CN107253919B

CN107253919B - Hydrazinolamine salt compound and preparation method and application thereof

Info

Publication number: CN107253919B
Application number: CN201710330621.XA
Authority: CN
Inventors: 毕戈华; 毕玉遂
Original assignee: Sky New Material Technology Co Ltd; Shandong University of Technology
Current assignee: The sky new material technology Co. Ltd.
Priority date: 2017-05-11
Filing date: 2017-05-11
Publication date: 2020-03-10
Anticipated expiration: 2037-05-11
Also published as: CN107253919A

Abstract

A hydrazinosolamine salt compound having the following general formula (I): a. the^n‑[B^m+]_p(I) In the formula, A^n‑Is as CO₂An anion of the donor having a valence of-n, wherein n ═ 1,2, or 3; b is^m+Is or comprises: ammonium ion, hydrazine ion and/or organic amine B cation; wherein m is 1-10;

and wherein A^n‑Is selected from one or more of the following anions: (a) carbamate or carbazate; (b) a carbonate group; (c) formate; (d) bicarbonate radical; (e) an organic monocarbonate radical; (f) an organic polycarbamate, (g) orthoformate; or (h) an organic polycarbonic acid radical, A^n‑And B^m+Comprises hydrazine and/or comprises a hydrazine group or a substituted hydrazine group; the compounds of the general formula (I) have at least one hydroxyalkyl group which is linked to the N atom, i.e.has an alcohol amine residue. They can be used as polyurethane blowing agents, most of which can be used as polystyrene blowing agents or polyvinyl chloride blowing agents.

Description

Hydrazinolamine salt compound and preparation method and application thereof

Technical Field

The invention relates to an alcohol amine salt compound with hydrazine group, a preparation method thereof and application of the alcohol amine salt compound as a foaming agent in foaming materials such as polyurethane foam or PVC foaming materials or polystyrene foaming 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 of 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 in 2009 and 2010 in 2013, eliminates the consumption of 20% in 2015 and promises to completely forbid production and use in 2025, the developed countries such as Europe and America currently use pentafluoropropane (HFC-245fa) and pentafluorobutane (HFC-365) which are the third generation foaming agents, and the GWP (potential for greenhouse effect) of the second generation of foaming agents and the third generation of foaming agents is high, so the European and the American countries forbid the use of the third generation of foaming agents before 2019. Therefore, the United states Honeywell company develops a fourth generation physical foaming agent, namely chlorotrifluoropropene (LBA), the ODP (potential value for damaging the ozone layer) of the product is zero, is relatively more environment-friendly than the third generation, but has GWP more than 1, and the product is expensive. 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 agent (e.g., water) of the prior art cannot be dispersed into the foaming composition at a molecular level, resulting in uneven distribution of cells 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 CO₂Anion of donor and having hydroxyalkyl or hydroxyalkylalkoxy group as solubilising group or C₂-C₁₄Novel organic amine salts of hydrocarbon radicals (such as 2-chloroethyl, 3-chloropropyl or phenethyl) as solubilising groups and their use in foamed materials such as polyurethane foams or PVC foamed materials or polystyrene foamed materials.

The novel organic amine salt compound is suitable for being used as a foaming agent. It generates CO during foaming₂A gas. The inventors of the present application have surprisingly found that as CO₂The anion of the donor having the valence of-n readily decomposes at elevated temperature to produce CO₂The gas, even when expanded at relatively low temperatures, is described below as CO₂The donor anion having a valence of-n can be activated by the NCO groups contained in isocyanate monomers such as MDI and TDI, releasing CO rapidly₂A gas. In addition, due to the solubilizing group, the foaming agent can be fully dissolved in foaming raw materials (such as polyether polyol or polyester polyol) or has good intersolubility with the foaming raw materials, 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 blowing agent compounds of the present invention contain hydroxyl and/or amino groups and decompose to release CO at the blowing agent₂Is then producedThe decomposition products of (a) still contain hydroxyl and/or amino groups, which are suitable as chain extenders or crosslinkers for the formation of polymers when the molecular weight of the decomposition products is relatively low, and which can replace a part of the polyester polyols or polyether polyols in the foaming composition when the molecular weight of the decomposition products is relatively high, for example a number average molecular weight of 100-3000, for example with suitably reduced amounts of polyester polyols or polyether polyols on the basis of the foaming compositions of the prior art. The person skilled in the art is able to calculate the amount of blowing agent according to the invention and the amount of polyester polyol and/or polyether polyol according to the average hydroxyl value of the blowing agent according to the invention and the average hydroxyl value of the polyester polyol or polyether polyol. Particularly, in the process of foaming by using the polyol and the polyisocyanate, if the organic amine salt compound is used as a foaming agent, the organic amine salt compound is used as a foaming point, a chain extending point and/or a crosslinking point, the mechanical strength and the mechanical strength of cells are obviously enhanced, and the obtained polyurethane foam has good dimensional stability. Accordingly, the present invention has been accomplished based on the above three aspects.

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

According to a first embodiment of the present invention, there is provided a hydrazinosolamine salt compound having the following general formula (I):

A^n-[B^m+]_p(I)

in the formula, A^n-Is as CO₂An anion of the donor having a valence of-n, wherein n ═ 1,2, or 3;

B^m+is or comprises: +1 valent ammonium ion and +1 valent hydrazine ion (H)₃ ⁺N-NH₂) And + 2-valent hydrazine ion (H)₃ ⁺N-NH₃ ⁺) And/or has m-⁺NR³R⁴H group and/or-⁺NR³One or more organic amine B cations of the H-group;

and, A^n-And B^m+Comprises hydrazine and/or comprises a hydrazine group or a substituted hydrazine group;

wherein m is 1-10, preferably m is 1-5; more preferably m is 1-2;

and

wherein A is^n-Is selected from one or more of the following anions:

(a) carbamate or carbazate: r¹R²N-COO^-Or R¹R²N-NH-COO^-；

(b) Carbonate radical: CO2₃ ^2-；

(c) Formate radical: HCOO^-；

(d) Bicarbonate radical: HO-COO^-；

(e) Organic monocarbonate radical: r^aO-COO^-Wherein R is^aIs C optionally substituted by hydroxy or amino or halogen₁-C₂₆Hydrocarbyl (preferably C)₁-C₁₀Hydrocarbyl, more preferably C₁-C₃Hydrocarbyl radical), or C₁-C₂₆Acyl (preferably C)₁-C₁₀Acyl, more preferably C₁-C₂Acyl);

(f) organic polycarbamate:^-OOC-N(R¹)-R^b-N(R²)-COO^-or R is^b'(-N(R¹)-COO^-)₃，

In the formula, R^bIs C optionally substituted by hydroxy or amino or halogen₁-C₁₆Alkylene (preferably C)₂-C₁₀Alkylene, more preferably C₂-C₆Alkylene) group, R^b' is trivalent C optionally substituted by hydroxy or amino or halogen₂-C₂₀Hydrocarbyl (more preferably trivalent C)₃-C₁₅Alkylene groups);

(g)

or

Wherein R' is H, C optionally substituted by hydroxy or amino or halogen₁-C₂₆Hydrocarbyl (preferably C)₁-C₁₀Hydrocarbyl, more preferably C₁-C₃Hydrocarbyl radical), or C₁-C₂₆Acyl (preferably C)₁-C₁₀Acyl, more preferably C₁-C₇Acyl); or

(h) Organic polycarbonates:^-OOC-OR^cO-COO^-，

in the formula, R^cIs C optionally substituted by hydroxy or amino or halogen₁-C₂₆Alkylene (preferably C)₂-C₁₀Alkylene, more preferably C₂-C₆Alkylene groups);

wherein R is¹,R²,R³Or R⁴Independently selected from: h, R, C optionally substituted by hydroxy or amino or halogen₁-C₇Aliphatic hydrocarbon group (preferably C)₁-C₄Alkyl), C optionally substituted by hydroxy or amino or halogen₃-C₇Cycloaliphatic hydrocarbon radicals (e.g. cyclobutyl or cyclohexyl), or, C optionally substituted by hydroxy or amino groups or by halogen₆-C₁₀An aromatic hydrocarbon group (preferably phenyl or methylphenyl);

the precondition is that: in the compounds of the above general formula (I) R¹,R²,R³Or R⁴At least one is an R group attached to the N atom, or the compound of formula (I) has at least one R group bonded to the N;

wherein the R group is selected from one or more of the following groups:

(1a)H[OCH(R_1a)CH(R_2a)]_q-, e.g. H (OCH)₂CH₂)_q-、H(OCH₂CH(CH₃))_q-、 H(OCH(CH₃)CH₂)_q-、H(OCH₂CH(C₆H₅))_q-、H(OCH(C₆H₅)CH₂)_q-、H(OCH₂CH(CH₂Cl))_q-、 H(OCH(CH₂Cl)CH₂)_q-or H (OCH)₂CH(CBr₃))_q-；

(2a)H[OCH(R_1a)CH(R_2a)CH(R_3a)]_q-; or

(3a)H[OCH(R_1a)CH(R_2a)CH(R_3a)CH(R_4a)]_q-；

Wherein the value or average value of q is q ═ 1 to 3, preferably q ═ 1 to 2.5, more preferably q ═ 1.5 to 2.0, calculated as the average value of q; r_1a、R_2a、R_3aOr R_4aEach independently selected from: h, C optionally substituted by hydroxy or amino or halogen₁-C₇Aliphatic hydrocarbon radicals, C optionally substituted by hydroxy or amino groups or halogen₃-C₇Cycloaliphatic hydrocarbon radicals, or, C optionally substituted by hydroxy or amino groups or by halogen₆-C₁₀An aromatic hydrocarbon group.

Preferably, the organic amines B have m to m +3 primary, secondary and/or tertiary amine groups and optionally quaternary ammonium groups.

Preferably, A^n-Is a combination or mixture of two or more of said anions selected from (a) - (h), and/or B^m+Is a combination or mixture of two or more of the above organic amine cations.

Preferably, R¹,R²,R³Or R⁴Independently selected from: h, R, C optionally substituted by hydroxy or amino or halogen₁-C₄Aliphatic hydrocarbon groups, cyclobutyl or cyclohexyl optionally substituted by hydroxy or amino or halogen, or phenyl or methylphenyl optionally substituted by hydroxy or amino or halogen; more preferably, R_1a、R_2a、R_3aOr R_4aEach independently selected from: h, methyl or ethyl optionally substituted with hydroxy or amino or halogen, or propyl or isopropyl optionally substituted with hydroxy or amino or halogen, cyclohexyl optionally substituted with hydroxy or amino or halogen, or phenyl or methylphenyl optionally substituted with hydroxy or amino or halogen.

Preferably, R_1a、R_2a、R_3aOr R_4aEach independently selected from: h, methyl, chloromethyl, bromomethyl, ethyl, cyclohexyl, or phenyl.

Preferably, A^n-Is selected from one or more of the following anions:

(a)R¹R²N-COO^-or R¹R²N-NH-COO^-(ii) a Wherein R is¹And R²Each independently hydrogen, methyl, ethyl, hydroxymethyl, hydroxyethyl or hydroxypropyl;

(b)CO₃ ^2-；

(c)HCOO^-；

(d)HO-COO^-(ii) a Or

(g)

(i.e., HC (OR') O)₂ ^2-) Or is or

(i.e., HCO)₃ ^3-)，

Wherein R' is H, C optionally substituted by hydroxy or amino or halogen₁-C₁₀Hydrocarbyl (more preferably methyl, ethyl, propyl), or C₁-C₁₀Acyl (more preferably formyl, acetyl or propionyl).

Preferably, R¹And R²At least one of which is H, more preferably R¹Is H and R²Is H or an R group.

Preferably, the compound of formula (I) has a water content of 0 to 40 wt.%, preferably 5 to 35 wt.%, more preferably 10 to 30 wt.%, more preferably 15 to 25 wt.%. Preferably, the compounds of formula (I) contain on average 1.5 to 5R groups per molecule.

In general, except that in which A^n-In addition to the compounds of the formula (I) which are formates, the other compounds of the formula (I) have a pH of from 7.5 to 10, preferably from 7.8 to 9.5, more preferably from 8 to 9.

In general, the compounds of the formula (I) have an alkali metal and alkaline earth metal content of from 0 to 200ppm by mass, more preferably less than 100ppm, more preferably less than 10ppm, most preferably less than the detection limit or 0 ppm.

Preferably, the compound or mixture of compounds of the general formula (I) contains from 25 to 95% by weight, preferably from 27 to 90% by weight, preferably from 30 to 85% by weight, preferably from 40 to 80% by weight, more preferably from 45 to 75% by weight, of salts of monoalkanolamines, such as monoethanolamine and/or monopropanolamine, and of dialcohols, such as diethanolamine and/or dipropanolamine, based on the total weight of the compound or mixture of compounds of the general formula (I).

Preferably, in the compound or mixture of compounds of formula (I), the molar ratio of the compound of formula (I) having one R group (e.g. the monoalcohol salt) to the compound of formula (I) having two R groups (e.g. the dialcohol salt) is from 1:0 to 1:2.5, preferably from 1:0.3 to 1:2, preferably from 1:0.5 to 1:1.

Preferably, the compound or mixture of compounds of the general formula (I) contains from 15 to 90% by weight, preferably from 17 to 88% by weight, preferably from 20 to 85% by weight, preferably from 25 to 80% by weight, more preferably from 30 to 70% by weight, of monoalkanolamine (e.g.monoethanolamine and/or monopropanolamine) and dialkanolamine (e.g.diethanolamine and/or dipropanolamine), based on the total weight of the compound or mixture of compounds of the general formula (I).

The invention also provides a process for the preparation of a compound of the general formula (I) above, wherein A^n-An anion of any one or more of (a), (b), (c), (d), (e), (f) or (h), which process comprises reacting a first starting material with a second starting material in a solvent (e.g. water), optionally in the presence of a catalyst, wherein the first starting material is one or more selected from the following compounds:

R¹R²N-COONH₄，R¹R²salts of N-COOH organic amine compounds (M), R¹R²Hydrazine salt of N-COOH, R¹R²N-NH-COONH₄,R¹R²Hydrazonium salt of N-NH-COOH, or R¹R²Salts of organic amines (M) of N-NH-COOH, wherein R¹Or R²Independently selected from: h, C optionally substituted by hydroxy or amino or halogen₁-C₇Aliphatic hydrocarbon group (preferably C)₁-C₄Alkyl), C optionally substituted by hydroxy or amino or halogen₃-C₇Cycloaliphatic hydrocarbon radicals (e.g. cyclobutyl or cyclohexyl), or, C optionally substituted by hydroxy or amino groups or by halogen₆-C₁₀An aromatic hydrocarbon group (preferably phenyl or methylphenyl);

(NH₄)₂CO₃hydrazine carbonate, ammonium carbonate hydrazine, or organic amine carbonate (M) salts;

HCOONH₄hydrazine formate, or an organic amine formate (M) salt;

HO-COONH₄hydrazine hydrogen carbonate, or hydrogen carbonate of an organic amine compound (M);

R^aO-COONH₄，R^ahydrazine salts of O-COOH, or R^aAn organic amine compound (M) salt of O-COOH,

NH₄OOC-N(R¹)-R^b-N(R²)-COONH₄，R^b'(-N(R¹)-COO)₃(NH₄)₃， HOOC-N(R¹)-R^b-N(R²) Salts of organic amines (M) of-COOH, HOOC-N (R)¹)-R^b-N(R²) Hydrazine salt of-COOH, R^b'(-N(R¹)-COOH)₃A hydrazine salt of (A), or R^b'(-N(R¹)-COOH)₃The organic amine compound (M) salt of (2); or

NH₄OOC-OR^cO-COONH₄，HOOC-OR^cHydrazine salts of O-COOH, OR HOOC-OR^cOrganic amine compound (M) salt of O-COOH;

the second starting material is selected from one or more of the following epoxides:

or styrene oxide;

wherein said organic amine compound (M) is an organic amine compound selected from the group consisting of:

C₁-C₂₄alkyl amines;

two (C)₁-C₁₆Hydrocarbyl) amines;

optionally at C₂-C₁₄C substituted by hydroxy on alkylene₂-C₁₄Alkylene diamines;

optionally at C₂-C₁₄C substituted by hydroxy on alkylene₄-C₁₆Polyalkylene polyamines;

c optionally substituted by hydroxy having three primary amine groups₃-C₁₈Organic triamines or C having four primary amino groups optionally substituted by hydroxy₅-C₁₈Organic tetraamines; or

C₂-C₁₀An alcohol-amine compound, an alcohol amine compound,

with the proviso that at least one of the first starting materials comprises hydrazine or contains a hydrazine group.

Preferably, when water is used as the solvent in the reaction, the amount of water is 70 to 250 wt%, preferably 85 to 200 wt%, more preferably 100 to 170 wt%, calculated on the weight of the first raw material.

Preferably, the epoxide is: ethylene oxide, propylene oxide, epichlorohydrin, epibromopropane, butylene oxide, or chlorobutylene oxide or styrene oxide, and mixtures of any two or more thereof.

The invention also provides a process for the preparation of a compound of the general formula (I) above, wherein A^n-Is an anion (g), the process comprising: the orthoformate compounds are hydrolyzed in a solvent, optionally in the presence of a catalyst, and in the presence of an organic amine M belonging to the class of organic alcanolamines or a compound B belonging to the class of organic alcanolamines having at least one of the abovementioned N-R groups, and water; wherein the water is present in an amount sufficient to hydrolyze at least two ester groups of the orthoformate compound, more preferably, in an amount sufficient to hydrolyze three ester groups of the orthoformate compound;

wherein the organic amine compound B is formed by reacting hydrazine and optionally ammonia as starting materials or as an initiator with an epoxide selected from one or more of the following epoxides:

or styrene oxide.

The invention also provides a compound prepared by the preparation method. Preferably, the compound contains 25 to 95 wt%, preferably 27 to 90 wt%, preferably 30 to 85 wt%, preferably 40 to 80 wt%, more preferably 45 to 75 wt% of the salt of a monoalkanolamine (e.g., monoethanolamine and/or monopropanolamine) and the salt of a dialcohol amine (e.g., diethanolamine and/or dipropanolamine), based on the total weight of the compound, or the compound contains 15 to 90 wt%, preferably 17 to 88 wt%, preferably 20 to 85 wt%, preferably 25 to 80 wt%, more preferably 30 to 70 wt% of the monoalkanolamine (e.g., monoethanolamine and/or monopropanolamine) and the dialcohol amine (e.g., diethanolamine and/or dipropanolamine), based on the total weight of the compound.

Preferably, the compound prepared by the above preparation method contains 25 to 95 wt%, preferably 27 to 90 wt%, preferably 30 to 85 wt%, preferably 40 to 80 wt%, more preferably 45 to 75 wt% of the salt of a monoalkanolamine (e.g., monoethanolamine and/or monopropanolamine) and the salt of a dialcohol amine (e.g., diethanolamine and/or dipropanolamine), based on the total weight of the compound, or the compound contains 15 to 90 wt%, preferably 17 to 88 wt%, preferably 20 to 85 wt%, preferably 25 to 80 wt%, more preferably 30 to 70 wt% of the monoalkanolamine (e.g., monoethanolamine and/or monopropanolamine) and the dialcohol amine (e.g., diethanolamine and/or dipropanolamine), based on the total weight of the compound.

The invention provides a foaming agent which comprises or consists of the hydralazine salt compound or the hydralazine salt compound mixture with the general formula (I). Preferably, A^n-Is selected from one or more of the following anions:

(a)R¹R²N-COO^-or R¹R²N-NH-COO^-；(b)CO₃ ^2-(ii) a Or (d) HO-COO^-。

The present invention also provides a foaming agent, wherein it acts as a polyurethane foaming agent, a polystyrene foaming agent or a polyvinyl chloride foaming agent and it comprises the compound prepared by the above preparation method.

The invention also provides the use of hydrazine formate as a polyurethane blowing agent. In this use, the hydrazine formate is in the form of an aqueous solution and contains 0.5 to 15 wt% (preferably 1 to 8 wt%) of an organic amine, the latter including but not limited to: methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine or monoethanolamine.

The present invention also provides a polyurethane foaming composition comprising:

0.01 to 100% by weight of a hydralazine salt compound or a mixture of hydralazine salt compounds of the general formula (I) described above, or a compound prepared by the above preparation method;

0-50 wt% of a physical blowing agent;

0-5% by weight of water, and

0.0 to 99.99 wt% of a polymer polyol; wherein the weight percentages are based on the total weight of the polyurethane foaming composition.

Preferably, the polyurethane foam composition comprises:

0.1 to 80 wt% (more preferably 1 to 70 wt%, more preferably 3 to 60 wt%, more preferably 5 to 50 wt%, more preferably 7 to 40 wt%, such as 10 wt%, 15 wt%) of a hydrazono-alcohol amine salt compound or a mixture of hydrazono-alcohol amine salt compounds having the general formula (I) described above, or a compound prepared by the above preparation method;

0-40 wt% of a physical blowing agent;

0-4% by weight of water, and

20.0 to 99.9 wt% (more preferably 30 to 99 wt%, more preferably 40 to 97 wt%, more preferably 50 to 95 wt%, more preferably 60 to 93 wt%, such as 90 wt% or 85 wt%) of a polymer polyol; wherein the weight percentages are based on the total weight of the polyurethane foaming composition.

Preferably, the polyurethane foaming composition contains a total of 0.5 to 4 wt% water, more preferably 0.8 to 2.5 wt%, more preferably 1 to 2.2 wt% water.

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.

Typically, the foaming composition is transparent or clear; preferably, the rigid polyurethane foam composition is transparent or clear or translucent or milky white but homogeneous, or the flexible polyurethane foam composition is transparent or milky white.

In general, the polyurethane foam composition described above has the following characteristics: 1) comprising an alkanolamine or alcohol amine compound; 2) a transparent or clear or translucent or milky white homogeneous liquid; 3) CO evolution under heating or with addition of organic or inorganic acids stronger than carbonic acid₂(ii) a 4) When the foaming composition is contacted or mixed with the isocyanate or polyisocyanate, the mass formed by mixing changes milky color in 0.2 to 4 seconds (preferably 1 to 2 seconds).

In general, when mixed with polyisocyanates, this leads to milky white color of the material formed by mixing, accompanied by rapid expansion of the volume, but this process is not a real initiation of the foam, after which the material begins to initiate.

The invention also provides a polyurethane foam material, which is formed by mixing the polyurethane foaming composition and polyisocyanate monomer and/or isocyanate-terminated prepolymer and then reacting.

Preferably, when A is^n-When it is (a) carbamate or carbazate, R in the compound of the above general formula (I)¹,R²,R³Or R⁴At least one (e.g. 1 or 2) is an R group attached to the N atom and the compound of formula (I) has at least one (e.g. 1 or 2) R group bonded to the N and at least one (e.g. 1 or 2) hydrazino or substituted hydrazino group; or when A^n-When (B), (c), (d), (e), (f), (g) or (h), the compound of formula (I) comprises an organic amine B having at least one (e.g., 1 or 2) R group bonded to N and at least one (e.g., 1 or 2) hydrazino or substituted hydrazino group.

In the present application, "A^n-And B^m+By at least one comprising hydrazine and/or comprising a hydrazine group or a substituted hydrazine group "is meant that the compound of general formula (I) comprises at least one hydrazine ion and/or comprises at least one hydrazine group or a substituted hydrazine group; more specifically, if A^n-When selected from one or more of (B), (c), (d), (e), (f), (g) or (h), then B^m+Is or comprises: +1 valent hydrazine ion (H)₃ ⁺N-NH₂) And + 2-valent hydrazine ion (H)₃ ⁺N-NH₃ ⁺) And/or having a hydrazine group or a substituted hydrazine group (e.g., the hydrazine group or the substituted hydrazine group corresponds to-⁺NR³R⁴H group and/or-⁺NR³H-group) of one or more organic amines B (i.e. organic amines B having a hydrazine group or a substituted hydrazine group), or if a has a hydrazine group or a substituted hydrazine group^n-Is (a) hydrazinoformate R¹R²N-NH-COO^-When it is, then B^m+Is or comprises: +1 valent ammonium ion and +1 valent hydrazine ion (H)₃ ⁺N-NH₂) And + 2-valent hydrazine ion (H)₃ ⁺N-NH₃ ⁺) And/or has m-⁺NR³R⁴H group and/or-⁺NR³H-group, with or without hydrazine or substituted hydrazine groups.

The present invention also provides an organic amine salt compound having the following general formula (I):

A^n-[B^m+]_p(I)

in the formula, A^n-Is as CO₂An anion of the donor having a valence of-n, wherein n ═ 1 or 2;

wherein m is 1-10, preferably m is 1-5, more preferably m is 1-2;

and

wherein A is^n-Is selected from one or more of the following anions:

(a) carbamate or carbazate: r¹R²N-COO^-Or R¹R²N-NH-COO^-；

(b) Carbonate radical: CO2₃ ^2-；

(c) Formate radical: HCOO^-(ii) a Or

(d) Bicarbonate radical: HO-COO^-；

Wherein R is¹,R²,R³Or R⁴Independently selected from: h, R, C optionally substituted by hydroxy or amino or halogen₁-C₇Aliphatic hydrocarbon group (preferably C)₁-C₄Alkyl, more preferably C₂-C₃Alkyl) (e.g. hydroxyethyl or hydroxypropyl), C optionally substituted by hydroxy or amino or halogen₃-C₇Cycloaliphatic hydrocarbon radicals (e.g. cyclobutyl or cyclohexyl), or, C optionally substituted by hydroxy or amino groups or by halogen₆-C₁₀An aromatic hydrocarbon group (preferably phenyl or methylphenyl);

the precondition is that: when A is^n-When it is (a) carbamate or carbazate, R in the compound of the above general formula (I)¹,R²,R³Or R⁴At least one is an R group attached to the N atom, or the compound of formula (I) has at least one R group bonded to the N; or when A^n-When (B), (c) or (d), the compound of the general formula (I) comprises an organic amine B having at least one R group bonded to N,

wherein the R group is selected from one or more of the following groups:

(1a)H[OCH(R_1a)CH(R_2a)]_q-, e.g. H (OCH)₂CH₂)_q-、H(OCH₂CH(CH₃))_q-、H(OCH(CH₃)CH₂)_q-、H(OCH₂CH(C₆H₅))_q-、H(OCH(C₆H₅)CH₂)_q-、H(OCH₂CH(CH₂Cl))_q-、 H(OCH(CH₂Cl)CH₂)_q-or H (OCH)₂CH(CBr₃))_q-；

(2a)H[OCH(R_1a)CH(R_2a)CH(R_3a)]_q-; or

(3a)H[OCH(R_1a)CH(R_2a)CH(R_3a)CH(R_4a)]_q-；

Wherein the value or average value of q is q ═ 1 to 50; r_1a、R_2a、R_3aOr R_4aEach independently selected from: h, C optionally substituted by hydroxy or amino or halogen₁-C₇Aliphatic hydrocarbon radicals, C optionally substituted by hydroxy or amino groups or halogen₃-C₇Cycloaliphatic hydrocarbon radicals, or, C optionally substituted by hydroxy or amino groups or by halogen₆-C₁₀An aromatic hydrocarbon group.

In the present application, it is preferred that the organic amine compound B having at least one N-R group is formed by substitution of the above-mentioned one or more R groups on at least one N atom of each molecule of the organic amine compound (M), ammonia and/or hydrazine.

In the present application, it is preferred when A is^n-When being (B), (c), (d), (e), (f), (g) or (h), the compound of the general formula (I) has on average 1 to 5.5R groups, preferably 1.3 to 5R groups, more preferably 1.5 to 2R groups per molecule, and these R groups are present in the organic amine compound B having at least one N-R group; or when A^n-In the case of (a) carbamate or carbazate, the compound of formula (I) has on average 1 to 5.5R groups, preferably 1.3 to 5R groups, more preferably 1.5 to 2R groups per molecule, and these R groups are present in the organic amine compound B and/or the anion (a).

In the present application, it is preferred that the R group is hydroxypropyl, i.e. HO-CH₂-CH₂(CH₃) -or HO-CH₂(CH₃)-CH₂-, hydroxyethyl, and/or, hydroxyAnd (3) a chloropropyl group.

In the present application, it is preferred that in the compound or mixture of compounds of formula (I) the molar ratio of the compound of formula (I) having one R group, e.g. the monoalcohol salt, to the compound of formula (I) having two R groups, e.g. the dialcohol amine salt, is from 1:0 to 1:2.5, preferably from 1:0.3 to 1:2, preferably from 1:0.5 to 1:1.

In this application, A^n-[B^m+]_pAnd may also be represented by formula or formula ABp. They are alkanolamine salt compounds. They are thus in the form of ionic compounds in the presence of water.

In the present application, preference is given to those in which A or A^n-Is selected from one or more of the following anions:

(a) carbamate or carbazate: r¹R²N-COO^-Or R¹R²N-NH-COO^-；

(b) Carbonate radical: CO2₃ ^2-(ii) a Or

(d) Bicarbonate radical: HO-COO^-。

In the present application, it is preferred that,

preferably, m is 1 or 2 or 3.

In the present application, preferably, the substituted hydrazino means substituted with the substituent R as described above¹,R²,R³Or R⁴Substituted hydrazino groups.

In the present application, in general, where A^n-The pH of the compound or mixture of compounds of the general formula (I) which is the formate (c) is from 5.5 to 6.5. Except that A^n-In addition to the compounds of the general formula (I) which are formate (c) (pH 5.5 to 6.5), the other compounds of the general formula (I) have a pH of 7.5 to 10, preferably 7.8 to 9.5, more preferably pH 8 to 9. Preferably, the compound or mixture of compounds of formula (I) has an alkali metal and alkaline earth metal content of 0 to 200ppm by mass, more preferably below 100ppm, more preferably below 10ppm, most preferably below the detection limit or at 0 ppm.

Preferably, in the present application, the compound or mixture of compounds of the general formula (I) has a water content of from 0 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. Accordingly, in the present application, the compound or compound mixture of the general formula (I) contains from 25 to 95% by weight, preferably from 27 to 90% by weight, preferably from 30 to 85% by weight, preferably from 40 to 80% by weight, more preferably from 45 to 75% by weight, of the salt of a monoalkanolamine (e.g.monoethanolamine and/or monopropanolamine) and the salt of a dialcohol amine (e.g.diethanolamine and/or dipropanolamine) (i.e.the sum of the two: salt of monoalkanolamine + salt of dialcohol amine), based on the total weight of the compound or compound mixture of the general formula (I). Alternatively, the compound or mixture of compounds of the general formula (I) contains 15 to 90 wt.%, preferably 17 to 88 wt.%, preferably 20 to 85 wt.%, preferably 25 to 80 wt.%, more preferably 30 to 70 wt.% of the monoalcohol amines (e.g. monoethanolamine and/or monopropanolamine) and the dialcohol amines (e.g. diethanolamine and/or dipropanolamine) (i.e. the sum of both: monoalkanolamine + dialkanolamine), based on the total weight of the compound or mixture of compounds of the general formula (I).

Preferably, the compounds of formula (I) contain on average 1.5 to 5R groups per molecule.

In the present application, hydrazine ions refer to: +1 valent hydrazine ion (H)₃ ⁺N-NH₂) Or + 2-valent hydrazine ion (H)₃ ⁺N-NH₃ ⁺). That is, the hydrazine ion is or includes: +1 valent hydrazine ion (H)₃ ⁺N-NH₂) And + 2-valent hydrazine ions (H)₃ ⁺N-NH₃ ⁺)。

In the present application, the compounds of the general formula (I) have at least one of the abovementioned R groups per molecule.

In the present application, the R group is the same or different from the following groups: c optionally substituted by hydroxy or amino or halogen₁-C₇Aliphatic hydrocarbon group (preferably C)₁-C₄Alkyl), C optionally substituted by hydroxy or amino or halogen₃-C₇Cycloaliphatic hydrocarbon radicals (e.g. cyclobutyl or cyclohexyl), or, C optionally substituted by hydroxy or amino groups or by halogen₆-C₁₀An aromatic hydrocarbon group (preferably phenyl or methylphenyl).

In the present application-⁺NR³R⁴The H group being-NR³R⁴⁺H group-⁺NR³H-radical means-NR³(⁺H) -a group. In general, the organic amines B have ≧ m (e.g., m to m + 3) primary, secondary and/or tertiary amine groups, and optionally quaternary ammonium groups. For example, CH₃CH₂ ⁺NH₂H (i.e. ethylamine cation, CH)₃CH₂NH₂ ⁺H) Is prepared from ethylamine and one⁺Formed by the combination of H ions, where B¹⁺＝CH₃CH₂ ⁺NH₂H or CH₃CH₂NH₂ ⁺H, m ═ 1, B ═ ethylamine. In the above formula, the primary, secondary and/or tertiary amine groups are selected from-NR³R⁴Group and-NR³-a group.

The organic amine compounds B are organic amines having m to m +3 primary, secondary and/or tertiary amine groups and optionally having quaternary ammonium groups. Preferably, the organic amine compound B is an organic amine compound having 2 to 200 carbon atoms (preferably 3 to 50, more preferably 3 to 20, and still more preferably 3 to 12). Typically, it has the R groups described above.

In the present application, the organic amine compound B, or an organic amine compound B having ≧ m (e.g., m to m + 3) primary, secondary and/or tertiary amine groups and optionally having a quaternary ammonium group, is reacted with m⁺H ions combine to become B^m+。

Preferably, A is^n-Is a combination or mixture of two or more of the above anions selected from (a) to (h), and/or B^m+Is a combination or mixture of two or more of the above mentioned organic amine cations, and thus the compound of formula (I) is a mixture.

In this application, p B^m+May be the same or different, or p B's may be the same or different. Preferably, p of B^m+Different, or p B's are different.

Additionally, an embodiment is provided wherein A^n-Is selected from one or more of the following anions: (a) (c), (d), (e), (f); or (h).

In general, in the formula (I), there are +2 or+3 valency of the individual A^n-Can be respectively connected with one or more B^m+And (4) salifying. And, has a plurality of-N⁺R³R⁴H group and/or-N⁺R³Single organic amine ion B of H-group^m+Can be associated with one or more A^n-And (4) salifying.

For (c) HCOO^-Ammonium formate, hydrazine formate or organic amine salts of formic acid are relatively stable compounds per se, the decomposition temperature generally being higher than 100 ℃, for example the melting point of ammonium formate is up to 116 ℃. However, when ammonium formate, hydrazine formate or organic amine formate salts are used as the polyurethane blowing agent, they are found to become unstable when exposed to isocyanates (such as MDI) because the ammonium formate, hydrazine formate or organic amine formate salts react with NCO groups to form unstable anhydride groups and then decompose rapidly to release carbon dioxide and also carbon monoxide, so that ventilation and explosion protection should be paid to practical use.

Similarly, the following anions become unstable when exposed to isocyanates (e.g., MDI): (e) r^aO-COO^-；(f)^-OOC-N(R¹)-R^b-N(R²)-COO^-Or R^b'(-N(R¹)-COO^-)₃(ii) a Or (h)^-OOC-OR^cO-COO^-；

Preferably, (e) R^aO-COO^-Is an anion or acid radical formed from a hydrocarbyl bicarbonate, such as methyl or ethyl bicarbonate.

Preferably, (f)^-OOC-N(R¹)-R^b-N(R²)-COO^-Or R^b'(-N(R¹)-COO^-)₃Are anions or acid groups formed by alkylene di (carbamic acid) or alkylene tri (carbamic acid), respectively.

Preferably, (h)^-OOC-OR^cO-COO^-From alkylene dicarbonates (e.g. ethylene-ammonium-dicarbonate NH)₄OOC-OCH₂CH₂O-COONH₄) The anion or acid radical formed.

Preferably, for example, when the compound of the formula (I) is used as a blowing agent for producing a polyurethane foam of heat insulation type, particularly a closed-cell type polyurethane foam, q is 1 to 5, more preferably 1 to 4, still more preferably 1 to 3, particularly preferably 1 to 2.5, still more particularly preferably 1.5 to 2.0, as calculated as the average value of q, from the viewpoints of foaming efficiency, odor of the blowing agent, heat insulation performance and cell size stability, and dimensional stability of the finished polyurethane foam. Therefore, it is more preferable that B is a mixture of two or more compounds. More preferably, B comprises at least one N-H group (N-H covalent bond, i.e., H attached to N).

R¹,R²,R³And R⁴Independently selected from: h, R, C optionally substituted by hydroxy or amino or halogen₁-C₄Aliphatic hydrocarbon groups (e.g., methyl or ethyl or propyl), cyclobutyl or cyclohexyl optionally substituted by hydroxy or amino or halogen, or phenyl or methylphenyl optionally substituted by hydroxy or amino or halogen.

Preferably, R_1a、R_2a、R_3aOr R_4aEach independently selected from: h, C optionally substituted by hydroxy or amino or halogen₁-C₃Aliphatic hydrocarbon radicals, C optionally substituted by hydroxy or amino groups or halogen₃-C₆Cycloaliphatic hydrocarbon radicals, or, C optionally substituted by hydroxy or amino groups or by halogen₆-C₇An aromatic hydrocarbon group (e.g., phenyl or methylphenyl).

More preferably, R_1a、R_2a、R_3aOr R_4aEach independently selected from: h, methyl or ethyl optionally substituted with hydroxy or amino or halogen, or propyl or isopropyl optionally substituted with hydroxy or amino or halogen, cyclohexyl optionally substituted with hydroxy or amino or halogen, or phenyl or methylphenyl optionally substituted with hydroxy or amino or halogen.

More preferably, R_1a、R_2a、R_3aOr R_4aEach independently selected from: h, methyl, chloromethyl, bromomethyl, ethyl, cyclohexyl, or phenyl.

Generally, the organic amine salt compound of formula (I) contains an alcohol amine compound or an alcohol amine compound residue. That is to sayThe organic amine salt compound of the formula (I) has the formula as CO₂Anion of donor A^n-And one or more organic amine salt compounds containing an alcohol amine compound or an alcohol amine compound residue.

Preferably, A^n-Is selected from one or more of the following anions:

(b)CO₃ ^2-；

(c)HCOO^-；

(d)HO-COO^-(ii) a Or

(g)

(i.e., HC (OR') O)₂ ^2-) Or is or

(i.e., HCO)₃ ^3-)，

Wherein R' is H, C optionally substituted by hydroxy or amino or halogen₁-C₂₆Hydrocarbyl (preferably C)₁-C₁₀Hydrocarbyl, more preferably methyl, ethyl, propyl), C₁-C₂₆Acyl (preferably C)₁-C₁₀Acyl, more preferably formyl, acetyl or propionyl).

In this application, "optionally" means with or without, and means substituted or unsubstituted. "optional" means with or without.

Typically, in the compounds of formula (I), the amino and/or amine group (i.e., -N-in the amine compound B) is ammonia, hydrazine or an organic amine compound⁺R³R⁴H group and/or-N⁺R³H-groups) are 50 to 100% substituted by anions A^n-Neutralization, that is to say, the salt formation rate of the amino groups and/or amine groups is 50 to 100%. Preferably, 65 to 100% of the amino and/or amine groups in the ammonia, hydrazine or organic amine compounds B are replaced by anions A^n-And (4) neutralizing. More preferably, 75 to 100% of the amino and/or amine groups in the ammonia, hydrazine or organic amine compound B are bound by the anion A^n-And (4) neutralizing. More preferably, 75 to 90% of the amino and/or amine groups in the ammonia, hydrazine or organic amine compound B are replaced by the anion A^n-And (4) neutralizing.

Except that A^n-In addition to the compounds of the general formula (I) which are formate (c) (pH 5.5 to 6.5), the pH of the other compounds of the general formula (I) is generally 7.5 to 10, preferably 7.8 to 9.5, more preferably 8 to 9. For example, when ammonia, hydrazine or the amino and/or amine groups of the organic amine compound B (i.e. -N)⁺R³R⁴H group and/or-N⁺R³H-groups) are 50-95% substituted by anions A^n-Upon neutralization, the compound of formula (1) is then relatively stable.

When 100% of the amino and/or amine groups in the ammonia, hydrazine or organic amine compound B are substituted by the anion A^n-Upon neutralization, the formula (I) becomes the following:

in the present application, for the sake of simplicity, there are m (where m is 1 to 10, such as 1,2, 3, 4, 5, 6, 7, 8, 9 or 10) -N⁺R³R⁴H group and/or-N⁺R³The organic amine ion of the H-group can be considered to be an organic amine ion having a valence of + m.

Preferably, for-N having m (e.g. m1 or m 2-10, such as 3, 4, 5) groups⁺R³R⁴H group and/or-N⁺R³Organic amine ion of H-group (B)^m+) Wherein compound B is formed from an organic amine compound (M) having at least one, preferably at least two, N-H covalent bonds, i.e.having at least one active hydrogen bonded to N, ammonia and/or hydrazine as starting materials. I.e. in B or B^m+The N-R group in (a) is formed by substitution with one or more of the above-mentioned R groups on at least one N atom of each molecule of the organic amine compound (M), ammonia and/or hydrazine. That is, compound B is a compound having an N-R group (or N-H covalent bond)An organic amine compound. Preferably, the organic amine compound B having N-R group is formed by substitution of one or more R groups on at least one N atom of each molecule of the organic amine compound (M), ammonia and/or hydrazine.

Preferably, R is¹And R²At least one of which is H, more preferably R¹Is H and R²Is H or an R group (e.g., hydroxyethyl or hydroxypropyl).

Preferably, the organic amine compound (M), i.e. the organic amine compound (M) having at least one N-H (i.e. an N-H covalent bond or having at least one H bonded to N, being an active hydrogen), is an organic amine compound selected from the following:

C₁-C₂₄hydrocarbylamines (primary amines) such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, tetracosylamine, unsubstituted or substituted (e.g., halogen-substituted) aniline, unsubstituted or substituted (e.g., halogen-substituted) benzylamine, cyclohexylamine, methylcyclohexylamine, cyclohexylmethylamine, N-methylcyclohexylamine or N-methylbenzylamine, and the like;

two (C)₁-C₁₆Hydrocarbyl) amines (secondary amines, i.e., monoamines having one secondary amine group), such as dimethylamine, diethylamine, methylethylamine, dipropylamine, methylpropylamine, ethylpropylamine, dibutylamine, ethylbutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, didicosylamine, or ditetradecylamine, and the like;

optionally at C₂-C₁₄C substituted by hydroxy on alkylene₂-C₁₄Alkylene diamines (in which the two amine groups are each independently a primary or secondary amine group), e.g. ethylenediamine, N-methylethylenediamine, N, N '-dimethylethylenediamine, 1, 3-propanediamine, N-methyl, N' -ethyl-1, 3-propanediamine, butanediamine (including various kinds of amines)Isomers such as 1,2 or 1, 3-or 1, 4-butanediamine), pentanediamine (including various isomers), hexanediamine (including various isomers), 3-hydroxymethyl-hexanediamine, heptanediamine (including various isomers), 3-hydroxymethyl-heptanediamine, octanediamine (including various isomers), 3, 5-dihydroxyoctanediamine, nonanediamine (including various isomers), decanediamine (including various isomers), 3, 6-dihydroxydecanediamine, dodecanediamine, tetradecanediamine, p-or m-phenylenediamine, 3,3 '-dichloro-4, 4' -diphenylmethanediamine (MOCA), or piperazine, and the like;

optionally at C₂-C₁₄C substituted by hydroxy on alkylene₄-C₁₆Polyalkylene polyamines, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine, triethylenediamine, dimethyldiethyltriamine, tris (2-hydroxy-1, 3-propylene) tetramine or tetrakis (2-hydroxy-1, 3-propylene) pentamine; etc.;

c optionally substituted by hydroxy having three primary amine groups₃-C₁₈Organic triamines or C having four primary amino groups optionally substituted by hydroxy₅-C₁₈Organic tetraamines, such as 1,3, 5-triamino-cyclohexane, 1,3, 5-tris (aminoethyl) -cyclohexane, 1,3, 5-tris (aminopropyl) -1,3, 5-hexahydrotriazine, 1,3, 5-tris (methylaminopropyl) -1,3, 5-hexahydrotriazine, or melamine, pentaenetetramine, and the like; or

C₂-C₁₀Alkanolamines such as monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, monoisopropanolamine, diisopropanolamine, monobutanolamine, or dibutanolamine, and the like.

More preferably, (M) is selected from:

methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, unsubstituted or substituted (e.g., halogen-substituted) aniline, unsubstituted or substituted (e.g., halogen-substituted) benzylamine, cyclohexylamine, or methylcyclohexylamine;

dimethylamine, diethylamine, methylethylamine, dipropylamine, or methylpropylamine;

ethylenediamine, N-methyl-ethylenediamine, N '-dimethylethylenediamine, 1, 3-propylenediamine, N-methyl, N' -ethyl-1, 3-propylenediamine, butylenediamine (including various isomers, such as 1,2 or 1, 3-or 1, 4-butylenediamine), pentylenediamine (including various isomers), hexylenediamine (including various isomers), 3-hydroxymethyl-hexylenediamine, p-or m-phenylenediamine, 3,3 '-dichloro-4, 4' -diphenylmethanediamine (MOCA), or piperazine;

diethylenetriamine, triethylenetetramine, or tetraethylenepentamine;

1,3, 5-triamino-cyclohexane, 1,3, 5-tris (aminoethyl) -cyclohexane, 1,3, 5-tris (aminopropyl) -1,3, 5-hexahydrotriazine, 1,3, 5-tris (methylaminopropyl) -1,3, 5-hexahydrotriazine, or melamine, pentaenetetramine;

or

Monoethanolamine, monopropanolamine, monoisopropanolamine, or monobutanolamine.

In general, when B is^m+Is free of +1 valent ammonium ion: (⁺NH₄) or-N with m (e.g. 2-10, such as 3, 4, 5) other than hydrazine ions⁺R³R⁴H group and/or-N⁺R³Organic amine ion of H-group (i.e., B)^m+Ammonium ion having a valence other than + 1: (⁺NH₄) Or hydrazine ions, i.e. when B is not ammonia or hydrazine), compound B is formed by reacting the above-mentioned organic amine compounds (M), ammonia and/or hydrazine as starting materials or as initiator with an epoxide, such as ethylene oxide, propylene oxide, epichlorohydrin, epibromopropylene oxide, butylene oxide, or chlorobutylene oxide or styrene oxide, and mixtures of any two or more thereof.

More specifically, compounds B and A^n-Salts formed, or salts of B with A, or simply, compounds B, are salts of the above-mentioned organic amine compounds (M), ammonia and/or hydrazine with one or more anions of (a), (B), (c), (d), (e), (f) or (h), as starting materials or as initiators, with epoxides, e.g. ethylene oxide, propylene oxide, epichlorohydrin, epibromohydrin, epoxypropaneButane, or chloroepoxybutane or styrene oxide, and mixtures of any two or more thereof).

In addition, when A^n-Is any one of (a), (B), (c), (d), (e), (f) or (h) and B^m+is-N having m (e.g. 1 or 2-10, such as 3, 4, 5)⁺R³R⁴H group and/or-N⁺R³Organic amine ion of H-group (i.e., B)^m+Ammonium ion having a valence other than + 1: (⁺NH₄) Or a hydrazine ion, i.e. when B is not ammonia or hydrazine), said compound (I) being an ammonium or hydrazonium salt [ e.g. ammonium carbamate, hydroxyalkyl or hydroxyalkylalkoxy substituted ammonium carbamate (R) in a solvent (preferably a protic solvent, an alcoholic solvent or DMF, e.g. water) formed from one or more anions selected from (a), (B), (c), (d), (e), (f) or (h) and ammonia or hydrazine, optionally in the presence of a catalyst (e.g. aqueous ammonia, or an organic amine, such as ethylamine, diethylamine or triethylamine)¹R²N-COO^-+NH₄) Hydrazine carbamate, ammonium carbazate, hydrazine formate, ammonium Carbonate (CO)₃ ^2-(⁺NH₄)₂) Hydrazine carbonate, ammonium bicarbonate, hydrazine formate or ammonium formate, and mixtures of two or more thereof]Or an organic amine salt of the above-mentioned one or more organic amine compounds (M) (e.g., an organic amine carbamate salt, an organic amine hydroxyalkyl-or hydroxyalkoxyalkoxy-substituted carbamate salt, an organic amine carbazate salt, an organic amine N-hydroxyalkyl-or N-hydroxyalkoxyalkoxy-substituted carbazate salt, an organic amine carbonate salt, an organic amine bicarbonate salt, an organic amine formate salt, and mixtures of two or more thereof), with an epoxide (e.g., ethylene oxide, propylene oxide, epichlorohydrin, epibromopropylene oxide, butylene oxide, or styrene oxide, and mixtures of any two or more thereof). Typically, the solvent described herein is selected from one or more of the following, but is not limited to: methanol, ethanol, ethylene glycol, polyethylene glycol with molecular weight less than 400, polypropylene glycol with molecular weight less than 300,Glycerol, glycerol formate or water.

In addition, when A^n-Is (a) R¹R²N-COO^-Anion and B^m+Is an ammonium ion having a valence of + 1: (⁺NH₄) Or a hydrazine ion [ i.e., +1 valent hydrazine ion (H)₃ ⁺N-NH₂) Or + 2-valent hydrazine ion (H)₃ ⁺N-NH₃ ⁺)]When said compound (I) is R¹R²N-COO^-+NH₄Or R¹R²N-COO^-H₃ ⁺N-NH₂Or (R)¹R²N-COO^-)₂(H₃ ⁺N-NH₃ ⁺) Wherein R is¹Or R²One or both of which are the aforementioned R groups. These compounds R¹R²N-COO^-+NH₄Or R¹R²N-COO^-H₃ ⁺N-NH₂Or (R)¹R²N-COO^-)₂(H₃ ⁺N-NH₃ ⁺) Already having R groups and therefore also being usable directly as compounds of the formula (I) or as blowing agents, these compounds R of course¹R²N-COO^-+NH₄Or R¹R²N-COO^-H₃ ⁺N-NH₂Or (R)¹R²N-COO^-)₂(H₃ ⁺N-NH₃ ⁺) It is also possible to further react with the above-mentioned epoxides to give compounds of the general formula (I) having an alcohol amine compound or an alcohol amine residue in the cationic moiety. When A is^n-Is (a) R¹R²N-NH-COO^-Anion and B^m+Is an ammonium ion having a valence of + 1: (⁺NH₄) Or a hydrazine ion [ i.e., +1 valent hydrazine ion (H)₃ ⁺N-NH₂) Or + 2-valent hydrazine ion (H)₃ ⁺N-NH₃ ⁺)]When said compound (I) is R¹R²N-NH-COO^-+NH₄Or R¹R²N-NH-COO^-H₃ ⁺N-NH₂Or (R)¹R²N-NH-COO^-)₂(H₃ ⁺N-NH₃ ⁺) Wherein R is¹Or R²One or both of which are the aforementioned R groups. These compounds R¹R²N-NH-COO^-+NH₄Or R¹R²N-NH-COO^-H₃ ⁺N-NH₂Or (R)¹R²N-NH-COO^-)₂(H₃ ⁺N-NH₃ ⁺) Already having R groups and therefore also being usable directly as compounds of the formula (I) or as blowing agents, these compounds R of course¹R²N-NH-COO^-+NH₄Or R¹R²N-NH-COO^-H₃ ⁺N-NH₂Or (R)¹R²N-NH-COO^-)₂(H₃ ⁺N-NH₃ ⁺) It is also possible to further react with the above-mentioned epoxides to give compounds of the general formula (I) having an alcohol amine compound or an alcohol amine residue in the cationic moiety.

In general, when A^n-Is (g) an anion and B^m+Is of m number (e.g. 2-10, such as 3, 4, 5) -N⁺R³R⁴H group and/or-N⁺R³Organic amine ion of H-group (i.e., B)^m+Ammonium ion having a valence other than + 1: (⁺NH₄) Or hydrazine ions, i.e. when B is not ammonia or hydrazine), said compound (I) being formed by hydrolysis of orthoformate compounds in a solvent, preferably a protic solvent, an alcoholic solvent or DMF, optionally in the presence of a catalyst, for example ammonia, or an organic amine, such as ethylamine, diethylamine or triethylamine, and in the presence of an organic amine M belonging to the class of organic alkanolamines or a compound B belonging to the class of organic alkanolamines having at least one N-R group as defined above and water. Preferably, the water is present in an amount sufficient to hydrolyze at least two ester groups of the orthoformate compound, and more preferably, in an amount sufficient to hydrolyze three ester groups of the orthoformate compound. The orthoformate hydrolysis catalyst is generally a basic compound, preferably an organic amine. Preferably, there is at least one of the N-R groups described above (i.e., at least one)An R group bonded to N) is prepared by reacting ammonia, hydrazine and/or the above-described organic amine compound (M) with the above-described epoxides (e.g., ethylene oxide, propylene oxide, epichlorohydrin, epibromopropane, butylene oxide (including various isomers such as 1, 2-butylene oxide, 2, 3-butylene oxide), chlorobutylene oxide (including various isomers such as 1, 2-epoxy-4-chlorobutane, 2, 3-epoxy-1-chlorobutane) or styrene oxide, and mixtures of any two or more thereof). In this R group, the average value of q (i.e. the degree of polymerization of the epoxide) is as defined above. The average value of q can be selected according to the particular application of the polyurethane foam. Preferably, when used for preparing a heat insulating type polyurethane foam, particularly a closed cell type polyurethane foam, q is 1 to 5, more preferably 1.2 to 4.5, still more preferably 1.3 to 4, and particularly preferably 1.5 to 3.5, in terms of the average value of q, from the viewpoints of foaming efficiency, odor of a blowing agent, heat insulating property, and cell size stability, and dimensional stability of a finished polyurethane foam, or when used for an open-cell or semi-open-cell type polyurethane foam, q is 1 to 5.

Preferably, the orthoformate compound is selected from one or more of the following compounds: original third (C)₁-C₈) Alkyl esters, preferably orthomethyltris (C)₁-C₇) Examples of the hydrocarbon-based esters include trimethyl orthoformate, triethyl orthoformate, methyl diethyl orthoformate, tripropyl orthoformate, methyl dipropyl orthoformate, tributyl 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 to 10)) orthoformate, tri (propylene glycol) orthoformate, tri (dipropylene glycol) orthoformate, tri (tripropylene glycol) orthoformate, tri (tetrapropylene glycol) orthoformate, and tri (polypropylene glycol (degree of polymerization: 5 to 10)) orthoformate.

Preferably, the solvent used during the hydrolysis of the orthoformate ester is selected from one or more of the following, but not limited to: methanol, ethanol, ethylene glycol, polyethylene glycol having a molecular weight of less than 400, polypropylene glycol having a molecular weight of less than 300, glycerol formate or water.

In order to prepare the compounds of the above general formula (I), they can be prepared by various preparation methods. By way of example only, several representative methods of preparation are described separately below.

According to another embodiment of the present invention, the present invention also provides a method of preparing a catalyst having the formula as CO₂Process for the preparation of organic amine salts of anions of donors, or process for the preparation of compounds of formula (I) wherein A^n-A process for the preparation of a compound of formula (I) as hereinbefore described which is an anion of any one or more of (a), (b), (c), (d), (e), (f) or (h), which process comprises reacting a first starting material with a second starting material in a solvent, preferably a protic or alcoholic solvent, optionally in the presence of a catalyst (e.g. aqueous ammonia, or an organic amine such as ethylamine, diethylamine or triethylamine), wherein the first starting material is selected from one or more of the following compounds:

R¹R²N-COONH₄，R¹R²salts of N-COOH organic amine compounds (M), R¹R²Hydrazine salts of N-COOH (e.g. hydrazine carbamate), R¹R²N-NH-COONH₄(e.g. ammonium carbazate), R¹R²Hydrazine salts of N-NH-COOH (e.g. hydrazinoformate), or R¹R²Salts of organic amines (M) of N-NH-COOH, wherein R¹Or R²Independently selected from: h, C optionally substituted by hydroxy or amino or halogen₁-C₇Aliphatic hydrocarbon group (preferably C)₁-C₄Alkyl), C optionally substituted by hydroxy or amino or halogen₃-C₇Cycloaliphatic hydrocarbon radicals (e.g. cyclobutyl or cyclohexyl), or, C optionally substituted by hydroxy or amino groups or by halogen₆-C₁₀An aromatic hydrocarbon group (preferably phenyl or methylphenyl);

(NH₄)₂CO₃hydrazine carbonate, ammonium hydrazine carbonate, or organic amines of carbonic acidA salt of compound (M);

HCOONH₄hydrazine formate, or an organic amine formate (M) salt;

HO-COONH₄(i.e., ammonium bicarbonate), hydrazine bicarbonate, or bicarbonate salts of organic amine compounds (M);

R^aO-COONH₄，R^ahydrazine salts of O-COOH, or R^aOrganic amine compound (M) salt of O-COOH;

NH₄OOC-N(R¹)-R^b-N(R²)-COONH₄，R^b'(-N(R¹)-COO)₃(NH₄)₃， HOOC-N(R¹)-R^b-N(R²) Hydrazine salt of-COOH, HOOC-N (R)¹)-R^b-N(R²) Salts of organic amines of-COOH (M), R^b'(-N(R¹)-COOH)₃A hydrazine salt of (A), or R^b'(-N(R¹)-COOH)₃The organic amine compound (M) salt of (2); or

the second starting material is one or more selected from the following compounds:

or styrene oxide (styrene oxide);

wherein R is¹，R²，R^a，R^b，R^b'，R^cAs defined above, R_1a、R_2a、R_3aOr R_4aAs defined above, and the organic amine compound (M) is as defined above.

Preferably, in the preparation of wherein A^n-In the reaction of the compound of the general formula (I) which is (a) to (f) or (h), the molar ratio of the first raw material to the second raw material is generally 1:1.3 to 5, preferably 1:1.5 to 4.5, more preferably 1:1.6 to 4, for example 1:1.5 to 1:3.

Preferably, the first starting material is one or more selected from the following compounds:

ammonium carbamate, organic ammonium carbamate M (for short, ammonium carbamate), hydrazine carbamate, ammonium carbazate, hydrazine carbazate, H₂Organic amine compound (M) salt of N-NH-COOH, N-substituted ammonium carbamate (R)¹R²N-COO^-+NH₄Or called R¹R²Ammonium salt of N-COOH, R¹And R²Not both H), N-substituted carbamic acid organic amine M salt (i.e., R)¹R²Salts of N-COOH with M, briefly carbamyl amine, R¹And R²Not both H), ammonium carbonate, organic amine carbonate M salt (i.e., H)₂CO₃Salts with M, abbreviated as amine carbonate), hydrazine carbonate, ammonium carbonate hydrazine, ammonium formate, formic acid organic amine M salts (i.e., salts of formic acid with M, abbreviated as amine formate), hydrazine formate, ammonium bicarbonate, hydrogen carbonate organic amine M salts (i.e., hydrogen carbonate of M, abbreviated as ammonium bicarbonate), hydrazine bicarbonate, R^aO-COONH₄，R^aM salt of O-COOH, R^aHydrazonium salt of O-COOH, NH₄OOC-N(R¹)-R^b-N(R²)-COONH₄，R^b'(-N(R¹)-COONH₄)₃，HOOC-N(R¹)-R^b-N(R²) M salt of-COOH, HOOC-N (R)¹)-R^b-N(R²) Hydrazine salt of-COOH, R^b'(-N(R¹)-COOH)₃M salt of (A), R^b'(-N(R¹)-COOH)₃Hydrazonium salts of (NH)₄OOC-OR^cO-COONH₄，HOOC-OR^cOrganic amine M salt of O-COOH, OR HOOC-OR^cA hydrazine salt of O-COOH, wherein M is the organic amine compound (M) described above.

In the context of the present application, it is,⁺MH refers to an organic amine M with one or more hydrogen ions (H)⁺) The formed cations are combined.

Preferably, the second starting material is one or more selected from the following compounds:

ethylene oxide, propylene oxide, epichlorohydrin, epibromohydrin, butylene oxide (including various isomers such as 1, 2-butylene oxide, 2, 3-butylene oxide), chlorobutylene oxide (including various isomers such as 1, 2-epoxy-4-chlorobutane, 2, 3-epoxy-1-chlorobutane) or styrene oxide.

Preferably, the invention also provides a process for the preparation of wherein A^n-A process for preparing a compound of formula (I) which is an anion of any one or more of (a), (b), (c), (d), (e), (f) or (h), which process comprises: ammonium or hydrazine salts formed from one or more anions selected from (a), (b), (c), (d), (e), (f) or (h) with ammonia or hydrazine (e.g. ammonium carbamate, ammonium carbamate substituted on the amino group by hydroxyalkyl or hydroxyalkyl alkoxy, hydrazine carbamate, ammonium hydrazinium formate, hydrazine carbazate, ammonium carbonate, hydrazine carbonate, ammonium carbonate hydrazine formate, ammonium formate, hydrazine bicarbonate, or ammonium bicarbonate, and mixtures of two or more thereof) or organic amine salts formed from said anions with one or more organic amine compounds (M) described above (e.g. organic amine carbamate M salts, organic amine carbamate M salts substituted on the amino group by hydroxyalkyl or hydroxyalkyl alkoxy), an organic amine M salt of hydrazinoformic acid, an organic amine M salt of N-hydroxyalkyl-or N-hydroxyalkylalkoxy-substituted hydrazinoformic acid, an organic amine M salt of carbonic acid, an organic amine M salt of formic acid or an organic amine M salt of hydrogencarbonate, and a mixture of two or more thereof) as a first raw material, with the above-mentioned epoxide (e.g., ethylene oxide, propylene oxide, epichlorohydrin, epibromohydrin, butylene oxide (including various isomers such as 1, 2-butylene oxide, 2, 3-butylene oxide), chlorobutylene oxide (including various isomers such as 1, 2-epoxy-4-chlorobutane, 2, 3-epoxy-1-chlorobutane) or styrene oxide, and a mixture of any two or more thereof) as a second raw material. Alternatively, as an alternative method, which is less preferred, a method comprising two steps of preliminary addition and post-neutralization may be employed, i.e., the above-mentioned method for producing the compound of the general formula (I) comprises: first, ammonia, hydrazine or one or more of the above-mentioned organic amine compounds (M) are reacted with the above-mentioned epoxide (e.g., ethylene oxide, or a mixture thereof) as a second raw material,Propylene oxide, epichlorohydrin, bromopropylene oxide, butylene oxide (including various isomers such as 1, 2-epoxybutane, 2, 3-epoxybutane), chlorobutylene oxide (including various isomers such as 1, 2-epoxy-4-chlorobutane, 2, 3-epoxy-1-chlorobutane) or styrene oxide, and mixtures of any two or more thereof), followed by reacting the resulting compound with a compound belonging to the anion A^n-I.e. one or more acid compounds or acidic compounds (e.g. CO) capable of generating one or more anions selected from (a) - (g) of the precursor(s) of (a) - (g)₂Carbamic acid, or formic acid) is subjected to a neutralization reaction. Preferably, the pH is neutralized to a pH of not less than 7.5, more preferably not less than 7.8, more preferably not less than 8. The pH of the ammonium formate (melting point 116 ℃ C.), hydrazine formate or formic acid organic amine M salt blowing agent is in the range of 5.5-6.5, more usually in the range of 5.5-6.0. Wherein A is^n-The pH of the compound of formula (I) which is formate (c) is in the range of 5.5-6.5, more usually in the range of 5.5-6.0.

According to yet another embodiment of the present invention, the present invention also provides a method of making a catalyst having a structure as a CO₂Process for the preparation of organic amine orthoformate salts of donor anions, or process for the preparation of compounds of formula (I) wherein A^n-A method for producing a compound of the general formula (I) which is an anion represented by (g), the method comprising: the orthoformate-based compound is subjected to hydrolysis reaction in a solvent (preferably a protic solvent, an alcoholic solvent such as water), optionally in the presence of a catalyst (e.g. aqueous ammonia, or an organic amine such as ethylamine, diethylamine or triethylamine), and in the presence of an organic amine M belonging to the organic alcanolamine or a compound B belonging to the organic alcanolamine having at least one of the above-mentioned N-R groups, and water. Preferably, the water is present in an amount sufficient to hydrolyze at least two ester groups of the orthoformate compound, and more preferably, in an amount sufficient to hydrolyze three ester groups of the orthoformate compound.

In general, when preparing the hydrazino alcoholamine salt compounds of the general formula (I), the organoamine compounds B are formed by reacting hydrazine and optionally ammonia as starting materials or as initiator with an epoxide selected from one or more of the following epoxides:

or styrene oxide.

In the present application, it is preferred that when the compound of formula (I) is a hydrazinohydramine salt compound, A is^n-Or B^m+Comprises a hydrazine group or a substituted hydrazine group. In a process for preparing the hydrazino alcoholamine salt compound of formula (I), at least one of the first starting materials comprises hydrazine or contains a hydrazine group. In the preparation of A^n-In the method for producing the hydrazinohydramine salt compound of the general formula (I) which is an anion represented by (g), at least one of the organic alcoholamine compounds B contains a hydrazine group or a substituted hydrazine group.

In the present application, it is preferred that the compound B belonging to the organic amine group having at least one N-R group as described above (i.e., at least one R group bonded to N) is prepared by reacting ammonia, hydrazine and/or the above-described organic amine compound (M) with an epoxide (e.g., ethylene oxide, propylene oxide, epichlorohydrin, epibromohydrin, butylene oxide (including various isomers such as 1, 2-butylene oxide, 2, 3-butylene oxide), chlorobutylene oxide (including various isomers such as 1, 2-epoxy-4-chlorobutane, 2, 3-epoxy-1-chlorobutane) or styrene oxide, and mixtures of any two or more thereof). In the R group, q is the average value (i.e., the degree of polymerization of the epoxide), as defined above. In the preparation of A^n-In the case of the compound of the formula (I) which is an anion represented by (g), the molar ratio of ammonia or the organic amine compound (M) to the epoxide is preferably 1.3 to 7, more preferably 1.5 to 4, still more preferably 1.5 to 3. Wherein A is^n-The compounds of the formula (I) which are (g) are suitable as blowing agents for producing polyurethane foams of the heat-insulating type. That is, the present invention also provides a process for the preparation of wherein A^n-A method for producing a compound of the general formula (I) which is an anion represented by (g), the method comprising: ammonia or the above-mentioned one or more organic amine compounds (M) with an epoxide as a second starting material to prepare an organic amine compound B having at least one of the above-mentioned N-R groups (i.e., at least one N-bonded R group); then, the orthoformate compound is dissolved in a solvent (preferably a protic solvent, an alcohol)Solvent, for example water), optionally in the presence of a catalyst (for example aqueous ammonia, or an organic amine, such as ethylamine, diethylamine or triethylamine), and in the presence of an organic amine M belonging to the class of organic alcanolamines or a compound B belonging to the class of organic alcanolamines having at least one N-R group as defined above and water. Preferably, the water is present in an amount sufficient to hydrolyze at least two ester groups of the orthoformate compound, and more preferably, in an amount sufficient to hydrolyze three ester groups of the orthoformate compound.

Preferably, the orthoformate compound is selected from one or more of the following compounds: original third (C)₁-C₈) Alkyl esters, preferably orthomethyltris (C)₁-C₇) The hydrocarbon-based esters, for example, trimethyl orthoformate, triethyl orthoformate, methyl diethyl orthoformate, tripropyl orthoformate, methyl dipropyl orthoformate, tributyl orthoformate, triphenyl orthoformate, tribenzyl orthoformate, acetyl diethyl orthoformate, acetyl ethyl methyl orthoformate, diethylene glycol orthoformate, propylene glycol orthoformate, polyethylene glycol orthoformate, or R groups in the orthoformate satisfy the characteristics of (1a), (2a) or (3 a).

Preferably, in the present application, the solvent is selected from one or more of the following: methanol, ethanol, ethylene glycol, propylene glycol, polyethylene glycol having a molecular weight of less than 400, polypropylene glycol having a molecular weight of less than 300, glycerol esters or water.

When making the hydrazine-olammonium salt, the first starting material comprises hydrazine or contains a hydrazine group, or at least one of the first starting materials comprises hydrazine or contains a hydrazine group. Hydrazine is a toxic, flammable and explosive compound, so that the relevant use knowledge is carefully read and the relevant requirements and regulations are strictly implemented when the hydrazine is used.

According to still another embodiment of the present invention, there is provided a catalyst having a structure of CO obtained by the above production method₂Organic amine salts of donor anions or mixtures of compounds. Preferably, the compound or the mixture of compounds contains 25 to 95 wt.%, preferably 27 to 90 wt.%, preferably 30 to 85 wt.%, preferably 40 to 80 wt.%, more preferablyFrom 45 to 75% by weight, based on the total weight of the compound or compound mixture, of a salt of a monoalkanolamine, for example monoethanolamine and/or monopropanolamine, and a salt of a dialcohol amine, for example diethanolamine and/or dipropanolamine, i.e. the sum of the weights of the two salts, is selected. Alternatively, it is preferred that the compound or the mixture of compounds contains from 15 to 90% by weight, preferably from 17 to 88% by weight, preferably from 20 to 85% by weight, preferably from 25 to 80% by weight, more preferably from 30 to 70% by weight, of monoalkanolamine (e.g. monoethanolamine and/or monopropanolamine) and dialkanolamine (e.g. diethanolamine and/or dipropanolamine) (i.e. the sum of the weights of the two alkylolamines) based on the total weight of the compound or mixture of compounds.

According to still another embodiment of the present invention, there are provided organic amine salt compounds having the general formula (I), and compounds obtained by the preparation method having the formula as CO₂The organic amine salt compound of the anion of the donor is used as a foaming agent, in particular as a polyurethane foaming agent, a polystyrene foaming agent or a polyvinyl chloride foaming agent. These compounds may be referred to herein simply as the blowing agent of the present invention or the polyurethane blowing agent of the present invention.

In addition, the invention provides the use of the blowing agents of the invention as polystyrene blowing agents or polyvinyl chloride blowing agents, wherein A^n-Is selected from one or more of the following anions:

(a)R¹R²N-COO^-or R¹R²N-NH-COO^-(ii) a Wherein R is¹And R²Each independently of the others is hydrogen, methyl, ethyl, H (OCH)₂CH₂)_q-、H(OCH₂CH(CH₃))_q-、H(OCH(CH₃)CH₂)_q-、H(OCH₂CH(C₆H₅))_q-、 H(OCH(C₆H₅)CH₂)_q-、H(OCH₂CH(CH₂Cl))_q-、H(OCH(CH₂Cl)CH₂)_q-or H (OCH)₂CH(CBr₃))_q-；

(b)CO₃ ^2-(ii) a Or

(d)HO-COO^-。

In addition, ammonium formate (melting point 116 ℃) or the organic amine M salts of formic acid are generally regarded as unsuitable for polyurethane foaming, given their high decomposition temperatures. However, the inventors of the present application have made extensive studies and have unexpectedly found that ammonium formate (melting point 116 ℃) or organic amine M formate salts react with NCO groups to form unstable acid anhydrides when they come into contact with isocyanate groups, and then decompose rapidly to release carbon dioxide gas and carbon monoxide, and therefore, in practical applications, ventilation and explosion prevention should be performed by taking necessary measures. In addition, hydrazine formate has similar properties.

In the present application, when ammonium formate and an epoxide are used for the preparation of the compound of the general formula (I), it is preferred that first an aqueous ammonium formate solution is obtained by reacting formic acid with aqueous ammonia, then a small amount of an organic amine (such as methylamine, dimethylamine or trimethylamine, ethylamine or diethylamine) is added, dehydrated by heating or concentrated under reduced pressure or concentrated under vacuum (for example, to a water content of 7 to 15% by weight, for example, around 10% by weight), and then an epoxide (such as ethylene oxide and/or propylene oxide) is introduced to carry out the reaction to obtain the alkanolamine formate (I). Here, the addition of a small amount of an organic amine, such as methylamine, dimethylamine or trimethylamine, ethylamine or diethylamine, makes it possible to prevent the crystallization, precipitation phenomena in the foaming composition ("white mass") when the ethanolamine salt (I) of formic acid is used to formulate the foaming composition ("white mass"). When using hydrazine formate and an epoxide for the preparation of the compound of the general formula (I), a similar or comparable performance or application effect is obtained as when using ammonium formate and an epoxide for the preparation of the compound of the general formula (I). In addition, formic acid can also be directly reacted with the alcohol amine compound to prepare the compound of the general formula (I).

In the present application, when ammonium bicarbonate is used as a first raw material to react with a second raw material to prepare the compound of the general formula (I), a catalyst such as methylamine, dimethylamine, alcoholamines, other amine catalysts, bimetallic catalyst(s), or heating under pressure may be used.

Further, there is provided a composition comprising at least one alkanolamine compound selected from the group consisting of the following alkanolamine compounds, which are organic amine compounds (M) having at least one N-H group:

C₂-C₁₂alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutanolamine, dibutanolamine, or tributanolamine,

by means of anions A^n-Corresponding acid (e.g. CO) of the precursor of (2)₂) An organic amine salt compound of the following general formula (Ia) formed by neutralization

A^n-[B^m+]_p(Ia)

It is also possible directly as a blowing agent, in particular as a polyurethane blowing agent, polystyrene blowing agent or polyvinyl chloride blowing agent, although these are not preferred. In the case of the alternative use of formic acid or formate as blowing agent, which generates CO during the reaction, measures are necessary for venting and explosion protection, and the presence of isocyanate is necessary when amine formates are used as blowing agent, since they react with isocyanate to give off carbon dioxide and carbon monoxide. . These compounds may be referred to herein simply as blowing agents of the present invention. Polyurethane foaming agents or in polyurethane foaming compositions. Of course, these compounds of formula (Ia) are not preferred because it or their pH values are generally below 8, even below 7.5, even below 7.1, even to pH values of 6-7. When used for preparing heat insulating type polyurethane foams, especially closed cell type polyurethane foams, these organic amine salt compounds (Ia), which are not prepared in situ by reacting an organic amine compound (M) with an epoxide, are not preferred from the viewpoints of foaming efficiency, odor of a blowing agent, heat insulating property and cell size stability as well as dimensional stability of polyurethane foams, or when used for open-cell or semi-open-cell polyurethane foams, from the viewpoints of foaming efficiency, odor of a blowing agent, cell fineness and dimensional stability of finished polyurethane foams.

That is, if the alcohol amine is prepared by reacting ammonia, hydrazine and/or an organic amine with an epoxide and then an acidic substance or acidic compound (e.g., corresponding to the anion of (a), (b), (c), (d), (e), (f), (g) and/or (h) is usedCarbon dioxide or carbamic acid) to obtain the organic amine salt compound of the general formula (I), the pH (usually pH) of the obtained organic amine salt compound (i.e., the alkanolamine salt) is<7)、CO₂Precursor content (with CO)₂Release amount) and activity in the foaming reaction are not satisfactory (unless there is an advantage in terms of safety or cost for a small number of compounds such as orthoformate or hydrazine). It is therefore preferred that the salts of the anions of (a), (b), (c), (d), (e), (f), (g) and/or (h) with ammonia, hydrazine and/or an organic amine (M) are reacted directly with epoxides to give compounds of the general formula (I).

In addition, bis (hydroxyethylamine) carbonates, bis (hydroxypropylamine) carbonates, bis (hydroxyethylamine) bicarbonates, and bis (hydroxypropylamine) bicarbonates are particularly suitable as blowing agents for polystyrene foams or polyvinyl chloride foams. These compounds belong to the above general formula (I). Furthermore, carbonates of polyalkylene polyamines which do not belong to the compounds of the general formula (I) are also suitable as blowing agents for polystyrene or polyvinyl chloride foams, for example carbonates of diethylenetriamine, carbonates of triethylenetetramine, carbonates of tetramethylenepentamine, carbonates of dipropylenetriamine, carbonates of tripropylenetetramine and carbonates of tetrapropylenepentamine.

Generally, amine formate-based blowing agents containing (c) formate groups cannot be used directly as polystyrene blowing agents or polyvinyl chloride blowing agents.

In addition, the inventors of the present application have surprisingly found that ammonium formate or hydrazine formate has a relatively good miscibility with polymer polyols, i.e. that ammonium formate or hydrazine formate can be dissolved directly in polymer polyols and can therefore be used directly as polyurethane blowing agent, and the present application therefore also provides for the use of ammonium formate as blowing agent, in particular as polyurethane blowing agent. When the aqueous solution of ammonium formate or the aqueous solution of hydrazine formate contains a small amount (e.g., 0.5 to 15 wt%, such as 1 to 8 wt%, more preferably 2 to 6 wt%) of an organic amine such as methylamine, dimethylamine, trimethylamine or monoethanolamine, the aqueous ammonium formate solution does not crystallize, precipitate.

The blowing agents of the invention (i.e., compounds of formula (I))Or having a structure as CO obtained by the method of the above fifth or sixth embodiment₂Organic amine salts of donor anions) have the following characteristics: 1) the blowing agents of the invention (i.e. the compounds of the formula I) have, in addition to the ammonium formate, the hydrazonium formate or the organoamine M formate compound, a pH in the range from 7.5 to 10, preferably in the range from pH 7.8 to 9.5, more preferably in the range from pH 8 to 9, and the ammonium formate (melting point 116 ℃ C.), the hydrazine formate or the organoamine M formate blowing agent have a pH in the range from 5.5 to 6, or where A is an alkaline compound which is not additionally or not additionally added^n-The pH of the compound of formula (I) which is formate (c) is in the range of 5.5-6.0; 2) the content of alkali metal or alkaline earth metal is 0 to 200ppm by mass, preferably less than 150ppm, more preferably less than 100ppm, more preferably less than 50ppm, more preferably less than 20ppm, more preferably less than 10ppm, more preferably less than 5ppm, most preferably less than the detection limit or 0 ppm; 3) the amount of water or the amount of water present as solvent is from 0 to 40 wt.%, preferably from 5 to 35 wt.%, more preferably from 10 to 30 wt.%, more preferably from 15 to 25 wt.%; 4) the thermal decomposition temperature is between 36 and 120 ℃ and CO is released during decomposition₂A gas; certain types of blowing agents of the invention in which the decomposition temperature is higher become less stable on contact with NCO groups and can decompose at temperatures between 45 and 70 ℃ to release CO₂(ii) a 5) Preferably, the blowing agents of the present invention contain at least 1R group per molecule, such as HOCH₂CH₂-、 HOCH₂CH(CH₃)-、HOCH(CH₃)CH₂-、HOCH₂CH(C₆H₅)-、HOCH(C₆H₅)CH₂-、 HOCH₂CH(CH₂Cl)-、HOCH(CH₂Cl)CH₂-、HOCH₂CH(CBr₃) -or HOCH (CBr)₃)CH₂-; further preferably, the blowing agents of the present invention comprise a plurality (preferably 2 to 5, such as 2 or 3) of compounds of the formula (I) and contain, on average, 1.5 to 5R groups per molecule, which are, for example, HOCH₂CH₂-、HOCH₂CH(CH₃)-、HOCH(CH₃)CH₂-、 HOCH₂CH(C₆H₅)-、HOCH(C₆H₅)CH₂-、HOCH₂CH(CH₂Cl)-、HOCH(CH₂Cl)CH₂-、 HOCH₂CH(CBr₃) -or HOCH (CBr)₃)CH₂-; 6) 30-100%, preferably 50-100%, more preferably 70-100%, more preferably 85-100% of all N atoms in the blowing agent of the present invention have N-H covalent bonds; 7) in the blowing agents of the invention, the total content of compound of formula (I) and water is from 70 to 100%, more generally from 80 to 99.999%, more generally from 85 to 99.0%, based on the total weight (containing the solvent and allowing small amounts of non-metallic impurities); 8. by infrared spectroscopic analysis, some of the blowing agents of the present invention have a blowing agent density at 2932-2970cm^-1Range of stretching vibration singlet of N-H secondary amine salt at 1555-1566cm^-1A bending vibration single peak of N-H, a range of secondary amine salts, and further, at 3200-3400cm^-1The strong and wide OH stretching vibration peak of hydrogen bonding indicates that the foaming agent contains hydroxyl and secondary amine groups and contains water. Thus, the blowing agents of the present invention comprise one or more alkanolamine compounds and typically contain water.

More preferably, the compounds of formula (I) contain on average 1.5 to 5R groups per molecule.

In the present application, preferably, the R group is HOCH₂CH₂-、HOCH₂CH(CH₃)-、HOCH(CH₃)CH₂-、 HOCH₂CH(C₆H₅)-、HOCH(C₆H₅)CH₂-、HOCH₂CH(CH₂Cl)-、HOCH(CH₂Cl)CH₂-、 HOCH₂CH(CBr₃) -or HOCH (CBr)₃)CH₂-。

According to a ninth embodiment of the present invention, the present invention also provides a polyurethane foaming composition comprising: 0.01 to 100% by weight of a compound of the general formula (I) as defined above (or having a structure as CO obtainable by the process of the second and third embodiments as defined above)₂Organic amine salts of donor anions); 0-50 wt% of a physical blowing agent; 0 to 5 weight percent water, and 0.0 to 99.99 weight percent polymer polyol; wherein the weight percentages are based on the total weight of the polyurethane foaming composition. Preferably, it comprises: 0.1-80% by weight(more preferably 1-70 wt%, more preferably 3-60 wt%, more preferably 5-50 wt%, more preferably 7-40 wt%, such as 10 wt%, 15 wt%) of a compound of formula (I) as described above; 0-40 wt% of a physical blowing agent; 0 to 4 wt% of water, and 20.0 to 99.9 wt% (more preferably 30 to 99 wt%, more preferably 40 to 97 wt%, more preferably 50 to 95 wt%, more preferably 60 to 93 wt%, such as 90 wt% or 85 wt%) of a polymer polyol; wherein the weight percentages are based on the total weight of the polyurethane foaming composition. Preferably, the foaming composition of the invention contains a total of from 0.5 to 4% by weight of water, more preferably from 0.8 to 2.5% by weight, more preferably from 1 to 2.2% by weight of water.

Preferably, the foaming composition further comprises: foam stabilizers, catalysts and flame retardants, and the like. These auxiliaries are customary in the polyurethane art.

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. The average functionality of the polymer polyol 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 boiling in the range of 0-100 ℃, esters such as methyl formate.

Generally, the foaming compositions of the present invention are transparent or clear; preferably, the rigid polyurethane foam composition is a transparent or clear or translucent or milky white but homogeneous or the flexible polyurethane foam composition is a transparent or milky white homogeneous liquid. This indicates that the blowing agent of the present invention is dissolved or uniformly dispersed in the polymer polyol. Generally, the blowing agents or blowing agent compositions of the present invention form clear or clear systems when mixed with a substantial portion of the polyether polyol. Generally, the blowing agent or blowing agent composition of the present invention forms a clear or clear system when mixed with polyester polyols, but it is possible that it forms a milky white but homogeneous system when mixed with a small number of polyester polyols.

The polyurethane foaming composition (commonly called "white material") of the invention has the following characteristics: 1. comprising an alkanolamine or alcohol amine compound (e.g. compounds of formula (I) release CO after thermal decomposition₂While leaving behind the alkanolamine); 2. a clear or translucent or opalescent but homogeneous liquid; 3. CO evolution under heating (e.g. temperatures of 40-80 ℃) or with addition of acids (mineral or organic acids stronger than carbonic acid)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 formula (I) of the present invention preferentially decompose to release CO₂I.e., preferential foaming, and therefore, the addition of small amounts of water does not affect the foaming process or the properties of the finished polyurethane foam. That is, in some cases a small amount of water is present in the compound of formula (I), i.e. in the blowing agent, in the form of a single molecule which is bound or associated with the compound of formula (I), either to facilitate blowing or not to participate in blowing, i.e. not to consume NCO groups. The inventors of the present application have found, through research, that the small amount of water (i.e. associated water) present in the compounds of formula (I), i.e. the blowing agents, does not even participate in the reaction, i.e. does not consume NCO groups. This finding was unexpected.

When the polyurethane foaming composition (commonly called "white material") of the invention contains A^n-Is (f) HCOO^-In the case of compounds of the formula (I) (formate) it is preferred that the polyurethane foam compositions of the invention (commonly known as "whiteFeed ") contains 1-5 weight percent water. The aim is to reduce the amount of carbon monoxide (CO) released during foaming.

The present invention also provides polyurethane foams formed by mixing and reacting the polyurethane foaming compositions described above with polyisocyanate monomers (e.g., MDI and/or TDI) and/or isocyanate-terminated prepolymers. In general, the weight ratio of the polyurethane foaming composition to the polyisocyanate monomer and/or isocyanate-terminated prepolymer is, for example, in the range of 0.5:1 to 2:1, preferably in the range of 0.5:1 to 1:1 (for polyurethane hard-foam type foaming compositions) or preferably in the range of 1:1 to 2:1 (for polyurethane soft-foam type foaming compositions). Preferably, the weight ratio should be such that the equivalent ratio of active hydrogen of the foaming composition to-NCO groups contained in the polyisocyanate monomer and/or isocyanate-terminated prepolymer is from 0.6 to 1.2:1, more preferably from 0.7 to 0.9:1, i.e. a slight excess of NCO relative to active hydrogen.

The invention also provides the application of the polyurethane foam material, which is used for polyurethane spraying, heat preservation of refrigerators and freezers, heat preservation of containers, heat preservation of buildings, color steel plates, cold storage plates, heat preservation of pipelines, heat preservation of LNG (liquefied natural gas) conveying, high-resilience foam, low-resilience foam and the like.

Preferably, the organic amine salt compound of formula (I) has at least two active hydrogens, for example 2 to 10, preferably 3 to 6. The active hydrogen is present as a primary amine group, a secondary amine group or a hydroxyl group. Thus, the organic amine salt compound of formula (I) is capable of releasing CO₂So as to participate in foaming and also participate in chain extension and/or crosslinking, and the strength (namely mechanical strength and/or mechanical strength) of the foam cells is enhanced, so that the obtained polyurethane foam (the foam is prepared in a self-made square die in a laboratory by manual stirring) has good dimensional stability. Especially when the density of the polyurethane foam is high<25kg/m³However, the polyurethane foams obtained using the compounds of the formula (I) according to the invention as blowing agents, which foams are prepared in self-made laboratory square moulds by manual stirring, have excellent dimensional stability, in particularWhich shows little macroscopic shrinkage at ambient or room temperature conditions for a period of at least 5 months. For example, according to the Chinese national standard GB/T8811-2008, the finished foam material (density) prepared by the invention is changed only by changing the placing time<25kg/m³) The polyurethane foam was left at room temperature (23. + -. 2 ℃ C.) for 5 months, and the shrinkage factor (. epsilon.) of the polyurethane foam was measured_LOr rate of change of width dimension ε_wOr the thickness dimension change epsilonr) is generally lower than 7%, more preferably lower than 5%, further preferably lower than 3%, even more preferably lower than 1%.

The organic amine salt compound of the general formula (I) of the present invention can be specifically designed according to various application fields of the polyurethane foam material to be produced.

For example, when the foaming composition (commonly referred to as "white material") of the present invention is used for the preparation of a polyurethane foam material used as a heat insulating material for refrigerators, freezers, refrigerated containers or refrigerated vehicles or for the preparation of a flexible polyurethane foam material having high resilience, low resilience or the like, in the preparation of a polyurethane foam material wherein A is^n-In the reaction of the compound of the general formula (I) which is (a) to (f) or (h), the molar ratio of the first raw material to the second raw material is generally 1:1.3 to 3.5, preferably 1:1.5 to 3. In addition, when the foaming composition of the present invention (commonly referred to as "white material") is used in spray construction, the molar ratio of the first material to the second material is generally 1:2.8 to 5, preferably 1:3 to 4.5, more preferably 1:3.3 to 4.

Preferably, the reaction temperature for the preparation of the compounds of formula (I) is between 0 and 200 deg.C, such as 10 deg.C, 20 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C. The pressure of the reaction is between 0.1 and 1.5MPa, for example 0.3MPa, 0.6MPa, 0.9MPa and 1.2 MPa. The reaction time is 0.5 to 20 hours, for example, 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours.

The decomposition temperature of the compounds of formula (I) according to the invention is generally between 45 and 120 ℃ and preferably between 50 and 70 ℃ or, when they are brought into contact with isocyanates, between 45 and 70 ℃.

Advantageous effects or advantages of the invention

1. The compounds of the general formula (I) according to the invention, for example hydralazine salt compounds, or the blowing agents according to the invention, have a suitable decomposition temperature, or a suitable decomposition temperature when brought into contact with isocyanates, which is stable on the one hand on storage at room temperature and on the other hand is capable of releasing carbon dioxide gas at a reasonable rate during the polyurethane foaming process when the foaming reaction system is warmed, so that the foamed material has the desired properties, such as cell distribution density, cell size uniformity. The most preferred blowing agents in the present invention are carbamates and/or carbonates having the general formula (I) due to their suitable decomposition temperature, suitable carbon dioxide release rate, excellent cell distribution density, excellent cell size uniformity, significantly smaller cell size than physical blowing agents such as water, cyclopentane, etc. forming a foam under the same foaming parameters, and much larger number of cells per unit volume than other blowing agents, thereby imparting good thermal insulation properties to the foam. The blowing agents according to the invention, in particular carbamates and/or carbonates, have a high pH value (pH >7.5), a high acid radical content (or a high CO2 emission) per unit weight and a high reactivity as blowing agents, in particular as polyurethane blowing agents. In particular, the hydrazino-hydramine salt compound has higher basicity than the amino compound due to two amino groups per one hydrazine group, and thus can bind more anions per unit weight, i.e., has a high acid content (or a greater amount of CO2 released), compared to an organic hydramine salt compound not containing a hydrazine group.

2. The compound of the general formula (I) of the present invention, for example, a hydrazinohydramine salt compound, having a solubilizing group, i.e., R group, can be uniformly dissolved or distributed in a polymer polyol such as polyether polyol and/or polyester polyol, or polyvinyl chloride (PVC) resin or Polystyrene (PS) resin at a molecular level, ensuring uniformity of foaming, avoiding local excessive foaming.

3. The invention is a chemical reaction of the general formula (I)Compounds, e.g. hydraminoalcohol salt compounds, having an alcohol amine residue or having an alcohol amine compound which decompose to release CO in the blowing agent (I)₂The resulting decomposition products, i.e. the alcohol amine compounds, still contain at least two active hydrogens, which are suitable as chain extenders and/or crosslinkers, the compounds of the general formula (I) according to the invention act both as "foaming points" and as "chain extension points" and/or "crosslinking points", significantly increase the mechanical strength and mechanical strength of the cells, the polyurethane foams obtained have good dimensional stability, and the shrinkage is hardly observed by the naked eye after the polyurethane foam products have been left for several months, even 1 year, without collapsing or collapsing. Particularly good dimensional stability after prolonged periods of time, e.g. 10 days, at higher temperatures, e.g. 40-60 c, even 40-70 c.

4. The compound (such as the hydrazino-alcohol amine salt 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 in the prior art.

5. When used as a blowing agent in combination with cyclopentane, the thermal insulation properties of the foam can be significantly improved compared to the use of cyclopentane alone. 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 compared to the use of a chlorofluorocarbon 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.

6. The foaming agent disclosed by the invention has amino groups and an autocatalysis function, so that the use of polyurethane foaming catalysts can be reduced, and at least the use of early-stage catalysts can be reduced or even the early-stage catalysts can be omitted.

7. Compared with the prior art, the polyurethane foaming agent provided by the invention does not contain chlorofluorocarbon or chlorofluorocarbon, 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 advantage that the heat conductivity coefficient at minus 160 ℃ is about 20% lower than that of the existing best physical foaming agent, and the excellent characteristic can be used for heat preservation of a long-distance natural gas transportation pipeline, and the other characteristic can be used for greatly reducing the heat conductivity coefficient of a foam material when being mixed with cyclopentane, so that the excellent heat preservation performance can greatly reduce the power consumption of equipment such as a refrigerator and a freezer. The polyurethane foaming agent provided by the invention can replace all existing physical foaming agents containing halohydrocarbon (containing halogen), and meets the production application of polyurethane materials.

8. The polyurethane foam prepared by using the foaming agent or the compound (such as the hydrazinohydramine salt compound) of the general formula (I) as the foaming agent (the foam is prepared in a self-made square mould in a laboratory by manual stirring) has the dimensional change rate or shrinkage rate of less than or equal to 4.5 percent, preferably less than or equal to 1.5 percent and more preferably less than or equal to 0.5 percent (according to the Chinese national standard GB/T8811-2008, the standing time can be required by 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.

9. The compound or mixture (such as hydrazino alcohol amine salt compound) of the general formula (I) contains a small amount of water, and the water is combined or associated with the molecule of the alcohol amine salt compound of the general formula (I) in a single molecule, so that the water in the form of the single molecule is very favorable for foaming and improving the performance of a foam product. Although the prior art also uses small amounts of water as a blowing agent or auxiliary blowing agent, this water is usually present in the form of clusters of water molecules or water molecules (i.e., in the form of micro-droplets), and in particular the clusters of water molecules are of different sizes, which can lead to uneven foaming of the foaming composition, and in particular to localized collapse of the foam, affecting various properties of the foam product.

Drawings

FIG. 1 is an infrared spectrum of the product of example A-3.

FIG. 2 is an infrared spectrum of the product of example A-4.

FIG. 3 is an infrared spectrum of the product of example B-6.

FIG. 4 is a Scanning Electron Micrograph (SEM) of the foam of example 4.

FIG. 5 is an SEM of comparative foam 4-1 of repeat example 4.

FIG. 6 is an SEM of reference foam 4-2 of repeat example 4.

FIG. 7 is an SEM of comparative foam 4-3 of repeat example 4.

FIG. 8 is an SEM of reference foam 4-4 of repeat example 4.

FIG. 9 is an SEM of the foam of example 16.

FIGS. 10, 12 and 14 are photographs showing the appearance of the polyurethane foam of the present invention using the compound A-4 as a blowing agent.

Fig. 11, 13 and 15 are photographs of the appearance of comparative polyurethane foams blown with water.

FIG. 16 is an SEM of the polystyrene foam of example 34.

FIG. 17 is an infrared spectrum of the compound (hydrazine alkylamine salt) of example 36.

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, monoethanolamine, diethanolamine, triethanolamine, JXP-508, JXP-509, TMR-2, TMR-3, and TMR-4. Common flame retardants: TCPP, TCEP, DMMP, ammonium chloride, aluminum hydroxide powder, DM1201, DM1301, tetrabromophthalic anhydride diol. 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.

Safety explanation: in the present invention, in the case of using the epoxy compound, it is necessary to perform the reaction under the treatment and protection of an inert gas (e.g., nitrogen or argon) before and after the reactants are charged into the reactor for safety, thereby preventing explosion. In addition, in the case of adding ethylene oxide, it is preferable to add it to the reactor in portions for safety, and propylene oxide may be added to the reactor at once or in portions. The reactor is generally a pressure reactor equipped with cooling means, unless otherwise specified. The epoxy compound is slowly added to the reactor in portions, and for those relatively safe epoxy compounds, the epoxy compound is slowly added to the reactor in portions, and the reaction conditions such as the reaction speed are controlled to ensure safety. Hydrazine hydrate is also a flammable and explosive toxic compound and must therefore be used in accordance with the relevant requirements and regulations.

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 between the cold plate and the hot plate is 15-20 ℃. The apparent (core) density was tested in accordance with GB/T6343-2009. The low temperature dimensional stability was tested according to GB/T8811-2008 at-30 ℃. + -. 2 ℃. The compressive strength was tested according to GB/T8813-2008. The closed cell fraction (i.e., the percentage of closed cell volume) was tested in accordance with GB/T10799-.

For the measurement of the content of various alcohol amines (e.g. monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine or tripropanolamine) in the compound or mixture of compounds of the formula (I), gas chromatography can be used. Wherein the gas chromatograph is equipped with a hydrogen Flame Ionization Detector (FID) and the mass concentration of the compound of formula (I) is about 10mg/mL as a standard solution. 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.

A) Preparation of compounds of general formula (I) from amino acid ammonium salts or carbamic acid organic amine (M) salts

Example A-1

1.4 tons of ammonium carbamate (molecular weight: 78.07), 0.7 tons of ethylene glycol and 0.9 tons of water are added into a stainless steel autoclave (hereinafter, referred to as a reactor in other examples) with a cooling water jacket, a stirrer is started to slowly dissolve the ammonium carbamate (not necessarily completely dissolved), the reactor is purged with nitrogen, then the reactor is closed and stirred, a total of 1.7 tons of propylene oxide (molecular weight: 58.08, boiling point: 34 ℃) is introduced, the feeding speed of the propylene oxide is controlled so as to control the pressure in the reactor to be not higher than 0.6MPa, the temperature is slowly increased under continuous stirring, the temperature is controlled to be below 70 ℃ for 15 hours, the reaction is completed, the temperature is slowly decreased to 50 ℃, and then the vacuum degree is controlled to be below 600 mmHg (preferably below 500mmHg) to slowly remove unnecessary water (for example, the water content is below 20 wt%) and unreacted propylene oxide, then the vacuum is released, the temperature is reduced to below 40 ℃, and then the reactant is released to obtain the compound A-1. Viscosity 200 cps, pH 9, and decomposition temperature of compound a-1 is 45-70 ℃ (very slow decomposition from 45 ℃ with peak decomposition temperature 57-62 ℃). 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). The mole ratio of monopropanolamine to dipropanolamine was 1:0.06, as determined by gas chromatography. Compound a-1 contains about 75 wt% of the salts of both monopropanolamine and dipropanolamine. And also contains a portion of water. In addition, compound A-1 contains about 55 wt% of monopropanolamine and dipropanolamine (after heating compound A-1 to liberate carbon dioxide).

Compound A-1 is a clear or clear liquid which is relatively stable at room temperature or at ambient conditions and is suitable as a polyurethane blowing agent, and has the basic properties of HFC-245fa, LBA and pentafluorobutane as follows:

	compound A-1	HFC245fa	Pentafluorobutane	LBA
					ODP	0	0	0	0
GWP	1	1030.01	793.98	5.00
					Boiling point (. degree.C.)	Slow decomposition at 45 deg.C	15.3	40.2	19.3

As can be seen from the above table, the GWP (potential value of greenhouse effect) of the compound A-1 is equal to 1, the decomposition temperature is higher, and the defects of certain low-boiling point (lower than 20 ℃) physical foaming agents such as HFC-245fa, LBA, pentafluorobutane and the like are overcome, such as the GWP which is far greater than 1, the boiling point which is lower and is volatile, while the GWP of the compound A-1 is equal to 1, the boiling point which is higher and is not volatile, and the ODP (potential value of destroying the ozone layer) which is 0 can not destroy the atmospheric ozone layer; is not easy to volatilize and is convenient for transportation and storage.

Example A-2

Adding 1.4 tons of ammonium carbamate, 0.7 tons of ethylene glycol and 0.9 tons of water into a stainless steel reactor with a cooling jacket, starting stirring to slowly dissolve the ammonium carbamate (not necessarily completely dissolved), heating the reaction system after nitrogen treatment and protection, controlling the temperature to be 45-70 ℃, controlling the pressure not to exceed 0.6MPa, then slowly adding 1.3 tons of ethylene oxide (molecular weight 44.05) in batches, controlling the temperature to be 45-70 ℃ after the addition is finished, stirring and reacting for 5 hours under the pressure of 0.6MPa, then cooling to 50 ℃, removing unnecessary water (for example, reaching the water content of less than 30 wt%) and unreacted ethylene oxide under reduced pressure of 600mHg, cooling to below 40 ℃, and discharging the product to obtain the compound A-2. Viscosity was about 250, pH 9, and decomposition temperature of compound a-2 was in the range of 45-70 ℃.

Examples A-3 (preferred according to the invention)

1kg of ammonium carbamate and 1kg of water are introduced into a reactor, dissolved with stirring (allowing the presence of undissolved ammonium carbamate), the reactor is purged with nitrogen and then 2kg of propylene oxide are introduced into a transparent quartz glass reactor, the reaction is carried out with stirring and with a slow temperature increase, controlled between 50 and 60 ℃ and at a pressure not higher than 0.6MPa, and a wonderful phenomenon suddenly appears when the reaction has proceeded for about 2 hours: the turbid and opaque mixture is instantly changed into transparent or clear solution, the reaction is continued for 8 hours, then the temperature is reduced to 50 ℃, unnecessary water and unreacted propylene oxide are removed under the vacuum degree of 600 mm Hg, and the product is released after the temperature is reduced to below 40 ℃. The reaction time ensures that the reaction is completed in molar ratio. Compound A-3 is obtained. Viscosity 200 centipoises, pH 9.1, decomposition temperature in 45-70 deg.C range. Liquid chromatography analysis and gas chromatography analysis showed that compound a-3 was a mixture containing a plurality of alcohol amines. The water content was 21.5 wt%. The infrared spectrum is shown in FIG. 1.

Examples A-4 (preferred according to the invention)

Adding 1 ton of ammonium carbamate and 1 ton of water into a stainless steel pressure reaction kettle with a cooling water jacket, dissolving under stirring (allowing insoluble ammonium carbamate to exist), purging the reactor with nitrogen, adding 2.2 tons of propylene oxide into the reactor in batches, closing the reactor, starting stirring, slowly raising the temperature under continuous stirring, controlling the temperature between 45 and 70 ℃, reacting for 10 hours under the condition that the pressure is not higher than 0.6MPa, then reducing the temperature to 50 ℃, removing unnecessary water under the condition that the vacuum degree is 600 mm Hg, and discharging the product after reducing the temperature to below 40 ℃. Compound A-4 is obtained. Viscosity 200 centipoises, pH 9, decomposition temperature 45-70 deg.C. Both liquid chromatography and gas chromatography showed that compound a-4 was a mixture comprising a plurality of alcohol amines. The infrared spectrum is shown in FIG. 2.

Examples A-5 (preferred according to the invention)

Adding 7kg of ammonium carbonate, 7kg of ammonium carbamate and 12kg of water into a reactor, dissolving the ammonium carbamate and the ammonium carbonate under stirring (insoluble ammonium carbamate and ammonium carbonate are allowed to exist), purging the reactor by using nitrogen, then adding 30kg of epoxypropane in batches, slowly raising the temperature under continuous stirring, controlling the temperature to be 45-70 ℃, controlling the pressure to be not higher than 0.6MPa, reacting for 10 hours, then reducing the temperature to 50 ℃, controlling the temperature to be below 50 ℃, controlling the vacuum degree to be below 600 mm Hg, removing unnecessary water and unreacted epoxypropane, reducing the temperature to be below 40 ℃, then discharging the vacuum and discharging a product to obtain the compound A-5. Viscosity was approximately 200 centipoise, pH 9, and decomposition temperature was in the range of 45-70 ℃.

Examples A-6 (preferred according to the invention)

Adding 16kg of aminoformic acid monoethanolamine salt and 10kg of water into a reactor, sweeping the reactor by nitrogen, stirring for dissolving, adding 12kg of propylene oxide into the reactor in batches, starting stirring, controlling the pressure to be not higher than 0.6MPa, slowly raising the temperature under continuous stirring, controlling the temperature to react for 5 hours when the temperature is raised to 70 ℃, then reducing the temperature to be below 50 ℃, controlling the vacuum degree to be below 600 mm Hg, removing unnecessary water and unreacted propylene oxide, reducing the temperature to be below 40 ℃, then discharging the vacuum and discharging the product, thus obtaining the compound A-6. Viscosity 230 centipoise. pH 9. The decomposition temperature is in the range of 45-70 ℃.

Examples A to 7

Adding 20kg of diethylenetriamine carbamate and 10kg of water into a reactor, stirring for dissolving, purging the reactor by nitrogen, controlling the pressure to be not higher than 0.6MPa and the temperature to be 45-70 ℃ under stirring, adding 15kg of propylene oxide into the reactor in batches, controlling the temperature to react for 5 hours after the propylene oxide is added, then cooling to 50 ℃, removing unnecessary water and unreacted propylene oxide under the reduced pressure of the vacuum degree below 600 mmHg, and discharging the vacuum and the product after the vacuum degree is reduced to below 40 ℃ to obtain the compound A-7. The viscosity was approximately 350 centipoise. pH 9 and decomposition temperature in the range of 45-70 ℃.

Examples A to 8

Adding 1 ton of ammonium carbamate (molecular weight is 78.07) and 1 ton of water into a reactor, dissolving the ammonium carbamate under stirring (insoluble ammonium carbamate is allowed to exist), purging the reactor by nitrogen, adding 2.8 tons of epichlorohydrin (namely, epichlorohydrin or 3-chloro-1, 2-epoxypropane, molecular weight is 92.52, boiling point is 117.9 ℃) into the reactor, starting stirring, slowly raising the temperature under continuous stirring, controlling the temperature to be between 45 and 70 ℃, reacting for 10 hours under the condition that the pressure is not higher than 0.6MPa, then reducing the temperature to 50 ℃, removing unnecessary water and unreacted epichlorohydrin under the vacuum degree of 600 mm Hg, and discharging the product after reducing the temperature to be below 40 ℃. Compound A-8 is obtained. Viscosity 450 centipoises, pH 9, decomposition temperature 45-70 deg.C.

Examples A to 9

Adding 0.65 ton of ammonium carbonate, 0.65 ton of ammonium carbamate and 1.2 ton of water into a reactor, dissolving the ammonium carbamate and the ammonium carbonate under stirring (insoluble ammonium carbamate and ammonium carbonate are allowed to exist), purging the reactor by using nitrogen, then adding 3.6 ton of styrene oxide (styrene oxide, molecular weight 120.15), slowly raising the temperature under continuous stirring, controlling the temperature to be between 45 and 70 ℃, controlling the pressure to be not higher than 0.6MPa, reacting for 10 hours, then cooling to 50 ℃, controlling the temperature to be below 50 ℃, removing unnecessary water from a mercury column with the vacuum degree of 600 mm, cooling to below 40 ℃, then discharging vacuum and discharging a product to obtain the compound A-9. Viscosity of about 460 centipoise, pH 9, decomposition temperature in the range of 45-70 ℃.

Examples A to 10

Adding 1kg of hydrazine carbamate and 0.9kg of water into a reactor, dissolving for 30 minutes under stirring (allowing a small amount of undissolved hydrazine carbamate to exist), purging the reactor with nitrogen, adding 1.8kg of propylene oxide in batches into a transparent quartz glass reactor, starting stirring, slowly raising the temperature under continuous stirring, controlling the temperature between 50 and 70 ℃, carrying out the reaction under the condition that the pressure is not higher than 0.6MPa, and when the reaction is carried out for about 2 hours, showing a wonderful phenomenon: the turbid and opaque mixture is instantly changed into a transparent or clear solution, the reaction is continued for 5 hours, then the temperature is reduced to 50 ℃, a part of water and unreacted propylene oxide are separated out under the vacuum degree of 600 mm Hg, and the product is released after the temperature is reduced to below 40 ℃. The reaction time is sufficient to ensure that the reaction is complete in molar ratios. Compound A-10 was obtained. pH 8.9, decomposition temperature 45-70 deg.C. Compound a-10 contained about 76 wt% of the salts of both monopropanolamine and dipropanolamine, analyzed by gas chromatography. And also contains a portion of water. In addition, compound A-10 contained about 56 wt% of monopropanolamine and dipropanolamine (after heating compound A-10 to liberate carbon dioxide).

₃ ^2-B) Preparation of Compounds of the general formula (I) having a CO anion

Example B-1

Adding 14kg of ammonium carbonate (with the molecular weight of 96), 6kg of ethylene glycol and 8kg of water into a reactor, starting stirring to slowly dissolve the ammonium carbonate (not necessarily completely dissolved), purging the reactor with nitrogen, adding 20kg of propylene oxide, starting stirring, controlling the pressure to be not higher than 0.6MPa, slowly heating while continuously stirring, controlling the temperature to be below 70 ℃ for reaction for 12 hours, slowly reducing the temperature to 50 ℃, controlling the vacuum degree to be below 600 mmHg to slowly remove unnecessary water and unreacted propylene oxide, then discharging the vacuum, cooling to below 40 ℃, and discharging reactants to obtain a compound B-1. Viscosity was approximately 300 centipoise, pH 9, and decomposition temperature of compound B-1 was 45-70 ℃. Liquid chromatography analysis and gas chromatography analysis show that the compound B-1 is a mixture containing various alcohol amines. 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). The mole ratio of monopropanolamine to dipropanolamine was 1:0.22 by gas chromatography. Compound B-1 contains about 78 wt% of the salt of both monopropanolamine and dipropanolamine. Compound B-1 contains about 56% by weight of monopropanolamine and dipropanolamine.

Example B-2

Adding 1.4 tons of ammonium carbonate and 1 ton of water into a stainless steel pressure reaction kettle with a cooling jacket, stirring and dissolving (allowing insoluble ammonium carbonate to exist), purging with nitrogen, sealing the reaction kettle, controlling the temperature to be between 45 and 70 ℃ and the pressure to be not higher than 0.6MPa under the condition of continuous stirring, adding 1.3 tons of ethylene oxide into the reactor in batches, controlling the temperature to react for 4 hours after the addition is finished, then cooling to 50 ℃, controlling the vacuum to remove unnecessary water and unreacted ethylene oxide under the reduced pressure of below 600mHg, cooling to below 40 ℃, then discharging the vacuum and discharging the product. Compound B-2 is obtained. The viscosity was 300 centipoise. pH 9.1. The decomposition temperature is 45-70 ℃. Liquid chromatography analysis and gas chromatography analysis show that the compound B-2 is a mixture containing a plurality of alcohol amines.

Example B-3

Adding 20kg of ammonium carbonate and 18kg of water into a transparent quartz glass reactor, stirring and dissolving (allowing insoluble ammonium carbonate to exist), purging the reactor with nitrogen, controlling the temperature to be 45-70 ℃ and the pressure to be not higher than 0.6MPa under continuous stirring, adding 45kg of propylene oxide into the reactor, controlling the temperature after the addition is finished, and suddenly generating wonderful phenomenon when the reaction is carried out for about 2 hours: the turbid and opaque mixture is instantly changed into a transparent or clear solution, the reaction is continued for 8 hours, then the temperature is reduced to 50 ℃, the vacuum is controlled to be below 600mHg, the unnecessary water and the unreacted propylene oxide are removed under reduced pressure, the temperature is reduced to below 40 ℃, the vacuum is released, and the product is discharged. Compound B-3 is obtained. The viscosity was approximately 250 centipoise. pH 9.1. The decomposition temperature is 45-70 ℃.

Example B-4

Adding 20kg of ammonia water (with the concentration of 25 wt%) into a reactor, purging the reactor with nitrogen, starting stirring, controlling the pressure to be not higher than 0.6MPa and the temperature to be not more than 120 ℃, adding 16kg of ethylene oxide in batches, and controlling the temperature to react for 1 hour after the addition is finished. After the reaction is finished, cooling to room temperature, decompressing and steaming to remove unnecessary water and unreacted ethylene oxide, introducing 4kg of carbon dioxide (molecular weight 44) until the pH value is about 8, controlling the temperature below 80 ℃, and cooling to room temperature after the reaction is finished. Compound B-4 is obtained. The viscosity was about 400 centipoise. The decomposition temperature is in the range of 45-75 ℃.

Example B-5

Adding 20kg of ammonia water (with the concentration of 25 wt%) and 5kg of ethylene glycol into a reactor, purging the reactor with nitrogen, starting stirring, controlling the pressure to be not higher than 0.6MPa and the temperature to be not more than 120 ℃, adding 20kg of propylene oxide in batches, and controlling the temperature to react for 2 hours after the addition is finished. And after the reaction is finished, cooling to room temperature, decompressing, steaming to remove unnecessary water and unreacted propylene oxide, introducing 5kg of carbon dioxide until the pH value is about 8, controlling the temperature to be below 80 ℃, and cooling to room temperature after the reaction is finished. Compound B-5 is obtained. The viscosity was approximately 450 centipoise. The decomposition temperature is in the range of 45-75 ℃.

Example B-6

10kg of diethylenetriamine (molecular weight: 103.17) and 15kg of water are added into a reactor, the reactor is purged by nitrogen, stirring is started, the pressure is controlled to be not higher than 0.6MPa, the temperature is not higher than 120 ℃, 15kg of propylene oxide is added in batches, and the temperature is controlled for reaction for 1 hour after the addition. And after the reaction is finished, cooling to room temperature, decompressing, steaming to remove unnecessary water and unreacted propylene oxide, introducing 6kg of carbon dioxide until the pH value is about 8, controlling the temperature to be below 80 ℃, and cooling to room temperature after the reaction is finished. Compound B-6 is obtained. The viscosity was about 500 centipoise. The decomposition temperature is in the range of 45-70 ℃. The IR spectrum is shown in FIG. 3.

Example B to 7

10kg of ethylenediamine (molecular weight of 60.12) and 15kg of water are added into a reactor, the reactor is purged by nitrogen, stirring is started, the pressure is controlled to be not higher than 0.6MPa, the temperature is not higher than 120 ℃, 10kg of ethylene oxide (molecular weight of 44.05) is added in batches, and the temperature is controlled to react for 1 hour after the addition is finished. And after the reaction is finished, cooling to room temperature, decompressing, steaming to remove unnecessary water and unreacted ethylene oxide, introducing 5kg of carbon dioxide until the pH value is 8, controlling the temperature to be below 80 ℃, and cooling to room temperature after the reaction is finished. Compound B-7 was obtained. The viscosity was about 500 centipoise. The decomposition temperature is in the range of 45-70 ℃.

Example B to 8

Adding 6kg of ethylenediamine (molecular weight of 60.12) and 3.4kg of liquid ammonia into a special pressure-resistant mixing tank, uniformly mixing, then adding into a mixing reactor by controlling a certain flow through a pipeline, controlling the pressure to be 0.6MPa and the temperature to be below 60 ℃, slowly mixing with 9kg of carbon dioxide gas, reducing the temperature to room temperature after the reaction is finished, adding all obtained products and 10kg of water into a reaction kettle, slowly dissolving under stirring (allowing insoluble substances to exist), purging the reactor by using nitrogen, controlling the pressure to be not higher than 0.6MPa, adding 35kg of propylene oxide in batches under the condition that the temperature is not higher than 70 ℃, and controlling the temperature to react for 5 hours after the addition is finished. After the reaction is finished, the temperature is reduced to room temperature, and a part of water and unreacted propylene oxide are evaporated under reduced pressure. Compound B-8 is obtained. pH 9.1, decomposition temperature in 45-70 deg.C range.

Examples B to 9

Adding 6kg of diethylenetriamine (molecular weight: 103.17) and 3kg of liquid ammonia into a special pressure-resistant mixing tank, uniformly mixing, then adding into a mixing reactor by controlling a certain flow through a pipeline, controlling the pressure to be 0.6MPa and the temperature to be below 60 ℃, slowly mixing with 7.6kg of carbon dioxide gas, reducing the temperature to room temperature after the reaction is finished, adding all obtained products and 10kg of water into a reaction kettle, slowly dissolving under stirring (allowing insoluble substances to exist), purging the reactor by using nitrogen, controlling the pressure to be not higher than 0.6MPa, adding 22kg of ethylene oxide in batches under the condition that the temperature is not higher than 70 ℃, and controlling the temperature to react for 5 hours after the addition is finished. After the reaction is finished, the temperature is reduced to room temperature, and a part of water and unreacted ethylene oxide are evaporated under reduced pressure. Compound B-9 is obtained. pH 8.8, decomposition temperature 45-70 deg.C.

Examples B to 10

Adding 6kg of diethylenetriamine (molecular weight: 103.17) and 3kg of liquid ammonia into a special pressure-resistant mixing tank, uniformly mixing, then adding into a mixing reactor through a pipeline at a certain flow rate, controlling the pressure to be 0.6MPa and the temperature to be below 60 ℃, slowly mixing and reacting with 7.6kg of carbon dioxide gas, reducing the temperature to room temperature after the reaction is finished, adding all obtained products and 10kg of water into a reaction kettle, slowly dissolving under stirring (allowing insoluble substances to exist), purging the reactor with nitrogen, controlling the pressure to be not higher than 0.6MPa, adding 9kg of ethylene oxide and 14kg of propylene oxide in batches under the condition that the temperature is not higher than 70 ℃, and controlling the temperature to react for 5 hours after the addition is finished. After the reaction is finished, the temperature is reduced to room temperature, and a part of water and unreacted ethylene oxide and propylene oxide are distilled off under reduced pressure. Compound B-10 was obtained. pH 9.0, decomposition temperature 45-70 deg.C.

Example B to 11

Adding 6kg of ethylenediamine (molecular weight: 60.12), 3kg of methylamine (molecular weight: 31.10) and 1.7kg of liquid ammonia into a special pressure-resistant mixing tank, uniformly mixing, then adding into a mixing reactor by controlling a certain flow through a pipeline, controlling the pressure to be 0.6MPa and the temperature to be below 60 ℃, slowly mixing with 8.5kg of carbon dioxide gas, reducing the temperature to room temperature after the reaction is finished, adding all the obtained products and 10kg of water into a reaction kettle, slowly dissolving under stirring (allowing insoluble substances to exist), purging the reactor with nitrogen, controlling the pressure to be not higher than 0.6MPa and the temperature to be not higher than 70 ℃, adding 31kg of propylene oxide in batches, and controlling the temperature to react for 5 hours after the addition is finished. After the reaction is finished, the temperature is reduced to room temperature, and a part of water and unreacted propylene oxide are evaporated under reduced pressure. Compound B-11 was obtained. pH 9.0, decomposition temperature 45-70 deg.C.

Examples B to 12

0.9kg of hydrazine carbonate and 0.8kg of water are added to the reactor, dissolved for 30 minutes with stirring (allowing insoluble ammonium carbamate to be present), the reactor is purged with nitrogen, then 1.8kg of propylene oxide is added in portions to a transparent quartz glass reactor, stirring is started, the temperature is slowly raised with continuous stirring, the temperature is controlled between 50 and 70 ℃, the pressure is not higher than 0.6MPa, the reaction is carried out, and wonderful phenomenon appears when the reaction is carried out for about 2 hours: the turbid and opaque mixture is instantly changed into a transparent or clear solution, the reaction is continued for 5 hours, then the temperature is reduced to 50 ℃, a part of water and unreacted propylene oxide are separated out under the vacuum degree of 600 mm Hg, and the product is released after the temperature is reduced to below 40 ℃. The reaction time ensures that the reaction is completed in molar ratio. Compound B-12 is obtained. pH 8.9, decomposition temperature 45-70 deg.C. Compound B-12 contained about 77% by weight of the salts of both monopropanolamine and dipropanolamine, as analyzed by gas chromatography. And also contains a portion of water. In addition, compound B-12 contains about 56 wt% of monopropanolamine and dipropanolamine (after heating compound B-12 to liberate carbon dioxide).

Examples B to 13

0.9kg of hydrazine carbonate and 0.8kg of water are added to the reactor, dissolved for 30 minutes with stirring (allowing insoluble ammonium carbamate to be present), the reactor is purged with nitrogen, then 1.3kg of ethylene oxide is added in portions to a transparent quartz glass reactor, stirring is started, the temperature is slowly raised with continuous stirring, the temperature is controlled between 50 and 70 ℃, the reaction is carried out under the condition that the pressure is not higher than 0.6MPa, and wonderful phenomenon appears when the reaction is carried out for about 2 hours: the turbid and opaque mixture is instantly changed into a transparent or clear solution, the reaction is continued for 5 hours, then the temperature is reduced to 50 ℃, a part of water and unreacted ethylene oxide are separated out under the vacuum degree of 600 mm Hg, and the product is released after the temperature is reduced to below 40 ℃. The reaction time ensures that the reaction is completed in molar ratio. Compound B-13 was obtained. pH 8.8, decomposition temperature 45-70 deg.C.

^-C) Preparation of Compounds of formula (I) having Formate (HCOO)

Example C-1

15kg of ammonium formate, 1kg of methylamine catalyst, 10kg of water and 5kg of ethylene glycol are added into a reactor, stirring is started, the reactor is purged by nitrogen, the pressure is controlled to be not higher than 0.5MPa, the temperature is controlled to be below 120 ℃, 12kg of ethylene oxide is added into the reactor in batches, and the reaction is carried out for 5 hours. And after the reaction is finished, cooling, controlling the vacuum degree to be below 600 mm Hg, decompressing at the temperature of below 100 ℃ to remove unnecessary water and unreacted ethylene oxide, removing the vacuum, cooling to the temperature of below 50 ℃ and discharging the product. Compound C-1 is obtained. Viscosity was about 200 centipoise, pH 8.5, and decomposition temperature above 100 ℃.

Example C-2

Example C-1 was repeated, except that 15kg of propylene oxide was used instead of 12kg of ethylene oxide, and propylene oxide was not added to the reactor in portions but added thereto all at once. Compound C-2 is obtained. Viscosity was about 350 centipoise, pH 8.6, and decomposition temperature above 100 ℃.

Example C-3

10kg of methyl formate, 10kg of ethyl formate, 13kg of ammonia water (the concentration is 25wt percent) and 35kg of diethanolamine are added into a reactor, stirring is started, the pressure is controlled to be not higher than 0.5MPa, the temperature is slowly increased under the condition of continuous stirring, and the temperature is controlled to react for 15 hours when the temperature is increased to 100 ℃. After the reaction is finished, the temperature is reduced, then the vacuum degree is controlled to be below 600 mm Hg, the methanol and the ethanol are removed under reduced pressure at the temperature of below 100 ℃, the vacuum is removed, and the temperature is reduced to below 50 ℃ to discharge the product. Compound C-3 is obtained. Viscosity was about 400 centipoise, pH 9, and decomposition temperature above 100 ℃.

The compounds C-1, C-2 and C-3 immediately release carbon dioxide gas when contacting with isocyanate, and release a small amount of carbon monoxide gas, thus overcoming the disadvantages of common physical foaming agents such as methyl formate.

Example C-4 (Compounds not of formula (I))

Adding 24kg of ammonia water (with the concentration of 25 wt%) into a reactor, controlling the temperature below 100 ℃, slowly dripping 20kg of formic acid (with the concentration of 85 wt%) into the ammonia water under continuous stirring, preserving the temperature for reaction for 1 hour after the addition is finished, and then controlling the vacuum degree below 600 mm Hg, and decompressing and removing unnecessary water at the temperature below 100 ℃. Compound C-4 is obtained. Viscosity was approximately 150 centipoise, pH 9.5, and decomposition temperature above 100 ℃.

Example C-5 (Compound not of formula (I))

Adding 23kg of ammonia water (with the concentration of 25 wt%) and 1.5kg of dimethylamine into a reactor, controlling the temperature below 100 ℃, slowly dripping 20kg of formic acid (with the concentration of 85 wt%) into the ammonia water under continuous stirring, preserving the temperature for reaction for 1 hour after the addition is finished, then controlling the vacuum degree below 600 mmHg, decompressing and removing unnecessary water at the temperature below 100 ℃, removing the vacuum, cooling to below 50 ℃, and discharging the product to obtain the compound C-5. Viscosity was approximately 150 centipoise, pH 9.2, and decomposition temperature above 100 ℃.

Example C-6 (Compound not of formula (I))

Adding 23kg of ammonia water (with the concentration of 25 wt%) and 1.5kg of methylamine into a reactor, controlling the temperature below 100 ℃, slowly dripping 20kg of formic acid (with the concentration of 85 wt%) into the ammonia water under continuous stirring, preserving the temperature for reaction for 1 hour after the addition is finished, then controlling the vacuum degree below 600 mm Hg, decompressing and removing unnecessary water (for example, the water content can reach about 10 wt%) at the temperature below 100 ℃, removing the vacuum, cooling to below 50 ℃, and discharging the product. Compound C-6 was obtained without crystallization, which may be disturbed by the addition of methylamine. Viscosity is about 150 centipoise, pH 9, decomposition temperature above 100 ℃.

The compound C-4, C-5 or C-6 immediately emits carbon dioxide gas when contacting with isocyanate, and simultaneously emits a small amount of carbon monoxide gas, thereby overcoming the defects of the common physical foaming agent.

Although the compounds C-1 to C-6 do not decompose even above 110 ℃, the inventors have found experimentally that these can easily decompose to release CO during polyurethane foaming₂The reason may be that when exposed to isocyanic acidThe ester compound first reacts with the NCO groups to form less stable carbonic anhydrides.

D) ^-Preparation of Compounds of formula (I) having bicarbonate radical (HO-COO)

Example D-1

Adding 10kg of ammonium bicarbonate (with the molecular weight of 79.06), 9.0kg of water and 1kg of ethylenediamine into a transparent quartz glass reactor, stirring for dissolving (allowing insoluble ammonium bicarbonate to exist), purging the reactor with nitrogen, sealing the reactor, controlling the temperature to be 45-65 ℃ and the pressure to be not higher than 0.6MPa under the condition of continuous stirring, adding 20kg of propylene oxide into the reactor in batches, controlling the temperature for reaction for 10 hours after adding, then cooling to 50 ℃, controlling the vacuum to be below 600mHg, removing unnecessary water and unreacted propylene oxide under reduced pressure, cooling to below 40 ℃, then discharging the vacuum, and discharging the product. Compound D-1 is obtained. The viscosity was approximately 250 centipoise. pH 8 and decomposition temperature 36-42 deg.C.

The inventors have surprisingly found that when compound D-1 is mixed with polyether polyols and/or polyester polyols, for example to formulate foaming compositions ("whitepacks"), the decomposition temperature of compound D-1 dissolved in the whitepack can be increased to 45-65 ℃. This gives compound D-1 a suitable decomposition temperature and is therefore suitable for polyurethane foaming.

E) ^b ^-Preparation of Compounds of the general formula (I) having a Monohydrocarbyl carbonate (RO-COO) anion

Example E-1

Adding 10kg of ammonium salt of methyl bicarbonate (molecular weight is 93), 9.0kg of water and 1kg of ethylenediamine into a transparent quartz glass reactor, stirring to dissolve (allowing insoluble ammonium salt to exist), purging the reactor with nitrogen, sealing the reactor, controlling the temperature to be 45-65 ℃ and the pressure to be not higher than 0.6MPa under continuous stirring, adding 20kg of propylene oxide into the reactor in batches, controlling the temperature to react for 10 hours after adding, then cooling to 50 ℃, controlling vacuum to remove unnecessary water and unreacted propylene oxide under reduced pressure below 600mHg, cooling to below 40 ℃, then discharging vacuum and discharging the product. Compound E-1 is obtained. The viscosity was approximately 350 centipoise. The pH is 8, and the decomposition temperature is 42-60 ℃.

F) ¹ ^a ² ^- ^a ¹ ^- ₃Preparation of Compounds of the general formula (I) having the anion-OOC-N (R) -R-N (R) -COO or R' (-N (R) -COO) Article (A)

Example F-1

10kg of NH₄OOC-NH-(CH₂)₅-NH-COO NH₄Adding 9.0kg of water with the molecular weight of 182 into a transparent quartz glass reactor, stirring and dissolving (allowing insoluble ammonium salt to exist), purging the reactor by using nitrogen, sealing the reactor, controlling the temperature to be 45-55 ℃ and the pressure to be not higher than 0.6MPa under the condition of continuous stirring, adding 20kg of propylene oxide into the reactor in batches, controlling the temperature to react for 10 hours after the addition is finished, then cooling to 50 ℃, removing unnecessary water and unreacted propylene oxide under the condition of controlling the vacuum to be reduced to be below 600mHg, cooling to be below 40 ℃, and then discharging the vacuum and discharging a product. Compound F-1 is obtained. The viscosity was approximately 600 centipoise. The pH is 9 and the decomposition temperature is 45-70 ℃.

Example F-2

12kg of benzene-1, 3, 5-tris (ammonium carbamate) (molecular weight 306) having the following formula:

adding 9.0kg of water into a transparent quartz glass reactor, stirring for dissolving (allowing insoluble ammonium salt to exist), purging the reactor with nitrogen, sealing the reactor, continuously stirring, controlling the temperature to be 45-60 ℃, controlling the pressure to be not higher than 0.6MPa, adding 20kg of propylene oxide into the reactor in batches, controlling the temperature for reaction for 10 hours after adding, then cooling to 50 ℃, controlling the vacuum to remove unnecessary water and unreacted propylene oxide under reduced pressure of below 600mHg, cooling to below 40 ℃, then discharging the vacuum, and discharging the product. Compound F-2 is obtained. The viscosity was approximately 510 centipoise. pH 9.6. The decomposition temperature is 45-70 ℃.

G)Preparation of orthoformic acidRadical anion of a compound of the formula (I)

Example G-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 G-1 with viscosity of about 500 centipoise, pH of 8.0, and decomposition temperature of 45-70 deg.C.

Example G-2

Adding 15kg of trimethyl orthoformate, 2.0kg of ethylene glycol, 10kg of water and 6.0kg of ethylenediamine 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 the compound G-2, wherein the viscosity is about 250 centipoises, the pH value is 8.3, and the decomposition temperature is 45-70 ℃.

Example G-3

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 G-3 in which two ester groups of the triethyl orthoformate are hydrolyzed. Viscosity is about 300 centipoise, pH 8.1, decomposition temperature 45-70 ℃.

Example G-4

20kg of ethylene glycol orthoformate, 11kg of diethanolamine and 10kg of ammonia water are added into a reactor, stirring is started, the temperature is slowly raised under continuous stirring, and the temperature is controlled not to exceed 100 ℃ for reaction for 8 hours. 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 a product to obtain the compound G-4. Viscosity is about 500 centipoise, pH 8, decomposition temperature 45-70 ℃.

Application examples

Example 1

8 parts by weight of the compound A-1 prepared in the above example A-1 as a blowing agent, 50 parts by weight of polyether polyol 4110 (produced by Binshi chemical group, Binzhou, Shandong), 1 part by weight of foam stabilizer DC3201 (produced by American air chemical Co., Ltd.), 12.5 parts by weight of flame retardant TCPP (produced by Jiangsu Yake chemical Co., Ltd.) and 2 parts by weight of catalyst A33(33LV, produced by American air chemical Co., Ltd.) were mixed uniformly to obtain a transparent foamed composition, and 95.5 parts by weight of isocyanate MDI (PM200, Tantawawa chemical group Co., Ltd.) was added thereto and foamed to obtain a polyurethane foam after stirring uniformly.

Example 2

8 parts by weight of the compound A-2 prepared in the above example A-2 as a blowing agent, 30 parts by weight of polyether polyol 4110, 20 parts by weight of polyester polyol CF6320 (Jiangsu Fusheng New materials Co., Ltd.), 1 part by weight of foam stabilizer DC3201, 12.5 parts by weight of flame retardant TCPP and 2 parts by weight of catalyst A33 were mixed uniformly to obtain a transparent foamed composition, 95.5 parts by weight of isocyanate MDI (PM200) was added thereto, and after stirring uniformly, a polyurethane foam was prepared.

Example 3

20 parts by weight of Compound A-3 as a blowing agent, 2 parts by weight of foam stabilizer DC3201, 0.5 part by weight of catalyst dibutyltin dilaurate, 0.5 part by weight of catalyst PC-5 (American Aikoku chemical industry), 1 part by weight of catalyst PC-8 (American air chemical industry), 1 part by weight of catalyst PT304 (American air chemical industry), 1 part by weight of catalyst A33, 40 parts by weight of flame retardant TCPP, 20 parts by weight of polyether polyol 4110, 10 parts by weight of AKS7004(AEKYUNGPETROCHEMICAL CO., LTD KOREA), 10 parts by weight of MN500 (Shandong Lanxingdong chemical Co., Ltd., hydroxyl value mgKOH/g: 330-.

Example 4

7 parts by weight of a compound A-4 as a foaming agent, 1 part by weight of a catalyst PC-41 (American air chemical industry), 0.5 part by weight of a catalyst PC-8 (American air chemical industry), 13 parts by weight of cyclopentane and 2 parts by weight of a foam stabilizer DC8545 (American air chemical industry) are added into a mixture of 50 parts by weight of polyether polyol 2010 (produced by Haian petrochemical plant of Jiangsu province), 25 parts by weight of polyether polyol SA380 (Shandong-one Noowei polyurethane Co., Ltd.) and 25 parts by weight of polyether polyol SA460 (Shandong-one Noowei polyurethane Co., Ltd.) and mixed uniformly to obtain a transparent foaming composition (called white material for short), then 148.2 parts by weight of isocyanate MDI (PM200) is added into the mixture, and the mixture is injected into a foaming mold to be foamed after being stirred uniformly to obtain the polyurethane foam with skin.

Samples were taken and sectioned with a razor blade and the cells were observed using SEM at 100 x magnification. As shown in fig. 4, the cell diameter was 205 microns.

For comparison, example 4 was repeated except that 5 parts by weight of water and 12 parts by weight of cyclopentane (1:2.4 weight ratio) were used as the blowing agent to obtain comparative foam 4-1; as shown in fig. 5, the cell diameter was 396 microns.

In addition, example 4 was repeated except that the compound A-4 of the present invention and cyclopentane (1:1.5 weight ratio) were used as blowing agents to obtain reference foam 4-2; as shown in fig. 6, the cell diameter was 306 microns. For comparison, example 4 was repeated except that water + LBA + cyclopentane (1:1:1 weight ratio) was used as the blowing agent to obtain comparative foams 4-3, as shown in FIG. 7, with cell diameters of 495 microns. This example 4 was repeated except that inventive compound a-4, LBA and cyclopentane (1:1.2:1.3 weight ratio) were used as blowing agents to obtain reference foams 4-4, as shown in fig. 8, with cell diameters of 335 microns.

As can be seen from FIGS. 4, 6 and 8, the foam appeared fine, uniform, dense, and had a significantly greater number of cells per unit area. As can be seen from fig. 5 and 7, the diameters of the cells are significantly uneven, and the number of cells per unit area is significantly smaller.

Example 5

6 parts by weight of a compound A-5 serving as a foaming agent, 1 part by weight of a foam stabilizer DC3201 (American air chemical industry), 30 parts by weight of polyether polyol 4110 (Binshanhuan group in Shandong Binshou), 20 parts by weight of polyester polyol CF6320 (Jiangsu Fusheng New Material Co., Ltd.), and 0.5 part by weight of a catalyst PC-41 (American air chemical industry) are uniformly mixed to obtain a foaming composition, 85 parts by weight of isocyanate MDI (PM200) is added into the foaming composition, and the foaming composition is uniformly stirred and foamed to obtain polyurethane foam.

Example 6

Uniformly mixing 20 parts by weight of a compound A-6 serving as a foaming agent, 50 parts by weight of polyether polyol 2010 (produced by Haian petrochemical plant of Jiangsu province), 25 parts by weight of polyether polyol SA380 (produced by Shandong-Nonwei polyurethane Co., Ltd.), 25 parts by weight of polyether polyol SA460 (produced by Shandong-Nonwei polyurethane Co., Ltd.), 0.5 part by weight of a catalyst PC-41 (American air chemical industry), and 0.5 part by weight of a catalyst PC-8 (American air chemical industry) to obtain a transparent foaming composition, adding 175 parts by weight of isocyanate MDI (PM200) into the transparent foaming composition, and uniformly stirring and foaming to obtain the polyurethane foam material.

Example 7

4 parts by weight of a compound A-7 serving as a foaming agent, 10 parts by weight of HFC-365mfc, 11 parts by weight of polyether polyol 4110 (Binshinhua group, Shandong), 39 parts by weight of polyester polyol DM2003 (Guangdong Germany fine chemical Co., Ltd.), 1.5 parts by weight of foam stabilizer DC3201 (American air chemical industry), 1 part by weight of catalyst JXP-508 (American air chemical industry), 0.6 part by weight of catalyst JXP-509 (American air chemical industry) and 1.5 parts by weight of catalyst K-15 (American air chemical industry) are uniformly mixed to obtain a foaming composition, and 155 parts by weight of isocyanate MDI (PM200) is added into 25 parts by weight of flame retardant TCPP to obtain polyurethane foam after being uniformly stirred and foamed.

Example 8

Uniformly mixing 4 parts by weight of compound A-1 serving as a foaming agent, 10 parts by weight of HFC-365mfc, 15 parts by weight of polyether polyol 4110 (Binshino group, Shandong), 35 parts by weight of polyester polyol DM2003 (Guangdong Germany fine chemical Co., Ltd.), 1.5 parts by weight of foam stabilizer DC3201, 0.5 part by weight of catalyst PC-8 (American air chemical industry), and 0.5 part by weight of catalyst PC-41 (American air chemical industry) to obtain a foaming composition, and 25 parts by weight of flame retardant TCPP, adding 160 parts by weight of isocyanate MDI (PM200), uniformly stirring, and foaming to obtain the polyurethane foam material.

Example 9

7 parts by weight of a compound A-3 as a foaming agent, 1 part by weight of a catalyst PC-41 (American air chemical industry), 0.5 part by weight of a catalyst PC-8 (American air chemical industry), 13 parts by weight of cyclopentane and 2 parts by weight of a foam stabilizer DC8545 (American air chemical industry) are added into a mixture of 50 parts by weight of polyether polyol 2010 (produced by Haian petrochemical plant of Jiangsu province), 25 parts by weight of polyether polyol SA380 (Shandong) and 25 parts by weight of polyether polyol SA460 (Noway polyurethane Co., Ltd., Shandong) to be uniformly mixed, then 150 parts by weight of isocyanate MDI (PM200) is added into the mixture, and the mixture is stirred uniformly and foamed to prepare polyurethane foam.

Example 10

5 parts by weight of compound A-2 serving as a foaming agent, 8 parts by weight of HFC-365mfc, 30 parts by weight of polyether polyol 4110 (Binshou beachdization group, Shandong), 20 parts by weight of polyester polyol CF6320 (Jiangsu Fusheng New Material Co., Ltd.) and 1 part by weight of foam stabilizer DC3201 (American air chemical industry), 12.5 parts by weight of flame retardant TCPP (Jiangsu Yake chemical industry Co., Ltd.), 1 part by weight of catalyst A33(33LV, American air chemical industry) and 1 part by weight of catalyst PC-41 (American air chemical industry) are uniformly mixed to obtain a foaming composition, 102 parts by weight of isocyanate MDI (PM200) is added into the foaming composition, and the foaming composition is prepared after uniform stirring.

Table 1: properties of polyurethane foams

Description of the drawings: the test data in the above list are those made for foam samples prepared using conventional foam boxes and self-made foam molds, and are free foam samples prepared by hand.

Wherein the shrinkage rate (size change rate) is measured according to the Chinese national standard GB/T8811-. The same applies below.

The product of example 4 appeared fine, uniform and dense, as shown in fig. 4, had good thermal insulation properties, and could meet the requirements of various properties in the field of refrigerators and freezers. The product of example 5 can meet the requirements of various properties in polyurethane pipeline heat preservation. The product of example 6 is very fine, uniform and dense, and can meet the requirements of various properties in LNG (liquefied natural gas) transportation and cold insulation applications. The product of example 7 can meet the requirements of various properties of the polyurethane thermal insulation board. The product of example 8 can meet the requirements of various properties of polyurethane color steel plates and cold storage plates.

Example 11

7 parts by weight of the compound B-1 prepared in the above example B-1 as a blowing agent, 50 parts by weight of polyether polyol 4110 (Binshai chemical group, Shandong Binshou), 1 part by weight of foam stabilizer DC3201 (American air chemical industry), 12.5 parts by weight of flame retardant TCPP (Jiangsu Yake chemical industry Co., Ltd.) and 2 parts by weight of catalyst A33(33LV, American air chemical industry) were mixed uniformly to obtain a transparent foamed composition, 95.5 parts by weight of isocyanate MDI (PM200) was added thereto, and the mixture was stirred uniformly and foamed to obtain a polyurethane foam.

Examples 12 to 20

Examples 12-20 examples 2-10 were repeated, respectively, except that the blowing agents were as shown in Table 2.

Table 2: properties of polyurethane foams

Description of the drawings: the test data in each of the above lists are test data made for foam samples prepared using conventional foam boxes and self-made foam molds, and are free foam samples prepared by hand.

The product of example 14, among others, has good thermal insulation properties, meeting the various performance requirements in the refrigerator and freezer field. The product of example 15 is able to meet the requirements of various properties in polyurethane pipe insulation. The foam product of example 16 appeared more fine, uniform and dense as shown in fig. 9, and thus it could satisfy various performance requirements for LNG (liquefied natural gas) transport cold insulation applications. The product of example 17 can meet the requirements of various properties of the polyurethane insulation board. The product of example 18 can meet the requirements of various properties of polyurethane color steel plates and cold storage plates.

Example 21

4 parts by weight of the compound C-1 prepared in example C-1 above as a blowing agent, 50 parts by weight of polyether polyol 4110, 1 part by weight of foam stabilizer DC3201, 12.5 parts by weight of flame retardant TCPP (Kogyo Seatt chemical Co., Ltd.) and 1 part by weight of catalyst A33(33LV, American air chemical industry) and 1 part by weight of catalyst PC-41 (American air chemical industry) were mixed uniformly to obtain a transparent foamed composition, 104.5 parts by weight of isocyanate MDI (PM200) was added thereto, and the mixture was stirred uniformly and foamed to obtain a polyurethane foam.

Example 22

4 parts by weight of the compound C-2 prepared in example C-2 above as a blowing agent, 30 parts by weight of polyether polyol 4110, 20 parts by weight of polyester polyol CF6320 (New Material Ltd. Jiangsu Fusheng), 12.5 parts by weight of flame retardant TCPP (Yake chemical Co., Ltd. Jiangsu), 1 part by weight of foam stabilizer DC3201 (American air chemical), 0.5 part by weight of catalyst PC-8 (American air chemical), and 1 part by weight of catalyst PC-41 (American air chemical) were mixed uniformly to obtain a transparent foamed composition, and isocyanate MDI (PM200) was added thereto and foamed after stirring uniformly to obtain a polyurethane foam.

Example 23

3.5 parts by weight of the compound C-3 prepared in the above example C-3, 2 parts by weight of a foam stabilizer DC3201 (American Aikoku chemical industry), 1 part by weight of a catalyst PC-8 (American Aikoku chemical industry), 1 part by weight of a catalyst PC-41 (American Aikoku chemical industry), 13 parts by weight of cyclopentane were added to a mixture of 50 parts by weight of polyether polyol 2010 (Haian petrochemical plant, Jiangsu province), 25 parts by weight of polyether polyol SA380 (produced by Shandong-Nonwei polyurethane Co., Ltd.) and 25 parts by weight of polyether polyol SA460 (produced by Shandong-Nonwei polyurethane Co., Ltd.) and mixed uniformly to obtain a transparent foam composition, and adding 145 parts of isocyanate MDI (PM200), stirring uniformly, and injecting into a foaming mold for foaming to obtain the polyurethane foam with the skin.

Examples 24 to 26

Examples 24-26 examples 21-23 were repeated, respectively, except that the blowing agents were as shown in Table 2. The closed pore rate is more than 97 percent.

Table 3: properties of polyurethane foams

Example 27

17 parts by weight of the compound D-1 prepared in example D-1 above as a blowing agent, 100 parts by weight of polyether polyol 4110 (Binshon, Shandong), 2 parts by weight of foam stabilizer DC3201 (American air chemical), 2 parts by weight of catalyst A33(33LV), and 2 parts by weight of catalyst PC-41 (American air chemical) were mixed uniformly to obtain a transparent foamed composition, 160 parts by weight of isocyanate MDI (PM200) was added thereto, and the mixture was stirred uniformly and foamed to obtain a polyurethane foam.

Example 28

Uniformly mixing 25 parts by weight of a compound E-1, 50 parts by weight of polyether polyol 2010 (produced by Haian petrochemical plant of Jiangsu province), 25 parts by weight of polyether polyol SA380 (produced by Shandong-Nowei polyurethane Co., Ltd.) and 25 parts by weight of polyether polyol SA460 (produced by Shandong-Nowei polyurethane Co., Ltd.), 2 parts by weight of a foam stabilizer DC3201 (American air chemical industry), 0.5 part by weight of a catalyst PC-8 (American air chemical industry) and 1 part by weight of a catalyst PC-41 (American air chemical industry) to obtain a transparent foaming composition, adding 155 parts by weight of isocyanate MDI (PM200) into the transparent foaming composition, and uniformly stirring and foaming to obtain the polyurethane foam.

Example 29

15 parts by weight of compound F-1, 10 parts by weight of cyclopentane, 2 parts by weight of foam stabilizer DC3201 (American air chemical industry), 1 part by weight of catalyst PC-8 (American air chemical industry) and 1.5 parts by weight of catalyst PC-41 (American air chemical industry) are added into 50 parts by weight of polyether polyol 2010 (Haian petrochemical plant of Jiangsu province), 25 parts by weight of polyether polyol SA380 (produced by Shandong-Noowei polyurethane Co., Ltd.) and 25 parts by weight of polyether polyol SA460 (produced by Shandong-Noowei polyurethane Co., Ltd.) to be uniformly mixed to obtain a transparent foaming composition, then 150 parts by weight of isocyanate MDI (PM200) is added into the transparent foaming composition, and the mixture is injected into a foaming mold to be foamed to obtain the skinned polyurethane foam after being uniformly stirred.

Comparative example 1

Example 28 was repeated, except that only 15 parts by weight of cyclopentane were used as blowing agent.

Table 4: properties of polyurethane foams

Example 30

12 parts by weight of the compound G-1 prepared in example G-1 above as a blowing agent, 50 parts by weight of polyether polyol 4110, 1 part by weight of foam stabilizer DC3201, 12.5 parts by weight of flame retardant TCPP (Kogyo Seatt chemical Co., Ltd.) and 1 part by weight of catalyst A33(33LV, American air chemical industry) and 1 part by weight of catalyst PC-41 (American air chemical industry) were mixed uniformly to obtain a foamed composition, 104.5 parts by weight of isocyanate MDI (PM200) was added thereto, and the mixture was stirred uniformly and foamed to obtain a polyurethane foam.

Example 31

7.5 parts by weight of the compound G-2 prepared in the above example G-2 as a blowing agent, 30 parts by weight of polyether polyol 4110, 20 parts by weight of polyester polyol CF6320 (Jiangsu Fusheng New Material Co., Ltd.), 12.5 parts by weight of flame retardant TCPP (Jiangsu Jack chemical Co., Ltd.), 1 part by weight of foam stabilizer DC3201 (American air chemical industry), 0.5 part by weight of catalyst PC-8 (American air chemical industry) and 1 part by weight of catalyst PC-41 (American air chemical industry) were mixed uniformly to obtain a foamed composition, and isocyanate MDI (PM200) was added thereto and foamed after stirring uniformly to obtain a polyurethane foam.

Example 32

A foaming composition was obtained by uniformly mixing 9 parts by weight of the compound G-3 prepared in example G-3 above, 2 parts by weight of a foam stabilizer DC3201 (American Airtight chemical industry), 1 part by weight of a catalyst PC-8 (American Airtight chemical industry), 1 part by weight of a catalyst PC-41 (American Airtight chemical industry), 13 parts by weight of cyclopentane, and adding 50 parts by weight of polyether polyol 2010 (Haian petrochemical plant, Jiangsu province), 25 parts by weight of polyether polyol SA380 (produced by Shandong-one Noway polyurethane Co., Ltd.) and 25 parts by weight of polyether polyol SA460 (produced by Shandong-one Noway polyurethane Co., Ltd.) to a mixture, and adding 145 parts of isocyanate MDI (PM200), stirring uniformly, and injecting into a foaming mold for foaming to obtain the polyurethane foam with the skin.

Example 33

9.5 parts by weight of the compound G-4 prepared in the above example G-4, 2 parts by weight of a foam stabilizer DC3201 (American Aikoku chemical industry), 1 part by weight of a catalyst PC-8 (American Aikoku chemical industry), 1 part by weight of a catalyst PC-41 (American Aikoku chemical industry), 13 parts by weight of cyclopentane, 50 parts by weight of polyether polyol 2010 (Haian petrochemical plant, Jiangsu province), 25 parts by weight of polyether polyol SA380 (produced by Shandong-one Nonwei polyurethane Co., Ltd.) and 25 parts by weight of polyether polyol SA460 (produced by Shandong-one Nonwei polyurethane Co., Ltd.) were mixed uniformly to obtain a foam composition, and adding 145 parts of isocyanate MDI (PM200), stirring uniformly, and injecting into a foaming mold for foaming to obtain the polyurethane foam with the skin.

Table 5: properties of polyurethane foams

Properties of chemical foaming agent (CFA for short) of the invention

1. Storage stability and foaming Properties of foaming compositions (white Material for short)

① stability test of CFA-CP (abbreviation for cyclopentane) mixture used for preparing white material

We configured the white material of the CFA-CP mixed system (white material in example 9 above) according to the parameters of the white material for refrigerator, the white material activity was measured after placing in the oven at 50 ℃, and the reaction activity of the white material was measured by sampling every few days, and the experimental results are as follows in table 6:

table 6: reactivity of white Material

Date	Reaction time(s)
		2015.8.28	CT:9 GT：55
2015.8.29	CT:9 GT：55
		2015.8.31	CT:8 GT：54
2015.9.3	CT:9 GT：55
		2015.9.6	CT:8 GT：56
2015.9.12	CT:9 GT：54
		2015.9.14	CT:9 GT：53
2015.9.16	CT:8 GT：56
		2015.9.18	CT:9 GT：55
2015.9.21	CT:8 GT：54
		2015.9.24	CT:9 GT：56
2015.9.28	CT:9 GT：54
		2015.10.5	CT:9 GT：56
2015.10.9	CT:10 GT：54
		2015.10.15	CT:9 GT：55
2015.10.19	CT:9 GT：56

CT in the table refers to the onset time; GT refers to the draw time.

As shown in the table above, the reactivity of the CFA-CP in the white material system is basically unchanged along with the change of time, and the CFA-CP can be stored for more than half a year at normal temperature after being stored for 51 days at 50 ℃.

In addition to the reactivity, the thermal conductivity of the foam prepared after CFA-CP mixing was also stable, and the following foam was prepared after sampling at different time intervals (same conditions as in example 9) and tested for the indexes such as thermal conductivity of the foam, and the results were as follows:

date	Density kg/m³	Thermal conductivity (10 ℃) lambda w/m.k
			2015.8.28	35	0.01917
2015.9.12	35	0.01923
			2015.9.24	35	0.01906
2015.10.15	35	0.01911

As seen from the table, the same white material was left to stand for different periods of time, but the foamed density was not changed, indicating that the foaming efficiency was not changed and the thermal conductivity was not substantially changed.

② stability test of white Material prepared Using CFA alone as blowing agent

As in example 5, we prepared a white material prepared entirely using CFA according to the conventional white material formulation and allowed to stand at room temperature for 3 months, and sampled every other month to determine the white material activity and the thermal conductivity of the foam, the results of which are as follows:

date	Reaction time	Thermal conductivity (10 ℃) lambda w/m.k
			2013.11.27	CT:9 GT:25 TFT:32	0.02085
2014.1.24	CT:9 GT:24 TFT:32	0.02123
			2014.2.26	CT:9 GT:24 TFT:35	0.02093
2014.3.27	CT:9 GT:25 TFT:36	0.02140

In the table, TFT refers to the skinning debonding time.

As can be seen from the above table, the reactivity and thermal conductivity of the CFA of the present invention remain stable over time in the above white material system.

③ comparison of stability of CFA free foam and Water foaming at Low Density

While the above example 5 was repeated but the amount of the blowing agent was changed to 15 parts by weight of Compound A-4, while, as a comparison, the above example 5 was repeated but each of the white materials and each of the foams were separately prepared using only water as the blowing agent, it was observed whether the stability with time of the two foams was changed in the case where the densities of the foams obtained were the same. The preparation time is 2015, 4 months and 16 days, and the density is 22kg/m³FIGS. 10 and 12 show the initial appearance of the foam of the present invention, and FIGS. 11 and 13 show the initial appearance of the foam prepared using water as a blowing agent. After standing for 9 and 29 months and for five months in 2015, the appearance of the foam was observed, fig. 14 shows that the product of the invention has little change in appearance and size, and fig. 15 shows that the comparative sample has shriveled and the expert in the polyurethane industry believes that when the foam has shrunkThe foam density is 25kg/m³The problem of shrinkage is inevitable in the case of foaming with water on the left and right, which is the greatest difference between CFA and water. In other words, the water foaming used in the fields of building exterior wall spraying and the like will cause the foam material to shrink and the heat conductivity coefficient to be deteriorated along with the change of time.

Other applications

1. Application of foaming agent of the invention in preparation of polystyrene foaming material

Example 34

100 parts by weight of polystyrene resin powder, 6 parts by weight of the foaming agent B-1 of the invention, calcium carbonate with the average particle size of 175 microns, 0.3 part by weight of zinc stearate and 0.3 part by weight of toner (produced by Weichang brand, Shenzhen Weichang pigment Co., Ltd.) are put into a mixer to be mixed at the temperature of 30-40 ℃ to obtain a polystyrene foaming composition, and then a single-screw extruder (the length-diameter ratio of a screw is 28:1) is utilized for extrusion molding, and the temperature of each section of the extruder is as follows: one section is 85-95 ℃, the second section is 95-105 ℃, the third section is 105-115 ℃, and the fourth section is 115-125 ℃; the temperature of the die is 125-130 ℃; the rotating speed of the screw is 5 rpm-9 rpm. The profile obtained had an apparent density of 587kg/m³. The SEM photograph is shown in FIG. 16 (at 100 magnification). As can be seen from the photographs, the diameter of the cells is relatively uniform.

2. Application of foaming agent in preparation of polyvinyl chloride foaming material

Example 35

85 parts by weight of PVC resin, 5 parts by weight of the foaming agent A-1 of the invention, 0.5 part by weight of polyethylene wax, calcium carbonate with the average particle size of 175 microns, 0.3 part by weight of zinc stearate, and 0.3 part by weight of toner (produced by Weichang brand, Shenzhen Weichang pigment Co., Ltd.) are put into a mixer to be mixed at the temperature of 30-40 ℃ to obtain a polyvinyl chloride foaming composition, and then a single-screw extruder (the length-diameter ratio of a screw is 28:1) is utilized for extrusion molding, wherein the temperature of each section of the extruder is as follows: the first section is 145-150 ℃, the second section is 155-165 ℃, the third section is 175-185 ℃, and the fourth section is 180-195 ℃; the temperature of the die is 195-205 ℃; the rotating speed of the screw is 5 rpm-9 rpm. The specific gravity of the resulting profile is 0.55 g-cm³。

3、Preparation of hydrazino-alcohol amine salt compound and application of hydrazino-alcohol amine salt compound as foaming agent

Example 36 (preparation example)

730g of 80% hydrazine hydrate and 450g of water are added into a stainless steel reaction kettle with a cooling jacket, stirring is started, fully mixing hydrazine hydrate with water, heating and raising the temperature of a reaction system after nitrogen treatment and protection, controlling the temperature to be 45-70 ℃, controlling the pressure not to exceed 0.3MPa, then 1200g of propylene oxide (molecular weight: 58.08) was gradually added in portions, and after the addition, the temperature was controlled to 45 to 70 ℃ and the reaction was stirred at a pressure of 0.3MPa or less for 1 hour, then cooling to 50 ℃, removing unnecessary water and unreacted propylene oxide under the reduced pressure of 600mHg, starting stirring, introducing 1200g of carbon dioxide 800-1200 ℃ into the reaction kettle, controlling the temperature to be 45-60 ℃, controlling the pressure not to exceed 0.3MPa, reacting for 4-8 hours, cooling to below 40 deg.c and discharging the product to obtain the compound, hydralazine salt compound. pH 8.9. The decomposition temperature of the compound is in the range of 45-70 ℃. Carbon dioxide is rapidly released after heating to 55 ℃. The infrared spectrum of the compound is shown in figure 17.

Example 37 (application example)

20 parts by weight of the compound prepared in example 36 above as a blowing agent, 30 parts by weight of polyether polyol 4110, 20 parts by weight of polyester polyol CF6320 (Jiangsu Fusheng New Material Co., Ltd.), 12.5 parts by weight of flame retardant TCPP (Jiangsu Yake chemical Co., Ltd.), 1 part by weight of foam stabilizer DC3201 (American air chemical industry), 0.5 part by weight of catalyst PC-8 (American air chemical industry), and 1 part by weight of catalyst PC-41 (American air chemical industry) were mixed uniformly to obtain a transparent foam composition, and isocyanate MDI (PM200) was added thereto and stirred uniformly to foam to obtain a polyurethane foam material. The cells are very uniform in size and the average diameter of the cells is larger, indicating a greater amount of carbon dioxide gas being released.

Example 38 (preparation example)

Adding 730g of 80% hydrazine hydrate and 450g of water into a stainless steel reaction kettle with a cooling jacket, starting stirring to fully mix the hydrazine hydrate and the water, heating and raising the temperature of the reaction system after nitrogen treatment and protection, controlling the temperature to be 45-70 ℃, controlling the pressure to be not more than 0.3MPa, then slowly adding 910g of ethylene oxide (molecular weight is 58.08) in batches, controlling the temperature to be 45-70 ℃, stirring and reacting for 1 hour under the pressure of 0.3MPa, then cooling to 50 ℃, removing unnecessary water and unreacted ethylene oxide under the reduced pressure of 600mHg, starting stirring, introducing 1200g of carbon dioxide into the reaction kettle, controlling the temperature to be 45-60 ℃, controlling the pressure to be not more than 0.3MPa, reacting for 4 hours, and discharging the product after cooling to be below 40 ℃ to obtain the compound. The pH was 8.8 and the decomposition temperature of the compound was in the range of 45-70 ℃. Carbon dioxide is rapidly released after heating to 56 ℃.

Example 39 (application example)

17 parts by weight of the compound produced in example 38 above as a blowing agent, 30 parts by weight of polyether polyol 4110, 20 parts by weight of polyester polyol CF6320 (Jiangsu Fusheng New Material Co., Ltd.), 12.5 parts by weight of flame retardant TCPP (Jiangsu Yake chemical Co., Ltd.), 1 part by weight of foam stabilizer DC3201 (American air chemical industry), 0.5 part by weight of catalyst PC-8 (American air chemical industry), and 1 part by weight of catalyst PC-41 (American air chemical industry) were mixed uniformly to obtain a transparent foam composition, and isocyanate MDI (PM200) was added thereto and foamed after stirring uniformly to obtain a polyurethane foam.

Claims

1. A blowing agent comprising a mixture of hydrahydralamine salt compounds having the following general formula (I):

A^n-[B^m+]_p(I)

B^m+comprises the following steps: +1 valent ammonium ion, +1 valent hydrazine ion H₃ ⁺N-NH₂+2 valent hydrazine ion H₃ ⁺N-NH₃ ⁺And/or, having m-⁺NR³R⁴H group and/or-⁺NR³One of the H-groupsOr cations of a plurality of organic amines (B);

and, the compounds of formula (I) comprise at least one hydrazino or substituted hydrazino group;

wherein m is 1-5;

and

wherein A is^n-Is selected from one or more of the following anions:

(b) carbonate radical: CO2₃ ^2-；

(c) Formate radical: HCOO^-；

(d) Bicarbonate radical: HO-COO^-；

Wherein R is³Or R⁴Independently selected from: h, R, C optionally substituted by hydroxy or amino or halogen₁-C₇Aliphatic hydrocarbon radicals, C optionally substituted by hydroxy or amino groups or halogen₃-C₇Cycloaliphatic hydrocarbon radicals, or, C optionally substituted by hydroxy or amino groups or by halogen₆-C₁₀An aromatic hydrocarbon group;

the precondition is that: the compounds of the general formula (I) have at least one R group bonded to N;

wherein the R group is selected from one or more of the following groups:

(1a)H[OCH(R_1a)CH(R_2a)]_q-；

(2a)H[OCH(R_1a)CH(R_2a)CH(R_3a)]_q-; or

(3a)H[OCH(R_1a)CH(R_2a)CH(R_3a)CH(R_4a)]_q-；

Wherein the value or average of q is q 1-3, calculated as the average of q; r_1a、R_2a、R_3aOr R_4aEach independently selected from: h, C optionally substituted by hydroxy or amino or halogen₁-C₇Aliphatic hydrocarbon radicals, C optionally substituted by hydroxy or amino groups or halogen₃-C₇Cycloaliphatic hydrocarbon radicals, or, C optionally substituted by hydroxy or amino groups or by halogen₆-C₁₀An aromatic hydrocarbon group;

wherein: the organic amine compound (B) is an organic amine compound having 2 to 50 carbon atoms, the amount of water in the blowing agent is 10 to 40% by weight, the pH of the blowing agent is 7.5 to 10, and the total amount of the compound of the general formula (I) and water is 70 to 100% based on the total weight of the blowing agent.

2. The blowing agent of claim 1, wherein:

(1a)H[OCH(R_1a)CH(R_2a)]_q-is H (OCH)₂CH₂)_q-、H(OCH₂CH(CH₃))_q-、H(OCH(CH₃)CH₂)_q-、H(OCH₂CH(C₆H₅))_q-、H(OCH(C₆H₅)CH₂)_q-、H(OCH₂CH(CH₂Cl))_q-、H(OCH(CH₂Cl)CH₂)_q-or H (OCH)₂CH(CBr₃))_q-; and/or

The mass content of alkali metal and alkaline earth metal of the foaming agent is 0-200 ppm.

3. The blowing agent of claim 1 or 2, wherein: the water content in the foaming agent is 10-35 wt%; and/or

The pH of the foaming agent is 7.8-9.5.

4. The blowing agent of claim 3, wherein: the water content in the foaming agent is 10-30 wt%; and/or

The foaming agent has a pH of 8 to 9.5.

5. The blowing agent of claim 4, wherein: the water content in the blowing agent is 15 to 25 wt.%.

6. The blowing agent of claim 1 or 2, wherein: the total content of compound of formula (I) and water in the blowing agent is from 80 to 99.999% based on the total weight of the blowing agent.

7. The blowing agent of claim 6, wherein: in the blowing agent, the total content of compound of the formula (I) and water is from 85 to 99.0% by weight, based on the total weight of the blowing agent.

8. The blowing agent of claim 1 or 2 wherein q is 1-2.5, calculated as the average of q.

9. Blowing agent according to claim 1 or 2, wherein organic amine (B) has m to m +3 primary, secondary and/or tertiary amine groups, and optionally quaternary ammonium groups; and/or

The organic amine compound (B) is an organic amine compound having 2 to 20 carbon atoms.

10. The blowing agent of claim 1 or 2, which is B^m+Is a combination or mixture of two or more of the above organic amine cations; and/or

The organic amine compound (B) is an organic amine compound having 3 to 12 carbon atoms.

11. The blowing agent of claim 1 or 2 wherein R³Or R⁴Independently selected from: h, R, C optionally substituted by hydroxy or amino or halogen₁-C₄Aliphatic hydrocarbon groups, cyclobutyl or cyclohexyl optionally substituted by hydroxy or amino or halogen, or phenyl or methylphenyl optionally substituted by hydroxy or amino or halogen; and, R_1a、R_2a、R_3aOr R_4aEach independently selected from: h, methyl or ethyl optionally substituted with hydroxy or amino or halogen, or propyl or isopropyl optionally substituted with hydroxy or amino or halogen, cyclohexyl optionally substituted with hydroxy or amino or halogen, or phenyl or methylphenyl optionally substituted with hydroxy or amino or halogen.

12. The blowing agent of claim 1 wherein R_1a、R_2a、R_3aOr R_4aEach independently selected from: h, methyl, chloromethyl, methyl-substituted methyl ether,bromomethyl, ethyl, cyclohexyl, or, phenyl.

13. The blowing agent according to claim 1 or 2, characterized in that the compounds of the general formula (I) contain on average from 1.5 to 5R groups per molecule;

and/or wherein the compound of formula (I) has a mass content of alkali metals and alkaline earth metals lower than 100 ppm.

14. The blowing agent according to claim 1 or 2, wherein the compound or compound mixture of the general formula (I) contains 40 to 95 wt% of salts of monoalcohols amines and salts of dialcohols amines, based on the total weight of the compound or compound mixture of the general formula (I); and/or

In the compound or compound mixture of formula (I), the molar ratio of the compound of formula (I) having one R group to the compound of formula (I) having two R groups is 1:0 to 1: 2.5.

15. The blowing agent according to claim 1 or 2,

the compound or compound mixture of the general formula (I) contains 30 to 90 wt.%, based on the total weight of the compound or compound mixture of the general formula (I), of a monoalkanolamine and a dialkanolamine.

16. A process for preparing the blowing agent of claim 1, which comprises reacting a first starting material with a second starting material in water, optionally in the presence of ammonia or organic amines as catalyst, wherein the first starting material is one or more compounds selected from the group consisting of:

NH₂a hydrazine salt of N-COOH;

HCOONH₄hydrazine formate, or an organic amine formate (M) salt;

or styrene oxide; wherein R is_1a、R_2a、R_3aOr R_4aEach independently selected from: h, C optionally substituted by hydroxy or amino or halogen₁-C₇Aliphatic hydrocarbon radicals, C optionally substituted by hydroxy or amino groups or halogen₃-C₇Cycloaliphatic hydrocarbon radicals, or, C optionally substituted by hydroxy or amino groups or by halogen₆-C₁₀An aromatic hydrocarbon group;

C₁-C₂₄alkyl amines;

two (C)₁-C₁₆Hydrocarbyl) amines;

C₂-C₁₄alkylene diamines;

C₄-C₁₆polyalkylene polyamines;

c with three primary amino groups₃-C₁₈Organic triamines or C having four primary amino groups₅-C₁₈Organic tetraamines; or

C₂-C₁₀An alcohol-amine compound, an alcohol amine compound,

with the proviso that at least one of the first starting materials contains a hydrazine group.

17. The method according to claim 16, wherein the epoxide is: ethylene oxide, propylene oxide, epichlorohydrin, epibromopropane, butylene oxide, or chlorobutylene oxide or styrene oxide, or a mixture of any two or more thereof; and/or

When water is used as the solvent in the reaction, the amount of water used is 70 to 250 wt% based on the weight of the first raw material.

18. A polyurethane foaming composition comprising:

0.01 to 100 wt% of the blowing agent according to any of claims 1 to 15;

0-50 wt% of a physical blowing agent;

0-5% by weight of water, and

19. The polyurethane foaming composition of claim 18, comprising:

0.1-80 wt% of the blowing agent of any of claims 1-15;

0-40 wt% of a physical blowing agent;

0-4% by weight of water, and

20.0 to 99.9 wt% of a polymer polyol; wherein the weight percentages are based on the total weight of the polyurethane foaming composition.

20. The polyurethane foaming composition of claim 19, comprising:

3 to 60 wt% of the blowing agent of any of claims 1 to 15;

0-40 wt% of a physical blowing agent;

0-4% by weight of water, and

40 to 97 weight percent of a polymer polyol; wherein the weight percentages are based on the total weight of the polyurethane foaming composition.

21. The polyurethane foaming composition according to any one of claims 18 to 20, which contains a total of 0.5 to 4% by weight of water.

22. The polyurethane foaming composition according to any one of claims 18 to 20, wherein the polymer polyol is selected from the group consisting of: polyether polyols, polyester polyols, polyether-polyester polyols, polycarbonate diols, polycarbonate-polyester polyols, polycarbonate-polyether polyols, polybutadiene polyols or polysiloxane polyols.

23. A polyurethane foam formed by mixing and reacting the polyurethane foaming composition of any one of claims 18-20 with a polyisocyanate monomer and/or an isocyanate-terminated prepolymer.

24. The polyurethane foam of claim 23, wherein the weight usage ratio of the polyurethane foaming composition to polyisocyanate monomer or isocyanate-terminated prepolymer is in the range of 0.5:1 to 2:1.

25. The polyurethane foam of claim 24, wherein the weight usage ratio of the polyurethane foaming composition to polyisocyanate monomer or isocyanate-terminated prepolymer is in the range of 0.5:1 to 1:1.