CN109422909B

CN109422909B - Ortho-and carbonate-alkanolamine-based blowing agents and use for producing polyurethane spray foam materials

Info

Publication number: CN109422909B
Application number: CN201710736192.6A
Authority: CN
Inventors: 毕玉遂; 毕戈华
Original assignee: Butian New Material Technology Co ltd; Shandong University of Technology
Current assignee: Butian New Material Technology Co ltd; Shandong University of Technology
Priority date: 2017-08-24
Filing date: 2017-08-24
Publication date: 2021-04-09
Anticipated expiration: 2037-08-24
Also published as: CN109422909A

Abstract

Disclosed is an alkaline polyurethane blowing agent comprising a salt of orthomethanolic amine and a salt of propanolamine carbonate, the alkaline blowing agent having a pH of between 8.5 and 9.5, the blowing agent comprising: 1) a first mixture of compounds (M1) comprising a carbinolamine orthoformate compound having the following general formula (I): a. the^‑B⁺(I) Wherein B is⁺Is a cation of an organic alcohol amine B, A^‑Is orthoformate; 2) a second compound mixture (M2) comprising an N-monohydroxypropyl-ammonium carbonate compound having the general formula (II) and an N, N' -di (hydroxypropyl) -ammonium carbonate compound having the general formula (II): (RN)⁺H₃)(N⁺H₄)CO₃ ^2‑(II), or (RN)⁺H₃)₂CO₃ ^2‑(III) in the formula, R is hydroxypropyl; the molar ratio of the compound of formula (II) to the compound of formula (III) is from 1:0 to 1: 1.0. The blowing agent is suitable for use in preparing polyurethane spray foam materials.

Description

Ortho-and carbonate-alkanolamine-based blowing agents and use for producing polyurethane spray foam materials

Technical Field

The invention relates to a catalyst having the formula of CO₂Use of organic amine salt compounds of donor anions as blowing agents, more specifically to provide compounds having not only CO as blowing agent₂The application of novel organic ammonium salt compounds which are donor anions and have carbinolamine orthoformate as catalytic groups and solubilizing groups in the preparation of polyurethane spray foam materials. More particularly, to an alkaline blowing agent of orthomethanolamine/carbonatamine and its use for preparing polyurethane spray foam materialsIts application is disclosed.

Technical Field

The polyurethane hard foam is a new polymer material, has light weight, high strength and extremely low thermal conductivity, is a high-quality heat insulation material, and is widely applied to the industries of refrigeration and heat preservation, particularly chemical weapon refrigeration and heat preservation, building energy conservation, solar energy, automobiles, refrigerators, freezers and other household appliances. The most important raw material in the production of polyurethane rigid foam is foaming agent. At present, the foaming agents are all chlorofluorocarbon substances except cyclopentane, and the governments of various countries have already signed an international convention of 'Montreal' agreement due to the damage of the foaming agents to the atmospheric ozone layer, so that the production and the use of the products are limited, eliminated and prohibited, and China is also a contracted country of the agreement.

Currently, HCFC-141b (monofluoroethane) and cyclopentane, which are the second generation chlorofluorocarbon foaming agents, are still used in China, developed countries such as Europe and America forbid the use of HCFC-141b, the China government freezes the consumption of HCFC-141b on the consumption level of 2009 and 2010 in 2013, eliminates the consumption of 20% in 2015 and promises to completely forbid production and use until 2025, the developed countries such as Europe and America currently use the pentafluoropropane (HFC-245fa) and pentafluorobutane (HFC-365mfc) which are the third generation foaming agents, the GWP (potential value for greenhouse effect) of the second generation foaming agent and the third generation foaming agent is high, and the damage to the atmospheric ozone layer is serious, so that the Europe and America forbid the use of the third generation foaming agent before 2017. Therefore, the fourth generation physical foaming agent, namely the chlorotrifluoropropene (LBA) is developed by the company Honeyville in the United states, but the product is expensive, ODP (potential value for damaging the ozone layer) is zero, and the product is relatively environment-friendly and expensive compared with the third generation. In conclusion, the physical foaming agents except cyclopentane relate to chlorine fluorine elements in the production process and the environmental protection problem is still difficult to completely solve and is eliminated.

The prior art discloses the direct CO condensation₂As polyurethane blowing agents, however, in view of CO₂The escape of gas and its poor solubility in the raw materials MDI and polyester polyols and/or polyether polyols make CO undesirable₂The gas is not uniformly dispersed in the foaming composition and the foaming processIt is not easy to control.

In addition, the prior art discloses the direct use of small amounts of water as polyurethane blowing agent, but, in view of the hydrogen bonding of water molecules and the poor solubility of water in polyester polyols and/or polyether polyols, water molecules are present in the form of droplets in the foaming composition (e.g. polyether polyol component) causing local over-reactions and foaming in the foamed material. If water is used as a blowing agent, there are more urea linkages in the polyurethane foam, greatly affecting the strength and thermal insulation properties of the foam. Furthermore, if the amount of water used as a blowing agent is increased slightly, the properties and dimensional stability of the polyurethane foam are significantly affected. If water is used as the sole blowing agent, polyurethane foams suffer from shrinkage, scorch, and poor thermal insulation properties (shrinkage, curing).

In summary, the blowing agents of the prior art cannot be dispersed into the foaming composition at a molecular level, resulting in uneven cell distribution and uneven cell size, ultimately affecting the strength properties and thermal insulation properties of the foamed material.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention aims to provide a polyurethane foaming agent and a preparation method thereof, wherein the polyurethane foaming agent does not contain chlorofluorocarbon and does not damage the atmospheric ozone layer.

It is an object of the present invention to provide a catalyst which has not only the function as CO₂Novel organic ammonium salts of anions of donors having carbinolaminyl orthoformate groups as solubilising groups and their use in foam materials such as polyurethane spray foam materials.

The novel organic ammonium salt compounds are suitable as blowing agents. It generates CO during foaming₂A gas. The inventors of the present application have surprisingly found that as CO₂The anion of the donor having the valence of-n readily decomposes at elevated temperature to produce CO₂The gas, even when expanded at relatively low temperatures, is described below as CO₂The donor anion having the valence-n can be activated by the NCO groups contained in isocyanate monomers such as MDI and TDI, quicklyQuick release of CO₂A gas. In addition, due to the solubilizing group, the foaming agent can be fully dissolved in foaming raw materials (such as polyether polyol or polyester polyol) or has good intersolubility with the foaming raw materials, the foaming agent can be uniformly dispersed in the foaming composition so as to be foamed uniformly, the distribution of cells in the polyurethane foam is uniform, and the sizes of the cells are uniform. In addition, the first compound mixture (M1) according to the invention contains an alcohol amine orthoformate, and the first compound mixture (M1) which is a blowing agent decomposes to release CO₂The decomposition products produced thereafter are alcohol amine compounds which are suitable for use as polyurethane catalysts in materials. Accordingly, the present invention has been accomplished based on the above two aspects.

In the present application, "as CO₂The anion of the donor "means that it can decompose under heating or during foaming to release CO₂The anion of (4).

According to a first embodiment of the present invention, there is provided an alkaline alkanolamine blowing agent comprising a alkanolamine orthoformate salt and a alkanolamine carbonate salt, the alkaline blowing agent having a pH of between 8.5 and 9.5. Because of the alkalinity and the high foaming activity, the polyurethane spray coating foaming agent is suitable for quick foaming, so that the polyurethane spray coating foaming agent is suitable for preparing a polyurethane spray coating foam material while spraying and foaming. The foaming agent comprises:

1) a first mixture of compounds (M1) comprising a family of orthomethanolic alkanolamine compounds having the following general formula (I):

A^-B⁺ (I)

wherein A is^-Is orthoformate radical

B⁺Is a cation of an organic alcohol amine B;

2) a second compound mixture (M2) comprising an N-monohydroxypropyl-ammonium carbonate compound having the general formula (II) and an N, N' -di (hydroxypropyl) -ammonium carbonate compound having the general formula (III), i.e. an alkanolamine salt compound mixture,

(RN⁺H₃)(N⁺H₄)CO₃ ^2-(II), or (RN)⁺H₃)₂CO₃ ^2- (III)，

Wherein R is hydroxypropyl, i.e.: HO-CH₂-CH₂(CH₃) -or HO-CH₂(CH₃)-CH₂-；

The molar ratio of the compound of formula (II) to the compound of formula (III) is from 1:0 to 1:1. Preferably 1:0 to 1:0.5, more preferably 1:0.1 to 1: 0.3.

Preferably, the first mixture of compounds (M1) is obtained by hydrolysis (and salification) of an orthoformate in the presence of an alcohol amine B and water; preferably, the amount of water in the reaction mixture is sufficient to allow complete hydrolysis of the orthoformate.

Preferably, the orthoformate compound is selected from one or more of the following compounds: tri (C1-C8) hydrocarbyl orthoformates, preferably tri (C1-C7) hydrocarbyl orthoformates; preferably, the orthoformate is selected from one or more of the following: trimethyl orthoformate, triethyl orthoformate, methyl diethyl orthoformate, tripropyl orthoformate, methyl dipropyl orthoformate, tributyl orthoformate, tripentyl orthoformate, trihexyl orthoformate, triphenyl orthoformate, tribenzyl orthoformate, acetyl diethyl orthoformate, acetyl ethyl methyl orthoformate, tri (ethylene glycol) orthoformate, tri (diethylene glycol) orthoformate, tri (triethylene glycol) orthoformate, tri (tetraethylene glycol) orthoformate, tri (polyethylene glycol (degree of polymerization: 5-10)) orthoformate, tri (propylene glycol) orthoformate, tri (dipropylene glycol) orthoformate, tri (tripropylene glycol) orthoformate, tri (tetrapropylene glycol) orthoformate, tri (polypropylene glycol (degree of polymerization: 5-10)) orthoformate.

More preferably, the orthoformate compound is one or more selected from the group consisting of: formic acid tri (C)₁-C₆Alkyl) esters. More preferably, it is selected from one or more of trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, tripentyl orthoformate or trihexyl orthoformate.

Generally, the second compound mixture (M2) was prepared by the following method: to a slurry (i.e., not completely dissolved) or saturated solution formed from ammonium carbonate and/or ammonium carbamate and water, propylene oxide is added to allow the reaction mixture to react, with or without the addition of aqueous ammonia, according to a molar ratio of ammonium carbonate and/or ammonium carbamate to propylene oxide of 1:1 to 5.5 (preferably 1:1.3 to 5) [ then, optionally, a portion of the water and unreacted propylene oxide is removed from the reaction mixture formed ] to obtain an aqueous mixture of organic alcohol amines (typically, its pH is 7.5 to 10, preferably pH 8 to 9.7, preferably pH 8.3 to 9.6, preferably pH 8.2 to 9.6, more preferably pH 8.5 to 9.5, e.g., pH 9), i.e., a second mixture of compounds (M2).

In this application, "optionally" means with or without.

Preferably, the weight ratio of the first mixture of compounds (M1) to the second mixture of compounds (M2) is from 0.3 to 1:1, more preferably from 0.5 to 0.8:1, more preferably from 0.6 to 0.7: 1.

Preferably, in the compound of the formula (I) or in the first mixture of compounds (M1), 50 to 100% of the amine groups in the carbinolamine orthoformate B are replaced by the anion A^-Preferably, 65 to 100% of the amine groups in the organic amine compound B are neutralized with the anion A^-Neutralizing; more preferably, 75 to 100% of the amine groups in the organic amine compound B are substituted with the anion A^-Neutralizing; more preferably, 75 to 90% of the amine groups in the organic amine compound B are substituted with the anion A^-And (4) neutralizing.

The water content of each of the first mixture of compounds (M1) or the second mixture of compounds (M2) (each) is independently from 2 to 40% by weight, preferably from 5 to 35% by weight, more preferably from 10 to 30% by weight, more preferably from 15 to 25% by weight.

Preferably, the pH of the first mixture of compounds (M1) is in the range of 7.0 to 8.8, preferably in the range of 7.3 to 8.6, more preferably in the range of 7.5 to 8.5.

Preferably, the pH of the second compound mixture (M2) is 8.6 to 10, preferably 8.7 to 9.5, more preferably 8.8 to 9.3.

Preferably, the organic alcohol amine B is selected from one or more of the following: c₂-C₁₂Alcamines; preferably, the first and second liquid crystal materials are,the organic alcohol amine B is one or more selected from monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutanolamine, dibutanolamine, or tributanolamine.

Preferably, in the above-mentioned second compound mixture (M2) (i.e. the aqueous organic alcohol amine mixture), the sum of the weight of both the compound of formula (II) and the compound of formula (III) represents 56 to 96wt%, more preferably 63 to 90 wt%, even more preferably 70 to 86 wt% of the total weight of the second compound mixture (M2).

Preferably, the water content of the second compound mixture (M2) is 2 to 40 wt.%, preferably 6 to 35 wt.%, more preferably 10 to 30 wt.%, more preferably 15 to 25 wt.%.

Generally, in the above-mentioned process for preparing the second compound mixture (M2), aqueous ammonia (e.g., in a concentration of 20 to 28% by weight, e.g., 25% by weight) is used as the catalyst. The amount of the aqueous ammonia to be used is 0.5 to 7% by weight, preferably 0.8 to 5% by weight, preferably 1.0 to 3% by weight, based on the total weight of the reaction mixture (or the total weight of all the raw materials).

According to a third aspect of the present invention, there is provided a composition for polyurethane foaming, that is, a polyurethane foaming composition.

The composition comprises: 0.5 to 100 wt.% (more preferably 2 to 80 wt.%, more preferably 4 to 60 wt.%, more preferably 6 to 40 wt.%, such as 8 wt.%, 10 wt.%, 15 wt.% or 20 wt.%) of the blowing agent described above; 0-50 wt% of a physical blowing agent; 0 to 5wt% of water, and 0.0 to 99.5 wt% (preferably 20.0 to 98.0 wt%, more preferably 40 to 96wt%, more preferably 60 to 94wt%, more preferably 70 to 88wt%, more preferably 75 to 85 wt%) of a polymer polyol; wherein the weight percentages are based on the total weight of the polyurethane foaming composition.

Preferably, the polymer polyol is selected from: polyether polyols, polyester polyols, polyether-polyester polyols, polycarbonate diols, polycarbonate-polyester polyols, polycarbonate-polyether polyols, polybutadiene polyols or polysiloxane polyols, and the average functionality of the polymer polyols is generally from 2 to 16, preferably from 2.5 to 10, more preferably from 3 to 8.

Preferably, the physical blowing agent is at least one selected from the group consisting of: n-pentane, isopentane, cyclopentane, other alkanes boiling in the range of 0-100 ℃, HCFC-141b, HFC-245fa, HFC-365mfc, LBA, FEA-1100, other chlorofluorocarbons or organic esters boiling in the range of 0-100 ℃.

According to a fourth aspect of the present invention there is provided the use of the above-described basic blowing agent for (preparing) a polyurethane spray foam material.

The inventors of the present application have surprisingly found that the compounds of formula (II) above and the compounds of formula (III) have suitable decomposition temperatures (typically in the range 55-70 c, preferably in the range 58-65 c) and readily decompose at elevated temperatures to produce CO2 gas, which can be activated by NCO groups contained in isocyanate monomers such as MDI and TDI to release CO2 gas rapidly, even when foaming is carried out at lower temperatures. In addition, the N-hydroxypropyl group as a solubilizing group is sufficiently miscible with foaming raw materials (such as polyether polyol or polyester polyol) and can be uniformly dispersed in the foaming composition for uniform foaming, so that the prepared polyurethane foam has very uniform cell distribution and cell size.

In addition, the compounds of the general formula (II) according to the invention contain both hydroxyl and amine groups together with the compounds of the general formula (III), i.e.they are organic alcohol amine carbonates. Release CO in decomposition₂The resulting decomposition product (i.e., the alcohol amine compound) still contains hydroxyl and amino groups and can serve as a chain extender or cross-linker in the foaming reaction. That is, the compound of the general formula (I), the compound of the general formula (II) and the compound of the general formula (III) of the present invention have both "foaming action" and "chain extending" or "crosslinking" action, resulting in a polyurethane foam having good dimensional stability, particularly long-term dimensional stability, without occurrence of deformation or collapse recognizable to the naked eye when left for 1 year under indoor environmental conditions.

The second compound mixture (M2) of the present invention, an aqueous organic alcohol amine mixture containing an N-hydroxypropylated ammonium carbonate salt compound, liberates a large amount of carbon dioxide by heating to 70 c, and then the remaining alcohol amine compound is subjected to gas chromatography analysis, and the molar ratio of N-monohydroxypropyl-ammonium carbonate to N, N' -bis (hydroxypropyl) -ammonium carbonate compound in the reaction product (i.e., mixture M2) is in the range of 1:0 to 1:2.5, preferably 1:0.3 to 1:2, preferably 1:0.5 to 1:1.

The compounds of the general formula (I) mentioned above are those having the formula as CO₂Organic amine salts of donor anions.

Preferably, the polyurethane foaming composition further comprises: foam stabilizers, catalysts, and the like. These auxiliaries are customary in the field of polyurethane spray foam materials or polyurethane refrigerator cabinets and are used in the customary amounts.

Preferably, the physical blowing agent is at least one selected from the group consisting of: n-pentane, isopentane, cyclopentane, other alkanes with boiling points in the range of 0-100 ℃, HCFC-141b, HFC-245fa, HFC-365mfc, LBA, FEA-1100, other chlorofluorocarbons with boiling points in the range of 0-100 ℃, organic esters and the like.

The inventors of the present application have unexpectedly found that the compatibility or miscibility between the compounds of the above general formula (I), general formula (II) and general formula (III) with the polyester polyol and/or polyether polyol for foaming is very good, resulting in a clear homogeneous system. The homogeneous foaming system can ensure the formation of uniform-sized cells in the polyurethane foam. The first mixture (M1) has a catalytic action and also a foaming action.

It has surprisingly been found that the difference in the decomposition temperatures of the compounds of the general formula (I) above, and of the compounds of the general formula (II) and of the general formula (III), facilitates the foaming process to proceed in a smooth, continuous manner.

In general, the rigid polyurethane foaming compositions of the present invention are transparent or clear or opaque but homogeneous. This indicates that the blowing agent of the present invention is dissolved or uniformly dispersed in the polyether polyol or polyester polyol. Especially, when polyether polyol is used as a main resin component for foaming, the miscibility of the blowing agent of the present invention with polyether polyol is very good, and the blowing agent can be dispersed in polyether polyol at a molecular level, as compared with polyester polyol.

According to the inventionPolyurethane foaming compositions (commonly known as "white stocks") have the following characteristics: 1. containing amine salt compounds (e.g. compounds of formula (I) release CO after thermal decomposition₂While leaving behind the alkanolamine); 2. transparent or clear or milky white; 3. CO evolution under heating (e.g. temperatures of 40-80 ℃) or with addition of acids (mineral or organic acids)₂The peak decomposition temperature is generally between 45 and 65 ℃; 4. when the foaming composition (i.e., the "white material") is contacted or mixed with an isocyanate or polyisocyanate (e.g., MDI or TDI), the mixed material instantaneously (e.g., 0.2 to 4 seconds, such as 1 to 2 seconds) turns milky white. In the present invention, the material quickly turns milky white with a rapid expansion of volume, but this process is not a true rise of foam, after which the material begins to rise. In contrast, with water, or water and a physical blowing agent as the blowing agent, foam creaming and rise occur simultaneously and with a delay.

Although in the present invention the foaming composition ("white mass") may contain small amounts of water as CO-blowing agent, the compounds of the general formulae (I), (II) and (III) of the present invention, however, decompose preferentially to release CO₂I.e., preferential foaming, so that the addition of a small amount of water does not affect the foaming process or the properties of the finished polyurethane foam; that is to say in some cases in a mixture with water.

The present invention provides a process for preparing a polyurethane spray foam material which comprises incorporating into the polyurethane preparation from 1 to 10%, preferably from 2 to 5% of the above-described orthocarbinol alkanolamine salt compound or mixture of orthocarbinol alkanolamine salt compounds, based on the total weight of the polyurethane starting materials (including isocyanate and polyol).

The invention also provides the use of the above carbinolamine orthoformate compound or mixture of carbinolamine orthoformate compounds for (preparing) foamed materials such as polyurethane spray foam materials.

Advantageous effects or advantages of the invention

1. The compounds of the formula (I), (II) or (III) according to the invention or the blowing agents according to the invention have a suitable decomposition temperature (50-70 ℃) or a suitable decomposition temperature when they come into contact with isocyanates, on the one hand are stable to storage at room temperature and on the other hand are capable of releasing carbon dioxide gas at a reasonable rate when the blowing reaction system is heated during the polyurethane foaming process, so that the foamed material has the desired properties, such as cell distribution density, cell size uniformity. The alkalinity is beneficial to improving the foaming activity and quickly foaming, so the polyurethane spray coating foaming agent is suitable for polyurethane spray coating foaming. The difference in the decomposition temperatures of the foams between the compounds of formula (I) and the compounds of formula (II) and (III) is advantageous in that the foaming process is carried out in a relatively smooth and continuous manner.

2. The compounds of the general formula (II) or (III) according to the invention have solubilizing groups, i.e. alcohol amine groups, which are capable of being dissolved or distributed uniformly at the molecular level in polymer polyols such as polyether polyols and/or polyester polyols, ensuring uniformity of foaming and avoiding local excessive foaming.

3. The compounds of the general formula (II) or (III) decompose to release CO₂Then generating decomposition product alcohol amine compound, wherein the alcohol amine compound is suitable to be used as chain extender and/or cross-linking agent, the general formula (II) and (III) compound of the invention are used as 'foaming point' and 'chain extending point' and/or 'cross-linking point', the mechanical strength and mechanical strength of cells are obviously enhanced, the obtained polyurethane foam has good dimensional stability, and the shrinkage phenomenon is hardly observed by naked eyes after the polyurethane foam is placed for several months or even 1 year, and no foam collapse or foam collapse phenomenon is generated. Particularly good dimensional stability after prolonged periods of time, e.g. 10 days, at higher temperatures, e.g. 40-70 c.

4. The compounds of the general formula (I) according to the invention decompose to release CO₂The decomposition products which are then produced, namely the alcohol amine compounds, are suitable as catalysts.

5. The compound of the general formula (I) is not easy to volatilize, does not contain metal ions (the metal ions are corrosive to metal substrates), and completely or mostly replaces a chlorofluorocarbon foaming agent, so that the compound has important significance for environmental protection, and the foaming effect is obviously better than that of other foaming agents used in the prior art.

6. When used as a blowing agent in admixture with a chlorofluorocarbon such as HCFC-141b, or HFC-365mfc, the thermal insulation properties of the foam can be significantly improved as compared to the use of a chlorofluorocarbon blowing agent alone. While it is common practice to select specific polyether polyols having good miscibility or miscibility with the blowing agent concerned around the blowing agent or specific chlorofluorocarbon blowing agent, the use of the blowing agent of the present invention eliminates the need to select specific polyether polyols or polyester polyols and has a wide range of utility, and various types of polyester polyols and/or polyether polyols can be used in the foaming composition. On the other hand, better properties are obtained if auxiliaries such as polyethers which are suitable for the polyurethane blowing agents prepared according to the invention are selected.

7. Compared with the prior art, the polyurethane foaming agent provided by the invention does not contain chlorine fluorine elements, has ODP (potential value for damaging the ozone layer) of 0 and GWP (potential value for greenhouse effect) of 1, is the most environment-friendly polyurethane foaming agent, has relatively excellent performance and extremely excellent low-temperature performance, and has the excellent characteristic that the thermal conductivity coefficient at minus 160 ℃ is lower by about 20 percent than that of the existing best physical foaming agent, and the excellent characteristic can be used for heat preservation of long-distance natural gas transportation pipelines. The polyurethane foaming agent provided by the invention can replace all existing physical foaming agents containing halogen elements, and meets the production application of polyurethane spraying foam materials.

8. The polyurethane foams prepared using the blowing agents of the invention or the compounds of the general formulae (I), (II) and (III) as blowing agents, which foams are produced in laboratory self-made square molds by manual stirring, have a dimensional change or shrinkage of 10% or less, preferably of 5% or less, more preferably of 1% or less (the standing time can be as required in the Chinese national standard GB/T8811-2008, or even 5 months). In addition, for example, in the range of 34 to 42Kg/m³The thermal conductivity w/m.k (10 ℃) of the foam of (1) is between 0.01900 and 0.02200, preferably between 0.01910 and 0.02150. In addition, within this density range, the compressive strength of the foams of the present invention is in the range of 110-220 kPa.

Drawings

FIG. 1 is an SEM of the polyurethane foam of example 1.

Detailed Description

The present invention will be further described with reference to the following examples.

In the present application, the usual polyether polyols and polyester polyols used for the preparation of polyurethane foams or in foaming compositions are selected from the following classes: polyethers 4110, 450, 400A, MN500, SU380, SA380, 403, SA460, G350; polyesters CF6320, DM2003, YD6004, AKS7004, CF 6255. The usual catalysts are selected from: 33LV (A-33): 33% dipropylene glycol solution of triethylene diamine, N-dimethylethanolamine, N-dimethylbenzylamine, 70% dipropylene glycol solution of bis (dimethylaminoethyl) ether, 70% potassium octoate in diethylene glycol solution, dibutyltin dilaurate, PT303, PT304, potassium acetate, PC-8(N, N-dimethylcyclohexylamine), PC-5, PC-41, triethanolamine, JXP-508, JXP-509, TMR-2, TMR-3, and TMR-4. Common silane surfactants: DC8545, AK-158, AK-8805, AK-8812, AK-8809, AK-8818, AK-8860, DCI990, DC5188, DC6070, DC3042, DC 3201. Non-silane surfactants: LK-221, LK-443.

In the present application, the polyether polyols and polyester polyols commonly used in the preparation of polyurethane foams or in foaming compositions are those commonly used in the prior art for polyurethane foams. For both the polyurethane catalyst and the surfactant, the auxiliaries commonly used in the art can be used.

In the examples, the foams were tested for their properties according to the Chinese national standard GB/T26689-2011 (rigid polyurethane foams for refrigerators and freezers). The sample size is typically 10 x 2.5 cm.

The thermal conductivity is performed according to GB/T10294-2008 or GB/T10295-2008. The average temperature is 10 ℃, and the temperature difference of the cold plate and the hot plate is 15-20 ℃. The apparent (core) density was tested in accordance with GB/T6343-2009. The compressive strength was tested according to GB/T8813-2008.

For the measurement of the content of compounds of the general formula (II) or (III) as blowing agents in the second compound mixture (M2), carbon dioxide is initially liberated by heating the mixture (M2) to above 70 ℃ and the remainder, i.e.the alcohol amine compound, is subjected to gas chromatography. Wherein the gas chromatograph is equipped with a hydrogen Flame Ionization Detector (FID) and the mass concentration of the blowing agent compound is about 10 mg/mL. Gas chromatography conditions: HP-5 capillary chromatography column (30m × 0.32mm i.d. × 0.25 μm, 5% phenyl methyl-siloxane); the column temperature is programmed temperature rise, the initial temperature is 80 ℃, the column temperature is maintained for 3min, then the column temperature is raised to 250 ℃ at the speed of 25 ℃/min, and the column temperature is maintained for 5 min; the temperature of a sample inlet is 250 ℃; the temperature of the detector is 260 ℃; the carrier gas is high-purity nitrogen, and the flow rate is 1.5 mL/min; the fuel gas is hydrogen, and the flow rate is 30 mL/min; the combustion-supporting gas is air, and the flow rate is 300 mL/min; the tail gas is blown by nitrogen gas, and the flow rate is 25 mL/min; the sample introduction mode is divided sample introduction, and the divided flow ratio is as follows: 30: 1; the amount of sample was 1. mu.L.

Preparation example 1

Adding 15kg of triethyl orthoformate, 20kg of diethanolamine and 10kg of water into a reactor, starting stirring, controlling the pressure to be not higher than 0.1MPa, slowly heating while continuously stirring, and controlling the temperature to react for 10 hours when the temperature is raised to 80 ℃. Cooling to 50 deg.C after reaction, controlling vacuum degree below 600 mm Hg, removing ethanol at 50 deg.C under reduced pressure, cooling to 40 deg.C below, and discharging to obtain compound 1 with pH not less than 7.8 and decomposition temperature of 45-70 deg.C.

Preparation example 2

Adding 15kg of triethyl orthoformate, 13kg of monoethanolamine and 7.0kg of water into a reactor, starting stirring, slowly raising the temperature under continuous stirring, and controlling the temperature below 100 ℃ to react for 8 hours. And after the reaction is finished, cooling, controlling the vacuum degree to be below 600 mm Hg, decompressing and removing ethanol at the temperature of below 50 ℃, removing vacuum, cooling to the temperature of below 50 ℃, and discharging a product to obtain a compound 2 in which two ester groups of the triethyl orthoformate are hydrolyzed. The pH value is more than or equal to 7.8, and the decomposition temperature is 45-70 ℃.

Preparation example 3

Adding 20kg of tripropylorthoformate, 11kg of diethanolamine and 10kg of ammonia water into a reactor, starting stirring, slowly heating while continuously stirring, and reacting for 8 hours at the temperature of not more than 100 ℃. And after the reaction is finished, cooling, controlling the vacuum degree to be below 600 mm Hg, decompressing and removing unnecessary water at the temperature of below 50 ℃, removing the vacuum, cooling to below 40 ℃, and discharging the product to obtain the compound 3. The pH value is more than or equal to 7.8, and the decomposition temperature is 45-70 ℃.

Preparation example 4

Adding 15kg of trimethyl orthoformate, 2.0kg of ethylene glycol, 10kg of water and 10.0kg of ethanolamine into a reactor, starting stirring, controlling the pressure to be not higher than 0.1MPa, slowly heating while continuously stirring, and controlling the temperature to react for 5 hours when the temperature is raised to 70 ℃. Cooling after the reaction is finished, controlling the vacuum degree to be below 600 mm Hg, decompressing and dealcoholizing at the temperature of below 50 ℃, removing vacuum, cooling to the temperature of below 40 ℃, and discharging a product to obtain a compound 4, wherein the pH is more than or equal to 7.8, and the decomposition temperature is 45-70 ℃.

Preparation example 5

Adding 1.4kg of ammonium carbonate (molecular weight 96) and 1kg of water into a stainless steel reactor, stirring to form ammonium carbonate slurry (the ammonium carbonate is not completely dissolved), adding 2.0kg of propylene oxide, stirring while cooling, controlling the pressure to be not higher than 0.6MPa, slowly heating for reaction, and controlling the temperature to be always lower than 60 ℃ for 14 hours. After the reaction is completed, the temperature is slowly reduced to below 50 ℃, a part of water and unreacted propylene oxide are slowly removed under the vacuum degree of about 600 mm Hg, then the vacuum is released, and the reactant is discharged after the temperature is reduced to below 40 ℃, so that an aqueous carbonate ethanolamine salt compound mixture (compound 5) which belongs to one of second compound mixtures M2 is obtained. The viscosity was approximately 400 centipoise, the pH was 9.1, and the decomposition temperature of compound 5 was 58-63 ℃. The content of alkali metal and alkaline earth metal ions was determined to be below the detection limit with an atomic absorption spectrophotometer (Seiko Instruments, Inc.; SAS/727).

Gas chromatography analysis indicated that compound 5 was a mixture comprising a plurality of alcohol amines (referred to herein as the second compound mixture M2), wherein the molar ratio of N-monohydroxypropyl-ammonium carbonate to N, N' -bis (hydroxypropyl) -ammonium carbonate compound in the reaction product (i.e., mixture M2) was about 1: 0.35.

Analysis by infrared spectroscopy of a mixture of the second compounds (M2) obtained by reaction of ammonium carbonate with propylene oxideThe N-hydroxypropylated ammonium carbonate salt compound (i.e., the aqueous organic alcohol amine mixture product) has a single peak of stretching vibration of N-H as a secondary amine salt in the range of 2930-15675 cm-1 and in the range of 1554-1567cm^-1Bending vibration singlet for N-H secondary amine salt in the range of 3200-3400cm^-1A range of strong and broad hydrogen-bonded OH stretching vibration peaks, which indicate that the N-hydroxypropylated ammonium carbonate compound of the present invention has both hydroxyl and secondary amine groups, while containing a small amount of water therein. Thus, the N-hydroxypropylated ammonium carbonate salt compounds of the invention comprise one or more alkanolamine carbonate compounds and generally contain a small amount of water.

Preparation example 6

Preparation example 5 was repeated, except that ammonium carbonate was replaced by the same molar amount of a salt consisting of ammonium carbamate and ammonium carbonate in a molar ratio of 1:1. Compound 6 was obtained at pH 9.2.

The application example is as follows:

example 1

A transparent foaming composition was obtained by uniformly mixing a basic blowing agent (consisting of 4 parts by weight of the compound 1 prepared in the above preparation example 1 as a blowing agent and 4.5 parts by weight of the compound 5 prepared in the above preparation example 5 as a blowing agent, pH 8.9), 30 parts by weight of polyether polyol 4110 (produced by hametui group, shozu, shandong), 20 parts by weight of polyester polyol (produced by sambuch chemical company ltd, santo, lan star), 1 part by weight of foam stabilizer DC3201 (produced by air chemical company, usa), 12.5 parts by weight of flame retardant TCPP (produced by sambuca chemical company ltd, jiangsu), 1 part by weight of PT-303, 1.5 parts by weight of potassium acetate and 5 parts by weight of HCFC-141b, then, 83 parts of isocyanate MDI (PM200, Tantawawa chemical group Co., Ltd.) was added thereto, and the mixture was stirred uniformly and foamed to obtain a polyurethane foam material. The material is useful as a polyurethane spray foam material. The size change rate or shrinkage of the obtained polyurethane foam material is less than or equal to 1 percent (according to the Chinese national standard GB/T8811-2008, the standing time is 5 months). In addition, the foam density was about 33Kg/m³The compressive strength was about 135 KPa.

The foam product of example 1 has good thermal insulation properties and can meet the requirements of various properties in the field of polyurethane spray foams.

Samples were taken and sectioned with a razor blade and the cells were observed using SEM at 100 x magnification. As shown in fig. 1, the average cell diameter was 225.7 microns. The size of the foam holes is uniform.

Example 2

A transparent foaming composition was obtained by uniformly mixing a basic blowing agent (consisting of 3.5 parts by weight of compound 2 prepared in the above preparation example 2 as a blowing agent and 4.5 parts by weight of compound 5 prepared in the above preparation example 5 as a blowing agent, pH 8.7), 30 parts by weight of polyether polyol 4110 (produced by hamanized group of shorea, shandong), 20 parts by weight of polyester polyol (produced by makeda chemical ltd. of Shandong Lanxindong), 1 part by weight of foam stabilizer DC3201 (produced by air chemical Co., Ltd., USA), 12.5 parts by weight of flame retardant TCPP (produced by Jiangsu Yake chemical ltd., Ltd.), 1 part by weight of PT-303, 1 part by weight of a33, 1.5 parts by weight of potassium acetate, and 6 parts by weight of HCFC-141b, and then 83 parts by weight of isocyanate MDI (PM200, Tantawa chemical group Ltd.) was added thereto, the polyurethane foam material is prepared by foaming after even stirring. The material is useful as a polyurethane spray foam material. The size change rate or shrinkage of the obtained polyurethane foam material is less than or equal to 1 percent (according to the Chinese national standard GB/T8811-2008, the standing time is 5 months). In addition, the foam density was about 34Kg/m³The compressive strength was about 139 KPa.

Example 3

A basic blowing agent (consisting of 4.0 parts by weight of compound 3 prepared in preparation example 3 above as a blowing agent and 4.5 parts by weight of compound 5 prepared in preparation example 5 above as a blowing agent, pH 8.7), 30 parts by weight of polyether polyol 4110 (produced by hamanized group of shorea, shandong), 20 parts by weight of polyester polyol (produced by mazao chemical ltd, santong, bluestar, usa), 1 part by weight of foam stabilizer DC3201 (produced by air chemical company, usa), 12.5 parts by weight of flame retardant TCPP (produced by yaakuke chemical ltd, jiangsu), 1 part by weight of PT-303, 1 part by weight of a33, 1 part by weight of potassium acetate, and 6 parts by weight of HCFC-141b were uniformly mixed to obtain a transparent foaming composition,then, 83 parts of isocyanate MDI (PM200, Tantawawa chemical group Co., Ltd.) was added thereto, and the mixture was stirred uniformly and foamed to obtain a polyurethane foam material. The material is useful as a polyurethane spray foam material. The size change rate or shrinkage of the obtained polyurethane foam material is less than or equal to 1 percent (according to the Chinese national standard GB/T8811-2008, the standing time is 5 months). In addition, the foam density was about 34Kg/m³The compressive strength was about 138 KPa.

Example 4

A basic blowing agent (consisting of 3.0 parts by weight of compound 3 prepared in the above preparation example 4 as a blowing agent and 4.5 parts by weight of compound 6 prepared in the above preparation example 6 as a blowing agent, pH 8.8), 30 parts by weight of polyether polyol 4110 (manufactured by hamanized group, shorea, Shandong), 20 parts by weight of polyester polyol (manufactured by Dainippon chemical Co., Ltd., Lanzhong, Shandong), 1 part by weight of foam stabilizer DC3201 (manufactured by American air chemical Co., Ltd.), 12.5 parts by weight of flame retardant TCPP (manufactured by Jiangsu Yak chemical Co., Ltd.), 1 part by weight of PT-303 (manufactured by American air chemical Co., Ltd.), 1 part by weight of potassium acetate and 6 parts by weight of HCFC-141b were uniformly mixed to obtain a transparent foamed composition, and 83 parts by weight of isocyanate MDI (PM200, Tantawa chemical Co., Ltd.) was added thereto, the polyurethane foam material is prepared by foaming after even stirring. The material is useful as a polyurethane spray foam material. The size change rate or shrinkage of the obtained polyurethane foam material is less than or equal to 1 percent (according to the Chinese national standard GB/T8811-2008, the standing time is 5 months). In addition, the foam density was about 36Kg/m³The compressive strength was about 156 KPa.

Claims

1. An alkaline alcohol amine blowing agent comprising a salt of carbinolamine orthoformate and a salt of propanolamine carbonate, said alkaline alcohol amine blowing agent having a pH of between 8.5 and 9.5, the blowing agent comprising:

A^-B⁺ (I)

wherein A is^-Is orthoformic acidRoot of herbaceous plant

，B⁺Is a cation of an organic alcohol amine B;

2) a second compound mixture (M2) comprising an N-monohydroxypropyl-ammonium carbonate compound having the general formula (II) and an N, N' -di (hydroxypropyl) -ammonium carbonate compound having the general formula (III),

(RN⁺H₃)(N⁺H₄) CO₃ ^2-(II), or (RN)⁺H₃)₂ CO₃ ^2- (III)，

Wherein R is HO-CH₂-CH(CH₃) -or HO-CH (CH)₃)-CH₂-；

The molar ratio of the compound of formula (II) to the compound of formula (III) is from 1:0.1 to 1: 1.0.

2. The blowing agent according to claim 1, wherein the first compound mixture (M1) is prepared by hydrolysis of orthoformates in the presence of an organic alcohol amine B and water.

3. The blowing agent of claim 2 wherein the amount of water in the reaction mixture is sufficient to allow complete hydrolysis of the orthoformate.

4. The blowing agent according to any of claims 1 to 3, wherein the second compound mixture (M2) is prepared by: to a slurry or saturated solution formed from ammonium carbonate and/or ammonium carbamate and water, propylene oxide is added with or without addition of aqueous ammonia in a molar ratio of ammonium carbonate and/or ammonium carbamate to propylene oxide of 1:1 to 5.5 to allow the reaction mixture to react, to obtain an aqueous mixture of organic alcohol amines, i.e., a second compound mixture (M2).

5. The blowing agent according to claim 4, the pH of the second compound mixture (M2) being from 7.5 to 10.

6. The blowing agent according to claim 4, the pH of the second compound mixture (M2) being from 8 to 9.7.

7. The blowing agent according to claim 4, the pH of the second compound mixture (M2) being from 8.3 to 9.6.

8. The blowing agent according to claim 4, the pH of the second compound mixture (M2) being from 8.5 to 9.5.

9. The blowing agent as claimed in any of claims 1 to 3, wherein the weight ratio of the first compound mixture (M1) to the second compound mixture (M2) is from 0.3 to 1:1.

10. The blowing agent according to claim 9, wherein the weight ratio of the first compound mixture (M1) to the second compound mixture (M2) is from 0.5 to 0.8: 1.

11. The blowing agent according to any of claims 1 to 3, wherein, in the compound of the general formula (I), from 50 to 100% of the amine groups of the organic alcohol amine B are replaced by anions A^-Neutralizing; and/or

The water content of each of the first mixture of compounds (M1) or the second mixture of compounds (M2) is independently from 2 to 40% by weight.

12. The blowing agent of claim 11 wherein in the compound of formula (I) 65 to 100% of the amine groups in the organic alcohol amine B are replaced by anions a^-The water content of each of the first compound mixture (M1) or the second compound mixture (M2) is independently 5 to 35% by weight.

13. The blowing agent of claim 11 wherein in the compound of formula (I) 75-100% of the amine groups in the organic alcohol amine B are replaced by anion a^-Neutralization, the water content of each of the first mixture of compounds (M1) or the second mixture of compounds (M2) being independentThe ground is 10-30 wt%.

14. The blowing agent of claim 11 wherein in the compound of formula (I) 75 to 90% of the amine groups in the organic alcohol amine B are replaced by an anion a^-The water content of each of the first compound mixture (M1) or the second compound mixture (M2) is independently 15 to 25 wt%.

15. The blowing agent according to any of claims 1 to 3, wherein the first compound mixture (M1) has a pH of from 7.0 to 8.8; and/or

The pH of the second compound mixture (M2) was 8.6-10.

16. The blowing agent according to claim 15, wherein the first compound mixture (M1) has a pH of 7.3 to 8.6; and/or the pH of the second compound mixture (M2) is 8.7-9.5.

17. The blowing agent according to claim 15, wherein the first compound mixture (M1) has a pH of 7.5 to 8.5; and/or the pH of the second compound mixture (M2) is 8.8-9.3.

18. The blowing agent of claim 2 wherein the organic alcohol amine B is selected from one or more of the following: c₂-C₁₂Alcamines; and/or

The orthoformate compound is selected from one or more of the following compounds: ortho-formic acid tris (C)₁-C₈) And (3) alkyl esters.

19. The blowing agent of claim 18 wherein the organic alcohol amine B is one or more selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutanolamine, dibutanolamine, and tributanolamine.

20. A polyurethane foaming composition, the composition comprising: 0.5 to 100 wt% of the blowing agent of any of claims 1 to 19; 0-50 wt% of a physical blowing agent; 0 to 5 weight percent water, and 0.0 to 99.5 weight percent polymer polyol; wherein the weight percentages are based on the total weight of the polyurethane foaming composition.

21. The polyurethane foaming composition of claim 20, the composition comprising: 2 to 80wt% of the blowing agent of any of claims 1 to 19; 20.0-98.0 wt% of a polymer polyol, wherein the weight percent is based on the total weight of the polyurethane foaming composition.

22. The polyurethane foaming composition of claim 20, the composition comprising: 4 to 60wt% of the blowing agent of any of claims 1 to 19; 40 to 96wt% of a polymer polyol, wherein the weight percentages are based on the total weight of the polyurethane foaming composition.

23. The polyurethane foaming composition of claim 20, the composition comprising: 6 to 40wt% of the blowing agent of any of claims 1 to 19; 60 to 94wt% of a polymer polyol, wherein the weight percentages are based on the total weight of the polyurethane foaming composition.

24. The polyurethane foaming composition of claim 20, the composition comprising: 70-88wt% of a polymer polyol.

25. The polyurethane foaming composition of claim 20, the composition comprising: 75-85wt% of a polymer polyol.

26. The polyurethane foaming composition of claim 20, wherein the polymer polyol is selected from the group consisting of: polyether polyols, polyester polyols, polyether-polyester polyols, polycarbonate diols, polycarbonate-polyester polyols, polycarbonate-polyether polyols, polybutadiene polyols or polysiloxane polyols, and the polymer polyols have an average functionality of 2 to 16; and/or

The physical blowing agent is at least one selected from the group consisting of: n-pentane, isopentane, cyclopentane, HCFC-141b, HFC-245fa, HFC-365mfc, LBA, FEA-1100.

27. The polyurethane foaming composition of claim 26, wherein the polymer polyol has an average functionality of from 2.5 to 10.

28. The polyurethane foaming composition of claim 26, wherein the polymer polyol has an average functionality of 3 to 8.

29. Use of the blowing agent of any of claims 1-19 in polyurethane spray foam materials.