CN109422916B - Blowing agents comprising secondary amine salts and ethanolamine salts and use for polyurethane slabstock foam materials - Google Patents

Blowing agents comprising secondary amine salts and ethanolamine salts and use for polyurethane slabstock foam materials Download PDF

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CN109422916B
CN109422916B CN201710741030.1A CN201710741030A CN109422916B CN 109422916 B CN109422916 B CN 109422916B CN 201710741030 A CN201710741030 A CN 201710741030A CN 109422916 B CN109422916 B CN 109422916B
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blowing agent
compound
mixture
weight
compound mixture
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CN109422916A (en
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毕玉遂
毕戈华
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Butian New Material Technology Co ltd
Shandong University of Technology
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Butian New Material Technology Co ltd
Shandong University of Technology
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/18Catalysts containing secondary or tertiary amines or salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00Manufacture of cellular products
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes

Abstract

Disclosed is a polyurethane blowing agent comprising a secondary amine salt and an ethanolamine salt, the blowing agent comprising: 1) a first compound mixture (M1) comprising a class of organic secondary amine salt compounds having the following general formula (I): a. the[B+]p(I) Wherein B is+Is a cation of a +1 valent organic secondary amine B, AThe method comprises the following steps: CO23 2‑,HCO3 Or CO3 2‑With HCO3 A conjugate of (a); 2) a second compound mixture (M2) comprising an N-monohydroxyethyl-ammonium carbonate compound having the general formula (II) and an N, N' -di (hydroxyethyl) -ammonium carbonate compound having the general formula (II): (RN)+H3)(N+H4)CO3 2‑(II), or (RN)+H3)2CO3 2‑(III), wherein R is hydroxyethyl; the molar ratio of the compound of formula (II) to the compound of formula (III) is from 1:0 to 1: 2.5. The blowing agent is suitable for preparing polyurethane batch plate foam materials.

Description

Blowing agents comprising secondary amine salts and ethanolamine salts and use for polyurethane slabstock foam materials
Technical Field
The invention relates to an organic secondary amine salt compound with an anion serving as a CO2 donor, a preparation method thereof and application of the compound serving as a foaming agent, and particularly provides a novel organic ammonium salt compound with the anion serving as a CO2 donor and an organic secondary amine serving as a catalytic group and a solubilizing group, a preparation method thereof and application of the compound in preparing a polyurethane batch plate foam material. The present invention relates to polyurethane blowing agents comprising secondary amine salts and ethanolamine salts and their use for (preparing) polyurethane slabstock foam materials
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 polyol and/or polyether polyol make CO poor2The gas is not uniformly dispersed in the foaming composition and the foaming process is not easily controlled.
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 the anionic donor and having organic secondary amino groups as solubilising groups and their use in foamed materials such as polyurethane slabstock 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 a valence of-n can be activated by the NCO groups contained in isocyanate monomers such as MDI and TDI, releasing CO rapidly2A 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, and the foaming agent can be uniformly dispersed in a foaming componentIn the composition so as to be foamed uniformly, the distribution of cells in the polyurethane foam is relatively uniform, and the size of cells is relatively uniform. In addition, the first compound mixture (M1) according to the invention contains secondary amine groups, and the first compound mixture (M1) which is a blowing agent decomposes to liberate CO2The decomposition products produced are then secondary amine compounds which are suitable as polyurethane catalysts for use 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 a blowing agent comprising a secondary amine salt and an ethanolamine salt for use in preparing polyurethane slabstock foam materials. The foaming agent comprises:
1) a first compound mixture (M1) comprising a class of organic secondary amine salt compounds having the following general formula (I):
A-[B+]p (I)
wherein, B+Is a cation of a +1 valent organic secondary amine B, A-The method comprises the following steps: CO23 2-,HCO3 -Or CO3 2-With HCO3 -A conjugate of (a); p is at A-Is HCO3 -In the case of (1), p is at A-Is CO3 2-2 in the case of (1);
2) comprising an N-monohydroxyethyl-ammonium carbonate compound having the general formula (II) and an N, N' -bis (hydroxyethyl) ether having the general formula (III)
Base) -ammonium carbonate compound (M2), a mixture of alkanolamine salt compounds,
(RN+H3)(N+H4)CO3 2-(II), or (RN)+H3)2CO3 2- (III),
In the formula, R is hydroxyethyl;
the molar ratio of the compound of formula (II) to the compound of formula (III) is from 1:0 to 1: 2.5. Preferably 1:0.3 to 1:2, more preferably 1:0.5 to 1:1.
For the compound mixture (M1), it is preferred that A-The method comprises the following steps: CO23 2-Or CO3 2-With HCO3 -A conjugate of (a); p is at A-Is HCO3 -In the case of (1), p is at A-Is CO3 2-In the case of (2).
Preferably, the first mixture of compounds (M1) is prepared by reacting a secondary organic amine B with CO in the presence of water2And (3) reaction. The amount of water is such that the first compound mixture (M1) obtained is in the form of a slurry or a saturated solution, preferably in the form of a slurry (i.e. with a portion of the carbonate undissolved).
Generally, the second compound mixture (M2) was prepared by the following method: to a slurry or saturated solution formed from ammonium carbonate and/or ammonium carbamate and water, ethylene oxide is added to allow the reaction mixture to react [ then, optionally, a portion of the water and unreacted ethylene oxide is removed from the resulting reaction mixture under vacuum, with or without addition of aqueous ammonia, to a molar ratio of ammonium carbonate and/or ammonium carbamate to ethylene oxide of 1:1 to 5.5 (preferably 1:1.3 to 5) [ typically, a mixture of organic alcohol amines having a pH of 7.5 to 10, preferably a pH of 8 to 9.7, preferably a pH of 8.3 to 9.6, preferably a pH of 8.2 to 9.6, more preferably a pH of 8.5 to 9.5, for example a pH of 9 ], i.e. a second mixture of compounds (M2), is obtained.
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 0.2 to 0.9:1, preferably from 0.25 to 0.85:1, more preferably from 0.3 to 0.8:1, more preferably from 0.5 to 0.75:1, more preferably from 0.6 to 0.75: 1.
Preferably, in the compound of the general formula (I) or in the first mixture of compounds (M1), 50 to 100% of the amine groups in the secondary organic amine compound B are neutralized by the anion A-, preferably 65 to 100% of the amine groups in the organic amine compound B are neutralized by the anion A-; more preferably, 75 to 100% of the amine groups in the organic amine compound B are neutralized with an anion A-; more preferably, 75 to 90% of the amine groups in the organic amine compound B are neutralized with the anion A-.
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 6.5 to 8.1, preferably in the range of 6.7 to 8.0, more preferably in the range of 7 to 7.5.
Preferably, the pH of the second compound mixture (M2) is 8.3-10, preferably 8.5-9.5, more preferably 8.8-9.2.
Preferably, the organic secondary amine B is one or more selected from the group consisting of: two (C)1-C4Hydrocarbyl) amines; for example, one or more selected from dimethylamine, diethylamine, dipropylamine, dibutylamine, methylethylamine, methylpropylamine, ethylpropylamine, methylbutylamine, ethylbutylamine, or propylbutylamine.
According to another aspect of the present invention, there is provided a process for the preparation of a first compound mixture (M1) comprising a compound of formula (I) as defined above, which process comprises: reacting secondary organic amines with CO in the presence of water2And (3) reacting to obtain the product. The reaction temperature is generally from 40 to 65 ℃ and preferably from 45 to 60 ℃ and the reaction pressure is less than 0.3MPa, for example from 0.1 to 0.2MPa, and the reaction time is from 6 to 20 hours and preferably from 8 to 12 hours. The amount of water used is such that the water content of the first compound mixture (M1) is 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.
The secondary organic amines are those described above.
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 96 wt%, 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 5 wt% of water, and 0.0 to 99.5 wt% (preferably 20.0 to 98.0 wt%, more preferably 40 to 96 wt%, more preferably 60 to 94 wt%, more preferably 70 to 88 wt%, 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 a blowing agent as described above for (preparing) an iced polyurethane slabstock 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, due to the N-hydroxyethyl group as a solubilizing group, the compound 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 (II) of the present invention has both "foaming effect" and "chain extension" or "crosslinking" effect with the compound of the general formula (III), 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) according to the invention, an aqueous organic alcohol amine mixture comprising N-hydroxyethylated ammonium carbonate compounds, liberates a substantial amount of carbon dioxide by heating to 70c and the remaining alcohol amine compound is then subjected to gas chromatographic analysis and the molar ratio of N-monohydroxyethyl-ammonium carbonate to N, N' -di (hydroxyethyl) -ammonium carbonate compounds in the reaction product (i.e. mixture M2) is in the range 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 batch board 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 (II) and the compounds of the general formula (III) with the polyester polyol and/or polyether polyol for foaming is very good, and a clear homogeneous system is formed. It has been found, particularly surprisingly, that the compatibility or miscibility of the first mixture (M1) with the polyester polyol and/or polyether polyol is less than optimal when used alone as a blowing agent, but that when the mixture obtained by mixing the first mixture (M1) with the second mixture (M2) is used as a blowing agent, the blowing agent has good compatibility or miscibility with the polyester polyol and/or polyether polyol used for foaming, and therefore the formation of uniform-sized cells in the polyurethane foam can likewise be ensured. The first mixture (M1) has a catalytic action and also a foaming action. That is, the miscibility or dispersibility of the first compound mixture (M1) in the polyester polyol and/or polyether polyol is significantly improved by the intermediary of the second compound mixture (M2).
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.
The polyurethane foaming composition (commonly called "white material") of the invention has the following characteristics: 1. containing amine salt compounds (e.g. compounds of formula (I) release CO after thermal decomposition2While leaving secondary amine compounds); 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 foaming compositions(i.e., the "white material") is contacted or mixed with an isocyanate or polyisocyanate (e.g., MDI or TDI) and 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 polyurethane batch plate foam materials which comprises incorporating into the polyurethane preparation from 1 to 10%, preferably from 2 to 5%, based on the total weight of the polyurethane raw materials (including isocyanate and polyol), of the above-described secondary organic amine salt compound or mixture of secondary organic amine salt compounds.
The invention also provides the use of the above-mentioned secondary organic amine salt compound or mixture of secondary organic amine salt compounds for (preparing) foamed materials such as polyurethane slabstock 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.
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 a chain extender and/or a cross-linking agent, the general formula (II) and the general formula (III) compound of the invention are used as a foaming point and a chain extending point and/or a cross-linking point, the mechanical strength and the 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 finished product of 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. When the compound of the general formula (I) of the present invention is a compound having a secondary amine group, CO is released by decomposition of the compound (I)2The decomposition products which are then produced, i.e. secondary 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 intermittent plate 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.
The present invention will be further described with reference to the following examples.
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 3kg of 40% dimethylamine aqueous solution (molecular weight 45) into a transparent quartz glass reactor, stirring for dissolving, sealing the reactor, then continuously stirring, controlling the temperature to be between 40 and 65 ℃, introducing carbon dioxide into the reactor, controlling the pressure to be not higher than 0.3MPa, controlling the temperature for reaction for 10 hours, cooling to below 40 ℃, releasing the pressure, and discharging the product. Compound 1 was obtained. The pH value is more than or equal to 7.5, and the decomposition temperature is 42-70 ℃.
Preparation example 2
Adding 3kg of 30% diethylamine aqueous solution (molecular weight 73) into a transparent quartz glass reactor, stirring for dissolving, sealing the reactor, continuously stirring, controlling the temperature to be between 40 and 65 ℃, introducing carbon dioxide into the reactor, controlling the pressure to be not higher than 0.3MPa, controlling the temperature for reaction for 10 hours, cooling to below 40 ℃, releasing the pressure, and discharging the product. Compound 2 was obtained. The pH value is more than or equal to 7.5, and the decomposition temperature is 42-70 ℃.
Preparation example 3
Adding 3kg of dipropylamine (molecular weight is 101) and 1.6kg of water into a transparent quartz glass reactor, stirring and dissolving, sealing the reactor, then controlling the temperature to be between 40 and 65 ℃ under continuous stirring, introducing carbon dioxide into the reactor, controlling the pressure to be not higher than 0.3MPa, controlling the temperature to react for 10 hours, cooling to below 40 ℃, releasing the pressure, and discharging the product. Compound 3 was obtained. The pH value is more than or equal to 7.5, and the decomposition temperature is 42-70 ℃.
Preparation example 4
Adding 3kg of methyl ethylamine (molecular weight 59) and 1.6kg of water into a transparent quartz glass reactor, stirring for dissolving, sealing the reactor, then continuously stirring, controlling the temperature to be between 40 and 65 ℃, introducing carbon dioxide into the reactor, controlling the pressure to be not higher than 0.3MPa, controlling the temperature for reaction for 10 hours, cooling to below 40 ℃, releasing the pressure, and discharging the product. Compound 4 was obtained. The pH value is more than or equal to 7.5, and the decomposition temperature is 42-70 ℃.
Preparation example 5
1.4kg of ammonium carbonate (molecular weight 96) and 1kg of water are added into a stainless steel reactor, stirring is started to form ammonium carbonate in slurry (ammonium carbonate is not completely dissolved), then 1.7kg of ethylene oxide is added, stirring and cooling are carried out, the pressure is controlled not to be higher than 0.6MPa, the temperature is slowly raised for reaction, and the temperature is controlled 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 ethylene 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 a hydrous alkanolamine carbonate salt compound mixture (compound 5 for short) is obtained, and belongs to one of second compound mixtures M2. Viscosity was approximately 376 centipoise, pH 9.2, and 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-monohydroxyethyl-ammonium carbonate to N, N' -bis (hydroxyethyl) -ammonium carbonate compound in the reaction product (i.e., mixture M2) was about 1: 0.36.
By infrared spectroscopic analysis, the N-hydroxyethylated ammonium carbonate salt compound (i.e., the aqueous organic alcohol amine mixture product) in the second compound mixture (M2) obtained by the reaction of ammonium carbonate with ethylene oxide had a stretching vibration single peak for the secondary amine salt N-H in the range of 2928-2970cm-1 at 1550-1565cm-1Bending vibration singlet for N-H secondary amine salts in the range of 3210-3405cm-1A range of strong and broad hydrogen-bonded OH stretching vibration peaks, which indicate that the N-hydroxyethylated ammonium carbonate compounds of the present invention have both hydroxyl and secondary amine groups, while containing a small amount of water therein. Thus, the N-hydroxyethylated ammonium carbonate 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
4 parts by weight of compound 1 prepared in the above preparation example 1 as a blowing agent and 4.5 parts by weight of compound 5 prepared in the above preparation example 5 as a blowing agent, 30 parts by weight of polyether polyol 4110 (manufactured by hamlet chemical group, Binzhou, Shandong), 20 parts by weight of polyester polyol (manufactured by Shandong Lanxingdong chemical Co., Ltd.), 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 Yake chemical Co., Ltd.), 1 part by weight of PT-303, 1.5 parts by weight of potassium acetate and 5 parts by weight of HCFC-141b were mixed uniformly to obtain a transparent foamed composition, and then 83 parts by weight of isocyanate MDI (PM200, Tantawawa chemical group Co., Ltd.) was added thereto and foamed after stirring uniformly to obtain a polyurethane foam material. The material is used as a polyurethane batch board 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 40Kg/m3The compressive strength was about 172 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 slabstock foam materials.
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 206.2 microns. The size of the foam holes is uniform.
Example 2
3 parts by weight of compound 2 prepared in the above preparation example 2 as a blowing agent and 5.0 parts by weight of compound 5 prepared in the above preparation example 5 as a blowing agent, 30 parts by weight of polyether polyol 4110 (manufactured by hamlet chemical group, Binzhou, Shandong province), 20 parts by weight of polyester polyol (manufactured by Shandong Lanxingdong chemical Co., Ltd.), 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 Yake chemical Co., 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 are mixed uniformly to obtain a transparent foaming composition, 83 parts of isocyanate MDI (PM200, Tantawawa chemical group Co., Ltd.) is added into the transparent foaming composition, and the mixture is stirred uniformly and then foamed to obtain the polyurethane foam material. The material is used as a polyurethane batch board 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 40Kg/m3The compressive strength was about 168 KPa.
Example 3
4 parts by weight of compound 3 prepared in the above example 3 as a blowing agent and 4.5 parts by weight of compound 5 prepared in the above preparation example 5 as a blowing agent, 30 parts by weight of polyether polyol 4110 (manufactured by hamlet chemical group, Binzhou, Shandong), 20 parts by weight of polyester polyol (manufactured by Shandong Lanxingdong chemical Co., Ltd.), 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 Yake chemical Co., Ltd.), 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 mixed uniformly 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 used as a polyurethane batch board 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 40Kg/m3The compressive strength was about 163 KPa.
Example 4
3 parts by weight of compound 4 prepared in the above example 4 as a blowing agent and 5.5 parts by weight of compound 6 prepared in the above preparation example 6 as a blowing agent, 30 parts by weight of polyether polyol 4110 (manufactured by Binshi group of Binzhou, Shandong), 20 parts by weight of polyester polyol (manufactured by Shandong Lanxindong Daihong chemical Co., Ltd.), 1 part by weight of foam stabilizer DC3201 (manufactured by American Aikogaku corporation), 12.5 parts by weight of a blowing agentThe flame retardant TCPP (produced by Jiangsu Yake chemical Co., Ltd.), 1 part by weight of PT-303 (produced by American air chemical Co., Ltd.), 1 part by weight of potassium acetate and 6 parts by weight of HCFC-141b are uniformly mixed to obtain a transparent foaming composition, then 83 parts of isocyanate MDI (PM200, produced by Tantai Wanhua chemical group Co., Ltd.) is added into the transparent foaming composition, and the mixture is stirred uniformly and foamed to prepare the polyurethane foam material. The material is used as a polyurethane batch board 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 40Kg/m3The compressive strength was about 165 KPa.

Claims (31)

1. A blowing agent comprising a secondary amine salt and an ethanolamine salt, the blowing agent comprising:
1) a first compound mixture (M1) comprising a class of organic secondary amine salt compounds having the following general formula (I):
A-[B+]p (I)
wherein, B+Is a cation of a +1 valent organic secondary amine B, A-The method comprises the following steps: CO23 2-Or CO3 2-With HCO3 -A conjugate of (a); p is at A-Is HCO3 -In the case of (1), p is at A-Is CO3 2-2 in the case of (1);
2) a second compound mixture (M2) comprising a N-monohydroxyethyl-ammonium carbonate compound having the general formula (II) and a N, N' -di (hydroxyethyl) -ammonium carbonate compound having the general formula (III),
(RN+H3)(N+H4)CO3 2-(II), or (RN)+H3)2CO3 2- (III),
In the formula, R is hydroxyethyl;
the molar ratio of the compound of formula (II) to the compound of formula (III) is from 1:0 to 1: 2.5.
2. The blowing agent of claim 1 wherein firstThe mixture of compounds (M1) is prepared by reacting an organic secondary amine B with CO in the presence of water2And (3) reaction.
3. The blowing agent of claim 1 wherein the second compound mixture (M2) is prepared by: ethylene oxide is added to a slurry or saturated solution formed from ammonium carbonate and/or ammonium carbamate and water, with or without addition of aqueous ammonia, in a molar ratio of ammonium carbonate and/or ammonium carbamate to ethylene 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).
4. The blowing agent according to claim 3, wherein the pH of the second compound mixture (M2) is from 7.5 to 10.
5. The blowing agent according to claim 3, wherein the pH of the second compound mixture (M2) is from 8 to 9.7.
6. The blowing agent according to claim 3, wherein the pH of the second compound mixture (M2) is from 8.3 to 9.6.
7. The blowing agent according to claim 3, wherein the pH of the second compound mixture (M2) is from 8.5 to 9.5.
8. The blowing agent of claim 3 wherein the pH of the second compound mixture (M2) is 9.
9. The blowing agent according to claim 1, wherein the weight ratio of the first compound mixture (M1) to the second compound mixture (M2) is from 0.2 to 0.9: 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 0.25 to 0.85: 1.
11. 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 0.3 to 0.8: 1.
12. 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 0.75: 1.
13. The blowing agent of claim 1 wherein in the compound of formula (I) 50-100% of the amine groups in the secondary organic amine B are bound by the anion 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.
14. The blowing agent of claim 13 wherein in the compound of formula (I) 65 to 100% of the amine groups in the secondary organic amine B are replaced by anion 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 5 to 35 wt.%.
15. The blowing agent of claim 13 wherein in the compound of formula (I) 75-100% of the amine groups in the secondary organic amine B are replaced by anion 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 10 to 30% by weight.
16. The blowing agent of claim 13 wherein, in the compound of formula (I), 75 to 90% of the amine groups in the secondary organic amine B are replaced by the anion 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 15 to 25 wt.%.
17. The blowing agent according to claim 1, wherein the first compound mixture (M1) has a pH of 6.5 to 8.1; and/or
The pH of the second compound mixture (M2) was 8.3-10.
18. The blowing agent according to claim 17, wherein the first compound mixture (M1) has a pH of 6.7-8.0; and/or the pH of the second compound mixture (M2) is 8.5-9.5.
19. The blowing agent according to claim 17, wherein the first compound mixture (M1) has a pH of 7-7.5; and/or the pH of the second compound mixture (M2) is 8.8-9.2.
20. The blowing agent of claim 1 wherein the secondary organic amine B is selected from one or more of the following: two (C)1-C4Hydrocarbyl) amines.
21. The blowing agent of claim 20 wherein the secondary organic amine B is one or more selected from dimethylamine, diethylamine, dipropylamine, dibutylamine, methylethylamine, methylpropylamine, ethylpropylamine, methylbutylamine, ethylbutylamine, or propylbutylamine.
22. A polyurethane foaming composition comprising: 0.5 to 100 wt% of the blowing agent of any of claims 1 to 21; 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.
23. The polyurethane foaming composition of claim 22, comprising: 2 to 80 wt% of the blowing agent of any of claims 1 to 21; 20.0 to 98.0 weight percent 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 22, comprising: 4 to 60 wt% of the blowing agent of any of claims 1 to 21; 40-96 wt% of a polymer polyol; wherein the weight percentages are based on the total weight of the polyurethane foaming composition.
25. The polyurethane foaming composition of claim 22, comprising: 6-40 wt% of the blowing agent of any of claims 1-21; 60 to 94 weight percent of a polymer polyol; wherein the weight percentages are based on the total weight of the polyurethane foaming composition.
26. The polyurethane foaming composition of claim 22, comprising: 70-88 wt% of a polymer polyol.
27. The polyurethane foaming composition of claim 22, comprising: 75-85 wt% of a polymer polyol.
28. The polyurethane foaming composition of claim 22, 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.
29. The polyurethane foaming composition of claim 28, wherein the polymer polyol has an average functionality of from 2.5 to 10.
30. The polyurethane foaming composition of claim 28, wherein the polymer polyol has an average functionality of 3 to 8.
31. Use of a blowing agent according to any of claims 1 to 21 in polyurethane slabstock foam materials.
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WO2007092060A1 (en) * 2006-02-09 2007-08-16 Stepan Company Method for preparing phthalate polyester polyol-based dimensionally stable spray polyurethane foam
CN101939350A (en) * 2008-02-09 2011-01-05 拜尔材料科学股份公司 Foamed, colour-fast polyurethane moulded parts
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