KR20220028843A - Polyol composition for polyisocyanuarte foam comprising eco-friendly blowing agents and polyisocyanurate foam for pipe cover using the same - Google Patents

Abstract

The present invention provides a polyol composition for forming a polyisocyanurate foam which comprises: at least one polyol comprising a polyether polyol and a polyester polyol; and a hydro fluoro olefin foaming agent and a polyisocyanurate foam formed from the polyol composition.

Description

Polyol composition for forming polyisocyanurate foam containing eco-friendly foaming agent and polyisocyanurate foam for pipe cover using the same

The present invention relates to a polyol premix composition for producing polyisocyanurate foam, and more particularly, to a polyisocyanurate foam-forming composition comprising an eco-friendly hydrofluoroolefin-based foaming agent, using the composition It relates to the produced polyisocyanurate foam and a method for manufacturing the same.

In general, polyurethane foam is widely used as an insulating material, a lightweight structural material, and a cushioning material, either alone or in combination with other materials by utilizing its properties such as insulation, lightness, and buffering properties. In addition, since polyurethane foam has excellent thermal insulation properties due to the presence of closed cells inside, it is also used as an insulator or cold insulation material. In recent years, by further improving the properties of polyurethane foam, rigid polyurethane foam excellent in mechanical properties such as compressive strength, tensile strength or low-temperature dimensional stability while maintaining excellent thermal insulation under ultra-low temperature has been used. Such polyurethane foam has been developed and used as a cryogenic insulation material for liquefied natural gas (LNG) ships.

Rigid polyurethane foam is generally prepared by mixing a polyol, a catalyst, a blowing agent, etc. to prepare a mixture, and reacting the prepared mixture with an isocyanate-based compound. Liquid fluorocarbon (CFC, HCFC, HFC)-based blowing agents have been mainly used as blowing agents because they are easy to handle under processing conditions and contribute to low thermal conductivity properties of rigid foams due to volatility. However, since the fluorocarbon-based foaming agent is a substance that increases the global warming potential, there are restrictions on its use, and its use is actually prohibited in many countries. As a blowing agent to replace the fluorocarbon-based, pentane-based hydrocarbons are often used.

Pentane-based hydrocarbons are readily available and advantageous in terms of cost. However, since pentane-based hydrocarbons have low solubility of the blowing agent itself due to non-polarity and hydrophobicity, in general, it should be added to the polyol immediately before dispensing the polyol through the mixing head. There is also a problem that limits the storage capacity of batches for later use due to the limited shelf life of the hydrocarbon-polyol mixture. Another problem with pentane-based hydrocarbon mixtures is the potential for phase separation. In the presence of phase separation during the manufacturing process, the hydrocarbon blowing agent tends to rise to the upper layer of the mixture and vaporize, which essentially poses a safety hazard that causes the concentration of hydrocarbons to reach explosive limits. And, phase separation during the process often causes a non-uniform cell structure in the resulting polyurethane foam or polyisocyanurate foam, and this non-uniform cell structure causes physical property deviations such as thermal conductivity of the final foam to achieve the desired thermal insulation performance. cannot be shown.

Hydrohaloolefin-based foaming agents are currently attracting attention as an alternative to HFC-based foaming agents. While the hydrohaloolefin foaming agent has the advantage of being environmentally friendly, when a polyurethane foam is manufactured using a hydrohaloolefin-based foaming agent, the thermal conductivity of the final rigid polyurethane foam is determined by using a hydrofluorocarbon (HFC)-based foaming agent. It is known to be inferior to the case of In addition, the hydrohaloolefin foaming agent has been mainly used for producing rigid polyurethane (PU) foams until now, but it is not applied to polyisocyanurate foam that forms an isocyanurate structure due to a reaction between isocyanate groups.

Accordingly, there is an urgent need to develop a polyol premix composition capable of simultaneously improving physical properties such as thermal insulation and storage stability of the produced polyisocyanate foam while using an eco-friendly hydrohaloolefin-based foaming agent.

The present invention has been devised to solve the above-described problems, and although an eco-friendly hydrohaloolefin-based foaming agent is used, it exhibits thermal insulation and mechanical properties equivalent to or higher than that of a conventional hydrofluorocarbon-based foaming agent, and excellent storage stability and environment-friendliness It is a technical task to provide a polyol composition for forming a polyisocyanurate foam that exhibits

Another technical object of the present invention is to provide a polyisocyanurate foam using the above-described polyol composition, a method for manufacturing the same, and an insulating material using the foam.

Other objects and advantages of the present invention may be more clearly explained by the following detailed description and claims.

In order to achieve the above technical object, the present invention provides at least one polyol containing a polyether polyol and a polyester polyol; And it provides a polyol composition for forming a polyisocyanurate foam comprising a hydrofluoroolefin (HFO)-based blowing agent.

In one embodiment of the present invention, the polyol composition may not include a hydrofluorocarbon (HFC)-based and hydrochlorofluoroolefin (HCFO)-based blowing agent.

In one embodiment of the present invention, the hydrofluoroolefin-based blowing agent is trans-1,1,1,4,4,4-hexafluoro-but-2-ene (HFO-1336mzz(E)), cis -1,1,1,4,4,4-hexafluoro-but-2-ene (HFO-1336mzz(Z)), 1,3,3,3-tetrafluoropropene (HFO-1234ze), Trans-1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze (E)), cis-1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze (HFO-1234ze (E)) Z)), and 2,3,3,3-tetrafluoropropene (HFO-1234yf) may include at least one selected from the group consisting of.

In one embodiment of the present invention, the polyether polyol is polymerized from at least one initiator of sorbitol and sucrose, has a number average molecular weight (Mn) of 600 to 800 g/mol, and an average hydroxyl group (OH) of 380 to 580 mgKOH/g, and the functional group may be 4 to 8.

In one embodiment of the present invention, the polyester polyol contains at least one raw material selected from the group consisting of terephthalic acid, isophthalic acid, adipic acid, dimethyl terephthalate, and phthalic anhydride and glycol. a polymerized mixture of at least one polyester polyol, and may have a number average molecular weight (Mn) of 300 to 500 g/mol, and an average hydroxyl group (OH) of 200 mgKOH/g to 400 mgKOH/g.

In one embodiment of the present invention, the at least one polyol has a functional group of 4 to 8, a number average molecular weight (Mn) of 600 to 800 g/mol, and an average hydroxyl group (OH) of 380 to 580 mgKOH/g phosphorous polyether polyols; a first polyester polyol having a functional group of 2 to 4, a number average molecular weight (Mn) of 300 to 500 g/mol, and an average hydroxyl group (OH) of 200 mgKOH/g to 400 mgKOH/g; and a second polyester polyol having a functional group of 2 to 4, a number average molecular weight (Mn) of 400 to 600 g/mol, and an average hydroxyl group (OH) of 100 mgKOH/g to 300 mgKOH/g.

For an embodiment of the present invention, the mixing ratio of the first polyester polyol and the second polyester polyol may be 45:55 to 65:35 by weight.

In one embodiment of the present invention, the mixing ratio of the polyether polyol and the polyester polyol may be 10: 90 to 30: 70 weight ratio based on the total weight of the polyol.

In one embodiment of the present invention, the polyol composition includes a blowing catalyst and a trimerization catalyst, and the trimerization catalyst may include at least one or more of an organometallic catalyst and a tertiary amine catalyst.

For an embodiment of the present invention, the ratio of the blowing catalyst, the organometallic catalyst, and the tertiary amine catalyst may be 1:20-40:35-55 by weight.

For one embodiment of the present invention, the polyol composition, based on 100 parts by weight of the polyol, 10 to 40 parts by weight of a hydrofluoroolefin-based foaming agent; and 0.5 to 3.5 parts by weight of a catalyst containing a blowing catalyst and a trimerization catalyst.

In one embodiment of the present invention, the polyol composition may further include at least one of a flame retardant, a foam stabilizer, a crosslinking agent, and a chain extender.

In one embodiment of the present invention, the polyol composition has a viscosity of 500 to 1,500 cps (based on 25° C.), has a storage stability of 90 days or more at 25° C., and the gel time of the polyol composition after 90 days has elapsed The rate of change may be 7% or less based on the initial gelation time.

In addition, the present invention is a polyol composition described above; And it provides a polyisocyanurate foam formed by reacting an isocyanate compound.

For one embodiment of the present invention, the polyisocyanurate foam has an average compressive strength (Z-axis) according to ASTM D1621 of 300 kPa or more, and an average thermal conductivity according to ASTM C177 is 0.022 W/m·K or less, The initial foaming density according to ASTM D1622 is 45 to 55 Kg/m ³ , and the density retention after 30 days of foaming may be 97% or more.

The polyol composition for forming polyisocyanurate foam according to an embodiment of the present invention has lower thermal conductivity and higher thermal conductivity than when using a conventional hydrofluorocarbon (HFC)-based foaming agent, even when an eco-friendly hydrofluoroolefin (HFO)-based foaming agent is used. By showing compressive strength, thermal insulation and mechanical properties can be improved.

In addition, the polyol composition is environmentally friendly and can exhibit excellent storage stability, and the polyisocyanurate foam prepared therefrom can exhibit properties equal to or higher than those of the prior art in terms of foam density, thermal insulation and compressive strength.

Accordingly, the polyisocyanurate foam according to the present invention can be usefully used for insulating materials such as sandwich panels for construction, spray foam for construction, interior materials for ships, pipe covers (insulation materials), container boxes, cold storage warehouses, and standard boards.

Effects according to the present invention are not limited by the contents exemplified above, and more various effects are included in the present specification.

1 is a graph showing the foaming profile (rising profile) over time of the polyisocyanurate foam prepared in Example 1 and Comparative Example 1-2.

Hereinafter, the present invention will be described in detail. However, it is not limited only by the following content, and each component may be variously modified or selectively mixed as needed. Therefore, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

All terms (including technical and scientific terms) used in this specification may be used in the meaning commonly understood by those of ordinary skill in the art to which the present invention pertains, unless otherwise defined. In addition, terms defined in a commonly used dictionary are not to be interpreted ideally or excessively unless clearly defined in particular.

Also, throughout this specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

<Polyol composition for forming polyisocyanurate foam>

The polyol composition according to an embodiment of the present invention is a premix composition for forming a polyisocyanurate foam, and specifically, a polyisocyanurate foam stock solution composition for a pipe cover foamed with an eco-friendly foaming agent.

In that the polyol composition uses at least one hydrofluoroolefin (HFO)-based blowing agent, a prior art using a hydrofluorocarbon (HFC)-based and/or hydrochlorofluoroolefin (HCFO)-based blowing agent is distinguished from In particular, the conventional polyol composition to which the HFO foaming agent is applied has a problem in that various physical properties such as thermal insulation and mechanical strength are essentially lowered compared to the case where the HFC-based foaming agent is applied. In contrast, the polyol composition of the present invention can secure physical properties equal to or greater than that of the existing HFC foaming agent despite including an eco-friendly HFO-based foaming agent by adjusting each component constituting the polyol composition and their blending ratio within a predetermined range.

For example, the polyol composition for forming a polyisocyanurate foam may include at least one polyol mixture containing a polyether polyol and a polyester polyol; hydrofluoroolefin (HFO)-based blowing agent; blowing catalyst; and at least one trimerization catalyst, and may include an additional foaming component such as a chemical foaming agent (eg, water). If necessary, it may further include at least one or more conventional flame retardants, foam stabilizers, crosslinking agents, chain extenders, and other additives known in the art.

Hereinafter, each component constituting the polyol composition will be described as follows.

polyol

The polyol composition according to the present invention includes at least one polyol.

As the polyol, a conventional polyol known in the art that can form polyisocyanurate may be used without limitation.

Non-limiting examples of usable polyols include polyether polyol, polyester polyol, polycaprolactone polyol, polytetramethylene ether diol, polybutadiene diol, polytetra methylene ether (polytetra methylene). ether) diol, polypropylene oxide diol, polybutyleneoxide diol, triol, or a mixture thereof. Specifically, it may be a polyether polyol, a polyester polyol, or a mixture thereof, and more specifically, it is preferably a mixture of a polyether polyol and a polyester polyol based on a polyhydric alcohol.

The polyether polyol may include at least one prepolyol polymerized from an initiator comprising a polyhydric alcohol, for example, an initiator comprising a compound having 2 to 8, specifically 4 to 8 hydroxyl groups per molecule. Addition polymerization can be carried out by adding propylene oxide (PO) and ethylene oxide (EO) to it. This polyether polyol has a flexible structure compared to polyester polyol, so it can exhibit flexible properties of polyisocyanate foam, and can exhibit excellent hydrolysis resistance and low temperature properties.

Non-limiting examples of usable initiators include sorbitol, sucrose, glucose, glycol, glycerol, glycerine, pentaerythritol, trimethylol, trimethylolpropane (TMP) ), ethylene glycol, and propylene glycol may include at least one selected from the group consisting of.

For example, the polyether polyol may be at least one polymerized from at least one initiator of sorbitol and sucrose, and a number average molecular weight (Mn) is 600 to 800 g/mol, and an average hydroxyl group (OH) Thin 380 to 580 mgKOH/g, functional groups can range from 4 to 8. When the average hydroxyl group (OH value) of the polyether polyol is less than 380 mgKOH/g, the mechanical strength and low-temperature dimensional stability of the final product are deteriorated, and when it exceeds 580 mgKOH/g, the thermal insulation property may be deteriorated. In addition, when the number average molecular weight (Mn) of the polyether polyol is less than 600 g/mol, impact resistance may be reduced, and when it exceeds 800 g/mol, mechanical strength may be reduced.

If necessary, a crosslinking agent may be further included, for example, 0.5 to 10 parts by weight, for example, 1,4-Butanediol (1,4 BD) may be used.

In addition, polyester polyol can be prepared by a dehydration condensation reaction between dibasic acid and glycol or triol, etc., and the properties and physical properties of the obtained polyester polyol can be variously adjusted depending on the type of acid and polyol used and their molecular weight. can For example, at least one raw material selected from the group consisting of phthalic anhydride, terephthalic acid, adipic acid, ethylene glycol, and diethylene glycol; , may include a mixture of at least one or more polyester polyols synthesized by polymerizing glycol. The glycol is not particularly limited, and for example, ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1, It may be at least one selected from the group consisting of 5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, triethanolamine, and pentaerythritol.

In one embodiment, the polyester polyol may include phthalic anhydride, terephthalic acid, and/or adipic acid in ethylene glycol, and/or diethylene glycol. ) may be one type of polyol or a mixture of two or more types of polyols obtained by reacting with, the number average molecular weight (Mn) is 300 to 500 g/mol, and the average hydroxyl group (OH value) is 200 mgKOH/g to 400 mgKOH/g can be

The polyester polyol may be a mixture of a plurality of polyols. In one example, the polyether polyol may include a first polyester polyol polymerized including terephthalic acid, dimethyl terephthalate, and phthalic anhydride; and a second polyester polyol polymerized including phthalic anhydride and diethylene glycol. In this case, the first polyester polyol may have a functional group of 2 to 4, a number average molecular weight (Mn) of 300 to 500 g/mol, and an average hydroxyl group (OH) of 200 mgKOH/g to 400 mgKOH/g. In addition, the second polyester polyol may have a functional group of 2 to 4, a number average molecular weight (Mn) of 400 to 600 g/mol, and an average hydroxyl group (OH) of 100 mgKOH/g to 300 mgKOH/g. In addition, the mixing ratio of the first polyester polyol and the second polyester polyol may be 45: 55 to 65: 35 weight ratio. In this case, the weight part is based on 100 parts by weight of the polyester polyol included in the polyol mixture.

At least one polyol (or polyol mixture) according to the present invention includes one polyether polyol and two polyester polyols by adjusting a predetermined mixing ratio. At this time, the use ratio between the polyether polyol and at least two types of polyester polyol is not particularly limited, and may be appropriately adjusted in consideration of the physical properties of the final polyisocyanurate foam. For example, the polyether polyol and the polyester polyol may be in a weight ratio of 10: 90 to 30: 70 based on the total weight (eg, 100 parts by weight) of the at least one polyol, specifically 15 : 75 to 25: 85 weight ratio may be

In one embodiment, the at least one polyol (or polyol mixture) has a functional group of 4 to 8, a number average molecular weight (Mn) of 600 to 800 g/mol, and an average hydroxyl group (OH) of 380 to 580 mgKOH/ g of 10 to 30 parts by weight of polyether polyol; 35 to 55 parts by weight of a first polyester polyol having a functional group of 2 to 4, a number average molecular weight (Mn) of 300 to 500 g/mol, and an average hydroxyl group (OH) of 200 mgKOH/g to 400 mgKOH/g; and 25 to 45 parts by weight of a second polyester polyol having a functional group of 2 to 4, a number average molecular weight (Mn) of 400 to 600 g/mol, and an average hydroxyl group (OH) of 100 mgKOH/g to 300 mgKOH/g can be configured. In this case, the weight part is based on 100 parts by weight of the polyol.

In the at least one polyol mixture, one polyether polyol is effective in improving the cryogenic dimensional stability and mechanical strength of the foam, and the first polyester polyol component is effective in improving thermal conductivity and uniform formation of foam cells Contributes to, and the second polyester polyol contributes to smooth flow by imparting fluidity to the liquid at the time of foam formation. Specifically, a polyol mixture containing one polyether polyol and two polyester polyols in a predetermined mixing ratio is reacted with a polyisocyanate having at least two or more isocyanate groups, a foaming agent, a catalyst, and a mixture of other additives. It can have high strength and excellent low-temperature dimensional stability even at ultra-low temperatures of -165° C. or less, while maintaining excellent thermal insulation, which is a characteristic of polyurethane foam. In particular, it is possible to manufacture a rigid polyisocyanurate foam with enhanced flame retardancy.

blowing agent

The foaming agent forms a foaming cell inside the heat insulating material by generating gas in the polymerization reaction process. Since it exists in the cell after the polyisocyanurate foam is formed, it is preferable to use a material with low thermal conductivity and high stability.

In the present invention, an eco-friendly hydrohalogenolefin is used instead of a hydrofluorocarbon (HFC)-based blowing agent having a high global warming potential (GWP), but among them, a hydrofluoroolefin (HFO)-based blowing agent is adopted. use.

For example, the global warming potential (GWP) of the HFC blowing agent is approximately 1,000 to 15,000, and the ozone depletion potential (ODP) is 0.5 or less, whereas the hydrofluoroolefin (HFO) blowing agent is a global warming agent. The index (GWP) is 10 or less, specifically 5 or less, and the ozone depletion potential (ODP) is 0, so it is environmentally friendly (see Table 1 below). Here, the ozone depletion potential (ODP) refers to the index assigned to each material based on the CFC material (Freon) set to 1.0. In addition, the global warming potential (GWP) is an index assigned to each substance based on the CO ₂ substance set to 1.0 (IPCC 2nd report, a value based on a duration of 100 years).

Meanwhile, the eco-friendly hydrohaloolefin blowing agent generally includes an HFO-based blowing agent and a hydrochlorofluoroolefin (HCFO) blowing agent. Among them, the HCFO-based foaming agent includes chlorine in its molecular structure, and this chlorine chemically reacts with the catalyst included in the polyisocyanurate foam composition, resulting in delayed reactivity and reduced storage stability. Accordingly, in the present invention, a hydrofluoroolefin (HFO)-based foaming agent is used as a foaming agent, and the conventional HFC foaming agent and HCFO foaming agent are not included.

The hydrofluoroolefin (HFO) foaming agent is not particularly limited, and at least one or more conventional hydrofluoroolefin-based foaming agents known in the art may be used. Specifically, it does not contain chlorine and may be a compound having 3 to 6 carbon atoms. Examples of usable hydrofluoroolefins (HFOs) include pentafluoropropane such as 1,2,3,3,3-pentafluoropropene (HFO1225ye); Tetrafluoropropenes such as 1,3,3,3-tetrafluoropropene (HFO1234ze, E and Z isomers), 2,3,3,3-tetrafluoropropene (HFO1234yf), and 1,2 ,3,3-tetrafluoropropene (HFO1234ye); trifluoropropenes such as 3,3,3-trifluoropropene (1243zf); tetrafluoro butenes such as (HFO1345); pentafluorobutene isomers such as (HFO1354); hexafluorobutene isomers such as (HFO1336); heptafluorobutene isomers such as (HFO1327); heptafluoropentene isomers such as (HFO1447); octafluoropentene isomers such as (HFO1438); and nonafluoropentene isomers such as (HFO1429).

In one embodiment, the hydrofluoroolefin blowing agent is trans-1,1,1,4,4,4-hexafluoro-but-2-ene (HFO-1336mzz(E)), cis-1,1 ,1,4,4,4-hexafluoro-but-2-ene (HFO-1336mzz(Z)), 1,3,3,3-tetrafluoropropene (HFO-1234ze), trans-1, 3,3,3-tetrafluoroprop-1-ene (HFO-1234ze (E)), cis-1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze (Z)); and 2,3,3,3-tetrafluoropropene (HFO-1234yf). For example, when using HFO-1336mzz-Z, excellent storage stability, high mechanical properties, and low thermal conductivity can be secured.

The content of the hydrofluoroolefin foaming agent is not particularly limited and may be appropriately adjusted within a content range known in the art. For example, the hydrofluoroolefin blowing agent may be included in an amount of 10 to 40 parts by weight based on 100 parts by weight of the polyol, and specifically 20 to 35 parts by weight.

In the present invention, if necessary, a chemical foaming agent (eg, water) and/or a physical foaming agent (eg, a volatile foaming agent) may be further included.

The physical blowing agent that can be used may be any known volatile blowing agent other than the HFO, HFC, and HCFO series described above, for example, low-boiling hydrocarbons (eg, pentane, cyclopentane, hexane, and mixtures thereof), carbon dioxide gas, or these may contain a mixture of In addition, the chemical foaming agent means that a gas generated through a chemical reaction causes foaming, for example, water may be used. Water reacts with isocyanate to generate carbon dioxide, thereby forming closed cells inside the polyisocyanurate foam.

In the present invention, a hydrofluoroolefin-based foaming agent may be used as the main foaming agent, and a chemical foaming agent (eg, water) may be used as an auxiliary foaming agent. In this case, the amount of water used is not particularly limited, and may be, for example, 0.5 to 3.5 parts by weight, specifically 0.5 to 2.0 parts by weight, based on 100 parts by weight of the polyol. If the amount of water used is less than 1.0 parts by weight, compressive strength or dimensional stability may be lowered, and if it exceeds 2.5 parts by weight, thermal conductivity may be significantly reduced.

catalyst

The polyol composition according to the present invention may include a conventional catalyst known in the art used to form a polyisocyanurate foam.

The catalyst comprises a blowing catalyst and at least one trimerization catalyst.

The blowing catalyst is used for resinization, for example, bis-(2-dimethylaminoethyl)ether, pentamethyldiethylenetriamine, triethylamine (TEA), triethylenediamine, methylcyclohexylamine, and At least one selected from the group consisting of tetramethylene-hexyldiamine may be used. The content of the blowing catalyst is not particularly limited, and may be, for example, 0.001 to 0.5 parts by weight, specifically 0.01 to 0.3 parts by weight, based on 100 parts by weight of the polyol. If the content of the blowing catalyst is out of the above numerical range, the reaction is delayed and productivity and quality are remarkably reduced due to poor curing, or the reaction is fast and cracks of the foam may occur, resulting in product defects.

In addition, the trimerization catalyst is a compound that promotes the reaction between isocyanate groups (NCO) without directly participating in the polymerization reaction, and a conventional catalyst known in the art may be used without limitation. An example is an organometallic catalyst, a tertiary amine catalyst, or a mixture thereof.

Organometallic catalysts that can be used include metal salts of carboxylic acids, in particular salts of ammonium, alkali metals or alkaline earth metals. For example, linear or branched, substituted or unsubstituted, saturated or unsaturated aliphatic or aromatic carboxylic acids having 1 to 20 carbon atoms, such as formic acid, acetic acid, octanoic acid, tartaric acid, citric acid, oleic acid, stearic acid and ricinoleic acid , or substituted or unsubstituted aromatic carboxylic acids having 6 to 20 carbon atoms, such as benzoic acid and salicylic acid. Specific examples include potassium formate, potassium acetate, potassium octanoate, ammonium formate, ammonium acetate, and ammonium octanoate, more specifically potassium formate. Non-limiting examples of tertiary amine catalysts that can also be used include dimethylcyclohexylamine (DMCHA), dimethylethanolamine (DMEA), pentamethyldiethylenetriamine (PMDETA), tetramethylhexamethylenediamine (TMHMDA), or these mixtures, etc. For example, commercially available trade names include DABCO K-15, DABCO TMR-30, DABCO TMR-2 (Air Product Co.), POLYCAT-46 (Sun Abott Co.), and the like. In particular, it is preferable to mix DABCO K-15 and DABCO TMR-2, and the mixing ratio between them is based on the total weight of the trimerization catalyst, DABCO K-15: DABCO TMR-2 20-50: 50-80 It is preferable to mix them in a weight ratio. The content of the trimerization catalyst is not particularly limited, and may be, for example, 0.3 to 2.0 parts by weight, specifically 0.5 to 2.0 parts by weight, based on 100 parts by weight of the polyol. If the content of the trimerization catalyst is out of the above numerical range, the rate of the trimerization reaction is delayed and the formation of isocyanurate that improves thermal stability is insufficient, so that the resistance to fire of the foam is weakened, or the internal reaction heat of the foam is It may increase and scorch may occur, and the hardness of the foam may be weakened by forming an excess of isocyanurate functional groups. In addition, the reaction rate according to the addition of the catalyst is no longer improved, so the effectiveness by the catalyst may decrease.

On the other hand, the catalyst controls the first and second trimerization reactions, and affects the productivity, processability, and conversion of polyisocyanurate of polyisocyanurate. In particular, in the present invention, the blowing catalyst, the organometallic compound and the tertiary amine catalyst are mixed as catalyst components, but it is preferable to adjust the mixing ratio to a predetermined ratio. In one embodiment, the use ratio of the blowing catalyst, the organometallic catalyst, and the tertiary amine catalyst is one embodiment of the present invention, the use ratio of the blowing catalyst, the organometallic catalyst, and the tertiary amine catalyst is 1: 20-40: It may be a 35-55 weight ratio, specifically 1: 20-35: It may be a 35-50 weight ratio.

In the present invention, the content of the catalyst is not particularly limited, and may be appropriately adjusted within the content range known in the art. For example, the catalyst may be used in an amount of 0.5 to 3.5 parts by weight, specifically 0.5 to 2.5 parts by weight, based on 100 parts by weight of the polyol.

flame retardant

The polyol composition according to the present invention may include a flame retardant, if necessary.

As the flame retardant, conventional components known in the art may be used without limitation, and examples thereof include a non-halogen type, a halogen type, and an inorganic type. Specifically, a phosphorus-based flame retardant, a bromine-based flame retardant, or a mixture thereof is suitable. In particular, phosphorus-based flame retardants are preferable because they are less harmful to the human body, have excellent environmental friendliness, and have high flame retardant efficiency. In addition, in the case of polyisocyanurate foam, the phosphorus-based flame retardant functions to prevent the conversion of combustible materials into combustible gas because the phosphorus-based compound increases the carbonization yield.

Examples of the phosphorus-based flame retardant include inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, and halogen phosphates. Examples of the inorganic phosphorus flame retardant include tricresyl phosphate, ammonium phosphate, ammonium polyphosphate, and the like, and examples of the organic phosphorus flame retardant include melamine phosphate, dimelamine phosphate, triethylene phosphate, and the like, and the halogen phosphate includes bromine phosphate. .

The content of the flame retardant is not particularly limited, and may be appropriately adjusted within the content range known in the art. For example, the flame retardant may be included in an amount of 10 to 40 parts by weight, specifically 25 to 35 parts by weight, based on 100 parts by weight of the polyol. If the content is out of the above range, the flame retardant effect by the addition of the flame retardant is insignificant, or it is harmful to the human body and the environment due to the toxicity of the flame retardant, and adhesion, demolding, flowability and processability may be reduced.

antifoaming agent

The polyol composition according to the present invention may contain a foam stabilizer if necessary.

The foam stabilizer is a foam stabilizer that promotes the formation of regular cell structures during foam formation. When cells are formed in the foam, cells are prevented from merging with each other or the resulting cells are destroyed, and miscibility between different compositions, cells can improve the stability and uniformity of

The foam stabilizer may use conventional components known in the art, and for example, a silicone-based foam stabilizer, a non-silicone-based foam stabilizer, or a mixture thereof may be used. At this time, when a silicone-based foam stabilizer and a non-silicone-based foam stabilizer are mixed, it is possible not only to suppress the occurrence of pinholes in the foam, but also to improve the quality of the produced foam by allowing the surface of the produced foam to be formed flat. .

Non-limiting examples of foam stabilizers that can be used include siloxane-oxyalkylene copolymers and other organopolysiloxanes. Fatty alcohol, oxo alcohol, fatty amine, alkylphenol, dialkylphenol, alkylcresol, alkylresorcinol, naphthol, alkylnaphthol, naphthylamine, aniline, alkylaniline, toluidine, bisphenol A, alkylated bisphenol A, polyvinyl alkoxylation products of alcohols, and formaldehyde and alkylphenol, formaldehyde and dialkylphenol, formaldehyde and alkylcresol, formaldehyde and alkylresorcinol, formaldehyde and aniline, formaldehyde and toluidine, formaldehyde and naphthol, alkoxylation products of formaldehyde with alkylnaphthol and condensation products of formaldehyde with bisphenol A, and mixtures of two or more of these foam stabilizers.

The content of the foam stabilizer is not particularly limited and may be appropriately adjusted within the content range known in the art. For example, the foam stabilizer may be included in an amount of 1 to 10 parts by weight, specifically 1 to 5 parts by weight, based on 100 parts by weight of the polyol.

additive

In addition to the above components, the polyol composition for forming a polyisocyanurate foam of the present invention may use at least one additive known in the art without limitation within a range that does not impair the effects of the present invention.

As an example of usable additives, surfactants, nucleating agents, antioxidants, fillers, crosslinking agents, chain extenders, solvents, and the like may be contained. These may be used alone or in combination of two or more. In this case, the content of the additive may be appropriately adjusted within a range known in the art, and for example, may be included in an amount of 0.01 to 5 parts by weight, specifically 0.01 to 2 parts by weight, based on the total weight of the polyol composition.

The polyol composition for forming a polyisocyanurate foam according to the present invention contains at least one polyol mixture, a hydrofluoroolefin-based foaming agent, a catalyst, a flame retardant, a foam stabilizer, and other additives or solvents blended as necessary. It may be prepared by mixing and stirring according to a conventional method known in the art.

The polyol premix composition of the present invention constituted as described above includes, based on 100 parts by weight of the at least one polyol, 10 to 40 parts by weight of a hydrofluoroolefin (HFO)-based blowing agent; 0.5 to 3.5 parts by weight of a catalyst comprising a blowing catalyst and at least one trimerization catalyst, further comprising 10 to 40 parts by weight of a flame retardant; and 1 to 10 parts by weight of a foam stabilizer. If necessary, a residual amount of a solvent or other additives satisfying a total of 100 parts by weight may be further included.

Meanwhile, the boiling point of a conventional hydrofluorocarbon (HFC)-based blowing agent, such as HFC-245fa, is 15.3° C., and the boiling point of a hydrochlorofluoroolefin (HCFO)-based blowing agent, such as HCFO-1233zd, is 19° C., so polyols containing the same The composition has poor storage stability at room temperature. In contrast, the boiling point of the hydrofluoroolefin-based blowing agent according to the present invention, such as HFO-1336mzz-Z, is 33°C. Accordingly, the storage stability of the stock solution of the polyol composition of the present invention including the HFO-based foaming agent can be significantly increased. For example, it may have storage stability of 90 days or more at room temperature (eg, 25° C.).

In addition, the polyol composition may have a viscosity at 25° C. of 2,000 cps or less, and specifically 500 to 1500 cps. As described above, by appropriately adjusting the viscosity of the polyol composition, excellent workability and processability can be imparted.

In addition, in the polyol composition according to the present invention, the gel time change rate of the polyol composition after 90 days may be 7% or less based on the initial gelation time, and specifically may be 3 to 5%. Here, the gel time (G/T) is the time taken from the point when the polyol composition and the isocyanate are mixed to the point at which the stock solution has a gel strength that can withstand a light impact and takes on a somewhat stable spatial shape (e.g., It means the point at which at least 3 to 4 urethane fibers come out when the reacting foam is stabbed with chopsticks, etc.), and is an index related to the reactivity of polyisocyanurate foam. And the initial gelation time is the preparation of the polyol composition It is based on the gelation time of the same day (1 day).

The polyol premix composition according to the present invention contains a hydrofluoroolefin-based foaming agent, and as the storage stability of the stock solution increases at low temperatures, the prepared polyisocyanurate foam has excellent reactivity, free-foaming density, thermal conductivity, compressive strength, and flame retardancy.

<Polyisocyanurate foam>

The polyisocyanurate foam according to an embodiment of the present invention includes a polyol composition containing the above-described hydrofluoroolefin (HFO)-based blowing agent.

The polyisocyanurate foam may be prepared by reacting the above-described polyol composition with an isocyanate.

The isocyanate compound is not particularly limited, and for example, aromatic isocyanate, aliphatic isocyanate, cycloaliphatic isocyanate, and modified products thereof (eg, carbodiimide-, allophanate-, urea-, biuret-, isocyanurate) -, and oxazolidone-modified products), isocyanate group-terminated prepolymers, and the like. Specific examples of the isocyanate compound that can be used include toluene diisocyanate (TDI), diphenylmethane diisocyanate (monomer MDI), polymethylene polyphenyl isocyanate (polymer MDI), and combinations thereof.

The content of the isocyanate compound is not particularly limited and may be appropriately adjusted within a content range known in the art. For example, 100 to 200 parts by weight of the isocyanate may be included per 100 parts by weight of the polyol, for example, 130 to 180 parts by weight may be included.

In addition, the isocyanate index (NCO / OH ratio) of the isocyanate compound may be 200 to 400, for example, may be 250 to 350. When the compound having an isocyanate index in the above range is reacted with the polyol composition according to an embodiment of the present invention, the prepared polyisocyanurate foam has excellent reactivity, free foaming density, thermal conductivity, compressive strength, flame retardancy, etc. All physical properties may be improved. In particular, the polyisocyanurate foam can exhibit lower thermal conductivity and higher compressive strength than when a conventional hydrofluorocarbon (HFC)-based foaming agent is used, and at the same time can secure excellent storage stability and environment-friendliness.

For example, the polyisocyanurate foam may satisfy at least one or more of the following properties (i) to (iii), and preferably satisfy all of the properties of (i) to (iii). As an example, (i) the average compressive strength (Z axis) according to ASTM D1621 is 300 kPa or more, and may specifically be 300 to 400 kPa. In addition, (ii) the average thermal conductivity according to ASTM C177 is 0.022 W/m·K or less, and specifically, it may be 0.019 to 0.022 W/m·K. In addition (iii) the initial foaming density according to ASTM D1622 is 45 to 55 Kg/m ³ , and specifically may be 46 to 53 Kg/m ³ , and the density retention is 97% or more after 30 days after foaming, specifically 97.5 to 99.9%.

<Method for producing polyisocyanurate foam>

The polyisocyanurate foam according to the present invention may be prepared according to a conventional method known in the art, and is not particularly limited.

For example, the polyisocyanurate foam may be manufactured by a slabstock method. The slab stock method is a method of discharging and foaming a mixture of a polyisocyanurate foam-forming composition on a conveyor in a certain ratio. During foam formation, the internal structure of the foam is uniform by receiving less resistance from the outside, resulting in a uniform distribution of physical properties. can have

For example, after preparing a polyol premix composition in which at least one polyol mixture, hydrofluoroolefin-based blowing agent, catalyst and other components are mixed, an isocyanate compound is added through a mixing machine or foaming machine It can be manufactured by mixing with a foaming machine and spraying it on a continuous conveyor belt.

The production of polyisocyanurate foam can be carried out by hand mixing or preferably by a foaming machine. At this time, if it is carried out using a foaming machine, a high-pressure or low-pressure machine may be used. It can also be carried out continuously as well as intermittently. For example, there is a molded foam such as a pipe cover and an injection-type panel in an intermittent type, and may be manufactured by a slab foam method in a continuous type.

In addition, the foaming machine may use a high-pressure or low-pressure foaming machine commonly used in the art. In this case, the foaming conditions may vary depending on the type of foaming machine used, but in general, the stock solution temperature may be 20 to 25° C., and the discharge amount may be about 500 to 1,500 g/sec.

On the other hand, if the initial reaction time of the foam is too late, curing may be delayed and productivity may be reduced. If the initial reaction time of the foam is too late, the viscosity rises rapidly during foaming and waves may occur on the surface of the foam, so it is desirable to maintain it at an appropriate line. For example, it is appropriate to maintain the reaction time of the foam in the range of 100 to 200 seconds. In addition, if the viscosity of the undiluted solution is high, it may be difficult to mix the undiluted solution or transport the undiluted solution in winter, so it is necessary to use a low-viscosity raw material as much as possible.

For another example, polyisocyanurate foam may be manufactured by a laminating method using a continuous double conveyor belt. In addition, it can be manufactured by a method of manufacturing by injection and foaming in a specific mold shape, or by a method of spraying on the surface of a tank such as LNG, LEG, LPG, etc. through a high-pressure spray device.

Since the polyisocyanurate foam of the present invention prepared as described above has lower thermal conductivity, higher compressive strength, and excellent storage stability than when using a conventional hydrofluorocarbon (HFC)-based foaming agent, this causes cracks, shrinkage, It does not cause torsion, etc., and has excellent mechanical properties while also being excellent in heat insulation and flame retardancy, and is environmentally friendly. Accordingly, the polyisocyanurate foam can be applied without limitation to various fields requiring excellent thermal insulation and mechanical properties. For example, for building sandwich panel, refrigerated warehouse panel, building spray foam, ship interior material, pipe cover (insulation material), container box, frozen low temperature warehouse, standard board, for internal/external insulation of tanks such as LNG, LEG, LPG, etc. It can be usefully used for insulation materials such as materials and insulation materials for pipelines for LNG transportation. Specifically, it may be applied to a pipe cover purpose.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to help the understanding of the present invention, and the scope of the present invention is not limited to the examples in any sense.

[Preparation example. Evaluation of blowing agent properties]

The physical properties of each foaming agent used in Examples and Comparative Examples according to the present invention are shown in Table 1 below.

division blowing agent 1 blowing agent 2 blowing agent 3 HFO foaming agent
(FEA-1100) HFC-based blowing agent (245fa) HCFO foaming agent (LBA) structure

chemical formula CF ₃ CH=CHCF ₃₍ Z) CF ₃ CH ₂ CHF ₂ C ₃ H ₂ ClF ₃ Molecular Weight (g/mol) 164 134 130 Boiling Point (℃) 33 15.3 19 Ozone Depletion Potential (ODP) 0 0 0 Global Warming Potential (GWP) 2 1,020 < 7 Gas K-factor
(mW/mk) 10.7 (25℃) 12.7 (25℃) 10.2 (20℃)

- Blowing agent 1: cis-1,1,1,4,4,4-Hexafluoro-2-butene (1336mzz-Z, Chemours)

- Foaming agent 2: 1,1,1,3,3-Pentafluoropropane (HFC-245fa, Honeywell)

- Blowing agent 3: Trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd, Honeywell Corporation)

[Example 1]

1-1. Preparation of polyol composition for forming polyisocyanurate foam

As shown in Table 2 below, a mixture of polyether polyol and polyester polyol was used as a polyol component, and a foaming agent, a flame retardant, a foam stabilizer, and a catalyst were mixed with the polyol component to prepare a polyol composition.

Specifically, polyether polyol containing sorbitol as an initiator and addition polymerization of propylene oxide (PO) and ethylene oxide (EO) [functional group: 6, number average molecular weight (Mn): 701 g/mol, average hydroxyl value: 480 mgKOH/g] 20 parts by weight of the first polyester polyol [functional group: 2.3, number average] including terephthalic acid, dimethyl terephthalate, and phthalic anhydride as an initiator Molecular weight (Mn): 430 g/mol, average hydroxyl value: 300 mgKOH/g] 45 parts by weight of a second polyester polyol containing phthalic anhydride and diethylene glycol as initiators [Functional group: 2, number average molecular weight (Mn): 561 g/mol, average hydroxyl value: 200 mgKOH/g] 35 parts by weight were blended to obtain a polyol mixture.

To 100 parts by weight of the polyol mixture, 31.5 parts by weight of foaming agent 1 (HFO-based foaming agent), 3 parts by weight of foaming agent (B-8563), blowing catalyst 1 [Polycat 5, Evonik] 0.02 parts by weight, trimerization catalyst 2 [DABCO K-15, AIR PRODUCTS and Chemicals] 0.5 parts by weight, trimerization catalyst 3 [DABCO TMR-2, AIR PRODUCTS and Chemicals] 0.75 parts by weight, and flame retardant [TCPP, Jiangsu Changyu Chemical] 30 parts by weight were mixed, A polyol composition for forming a polyisocyanurate foam was prepared.

1-2. Polyisocyanurate Foam Manufacturing

157 parts by weight of polymethylene polyphenyl diisocyanate was added to the polyol composition prepared in 1-1, based on 100 parts by weight of the polyol component, followed by stirring and foaming to prepare a polyisocyanurate foam.

Example 1 Comparative Example 1 Comparative Example 2 polyol polyether polyol 20 20 20 polyester polyol 1 45 45 45 polyester polyol 2 35 35 35 blowing agent Blowing Agent 1 (HFO) 31.5 - - Blowing Agent 2 (HFC) - 26 - Blowing Agent 3 (HCFO) - - 30.3 Auxiliary blowing agent (water) One One One catalyst Catalyst 1 (blowing catalyst) 0.02 0.02 0.02 Catalyst 2 (trimerization catalyst) 0.5 0.5 0.5 Catalyst 3 (trimerization catalyst) 0.75 0.75 0.75 Other
ingredient antifoaming agent 3 3 3 flame retardant 30 30 30

[Comparative Example 1]

Polyisocyanurate was formed in the same manner as in Example 1, except that hydrofluorocarbon (HCF)-based blowing agent 2 (HFC-245fa) was used instead of hydrofluoroolefin (HFO)-based blowing agent 1 (1336mzz-Z) A polyol composition for use and a polyisocyanurate foam were prepared using the same.

[Comparative Example 2]

Except for using a chlorine-containing hydrochlorofluoroolefin (HCFO)-based blowing agent 3 (HCFO-1233zd) instead of the hydrofluoroolefin (HFO)-based blowing agent 1 (1336mzz-Z), in the same manner as in Example 1, A polyol composition for forming polyisocyanurate and a polyisocyanurate foam were prepared using the same.

[Evaluation Example 1. Evaluation of physical properties]

The physical properties of the polyisocyanurate foams prepared in Examples 1 to 2 and Comparative Example 1 were evaluated as follows, and the results are shown in Table 3 below.

(1) Measurement of free foaming density

The density of the foam prepared by foaming the polyol premix composition in a state of minimizing interference from the outside was measured. That is, in a state without overpacking, the foam produced in a cup, box, or plastic bag without a lid was cut to a certain size, and the volume and weight were measured to calculate the density. At this time, the density was measured by the weight per unit volume of the prepared polyisocyanurate foam, and specifically, it was measured according to ASTM D1622 regulations.

(2) Compressive strength measurement

According to ASTM D1621, the strength was measured by compressing 10% of the foam height vertically or horizontally with respect to the foaming direction, and the result value was converted into kPa and recorded.

(3) Measurement of thermal conductivity

The thermal conductivity was measured according to ASTM C177, and the result was converted into a thermal insulation value (W/mK) and recorded.

(4) gel time

The time taken from the time the PU stock solution is mixed to the point when the stock solution has gel strength that can withstand light impact and takes on a somewhat stable spatial shape (for example, when the reacting foam is pierced with a wooden chopstick, etc.) It means the point when at least 3 or 4 urethane fibers come out).

(5) Liquid ratio: The ratio between the isocyanate (A) and the polyol (B).

Example 1 Comparative Example 1 Comparative Example 2 Molecular Weight (g/mol) 164 134 130 Boiling Point (℃) 33 15.3 19 catalyst
(g) catalyst 1
Blowing cat.
(tertiary amine) 0.02 0.02 0.02 Catalyst 2
potassium-octoate in diethylene glycol 0.5 0.5 0.5 Catalyst 3Tertiary amine 0.75 0.75 0.75 Gel time (s) 165 160 170 Liquid fertilizer (A/B) 158.3 161.3 165.8 Density (kg/㎤) 46.1 46.2 46.4 Thermal Conductivity (W/mK)
(Based on 20℃) 0.02179 0.02287 0.02235 compressive strength
(kPa, Z-axis) Top 323.7 322.0 322.0 Middle 304.0 293.7 293.7 Bottom 312.0 308.7 308.7 Average 314.2 308.1 308.1

As shown in Table 3, Example 1 using a hydrofluoroolefin (HFO)-based blowing agent has the lowest thermal conductivity compared to Comparative Example 1 using an HFC-based blowing agent, and Comparative Example 2 using an HCFO-based blowing agent It was also found to have high compressive strength.

[Evaluation Example 2. Evaluation of Density Retention Rate]

The density change over time of the polyisocyanurate foams prepared in Examples 1 to 2 and Comparative Example 1 was measured, and the results are shown in Table 4 below.

Density (Kg/㎤) Example 1 Comparative Example 1 Comparative Example 2 day 52.3 50.6 53.7 1 day elapsed 51.0 50.9 53.0 3 days passed 50.6 50.1 52.0 1 week elapsed 50.2 50.0 52.1 2 weeks passed 50.6 50.1 52.7 1 month passed 51.1 50.2 53.4

As shown in Table 4, Example 1 using a hydrofluoroolefin (HFO)-based blowing agent, Comparative Example 1 using an HFC-based blowing agent, and Comparative Example 2 using a HCFO-based blowing agent Compared with Comparative Example 2, the initial foaming It was found that the same or more physical properties were exhibited in terms of density and density retention.

[Evaluation Example 3. Evaluation of the foaming reaction rate]

Since the results regarding density deviation, rising profile, and reactivity according to the characteristics of the foaming agent are different under the same formulation conditions, the reaction profile according to the type of foaming agent was analyzed.

Specifically, the foaming rates of the polyisocyanurate foams prepared in Example 1 and Comparative Examples 1 and 2 were measured, and the results are shown in FIG. 1 .

As a result of measuring the foaming profile according to each foaming agent, Comparative Example 1 using an HFC-based foaming agent and Comparative Example 2 using an HCFO-based foaming agent showed comparable foaming rates. In the case of Example 1, the change in height appeared late.

On the other hand, even if the HFO-based blowing agent is used, it can be seen that when the ratio of catalyst 2 and catalyst 3, which are trimerization catalysts, is adjusted upward, it can be adjusted to exhibit a reaction profile similar to those of Comparative Examples 1 and 2.

[Evaluation Example 4. Storage stability evaluation]

The change in reactivity (Gel Time) over time of the polyisocyanurate foams prepared in Example 1 and Comparative Examples 1 and 2 was measured, and the results are shown in Table 5 below.

Gel Time (Sec) Example 1 Comparative Example 1 Comparative Example 2 day 147 160 180 1 day elapsed 157 148 191 3 days passed 155 149 190 1 week elapsed 153 150 189 2 weeks passed 153 150 188 1 month passed 153 152 189 2 months passed 152 165 194 3 months elapsed (90 days) 153 173 199 Gelation time change rate (%) 4.1 8.1 10.5

As a result of measuring the degree of change by periodically checking the reactivity while keeping the stock solution prepared according to the formulation of the polyisocyanurate foam-forming composition, Example 1 using a hydrofluoroolefin (HFO)-based blowing agent is hydrofluoro Compared to Comparative Examples 1 and 2 using a carbon (HFC)-based foaming agent and a hydrochlorofluoroolefin (HCFO)-based foaming agent, respectively, it exhibits a reactivity change within 5% (based on 90 days) based on the initial reactivity, resulting in excellent storage It was found to have stability.

Claims (15)

at least one polyol containing polyether polyols and polyester polyols; and
hydrofluoroolefin foaming agent;
A polyol composition for forming a polyisocyanurate foam comprising a. The method of claim 1,
A polyol composition for forming a polyisocyanurate foam, which does not contain a hydrofluorocarbon-based and hydrochlorofluoroolefin-based blowing agent. According to claim 1,
The hydrofluoroolefin-based blowing agent is trans-1,1,1,4,4,4-hexafluoro-but-2-ene (HFO-1336mzz(E)), cis-1,1,1,4 ,4,4-hexafluoro-but-2-ene (HFO-1336mzz(Z)), 1,3,3,3-tetrafluoropropene (HFO-1234ze), trans-1,3,3, 3-tetrafluoroprop-1-ene (HFO-1234ze (E)), cis-1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze (Z)), and 2,3 , A polyol composition for forming polyisocyanurate foam, comprising at least one selected from the group consisting of 3,3-tetrafluoropropene (HFO-1234yf). The method of claim 1,
The polyether polyol is polymerized from at least one initiator of sorbitol and sucrose, has a number average molecular weight (Mn) of 600 to 800 g/mol, and an average hydroxyl group (OH) of 380 to 580 mgKOH/g, polyisocyanu A polyol composition for forming a late foam. According to claim 1,
The polyester polyol is at least one polyester polyol in which glycol is polymerized with one or more raw materials selected from the group consisting of terephthalic acid, isophthalic acid, adipic acid, dimethyl terephthalate, and phthalic anhydride. Including, a number average molecular weight (Mn) of 300 to 500 g / mol, and an average hydroxyl group (OH) of 200 mgKOH / g to 400 mgKOH / g, polyisocyanurate polyol composition for forming foam. The method of claim 1,
The at least one polyol is
polyether polyols having a functional group of 4 to 8, a number average molecular weight (Mn) of 600 to 800 g/mol, and an average hydroxyl group (OH) of 380 to 580 mgKOH/g;
a first polyester polyol having a functional group of 2 to 4, a number average molecular weight (Mn) of 300 to 500 g/mol, and an average hydroxyl group (OH) of 200 mgKOH/g to 400 mgKOH/g; and
Polyisocyanu comprising a second polyester polyol having a functional group of 2 to 4, a number average molecular weight (Mn) of 400 to 600 g/mol, and an average hydroxyl group (OH) of 100 mgKOH/g to 300 mgKOH/g A polyol composition for forming a late foam. 7. The method of claim 6,
The mixing ratio of the first polyester polyol and the second polyester polyol is 45: 55 to 65: 35 by weight, a polyol composition for forming a polyisocyanurate foam. The method of claim 1,
The mixing ratio of the polyether polyol and the polyester polyol is 10: 90 to 30: 70 weight ratio based on the total weight of the polyol, a polyol composition for forming a polyisocyanurate foam. The method of claim 1,
The polyol composition comprises a blowing catalyst and a trimerization catalyst,
The trimerization catalyst is a polyol composition for forming a polyisocyanurate foam comprising at least one of an organometallic catalyst and a tertiary amine catalyst. 13. The method of claim 12,
The use ratio of the blowing catalyst, the organometallic catalyst, and the tertiary amine catalyst is 1: 20-40: 35-55 weight ratio, polyol composition for forming polyisocyanurate foam. 10. The method of claim 9,
The polyol composition is
Based on 100 parts by weight of the polyol,
10 to 40 parts by weight of a hydrofluoroolefin-based blowing agent;
0.5 to 3.5 parts by weight of a catalyst containing a blowing catalyst and a trimerization catalyst; and
A polyol composition for forming a polyisocyanurate foam comprising a. According to claim 1,
A polyol composition for forming polyisocyanurate foam, further comprising at least one of a flame retardant, a foam stabilizer, a crosslinking agent, and a chain extender. The method of claim 1,
The viscosity is 500 to 1,500 cps (based on 25 ° C.),
It has a storage stability of more than 90 days at 25℃,
The gel time change rate of the polyol composition after 90 days is 7% or less based on the initial gelation time, the polyol composition for forming a polyisocyanurate foam. The polyol composition according to any one of claims 1 to 14; and
Isocyanate compound; Polyisocyanurate foam formed by reacting. 15. The method of claim 14,
Average compressive strength (Z axis) according to ASTM D1621 is 300 kPa or more,
Average thermal conductivity according to ASTM C177 is 0.022 W/m·K or less,
The initial foaming density according to ASTM D1622 is 45 to 55 Kg/m ³ , and the density retention rate is 97% or more after 30 days after foaming, polyisocyanurate foam.

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