Building Heat-insulating Materials Based on the ... - Science Direct

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ScienceDirect Procedia Engineering 165 (2016) 1455 – 1459

15th International scientific conference “Underground Urbanisation as a Prerequisite for Sustainable Development”

Building heat-insulating materials based on the products of the transesterification of polyethylene terephthalate and dibutyltin dilaurate Vladimir Erofeeva,*, Alexander Bobryshevb, Lenar Shafigullinb, Pavel Zubarevc, Alexander Lakhnoc, Ilia Darovskikhc, Ilia Tretiakova b

a Ogarev Mordovia State University, Saransk, 430005, Russia Naberezhnye Chelny Institute of Kazan Federal University, Naberezhnye Chelny, 423812, Russia c Russia Penza State University of Architecture and Construction, Penza, 440028, Russia

Abstract In this paper, we offered a technological basis for production of heat-insulating polyurethane materials based on the aromatic polyester – the product of transesterification of polyethylene terephthalate and corrective additive - dibutyltin dilaurate. Also, we presented the formulation and properties of the developed polyurethanes. © 2016 2016Published The Authors. Published by Elsevier Ltd. © by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). Peer-review under responsibility of the scientific committee of the 15th International scientific conference “Underground Peer-review under scientific committee of the 15th International scientific conference “Underground Urbanisation as a Urbanisation as aresponsibility Prerequisiteof fortheSustainable Development. Prerequisite for Sustainable Development Keywords: building materials, heat-insulating materials, foamed polyurethane, aromatic polyester, corrective additives.

1. Main text One of the most common and efficient insulation materials today is polyurethane foam because it has a number of unique characteristics. Its application is possible directly on site using simple deposition and filling installations, it

* Corresponding author. E-mail address: [email protected]

1877-7058 © 2016 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license

(http://creativecommons.org/licenses/by-nc-nd/4.0/). Peer-review under responsibility of the scientific committee of the 15th International scientific conference “Underground Urbanisation as a Prerequisite for Sustainable Development

doi:10.1016/j.proeng.2016.11.879

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Vladimir Erofeev et al. / Procedia Engineering 165 (2016) 1455 – 1459

does not require additional operations and resources, as polyurethane has good adhesion to most building materials. The lifetime of the PU without loss of physico-chemical properties is more than 30 years. Polyurethane foams have one of the lowest thermal conductivity of foams (0,02 – 0,04 W/m∙K). They can possess, depending on requirements, open and closed pores. Foams based on polyurethanes have a high prochnost-deformation indicators, in comparison with other common foams [1,5,6]. Its starting components are liquid and viscous substance with a density of 1100 – 1200 kg/m3, while the density of heat-insulating polyurethane foams may be only 20 kg/m3. Thus, the cost of polyurethane foam overlap low transport costs. World consumption of polyurethanes in 2013 amounted to 19 million tonnes (an increase since 2010 - 24%) [1-9]. Changing the major operational and technological parameters of heat insulation and structural-heat insulating polyurethane foam is most often made due to the correction of the composition of component "A". In our case, the base material of the component "A" (hydroxyl component) is an aromatic polyester (Arpol) obtained because of the transesterification of waste polyethyleneterephtalate (PET) complex of glycols having a hydroxyl number of 350360 mg KOH/g. As component "B" was used, polyisocyanate WANNATE PM-200 (PIC). By corrective additives in the General case include: catalysts for the hydrolysis and retinoblastoma, foaming agents and instabilization. The process of obtaining Arpol includes: x Download all the necessary components: waste polietilentereftalata, monoethylene glycol, diethylene glycol, 1,4butandiol, dibutylthiourea tin, in the appropriate proportions in laboratory and industrial reactor-mixer in stainless steel, is equipped with a slow stirrer and thermostabilization, with node a high-temperature organic heat carrier. x the Abstraction of water vapor and excess ethylene glycol, and vapor of diethylene glycol and 1,4-butanediol, which is carried out using a Packed distillation column with reflux drum number 10. x Completion of the process of depolymerization and transesterification until the reaction mass needed calculated hydroxyl number (MS) 350-360 mg KOH/g, and the resulting Arpol merges with simultaneous filtration, x Cooling and packing in an airtight container for further research or the production of heat-insulating material. Next, the resulting aromatic polyester in combination with polyisocyanate and corrective additives are mixed and with the help of special equipment applied to the surface you want to insulate. Spraying foam allows you to quickly generate seamless water insulation coating, has a number of unique properties. The fill of polyurethane foam allows the insulation of the reach spraying areas, and also allows you to create decorative thermal insulation products. Currently there are different installation for spraying and pouring polyurethane foam, the main differences honey which are in the process of mixing the components. In high-pressure mixing of components is carried out by supplying components in the opposite direction under high pressure into a mixing chamber having a small volume. In installations of low-pressure mixing is carried out by mechanical or aerodynamic effects on the components in the mixing chambers. For pouring and spraying on some foreign domestic installations it is possible to change the ratio of the components "A" and "B" in the range from 1:2 to 2:1, which is connected with the necessity to maintain the required balance of the active groups of components in the mixture. However, advances in modern technology foam allows components at a ratio of 1:1 by volume, through the adjustment of those or other active substances to the most common rigid polyurethane foams. In this regard, the most widely sputtering and casting machines, high and low pressure, allowing to work with a fixed ratio of components 1:1 by volume. Between casting and sputtering systems, there are differences of technological parameters, namely the start time and rise time, which is achieved through the use of various amounts of catalysts. In turn, the variation amount of the catalysts leads to a change in temperature parameters of the reaction mass and, consequently, to obtain the required density, polyurethane foam in addition to the number of foaming agents you must consider the number of catalysts. To obtain the integral polyurethane foam application as blowing agent water is not acceptable, as allocated in its reaction with isocyanates carbon dioxide has a very high critical pressure and low critical temperature. Therefore, to maintain the balance of active groups when used as a foaming agent an inert component Freon 141B and the ratio of components 1:1 by volume was introduced glycerol (GL) with significant amount of active OH groups. The main component used in the work is active through the use of the catalyst of penetritiary – dibutylthiourea tin. As


additional catalysts for sputtering systems were introduced additional amount of dibutyltin dilaurate and amine catalyst DABCO 33-LV [1]. As blowing agents were injected water as a chemical foaming agent and Freon 141B physical foaming agent. By the reaction of water and isocyanate, 2ОСNRNCO+H2OoОСNRNHCONHRNCO+CO2, the formation of urea cross-linking and release carbon dioxide. As can be seen from the equation, the introduction of water leads to the necessity of introducing an additional amount of isocyanate. The introduction of one mole of water leads to the release of one mole of carbon dioxide, due to the difference of molecular masses of water and carbon dioxide we have mCO2=mH2O∙MCO2/MH2O=mH2O∙44/18=2,44mH2O, that the mass of carbon dioxide produces more mass of reacted water. From the ideal gas law, knowing the molecular weight, we are able to determine the amount of the blowing gas temperature and weight of blowing agents VCO2=mCO2∙R∙T/(MCO2∙p)=2,44mH2O∙R∙T/(44∙p)=0,05545mH2O∙R∙T/p. Freon 141B has a low boiling point and by heating the reaction mass passes in a gaseous state volume, which is determined in a similar way. VKhladon141B= mKhladon141B∙R∙T/(MKhladon141B∙p)=mKhladon141B∙R∙T/(116,95∙p) R – the universal gas constant; p – the pressure of the foaming gas in a free expansion is assumed equal to atmospheric; T – the temperature of this blowing gas depends on the temperature of the feedstock from ambient temperature and the speed of the exothermic reaction of formation of polyurethane. The need for the introduction of instabilities additives based on surface-active substances, due to the fact that without their use in foaming the formation of heterogeneous structure, and foaming gases leaving the forming polymer. Which does not allow to obtain the required thermal insulation foams density and structure. Foaming additives raise the weight of emerging polymer composite, but to maintain it in a certain state, providing cells of a certain size and shape, it is necessary to introduce surfactants. The surfactant also can provide the stability of the mixture comprising the hydroxyl-containing component, stabilize and regulate the size of the cells. As surfactants in polyurethane foam using different types of substances, but the most widely surfactants based on copolymers of alkylchlorosilanes [10]. Figure 2 shows photographs of the structure of samples without application and with application of surfactants. a) b)

Fig. 1. Structure of the foamed PU based on the Arpol: (a) without surfactant; (b) using Penta®-484.

Based on the foregoing studies have been conducted in accordance with GOST 17177-94 "Materials and products building insulation. Test methods" [11]. The developed formulations dosing systems with start times that are in the

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range of 25-35 seconds, and sputtering with a startup time of 1-3 seconds, for which a certain apparent density, kg/m3, was determined by the method GOST 23206-78 "Mesh hard plastic " [12]. Table 1. Some characteristics of the developed polyurethane formulations. №

Composition, mass fraction

Start time,

Conventional compression strength, MPa

Thermal conductivity,

35

0,02

less 0,03

16

32

0,24

less 0,03

35

27

0,43

less 0,03

80

≈2

0,02

less 0,03

18

≈2

0,26

Менее 0,03

37

≈2

0,44

Менее 0,03

83

s. 1

Arpol - 100

Apparent density, kg / m3

W/m2∙C

Water - 3.6 Freon 141B – 34 Penta®-484 – 5 PIZ - 145 2

Arpol –100 Water – 2,2 Khladon 141B – 15 Penta®-484 – 2 PIZ – 122 масс.ч.

3

Arpol –90 GL–15 Khladon 141B – 27 Penta®-484 – 3 PIZ – 140

4

Arpol –100 Water – 3,2 Khladon 141B – 33 Penta®-484 – 5 DIBUTYLTIN DILAURATE – 0,2 DABCO 33-LV – 0,6 PIZ – 140 масс.ч.

5

Arpol –100 Water – 1,9 Khladon 141B – 12 Penta®-484 – 2 DIBUTYLTIN DILAURATE – 0,1 DABCO 33-LV – 0,5 PIZ – 120 масс.ч

6

Arpol –90 Water – 1,5 Khladon 141B – 5 Penta®-484 – 3 DIBUTYLTIN DILAURATE – 0,1 DABCO 33-LV – 0,4 PIZ –100 масс.ч.


Test method for compression: conventional compression strength was determined by the method on a tensile testing machine IR 5057-50 has a supporting pad for compression with a constant loading rate of 5 mm/min; the thermal conductivity was determined using the ITP tool MG-4 by the method of GOST 30256-94 "construction Materials and products. Method of determination of thermal conductivity of the cylindrical probe" [13]. The primary hydroxyl-bearing component, which was used in the work for the formation of the stable active foam is the catalyst the product of penetritiary – dibutylthiourea tin. As additional catalysts for sputtering systems were introduced additional amount of DIBUTYLTIN DILAURATE and amine catalyst DABCO 33-LV. Thus, to obtain high-quality thermal insulation polyurethane composite materials using various deposition or filling installations need to correctly pick up the prescription formulations [14-16] the initial components and catalysts. References [1] E.V. Novikov, P.A. Zubarev, A.V. Lakhno, A.N. Bobryshev, A.P. Goncharuk, Heat insulation polyurethane foam materials based on aromatic polyesters, Mezhdunarodny tekhniko-ekonomicheskiy zhurnal. 6 (2015) 76-81. [2] V.A. Vorobev, R.A. Andrianov, Polymeric insulation materials, Tekhnologiia polimerov, 1972. [3] SNIP 2.04.14-88 Thermal insulation of equipment and pipelines (1988) Gosstroy of the USSR [4] SNIP 23-02-2003 Thermal protection of buildings. Revised edition (2012) FAU «FCS» [5] K.N. Potapov, M.B. Kaddo, Building materials and products, 2001. [6] V.V. Korshak, Technology of plastics, Himia, 1985. [7] Poliuretany, Copyright © CREON Energy, 2014. Information on http://www.creonenergy.ru/consulting/detailConf.php?ID=109742 [8] Poliuretany, LLC Plastinfo, 2013. Information on http://plastinfo.ru/information/articles/431/ [9] Poliuretany, Copyright © CREON Energy, 2015. Information on http://www.creonenergy.ru/consulting/detailConf.php?ID=114711 [10] I.G. Maslova, Composition and physico-chemical properties of the raw material for producing rigid polyurethane foams by Korund company, Copyright, Korund, 2004. Information on http://www.korund-nn.ru/?id=2427 [11] GOST 17177-94. Building insulation materials and products. Test methods (1994) MNTKS [12] GOST 23206-78. Mesh hard plastics (1979) Izdatelstvo standartov [13] GOST 30256-94. The construction materials and products. Measuring thermal conductivity with cylindrical probe (1994) MNTKS [14] P.A. Zubarev, V.O. Petrenko, A.V. Lakhno, E.G. Ryliakin, Planning the optimal ratio of components in the polyurethane system, Molodoy ucheny. 6 (65) (2014) 164-166. [15] A.I. Shveyov, M.I. Gumerov, I.F. Shaehova, L.N. Shafigullin, Properties of particulate-filled cast polyurethane, Avtomobil`naia promyshlennost. 1(2016) 128-132. [16] A.N. Bobryshev, V.T. Erofeev, V.N. Kozomazov, Polymer composite materials, Textbook, 2013.

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