WO2023136791A1 - A rigid polyurethane foam composition suitable for use in sandwich panel industry applications - Google Patents

A rigid polyurethane foam composition suitable for use in sandwich panel industry applications Download PDF

Info

Publication number
WO2023136791A1
WO2023136791A1 PCT/TR2022/050244 TR2022050244W WO2023136791A1 WO 2023136791 A1 WO2023136791 A1 WO 2023136791A1 TR 2022050244 W TR2022050244 W TR 2022050244W WO 2023136791 A1 WO2023136791 A1 WO 2023136791A1
Authority
WO
WIPO (PCT)
Prior art keywords
amount
blend
polyol
hfo
polyether siloxane
Prior art date
Application number
PCT/TR2022/050244
Other languages
French (fr)
Inventor
Asli KAFALI
Seda PUR
Tuba GÜNER
Original Assignee
Assan Panel Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Assan Panel Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇ filed Critical Assan Panel Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇
Publication of WO2023136791A1 publication Critical patent/WO2023136791A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0019—Use of organic additives halogenated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0038—Use of organic additives containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes

Definitions

  • the present invention relates to a rigid polyurethane foam composition used as an insulating material in the construction and building materials industry.
  • Polyurethane is a polymer widely used in the industry. It is preferred in various industries due to its outstanding performance features. Polyurethane appears in two main types: thermoset polymers and thermoplastic polymers.
  • the existing polyurethane reaction mechanism is obtained by the condensation polymerization of a diol having at least two hydroxyl (-OH) functional groups and a diisocyanate having at least two isocyanate (-NCO) functional groups. Polyester polyol, polyether polyol, alcohols, diols, and triols can form hydroxyl groups while polymeric MDI (polymethylene diphenylmethane diisocyanate) is used as an isocyanate material.
  • Catalysts are used in the reaction mechanism to adjust reaction time. Catalyst sources are amine-based, metal-based and organometal-based compounds.
  • Blowing agents are used for forming the rigid polyurethane cellular foam structure of thermoset polymers. Blowing agents are classified into two categories as physical blowing agents and chemical blowing agents. Water is used as a chemical blowing agent. Water serves as a CO2 source in the reaction. Physical blowing agents used in the field are shown in Table 1 . Based on the applicable regulations, pentane isomers are currently used as physical blowing agents in rigid polyurethane foam production. Pentane isomers form the polyurethane foam cellular structure as part of the reaction mechanism. As shown in Table 1 , global warming potential (GWP) values of pentane isomers used in the field are high. Due to these high values, its use remains limited under the advancing global technology and regulation conditions.
  • GWP global warming potential
  • Polyurethane materials are preferred particularly in the construction industry due to their outstanding insulation performance features.
  • the insulation performance of an insulation material depends on the thermal conductivity coefficient of the material. Materials with low coefficient of thermal conductivity have high insulation performance. Accordingly, thermal conductivity coefficient of blowing gases used inside the polyurethane foam directly determine the insulation performance. As shown in Table 1 , ozone depletion potential (ODP) and global warming potential (GWP) values of blowing agents have been improved with the introduction of environmental regulations, but on the contrary, thermal conductivity coefficient values have increased. This has a negative impact on the expected performance features of polyurethane.
  • ODP ozone depletion potential
  • GWP global warming potential
  • New generation blowing agents are used in the white goods industry, which is a prominent industry in terms of sustainability activities.
  • patent application no. WO2018141716 relates to a polyurethane formulation containing HFO.
  • the composition comprises a polyetherol based on a polyhydric alcohol and a polyetherol (P2) based on a diamine.
  • P2 polyetherol
  • the present invention relates to a polyurethane foam formulation and preparation, which satisfies the requirements listed above, eliminates the disadvantages of the prior art while bringing new benefits to the technical field.
  • the primary object of the intervention is to develop a product suitable for use in sandwich panel industry applications, whereby greenhouse gas emissions are reduced while the insulation performance is maintained and/or increased.
  • Another object of the intervention is to ensure uniformity of cellular size, hence improve the thermal conductivity coefficient of PU foam thanks to its surfactant blend content.
  • the invention relates to a polyisocyanurate foam formulation
  • a polyisocyanurate foam formulation comprising at least one hydrofluoroolefin (HFO) blowing agent selected from the group consisting of c-pentane, isopentane, n-pentane, 1 , 1 -Dichloro-1 -fluoroethane (HCFC-141 b) and 1 -Chloro-3,3,3-trifluoropropene (HFO- 1233zd(E)); a combination of perfluoro compounds, C5-18 (PF 5056), modified polyether siloxane (Tegostab B8498) and polyether siloxane (Tegostab B8490) as a surfactant blend; and a polyol blend consisting of polyester polyol, polyether polyol and dipropylene glycol for use in sandwich panel industry applications.
  • HFO hydrofluoroolefin
  • HFO hydrofluoroolefin blowing agent selected from the group consisting of c-pentane, isopentane, n-pentane, 1 , 1 -Dichloro-1 -fluoroethane (HCFC-141 b) and 1 -Chloro-3,3,3-trifluoropropene (HFO-1233zd(E));
  • HFO hydrofluoroolefin
  • PU foam a new generation blowing agent.
  • HFO is the key input that forms the foam structure of the material. Thanks to its low thermal conductivity value, it contributes to improvement of the thermal conductivity coefficient of PU foam.
  • Polyester polyol, polyether polyol and dipropylene glycol are sources of -OH for the polyurethane reaction. Polyester polyol is derived from diethylene glycol and phtalic anhydride-based aromatic polyester polyol. Polyether polyol is used as a chain extender with three functionalities. Dipropylene glycol is a different chain extender with two functionalities.
  • the present invention derives polyisocyanurate foam by using aromatic polyester polyol.
  • the polyester polyol used in the composition has a low functionality of around 2 and low OH number (260-300 mgKOH/g). This makes it possible to derive polyisocyanurate foams with much better fire performance.
  • HFO-1233zd(E) is the blowing agent of choice in the preferred embodiment of the invention.
  • the chosen HFO (hydrofluoroolefin) is a new generation blowing agent and its specifications are shown in Table 2. Table 2. HFO-1233zd (E) Specifications
  • This blowing agent was chosen for the new formulation of the polyurethane foam due to having no ozone depletion potential and low GWP value. By using an environmentally friendly blowing agent, it is aimed to reduce greenhouse gas emissions. Moreover, thermal conductivity coefficient value is considerably lower compared to traditional blowing agents listed in Table 1. This improves the insulation performance value of the polyurethane foam produced according to the invention while contributing to global energy efficiency.
  • the formulation contains flame retardants and catalysts. These materials are used to derive the polyol blend (source of -OH), which is the first component to form polyurethane foam.
  • Polymeric isocyanate (source of -NCO) is another primary raw material of PU foam.
  • flame retardants are preferably selected from halogenated organic phosphates, and more preferably tris(chloropropyl) phosphate (TCPP) and/or triethyl phosphate (TEP). They are used as flame retardants in polyurethane foams to improve fire resistance.
  • TCPP tris(chloropropyl) phosphate
  • TEP triethyl phosphate
  • the catalyst blend contains an isocyanate trimerization catalyst (preferably Kosmos 33 and Egecat E2269) and an amine-based catalyst (preferably Polycat 41 or Dabco BL1 1 ).
  • the chemical name of Polycat 41 is N,N,N',N',N",N"-Hexamethyl-1 ,3,5-triazine-1 ,3,5(2H,4H,6H)-tripropanamine, while the chemical name of Dabco BL1 1 is Ethanamine, 2,2'-oxybis[N,N-dimethyl],
  • Kosmos 33 and Egecat E2269 are preferred as the isocyanate trimerization catalysts.
  • Kosmos 33 is a potassium acetate solution dissolved in diethylene glycol
  • Egecat E2269 is a potassium octoate solution dissolved in diethylene glycol.
  • Isocyanate trimerization catalysts are used in the isocyanurate reactions of various rigid foam applications.
  • Polycat 41 or Dabco BL1 1 is preferably used as an amine-based catalyst. Polycat 41 improves the curing (hardening) properties of polyurethane foam. Dabco BL 1 1 is effective during the first stage of the reaction between the source of OH and the source of NCO.
  • the formulation contains water.
  • a small amount of water is used in the reaction. It is a rich source of OH used for adjusting the polyurethane foam density in the reaction. Since water is also a chemical blowing agent, it serves as a cellular CO2 source in PU foam production.
  • the surfactant/silicon blend mention in the invention is a combination of perfluoro compounds, C5-18 (PF 5056), modified polyether siloxane (Tegostab B8498) and polyether siloxane (Tegostab B8490). These are also used as performance additives.
  • PF 5056 arranges the cellular structure of the foam in a way to improve the thermal conductivity coefficient value.
  • Tegostab B8498 contributes to nucleation in PU foam formation.
  • Tegostab 8490 contributes to solubility of all components and supports the formation of a homogenous foam structure. It also improves the fire performance of the foam.
  • PF 5056 performance additive arranges to cellular size to help in reducing the thermal conductivity coefficient of the PU foam.
  • a sample composition of the formulation according to the invention is shown in Table 3. Accordingly, the developed formulation comprises the following ingredients, based on the total weight of the composition:
  • Aromatic polyester polyol in an amount between 40% and 50% (preferably 45.18%); Polyether polyol in an amount between 8% and 12% (preferably 10.54%);
  • Dipropylene glycol in an amount between 2% and 4% (preferably 2.75%); Hydrofluoroolefin (HFO) in an amount between 18% and 25% (preferably 18.82%); Tris(chloropropyl) phosphate (TCPP) in an amount between 10% and 15% (preferably 12.52%);
  • HFO Hydrofluoroolefin
  • TCPP Tris(chloropropyl) phosphate
  • Triethyl phosphate in an amount between 3% and 5% (preferably 3.77%);
  • Perfluoro compounds C5-18 (PF 5056) in an amount between 2% and 3% (preferably 2.48%);
  • TEGOSTAB B 8498 in an amount between 1% and 2% (preferably 1 .51 %);
  • TEGOSTAB B 8490 in an amount between 0.3% and 0.4% (preferably 0.38%);
  • Potassium acetate solution dissolved in diethylene glycol in an amount between 0.5% and 1 % (preferably 0.75%); Water in an amount between 0.5% and 0.6% (preferably 0.56%);
  • EGECAT E2269 Potassium octoate dissolved in diethylene glycol (EGECAT E2269) in an amount between 0.3% and 0.4% (preferably 0.38%);
  • Polycat 41 in an amount between 0.2% and 0.4% (preferably 0.30%); - Dabco BL 11 in an amount between 0.1% and 0.2% (preferably 0.15%).
  • the present invention also relates to a method for forming a polyisocyanurate foam suitable for use in sandwich panel industry applications.
  • this method comprises the following process steps: a) Preparing the polyol blend consisting of aromatic polyester polyol, polyether polyol and dipropylene glycol preferably in amounts shown in Table 3 in an ultrasonic bath and removing air bubbles in the blend; b) Adding the catalyst blend and at least one flame retardant to polyol blend, preferably in amounts shown in Table 3, preferably with a mechanical mixer at preferably 1000 rpm; c) Adding a combination of perfluoro compounds, C5-18 (PF 5056), modified polyether siloxane (Tegostab B8498) and polyether siloxane (Tegostab (B8490) in an amount of 1 % with respect to the total weight of the formulation as a surfactant blend, and mixing it preferably with a mechanical mixer at 3000 ⁇ 200 rpm for 1 -2 minutes; d) Bringing the surfact
  • the blend takes a white colour when the performance additive is mixed. If the mixing speed is slow, the performance additive would not mix homogenously with the formulation and the formulation would not yield the expected results.
  • a homogenous mixture is required to produce a PU foam with low coefficient of thermal conductivity. Since the boiling point of the blowing agent HFO is 19 X3, polyol blend mixture must be kept at 17 ⁇ 0,5X3 before adding the HFO. Following this stage, the temperature of the polyol blend mixture with blowing agent is increased from 17 oC to 20X3, and the mixture amount is check ed at both temperature values to ensure they are equal. When the amounts are equal, reaction profile is recorded at 20X3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to a polyurethane foam formulation comprising at least one hydrofluoroolefin (HFO) blowing agent selected from the group consisting of c-pentane, isopentane, n-pentane, 1,1-Dichloro-1-fluoroethane (HCFC-141b) and 1-Chloro-3,3,3-trifluoropropene (HFO-1233zd(E)); a combination of perfluoro compounds, C5-18 (PF 5056), modified polyether siloxane (Tegostab B8498) and polyether siloxane (Tegostab B8490) as a surfactant blend; and a polyol blend consisting of polyester polyol, polyether polyol and dipropylene glycol for use in sandwich panel industry applications and a preparation method thereof.

Description

A RIGID POLYURETHANE FOAM COMPOSITION SUITABLE FOR USE IN SANDWICH PANEL INDUSTRY APPLICATIONS
Field of the Invention
The present invention relates to a rigid polyurethane foam composition used as an insulating material in the construction and building materials industry.
State of Art
Polyurethane (PU) is a polymer widely used in the industry. It is preferred in various industries due to its outstanding performance features. Polyurethane appears in two main types: thermoset polymers and thermoplastic polymers. The existing polyurethane reaction mechanism is obtained by the condensation polymerization of a diol having at least two hydroxyl (-OH) functional groups and a diisocyanate having at least two isocyanate (-NCO) functional groups. Polyester polyol, polyether polyol, alcohols, diols, and triols can form hydroxyl groups while polymeric MDI (polymethylene diphenylmethane diisocyanate) is used as an isocyanate material. Catalysts are used in the reaction mechanism to adjust reaction time. Catalyst sources are amine-based, metal-based and organometal-based compounds.
Blowing agents are used for forming the rigid polyurethane cellular foam structure of thermoset polymers. Blowing agents are classified into two categories as physical blowing agents and chemical blowing agents. Water is used as a chemical blowing agent. Water serves as a CO2 source in the reaction. Physical blowing agents used in the field are shown in Table 1 . Based on the applicable regulations, pentane isomers are currently used as physical blowing agents in rigid polyurethane foam production. Pentane isomers form the polyurethane foam cellular structure as part of the reaction mechanism. As shown in Table 1 , global warming potential (GWP) values of pentane isomers used in the field are high. Due to these high values, its use remains limited under the advancing global technology and regulation conditions. Polyurethane materials are preferred particularly in the construction industry due to their outstanding insulation performance features. The insulation performance of an insulation material depends on the thermal conductivity coefficient of the material. Materials with low coefficient of thermal conductivity have high insulation performance. Accordingly, thermal conductivity coefficient of blowing gases used inside the polyurethane foam directly determine the insulation performance. As shown in Table 1 , ozone depletion potential (ODP) and global warming potential (GWP) values of blowing agents have been improved with the introduction of environmental regulations, but on the contrary, thermal conductivity coefficient values have increased. This has a negative impact on the expected performance features of polyurethane.
Table 1. Conventional physical blowing agents
Figure imgf000003_0001
New generation blowing agents are used in the white goods industry, which is a prominent industry in terms of sustainability activities. For example, patent application no. WO2018141716 relates to a polyurethane formulation containing HFO. The composition comprises a polyetherol based on a polyhydric alcohol and a polyetherol (P2) based on a diamine. However, the said patent is inadequate due to its limited areas of use, non- uniform cellular size and high thermal conductivity coefficient.
In light of the above, new generation blowing agents are needed for use in rigid polyurethane foam composition, which is preferred as an insulation material particularly in the sandwich panel subsector of the construction and building materials industry due to their environmental impacts.
In conclusion, the drawbacks explained above and the shortcomings in existing solutions to the problems have necessitated improvement in the related technical field in order to prevent and eliminate these problems.
Aim of the Invention
The present invention relates to a polyurethane foam formulation and preparation, which satisfies the requirements listed above, eliminates the disadvantages of the prior art while bringing new benefits to the technical field.
The primary object of the intervention is to develop a product suitable for use in sandwich panel industry applications, whereby greenhouse gas emissions are reduced while the insulation performance is maintained and/or increased.
Another object of the intervention is to ensure uniformity of cellular size, hence improve the thermal conductivity coefficient of PU foam thanks to its surfactant blend content.
In order to achieve the objectives set out above, the invention relates to a polyisocyanurate foam formulation comprising at least one hydrofluoroolefin (HFO) blowing agent selected from the group consisting of c-pentane, isopentane, n-pentane, 1 , 1 -Dichloro-1 -fluoroethane (HCFC-141 b) and 1 -Chloro-3,3,3-trifluoropropene (HFO- 1233zd(E)); a combination of perfluoro compounds, C5-18 (PF 5056), modified polyether siloxane (Tegostab B8498) and polyether siloxane (Tegostab B8490) as a surfactant blend; and a polyol blend consisting of polyester polyol, polyether polyol and dipropylene glycol for use in sandwich panel industry applications.
The below detailed description provides for a clearer understanding of the structural and characteristics properties and all benefits of the present invention; therefore, the evaluation needs to take these drawings and the detailed description into account. Detailed Description of the Invention
In order to facilitate a better understanding of the present invention, this detailed description demonstrates the composition according to the invention in a non-limiting manner.
In its most basic form, the polyisocyanurate foam formulation which contains a polyol blend that includes aromatic polyester polyol, polyether polyol and dipropylene glycol and is suitable for use in sandwich panel industry applications comprises:
• at least one hydrofluoroolefin (HFO) blowing agent selected from the group consisting of c-pentane, isopentane, n-pentane, 1 , 1 -Dichloro-1 -fluoroethane (HCFC-141 b) and 1 -Chloro-3,3,3-trifluoropropene (HFO-1233zd(E));
• a combination of perfluoro compounds, C5-18 (PF 5056), modified polyether siloxane (Tegostab B8498) and polyether siloxane (Tegostab B8490) as a surfactant blend.
HFO (hydrofluoroolefin) is classified as a new generation blowing agent. With a significant concentration in the polyurethane formulation, HFO is the key input that forms the foam structure of the material. Thanks to its low thermal conductivity value, it contributes to improvement of the thermal conductivity coefficient of PU foam. Polyester polyol, polyether polyol and dipropylene glycol are sources of -OH for the polyurethane reaction. Polyester polyol is derived from diethylene glycol and phtalic anhydride-based aromatic polyester polyol. Polyether polyol is used as a chain extender with three functionalities. Dipropylene glycol is a different chain extender with two functionalities. These are among the essential components required for polyurethane foam formation due to the hydroxyl groups they contain. The present invention derives polyisocyanurate foam by using aromatic polyester polyol. The polyester polyol used in the composition has a low functionality of around 2 and low OH number (260-300 mgKOH/g). This makes it possible to derive polyisocyanurate foams with much better fire performance.
HFO-1233zd(E) is the blowing agent of choice in the preferred embodiment of the invention. The chosen HFO (hydrofluoroolefin) is a new generation blowing agent and its specifications are shown in Table 2. Table 2. HFO-1233zd (E) Specifications
Figure imgf000006_0001
This blowing agent was chosen for the new formulation of the polyurethane foam due to having no ozone depletion potential and low GWP value. By using an environmentally friendly blowing agent, it is aimed to reduce greenhouse gas emissions. Moreover, thermal conductivity coefficient value is considerably lower compared to traditional blowing agents listed in Table 1. This improves the insulation performance value of the polyurethane foam produced according to the invention while contributing to global energy efficiency.
In one preferred embodiment of the invention, the formulation contains flame retardants and catalysts. These materials are used to derive the polyol blend (source of -OH), which is the first component to form polyurethane foam. Polymeric isocyanate (source of -NCO) is another primary raw material of PU foam.
In one preferred embodiment of the invention, flame retardants are preferably selected from halogenated organic phosphates, and more preferably tris(chloropropyl) phosphate (TCPP) and/or triethyl phosphate (TEP). They are used as flame retardants in polyurethane foams to improve fire resistance.
In one preferred embodiment of the invention, the catalyst blend contains an isocyanate trimerization catalyst (preferably Kosmos 33 and Egecat E2269) and an amine-based catalyst (preferably Polycat 41 or Dabco BL1 1 ). The chemical name of Polycat 41 is N,N,N',N',N",N"-Hexamethyl-1 ,3,5-triazine-1 ,3,5(2H,4H,6H)-tripropanamine, while the chemical name of Dabco BL1 1 is Ethanamine, 2,2'-oxybis[N,N-dimethyl],
Catalysts are used for accelerating the reaction. Kosmos 33 and Egecat E2269 are preferred as the isocyanate trimerization catalysts. Kosmos 33 is a potassium acetate solution dissolved in diethylene glycol, while Egecat E2269 is a potassium octoate solution dissolved in diethylene glycol. Isocyanate trimerization catalysts are used in the isocyanurate reactions of various rigid foam applications. Polycat 41 or Dabco BL1 1 is preferably used as an amine-based catalyst. Polycat 41 improves the curing (hardening) properties of polyurethane foam. Dabco BL 1 1 is effective during the first stage of the reaction between the source of OH and the source of NCO.
In one preferred embodiment of the invention, the formulation contains water. A small amount of water is used in the reaction. It is a rich source of OH used for adjusting the polyurethane foam density in the reaction. Since water is also a chemical blowing agent, it serves as a cellular CO2 source in PU foam production.
The surfactant/silicon blend mention in the invention is a combination of perfluoro compounds, C5-18 (PF 5056), modified polyether siloxane (Tegostab B8498) and polyether siloxane (Tegostab B8490). These are also used as performance additives. PF 5056 arranges the cellular structure of the foam in a way to improve the thermal conductivity coefficient value. Tegostab B8498 contributes to nucleation in PU foam formation. Tegostab 8490 contributes to solubility of all components and supports the formation of a homogenous foam structure. It also improves the fire performance of the foam. PF 5056 performance additive arranges to cellular size to help in reducing the thermal conductivity coefficient of the PU foam.
A sample composition of the formulation according to the invention is shown in Table 3. Accordingly, the developed formulation comprises the following ingredients, based on the total weight of the composition:
Aromatic polyester polyol in an amount between 40% and 50% (preferably 45.18%); Polyether polyol in an amount between 8% and 12% (preferably 10.54%);
Dipropylene glycol in an amount between 2% and 4% (preferably 2.75%); Hydrofluoroolefin (HFO) in an amount between 18% and 25% (preferably 18.82%); Tris(chloropropyl) phosphate (TCPP) in an amount between 10% and 15% (preferably 12.52%);
Triethyl phosphate (TEP) in an amount between 3% and 5% (preferably 3.77%);
Perfluoro compounds, C5-18 (PF 5056) in an amount between 2% and 3% (preferably 2.48%);
TEGOSTAB B 8498 in an amount between 1% and 2% (preferably 1 .51 %);
TEGOSTAB B 8490 in an amount between 0.3% and 0.4% (preferably 0.38%);
Potassium acetate solution dissolved in diethylene glycol (Kosmos 33) in an amount between 0.5% and 1 % (preferably 0.75%); Water in an amount between 0.5% and 0.6% (preferably 0.56%);
Potassium octoate dissolved in diethylene glycol (EGECAT E2269) in an amount between 0.3% and 0.4% (preferably 0.38%);
Polycat 41 in an amount between 0.2% and 0.4% (preferably 0.30%); - Dabco BL 11 in an amount between 0.1% and 0.2% (preferably 0.15%).
Table 3
Figure imgf000008_0001
The present invention also relates to a method for forming a polyisocyanurate foam suitable for use in sandwich panel industry applications. In its most basic form, this method comprises the following process steps: a) Preparing the polyol blend consisting of aromatic polyester polyol, polyether polyol and dipropylene glycol preferably in amounts shown in Table 3 in an ultrasonic bath and removing air bubbles in the blend; b) Adding the catalyst blend and at least one flame retardant to polyol blend, preferably in amounts shown in Table 3, preferably with a mechanical mixer at preferably 1000 rpm; c) Adding a combination of perfluoro compounds, C5-18 (PF 5056), modified polyether siloxane (Tegostab B8498) and polyether siloxane (Tegostab (B8490) in an amount of 1 % with respect to the total weight of the formulation as a surfactant blend, and mixing it preferably with a mechanical mixer at 3000±200 rpm for 1 -2 minutes; d) Bringing the surfactant blend-added blend to a temperature of 17 ± 0,5 ºC in water bath; e) Adding blowing agent to the blend preferably in an amount specified in Table 3, mixing it preferably with a mechanical mixer at 1000 rpm, and reweighing the blend; f) Adding blowing agent in an amount equal to the weighing difference and remixing the blend; g) Bringing the blend to a temperature of 20 ºC in p olymeric MDI water batch, mixing the blend and casting in mould preferably at 65X3.
According to the method of the invention, the blend takes a white colour when the performance additive is mixed. If the mixing speed is slow, the performance additive would not mix homogenously with the formulation and the formulation would not yield the expected results. A homogenous mixture is required to produce a PU foam with low coefficient of thermal conductivity. Since the boiling point of the blowing agent HFO is 19 X3, polyol blend mixture must be kept at 17 ± 0,5X3 before adding the HFO. Following this stage, the temperature of the polyol blend mixture with blowing agent is increased from 17 ºC to 20X3, and the mixture amount is check ed at both temperature values to ensure they are equal. When the amounts are equal, reaction profile is recorded at 20X3.

Claims

CLAIMS A polyisocyanurate foam formulation containing a polyol blend mixture of polyester polyol, polyether polyol and dipropylene glycol for use in sandwich panel industry applications, characterized in comprising: at least one hydrofluoroolefin (HFO) blowing agent selected from the group consisting of c-pentane, isopentane, n-pentane, 1 , 1 -Dichloro-1 -fluoroethane (HCFC-141 b) and 1 -Chloro-3,3,3-trifluoropropene (HFO-1233zd(E)); and a combination of perfluoro compounds, C5-18 (PF 5056), modified polyether siloxane (Tegostab B8498) and polyether siloxane (Tegostab B8490) as a surfactant blend. A formulation according to Claim 1 , characterized in comprising hydrofluoroolefin (HFO) blowing agent HFO-1233zd(E). A formulation according to Claim 1 , characterized in comprising water, flame retardant and a catalyst blend. A formulation according to Claim 3, characterized in that, wherein flame retardants are selected from halogenated organic phosphates. A formulation according to Claim 4, characterized in that, wherein the flame retardant is tris(chloropropyl) phosphate (TCPP) and/or triethyl phosphate (TEP). A formulation according to Claim 3, characterized in that, wherein the catalyst blend is a mixture of isocyanate trimerization catalyst and amine-based catalyst. A formulation according to Claim 6, characterized in that, wherein the isocyanate trimerization catalyst is a potassium acetate solution dissolved in glycol and/or a potassium octoate solution dissolved in diethylene glycol. A formulation according to any of the preceding claims, characterized in comprising:
Aromatic polyester polyol in an amount between 40% and 50%;
Polyether polyol in an amount between 8% and 12%;
Dipropylene glycol in an amount between 2% and 4%;
Hydrofluoroolefin (HFO) in an amount between 18% and 25%;
Tris(chloropropyl) phosphate (TCPP) in an amount between 10% and 15%; Triethyl phosphate (TEP) in an amount between 3% and 5%;
Perfluoro compounds, C5-18 (PF 5056) in an amount between 2% and 3%;
Modified polyether siloxane in an amount between 1 % and 2%;
Polyether siloxane in an amount between 0.3% and 0.4%;
Potassium acetate solution dissolved in diethylene glycol in an amount between 0.5% and 1 %;
Water in an amount between 0.5% and 0.6%;
Potassium octoate dissolved in diethylene glycol in an amount between 0.3% and 0.4%;
N,N,N',N',N",N"-Hexamethyl-1 ,3,5-triazine-1 ,3,5(2H,4H,6H)-tripropanamine in an amount between 0.2% and 0.4%;
Ethanamine, 2,2'-oxybis[N,N-dimethyl] in an amount between 0.1% and
O.2%. rmulation according to Claim 8, characterized in comprising:
Aromatic polyester polyol in an amount of 45.18%;
Polyether polyol in an amount of 10.54%;,
Dipropylene glycol in an amount of 2.75%;
Hydrofluoroolefin (HFO) in an amount of 18.82%;
Tris(chloropropyl) phosphate (TCPP) in an amount of 12.52%;
Triethyl phosphate (TEP) in an amount of 3.77%;
Perfluoro compounds, C5-18 (PF 5056) in an amount of 2.48%;
Modified polyether siloxane in an amount of 1 .51 %;
Polyether siloxane in an amount of 0.38%;
Potassium acetate solution dissolved in diethylene glycol in an amount of 0.75%;
Water in an amount of 0.56%;
Potassium octoate dissolved in diethylene glycol in an amount of 0.3%;
N,N,N',N',N",N"-Hexamethyl-1 ,3,5-triazine-1 ,3,5(2H,4H,6H)-tripropanamine in an amount of 0.30%;
Ethanamine, 2,2'-oxybis[N,N-dimethyl] in an amount of 0.15%. A method according to any of the preceding claims, designed for forming a polyisocyanurate foam suitable for use in sandwich panel industry applications, characterized in comprising the process steps of: a. Preparing the polyol blend consisting of aromatic polyester polyol, polyether polyol and dipropylene glycol in an ultrasonic bath and removing air bubbles in the blend; b. Adding and mixing the catalyst blend and at least one flame retardant to polyol blend; c. Adding a combination of perfluoro compounds, C5-18 (PF 5056), modified polyether siloxane (Tegostab B8498) and polyether siloxane (Tegostab (B8490) in an amount of 1 % with respect to the total weight of the formulation as a surfactant blend, and mixing it; d. Bringing the surfactant blend-added blend to a temperature of 17 ± 0,5 <0 in water bath; e. Adding blowing agent to the blend, mixing and reweighing the blend; f. Adding blowing agent in an amount equal to the weighing difference and remixing the blend; g. Bringing the blend to a temperature of 20 ºC in p olymeric MDI water batch, mixing the blend and casting it in mould. A method according to Claim 10, characterized in that, wherein the catalyst blend and at least one flame retardant is added to polyol blend with a mechanical mixer at 1000 rpm in process step “b”. A method according to Claim 10, characterized in that, wherein a combination of perfluoro compounds, C5-18 (PF 5056), modified polyether siloxane (Tegostab B8498) and polyether siloxane (Tegostab (B8490) are added in an amount of 1 % with respect to the total weight of the formulation as a surfactant blend and mixed with a mechanical mixer at 3000±200 rpm for 1 -2 minutes in process step “c”. A method according to Claim 10, characterized in that, wherein blowing agent is added to the blend, mixed with a mechanical mixer at 1000 rpm and the blend is reweighed in process step “e”. A method according to Claim 10, characterized in that, wherein the blend is brought to a temperature of 20 ºC in polymeric MDI w ater batch, mixed and cast in mould at 65ºC in process step “g”.
PCT/TR2022/050244 2022-01-12 2022-03-16 A rigid polyurethane foam composition suitable for use in sandwich panel industry applications WO2023136791A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2022/000370A TR2022000370A2 (en) 2022-01-12 2022-01-12 HARD POLYURETHANE FOAM COMPOSITION SUITABLE FOR USE IN SANDWICH PANEL INDUSTRY APPLICATIONS
TR2022/000370 2022-01-12

Publications (1)

Publication Number Publication Date
WO2023136791A1 true WO2023136791A1 (en) 2023-07-20

Family

ID=85117769

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/TR2022/050244 WO2023136791A1 (en) 2022-01-12 2022-03-16 A rigid polyurethane foam composition suitable for use in sandwich panel industry applications

Country Status (2)

Country Link
TR (1) TR2022000370A2 (en)
WO (1) WO2023136791A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120157558A1 (en) * 2010-12-16 2012-06-21 Evonik Goldschmidt Gmbh Silicone stabilizers for rigid polyurethane or polyisocyanurate foams
US20150057384A1 (en) * 2009-07-29 2015-02-26 Evonik Degussa Gmbh Method for producing polyurethane foam
KR20170044713A (en) * 2014-10-08 2017-04-25 도요 고무 고교 가부시키가이샤 Polyol composition for rigid polyurethane foam and process for producing rigid polyurethane foam
WO2020262881A1 (en) * 2019-06-26 2020-12-30 한국가스공사 Rigid urethane foam and method for manufacturing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150057384A1 (en) * 2009-07-29 2015-02-26 Evonik Degussa Gmbh Method for producing polyurethane foam
US20120157558A1 (en) * 2010-12-16 2012-06-21 Evonik Goldschmidt Gmbh Silicone stabilizers for rigid polyurethane or polyisocyanurate foams
KR20170044713A (en) * 2014-10-08 2017-04-25 도요 고무 고교 가부시키가이샤 Polyol composition for rigid polyurethane foam and process for producing rigid polyurethane foam
WO2020262881A1 (en) * 2019-06-26 2020-12-30 한국가스공사 Rigid urethane foam and method for manufacturing same

Also Published As

Publication number Publication date
TR2022000370A2 (en) 2022-02-21

Similar Documents

Publication Publication Date Title
US9926403B2 (en) Process for making rigid polyurethane or urethane-modified polyisocyanurate foams
EP1984415B1 (en) Compatibilizing surfactants for polyurethane polyols and resins
US20110062370A1 (en) Lecithin-containing composition suitable for producing rigid polyurethane foams
BRPI0620510A2 (en) rigidly molded polyurethane foam
CA2841878A1 (en) Polyol composition for rigid polyurethane foam and production method for rigid polyurethane foam
CN113272352B (en) Rigid polyurethane foam comprising a silicone-rich nucleating agent
KR101699098B1 (en) Polyester polyols from terephthalic acid and oligoalkyl oxides
JP2018508635A (en) Method for forming polyurethane foam products
JP7477519B2 (en) Rigid polyurethane foam formulations and foams made therefrom
JP2012528894A (en) Polyester polyols made from isophthalic acid and / or terephthalic acid and oligoalkylene oxide
CN107880314B (en) Composite flame retardant and polyurethane material containing same
JP2020180169A (en) Polyurethane foam-forming composition
EP3710506A1 (en) Polyurethane foam composite panel
CN106715506A (en) Polyol composition for rigid polyurethane foam and method for preparing rigid polyurethane foam
JP7459112B2 (en) Manufacturing of rigid polyurethane foam
EP3677610B1 (en) Preparation of polyurethane foam
WO2023136791A1 (en) A rigid polyurethane foam composition suitable for use in sandwich panel industry applications
JP6768631B2 (en) Flame-retardant polyisocyanurate foam
WO2020023223A1 (en) A foam composition and a foam composite made therefrom
KR102401314B1 (en) Method for producing polyisocyanurate rigid foam
JP7088763B2 (en) Chemical composition for polyurethane foam
WO2021131378A1 (en) Polyether-polysiloxane block copolymer composition, foam stabilizer and method for producing polyurethane foam
EP3601394A1 (en) Polyol compositions for foam insulation
JP4178390B2 (en) Rigid polyurethane foam molding composition and method for producing rigid polyurethane foam using the composition
JP2023094361A (en) Composition for preparing polyisocyanurate foam and use thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22920881

Country of ref document: EP

Kind code of ref document: A1