2-ethylhexoxide, Al hydroxide, Al oxide, Al chloride, triethylaluminium, Fe(III) oxide, Cu(II) oxide, Zn oxide, Cu(I) oxide, Ca oxide, and mixtures thereof, and (iii) a non-sulfonated polymer having at least one block D′, and optionally a block selected from A′, B′, and mixtures thereof, each block D′ is derived from a conjugated diene monomer, having a vinyl content of at least 35 wt. %, based on total weight of the polymerized conjugated diene monomer in the block D′; each block A′ is derived from at least one compound selected from polymerized (i) para-substituted styrene, (ii) ethylene, (iii) alpha olefins of 3 to 18 carbon atoms, (iv) 1,3-cyclodiene, (v) conjugated dienes, (vi) acrylic esters, (vii) methacrylic esters, and (viii) mixtures thereof, and each block B′ is derived from a vinyl aromatic monomer; and wherein a film prepared from the composition containing the cross-linked sulfonated styrenic block copolymer has a toughness in wet state measured after 1 week of 1.2 to 8 MJ/m.sup.3, and a tensile stress in wet state measured after 1 week of 3.2 to 8 MPa, both measurements according to ASTM D412.

2. The composition of claim 1, wherein the styrenic block copolymer precursor has a general configuration of: A-B-A, (A-B).sub.n(A), (A-B-A).sub.n, (A-B-A).sub.nX, (A-B).sub.nX, A-D-B, A-B-D, A-D-B-D-A, A-B-D-B-A, (A-D-B).sub.nA, (A-B-D).sub.nA (A-D-B).sub.nX, (A-B-D).sub.nX, (A-D-B-D-A).sub.nX, (A-B-D-B-A).sub.nX, or mixtures thereof; wherein n is an integer from 2 to 30, and X is a residue of a coupling agent; blocks A and D are resistant to sulfonation; and block B is susceptible to sulfonation; and wherein: each block A comprises polymerized para-substituted styrene monomers selected from the group consisting of para-methylstyrene, para-ethylstyrene, para-n-propyl styrene, para-iso-propyl styrene, para-n-butyl styrene, para-sec-butyl styrene, para-iso-butylstyrene, para-t-butylstyrene, isomers of para-decylstyrene, isomers of para-dodecylstyrene, and mixtures thereof; each block B comprises the polymerized vinyl aromatic monomers selected from the group consisting of unsubstituted styrene, ortho-substituted styrene, meta-substituted styrene, alpha-methyl styrene, 1,1-diphenylethylene, 1,2-diphenylethylene, and mixtures thereof and each block D comprises the polymerized conjugated diene monomers selected from the group consisting of isoprene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-1,3-octadiene, farnesene, myrcene, piperylene, cyclohexadiene, and mixtures thereof

3. The composition of claim 2, wherein the block B has a degree of sulfonation from 10 to 100 mol %, based on total mol of the block B.

4. The composition of claim 2, wherein the block D has a hydrogenation level of 60 to 99%; and each block A and B independently has a hydrogenation level of up to 20%.

5. The composition of claim 1, wherein the sulfonated styrenic block copolymer has a molecular weight (M.sub.p) of 25 to 500 kg/mol.

6. The composition of claim 1, wherein the sulfonated styrenic block copolymer has an ion exchange capacity (IEC) of 0.5 to 2.6 meq/g.

7. The composition of claim 1, wherein the sulfonated styrenic block copolymer has a glass transition temperature (Tg) of 80 to 180° C., measured by Dynamic Mechanical Analysis (DMA) according to ASTM 4065.

8. The composition of claim 1, wherein the compound which reacts with the sulfonated styrenic block copolymer to form a cross-linked sulfonated styrenic block copolymer is a non-sulfonated polymer having at least one block D′, wherein the block D′ has a vinyl content of 40 to 90 wt. %, based on total weight of the polymerized conjugated diene monomers in the block D′.

9. The composition of claim 8, wherein the non-sulfonated polymer is an unhydrogenated styrenic block copolymer having a block D′ and a block B′.

10. The composition of claim 9, wherein the block B′ constitutes from 5 to 40 wt. % and the block D′ constitutes from 60 to 95 wt. %, based on total weight of the unhydrogenated styrenic block copolymer.

11. The composition of claim 8, wherein the non-sulfonated polymer has a molecular weight (M.sub.p) of 20 to 400 kg/mol, and a coupling efficiency of 50 to 95%.

12. The composition of claim 8, wherein the non-sulfonated polymer has a general configuration of: (B′-D′-B′).sub.nX, (D′-B′-D′).sub.nX, (B′-D′).sub.nX, (B′D′).sub.nX(D′).sub.m or mixtures thereof, wherein each m and n is a positive integer from 2 to 30, and X is a residue of a coupling agent.

13. The composition of claim 1, wherein the compound which reacts with the sulfonated styrenic block copolymer to form a cross-linked sulfonated styrenic block copolymer is a non-sulfonated polymer, and wherein the non-sulfonated polymer is a polybutadiene having a 1,2 vinyl content of at least 70%.

14. The composition of claim 1, wherein the compound which reacts with the sulfonated styrenic block copolymer to form a cross-linked sulfonated styrenic block is a non-sulfonated polymer, and wherein the sufficient amount is 1 to 45 wt. %, based on total weight of the composition.

15. The composition of claim 1, wherein the compound which reacts with the sulfonated styrenic block copolymer to form a cross-linked sulfonated styrenic block copolymer is a cross-linking agent or a metal cation, wherein the sufficient amount is 0.1 to 15 wt. %, based on total weight of the composition.

16. The composition of claim 1, wherein the compound which reacts with the sulfonated styrenic block copolymer to form a cross-linked sulfonated styrenic block copolymer is a metal cation, and wherein the metal cation is at least one selected from the group consisting of Zn acetate, Fe(II) oxolate, Cu(II) i-butyrate, Ca stearate, Al 2-ethylhexanoate, Ti(IV) 2-ethylhexoxide, Al hydroxide, Al oxide, Al chloride, triethylaluminium, Fe(III) oxide, Cu(II) oxide, Zn oxide, Cu(I) oxide, Ca oxide, and mixtures thereof.

17. The composition of claim 1, wherein the compound which reacts with the sulfonated styrenic block copolymer to form a cross-linked sulfonated styrenic block copolymer is a cross-linking agent, and wherein the cross-linking agent is selected from a polyisocyanate, a polyester diol, and mixtures thereof

18. The composition of claim 1, wherein the film has a thickness of 1 to 400 μm, and wherein the film is cross-linked/cured by heat, UV radiation, gamma radiation, electron-beam, or microwave, in the presence or absence of an initiator, wherein the initiator is any of a thermal initiator or a photo initiator.

19. The composition of claim 1, wherein the film has at least one of: a tensile stress in dry state of 6.2 to 20 MPa; a toughness in dry state of 3 to 25 MJ/m.sup.3; a Young's modulus in dry state of 190 to 600 MPa; a Young's modulus in wet state after 1 week of 7.5 to 70 MPa; an elongation at break in dry state of 75 to 250%; and an elongation at break in wet state after 1 week of 60 to 150%; all measurements according to ASTM D412.

20. The composition of claim 1, wherein the film has at least one of: a moisture vapor transmission rate (MVTR) in an upright manner of 1000 to 30000 g/m.sup.2/day; and a moisture vapor transmission rate (MVTR) in an upside down manner of 1000 to 150000 g/m.sup.2/day, both measurements according to ASTM E96/E96M.

Description

EXAMPLES

[0109] The following examples are intended to be non-limiting.

[0110] Polymer molecular weights are determined by GPC using polystyrene calibration standards according to ASTM 5296.

[0111] The viscoelastic behavior is measured by DMA according to ASTM 4065.

[0112] Mechanical properties, including toughness, Young's modulus, tensile strength, and elongation at break, in the dry state are measured according to ASTM D412.

[0113] Mechanical properties, including Young's modulus, tensile strength, and elongation at break, in the wet state are measured similar to the method according to ASTM

[0114] D412 using samples that have been equilibrated under water prior to testing.

[0115] MVTR measurements of samples are performed according to ASTM E96/E96M.

[0116] The degree of sulfonation of samples is determined by potentiometric titration.

[0117] The components used in examples include:

[0118] SSBC-1: A sulfonated penta-block copolymer of the structure poly[tert-butylstyrene-b-(ethylene-alt-propylene)-b-(styrene-co-styrene—sulfonate)-b-(ethylene-alt-propylene)-tert-butylstyrene] (tBS-EP-sPS-EP-tBS) with 52% degree of sulfonation. The tBS block has a Mp of about 15 kg/mol, the EP blocks each has a Mp of about 12 kg/mol, and the interior sPS block has a Mp of about 22 kg/mol. The SSBC-1 has an IEC of 2.0 mmol/g at 10.5 wt. % solids in an apolar solvent mixture of 1:1 cyclohexane/heptane).

[0119] nSP-1: A styrenic block copolymer of structure (A′B′).sub.2X(B′).sub.2, wherein A is a polystyrene block and B is a butadiene block having a 1,2-vinyl content of 57% by weight,

[0120] X is gamma-glycidoxypropyltrimethoxy silane, and a coupling efficiency is 89%. nSP-1 has a PSC of 20 wt. %, a butadiene content of 80 wt. %, a vinyl content of 60 wt. %, a coupling efficiency of >84%, and a Mp of 230 kg/mol.

[0121] nSP-2: A polybutadiene resin from Cray Valley USA, LLC, having a number average molecular weight of 4.7 kg/mol, and a 1,2 vinyl content of 85%.

[0122] Tolonate™ HDB 75 is an aliphatic polyisocyanate from Vencorex Chemicals.

[0123] K-FLEX® 188 is an aliphatic polyester diol from King Industries.

Example 1

[0124] SSBC-1 films were thermally treated at 120° C. for 10 and 30 minutes. Some film samples were not placed in grill plate inside the oven but exposed to heat in open air, indicated as “Air.”

Example 2

[0125] SSBC-1 (98 wt. %) and nSP-2 (2 wt. %) were mixed in toluene/1-proponal solvent mixture (50/50 wt. %) to yield a 20 wt. % concentrated dispersion/solution. The dispersion/solution was left overnight on roller to achieve complete dissolution. Film samples were prepared of 25 μm (1 mil) thickness each by automatic film applicator. The thermal curing of films was conducted at 120° C. for different period in an oven.

Example 3

[0126] The procedure of example 2 was repeated except for the amount of nSP-2. The amounts of SSBC-1 and nSP-2 were 95 wt. % and 5 wt. % respectively.

Example 4

[0127] The procedure of example 2 was repeated having 95 wt. % of the SSBC-1 and 5 wt. % of the nSP-1.

Example 5

[0128] The procedure of example 2 was repeated for multiple samples with varying weights of SSBC-1 and nSP-1 or nSP-2 and films were cured by E-beam at 200 kGy.

Example 6

[0129] The procedure of example 2 was repeated except nSP-1 was used instead. The film was prepared containing 94.4 wt. % of the SSBC-1, 5 wt. % of the nSP-1, 0.5 wt. % of 1,6-hexanediol diacrylate (HDDA), and 0.1 wt. % of Irgacure-651 photoinitiator. The film was cured by using UV radiation.

Example 7

[0130] The procedure of example 2 was repeated except cross-linking agents were used instead of nSP-2. The SSBC-1 was mixed with mixture of cross-linking agents for multiple samples: (a) 4 wt. % of Tolonate™ HDB 75 and 1 wt. % K-FLEX® 188, (b) 2 wt. % of Tolonate™ HDB 75 and 1 wt. % K-FLEX® 188, and (c) 3 wt. % of Tolonate™ HDB 75 and 1 wt. % K-FLEX® 188. The amount of 95 wt. % of the SSBC-1 was mixed with (a), 97 wt. % of the SSBC-1 was mixed with (b), and 96 wt. % of the SSBC-1 was mixed with (c).

Example 8

[0131] The procedure of example 2 was repeated except nSP-1 was used instead for multiple samples with varying weights of SSBC-1 and nSP-1. Films were cured by UV radiation in the presence of 4 wt. % of Omnirad 819 photoinitiator. In example 8a, the film is prepared from 96 wt. % of SSBC-1 and 4 wt. % of Omnirad 819 photoinitiator.

[0132] Mechanical properties of films obtained from examples 1 to 8 are shown in tables 1, 2, and 3. WVTR properties are shown in table 4.

Example 9

[0133] SSBC-1 was dissolved in cyclohexane to have 20 wt. % concentration. A suitable amount of the metal cation (triethylaluminium, TEA) was added drop by drop to obtain desired degree of neutralization (based on stoichiometry of SSBC-1 and TEA, in mol %). Table 5 shows mechanical performance of compositions (dry state).

TABLE-US-00001 TABLE 5 Toughness Elongation at Tensile Young's Examples (MJ/m.sup.3) break (%) strength (MPa) Modulus (MPa) 5a. SSBC-1 (No neutralization) 5.46 70.0 12.72 8.98 SSBC-1 with degree of — — — — neutralization (%) 5b. 10 3.03 28.6 16.73 11.89  5c. 20 5.67 45.4 18.06 6.16 5d. 30 5.52 37.2 20.54 6.82

[0134] As used herein, the term “comprising” means including elements or steps that are identified following that term, but any such elements or steps are not exhaustive, and an embodiment can include other elements or steps. Although the terms “comprising” and “including” have been used herein to describe various aspects, the terms “consisting essentially of” and “consisting of” can be used in place of “comprising” and “including” to provide for more specific aspects of the disclosure and are also disclosed.

[0135] For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained. It is noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the,” include plural references unless expressly and unequivocally limited to one referent. As used herein, the term “includes” and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items.

[0136] Unless otherwise specified, all technical and scientific terms used herein have the same meanings as commonly understood by one of skill in the art to which the disclosed disclosure belongs. The recitation of a genus of elements, materials, or other components, from which an individual component or mixture of components can be selected, is intended to include all possible sub-generic combinations of the listed components and mixtures thereof.

[0137] The patentable scope is defined by the claims, and can include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims. To an extent not inconsistent herewith, all citations referred to herein are hereby incorporated by reference.

TABLE-US-00002 DRY STATE Elongation Tensile Yo SSBC-1 Cross-linking agent Curing Time of Toughness at break Stress Mo ples (wt. %) nSP (wt. %) and/or initiator (wt. %) conditions curing (MJ/m.sup.3) (%) (MPa) (M x. 100 — — — — 2.8 72.2 6.1 1a 100 — — 120° C. 10 min. (Air) 3.1 46.0 7.9 1b 100 — — 120° C. 30 min. (Air) 5.5 76.3 9.4 1c 100 — — 120° C. 10 min. 9.4 134.2 9.6 1d 100 — — 120° C. 30 min. 8.3 110.3 9.5 2a 98 2 (nSP-2) — — — 12.8 165.9 10.8 2b 98 2 (nSP-2) — 120° C. 10 min. 7.8 135.6 7.8 2c 98 2 (nSP-2) — 120° C. 30 min. 9.2 131.1 9.5 3a 95 5 (nSP-2) — — — 13.2 201.1 9.9 3b 95 5 (nSP-2) — 120° C. 10 min. 11.0 143.6 10.5 3c 95 5 (nSP-2) — 120° C. 30 min. 6.1 93.3 10.5 4a 95 5 (nSP-1) — — — 7.9 118.8 7.9 4b 95 5 (nSP-1) — 120° C. 10 min. 11.2 167.7 9.9 4c 95 5 (nSP-1) — 120° C. 30 min. 15.7 205.4 12.1 5a 100 — EB - 200 — 3.2 45.2 8.6 5b 98 2 (nSP-2) — EB - 200 — 3.2 50.9 7.2 5c 95 5 (nSP-2) — EB - 200 — 4.0 65.6 7.0 5d 95 5 (nSP-1) — EB - 200 — 5.6 88.5 7.3 6 94.4 5 (nSP-1) HDDA (0.5) + UV — 6.5 132.4 6.4 Irgacure-651 (0.1) 7a-i 95 — Tolonate ™ HDB 75 (4) + 90° C. 10 min. 22.3 288.8 13.2 K-FLEX ® 188 (1) 7a-ii 95 — Tolonate ™ HDB 75 (4) + 60° C. 10 min. 17.5 238.6 12.2 K-FLEX ® 188 (1) 7b-i 97 — Tolonate ™ HDB 75 (2) + 60° C. 10 min. 16.5 230.4 12.1 K-FLEX ® 188 (1) 7b-ii 97 — Tolonate ™ HDB 75 (2) + 90° C. 10 min. 21.4 229.7 14.3 K-FLEX ® 188 (1) 7c 96 — Tolonate ™ HDB 75 (3) + 90° C. 10 min. 23.3 269.0 14.7 K-FLEX ® 188 (1) — Omnirad 819 (4) UV — 14.6 176.1 10.2 324.2 5.3 (nSP-1) Omnirad 819 (4) UV — 17.4 201.1 11.8 354.8 7.5 (nSP-1) Omnirad 819 (4) UV — 16.4 190.6 11.2 310.8 11.1 (nSP-1) Omnirad 819 (4) UV — 14.4 180.5 10.1 309.2 17.6 (nSP-1) Omnirad 819 (4) UV — 8.6 145.7 7.1 237.4 25.0 (nSP-1) Omnirad 819 (4) UV — 6.8 154.1 6.0 125.7 33.3 (nSP-1) Omnirad 819 (4) UV — 14.5 208.5 10.0 254.3 42.9 (nSP-1) Omnirad 819 (4) UV — 17.9 273.6 10.5 192.6 indicates data missing or illegible when filed

TABLE-US-00003 WET STATE (after 1 day) Elongation Tensile Young's SSBC-1 Cross-linking agent Curing Time of Toughness at break Stress Modulus les (wt. %) nSP (wt. %) and/or initiator (wt. %) conditions curing (MJ/m.sup.3) (%) (MPa) (MPa) Ex. 100 — — — — 1.4 82.8 2.8 6.0 e 1a 100 — — 120° C. 10 min. (Air) 3.1 95.2 4.5 45.9 e 1b 100 — — 120° C. 30 min. (Air) 4.0 107.6 5.1 45.3 e 1c 100 — — 120° C. 10 min. 2.0 95.0 3.4 8.0 e 1d 100 — — 120° C. 30 min. 2.8 97.8 4.2 20.2 e 2a 98 2 (nSP-2) — — — 1.2 86.5 2.2 5.4 e 2b 98 2 (nSP-2) — 120° C. 10 min. 1.9 74.5 3.6 15.9 e 2c 98 2 (nSP-2) — 120° C. 30 min. 3.5 107.2 4.9 29.4 e 3a 95 5 (nSP-2) — — — 1.8 99.6 3.0 5.6 e 3b 95 5 (nSP-2) — 120° C. 10 min. 3.1 101.1 4.8 21.5 e 3c 95 5 (nSP-2) — 120° C. 30 min. 2.2 67.2 4.7 32.0 e 4a 95 5 (nSP-1) — — — 2.1 94.5 3.6 8.1 e 4b 95 5 (nSP-1) — 120° C. 10 min. 2.8 106.8 3.9 17.7 e 4c 95 5 (nSP-1) — 120° C. 30 min. 5.4 147.2 5.5 43.7 e 5a 100 — — — — 2.6 75.4 4.9 22.7 e 5b 98 2 (nSP-2) — EB - 200 — 1.1 58.5 2.9 12.3 e 5c 95 5 (nSP-2) — EB - 200 — 1.1 55.4 3.0 11.2 e 5d 95 5 (nSP-1) — EB - 200 — 1.4 73.6 2.9 15.2 e 6 94.4 5 (nSP-1) HDDA (0.5) + UV — 2.1 81.9 3.9 27.8 Irgacure-651 (0.1) e 95 — Tolonate ™ HDB 75 (4) + 90° C. 10 min. 5.2 156.8 5.3 10.6 K-FLEX ® 188 (1) e 95 — Tolonate ™ HDB 75 (4) + 60° C. 10 min. 1.8 100.2 3 6.4 K-FLEX ® 188 (1) e 97 — Tolonate ™ HDB 75 (2) + 60° C. 10 min. 1.7 87.3 3.1 9.1 K-FLEX ® 188 (1) e 97 — Tolonate ™ HDB 75 (2) + 90° C. 10 min. 4.6 157.0 5.3 6.8 K-FLEX ® 188 (1) e 7c 96 — Tolonate ™ HDB 75 (3) + 90° C. 10 min. 3.4 140.6 4.3 6.2 K-FLEX ® 188 (1) 96 — Omnirad 819 (4) UV — 2.6 111.2 3.3 11.0 0.7 5.3 (nSP-1) Omnirad 819 (4) UV — 4.1 149.6 4.3 10.2 8.5 7.5 (nSP-1) Omnirad 819 (4) UV — 3.0 118.0 3.8 16.4 4.9 11.1 (nSP-1) Omnirad 819 (4) UV — 3.0 120.7 3.7 15.4 8.4 17.6 (nSP-1) Omnirad 819 (4) UV — 4.1 160.1 4.0 9.1 71 25.0 (nSP-1) Omnirad 819 (4) UV — 2.5 115.3 3.3 12.1 2.7 33.3 (nSP-1) Omnirad 819 (4) UV — 2.5 111.7 3.5 11.9 3.1 42.9 (nSP-1) Omnirad 819 (4) UV — 4.3 179.1 4.2 7.0 indicates data missing or illegible when filed

TABLE-US-00004 WET STATE (after 1 week) Tensile Young' SSBC-1 Cross-linking agent Curing Time of Toughness Elongation Stress Modulu les (wt. %) nSP (wt. %) and/or initiator (wt. %) conditions curing (MJ/m.sup.3) at break (%) (MPa) (MPa) Ex. 100 — — — — 1.0 57.4 3.0 7. e 1a 100 — — 120° C. 10 min. (Air) 2.0 95.8 3.3 27. e 1b 100 — — 120° C. 30 min. (Air) 2.0 77.5 3.6 41. e 1c 100 — — 120° C. 10 min. 1.3 69.5 2.9 8. e 1d 100 — — 120° C. 30 min. 1.7 73.0 3.4 19. e 2a 98 2 (nSP-2) — — — 1.3 87.2 2.4 5. e 2b 98 2 (nSP-2) — 120° C. 10 min. 1.2 65.3 2.6 15. e 2c 98 2 (nSP-2) — 120° C. 30 min. 2.4 73.8 4.2 37. e 3a 95 5 (nSP-2) — — — 1.5 87.4 2.8 5. e 3b 95 5 (nSP-2) — 120° C. 10 min. 1.1 49.6 3.2 28. e 3c 95 5 (nSP-2) — 120° C. 30 min. 1.0 49.1 2.8 23. e 4a 95 5 (nSP-1) — — — 1.4 83.9 2.6 6. e 4b 95 5 (nSP-1) — 120° C. 10 min. 2.1 87.6 3.5 22. e 4c 95 5 (nSP-1) — 120° C. 30 min. 5.0 131.7 5.5 59. e 5a 100 — EB - 200 — 1.5 62.6 3.4 39. e 5b 98 2 (nSP-2) — EB - 200 — 1 57.9 2.7 11. e 5c 95 5 (nSP-2) — EB - 200 — 0.6 41.1 2.1 10. e 5d 95 5 (nSP-1) — EB - 200 — 1.4 70.7 2.8 20. e 6 94.4 5 (nSP-1) HDDA (0.5) + UV — 2.5 91.2 4 32. Irgacure-651 (0.1) e 95 — Tolonate ™ HDB 75 (4) + 90° C. 10 min. 4.8 152.3 5.1 10. K-FLEX ® 188 (1) e 95 — Tolonate ™ HDB 75 (4) + 60° C. 10 min. 1.6 96 2.8 6. K-FLEX ® 188 (1) e 97 — Tolonate ™ HDB 75 (2) + 60° C. 10 min. 1.7 85.6 3.1 9. K-FLEX ® 188 (1) e 97 — Tolonate ™ HDB 75 (2) + 90° C. 10 min. 1.8 86.0 3.3 8. K-FLEX ® 188 (1) e 7c 96 — Tolonate ™ HDB 75 (3) + 90° C. 10 min. 2.5 113.2 3.7 7. K-FLEX ® 188 (1) — Omnirad 819 (4) UV — 2.7 105.8 3.5 16.3 7 5.3 (nSP-1) Omnirad 819 (4) UV — 3.8 147.4 4.1 11.5 5 7.5 (nSP-1) Omnirad 819 (4) UV — 2.8 112.8 3.6 15.5 9 11.1 (nSP-1) Omnirad 819 (4) UV — 3.2 121.5 3.9 16.8 4 17.6 (nSP-1) Omnirad 819 (4) UV — 3.6 145.1 3.8 13.3 25.0 (nSP-1) Omnirad 819 (4) UV — 2.4 112.8 3.2 13.4 7 33.3 (nSP-1) Omnirad 819 (4) UV — 2.4 116.3 3.3 12.3 1 42.9 (nSP-1) Omnirad 819 (4) UV — 2.5 129.0 3.1 9.8 indicates data missing or illegible when filed

TABLE-US-00005 WVTR Data (at 50° C. and 10% Relative Humidity Comparison Comparis SSBC-1 Cross-linking agent Curing Time of with Comp. Upside with Com ples (wt. %) nSP (wt. %) and/or initiator (wt. %) conditions curing Upright Ex. (%) down Ex. (%) Ex. 100 — — — — 10000.0 NA 101303.0 e 1a 100 — — 120° C. 10 min. (Air) 9106.0 91.0 102378.0 10 e 1b 100 — — 120° C. 30 min. (Air) 9384.0 94.0 86145.0 8 e 1c 100 — — 120° C. 10 min. 9619.0 96.0 93264.0 9 e 1d 100 — — 120° C. 30 min. 9677.0 97.0 96227.0 9 e 2a 98 2 (nSP-2) — 9790.0 98.0 109230.0 10 e 2b 98 2 (nSP-2) — 120° C. 10 min. 10006.0 100.0 101372.0 10 e 2c 98 2 (nSP-2) — 120° C. 30 min. 9549.0 95.0 98206.0 9 e 3a 95 5 (nSP-2) — 10096.0 101.0 124590.0 12 e 3b 95 5 (nSP-2) — 120° C. 10 min. 9590.0 96.0 105964.0 10 e 3c 95 5 (nSP-2) — 120° C. 30 min. 10239.0 102.0 98364.0 9 e 4a 95 5 (nSP-1) — 9900.0 99.0 100950.0 10 e 4b 95 5 (nSP-1) — 120° C. 10 min. 9851.0 99.0 95070.0 9 e 4c 95 5 (nSP-1) — 120° C. 30 min. 9793.0 98.0 89793.0 8 e 5a 100 — EB - 200 — 10307.0 103.0 94993.0 9 e 5b 98 2 (nSP-2) — EB - 200 — 10234.0 102.0 95956.0 9 e 5c 95 5 (nSP-2) — EB - 200 — 9914.0 99.0 100150.0 9 e 5d 95 5 (nSP-1) — EB - 200 — 10081.0 101.0 103115.0 10 e 6 94.4 5 (nSP-1) HDDA (0.5) + UV — 9659.0 97.0 99980.0 9 Irgacure-651 (0.1) e 7a-i 95 Tolonate ™ HDB 75 (4) + 90° C. 10 min. 7111 71 82331 K-FLEX ® 188 (1) e 7a-ii 95 Tolonate ™ HDB 75 (4) + 60° C. 10 min. 7915 79 102949 K-FLEX ® 188 (1) Tolonate ™ HDB 75 (2) + 60° C. 10 min. 9502 95 105076 104 K-FLEX ® 188 (1) Tolonate ™ HDB 75 (2) + 90° C. 10 min. 8335 83 104621 103 K-FLEX ® 188 (1) Tolonate ™ HDB 75 (3) + 90° C. 10 min. 8463 85 113126 112 K-FLEX ® 188 (1) Omnirad 819 (4) UV — 7515 75 95485 94 5.3 (nSP-1) Omnirad 819 (4) UV — 8179 82 98562 97 7.5 (nSP-1) Omnirad 819 (4) UV — 8116 81 97389 96 11.1 (nSP-1) Omnirad 819 (4) UV — 8033 80 100097 99 17.6 (nSP-1) Omnirad 819 (4) UV — 8096 81 107305 106 25.0 (nSP-1) Omnirad 819 (4) UV — 7488 75 112724 111 33.3 (nSP-1) Omnirad 819 (4) UV — 6665 67 112714 111 42.9 (nSP-1) Omnirad 819 (4) UV — 7477 75 102294 101 indicates data missing or illegible when filed