CN109422910B

CN109422910B - Blowing agents comprising orthoformate and carbonate alkanolamine salts and use in polyurethane continuous panel foam materials

Info

Publication number: CN109422910B
Application number: CN201710736193.0A
Authority: CN
Inventors: 毕戈华; 毕玉遂
Original assignee: Butian New Material Technology Co ltd; Shandong University of Technology
Current assignee: Butian New Material Technology Co ltd; Shandong University of Technology
Priority date: 2017-08-24
Filing date: 2017-08-24
Publication date: 2021-04-13
Anticipated expiration: 2037-08-24
Also published as: CN109422910A

Abstract

Disclosed is a polyurethane blowing agent comprising a carbinolamine orthoformate salt and a carbinolamine carbonate salt, the blowing agent comprising: 1) a first mixture of compounds (M1) comprising a family of orthomethanolic alkanolamine compounds having the following general formula (I): a. the^‑[B⁺]_p(I) Wherein B is⁺Is a cation of an organic alcohol amine B, A^‑Is orthoformate; 2) a second mixture of compounds (M2) comprising a N-monohydroxypropyl/monohydroxyethyl-ammonium carbonate compound having the general formula (II) and a N, N' -bis (hydroxypropyl/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 a combination of hydroxypropyl and hydroxyethyl; the molar ratio of monoalcohol amine compound of formula (II) to dialcohol amine compound of formula (III) is from 1:0 to 1: 2.5. The blowing agent is suitable for preparing polyurethane continuous plate foam materials.

Description

Blowing agents comprising orthoformate and carbonate alkanolamine salts and use in polyurethane continuous panel foam materials

Technical Field

The invention relates to a carbinolamine orthoformate salt compound with anion as CO2 donor, a preparation method thereof and an application as a foaming agent, in particular to a novel organic ammonium salt compound with anion as CO2 donor and organic alcohol amine as a catalytic group and a solubilizing group, a preparation method thereof and an application in preparing polyurethane continuous plate foam material. The invention relates to blowing agents containing orthoformate and carbonate alkanolamine salts and their use for (producing) polyurethane continuous panel 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 CO₂Gas (es)And its poor solubility in the raw materials MDI and polyester polyols and/or polyether polyols, so that CO is not readily available₂The 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 having an alcohol amine group as solubilising group and their use in foam materials such as polyurethane continuous panel 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 CO₂Gases, evenWhen foaming is carried out at a relatively low temperature, the following is referred to 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, the foaming agent can be uniformly dispersed in the foaming composition so as to be foamed uniformly, the distribution of cells in the polyurethane foam is uniform, and the sizes of the cells are uniform. In addition, the first compound mixture (M1) according to the invention contains an alcohol amine, and the first compound mixture (M1) which is a blowing agent decomposes to release CO₂The decomposition products produced thereafter are alcohol amine compounds which are suitable for use as polyurethane catalysts in materials. Accordingly, the present invention has been accomplished based on the above two aspects.

In the present application, "as CO₂The anion of the donor "means that it can decompose under heating or during foaming to release CO₂The anion of (4). In this application, "hydroxypropyl/hydroxyethyl" denotes a combination or mixed group of hydroxypropyl and hydroxyethyl groups.

According to a first embodiment of the present invention, there is provided a blowing agent comprising an alkanolamine salt, more specifically a blowing agent comprising a carbinolamine orthoformate salt and a carbinolamine carbonate salt, for use in polyurethane continuous panel foam materials. The foaming agent comprises:

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

A^-B⁺ (I)

wherein A is^-Is orthoformate radical

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

2) the second compound mixture (M2) comprising the N-monohydroxypropyl-ammonium carbonate compound and/or the N-monohydroxyethyl-ammonium carbonate compound as the monoalcohol amine compound having the general formula (II) and the N, N ' -bis (hydroxypropyl) -ammonium carbonate compound and/or the N, N ' -bis (hydroxyethyl) -ammonium carbonate compound as the dialcohol amine compound having the general formula (III), i.e., the second compound mixture (M2) comprising the N-monohydroxypropyl/monohydroxyethyl-ammonium carbonate compound having the general formula (II) and the N, N ' -bis (hydroxypropyl/hydroxyethyl) -ammonium carbonate compound having the general formula (III), is one of the alkanolamine salt compound mixtures,

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

Wherein R is hydroxypropyl (i.e., HO-CH)₂-CH₂(CH₃) -or HO-CH₂(CH₃)-CH₂-) in combination with 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.

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

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

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

Generally, the second compound mixture (M2) was prepared by the following method: to a slurry (i.e., not completely dissolved) or saturated solution formed from ammonium carbonate and/or ammonium carbamate and water, a propylene oxide/ethylene oxide mixture is added, with or without addition of aqueous ammonia, in a molar ratio of ammonium carbonate and/or ammonium carbamate to the two epoxides propylene oxide/ethylene oxide of 1:1-5.5 (preferably 1:1.3-5) to allow the reaction mixture to react [ then a portion of the water and unreacted propylene oxide and ethylene oxide are removed from the resulting reaction mixture by vacuum ], to obtain an aqueous organic alcohol amine mixture (typically, having a pH of 7.5-10, preferably a pH of 8-9.7, preferably a pH of 8.3-9.6, more preferably a pH of 8.5-9.5, e.g., a pH of 9), i.e., a second compound mixture (M2). In addition, the two epoxides propylene oxide/ethylene oxide are used in a molar ratio of: 0.3-3:1, preferably 0.5-2:1, more preferably 0.8-1.2: 1.

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 formula (I) or in the first mixture of compounds (M1), 50 to 100% of the amine groups in the carbinolamine orthoformate 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 alcohol amine B is selected from one or more of the following: c₂-C₁₂Alcamines; preferably, the organic alcohol amine B is one or more selected from monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutanolamine, dibutanolamine, or tributanolamine.

Preferably, in the above-mentioned second compound mixture (M2) (i.e. the aqueous organic alcohol amine mixture), the sum of the weight of both the compound of formula (II) and the compound of formula (III) represents 56 to 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) a polyurethane continuous panel 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-hydroxypropyl and N-hydroxyethyl groups as solubilizing groups, 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 decomposition products (i.e. the alcohol amine compounds) produced thereafter still contain hydroxyl and amino groups and can be used as suchChain extenders or crosslinkers 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 N-hydroxypropylated/hydroxyethylated ammonium carbonate salt compounds, 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/monohydroxyethyl-ammonium carbonate to N, N' -bis (hydroxypropyl/hydroxypropyl) -ammonium carbonate compound in the reaction product (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 continuous-slab foam materials or polyurethane refrigerator-freezers and are used in the customary amounts.

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

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

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

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

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

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

The present invention provides a process for the preparation of polyurethane continuous panel foam materials which comprises incorporating in the polyurethane preparation from 1 to 10%, preferably from 2 to 5% of the above-described orthocarbinolamine salt compound or mixture of orthocarbinolamine salt compounds, based on the total weight of the polyurethane raw materials (including isocyanate and polyol).

The invention also provides the use of the above-described orthoformate alkanolamine salt compound or orthoformate alkanolamine salt compound mixture for (preparing) foamed materials such as polyurethane continuous sheet foam materials.

Advantageous effects or advantages of the invention

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

2. The compounds of the general formula (I), (II) or (III) according to the invention, which have solubilizing groups, i.e. alcohol amine groups, can be 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. Especially at higher temperatures (e.g. 40-70 deg.C)) Still have good dimensional stability after being left for a long time, e.g. (10 days).

4. The compounds of the general formula (I) according to the invention decompose to release CO₂The decomposition products which are then produced, namely the alcohol amine compounds, are suitable as catalysts, the compounds of the general formula (I) according to the invention acting both as "bubble points" and 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 continuous plate foam materials.

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

Drawings

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

Detailed Description

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

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

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

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

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

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

Preparation example 1

Adding 15kg of triethyl orthoformate, 20kg of diethanolamine and 10kg of water into a reactor, starting stirring, controlling the pressure to be not higher than 0.1MPa, slowly heating while continuously stirring, and controlling the temperature to react for 10 hours when the temperature is raised to 80 ℃. Cooling to 50 deg.C after reaction, controlling vacuum degree below 600 mm Hg, removing ethanol at 50 deg.C under reduced pressure, cooling to 40 deg.C below, and discharging to obtain compound 1 with pH not less than 7.5 and decomposition temperature of 45-70 deg.C.

Preparation example 2

Adding 15kg of triethyl orthoformate, 13kg of monoethanolamine and 7.0kg of water into a reactor, starting stirring, slowly raising the temperature under continuous stirring, and controlling the temperature below 100 ℃ to react for 8 hours. And after the reaction is finished, cooling, controlling the vacuum degree to be below 600 mm Hg, decompressing and removing ethanol at the temperature of below 50 ℃, removing vacuum, cooling to the temperature of below 50 ℃, and discharging a product to obtain a compound 2 in which two ester groups of the triethyl orthoformate are hydrolyzed. The pH value is more than or equal to 7.5, and the decomposition temperature is 45-70 ℃.

Preparation example 3

Adding 20kg of tripropylorthoformate, 11kg of diethanolamine and 10kg of ammonia water into a reactor, starting stirring, slowly heating while continuously stirring, and reacting for 8 hours at the temperature of not more than 100 ℃. And after the reaction is finished, cooling, controlling the vacuum degree to be below 600 mm Hg, decompressing and removing unnecessary water at the temperature of below 50 ℃, removing the vacuum, cooling to below 40 ℃, and discharging the product to obtain the compound 3. The pH value is more than or equal to 7.5, and the decomposition temperature is 45-70 ℃.

Preparation example 4

Adding 15kg of trimethyl orthoformate, 2.0kg of ethylene glycol, 10kg of water and 10.0kg of ethanolamine into a reactor, starting stirring, controlling the pressure to be not higher than 0.1MPa, slowly heating while continuously stirring, and controlling the temperature to react for 5 hours when the temperature is raised to 70 ℃. Cooling after the reaction is finished, controlling the vacuum degree to be below 600 mm Hg, decompressing and dealcoholizing at the temperature of below 50 ℃, removing vacuum, cooling to the temperature of below 40 ℃, and discharging a product to obtain a compound 4, wherein the pH is more than or equal to 7.5, and the decomposition temperature is 45-70 ℃.

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 (the ammonium carbonate is not completely dissolved), then 1.2kg of propylene oxide and 0.8kg of ethylene oxide are added, stirring and cooling are carried out while 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 reaction for 14 hours. After the reaction is completed, the temperature is slowly reduced to below 50 ℃, a part of water and unreacted propylene oxide and ethylene oxide are slowly removed under the vacuum degree of about 600 mm Hg, then the vacuum is released, the temperature is reduced to below 40 ℃, and then the reactant is discharged, so that a hydrous alkanolamine carbonate salt compound mixture (compound 5 for short) is obtained, and the hydrous alkanolamine carbonate salt compound mixture belongs to one of second compound mixtures M2. Viscosity was approximately 420 centipoise, pH 9.1, 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-monohydroxypropyl/monohydroxyethyl-ammonium carbonate to N, N' -bis (hydroxypropyl/hydroxyethyl) -ammonium carbonate compound in the reaction product (i.e., mixture M2) was about 1: 0.25.

By infrared spectroscopic analysis, the N-hydroxypropylated/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 propylene oxide/ethylene oxide had a stretching vibration single peak of N-H as a secondary amine salt in the range of 2920-^-1Flexural vibration singlet for a range of N-H secondary amine salts, and at 3202-^-1A range of strong and broad hydrogen-bonded OH stretching vibration peaks, which indicate that the N-hydroxypropylated/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-hydroxypropylated/hydroxyethylated ammonium carbonate salt compounds of the invention comprise one or more alkanolamine carbonate compounds and generally contain a small amount of water.

Preparation example 6

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

The application example is as follows:

example 1

3 parts by weight of Compound 1 prepared in preparation example 1 above as a blowing agent and 4.5 parts by weight of Compound 5 prepared in preparation example 5 above as a blowing agent, 40 parts by weight of polyether polyol 4110 (manufactured by Binshi group of Binzhou, Shandong province), 10 parts by weight of polyester polyol (manufactured by Shandong Lanxindong Daihong chemical Co., Ltd.), 1 part by weight of polyester polyolThe foam stabilizer DC3201 (manufactured by American air chemical company), 12.5 parts by weight of flame retardant TCPP (manufactured by Jiangsu Jack chemical company, Ltd.), 1 part by weight of N, N-dimethylcyclohexylamine (manufactured by American air chemical company, USA), 1.5 parts by weight of potassium octoate and 6 parts by weight of HCFC-141b are uniformly mixed to obtain a transparent foaming composition, then 110 parts of isocyanate MDI (PM200, Tantawawa chemical group, Ltd.) is added into the transparent foaming composition, and the transparent foaming composition is foamed after being uniformly stirred to obtain the polyurethane foam material. The foaming process is stable and continuous, and no explosive foaming moment occurs. The material is used as a polyurethane continuous panel 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 37Kg/m³The compressive strength was about 157 KPa.

The foam product of example 1 has good thermal insulation properties and is also able to meet the various performance requirements in the refrigerator and freezer field.

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 215.8 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 4.5 parts by weight of compound 5 prepared in the above preparation example 5 as a blowing agent, 40 parts by weight of polyether polyol 4110 (manufactured by hamlet chemical group, Binzhou, Shandong), 10 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 PC-41, 1 part by weight of potassium octylate and 6 parts by weight of HCFC-141b were mixed uniformly to obtain a transparent foamed composition, and then 110 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 continuous panel foam material. The size change rate or the shrinkage rate of the obtained polyurethane foam material is less than or equal to 1 percent (according to the Chinese national standard GB/T8811-2008 when placed)In the middle of 5 months). In addition, the foam density was about 36Kg/m³The compressive strength was about 150 KPa.

Example 3

3 parts by weight of the compound 3 prepared in preparation example 3 above as a blowing agent and 4.0 parts by weight of the compound 5 prepared in preparation example 5 above as a blowing agent, 40 parts by weight of polyether polyol 4110 (manufactured by hamlet chemical group, Binzhou, Shandong), 10 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 PC-41 (manufactured by American air chemical Co., Ltd.), 1 part by weight of potassium octylate and 6 parts by weight of HCFC-141b were mixed uniformly to obtain a transparent foaming composition, then 112 parts of isocyanate MDI (PM200, Nicotiana Wanhua 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 continuous panel 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 39Kg/m³The compressive strength was about 160 KPa.

Example 4

3 parts by weight of the compound 4 prepared in preparation example 4 above as a blowing agent and 4.5 parts by weight of the compound 6 prepared in preparation example 6 above as a blowing agent, 40 parts by weight of polyether polyol 4110 (manufactured by hamlet chemical group, Binzhou, Shandong), 10 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 PC-41 (manufactured by American air chemical Co., Ltd.), 1 part by weight of potassium octylate and 6 parts by weight of HCFC-141b were mixed uniformly to obtain a transparent foaming composition, then 112 parts of isocyanate MDI (PM200, Nicotiana Wanhua 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 continuous panel foam material. What is needed isThe size change rate or the shrinkage rate 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 37Kg/m³The compressive strength was about 155 KPa.

Claims

1. A blowing agent comprising a carbinolamine orthoformate and a carbinolamine carbonate salt, the blowing agent comprising:

A^- B⁺ (I)

wherein A is^-Is orthoformate radical

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

2) a second compound mixture (M2) comprising an N-monohydroxypropyl/monohydroxyethyl-ammonium carbonate compound having the general formula (II) as a monoalcohol amine compound and an N, N' -bis (hydroxypropyl/hydroxyethyl) -ammonium carbonate compound having the general formula (III) as a dialcohol amine compound,

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

Wherein R is a combination of hydroxypropyl and hydroxyethyl;

the molar ratio of the compound of formula (II) to the compound of formula (III) is from 1:0.3 to 1: 2.5.

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

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

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

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

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

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

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

9. The blowing agent according to any of claims 1 to 3, wherein the weight ratio of the first compound mixture (M1) to the second compound mixture (M2) is from 0.2 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 according to any of claims 1 to 3, wherein, in the compound of the general formula (I), from 50 to 100% of the amine groups of the organic alcohol amine B are replaced by anions A^-Neutralizing; and/or

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

14. The blowing agent of claim 13 wherein in the compound of formula (I) 65 to 100% of the amine groups in the organic alcohol amine B are replaced by anion a^-The water content of each of the first compound mixture (M1) or the second compound mixture (M2) is independently 5 to 35% by weight.

15. The blowing agent of claim 13 wherein in the compound of formula (I) 75 to 100% of the amine groups in the organic alcohol amine B are replaced by anion a^-The water content of each of the first compound mixture (M1) or the second compound mixture (M2) is independently 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 organic alcohol amine B are replaced by an anion a^-The water content of each of the first compound mixture (M1) or the second compound mixture (M2) is independently 15 to 25 wt%.

17. The blowing agent according to any of claims 1 to 3, wherein the first compound mixture (M1) has a pH of from 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 2 wherein the organic alcohol amine B is selected from one or more of the following: c₂-C₁₂Alcamines; and/or

The orthoformate compound is selected from one or more of the following compounds: tri (C1-C8) hydrocarbyl orthoformates.

21. The blowing agent of claim 20 wherein the organic alcohol amine B is one or more selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutanolamine, dibutanolamine, and tributanolamine.

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

24. The polyurethane foaming composition of claim 22, the composition comprising: 4 to 60 wt% of the blowing agent of any of claims 1 to 21; 40 to 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, the composition comprising: 6-40 wt% of the blowing agent of any of claims 1-21; 60 to 94 wt% 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, the composition comprising: 70-88 wt% of a polymer polyol.

27. The polyurethane foaming composition of claim 22, the composition 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 a polyurethane continuous panel foam material.