阅读说明：本技术 聚氨酯泡沫的生产 (Production of polyurethane foams ) 是由 M·瓦格纳 P·阿尔滕布赫纳 于 2021-06-03 设计创作，主要内容包括：本发明涉及聚氨酯泡沫的生产,公开了用于生产聚氨酯泡沫的组合物,其至少包含异氰酸酯组分、多元醇组分、任选存在的催化氨基甲酸酯键或异氰脲酸酯键形成的催化剂、任选存在的发泡剂,其中所述组合物包含基于OH官能化的或氨基官能化的聚烯烃和聚酯的嵌段共聚物作为泡沫稳定剂。(The invention relates to the production of polyurethane foams, and discloses a composition for producing polyurethane foams, comprising at least an isocyanate component, a polyol component, optionally a catalyst which catalyzes the formation of urethane or isocyanurate bonds, optionally a blowing agent, wherein the composition comprises as a foam stabilizer a block copolymer based on an OH-functionalized or amino-functionalized polyolefin and a polyester.)

1. Composition for producing polyurethane foams, preferably rigid polyurethane foams, comprising at least an isocyanate component, a polyol component, optionally a catalyst which catalyzes the formation of urethane or isocyanurate bonds, optionally a blowing agent, characterized in that the composition comprises a block copolymer based on an OH-functionalized or amino-functionalized polyolefin and a polyester.

2. Composition according to claim 1, characterized in that the block copolymer is a B (A) x block system, wherein A ═ polyester, wherein B ═ OH-functionalized or amino-functionalized polyolefin, and wherein x ≧ 1, preferably x ═ 1.5 to 5, in particular x ═ 2 to 3.

3. Composition according to claim 2, characterized in that the OH-functional or amino-functional polyolefin B used is a polybutadiene comprising or preferably consisting of 1, 3-butadiene-derived monomer units

With the proviso that the monomer units (II), (III) and (IV) can be arranged in blocks or in a randomly distributed manner, wherein the square brackets in the selected formula representing the 1, 3-butadiene-derived monomer units (II), (III) and (IV) present in the polybutadiene indicate that the bond with the corresponding square bracket does not terminate in a methyl group, but that, for example, the corresponding monomer unit is bonded via this bond to other monomer units, hydroxyl groups or amino groups.

4. Composition according to claim 3, characterized in that the polyalkylene group B additionally comprises one or more branched structures of the formula (V), (VI) or (VII) in a proportion of up to 5 mol%, based on polybutadiene

And/or

Wherein "(C)₄H₆)_n"corresponds to a butadiene oligomer comprising or preferably consisting of the repeating units (II), (III) and (IV).

5. Composition according to claim 3 or 4, characterized in that the polybutadiene is in the unhydrogenated, partially hydrogenated or fully hydrogenated form.

6. Composition according to any one of claims 2 to 5, characterized in that the polyester residue A has the structure I:

wherein Z is the same or different hydrocarbyl, preferably-C₅H₁₀-and/or-C (CH)₃) H-group, and n ═ 1 to 150.

7. Composition according to any one of claims 1 to 6, characterized in that the block copolymer is based on a polyester prepared from a lactone and/or lactide, more preferably caprolactone and/or lactide.

8. Composition according to any one of claims 1 to 7, characterized in that the mass proportion of the total amount of block copolymers according to the invention is from 0.1 to 10pphp, preferably from 0.5 to 5pphp and more preferably from 1 to 4pphp, based on 100 parts by mass of polyol component.

9. Composition according to any one of claims 1 to 8, characterized in that the silicon-containing foam stabilizer, if any, is present to an extent of less than 15% by weight, preferably less than 10% by weight, in particular less than 5% by weight, based on the total amount of foam stabilizer of the block copolymer according to the invention which also comprises an OH-functionalized or amino-functionalized polyolefin and a polyester.

10. Composition according to any one of claims 1 to 8, characterized in that the silicon-containing foam stabilizer is present to an extent of more than 10% by weight, in particular more than 20% by weight and more preferably more than 50% by weight, based on the total amount of foam stabilizer also comprising the block copolymer according to the invention based on OH-functionalized or amino-functionalized polyolefin and polyester.

11. Composition according to any one of claims 2 to 10, characterized in that the mass-weighted proportion of polyester residues a is at least 20%, preferably at least 30%, more preferably at least 35%.

12. Process for producing polyurethane foams, preferably rigid polyurethane foams, by reacting one or more polyol components with one or more isocyanate components, characterized in that the reaction is carried out in the presence of a block copolymer based on OH-functionalized or amino-functionalized polyolefins and polyesters, in particular using a composition according to any one of claims 1 to 11.

13. Use of block copolymers based on OH-functionalized or amino-functionalized polyolefins and polyesters, in particular for the production of polyurethane foams, preferably rigid polyurethane foams, preferably as foam stabilizers, preferably for improving the thermal insulation properties of the foams, using a composition according to any of claims 1 to 11.

14. Polyurethane foam, preferably rigid polyurethane foam, obtainable by the process according to claim 12.

15. Use of a polyurethane foam according to claim 14, preferably a rigid polyurethane foam, as a thermal insulation plate and/or a thermal insulation material, preferably for cooling equipment.

Technical Field

The present invention is in the field of polyurethane foams. The invention relates in particular to the use of block copolymers based on OH-or amino-functionalized polyolefins and polyesters as foam stabilizers for the production of rigid polyurethane foams. The invention also relates to the corresponding compositions and to the use of the foams produced according to the invention. The polyurethane foam is in particular a rigid polyurethane foam.

Background

In the context of the present invention, Polyurethane (PU) is understood in particular to mean the products obtainable by reacting polyisocyanates with polyols or compounds having isocyanate-reactive groups. In addition to polyurethanes, other functional groups may be formed in the reaction, such as uretdiones, carbodiimides, isocyanurates, allophanates, biurets, ureas and/or uretonimines. Thus, for the purposes of the present invention, PU is understood to mean not only polyurethanes, but also polyisocyanurate, polyurea, and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret, and uretonimine groups. In the context of the present invention, polyurethane foams (PU foams) are understood to mean foams obtained as reaction products based on polyisocyanates and polyols or compounds having isocyanate-reactive groups. In addition to groups of the same name as urethanes, other functional groups may also be formed, such as allophanates, biurets, ureas, carbodiimides, uretdione, isocyanurate, or uretonimine. In the context of the present invention, the most preferred foams are rigid polyurethane foams.

Polyurethane and polyisocyanurate foams, especially corresponding rigid foams, are produced using cell-stabilizing additives to ensure a fine-celled, homogeneous and low-defect foam structure and thus to have a substantially positive effect on the performance properties, especially of rigid foams, such as thermal insulation properties. Surfactants based on polyether-modified siloxanes are particularly effective and therefore represent a preferred type of foam stabilizer.

Various publications relating to the use of silicone-based additives have been disclosed. Usually, polyether siloxane foam stabilizers (PES) are used here.

EP 0570174B 1 describes polyether siloxanes suitable for the production of rigid polyurethane foams using organic blowing agents, in particular chlorofluorocarbons such as CFC-11.

EP 0533202 a1 describes polyether siloxanes which contain SiC-bonded polyoxyalkylene groups and are suitable as blowing agents in the case of hydrochlorofluorocarbons such as HCFC-123.

EP 0877045B 1 describes similar structures for this production process which differ from the previous foam stabilizers in that they have a relatively high molecular weight and have a combination of two polyether substituents on the siloxane chain.

EP1544235 describes typical polyether-modified siloxanes for rigid PU foam applications. Siloxanes having 60 to 130 silicon atoms and different polyether substituents R, whose mixed molar masses are 450 to 1000g/mol and whose ethylene oxide contents are 70 to 100 mol%, are used here.

CN103055759 describes polyether modified siloxanes which result in improved cell opening. At least 18 silicon units are present in the siloxane and are modified with various types of side chains.

EP 1873209 describes polyether-modified siloxanes for producing rigid PU foams having improved flame-retardant properties. Here, 10 to 45 silicon atoms are present in the siloxane and the polyether side chains consist to the extent of 90% of ethylene oxide units.

EP 2465891A 1 describes polyether-modified siloxanes in which some of the polyether side chains bear OH groups. The siloxane here contains at least 10 silicon atoms.

EP 2465892 a1 describes polyether-modified siloxanes in which the polyether side chains bear predominantly secondary OH end groups, wherein the siloxanes here also contain at least 10 silicon atoms.

DE 3234462 describes silicones for flexible foams, in particular molded flexible foams. Described herein is a combination of polyether modified siloxane (PES) and polydimethylsiloxane, wherein the PES comprises from 4 to 15 silicon units.

However, there is still a need for further cell stabilizers for PU foams, preferably for rigid PU foams, and in particular for those which are fundamentally capable of stabilizing silicone-free cells.

It is therefore a particular object of the present invention to make it possible to provide PU foams, in particular rigid PU foams, in which silicone-free cell stabilization can be achieved fundamentally.

Disclosure of Invention

It has surprisingly been found that PU foams, in particular rigid PU foams, can be produced in an unproblematic quality when block copolymers based on OH-or amine-functionalized polyolefins and polyesters are used as foam stabilizers. The block copolymers according to the invention fundamentally enable silicone-free cells to be stabilized, i.e. silicone-based additives, such as the known polyether siloxane foam stabilizers, can be dispensed with altogether. However, they also allow the use in combination with silicone-containing stabilizers known from the prior art. Both are covered by the present invention.

Against this background, the present invention provides a composition for producing polyurethane foams, in particular rigid polyurethane foams, comprising at least an isocyanate component, a polyol component, optionally a catalyst which catalyzes the formation of urethane or isocyanurate bonds, optionally a blowing agent, wherein the composition comprises a block copolymer based on an OH-functionalized or amino-functionalized polyolefin and a polyester. The block copolymers according to the invention are used as foam stabilizers in the production of polyurethane foams, in particular rigid PU foams.

The subject matter of the present invention makes it possible to provide PU foams, preferably rigid PU foams, dispensing with the known silicone-containing stabilizers. Nevertheless, the PU foams obtained meet the known requirements. They are advantageously dimensionally and hydrolytically stable and have excellent long-term properties. They advantageously have very good thermal insulation properties, very high thermal insulation capacity, high mechanical strength, high stiffness, high compressive strength. The subject matter of the present invention is also able to provide PU foams, preferably rigid PU foams, which are used in combination with silicone-containing stabilizers known from the prior art.

Block copolymers based on OH-functionalized or amino-functionalized polyolefins and polyesters are known per se from the prior art. For this purpose, reference is made in particular to european patent application EP 3243863 a1, which relates however to adhesives or sealants and neither mentions nor refers to the subject matter of PU foams.

The following are preferred embodiments of the present invention: the block copolymers used according to the invention are B (a) x block systems, where a ═ polyester, where B ═ OH-functionalized or amino-functionalized polyolefins and where x ≧ 1, preferably x ═ 1.5 to 5, in particular x ═ 2 to 3.

The following is another preferred embodiment of the present invention: the OH-functionalized or amino-functionalized polyolefin B used is a polybutadiene containing 1, 3-butadiene-derived monomer units or a polybutadiene preferably consisting of 1, 3-butadiene-derived monomer units

With the proviso that the monomer units (II), (III) and (IV) can be arranged in blocks or in a randomly distributed manner, wherein the brackets in the selected formula representing the 1, 3-butadiene-derived monomer units (II), (III) and (IV) present in the polybutadiene indicate that the bond with the respective bracket does not terminate in a methyl group, but rather, for example, the respective monomer unit is bonded via this bond to a further monomer unit, a hydroxyl group or an amino group.

The following is also another preferred embodiment of the present invention: the polyalkylene groups B additionally comprise up to 5 mol%, based on the polybutadiene, of one or more branched structures of the formula (V), (VI) or (VII),

wherein "(C)₄H₆)_n"corresponds to a butadiene oligomer comprising or preferably consisting of the repeating units (II), (III) and (IV).

In another preferred embodiment of the invention, the polybutadiene is in the unhydrogenated, partially hydrogenated or fully hydrogenated form.

For example, in EP 2492292Suitable processes for preparing usable polybutadienes. Examples of polybutadienes which can be used in the context of the present invention are also commercially available, for example in order toForm HT OH-functionalized polybutadiene from Evonik Resource Efficiency GmbH.

In addition to the OH-functionalized or amino-functionalized polyolefins, the block copolymers used according to the invention also comprise blocks formed from polyesters; more particularly, the block copolymers are based on polyesters formed from lactones and/or lactides.

In yet another preferred embodiment of the present invention, the polyester group a has structure I:

wherein Z is the same or different hydrocarbyl, preferably-C₅H₁₀-and/or-C (CH)₃) H-group, and n ═ 1 to 150.

It is a further preferred embodiment of the present invention if the block copolymer is based on polyesters of lactones and/or lactides, more preferably of caprolactone and/or lactide.

Examples of suitable lactones are in particular C₃Lactones such as beta-propiolactone; c₄Lactones such as beta-butyrolactone or gamma-butyrolactone; c₅Lactones such as 4-hydroxy-3-pentenoate-gamma-lactone, alpha-methylene-gamma-butyrolactone, gamma-methylene-gamma-butyrolactone, 3-methyl-2 (5H) -furanone, gamma-valerolactone, delta-valerolactone; c₆Lactones such as delta-caprolactone, epsilon-caprolactone or gamma-caprolactone or other lactones such as 5-butyl-4-methyldihydro-2 (3H) -furanone, delta-octalactone, gamma-phenyl-epsilon-caprolactone, oxacyclododecan-2-one, oxatridecan-2-one, pentadecanolide, 16-hexadecanolide, gamma-undecalactone, delta-undecalactone, gamma-methylene-gamma-butyrolactone and mixtures thereof.

In the context of the present invention, lactide is understood to mean a cyclic ester of lactic acid which may exist in three isomers: (S, S) -3, 6-dimethyl-1, 4-dioxane-2, 5-dione (CAS No.4511-42-6), (R, R) -3, 6-dimethyl-1, 4-dioxane-2, 5-dione (CAS No.25038-75-9), and (m) -3, 6-dimethyl-1, 4-dioxane-2, 5-dione (CAS No. 13076-19-2). There are no particular preference for isomeric forms.

Preferably, a mixture of at least two lactones and/or lactides, preferably a mixture of one lactone and one lactide, particularly preferably a mixture of epsilon-caprolactone and lactide, is used to prepare the block copolymer. In this way, the properties of the block copolymers, in particular with respect to miscibility with other polyester polyols, polyether siloxanes or with respect to thermal properties, can be varied in a controlled manner.

The block copolymers used according to the invention can be obtained in particular by OH-initiated or amino-initiated ring-opening polymerization. The OH-functional or amino-functional polymers are used here as initiators in the opening of the lactones and/or lactides, which leads to the formation of polyester chains on the OH-functional or amino-functional polymers.

Standard homogeneous catalysts for ring-opening polymerization are, for example, tin (II) ethylhexanoate; dibutyltin dilaurate; organic amidine bases such as 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, 1, 4-diazabicyclo [2.2.2] octane and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene; or a titanium (IV) alkoxide such as tetramethyl titanate, tetrabutyl titanate, tetraisopropyl titanate, tetraphenyl titanate, triethanolamine dibutyl titanate (dibutylrietholamine titanate), tetrahexyl titanate, or triethanolamine isopropyl titanate (triethanolaminatopropyl titanate). The ring-opening reaction is usually carried out at a temperature of from 20 to 250 ℃ and in particular in the molten state or in the presence of a solvent within from 1 to 20 hours. The molar ratio of lactone and/or lactide to OH or amino group containing polymer is typically 1:1 to 200: 1.

The concentration of hydroxyl end groups in the block copolymers used according to the invention, determined by titration means in accordance with DIN 53240-2, is preferably between 0 and 300mgKOH/g, preferably between 5 and 50 mgKOH/g.

The number average molecular weight of the block copolymers used according to the invention is preferably 600-60000g/mol, in particular 1000-30000 g/mol. It was determined by gel permeation chromatography according to DIN 55672-1 using tetrahydrofuran as eluent and polystyrene for calibration.

It is also a preferred embodiment of the present invention if the mass ratio based on 100 parts by mass of the total amount of the polyol component of the block copolymer according to the present invention is 0.1 to 10pphp, preferably 0.5 to 5pphp, and more preferably 1 to 4 pphp.

This case is also a preferred embodiment of the present invention: the compositions according to the invention are characterized by a mass-weighted proportion of polyester groups A of at least 20%, preferably at least 30%, more preferably at least 35%.

The invention makes it possible to dispense with silicon-containing foam stabilizers. In this case, a composition according to the invention which comprises silicon-containing foam stabilizers, if any, to an extent of less than 15% by weight, preferably less than 10% by weight, further preferably less than 5% by weight, more preferably less than 3% by weight, even more preferably less than 1% by weight, in particular less than 0.5% by weight, based on the total amount of foam stabilizers, is a preferred embodiment of the invention.

As mentioned, the invention additionally enables the use of silicon-containing foam stabilizers in parallel. In this case, compositions according to the invention which comprise silicon-containing foam stabilizers to an extent of more than 1% by weight, preferably more than 10% by weight, in particular more than 20% by weight, based on the total amount of foam stabilizers, are a preferred embodiment of the invention. In the case of such embodiments, for example, 50% by weight: mixtures of 50% by weight are also possible; in other words, the composition will comprise equal parts of the block copolymer according to the invention and the silicon-containing foam stabilizer. This is because it has surprisingly been found that the block copolymers according to the invention greatly improve the emulsifying power of silicon-containing foam stabilizers.

In addition to the block copolymers according to the invention based on OH-or amino-functionalized polyolefins and polyesters, it is in principle also possible to additionally use any foam-stabilizing component known from the prior art.

The block copolymers according to the invention can be used in pure form or in solvents. In this case, all suitable substances which can be used in the production of PU foams can be used. The solvents used are preferably those which have been used in standard formulations, such as OH-functional compounds, polyols, flame retardants, etc.

A preferred composition according to the invention comprises the following ingredients:

a) the block copolymer according to the present invention as described above,

b) at least one polyol component selected from the group consisting of,

c) at least one polyisocyanate and/or polyisocyanate prepolymer,

d) optionally a catalyst which promotes or controls the reaction of the polyol b) with the isocyanate c),

e) optionally present, further foam stabilizers, in particular corresponding silicon compounds,

f) optionally one or more blowing agents, optionally present,

g) optionally other additives, fillers, flame retardants, etc.

It is preferred here that components d) and f) are necessary.

In a preferred embodiment of the present invention, polyurethane foams are produced using components having at least two isocyanate-reactive groups, preferably a polyol component, a catalyst and a polyisocyanate and/or polyisocyanate prepolymer, and a block copolymer according to the present invention. The catalyst is introduced here in particular via the polyol component. Suitable polyol components, catalysts and polyisocyanates and/or polyisocyanate prepolymers are well known to those skilled in the art, but will be described in more detail below.

For the purposes of the present invention, suitable polyols as polyol component b) are all organic substances having one or more isocyanate-reactive groups, preferably OH groups, and also formulations containing them. Preferred polyols are all polyether polyols and/or polyester polyols and/or hydroxyl-containing aliphatic polycarbonates, in particular polyether polycarbonate polyols, and/or polyols of natural origin, known as "natural oil-based polyols" (NOPs), which are generally used for producing polyurethane systems, in particular polyurethane coatings, polyurethane elastomers or foams. The polyols typically have a functionality of 1.8 to 8 and a number average molecular weight in the range of 500 to 15000. Polyols having OH numbers in the range of from 10 to 1200mgKOH/g are generally used.

For the production of rigid PU foams, preference may be given to using polyols or mixtures thereof, with the proviso that at least 90 parts by weight of the polyols present have an OH number of greater than 100, preferably greater than 150, in particular greater than 200, based on 100 parts by weight of the polyol component. The fundamental difference between flexible foams and rigid foams is that flexible foams exhibit elastic characteristics and are reversibly deformable. When the flexible foam is deformed by the application of force, it returns to its original shape once the force is stopped. In contrast, rigid foams are permanently deformed. As is well known to those skilled in the art.

Polyether polyols can be obtained by known processes, for example by anionic polymerization of alkylene oxides in the presence of alkali metal hydroxides, alkali metal alkoxides or amines as catalysts and by addition of at least one starter molecule which preferably contains 2 or 3 reactive hydrogen atoms in bonded form, or by cationic polymerization of alkylene oxides in the presence of Lewis acids, such as antimony pentachloride or boron trifluoride etherate, or by double metal cyanide catalysis. Suitable alkylene oxides contain 2 to 4 carbon atoms in the alkylene radical. Examples are tetrahydrofuran, 1, 3-propylene oxide, 1, 2-butylene oxide and 2, 3-butylene oxide; preference is given to using ethylene oxide and 1, 2-propylene oxide. The alkylene oxides can be used individually, cumulatively in block form, in alternating form or in mixed form. The starter molecules used are, in particular, compounds which can have at least 2, preferably 2 to 8, hydroxyl groups or at least two primary amino groups in the molecule. The starter molecule used may be, for example, water; dihydric/trihydric or tetrahydric alcohols such as ethylene glycol, propane-1, 2-diol and propane-1, 3-diol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, castor oil and the like; higher multifunctional polyols, especially sugar compounds such as glucose, sorbitol, mannitol, and sucrose; a polyhydric phenol; resols such as oligomeric condensates of phenol and formaldehyde and mannich condensates of phenol, formaldehyde and dialkanolamines; and melamine; or amines such as aniline, EDA, TDA, MDA and PMDA, more preferably TDA and PMDA. The choice of suitable starter molecules depends on the respective field of application of the polyether polyols obtained in the production of polyurethanes.

The polyester polyols are based on esters of polybasic aliphatic or aromatic carboxylic acids, which preferably have from 2 to 12 carbon atoms. Examples of aliphatic carboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid and fumaric acid. Examples of aromatic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and the isomeric naphthalenedicarboxylic acids. The polyester polyols are obtained by condensing these polycarboxylic acids with polyhydric alcohols, preferably diols or triols having from 2 to 12, more preferably from 2 to 6, carbon atoms, preferably ethylene glycol, diethylene glycol, trimethylolpropane and glycerol.

In a particularly preferred embodiment of the present invention, polyester polyols are present in the composition according to the invention.

Polyether polycarbonate polyols are polyols containing carbon dioxide in carbonate-bonded form. The use of carbon dioxide as a comonomer in the polymerization of alkylene oxides is of particular interest from a commercial point of view, since carbon dioxide is formed in large amounts as a by-product in many processes in the chemical industry. Partial replacement of alkylene oxides in polyols with carbon dioxide has the potential to significantly reduce the cost of polyol production. In addition, CO is used₂Being a comonomer is very environmentally advantageous, since this reaction converts greenhouse gases into polymers. It is well known to prepare polyether polycarbonate polyols by addition of alkylene oxides and carbon dioxide to H-functional starter substances using catalysts. Various catalyst systems can be used here: the first generation is heterogeneous zinc or aluminium salts, for example as described in US-a 3900424 or US-a 3953383. Furthermore, mononuclear and binuclear metal complexes have been successfully used for CO₂And alkylene oxides (WO 2010/028362, WO 2009/130470, WO 2013/02293)2 or WO 2011/163133). The most important class of catalyst systems for the copolymerization of carbon dioxide and alkylene oxides is double metal cyanide catalysts, also known as DMC catalysts (U.S. Pat. No. 3, 4500704, 2008/058913). Suitable alkylene oxide and H-functional starter substances are those which, as described above, are also used for the preparation of carbonate-free polyether polyols.

In view of the long-term limitations in the availability of fossil resources, i.e. petroleum, coal and natural gas, and the increasing background of crude oil prices, polyols based on renewable raw materials, natural oil-based polyols (NOPs), for the production of polyurethane foams, are attracting increasing attention and have been described many times in such applications (WO 2005/033167, US 2006/0293400, WO 2006/094227, WO 2004/096882, US 2002/0103091, WO 2006/116456 and EP 1678232). Many such polyols are now available on the market from a number of manufacturers (WO2004/020497, US2006/0229375, WO 2009/058367). Polyols with varying performance profiles are obtained depending on the base stock (e.g. soybean oil, palm oil or castor oil) and subsequent post-treatment. Basically, two categories can be distinguished: a) polyols based on renewable raw materials, these polyols being modified so as to be usable to the extent of 100% in polyurethane production (WO2004/020497, US 2006/0229375); b) polyols based on renewable raw materials can only replace petrochemical-based polyols in up to a certain proportion because of their processing and properties (WO 2009/058367).

Another useful class of polyols are the so-called filled polyols (polymer polyols). These polyols are characterized in that they contain dispersed solid organic fillers having a solids content of up to 40% or more. Useful polyols include SAN, PUD and PIPA polyols. SAN polyols are highly reactive polyols comprising dispersed copolymers based on styrene-acrylonitrile (SAN). PUD polyols are highly reactive polyols comprising polyurea, also in dispersed form. PIPA polyols are highly reactive polyols containing dispersed polyurethanes, formed for example by reacting isocyanates with alkanolamines in situ in conventional polyols.

Another useful class of polyols are those obtained as prepolymers via reaction of polyols with isocyanates in a molar ratio of preferably 100:1 to 5:1, more preferably 50:1 to 10: 1. Such prepolymers are preferably constructed in the form of a solution in the polymer, wherein the polyol preferably corresponds to the polyol used to prepare the prepolymer.

In the context of the present invention, the preferred ratio of isocyanate to polyol, i.e. the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g. OH groups, NH groups), multiplied by 100, expressed as index of the formulation (formulation) is in the range of 10 to 1000, preferably in the range of 40 to 500. This is a preferred embodiment of the present invention. An index of 100 indicates a molar ratio of reactive groups of 1: 1.

The isocyanate component c) used is preferably one or more organic polyisocyanates having two or more isocyanate functions.

For the purposes of the present invention, isocyanates suitable as isocyanate component are all isocyanates which contain at least two isocyanate groups. In general, all aliphatic, cycloaliphatic, arylaliphatic polyfunctional isocyanates known per se and preferably aromatic polyfunctional isocyanates can be used. The isocyanate is more preferably used in the range of 60 to 200 mol% with respect to the total of the components consuming the isocyanate.

Specific examples are: alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene moiety, such as dodecane-1, 12-diisocyanate, 2-ethyltetramethylene 1, 4-diisocyanate, 2-methylpentamethylene 1, 5-diisocyanate, tetramethylene 1, 4-diisocyanate and preferably hexamethylene 1, 6-diisocyanate (HMDI); cycloaliphatic diisocyanates such as cyclohexane 1, 3-and 1, 4-diisocyanate and any mixture of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (1-isocyanato-3,3, 5-trimethyl-5-isocyanatodimethylcyclohexane) (isophorone diisocyanate or IPDI for short), hexahydrotoluene 2, 4-and 2, 6-diisocyanate and corresponding isomer mixtures, preferably aromatic diisocyanates and polyisocyanates such as toluene 2, 4-and 2, 6-diisocyanate (TDI) and corresponding isomer mixtures, naphthalene diisocyanate, diethyltoluene diisocyanate, diphenylmethane 2,4 '-and 2,2' -diisocyanate (MDI) and polyphenyl polymethylene polyisocyanate (crude MDI), And mixtures of crude MDI and Toluene Diisocyanate (TDI). The organic diisocyanates and polyisocyanates can be used individually or in the form of mixtures thereof. The corresponding "oligomers" (IPDI trimers based on isocyanurates, biurets, uretdione) of diisocyanates can likewise be used. In addition, prepolymers based on the above-mentioned isocyanates may be used.

Isocyanates which have been modified by the introduction of urethanes, uretdiones, isocyanurates, allophanates and other groups, known as modified isocyanates, may also be used.

Particularly suitable organic polyisocyanates which are particularly preferably used are therefore the various isomers of toluene diisocyanate (toluene 2, 4-and 2, 6-diisocyanate (TDI), in pure form or as a mixture of isomers with different composition), diphenylmethane 4,4 '-diisocyanate (MDI), "crude MDI" or "polymeric MDI" (comprising the 4,4' isomer of MDI and the 2,4 'and 2,2' isomers and products with more than two rings) and also the bicyclic products which are referred to as "pure MDI" and which consist predominantly of a mixture of the 2,4 'and 4,4' isomers, and also prepolymers derived therefrom. Examples of particularly suitable isocyanates are described in detail in, for example, EP 1712578, EP 1161474, WO 00/58383, US 2007/0072951, EP 1678232 and WO 2005/085310, which are all incorporated herein by reference.

d) Catalyst and process for preparing same

Suitable optionally usable catalysts d) in the context of the present invention are all compounds which are capable of accelerating the reaction of isocyanates with OH functions, NH functions or other isocyanate-reactive groups. Conventional catalysts known in the art, such as those comprising amines (cyclic, acyclic; monoamines, diamines, oligomers having one or more amino groups), organometallic compounds and metal salts, preferably tin, iron, bismuth and zinc, may be utilized here. In particular, mixtures of various components can be used as catalysts.

Component e) is an optionally usable further foam stabilizer which is not a block copolymer according to the invention. They may preferably be surface-active silicon compounds, which serve to further optimize the desired cell structure and foaming process. In the context of the present invention, any silicon-containing compound that promotes foam generation (stabilization, cell conditioning, cell opening, etc.) may be used. These compounds are well known in the art. The surface-active silicon-containing compound may be any known compound suitable for the production of PU foams.

Siloxane structures of this type that can be used in the context of the present invention are described, for example, in the following patent documents: CN 103665385, CN 103657518, CN103055759, CN 103044687, US 2008/0125503, US 2015/0057384, EP 1520870 a1, EP 1211279, EP 0867464, EP 0867465, EP 0275563, although these only describe the use in conventional polyurethane foams such as moulded foams, mattresses, thermal insulation materials, building foams and the like. These documents are now incorporated by reference herein and are considered to form part of the disclosure of the present invention.

The use of the blowing agent f) is optional depending on the foaming process used. Chemical and physical blowing agents may be used. The choice of blowing agent here depends to a large extent on the type of system.

Depending on the amount of blowing agent used, foams of high or low density are produced. For example, a density of 5kg/m can be produced³To 900kg/m³The foam of (1). The preferred density is 8-800kg/m³More preferably 10 to 600kg/m³In particular from 30 to 150kg/m³。

The physical blowing agents used may be the corresponding compounds having a suitable boiling point. Chemical blowing agents that react with NCO groups to release gases such as water or formic acid may also be used. These blowing agents are, for example, liquefied CO₂Nitrogen, air, volatile liquids, for example hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane and n-pentane, hydrofluorocarbons (preferably HFC 245fa, HFC 134a and HFC 365mfc), chlorofluorocarbons (preferably HCFC 141b), Hydrofluoroolefins (HFO) or hydrohaloolefins (for example 1234ze, 1233zd (E) or 1336mzz), oxygenates such as formic acidMethyl ester, acetone and dimethoxymethane; or chlorinated hydrocarbons (preferably dichloromethane and 1, 2-dichloroethane).

Optional additives g) which may be used include all substances known in the art and which are useful for the production of polyurethanes, preferably polyurethane foams, especially rigid polyurethane foams, such as crosslinking and chain extenders, stabilizers against oxidative degradation (known as antioxidants), flame retardants, surfactants, biocides, cell-refining additives, cell-opening agents, solid fillers, antistatic additives, nucleating agents, thickeners, dyes, pigments, color pastes, fragrances, emulsifiers and the like.

The flame retardant comprised in the composition according to the invention may be any known flame retardant suitable for the production of polyurethane foams. Suitable flame retardants for the purposes of the present invention are preferably liquid organic phosphorus compounds such as halogen-free organic phosphates, for example triethyl phosphate (TEP); halogenated phosphates, such as tris (1-chloro-2-propyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP); and organic phosphonates such as dimethyl methanephosphonate (DMMP), dimethyl propanephosphonate (DMPP); or solids such as ammonium polyphosphate (APP) and red phosphorus. Furthermore, halogenated compounds, for example halogenated polyols, and solids such as expandable graphite, aluminum oxide, antimony compounds and melamine are suitable as flame retardants. The use of the block copolymers of the invention makes it possible to use very large amounts of flame retardants, especially liquid flame retardants, such as TEP, TCPP, TCEP, DMMP, which generally lead to relatively unstable formulations.

The present invention also provides a process for producing polyurethane foams, in particular rigid polyurethane foams, by reacting one or more polyol components with one or more isocyanate components, wherein the reaction is carried out in the presence of the block copolymers according to the invention based on OH-functionalized or amino-functionalized polyolefins and polyesters, in particular using the compositions according to the invention as described above. To avoid repetition, reference is made in this respect to the preceding. In particular, reference is made to the foregoing for preferred embodiments of the invention. The block copolymers according to the invention are used as foam stabilizers.

The density of the foams produced according to the invention, in particular of the rigid PU foams, is preferably 5kg/m³To 900kg/m³More preferably 8 to 800kg/m³Particularly preferably from 10 to 600kg/m³More particularly from 20 to 150kg/m³。

More particularly, closed-cell PU foams, preferably rigid PU foams, can be obtained, wherein the closed-cell content is advantageously > 80%, preferably > 90%. This is a very particularly preferred embodiment of the invention. In the context of the present invention, the closed cell content is preferably determined by means of a densitometer according to DIN ISO 4590.

The process according to the invention for producing PU foams can be carried out by known methods, for example by manual mixing or preferably by means of foaming machines. If the process is carried out by using a foaming machine, high-pressure or low-pressure machines can be used. The process according to the invention can be carried out batchwise or continuously.

The preferred rigid polyurethane or polyisocyanurate foam formulations according to the invention have foam densities of from 5 to 900kg/m³And has the composition shown in table 1.

Table 1: preferred compositions of rigid polyurethane or polyisocyanurate foam formulations

For other preferred embodiments and configurations of the process of the invention, reference is also made to the details which have been given above in connection with the composition of the invention, in particular to the preferred embodiments specified there.

The invention further provides polyurethane foams, preferably rigid PU foams, obtainable by said process.

A preferred embodiment relates to a foam having a density of from 5 to 750kg/m³Preferably 5 to 350kg/m³The rigid polyurethane foam of (1).

In another preferred embodiment of the invention, the polyurethane foam is, preferably, rigidThe PU foam has a weight of 5-900kg/m³More preferably 8 to 800kg/m³Particularly preferably from 10 to 600kg/m³More particularly 20 to 150kg/m³With a closed cell content of advantageously>80%, preferably>90％。

Advantageously, the polyurethane foams according to the invention are characterized in that they comprise at least one block copolymer according to the invention as described above and are preferably obtainable by the process according to the invention.

The PU foam (polyurethane or polyisocyanurate foam), in particular the rigid PU foam, according to the invention can be used as thermal insulation or for producing thermal insulation, preferably insulation sheeting, refrigerators, thermal insulation foams, vehicle seats, in particular car seats, roof linings, mattresses, filter foams, packaging foams or spray foams.

The PU foams, in particular rigid PU foams, according to the invention can advantageously be used in particular in the refrigerated warehouses, refrigeration plants and the household appliance industry, for example for producing insulation sheeting for roofs and walls, as insulation material in containers and warehouses for frozen foods, and in refrigeration and freezing plants

Further preferred fields of use are in vehicle construction, in particular for producing vehicle interior headliners, body parts, interior trim, cooled vehicles, bulk containers, transport trays, laminates for packaging, in the furniture industry, for example for furniture parts, doors, in interior linings in electronic applications.

The cooling device of the invention has a PU foam according to the invention, in particular a rigid PU foam (polyurethane or polyisocyanurate foam), as a heat-insulating material.

The invention also provides the use of the PU foams, in particular rigid PU foams, as heat-insulating materials, as heat-insulating panels, as spray foams, as single-component foams in the refrigeration technology, refrigeration plant, construction industry, automotive industry, shipbuilding industry and/or electronics industry.

The present invention also provides the use of the block copolymers according to the invention as described above, preferably as foam stabilizers, more preferably for improving the thermal insulation properties of foams, in the production of PU foams, especially rigid PU foams, especially for improving the thermal insulation properties of foams, especially using the compositions according to the invention as described above.

The subject matter of the invention is described above or below by way of examples without the intention to limit the invention to these illustrative embodiments. Where ranges, general formulae or groups of compounds are specified above or below, they are intended to include not only the corresponding ranges or groups of the explicitly mentioned compounds but also all subranges and subsets of compounds which can be obtained by removing individual values (ranges). Where a document is cited in the context of this specification, its entire content, in particular that relating to the subject matter forming the context in which it is cited, is intended to form part of the disclosure of the present invention. Percentages are by weight unless otherwise indicated. Unless otherwise indicated, the average values reported above or below refer to weight average values. Unless otherwise stated, in the case where the parameters which have been determined by measurement are given above or below, the measurement is carried out at a temperature of 25 ℃ and a pressure of 101325 Pa.

The following examples illustrate the invention by way of example and are not intended to limit the scope of the invention to the embodiments set forth in the examples, which are apparent from the examples and the full scope of the claims.

Detailed Description

Example (b):

example 1:

synthesis of Block copolymer 1 based on OH-functionalized or amino-functionalized Block copolymer of polyolefin and polyester

225g were placed in a 2 l multi-neck flask with reflux condenser under a nitrogen flowHT (hydroxyl-terminated polybutadiene, available from Evonik Resource Efficiency GmbH) was blended with 525g of ε -caprolactone and 0.75g of titanium catalyst. Subsequently, the mixture was heated to 160 ℃ for 6 hours under a constant nitrogen flow while stirringThen (c) is performed. GPC analysis of the Block copolymer gave a PDI of 3.7 and the average molecular weight M_n6300 g/mol; melting Point T by DSC analysis_mIs 54.3 ℃ and has a glass transition temperature T_gIt was-74.0 ℃. The OH value of the polymer was 17mgKOH/g polymer.

Synthesis of Block copolymer 2

450g of this was placed in a 2 liter multi-neck flask with reflux condenser under a nitrogen streamHT was blended with 750g of epsilon-caprolactone, 300g of lactide and 1.50g of titanium catalyst. Subsequently, the mixture was heated to 160 ℃ for 6 hours under a constant nitrogen flow while stirring. GPC analysis of the Block copolymer gave an average molecular weight M of PDI of 3.0_n7500 g/mol; DSC analysis gave two glass transition temperatures: t is_g1Is-82.2 ℃ and T_g2Is-50.4 ℃. The OH value of the polymer was 17mgKOH/g polymer.

Synthesis of Block copolymer 3

In a 2 liter multi-necked flask with a reflux condenser, 750g were placed under a nitrogen streamHT was blended with 375g of epsilon-caprolactone, 375g of lactide and 1.50g of titanium catalyst. Subsequently, the mixture was heated to 160 ℃ for 6 hours under a constant nitrogen flow while stirring. GPC analysis of the Block copolymer gave a PDI of 2.4 and the average molecular weight M_n6600 g/mol; DSC analysis gave two glass transition temperatures: t is_g1Is-79.5 ℃ and T_g2It was-38.7 ℃. The OH value of the polymer was 26mgKOH/g polymer.

Synthesis of Block copolymer 4

In a 2 liter multi-necked flask with a reflux condenser, 750g were placed under a nitrogen streamHT was blended with 600g of epsilon-caprolactone, 150g of lactide and 1.50g of titanium catalyst. Subsequently, the mixture was heated to 160 ℃ for 6 hours under a constant nitrogen flow while stirringThen (c) is performed. GPC analysis of the Block copolymer gave a PDI of 2.4 and the average molecular weight M_n7000 g/mol; melting Point T by DSC analysis_mIs 19.8 ℃ and has a glass transition temperature T_gIt was-71.0 ℃. The OH value of the polymer was 27mgKOH/g polymer.

Synthesis of Block copolymer 5

750g of Nisso GI1000 (hydroxyl-terminated polybutadiene from Nippon Soda Co Ltd.) was blended with 600g of ε -caprolactone, 150g of lactide and 1.50g of titanium catalyst under a nitrogen flow in a 2 liter multi-neck flask with a reflux condenser. Subsequently, the mixture was heated to 160 ℃ for 6 hours under a constant nitrogen flow while stirring. GPC analysis of the Block copolymer gave an average molecular weight M of PDI of 1.8_n4000 g/mol; DSC analysis gave a melting point T_m24.6 ℃ and two glass transition temperatures: t is_g1Is-60.4 ℃ and T_g2It was-47.9 ℃. The OH value of the polymer was 34mgKOH/g polymer.

Synthesis of Block copolymer 6

600g were placed in a 2 l multi-necked flask with reflux condenser under a nitrogen streamHT was blended with 720g of epsilon-caprolactone, 180g of lactide and 1.50g of titanium catalyst. Subsequently, the mixture was heated to 160 ℃ for 6 hours under a constant nitrogen flow while stirring. GPC analysis of the Block copolymer gave a PDI of 2.6-average molecular weight M_nIs 7300 g/mol; melting Point T by DSC analysis_mIs 22.4 ℃ and has a glass transition temperature T_gIt was-68.8 ℃. The OH value of the polymer was 22mgKOH/g polymer.

The number average molecular weight of the block copolymers according to the invention was determined by gel permeation chromatography according to DIN 55672-1 using tetrahydrofuran as eluent and polystyrene for calibration.

The thermal properties of the block copolymers used in the context of the present invention were determined by Differential Scanning Calorimetry (DSC) according to DSC method DIN 53765. The value of the second heating interval is recorded. The heating rate was 10K/min.

The concentration of OH groups (OH number) was determined by titration in accordance with DIN 53240-2 in mg KOH/g of polymer.

Example 2: rigid PUR foam

The following foam formulations were used for performance comparison:

derived from HuntsmanR471, OH number 470mg KOH/g

From Evonik Industries AG8

Block copolymers as described in example 1 or from Evonik Industries AGB 8491

Polymeric MDI,200 mPas, 31.5% NCO, functionality 2.7

Comparative foaming was performed by hand mixing. For this purpose, polyol, catalyst, water, foam stabilizer and blowing agent were weighed into a beaker and mixed by means of a disk stirrer (diameter 6cm) for 30 seconds at 1000 rpm. The amount of blowing agent evaporated in the mixing operation is determined by re-weighing and added again. MDI is now added and the reaction mixture is stirred with the stirrer at 2500rpm for 7 seconds and immediately transferred to an open mould with dimensions 27.5x14x14cm (W x H x D).

After 10 minutes, the foam was demolded. After one day of foaming, the foam was analyzed. The cell structure was subjectively evaluated on a scale of 1 to 10, where 10 represents (idealized) a very fine foam without being critical and 1 represents a coarse foam with very pronounced defects.

The results are summarized in the following table:

surface active agent	Grade
		TEGOSTAB B 8491	7.0
Block copolymer 1	6.0
		Block copolymer 2	6.0
Block copolymer 3	7.0
		Block copolymer 4	7.0
Block copolymer 5	7.5

The results show that the use of block copolymers 3 to 5 makes it possible in particular to achieve the same level or slightly better cell structures and foam qualities than silicone-based cell stabilizers.

All other application-relevant foam properties are only insignificantly influenced by the block copolymers according to the invention, if at all.

Example 3: rigid PIR foams

The following foam formulations were used for performance comparison:

components	Weight ratio of
		Polyester polyols	100
Amine catalyst	0.6
		Catalyst for trimerization of potassium	4
Surfactant	2
		Water (W)	1
Cyclopentane	16
		MDI*****	199

From StepanPS 2352, OH number 250mg KOH/g

From Evonik Industries AG5

From Evonik Industries AG75

Block copolymers as described in example 1 or from Evonik Industries AGB 8491

Polymeric MDI,200 mPas, 31.5% NCO, functionality 2.7

Comparative foaming was performed by hand mixing. For this purpose, polyol, catalyst, water, foam stabilizer, flame retardant and blowing agent were weighed into a beaker and mixed by means of a disk stirrer (diameter 6cm) for 30 seconds at 1000 rpm. The amount of blowing agent evaporated in the mixing operation is determined by re-weighing and added again. MDI is now added and the reaction mixture is stirred with a stirrer at said 3000rpm for 5 seconds and immediately transferred to an open mould with dimensions 27.5x14x14cm (W x H x D).

After 10 minutes, the foam was demolded. After one day of foaming, the foam was analyzed. The cell structure was subjectively evaluated on a scale of 1 to 10, where 10 represents (idealized) a very fine foam without being critical and 1 represents a coarse foam with very pronounced defects.

The results are summarized in the following table:

surface active agent	Grade
		TEGOSTAB B 8491	7.5
Block copolymer 1	7.5
		Block copolymer 2	8.0
Block copolymer 3	6.5
		Block copolymer 4	7.0
Block copolymer 5	6.0

The results show that the use of block copolymers 1 to 2 makes it possible in particular to achieve the same level or slightly better cell structures and foam qualities than silicone-based cell stabilizers.

All other application-relevant foam properties are only insignificantly influenced by the block copolymers according to the invention, if at all.

Example 4: rigid PIR foams

The following foam formulations were used for performance comparison:

components	Weight ratio of
		Polyester polyols	100
Amine catalyst	0.6
		Catalyst for trimerization of potassium	4
Surfactant	4
		Water (W)	0.8
Cyclopentane/isopentane 70:30	16
		TCPP	15
MDI*****	230

From StepanPS 2352, OH number 250mg KOH/g

From Evonik Industries AG5

From Evonik Industries AG75

Block copolymers as described in example 1 or from Evonik Industries AGB8871

Polymeric MDI,200 mPas, 31.5% NCO, functionality 2.7

Comparative foaming was performed by hand mixing. For this purpose, polyol, catalyst, water, foam stabilizer, flame retardant and blowing agent were weighed into a beaker and mixed by means of a disk stirrer (diameter 6cm) for 30 seconds at 1000 rpm. The amount of blowing agent evaporated in the mixing operation is determined by re-weighing and added again. MDI was now added and the reaction mixture was stirred with the stirrer at 3000rpm for 5 seconds and immediately transferred to a 25cm x 50cm x 7cm aluminium mould lined with polyethylene film and thermostatted to 60 ℃.

After 10 minutes, the foam was demolded. After one day of foaming, the foam was analyzed. Surface and internal defects were subjectively evaluated on a scale of 1 to 10, where 10 represents (idealized) foam without criticality and 1 represents foam with very pronounced defects. The thermal conductivity (Lambda value, in mW/m.K) is measured according to the provisions of standard EN12667:2001 at an average temperature of 10 ℃ on 2.5 cm thick disks using an apparatus of the type HLC X206 from Hesto Lambda Control.

The results are summarized in the following table:

the results show that the same level or slightly better foam quality and thermal conductivity than silicone-based cell stabilizers can be achieved using these block copolymers.

All other application-relevant foam properties are only insignificantly influenced by the block copolymers according to the invention, if at all.

Example 5: rigid PIR foams

The following foam formulations were used for performance comparison:

components	Weight ratio of
		Polyester polyPolyhydric alcohol	100
Amine catalyst	0.4
		Catalyst for trimerization of potassium	5
Surfactant	2
		Water (W)	0.4
Cyclopentane/isopentane 70:30	21
		TCPP	10
MDI*****	202

From StepanPS 2412, OH number 240mg KOH/g

From Evonik Industries AG5

From Evonik Industries AG70LO

Block copolymers as described in example 1 or from EvoOf nik Industries AGB 8871

Polymeric MDI,200 mPas, 31.5% NCO, functionality 2.7

Comparative foaming was performed by hand mixing. For this purpose, polyol, catalyst, water, foam stabilizer, flame retardant and blowing agent were weighed into a beaker and mixed by means of a disk stirrer (diameter 6cm) for 30 seconds at 1000 rpm. The amount of blowing agent evaporated in the mixing operation is determined by re-weighing and added again. MDI was now added and the reaction mixture was stirred with the stirrer at 3000rpm for 5 seconds and immediately transferred to a 25cm x 50cm x 7cm aluminium mould lined with polyethylene film and thermostatted to 60 ℃.

After 10 minutes, the foam was demolded. After one day of foaming, the foam was analyzed. Surface and internal defects were subjectively evaluated on a scale of 1 to 10, where 10 represents (idealized) foam without criticality and 1 represents foam with very pronounced defects. The thermal conductivity (Lambda value, in mW/m.K) is measured according to the provisions of standard EN12667:2001 at an average temperature of 10 ℃ on a 2.5 cm thick disc using an apparatus of the type HLC X206 from Hesto Lambda Control.

The results are summarized in the following table:

the results show that the same level of foam quality and thermal conductivity can be achieved with these block copolymers compared to silicone-based cell stabilizers.

All other application-relevant foam properties are only insignificantly influenced by the block copolymers according to the invention, if at all.