阅读说明：本技术 包括含活性基团的聚氨酯催化剂的组合聚醚多元醇及其制备方法 (Combined polyether polyol containing polyurethane catalyst containing active group and preparation method thereof ) 是由 傅东海 于 2020-06-22 设计创作，主要内容包括：本申请涉及包括含活性基团聚氨酯催化剂的组合聚醚多元醇及其制备方法。本申请还涉及通过如上所述的组合聚醚多元醇和异氰酸酯反应形成的聚氨酯泡沫。本文所述的组合聚醚多元醇包括含活性基团聚氨酯催化剂以及含羧酸盐催化剂的聚醚多元醇,使得组合聚醚多元醇可长期稳定储存。在储存14天之后,根据标准《HG/T 4574-2014聚氨酯原料发泡反应特性的测定方法》测定的组合聚醚多元醇的起始时间和凝胶时间的变化在许可的误差范围之内。(The present application relates to a combination polyether polyol comprising a reactive group-containing polyurethane catalyst and a process for its preparation. The present application also relates to polyurethane foams formed by the reaction of a combination polyether polyol and an isocyanate as described above. The combination polyether polyols described herein include a polyether polyol containing an active group polyurethane catalyst as well as a carboxylate salt catalyst such that the combination polyether polyol is stable for long term storage. After 14 days of storage, the variation in the onset time and gel time of the combined polyether polyols, determined according to the standard "determination of the foaming reaction characteristics of the HG/T4574-2014 polyurethane raw materials", is within the permitted error range.)

1. A combination polyether polyol including a reactive group-containing polyurethane catalyst, comprising the following components:

a) a polyurethane catalyst containing an active group;

b) a foaming agent;

c) water;

d) a polyether polyol containing a carboxylate catalyst;

wherein the carboxylate salt catalyst-containing polyether polyol is synthesized by: reacting a polyol initiator with an epoxide in the presence of a basic catalyst, then neutralizing the basic catalyst by adding an excess of a dicarboxylic acid relative to the basic catalyst, and retaining the carboxylate formed by the reaction of the dicarboxylic acid and the basic catalyst in the polyether polyol to provide a carboxylate salt catalyst-containing polyether polyol.

2. The combination polyether polyol including a reactive group-containing polyurethane catalyst of claim 1, wherein the reactive group-containing polyurethane catalyst is N, N-dimethylethanolamine, N, N-dimethyl-1, 3-diaminopropylamine, diethanolamine, triethanolamine, 2,2 ' - [ (1-methylethyl) imino ] diethanol, 2- [2- (dimethylamino) ethoxy ] ethanol, 2,2 ' - (cyclohexylimino) diethanol, 1-hydroxyethyl-4-methylpiperazine, 1, 3-bis (dimethylamino) -2-propanol, 1,1' - [ [2- [ (2-hydroxypropyl) amino ] ethyl ] imino ] di-2-propanol, trimethylhydroxyethylpropanediamine, 2- [ [2- [2- (dimethylamino) ethoxyethyl ] methylamino ] -ethanol, N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine, 3,3' -iminobis (N, N-dimethylpropylamine), and 2-hydroxypropyltrimethyl ammonium formate.

3. The combination polyether polyol including a reactive group-containing polyurethane catalyst of claim 1, wherein said catalyst is a mixture of 2- [ [2- [2- (dimethylamino) ethoxyethyl ] methylamino ] -ethanol, 3' -iminobis (N, N-dimethylpropylamine) and 2-hydroxypropyl trimethyl ammonium formate.

4. The combination polyether polyol including a reactive group-containing polyurethane catalyst of claim 1 wherein the blowing agent is one or more of pentane, 1-chloro-3, 3, 3-trifluoropropene (HFO-1233ZD), and 1,1,1,4,4, 4-hexafluoro-2-butene (HFO 1336 mmz);

the dicarboxylic acid is one or more of malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and glutaric acid.

5. The combination polyether polyol including a reactive group-containing polyurethane catalyst according to claim 1, wherein the molar ratio of the dicarboxylic acid to the basic catalyst is 2-5:1 on a molar basis in preparing the carboxylate salt catalyst-containing polyether polyol.

6. The combination polyether polyol including a reactive group-containing polyurethane catalyst of claim 1, wherein the carboxylate salt catalyst-containing polyether polyol is a mixture of a first polyether polyol and a second polyether polyol;

wherein the first polyether polyol is prepared by: under the protection of inert gas and in the presence of an alkaline catalyst, allowing glycerol, sucrose and epoxide in a predetermined weight ratio to react at the temperature of 110-120 ℃ for a first predetermined period of time, and then adding excessive dicarboxylic acid to obtain a first polyether polyol;

wherein the second polyether polyol is prepared by: under the protection of inert gas and in the presence of a basic catalyst, pre-melted o-toluenediamine and epoxide in a predetermined weight ratio are reacted at a temperature of 110-120 ℃ for a second predetermined period of time, and then an excess of dicarboxylic acid is added to obtain a second polyether polyol.

7. The combination polyether polyol including a reactive group-containing polyurethane catalyst according to claim 1, further comprising one or more of a surfactant and a flame retardant.

8. The combination polyether polyol including a reactive group-containing polyurethane catalyst according to claim 1, comprising the following components in parts by weight:

9. a process for preparing a combination polyether polyol comprising a reactive group-containing polyurethane catalyst according to claim 1, the process comprising the steps of:

s1: preparation of said carboxylate salt catalyst-containing polyether polyol

Under the protection of inert gas and in the presence of a basic catalyst, enabling polyether polyol initiator and epoxide in a predetermined weight ratio to react at the temperature of 110-120 ℃ for a predetermined period of time, and then adding excessive dicarboxylic acid to obtain polyether polyol containing carboxylate catalyst;

s2: a predetermined weight ratio of the active group-containing polyurethane catalyst, the blowing agent, water and the carboxylate salt catalyst-containing polyether polyol obtained in step S1 is mixed.

10. A polyurethane foam made by reacting the combined polyether polyol including the reactive group-containing polyurethane catalyst of any one of claims 1-8 with an isocyanate.

Technical Field

The present application relates to the field of catalysts and polyurethane technology. In particular, the present application relates to combination polyether polyols comprising reactive group-containing polyurethane catalysts and methods for their preparation. The present application also relates to polyurethane foams formed by the reaction of a combination polyether polyol and an isocyanate as described above.

Background

Rigid polyurethane foams are prepared by reacting an isocyanate with a combination polyether polyol. In addition to the polyether polyol, the combination polyether polyol contains other ingredients such as water, flame retardants, blowing agents, foam stabilizing surfactants and catalysts. To promote the reaction of the isocyanate with the polyol to form urethane, with water to form carbon dioxide and ureido compounds, and with excess isocyanate to form isocyanurate (trimer). The blowing agent in the combined polyether polyol is typically a liquid or gas having a boiling point sufficiently low to be vaporized by the heat released during the polymerization reaction. Examples of blowing agents that may be used in the production of polyurethane foams include, but are not limited to, hydrofluorocarbons, hydrofluoroolefins, hydrofluorochloroolefins, hydrochlorofluorocarbons, formates, and hydrocarbons. The polyurethane foam is prepared by spraying or pouring the combined polyether polyol and isocyanate through special equipment and is generally applied to heat preservation industries such as refrigerators, freezers, hot water boilers, heat preservation plates, garages and the like. The combined polyether polyol should be stored for one day to one year before reacting with the isocyanate to form the polyurethane foam. This is common in spray foam applications where the drum-packed syntactic polyether polyols and isocyanates are shipped to the site for on-site application. Thus, it is desirable that the combined polyether polyols be both chemically and physically stable.

However, the catalysts useful for promoting the polyurethane reaction may also participate in or cause undesirable reactions with the blowing agent present in the combined polyether polyol, resulting in reduced storage stability of the combined polyether polyol. These undesirable reactions are prevalent in halogen-containing blowing agents and are particularly problematic in halogenated blowing agents containing unsaturated bonds and olefinic carbons. Common amine catalysts that can be used in the production of polyurethane foams include tertiary amines, such as N, N', N "-pentamethyldiethylenetriamine or N, N-dimethylcyclohexylamine or 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine. However, the tertiary amine reacts with the organic halogen-containing compound, thereby causing deactivation of the tertiary amine catalyst. The reaction between the tertiary amine and the halogen-containing organic compound occurs more rapidly when the halogen atom is bonded to the olefin carbon because the halogen-substituted olefin is susceptible to nucleophilic attack by the tertiary amine. This results in rapid deactivation of the tertiary amine catalyst, rendering the premix insufficiently reactive to react with isocyanate. The deactivation of the tertiary amine by reaction with the halogen-containing compound can also occur in the halogen-containing aliphatic compound by both the formation of quaternary ammonium salts or dehydrohalogenation, resulting in the deactivation of the tertiary amine. This results in a short storage period of the premix, thereby limiting the application field and development space of the premix.

Since 1991, the countries have added the Montreal protocol and the alternative act of depleting ozone layer substances (ODS). The polyurethane blowing agent also completed the replacement of the original monofluorotrichloromethane (CFC-11) by the currently marketed mainstream blowing agent 1-fluoro-1, 1-dichloroethane (HCFC-141b), and with the global labeling of the Bulgarian amendments, HFC-245fa (1,1,1,3, 3-pentafluoropropane) and HFC-365mfc (1,1,1,3, 3-pentafluorobutane) will also enter the phase-out process from 2032 years. The most recent mainstream alternative for blowing agents is the use of pentane in combination with 1-chloro-3, 3, 3-trifluoropropene (HFO-1233ZD), 1,1,1,4,4, 4-hexafluoro-2-butene (HFO 1336mmz) (2-2.5: 1). The catalyst used in combination with the catalyst is still conventional N, N, N' -pentamethyldiethylenetriamine, N, N-dimethylcyclohexylamine, 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine, N, N-dimethylethanolamine, N, N-dimethylbenzylamine, etc. or a combination thereof. The simultaneous presence of the blowing agent and the tertiary amine catalyst in the combined polyether polyol causes the defect that the storage stability of the combined polyether polyol cannot be stored for a long time, so that the combined polyether polyol cannot be popularized and used in a large range.

For this reason, there is a continuing need in the art to develop a combination polyether polyol that is stable for long term storage.

Disclosure of Invention

It is an object of the present application to provide a combination polyether polyol comprising a polyurethane catalyst containing reactive groups which can be stored stably for a long period of time.

It is also an object of the present application to provide a process for the preparation of a combination polyether polyol as described above comprising a polyurethane catalyst comprising reactive groups.

It is also an object of the present application to provide a polyurethane foam formed by reacting a combination polyether polyol as described above including a reactive group-containing polyurethane catalyst with an isocyanate.

In order to solve the above technical problems, the present application provides the following technical solutions.

In a first aspect, the present application provides a combination polyether polyol comprising a reactive group-containing polyurethane catalyst, characterized by comprising the following components:

a) a polyurethane catalyst containing an active group;

b) a foaming agent;

c) water;

d) a polyether polyol containing a carboxylate catalyst;

wherein the carboxylate salt catalyst-containing polyether polyol is synthesized by: reacting a polyol initiator with an epoxide in the presence of a basic catalyst, then neutralizing the basic catalyst by adding an excess of a dicarboxylic acid relative to the basic catalyst, and retaining the carboxylate formed by the reaction of the dicarboxylic acid and the basic catalyst in the polyether polyol to provide a carboxylate salt catalyst-containing polyether polyol.

In one embodiment of the first aspect, the reactive group-containing polyurethane catalyst is N, N-dimethylethanolamine, N, N-dimethyl-1, 3-diaminopropylamine, diethanolamine, triethanolamine, 2,2 ' - [ (1-methylethyl) imino ] diethanol, 2- [2- (dimethylamino) ethoxy ] ethanol, 2,2 ' - (cyclohexylimino) diethanol, 1-hydroxyethyl-4-methylpiperazine, 1, 3-bis (dimethylamino) -2-propanol, 1,1' - [ [2- [ (2-hydroxypropyl) amino ] ethyl ] imino ] di-2-propanol, trimethylhydroxyethylpropylenediamine, 2- [ [2- [2- (dimethylamino) ethoxyethyl ] methylamino ] -ethanol, one or more of N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine, 3,3' -iminobis (N, N-dimethylpropylamine), and 2-hydroxypropyl trimethyl ammonium formate.

In one embodiment of the first aspect, the catalyst is a mixture of 2- [ [2- [2- (dimethylamino) ethoxyethyl ] methylamino ] -ethanol, 3' -iminobis (N, N-dimethylpropylamine) and 2-hydroxypropyltrimethyl ammonium formate.

In one embodiment of the first aspect, the blowing agent is one or more of pentane, 1-chloro-3, 3, 3-trifluoropropene (HFO-1233ZD), and 1,1,1,4,4, 4-hexafluoro-2-butene (HFO 1336 mmz).

In one embodiment of the first aspect, the dicarboxylic acid is one or more of malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and glutaric acid.

In one embodiment of the first aspect, the molar ratio of the dicarboxylic acid to the basic catalyst is from 2 to 5:1, on a molar basis, in preparing the carboxylate salt catalyst-containing polyether polyol.

In one embodiment of the first aspect, the carboxylate salt catalyst-containing polyether polyol is a mixture of a first polyether polyol and a second polyether polyol;

wherein the first polyether polyol is prepared by: under the protection of inert gas and in the presence of an alkaline catalyst, allowing glycerol, sucrose and epoxide in a predetermined weight ratio to react at the temperature of 110-120 ℃ for a first predetermined period of time, and then adding excessive dicarboxylic acid to obtain a first polyether polyol;

wherein the second polyether polyol is prepared by: under the protection of inert gas and in the presence of a basic catalyst, pre-melted o-toluenediamine and epoxide in a predetermined weight ratio are reacted at a temperature of 110-120 ℃ for a second predetermined period of time, and then an excess of dicarboxylic acid is added to obtain a second polyether polyol.

In one embodiment of the first aspect, the combination polyether polyol comprising a reactive group-containing polyurethane catalyst further comprises one or more of a surfactant and a flame retardant.

In one embodiment of the first aspect, the combined polyether polyol comprising the reactive group-containing polyurethane catalyst comprises the following components, based on parts by weight:

in a second aspect, the present application provides a process for preparing a combination polyether polyol comprising a reactive group-containing polyurethane catalyst as described in the first aspect, said process comprising the steps of:

s1: preparation of said carboxylate salt catalyst-containing polyether polyol

Under the protection of inert gas and in the presence of a basic catalyst, enabling polyether polyol initiator and epoxide in a predetermined weight ratio to react at the temperature of 110-120 ℃ for a predetermined period of time, and then adding excessive dicarboxylic acid to obtain polyether polyol containing carboxylate catalyst;

s2: a predetermined weight ratio of the active group-containing polyurethane catalyst, the blowing agent, water and the carboxylate salt catalyst-containing polyether polyol obtained in step S1 is mixed.

In a third aspect, the present application provides a polyurethane foam made by reacting a combination polyether polyol comprising a reactive group-containing polyurethane catalyst as described in the first aspect with an isocyanate.

Compared with the prior art, the method has the advantages that the storage stability problem of the halogen-containing foaming agent combined polyether polyol is solved by the organic combination of the amine polyurethane catalyst and the special polyether polyol refining method, and the combined polyether polyol prepared by the method can be stably stored for a long time.

Detailed Description

Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.

The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical, or other property (e.g., molecular weight, melt index, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. These are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. It should also be noted that the terms "first," "second," and the like herein do not define a sequential order, but merely distinguish between different structures.

When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.

The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.

As described above, the presence of conventional amine-based polyurethane catalysts with halogen blowing agents results in a decrease in the storage stability of the combined polyether polyols. It is an object of the present application to provide a combination polyether polyol which is storage stable for extended periods of time by the simultaneous use of a polyurethane catalyst containing reactive groups and a polyether ether polyol containing a carboxylate catalyst.

In one embodiment, the present application provides a combination polyether polyol comprising a reactive group-containing polyurethane catalyst, characterized by comprising the following components:

a) a polyurethane catalyst containing an active group;

b) a foaming agent;

c) water;

d) a polyether polyol containing a carboxylate catalyst;

wherein the carboxylate salt catalyst-containing polyether polyol is synthesized by: reacting a polyol initiator with an epoxide in the presence of a basic catalyst, then neutralizing the basic catalyst by adding an excess of a dicarboxylic acid relative to the basic catalyst, and retaining the carboxylate formed by the reaction of the dicarboxylic acid and the basic catalyst in the polyether polyol to provide a carboxylate salt catalyst-containing polyether polyol.

The traditional polyether polyol reacts with epoxide under the action of potassium hydroxide as a catalyst, and then is subjected to a refining treatment process of phosphoric acid neutralization, evaporation, crystallization and filter pressing, wherein the refining treatment process comprises the following steps: sucrose and glycerol initiated 835 polyether polyols, o-tolylenediamine initiated 400 polyether polyols for rigid polyurethane foams, and the like.

The invention improves the refining treatment method of polyether polyol, adopts dicarboxylic acid as a neutralizer of a neutralization catalyst, and does not need crystallization and filter pressing after neutralization. The product of the reaction of the dicarboxylic acid with the catalyst is retained in the polyether polyol and used as a carboxylate catalyst. The method not only shortens the production process of the polyether polyol, improves the production efficiency, but also saves the cost. Also, the remaining dicarboxylic acid salts will be effective ingredients in the present invention to address the storage stability of the combined polyether polyols.

The dicarboxylic acid may be malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glutaric acid, and the like. In one embodiment, the molar ratio of the dicarboxylic acid to the basic catalyst is 2-5:1 on a molar basis in preparing the carboxylate salt catalyst-containing polyether polyol.

The traditional catalyst adopts N, N, N' -pentamethyl diethylene triamine or N, N-dimethyl cyclohexylamine or 1,3, 5-tri (dimethylamino propyl) hexahydro triazine. A common feature of such catalysts is the absence of active hydrogen and other functional groups. The catalyst scheme adopted by the invention is that the catalyst at least contains one or more than one active group-containing catalyst, such as an active hydrogen-containing or hydroxyl-containing catalyst. Such catalysts may be selected from: n, N-dimethylethanolamine, N, N-dimethyl-1, 3-diaminopropylamine, diethanolamine, triethanolamine, 2,2 ' - [ (1-methylethyl) imino ] diethanol, 2- [2- (dimethylamino) ethoxy ] ethanol, 2,2 ' - (cyclohexylimino) diethanol, 1-hydroxyethyl-4-methylpiperazine, 1, 3-bis (dimethylamino) -2-propanol, 1,1' - [ [2- [ (2-hydroxypropyl) amino ] ethyl ] imino ] bis-2-propanol, trimethylhydroxyethylpropylenediamine, 2- [ [2- [2- (dimethylamino) ethoxyethyl ] methylamino ] -ethanol, N-methyl-N- (N, n-dimethylaminoethyl) ethanolamine, 3,3' -iminobis (N, N-dimethylpropylamine), 2-hydroxypropyl trimethyl ammonium formate and the like, or a combination of two or more thereof.

In one embodiment, the composition comprises the following components in parts by weight: a) 3-5 parts by weight of polyurethane catalyst containing active groups; b) 15-30 parts of foaming agent; c) 0.5-2.5 parts by weight of water; d) 100 parts by weight of a polyether polyol containing a carboxylate catalyst.

In a preferred embodiment, the combined polyether polyol including the reactive group-containing polyurethane catalyst may include 3, 3.5, 4.0, 4.5, 5.0, or ranges and subranges between any two of these values of a) the reactive group-containing polyurethane catalyst in the case of 100 parts by weight of d) the carboxylate salt catalyst-containing polyether polyol.

In a preferred embodiment, the combined polyether polyol including the reactive group-containing polyurethane catalyst may include 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, or ranges and subranges between any two of them b) blowing agent in the case that 100 parts by weight of d) carboxylate catalyst-containing polyether polyol is included, based on parts by weight.

In a preferred embodiment, the combined polyether polyol including the active group-containing polyurethane catalyst may include c) water in an amount of 0.5, 1.0, 1.5, 2.0, 2.5, or ranges and subranges between any two of these values, in the case that 100 parts by weight of d) the carboxylate salt catalyst-containing polyether polyol is included, based on parts by weight.

The reagents and starting materials used in the present invention are commercially available.

The percentage in the invention is the mass percentage of each component in the total amount of the raw materials.