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KR-102964219-B1 - Polyol components for manufacturing rigid polyurethane foam and their uses

KR102964219B1KR 102964219 B1KR102964219 B1KR 102964219B1KR-102964219-B1

Abstract

The present invention relates to a method for producing a rigid polyurethane foam using a polyol component P) comprising at least two different polyether polyols A) and C) and at least one polyether ester polyol D), and to a rigid polyurethane foam produced therefrom.

Inventors

  • 클라쎈 요한
  • 바그너 헨드릭

Assignees

  • 바스프 에스이

Dates

Publication Date
20260512
Application Date
20200623
Priority Date
20190628

Claims (14)

  1. As polyol component P), a) one or more polyether polyols selected from monosaccharides, oligosaccharides, polysaccharides, polyhydric alcohols, alkoxylation products of the aforementioned compounds or mixtures thereof and reaction products of alkylene oxides, having an OH value in the range of 300 to 520 mg KOH/g; A) >0 wt% to 70 wt%; b) one or more polyether polyols selected from the reaction products of an aromatic diamine and an alkylene oxide having an OH value in the range of 320 to 500 mg KOH/g; B) 0 wt% to <5 wt%; c) one or more polyether polyols selected from the reaction products of amines, polyhydric alcohols, or mixtures thereof and alkylene oxides, having an OH value in the range of 100 to 240 mg KOH/g; C) >0 wt% to 30 wt%; d) 5% to 80% by weight of one or more polyether ester polyols D) having an OH value of 380 to 480 mg KOH/g and a fatty acid content of 5% to 25% by weight based on polyether ester polyol D); e) Optionally one or more catalysts E); f) one or more additional ingredients F selected from adjuvants and additives, optionally; g) optionally comprising one or more blowing agents selected from chemical blowing agents G1) and physical blowing agents G2), Here, the weight % concentration values of A) to D) are based on the total amount of components A) to G1) in the polyol component P). Polyol component P).
  2. In claim 1, the polyether polyol A) is a polyol component P having a functionality in the range of 4.6 to 6.5.
  3. In claim 1 or 2, the polyether polyol B) has a functional value in the range of 3.0 to 4.0, and the polyol component P).
  4. In claim 1 or 2, the polyether polyol B) is a polyol component P selected from the reaction product of C2 - C4 alkylene oxide and tolylene-2,3-, -3,4-, -2,4-, -2,5-, -2,6-diamine or a mixture thereof.
  5. In claim 1 or 2, the polyether polyol C) has a functional value in the range of 2.8 to 5.0, and the polyol component P).
  6. In claim 1 or 2, the polyether polyol C) comprises a polyol component P, which includes ethylene oxide and propylene oxide units.
  7. The polyol component P according to claim 1 or 2, wherein the polyether polyol C) comprises a reaction product of an amine selected from ethylenediamine, propylene-1,3-diamine, butylene-1,3-, -1,4-diamine, hexamethylene-1,2-, -1,3-, -1,4-, -1,5-, -1,6-diamine, phenylenediamine, tolylene-2,3-, -3,4-, -2,4-, -2,5-, -2,6-diamine and 4,4'-, 2,4'-, 2,2'-diaminodiphenylmethane or a mixture thereof and an alkylene oxide.
  8. In claim 1 or 2, the polyether polyol C) comprises a polyol component P comprising a reaction product of an alkylene oxide and a polyhydric alcohol selected from glycerol, trimethylolpropane, monopropylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol (2,2'-oxydi-1-propanol, 1,1'-oxydi-2-propanol, 2-(2-hydroxypropoxy)-1-propanol) or a mixture thereof.
  9. In claim 1 or 2, the polyether ester polyol D) is a polyol component P having a functional value of 3.0 to 5.0.
  10. In claim 1 or 2, the polyether polyol A) has a functional value of 5.7 to 6.5, and the polyol component P).
  11. I) di- or polyisocyanate PI) or a mixture thereof II) A method for producing a rigid polyurethane foam by reacting it with a polyol component P according to claim 1 or 2.
  12. Rigid polyurethane foam obtainable by the method according to paragraph 11.
  13. In paragraph 1 or 2, the polyol component P used for the manufacture of rigid polyurethane foam).
  14. A rigid polyurethane foam manufactured by the method of claim 11, used for thermal insulation and refrigeration applications.

Description

Polyol components for manufacturing rigid polyurethane foam and their uses The present invention relates to a method for manufacturing a rigid polyurethane foam using polyol component P) and a rigid polyurethane foam manufactured with polyol component P). Rigid polyurethane (PU) foam can be produced by known methods by reacting an organic polyisocyanate with one or more compounds containing at least two reactive hydrogen atoms, preferably polyether, polyester and/or polyether ester alcohol (polyol), in the presence of a blowing agent, a catalyst and optionally an auxiliary and/or additive. Rigid PU foam is widely used in the manufacture of refrigeration units. In this context, the housing of the refrigeration unit is typically foam-filled with a polyol/isocyanate mixture, and the rigid PU foam is formed in its original position between two covers that form the inner and outer casings of the refrigerator, respectively. To ensure the stability of the composite structure thus produced, the rigid PU foam must form a sufficiently rigid connection with the outer and inner casings; that is, the rigid PU foam must exhibit excellent adhesion. For high throughput and consequently high productivity during the foam filling stage, the excellent release performance of the rigid PU foam is crucial. This is evident, for example, from the fact that freshly cured rigid PU foam exhibits very low post-expansion. Furthermore, the rigid PU foam must, of course, provide the best possible thermal insulation effect. For instance, rigid PU foam manufactured using physical blowing agents such as hydrocarbons (e.g., C5 hydrocarbons, particularly cyclopentane) exhibits excellent thermal insulation properties. However, this requires that the polyol component used in the manufacture of rigid PU foam have excellent compatibility with hydrocarbons. In particular, such combination characteristic profiles are not yet sufficiently guaranteed by the polyol components of the prior art. To ensure optimal crosslinking of the foam, polyols with high functional numbers and low molecular weights are typically used in the production of isocyanate-based rigid PU foams. Preferably used polyether polyols have a functional number of 4 to 8 in most cases and a hydroxyl number in the range of 300 to 600 mg KOH/g, particularly 400 to 500 mg KOH/g. Polyols with very high functional numbers and hydroxyl numbers in the range of 300 to 600 mg KOH/g are known to have very high viscosity. In addition, because this type of polyol is relatively polar, it is known to have poor solubility for typical blowing agents, particularly hydrocarbons such as pentane and especially cyclopentane. To mitigate these disadvantages, the polyol component is often mixed with a polyether alcohol having a functional number of 2 to 4 and a hydroxyl number of 100 to 250 mg KOH/g. A European patent application not yet published as application number 18196648.2 describes polyol components for producing a rigid PU foam comprising a polyether polyol having a high functional number and a hydroxyl number of 400 to 520 mg KOH/g, a polyether polyol having a functional number of 3 to 5 and a hydroxyl number of 100 to 290 mg KOH/g, a polyether polyol having a functional number of 3 to 5 and a hydroxyl number of 300 to 500 mg KOH/g, and a polyether ester polyol having a hydroxyl number of 380 to 480 mg KOH/g. WO 2017/072152 A1 discloses polyol components for producing a rigid PU foam comprising a polyether polyol having a high functional number and a hydroxyl number of 400 to 520 mg KOH/g, a polyether polyol having a functional number of 3.7 to 4 and a hydroxyl number of 300 to 420 mg KOH/g, and a polyether ester polyol having a fatty acid content of 8 to 17 weight% (polyether ester polyols). The present invention will be described in more detail below. The OH value (hydroxyl value) can be measured by widely established methods. For example, the OH value can be measured according to DIN 53240 (1971-12). The functional value of polyols, particularly polyether polyols A), B), and C) used according to the present invention, and also the functional value of polyether ester polyol D) refers to the number of alkylene oxide-reactive hydrogen atoms per mole of starting compound or per mole of mixture of starting compounds before weighing the alkylene oxide within the context of the present invention. In this case, the time for weighing the alkylene oxide is the point at which the alkylene oxide component begins to be added to the starting compound(s). The calculation takes into account all alkylene oxide-reactive hydrogen atoms of the starting compound(s) present in the starting mixture. In the context of the present invention, the action value F is calculated according to the following general formula (I): (I) moles of starting material i The function of starting material i = Number of starting materials in the starting mixture F = Action value The functional value F of a polyol prepared from a mixture of