CN109422917B

CN109422917B - Secondary and alcohol amine alkaline blowing agents and use for producing polyurethane spray foam materials

Info

Publication number: CN109422917B
Application number: CN201710734826.4A
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: 2021-02-12
Anticipated expiration: 2037-08-24
Also published as: CN109422917A

Abstract

仲胺和醇胺碱性发泡剂和用于制备聚氨酯喷涂泡沫体材料的用途。公开了包含仲胺盐和丙醇胺盐的一种聚氨酯碱性发泡剂，该碱性发泡剂的pH值是在8.5‑9.5之间，该发泡剂包括：1)包含具有以下通式(I)的有机仲胺盐化合物类的第一种化合物混合物(M1)：A^‑[B⁺]_p(I)，其中，B⁺是+1价的有机仲胺B的阳离子，A^‑是：CO₃ ^2‑，HCO₃ ^‑，或CO₃ ^2‑与HCO₃ ^‑的结合物；2)包含具有通式(II)的N‑单羟丙基‑碳酸铵化合物和具有通式(II)的N,N'‑二(羟丙基)‑碳酸铵化合物的第二种化合物混合物(M2)：(RN⁺H₃)(N⁺H₄)CO₃ ^2‑(II)，或(RN⁺H₃)₂CO₃ ^2‑(III)，式中，R为羟丙基；通式(II)的化合物与通式(III)的化合物的摩尔比是1:0至1:1.0。发泡剂适合用于制备聚氨酯喷涂泡沫体材料。Secondary and alkanolamine basic blowing agents and their use in the preparation of polyurethane spray foam materials. Disclosed is a polyurethane alkaline foaming agent comprising a secondary amine salt and a propanolamine salt, the pH value of the alkaline foaming agent is between 8.5-9.5, and the foaming agent comprises: 1) comprising the following general formula: The first compound mixture (M1) of the organic secondary amine salt compounds of the formula (I): A ^- [B ⁺ ] _p (I), wherein B ⁺ is a cation of a +1-valent organic secondary amine B, A ^- Is: CO ₃ ^2- , HCO _3- ^, or the combination of CO ₃ ^2- and HCO _3- ; 2) comprising a N ^- monohydroxypropyl-ammonium carbonate compound having the general formula (II) and a compound having the general formula (II) ) of the N,N'-bis(hydroxypropyl)-ammonium carbonate compound of the second compound mixture (M2): (RN ⁺ H ₃ ) (N ⁺ H ₄ )CO ₃ ^2- (II), or (RN + H 3 ) ⁺ H ₃ ) ₂ CO ₃ ^2- (III), in the formula, R is hydroxypropyl; the molar ratio of the compound of the general formula (II) to the compound of the general formula (III) is 1:0 to 1:1.0. Blowing agents are suitable for use in the preparation of polyurethane spray foam materials.

Description

Secondary and alcohol amine alkaline 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 with donor anions and organic secondary amines as catalytic groups and solubilizing groups in the preparation of polyurethane spray foam materials. More particularly, it relates to secondary amine/alcohol amine alkaline blowing agents and their use for making polyurethane spray 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 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 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, because of 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 uniformly foamed, the distribution of cells in polyurethane foam is relatively uniform,and the size of the 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 an alkaline alcohol amine blowing agent comprising a secondary amine salt and a propanol amine 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 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) 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.

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, propylene oxide is added to allow the reaction mixture to react [ then, optionally, a portion of water and unreacted propylene oxide are 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 propylene 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 0.3 to 1:1, more preferably from 0.5 to 0.8:1, more preferably from 0.6 to 0.7: 1.

Preferably, in the compounds of the 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 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 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 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 (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) 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 (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. under heating (e.g. at a temperature of 40-80 ℃ C.) orCO evolution with addition of acid (mineral or organic)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%, 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 organic secondary amine salt compound or the organic secondary amine salt compound mixture for (preparing) foaming materials such as polyurethane spray foaming 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.

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 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 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 7.9, 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 7.8, 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 7.8, 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 7.9, and the decomposition temperature is 42-70 ℃.

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 (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.

By infrared spectroscopic analysis, the N-hydroxypropylated 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 propylene oxide had a stretching vibration single peak 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 ofThe water of (2).

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 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 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 204.6 microns. The size of the foam holes is uniform.

Example 2

A basic blowing agent (composed of 3.5 parts by weight of compound 2 prepared in preparation example 2 above as blowing agent and 4.5 parts by weight of compound 5 prepared in preparation example 5 above as blowing agent, pH 8.7), 30 parts by weight of polyether polyol 4110 (prepared by Shandong)Manufactured by Binshi chemical group of Binzhou city, province), 20 parts by weight of polyester polyol (manufactured by Shandong Lanxindong Daihang 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 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 to obtain a polyurethane foam material after being stirred uniformly. 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 40Kg/m³The compressive strength was about 160 KPa.

Example 3

A basic blowing agent (consisting of 4.0 parts by weight of compound 3 prepared in the above preparation 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, pH 8.7), 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 air chemical Co., Ltd., USA), 12.5 parts by weight of flame retardant TCPP (manufactured by Yak chemical Co., 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 foamed composition, to which 83 parts of isocyanate MDI (PM200, Tantanhua chemical Co., Ltd.) was added, 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 40Kg/m³The compressive strength was about 163 KPa.

Example 4

A basic blowing agent (3.0 parts by weight of the above as a blowing agent)Preparation example 4 and 4.5 parts by weight of compound 3 prepared in preparation example 6 above as a blowing agent, with a pH of 8.8, 30 parts by weight of polyether polyol 4110 (manufactured by Binzhi 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 (manufactured by American air chemical Co., Ltd.), 1 part by weight of potassium acetate and 6 parts by weight of HCFC-141b were mixed uniformly to obtain a transparent foamed 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 40Kg/m³The compressive strength was about 166 KPa.

Claims

1. A kind of basic alkanolamine foaming agent comprising secondary amine salt and propanolamine salt, the pH value of this basic foaming agent is between 8.5-9.5, and this foaming agent comprises:

1) A first compound mixture (M1) comprising organic secondary amine salt compounds having the following general formula (I):

A ^- [B ⁺ ] _p (I)

Wherein, B ⁺ is the cation of +1-valent organic secondary amine B, A ^- is: CO ₃ ^2- , HCO ₃ ^- , or the combination of CO ₃ ^2- and HCO ₃ ^- ; p in A ^- is HCO ₃ ^- is 1 in the case of , and p is 2 in the case of A ^- being CO ₃ ^2- ;

2) A second compound mixture comprising an N-monohydroxypropyl-ammonium carbonate compound of general formula (II) and an N,N'-bis(hydroxypropyl)-ammonium carbonate compound of general formula (III) ( M2),

(RN ⁺ _H3 )( ^N ⁺ H4) _CO32- (II), or ( ^RN ⁺ _H3 ₎ _2CO32- ( _III ),

In the formula, R is HO-CH ₂ -CH(CH ₃ )- or HO-CH(CH ₃ )-CH ₂ -;

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

2. The blowing agent according to claim 1, wherein the first compound mixture (M1) is prepared by reacting secondary organic amines B with _CO2 in the presence of water.

3. The blowing agent according to claim 1 or 2, wherein the second compound mixture (M2) is prepared by the following method: with or without addition of ammonia, according to ammonium carbonate and/or carbamic acid The molar ratio of ammonium to propylene oxide is 1:1 to 5.5, and propylene oxide is added to a slurry or saturated solution of ammonium carbonate and/or ammonium carbamate and water to allow the reaction mixture to react to obtain an aqueous Organic alcohol amine mixture, ie the second compound mixture (M2).

4. The blowing agent according to claim 3, the pH of the second compound mixture (M2) is 7.5-10.

5. The blowing agent according to claim 3, the pH of the second compound mixture (M2) is 8-9.7.

6. The blowing agent according to claim 3, the pH of the second compound mixture (M2) is 8.3-9.6.

7. The blowing agent according to claim 3, the pH of the second compound mixture (M2) is 8.5-9.5.

8. The blowing agent according to claim 3, the pH of the second compound mixture (M2) is 9.

9. The blowing agent according to claim 1 or 2, wherein the weight ratio of the first compound mixture (M1) to the second compound mixture (M2) is 0.3-1:1.

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

11. The blowing agent according to claim 1 or 2, wherein, in the compound of the general formula (I), 50-100% of the amine groups in the organic secondary amine compound B are neutralized by the anion A- ^; and/ or

The water content of each of the first compound mixture (M1) or the second compound mixture (M2) is independently 2 to 40 wt%.

12. The blowing agent according to claim 11, wherein, in the compound of general formula (I), 65-100% of the amine groups in the organic secondary amine B are neutralized by anion A- ^, the first compound mixture The water content of each of (M1) or the second compound mixture (M2) is independently 5 to 35 wt%.

13. The blowing agent according to claim 11, wherein, in the compound of general formula (I), 75-100% of the amine groups in the secondary organic amine B are neutralized by the anion A- ^, the first compound mixture The water content of each of (M1) or the second compound mixture (M2) is independently 10-30 wt%.

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

15. The blowing agent according to claim 1 or 2, wherein the pH of the first compound mixture (M1) is 7.0-8.8; and/or

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

16. The blowing agent according to claim 15, wherein the pH of the first compound mixture (Ml) is 7.3-8.6; 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 pH of the first compound mixture (Ml) is 7.5-8.5; and/or the pH of the second compound mixture (M2) is 8.8-9.3.

18. The blowing agent of claim 1 or 2, wherein the organic secondary amine B is one or more selected from the group consisting of di( _C1 - _C4 hydrocarbyl)amines.

19. The foaming agent according to claim 18, wherein the organic secondary amine B is selected from dimethylamine, diethylamine, dipropylamine, dibutylamine, methylethylamine, methylpropylamine One or more of amine, ethylpropylamine, methylbutylamine, ethylbutylamine, or propylbutylamine.

20. A polyurethane foaming composition comprising: 0.5-80% by weight of the foaming agent according to any one of claims 1-19; 0-50% by weight of a physical foaming agent; 0-5 wt% water, and 20.0-99.5 wt% polymer polyol; wherein the weight percentages are based on the total weight of the polyurethane foam composition.

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

22. The polyurethane foam composition of claim 20, comprising: 4-60 wt% of the blowing agent according to any one of claims 1-19; 40-96 wt% of a polymer A polyol, wherein the weight percent is based on the total weight of the polyurethane foam composition.

23. The polyurethane foam composition of claim 20, comprising: 6-40 wt% of the blowing agent according to any one of claims 1-19; 60-94 wt% of a polymer A polyol, wherein the weight percent is based on the total weight of the polyurethane foam composition.

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

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

26. The polyurethane foam composition of claim 20, wherein the polymer polyol is selected from the group consisting of: polyether polyol, polyester polyol, polyether-polyester polyol, polycarbonate diol, polycarbonate Ester-polyester polyol, polycarbonate-polyether polyol, polybutadiene polyol, or polysiloxane polyol, and the average functionality of the polymer polyol is 2-16; and/or

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

27. The polyurethane foam composition of claim 26, wherein the polymer polyol has an average functionality of 2.5-10.

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

29. Use of a blowing agent according to any one of claims 1-19 in a polyurethane spray foam material.