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WO 2018/008003 Al 11 January 2018 (11.01.2018) W !P O PCT

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WO 2018/008003 Al 11 January 2018 (11.01.2018) W !P O PCT (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2018/008003 Al 11 January 2018 (11.01.2018) W !P O PCT (51) International Patent Classification: mar P.; 120 Governors Drive, Amherst, Massachusetts C08L 61/26 (2006.01) C08K 5/17 (2006.01) 10003 (US). DESHMUKH, Subrajeet; 120 Governors C08K5/00 (2006.01) C08K 3/34 (2006.01) Drive, Amherst, Massachusetts 01003 (US). ZHAO, Caix- C08K 5/09 (2006.01) C08K 3/22 (2006.01) ia; 120 Governors Drive, Amherst, Massachusetts 01003 C08K 5/07 (2006.01) C08K 3/30 (2006.01) (US). (21) International Application Number: (81) Designated States (unless otherwise indicated, for every PCT/IB20 17/05413 1 kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ, (22) International Filing Date: CA, CH, CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM, DO, 07 July 2017 (07.07.2017) DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, (25) Filing Language: English HR, HU, ID, IL, IN, IR, IS, JO, JP, KE, KG, KH, KN, KP, KR, KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, (26) Publication Language: English MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, (30) Priority Data: OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, 62/359,865 08 July 2016 (08.07.2016) US SC, SD, SE, SG, SK, SL, SM, ST, SV, SY,TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (71) Applicant: THE UNIVERSITY OF MASSACHUSET¬ TS [US/US]; One Beacon Street, 31st Floor, Boston, Mass (84) Designated States (unless otherwise indicated, for every achusetts 02108 (US). kind of regional protection available): ARIPO (BW, GH, GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ, (72) Inventors: HSU, Shaw Ling; 120 Governors Drive, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, Amherst, Massachusetts 01003 (US). PATEL, Jigneshku- TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, (54) Title: PLASTICIZED THERMOSET RESIN, AND ASSOCIATED CURED RESIN, METHOD OF CURING, AND ARTICLE COMPRISING CURED RESIN (I") 70 60 50 P 40 30 20 10 0 0.00 0.02 0.04 0.06 0.08 0. 0 0.12 Mole fraction of plasticizer FIG. 1 o 0 ©o0 (57) Abstract: A curable composition includes a hydrogen-bonded prepolymer, a plasticizer, and, optionally, a crosslinking agent. 00 The plasticizer includes a reactive plasticizer having structure (I), (II), or (III), wherein X is -OR 1, -N(R 1)2, -R -OR1, or -R -N(R 1)2, o 1 4 2 wherein R is independently at each occurrence hydrogen or C\_(, alkyl, and R is C alkylene; y is zero or 1; z is zero or 1; R is Ci_ 3 3 12 alkyl; and R is Ci_i2 alkyl when z is 1, or R is C142 alkyl or H when z is zero. [Continued on nextpage] W O 2018/008003 A l Illlll II lllll lllll lllll ill III III Hill Hill lllll Hill Hill llll III llll llll EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, KM, ML, MR, NE, SN, TD, TG). Published: — with international search report (Art. 21(3)) — before the expiration of the time limit for amending the claims and to be republished in the event of receipt of amendments (Rule 48.2(h)) PLASTICIZED THERMOSET RESIN, AND ASSOCIATED CURED RESIN, METHOD OF CURING, AND ARTICLE COMPRISING CURED RESIN BACKGROUND [0001] For many thermoset systems, in order to produce a cured product with the desired mechanical properties, it is necessary to induce reactions of the thermoset with itself and/or of the thermoset with a curing or crosslinking agent. For example, reactants can differ in molecular weight, inter-molecular interactions within and between reactants, and inter-molecular interactions between reactants and solvents or plasticizers. Reaction kinetics and reaction products of multi-component systems are difficult to predict when t e reaction mixture is not homogeneous (that is, when it includes at least two phases). [0002] One category of such systems involves the reaction of a hydrogen-bonded thermoset resin with itself, particularly when the resin is solid or viscous under the reaction conditions. Another category of such systems involves the reaction of a hydrogen-bonded thermoset resin, and a crosslinking agent with low solubility in the resin. For example, a thermoset system can include a phenol-formaldehyde resin and a hexamethylenetetramine (HMTA; CAS Registry Number 100-97-0) crosslinking agent. Although this combination was first introduced in the late 1920s, the extreme rigidity of its cured product has hindered a detailed analysis of the crosslinking reaction. H . Baekeland, J. Ind. Eng. Chem.-US, 1909, vol. 1, pp. 149-161; L. H . Baekeland, J. Ind. Eng. Chem.-US, 1909, vol. 1, pp. 545-549; M . Harvey, L. H . Baekeland, J. Ind. Eng. Chem.-US, 1921, vol. 13, pp. 135-141. Even before crosslinking, the phenol-formaldehyde resin exhibits extensive intra- and inter-molecular hydrogen bonding. The crosslinking agent HMTA is highly crystalline (>99% crystallinity) and has a high melting temperature of nearly 280 °C. A . Knop and L. Pilato, "Phenolic resins : chemistry, applications, and performance : future directions", Springer-Verlag: Berlin; New York, 1985; A . Knop and W . Scheib, "Chemistry and Application of Phenolic Resins", Berlin; Springer-Verlag, 1983; Z . Katovic, M . Stefanic, Ind. &Eng. Chem. Prod. Res. Dev., 1985, vol. 24, pp. 179-185; X . Q. Zhang, et al., Polymer, 1997, vol. 38, pp. 5835-5848; J. P. Patel, et al, J. Polymer Set PartB: Polymer Phys ., 2015, vol. 53, pp. 1519-1526. In order to induce a crosslinking reaction between the dissimilar phenol-formaldehyde resin and HMTA, a plasticizer, such as furfural, is typically used. Furfural has been shown to disrupt the hydrogen bonds of the resin, providing mobility to the resin, which in turn facilitates dissolution and dispersion of the crosslinking agent. J . P. Patel, et al., J. Polymer Sci. PartB: Polymer Phys., 2015, vol. 53, pp. 1519-1526. Due to the rigidity of the phenyl ring of the phenol-formaldehyde resin, the glass transition temperature of the reaction product can rise quickly during the crosslinking reaction, rapidly creating a vitrified structure. V . R . Landi, J. M . Mersereau, Adv. Polymer Tech., 1987, vol. 7, pp. 49-57; V . R. Landi, Adv. Polymer Tech., 1987, vol. 7, pp. 209-218. When the vitrification point is approached, curing kinetics become diffusion controlled and strongly dependent on the local viscosity. J. B . Enns, J. K . Gillham, J. App. Polymer Sci., 1983, vol. 28, pp. 2567-2591; C. Feger, W . J. MacKnight, Macromolecules, 1985, vol. 18, pp. 280-284; M . B. M . Mangion, G . P. Johari, Macromolecules , 1990, vol. 23, pp. 3687-3695. The plasticizer can decrease the local viscosity and increase the extent of crosslinking, which is important in the increase in cohesive strength. [0003] As previously noted, one plasticizer commonly used with phenol-formaldehyde resin and HMTA is furfural, as described in US 4682988 (July 28, 1987) and US2201321 (May 21, 1940) for example. Notwithstanding many decades of use, furfural's mechanism of action has only recently begun to come into focus. Mechanistic studies suggest that furfural can disrupt various inter-molecular interactions including hydrogen bonding in t e phenol-formaldehyde resin. Although the freed hydroxyl groups of the phenol-formaldehyde resin do not appear to participate directly in the crosslinking reaction, they may interact through hydrogen bonding to help dissolve the HMTA, thereby facilitating the crosslinking reaction. The solubility of HMTA in furfural is extremely low at less than two percent by weight, so furfural is not expected to dissolve HMTA directly. J. P. Patel, et al., J. Polymer Sci. Part B: Polymer Phys., 2015, vol. 53, pp. 1519-1526. [0004] Although furfural is an effective plasticizer for curing of hydrogen-bonded prepolymers such as phenol-formaldehyde resin, there is a desire for plasticizers that enable a higher extent of crosslinking, or a higher extent of polymerization, or both. It would be a further advantage if the plasticizer could offer improved health and safety characteristics. BRIEF SUMMARY [0005] One embodiment is a curable composition, comprising: a hydrogen-bonded prepolymer; a reactive plasticizer; and, optionally, a crosslinking agent; wherein the reactive plasticizer has structure (I), (II), or (III), 1 1 4 1 4 1 1 wherein X is -OR , -NiR , -R -OR , or - R -N(R )2, wherein R is independently at each occurrence hydrogen or Ci-6 alkyl, and R4 is Ci-12 alkylene; y is zero or 1; z is zero or 1; R2 is Ci- 3 3 12 alkyl; and R is Ci-12 alkyl when z is 1, or R is Ci-12 alkyl or H when z is zero. [0006] Another embodiment is a method of forming a cured resin, the method comprising curing the curable composition above, in any of its variations. [0007] Another embodiment is a method of forming a cured resin, the method comprising: reacting a hydrogen-bonded prepolymer and, optionally, a crosshnking agent, in the presence of a plasticizer; wherein the plasticizer comprises a reactive plasticizer having structure (I), 1 4 1 4 1 1 wherein X is -OR , -N(R 1)2, -R -OR , or - R -N(R )2, wherein R is independently at each occurrence hydrogen or Ci-6 alkyl, and R4 is Ci-12 alkylene; y is zero or 1; z is zero or 1; R2 is Ci- 3 3 12 alkyl; and R is Ci-12 alkyl when z is 1, or R is Ci-12 alkyl or H when z is zero.
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