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Fully Water-Blown Polyisocyanurate-Polyurethane Foams with Improved Mechanical Properties Prepared from Aqueous Solution of Gell

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Fully Water-Blown Polyisocyanurate-Polyurethane Foams with Improved Mechanical Properties Prepared from Aqueous Solution of Gell Spec. Matrices 2019; 7:1–19 Research Article Open Access Kazumasa Nomura* and Paul Terwilliger e-Polymers 2019; 19: 277–289 Self-dual Leonard pairs Research Article Open Access https://doi.org/10.1515/spma-2019-0001 Received May 8, 2018; accepted September 22, 2018 Benjatham Sukkaneewat, Duangruthai Sridaeng and Nuanphun Chantarasiri* Abstract: Let F denote a eld and let V denote a vector space over F with nite positive dimension. Consider Fully water-blown polyisocyanurate-polyurethanea pair A, A∗ of diagonalizable F-linear maps on V, each of which acts on an eigenbasis for the other one in an irreducible tridiagonal fashion. Such a pair is called a Leonard pair. We consider the self-dual case in which foams with improvedthere mechanical exists an automorphism properties of the endomorphism algebra of V that swaps A and A∗. Such an automorphism is unique, and called the duality A A∗. In the present paper we give a comprehensive description of this ↔ prepared from aqueousduality. In solution particular, we display of angelling/ invertible F-linear map T on V such that the map X TXT− is the duality → A A∗. We express T as a polynomial in A and A∗. We describe how T acts on ags, decompositions, blowing and trimerization↔ catalysts and 24 bases for V. https://doi.org/10.1515/epoly-2019-0028 Keywords: Leonardmechanical pair, properties; tridiagonal self-extinguishing matrix, self-dual properties; HF1 Received October 21, 2018; accepted December 17, 2018. materials Classication: 17B37,15A21 Abstract: Fully water-blown polyisocyanurate-polyure- thane (PIR-PUR) foams with improved mechanical proper- ties have been prepared using aqueous solutions of metal- 1 Introduction ammonia complex, Cu(Am) or Zn(Am), as gelling/blowing Introduction catalysts and potassium octoate (KOct) solution in diethy- Polyisocyanurate (PIR) foams are recognized as the lene glycol as a trimerization catalyst. Two catalystLet F denote mix- aefficient eld and thermo-insulations let V denote a vectorutilized space for constructions. over F with nite positive dimension. We consider a tures, Cu(Am)+KOct and Zn(Am)+KOct, were pairobtainedA, A ∗asof diagonalizableManufacturing Fprocesses-linear maps of PIR on foamsV, each are of whichsimilar actsto on an eigenbasis for the other one in an homogeneous aqueous solutions. In comparisonirreducible to com- tridiagonalthose of rigid fashion. polyurethane Such a pair (RPUR) is called foams. a LeonardIsocyanurate pair (see [13, Denition 1.1]). The Leonard pair mercial catalyst system, DMCHA+KOct (DMCHA = N,N- linkages are formed by cyclotrimerization of excess A, A∗ is said to be self-dual whenever there exists an automorphism of the endomorphism algebra of V that dimethylcyclohexylamine), Cu(Am) and Zn(Am) could isocyanate compounds using suitable trimerization swaps A and A∗. In this case such an automorphism is unique, and called the duality A A∗. be miscible with KOct solution and water easier than catalysts. The outstanding properties of PIR foams over ↔ DMCHA. This miscibility improvement led Cu(Am)+KOctThe literature conventional contains RPUR many foams examples are inherent of self-dual thermal Leonard stability pairs. For instance (i) the Leonard pair associ- and Zn(Am)+KOct to show faster catalytic atedreactivity with in an irreducibleand low flammability module for the (1-4). Terwilliger Meanwhile, algebra unmodified of the hypercube (see [4, Corollaries 6.8, 8.5]); (ii) a PIR-PUR foam reactions than DMCHA+KOct. AllLeonard obtained pair ofPIR Krawtchouk foams with type too (see many [10, Denition isocyanurate 6.1]); crosslinks (iii) the Leonard pair associated with an irreducible PIR-PUR foams showed self-extinguishing propertiesmodule and for theare Terwilliger extremely algebra fragile ofand a distance-regular unable to use in graph practical that has a spin model in the Bose-Mesner alge- achieved HF1 materials. However, PIR-PUR foamsbra (see prepa [1,- Theorem],applications [3, Theorems(2,5). Several 4.1, 5.5]);attempts (iv) anhave appropriately been made normalized totally bipartite Leonard pair red from Cu(Am)+KOct and Zn(Am)+KOct at NCO:OH(see [11, ratio Lemma to 14.8]);reduce (v)the the brittleness Leonard of pair PIR consisting foams by ofsubstituting any two of a modular Leonard triple A, B, C (see [2, of 2:1 had suitable density for industrial applicationsDenition and 1.4]); some (vi) isocyanurate the Leonard linkages pair consisting with other of linkages, a pair of such opposite as generators for the q-tetrahedron alge- showed higher compressive strength than thatbra, prepared acting onoxazolidone, an evaluation urethane module and (see carbodiimide [5, Proposition linkages 9.2]). (6-8). The In example (i) is a special case of (ii), and the from DMCHA+KOct. These foams have high potential to the case of polyisocyanurate modified with polyurethane examples (iii), (iv) are special cases of (v). apply as insulations for constructions, core laminates in (PIR-PUR) foams, attention has been paid to improve their Let A, A∗ denote a Leonard pair on V. We can determine whether A, A∗ is self-dual in the following way. wall panel or storage tanks. properties. The modification methodology for PIR-PUR d By [13, Lemmafoams 1.3] each includes eigenspace a choice of polyolsA, A∗ has(9-12), dimension catalysts (13) one. and Let θi i= denote an ordering of the eigen- { } d Keywords: fully water-blown polyisocyanurate-polyvalues of A-. Forblowing ≤ iagents≤ d let (14).vi Typicaldenote blowing a θi-eigenvector agents for forPIR-PURA. The ordering θi i= is said to be standard d { } d urethane (PIR-PUR) foams; aqueous catalystwhenever solutions;A ∗ actsfoams on are the hydrochlorofluorocarbons basis vi i= in an irreducible (HCFCs), tridiagonal pentane fashion. If the ordering θi i= is standard d { } { } then the orderingor theirθd mixtures−i i= is alsowith standard,water. Meanwhile, and no furtherthe use orderingof only is standard. Similar comments apply to d { } d A∗. Let θ waterdenote for a standardfully water-blown ordering ofPIR-PUR the eigenvalues foams have of Athe. Then A, A∗ is self-dual if and only if θ { i}i= { i}i= * Corresponding author: Nuanphun Chantarasiri, Supramolecularis a standard orderingadvantages of due the to eigenvalues no ozone depleting of A∗ (see potential [7, Proposition and lower 8.7]). Chemistry Research Unit, Department of Chemistry, Faculty of costs than HCFCs (2,14). The good dimensional stability Science, Chulalongkorn University, Bangkok, 10330, Thailand, of fully water-blown PIR-PUR foams can be reached with e-mail: [email protected]. foam density ≥ 43.2 kg/m3 (2). Benjatham Sukkaneewat, Program of Petrochemistry and Polymer In the production of PIR-PUR foams, catalysts serve Science, Faculty of Science, Chulalongkorn University,*Corresponding Bangkok, Author: Kazumasa Nomura: Tokyo Medical and Dental University, Ichikawa, 272-0827,Japan, 10330, Thailand. E-mail: [email protected] important components in determining the final foam Duangruthai Sridaeng, Department of Chemistry, FacultyPaul of Terwilliger:Science, properties.Department Catalyst of Mathematics, mixtures University between of Wisconsin, trimerization Madison, WI53706, USA, E-mail: Rangsit University, Pathumthani, 12000, Thailand. [email protected] gelling/blowing catalysts are required to balance Open Access. © 2019 Sukkaneewat et al., published byOpen De Gruyter. Access. ©This2019 work Kazumasa is licensed Nomura under and the Paul Creative Terwilliger, Commons published by De Gruyter. This work is licensed under the Creative Commons Attribution alone 4.0 License. Attribution alone 4.0 License. 278 B. Sukkaneewat et al.: Fully water-blown polyisocyanurate-polyurethane foams the reaction rate of isocyanurate formation, urethane the investigation of copper- and zinc-ammonia complex formation and CO2 generation. This results in PIR-PUR structures in an ammonia solution (22-25). The chemistry foams with desirable properties (15). Typical trimerization of metal-ammonia complexes was applied to prepare catalysts used for isocyanurate formation are carboxylic hollow copper- and zinc-oxides/nitrogen doped graphene acid salts, namely potassium octoate (KOct) and hybrids using metal–ammonia complexes as precursors 2+ potassium acetate (KOAc), and quaternary ammonium (26). The [Cu(NH3)x] form of heulandite (CuammHEU) salts. Tertiary amines, which are commercial catalysts was prepared by the treatment of the Na-form of natural of RPUR foam, have been used as co-catalysts with heulandite crystals with the copper-ammonia complex trimerization catalysts for PIR-PUR foam preparation. solution. The structure of the complex contained in the For examples, Gao et al. (16) used the catalyst mixture A channel of CuammHEU was disordered square planar 2+ between the KOct solution in diethylene glycol and N,N- [Cu(NH3)4] having two axial H2O ligands to give the dimethylcyclohexylamine (DMCHA) in the preparation elongated octahedron structure (27). Copper–substituted of PIR-PUR foam nanocomposites. Lövenich et al. (17) ZSM-5 catalysts were obtained from the ion exchange investigated starting material effects on trimer formation process of H–ZSM-5 in the solution of copper-ammonia 2+ of PIR-PUR foams, whose reactions were accelerated by complex, [Cu(NH3)n(H2O)6-n] . The composition of the KOAc and DMCHA. Modesti et al. (18) prepared PIR-PUR complexes in the solution related to copper:ammonia ratio 2+ foams with different charring agents using KOct and and pH of the solution. The [Cu(NH3)4(H2O)2] complex pentamethyldiethylenetriamine as catalysts. was predominant at pH 8.5–10.5 and appeared as the most DMCHA is a good gelling/blowing catalyst. However, stable form (28). for fully water-blown PIR-PUR foams, the drawback of To the best of our knowledge, aqueous solution of using DMCHA is its non-homogeneous mixture with metal-ammonia complexes has never been reported as the KOct in diethylene glycol. Therefore, we proposed to use catalyst in PIR-PUR foam preparation. Therefore, the aims gelling/blowing catalysts as aqueous solutions, which of this study are to synthesize metal-ammonia complexes should be easily miscible with KOct in diethylene glycol.
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