CN107253919A

CN107253919A - Diazanyl alcohol amine compoundses and its production and use

Info

Publication number: CN107253919A
Application number: CN201710330621.XA
Authority: CN
Inventors: 毕戈华; 毕玉遂
Original assignee: 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: 2017-10-17
Anticipated expiration: 2037-05-11
Also published as: CN107253919B

Abstract

Diazanyl alcohol amine salt compound with below general formula (I)：A^n‑[B^m+]_p(I) in formula, A^n‑It is as CO₂The anion with n valencys of donor, wherein n=1,2 or 3；B^m+Be or comprising：Ammonium ion, hydrazine ion and/or organic amine B cations；Wherein m=1 10；Wherein A^n‑It is the one or more in following anion：(a) carbamic acid root or carbazic acid root；(b) carbonate；(c) formate；(d) bicarbonate radical；(e) organic single carbon acid group；(f) organic polyamino formate, (g) primitive nail acid group；Or (h) organic many carbonates, A^n‑And B^m+At least one of comprising hydrazine and/or include diazanyl or substitution diazanyl；There is the logical formula (I) compound at least one to be the hydroxyalkyl being connected with N atoms, i.e., with hydramine residue.They can be as polyurethane foams, and most foaming agent can be used as foamed polystyrene agent or foam polyvinyl chloride agent.

Description

Diazanyl alcohol amine compoundses and its production and use

Technical field

The present invention relates to alcohol amine compoundses with diazanyl and preparation method thereof and as foaming agent in expanded material Application in such as polyurethane foam or PVC foam material or foamed polystyrene material.

Technical background

Hard polyurethane foam is as a kind of macromolecule new material, and its light weight, intensity are high and with extremely low thermal conductivity, are excellent The heat-insulating material of matter, is widely used in cold-storage insulation, especially chemical weapons cold-storage insulation, building energy conservation, solar energy, vapour The industries such as the household electrical appliances such as car, refrigerator ice cabinet.Most important raw material is foaming agent in hard polyurethane foam production.These current foaming agents are removed All it is chlorofluorocarbon material beyond pentamethylene, because their destructions to atmospheric ozone layer are so national governments sign already The international convention of " Montreal Protocol book ", limits and is phased out, forbids the production of such product and use, China is also this The signatories to a treaty of memorandum of agreement.

China is also using second generation chlorofluorocarbon blowing agent H CFC-141b (a fluorine dichloroethanes) and ring penta at present Alkane, the developed country such as America and Europe prohibits the use of HCFC-141b already, and Chinese Government just freezes HCFC-141b consumption figure for 2013 Knot in the level of consumption of 2009 and 2010,2015 eliminate freeze 20% consumption figure, and promise be advanced to 2025 Total ban is produced and used, and the developed country such as current America and Europe uses third generation blowing agents pentafluoropropane (HFC-245fa) With 3-pentafluorobutane (HFC-365), the GWP (chamber effect potential value) of second and third generation foaming agent is very high, therefore America and Europe will be Forbade the use of third generation blowing agents before 2019.Forth generation physical blowing is have developed again for this Honeywell Inc. of U.S. Agent chlorotrifluoropropylene (LBA), its ODP (to the latent energy value of the destruction of ozone layer) is more relatively environment-friendly than the third generation although being zero, But GWP is more than 1, and the valuable product.In a word these physical blowing agents in addition to pentamethylene in itself and production During be directed to chlorine fluorine element, environmental issue is still difficult to thorough solution, will all be eliminated.

Prior art discloses directly by CO₂As polyurethane foams, still, in view of CO₂The escape of gas is with it in original Expect that the solubility in MDI and PEPA and/or PPG is bad so that CO₂Gas can not in composition, foam It is uniformly dispersed, and foaming process is not easily controlled.

In addition, prior art discloses directly using a small amount of water as polyurethane foams, still, in view of the hydrogen of hydrone Key is acted on and solubility of the water in PEPA and/or PPG is bad, and hydrone is present in the form of droplet In composition, foam (such as polyether polyatomic alcohol component), local excessive is caused to react and foam in expanded material.If made with water For foaming agent, then more urea bond is included in polyurethane foamed material, the intensity and heat-insulating property of foamed material is largely effected on. If in addition, being improved slightly as the consumption of the water of foaming agent, the performance and size of polyurethane foam can be significantly impacted Stability.If using water as unique foaming agent, polyurethane foam, which is known from experience, meets with asking for contraction, incipient scorch and poor insulation property Inscribe (shrinkage, scorching, inadequate heat insulation).

In a word, foaming agent (such as water) of the prior art can not be dispersed in composition, foam with molecular level, from And cause the size of the uniform abscess of skewness of abscess uneven, eventually affect the strength character and thermal insulation of expanded material Matter.

The content of the invention

To overcome shortcoming present in prior art, goal of the invention of the invention be to provide a kind of polyurethane foams and its Preparation method, chlorofluorocarbon, will not destroy atmospheric ozone layer.

It is an object of the invention to provide not only have to be used as CO₂The anion of donor and with hydroxyalkyl or hydroxyalkyl alkane Epoxide group is used as solubilizing group or C₂-C₁₄Alkyl (such as 2- chloroethyls, 3- chloropropyls or phenethyl) is used as the new of solubilizing group Type organic amine salt compounds, and its in expanded material such as polyurethane foam or PVC foam material or polystyrene foam Application in material.

The new organic amine salt compounds are suitable as foaming agent.It produces CO in foaming process₂Gas.The application Inventor it was unexpectedly observed that being used as CO₂The anion with-n valencys of donor easily decomposes produce CO at elevated temperatures₂ Gas, or even when being foamed at a lower temperature, it is described below to be used as CO₂The anion with-n valencys of donor can By NCO group activation of the isocyanate-monomer as contained by MDI and TDI, quick release goes out CO₂Gas.Further, since with solubilising Group so that foaming agent can be substantially soluble in foaming raw material (such as PPG or PEPA) or with foaming raw material it Between have good intersolubility, foaming agent of the invention can be homogeneously dispersed in equably to foam in composition, foam, The distribution of abscess is also than more uniform in polyurethane foam, and abscess size than more uniform.In addition, the foaming agent of the present invention Compound contains hydroxyl and/or amino, is decomposed in the foaming agent and discharges CO₂Catabolite produced afterwards still contains hydroxyl Base and/or amino, when the molecular weight of catabolite is relatively low, they are suitable as chain extender or crosslinking agent occurs with isocyanates Reaction forms polymer, and when the molecular weight of catabolite higher (such as number-average molecular weight is 100-3000), they can be replaced For a part of PEPA or PPG in composition, foam, for example prior art composition, foam basis The upper appropriate consumption for reducing PEPA or PPG.Those skilled in the art can be according to hair of the present invention The average hydroxyl value and PEPA of infusion or the average hydroxyl value of PPG come calculate foaming agent of the present invention consumption and The consumption of PEPA and/or PPG.Especially, in the process foamed using polyalcohol and polyisocyanates In, if using the organic amine salt compounds of the present invention as foaming agent, organic amine salt compounds are both as " foaming Point " is used as " chain extension point " and/or " crosslinking points " again, significantly enhances the mechanical strength and mechanical strength of abscess, and what is obtained is poly- Urethane foams have good dimensional stability.Therefore, based in terms of above three, the present invention is completed.

In this application, " it is used as CO₂The anion of donor " refers in case of heating or can in foaming process Decompose and discharge CO₂Anion.

There is provided the diazanyl alcohol amine salt compound with below general formula (I) according to the first embodiment of the present invention：

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

In formula, A^n-It is as CO₂The anion with-n valencys of donor, wherein n=1,2 or 3；

B^m+Be or comprising：Hydrazine ion (the H of the ammonium ion of+1 valency ,+1 valency₃ ⁺N-NH₂), the hydrazine ion (H of+divalent₃ ⁺N-NH₃ ⁺) And/or individual with m-⁺NR³R⁴H groups and/or-⁺NR³One or more organic amine B of H- groups cation；

Also, A^n-And B^m+At least one of comprising hydrazine and/or include diazanyl or substitution diazanyl；

Wherein m=1-10, preferably m=1-5；More preferably m=1-2；With

Wherein A^n-It is the one or more in following anion：

(a) carbamic acid root or carbazic acid root：R¹R²N-COO^-Or R¹R²N-NH-COO^-；

(b) carbonate：CO₃ ^2-；

(c) formate：HCOO^-；

(d) bicarbonate radical：HO-COO^-；

(e) organic single carbon acid group：R^aO-COO^-, wherein R^aIt is the C optionally replaced by hydroxyl or amino or halogen₁-C₂₆Alkyl (preferably C₁-C₁₀Alkyl, more preferably C₁-C₃Alkyl), or C₁-C₂₆Acyl group (preferably C₁-C₁₀Acyl group, more preferably C₁-C₂Acyl group)；

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

In formula, R^bIt is the C optionally replaced by hydroxyl or amino or halogen₁-C₁₆Alkylene (preferably C₂-C₁₀It is alkylene, more excellent Select C₂-C₆Alkylene), R^b' it is the trivalent C optionally replaced by hydroxyl or amino or halogen₂-C₂₀Alkyl (more preferably trivalent C₃-C₁₅ Alkylene)；

(g)Or

In formula, R ' is H, the C optionally replaced by hydroxyl or amino or halogen₁-C₂₆Alkyl (preferably C₁-C₁₀Alkyl, more preferably C₁-C₃Alkyl), or C₁-C₂₆Acyl group (preferably C₁-C₁₀Acyl group, more preferably C₁-C₇Acyl group)；Or

(h) organic many carbonates：^-OOC-OR^cO-COO^-,

In formula, R^cIt is the C optionally replaced by hydroxyl or amino or halogen₁-C₂₆Alkylene (preferably C₂-C₁₀It is alkylene, more excellent Select C₂-C₆Alkylene)；

Wherein, R¹,R²,R³Or R⁴Independently selected from：H, R, the C optionally replaced by hydroxyl or amino or halogen₁-C₇Aliphatic Alkyl (preferably C₁-C₄Alkyl), the C optionally replaced by hydroxyl or amino or halogen₃-C₇Cyclic aliphatic alkyl (such as cyclobutyl or hexamethylene Base), or, the C optionally replaced by hydroxyl or amino or halogen₆-C₁₀Aromatic hydrocarbyl (preferably phenyl or aminomethyl phenyl)；

Precondition is：The R in the compound of above-mentioned logical formula (I)¹,R²,R³Or R⁴In at least one be to be connected with N atoms R group, or the logical formula (I) compound have at least one R group bonded with N；

Wherein one or more of the R group in following groups：

(1a)H[OCH(R_1a)CH(R_2a)]_q-, such as H (OCH₂CH₂)_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 (OCH₂CH(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 q value or average value are q=1-3, preferably q=1-2.5, more preferably q=1.5-2.0, based on q average value Calculate；R_1a、R_2a、R_3aOr R_4aIt is each independently selected from：H, the C optionally replaced by hydroxyl or amino or halogen₁-C₇Aliphatic alkyl, The C optionally replaced by hydroxyl or amino or halogen₃-C₇Cyclic aliphatic alkyl, or, the C optionally replaced by hydroxyl or amino or halogen₆- C₁₀Aromatic hydrocarbyl.

Preferably, organic amine B has primary amine, secondary amine and/or the tertiary amine group of m to m+3, and optionally has quaternary ammonium Group.

It is preferred that, A^n-It is combination or the mixture for the two or more anion being selected from (a)-(h), and/or B^m+It is The combination of two or more above-mentioned organic amine cations or mixture.

It is preferred that, R¹,R²,R³Or R⁴Independently selected from：H, R, the C optionally replaced by hydroxyl or amino or halogen₁-C₄Aliphatic Alkyl, the cyclobutyl optionally replaced by hydroxyl or amino or halogen or cyclohexyl, or, optionally replaced by hydroxyl or amino or halogen Phenyl or aminomethyl phenyl；It is further preferred that R_1a、R_2a、R_3aOr R_4aIt is each independently selected from：H, methyl or optionally by hydroxyl or amino Or the ethyl of halogen substitution, or the propyl group or isopropyl optionally replaced by hydroxyl or amino or halogen, optionally by hydroxyl or ammonia Base or the cyclohexyl of halogen substitution, or, the phenyl or aminomethyl phenyl optionally replaced by hydroxyl or amino or halogen.

It is preferred that, R_1a、R_2a、R_3aOr R_4aIt is each independently selected from：H, methyl, chloromethyl, bromomethyl, ethyl, cyclohexyl, or, Phenyl.

It is preferred that, A^n-It is the one or more in following anion：

(a)R¹R²N-COO^-Or R¹R²N-NH-COO^-；Wherein R¹And R²Be independently of one another hydrogen, methyl, ethyl, methylol, Ethoxy or hydroxypropyl；

(b)CO₃ ^2-；

(c)HCOO^-；

(d)HO-COO^-；Or

(g)(i.e. HC (OR ') O₂ ^2-), or(i.e. HCO₃ ^3-),

In formula, R ' is H, the C optionally replaced by hydroxyl or amino or halogen₁-C₁₀Alkyl (more preferably methyl, ethyl, third Base) or C₁-C₁₀Acyl group (more preferably formoxyl, acetyl group or propiono).

It is preferred that, R¹And R²In at least one be H, more preferably R¹It is H and R²It is H or R group.

It is preferred that, the content for leading to the water of formula (I) compound is 0-40wt%, more preferably preferably 5-35wt%, 10-30wt%, More preferably 15-25wt%.It is preferred that, the compound average per molecule of logical formula (I) contains 1.5-5 R group.

Typically, except wherein A^n-Be formate logical formula (I) compound outside, the pH of other compounds of logical formula (I) is 7.5-10, preferably 7.8-9.5, more preferably pH 8-9.

Typically, the content for leading to the alkali and alkaline earth metal ions of formula (I) compound is 0-200ppm (quality), more preferably less than 100ppm, more preferably less than 10ppm, most preferably below detectable limit or for 0ppm.

It is preferred that, the compound or compound mixture of logical formula (I) contain 25-95wt%, preferably preferably 27-90wt%, 30- The salt of 85wt%, preferably 40-80wt%, more preferably 45-75wt% single methanol amine (such as MEA and/or single Propanolamine) and The salt of glycol amine (such as diethanol amine and/or dipropanolamine), the gross weight of compound or compound mixture based on logical formula (I) Amount.

It is preferred that, in the compound or compound mixture of logical formula (I), the logical formula (I) compound with a R group (such as single methanol amine salt) and the mol ratio of the logical formula (I) compound (such as glycol amine salt) with two R groups are 1:0 to 1: 2.5, preferably 1:0.3 to 1:2, preferably 1:0.5 to 1:1.

It is preferred that, the compound or compound mixture of logical formula (I) contain 15-90wt%, preferably preferably 17-88wt%, 20- 85wt%, preferably 25-80wt%, more preferably 30-70wt% single methanol amine (such as MEA and/or single Propanolamine) and glycol Amine (such as diethanol amine and/or dipropanolamine), the gross weight of compound or compound mixture based on logical formula (I).

The present invention also provides the method for the compound for preparing formula above (I), wherein A^n-Be (a), (b), (c), (d), (e), the anion of any one or more of (f) or (h), this method includes the first raw material and the second raw material in solvent (example Such as water) in, optionally in the presence of a catalyst, reacted, wherein the first raw material is in these following compounds It is one or more：

R¹R²N-COONH₄, R¹R²N-COOH organic amine compound (M) salt, R¹R²N-COOH hydrazonium salt, R¹R²N-NH- COONH₄,R¹R²N-NH-COOH hydrazonium salt, or R¹R²N-NH-COOH organic amine compound (M) salt, wherein R¹Or R²It is independent Ground is selected from：H, the C optionally replaced by hydroxyl or amino or halogen₁-C₇Aliphatic alkyl (preferably C₁-C₄Alkyl), optionally by hydroxyl Or amino or the C of halogen substitution₃-C₇Cyclic aliphatic alkyl (such as cyclobutyl or cyclohexyl), or, optionally by hydroxyl or amino or halogen Substituted C₆-C₁₀Aromatic hydrocarbyl (preferably phenyl or aminomethyl phenyl)；

(NH₄)₂CO₃, carbonic acid hydrazine, ammonium carbonate hydrazine, or carbonic acid organic amine compound (M) salt；

HCOONH₄, formic acid hydrazine, or formic acid organic amine compound (M) salt；

HO-COONH₄, bicarbonate hydrazine, or organic amine compound (M) bicarbonate；

R^aO-COONH₄, R^aO-COOH hydrazonium salt, or R^aO-COOH organic amine compound (M) salt,

NH₄OOC-N(R¹)-R^b-N(R²)-COONH₄, R^b'(-N(R¹)-COO)₃(NH₄)₃, HOOC-N (R¹)-R^b-N(R²)- COOH organic amine compound (M) salt, HOOC-N (R¹)-R^b-N(R²)-COOH hydrazonium salt, R^b'(-N(R¹)-COOH)₃Hydrazine Salt, or R^b'(-N(R¹)-COOH)₃Organic amine compound (M) salt；Or

NH₄OOC-OR^cO-COONH₄, HOOC-OR^cO-COOH hydrazonium salt, or HOOC-OR^cO-COOH organic amine chemical combination Thing (M) salt；

Second raw material is the one or more in these following epoxides：

Or benzene Ethylene oxide；

Wherein described organic amine compound (M) is selected from following organic amine compound in these：

C₁-C₂₄Alkyl amine；

Two (C₁-C₁₆Alkyl) amine；

Optionally in C₂-C₁₄The C being optionally substituted by a hydroxyl group on alkylene₂-C₁₄Alkylene Diamines；

Optionally in C₂-C₁₄The C being optionally substituted by a hydroxyl group on alkylidene₄-C₁₆Polyalkylenepolyamines class；

The C being optionally optionally substituted by a hydroxyl group with three primary amine groups₃-C₁₈Organic three amine is optional with four primary amine groups The C being optionally substituted by a hydroxyl group₅-C₁₈Organic tetraamine；Or

C₂-C₁₀Alcamines,

Precondition is that at least one of the first raw material is comprising hydrazine or contains diazanyl.

It is preferred that, in the reaction when using water as solvent, the consumption of water is calculated based on the weight of the first raw material 70-250wt%, preferably 85-200wt%, more preferably 100-170wt%.

It is preferred that, the epoxides is：Oxirane, expoxy propane, epoxychloropropane, epoxy bromopropane, epoxy butane or Epoxy chlorobutane or styrene oxide, and any two or a variety of mixtures in them.

The present invention also provides the method for the compound for preparing formula above (I), wherein A^n-It is anion (g), this method bag Include：Orthoformic acid ester type compound in a solvent, optionally in the presence of a catalyst, and in the organic amine for belonging to Organic Alcohol amine Reaction is hydrolyzed in the presence of M or the compound B and water that belong to Organic Alcohol amine with least one above-mentioned N-R group； Wherein, the amount of the water is sufficient so that at least two ester group hydrolyses of orthoformic acid ester type compound, it is further preferred that water Amount is sufficient so that three ester group hydrolyses of orthoformic acid ester type compound；

Wherein organic amine compound B is hydrazine and optional ammonia enters as initiation material or as initiator with epoxides Row reaction is formed, one or more of the epoxides in these following epoxides：

Or benzene Ethylene oxide.

It is preferred that, the epoxides is：Oxirane, expoxy propane, epoxychloropropane, epoxy bromopropane, epoxy butane, Or epoxy chlorobutane or styrene oxide, and any two or a variety of mixtures in them.

The present invention is also provided as the compound prepared by above-mentioned preparation method.Preferably, the compound contains 25- 95wt%, preferably 27-90wt%, preferably 30-85wt%, preferably 40-80wt%, more preferably 45-75wt% single methanol amine are (for example MEA and/or single Propanolamine) salt and glycol amine (such as diethanol amine and/or dipropanolamine) salt, based on compound Gross weight, or, the compound contains 15-90wt%, preferably preferably 17-88wt%, preferably 20-85wt%, 25- 80wt%, more preferably 30-70wt% single methanol amine (such as MEA and/or single Propanolamine) and glycol amine (such as diethanol Amine and/or dipropanolamine), the gross weight based on compound.

Preferably, 25-95wt%, preferably 27-90wt% are contained as the compound prepared by above-mentioned preparation method, preferably 30-85wt%, preferably 40-80wt%, more preferably 45-75wt% single methanol amine (such as MEA and/or single Propanolamine) The salt of salt and glycol amine (such as diethanol amine and/or dipropanolamine), the gross weight based on compound, or, the compound contains There are 15-90wt%, preferably 17-88wt%, preferably 20-85wt%, preferably 25-80wt%, more preferably 30-70wt% single methanol amine (such as MEA and/or single Propanolamine) and glycol amine (such as diethanol amine and/or dipropanolamine), based on the total of compound Weight.

The present invention provides a kind of foaming agent, and it includes the above-mentioned diazanyl alcohol amine salt compound or diazanyl alcohol for having and leading to formula (I) Amine salt compound mixture, or mixed by the above-mentioned diazanyl alcohol amine salt compound or diazanyl alcohol amine salt compound with logical formula (I) Thing is constituted.It is preferred that, A^n-It is the one or more in following anion：

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

The present invention also provides a kind of foaming agent, and wherein it is used as polyurethane foams, foamed polystyrene agent or polychlorostyrene second Alkene foaming agent and it include as the compound prepared by above-mentioned preparation method.

The present invention also provides the purposes that formic acid hydrazine is used as polyurethane foams.In the purposes, formic acid hydrazine is the aqueous solution Form and the organic amine containing 0.5-15wt% (preferably 1-8wt%), the latter include but is not limited to：Methylamine, dimethylamine, front three Amine, ethamine, diethylamine, triethylamine or monoethanolamine.

The present invention also provides polyurethane foamed composite thing, and it is included：

The 0.01-100 weight % above-mentioned diazanyl alcohol amine salt compound or diazanyl alcohol amine salt compound with logical formula (I) is mixed Compound, or as the compound prepared by above-mentioned preparation method；

0-50 weight % physical blowing agent；

0-5 weight % water, and

0.0-99.99 weight % polymer polyatomic alcohol；Wherein, the percentage by weight is based on polyurethane foamed composite thing Gross weight.

It is preferred that, above-mentioned polyurethane foamed composite thing is included：

0.1-80 weight % (more preferably 1-70wt%, more preferably 3-60wt%, more preferably 5-50wt%, more preferably 7- 40wt%, such as 10wt%, 15wt%) the above-mentioned diazanyl alcohol amine salt compound or diazanyl alcohol amine salt compound with logical formula (I) Mixture, or as the compound prepared by above-mentioned preparation method；

0-40 weight % physical blowing agent；

0-4 weight % water, and

20.0-99.9 weight % (more preferably 30-99wt%, more preferably 40-97wt%, more preferably 50-95wt%, it is more excellent Select 60-93wt%, such as 90wt% or 85wt%) polymer polyatomic alcohol；Wherein, the percentage by weight is based on polyurethane foam The gross weight of composition.

It is preferred that, polyurethane foamed composite thing contains the water of 0.5-4wt% altogether, more preferably more preferably 0.8-2.5wt%, 1- 2.2wt% water.

It is preferred that, polymer polyatomic alcohol is selected from：PPG, PEPA, polyether-polyester polyol, makrolon Glycol, polycarbonate-polyester polyalcohol, makrolon-PPG, polybutadiene polyol or polysiloxane polyhydric alcohol.

Typically, composition, foam is transparent or clarification；Preferably, hard polyurethane foam composition, foam is transparent Clarification or translucent or milky but it is uniform, or, soft polyurethane foam composition, foam is transparent or milky 's.

Typically, above-mentioned polyurethane foamed composite thing has following characteristics：1) alcohol amine salt or alcohol amine compound are included；2) it is transparent Or clarification or translucent or milky uniform liquid；3) in case of heating or add the organic acid more stronger than carbonic acid or CO is discharged in the case of inorganic acid₂；4) when composition, foam is contacted or mixed with isocyanates or polyisocyanates, mixing The material of formation becomes milky in 0.2-4 seconds (preferably 1-2 seconds).

Typically, the material being mixed to form is caused to become milky when it is mixed with polyisocyanates, it is quickly swollen with volume Swollen phenomenon, but this process and it is non-foam it is real rise, material just starts to rise afterwards.

The present invention also provides polyurethane foamed material, and it passes through above-mentioned polyurethane foamed composite thing and polyisocynate monomer And/or isocyanate-terminated prepolymer mixed after react and formed.

Preferably, A is worked as^n-When being (a) carbamic acid root or carbazic acid root, the R in the compound of above-mentioned logical formula (I)¹, R²,R³Or R⁴In at least one (such as 1 or 2) be the R group being connected with N atoms, and the compound tool of the logical formula (I) There are at least one (such as 1 or 2) and R group bonded N and at least one (such as 1 or 2) diazanyl or substitution diazanyl；Or work as A^n-When being (b), (c), (d), (e), (f), (g) or (h), the compound of the logical formula (I) includes organic amine B and the organic amine B has at least one (such as 1 or 2) and R group bonded N and at least one (such as 1 or 2) diazanyl or substitution diazanyl.

In this application, " A^n-And B^m+At least one of comprising hydrazine and/or include diazanyl or substitution diazanyl " refer to formula (I) compound includes at least one hydrazine ion and/or includes at least one diazanyl or substitution diazanyl；More specifically, if A^n- When being the one or more being selected from (b), (c), (d), (e), (f), (g) or (h), then B^m+Be or comprising：The hydrazine of+1 valency from Son (H₃ ⁺N-NH₂), the hydrazine ion (H of+divalent₃ ⁺N-NH₃ ⁺) and/or with diazanyl or substitution diazanyl (such as diazanyl or substitution hydrazine Base correspond to-⁺NR³R⁴H groups and/or-⁺NR³H- groups) one or more organic amine B cation (that is, organic amine B has Diazanyl or substitution diazanyl), or if A^n-It is (a) carbazic acid root R¹R²N-NH-COO^-When, then B^m+Be or comprising：The ammonium of+1 valency Hydrazine ion (the H of ion ,+1 valency₃ ⁺N-NH₂), the hydrazine ion (H of+divalent₃ ⁺N-NH₃ ⁺) and/or individual with m-⁺NR³R⁴H groups and/ Or-⁺NR³One or more organic amine B of H- groups cation, organic amine B is with or without diazanyl or substitution diazanyl.

The present invention also provides the organic amine salt compound with below general formula (I)：

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

In formula, A^n-It is as CO₂The anion with-n valencys of donor, wherein n=1 or 2；

Wherein m=1-10, preferably m=1-5, more preferably m=1-2；With

Wherein A^n-It is the one or more in following anion：

(b) carbonate：CO₃ ^2-；

(c) formate：HCOO^-；Or

(d) bicarbonate radical：HO-COO^-；

Wherein, R¹,R²,R³Or R⁴Independently selected from：H, R, the C optionally replaced by hydroxyl or amino or halogen₁-C₇Aliphatic Alkyl (preferably C₁-C₄Alkyl, more preferably C₂-C₃Alkyl) (for example, ethoxy or hydroxypropyl), optionally by hydroxyl or amino or halogen The C of element substitution₃-C₇Cyclic aliphatic alkyl (such as cyclobutyl or cyclohexyl), or, the C optionally replaced by hydroxyl or amino or halogen₆-C₁₀ Aromatic hydrocarbyl (preferably phenyl or aminomethyl phenyl)；

Precondition is：Work as A^n-When being (a) carbamic acid root or carbazic acid root, in the compound of above-mentioned logical formula (I) R¹,R²,R³Or R⁴In at least one be the R group being connected with N atoms, or the logical formula (I) compound have at least one with R group bonded N；Or work as A^n-When being (b), (c) or (d), the compound of the logical formula (I) includes organic amine B and this is organic Amine B has at least one R group bonded with N,

Wherein one or more of the R group in following groups：

(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 q value or average value are q=1-50；R_1a、R_2a、R_3aOr R_4aIt is each independently selected from：H, optionally by hydroxyl or Amino or the C of halogen substitution₁-C₇Aliphatic alkyl, the C optionally replaced by hydroxyl or amino or halogen₃-C₇Cyclic aliphatic alkyl, Or, the C optionally replaced by hydroxyl or amino or halogen₆-C₁₀Aromatic hydrocarbyl.

In this application, it is preferable that the organic amine compound B with least one N-R group is by described organic Taken at least one N atom of each molecule of aminated compounds (M), ammonia and/or hydrazine by said one or multiple R groups Formed by generation.

In this application, it is preferred that work as A^n-When being (b), (c), (d), (e), (f), (g) or (h), lead to the change of formula (I) Compound per molecule averagely has a 1-5.5 R group, the R group of preferably 1.3-5, the R group of more preferably 1.5-2, and These R groups are present in the organic amine compound B with least one N-R group；Or work as A^n-Be (a) carbamic acid root or During carbazic acid root, lead to the R group that the compound per molecule of formula (I) averagely has 1-5.5, the R group of preferably 1.3-5, More preferably 1.5-2 R group, and these R groups are present in organic amine compound B and/or anion (a).

In this application, it is preferred that R group is hydroxypropyl, i.e. HO-CH₂-CH₂(CH₃)-or HO-CH₂(CH₃)-CH₂-, Ethoxy, and/or, hydroxyl chloropropyl.

In this application, it is preferred that in the compound or compound mixture of logical formula (I), with R group Mole of logical formula (I) compound (such as single methanol amine salt) and the logical formula (I) compound (such as glycol amine salt) with two R groups Than being 1:0 to 1:2.5, preferably 1:0.3 to 1:2, preferably 1:0.5 to 1:1.

In this application, A^n-[B^m+]_pChemical formula or formula ABp can also be expressed as.They are alcohol amine salt compounds.Therefore They are rendered as the form of ionic compound in presence of water.

In this application, it is preferred that wherein A or A^n-It is the one or more in following anion：

(b) carbonate：CO₃ ^2-；Or

(d) bicarbonate radical：HO-COO^-。

In this application, it is preferred thatIt is preferred that, m=1 or 2 or 3.

In this application, it is preferable that substitution diazanyl refers to by above-described substituent R¹,R²,R³Or R⁴The hydrazine replaced Base.

In this application, in general, wherein A^n-It is the logical formula (I) compound or compound mixture of formate (c) PH is 5.5-6.5.Except wherein A^n-Be formate (c) logical formula (I) compound (pH=5.5-6.5) outside, lead to formula (I) its The pH of its compound is 7.5-10, preferably 7.8-9.5, more preferably pH 8-9.It is preferred that, the compound or compound for leading to formula (I) are mixed The content of the alkali and alkaline earth metal ions of compound is 0-200ppm (quality), more preferably less than 100ppm, is more preferably less than 10ppm, most preferably below detectable limit or for 0ppm.

It is preferred that, in this application, the content of the compound or compound mixture reclaimed water of leading to formula (I) is 0-40wt%, excellent Select 5-35wt%, more preferably more preferably 10-30wt%, 15-25wt%.Correspondingly, in this application, the compound of formula (I) is led to Or compound mixture contains 25-95wt%, preferably preferably 27-90wt%, preferably 30-85wt%, 40-80wt%, more preferably The salt and glycol amine (such as diethanol amine and/or two of 45-75wt% single methanol amine (such as MEA and/or single Propanolamine) Propanolamine) salt (i.e. both sums：The salt of salt+glycol amine of single methanol amine), compound or compound mixing based on logical formula (I) The gross weight of thing.Or, the compound or compound mixture of logical formula (I) contain 15-90wt%, preferably 17-88wt%, preferably 20-85wt%, preferably 25-80wt%, more preferably 30-70wt% single methanol amine (such as MEA and/or single Propanolamine) and Glycol amine (such as diethanol amine and/or dipropanolamine) (i.e. both sums：Single methanol amine+glycol amine), the chemical combination based on logical formula (I) The gross weight of thing or compound mixture.

It is preferred that, the compound average per molecule of logical formula (I) contains 1.5-5 R group.

In this application, hydrazine ion refers to：Hydrazine ion (the H of+1 valency₃ ⁺N-NH₂) or+divalent hydrazine ion (H₃ ⁺N-NH₃ ⁺)。 That is, hydrazine ion be or including：Hydrazine ion (the H of+1 valency₃ ⁺N-NH₂) and+divalent hydrazine ion (H₃ ⁺N-NH₃ ⁺)。

In this application, leading to formula (I) compound per molecule has at least one above-mentioned R group.

In this application, R group and following groups are identical or different：The C optionally replaced by hydroxyl or amino or halogen₁-C₇ Aliphatic alkyl (preferably C₁-C₄Alkyl), the C optionally replaced by hydroxyl or amino or halogen₃-C₇Cyclic aliphatic alkyl (such as cyclobutyl Or cyclohexyl), or, the C optionally replaced by hydroxyl or amino or halogen₆-C₁₀Aromatic hydrocarbyl (preferably phenyl or aminomethyl phenyl).

In this application ,-⁺NR³R⁴H groups refer to-NR³R⁴⁺H groups ,-⁺NR³H- groups refer to-NR³(⁺H)-group.One As, organic amine B has >=m (such as m to m+3) primary amine, secondary amine and/or tertiary amine group, and optionally there is quaternary ammonium group Group.For example, CH₃CH₂ ⁺NH₂H (i.e. ethamine cation, CH₃CH₂NH₂ ⁺H it is) by ethamine and one⁺H ions are combined institute's shape Into, B here¹⁺=CH₃CH₂ ⁺NH₂H or CH₃CH₂NH₂ ⁺H, m=1, B=ethamine.In above formula, primary amine, secondary amine and/or tertiary amine Group is selected from-NR³R⁴Group and-NR³- group.

Organic amine compound B is primary amine, secondary amine and/or tertiary amine group with m to m+3, and optionally has season The organic amine of ammonium group.It is preferred that, organic amine compound B has 2-200 carbon atom (preferably 3-50, more preferably 3-20 Individual, more preferably 3-12) organic amine compound.Typically, it has above-described R group.

In this application, organic amine compound B, or the primary amine with >=m (such as m to m+3), secondary amine and/or Tertiary amine group and the organic amine compound B optionally with quaternary ammonium group, with m⁺H ions are combined and become B^m+。

Preferably, A^n-It is combination or the mixture for the two or more above-mentioned anion being selected from (a)-(h), and/ Or B^m+It is combination or the mixture of two or more above-mentioned organic amine cations, therefore, it is a kind of mixing to lead to formula (I) compound Thing.

In the application, p B^m+It may be the same or different, or p B may be the same or different.Preferably, p B^m+Difference, or p Individual B is different.

Additionally, it is provided a kind of embodiment, wherein A^n-It is the one or more in following anion：(a)、(c)、 (d)、(e)、(f)；Or (h).

Typically, in logical formula (I), the single A with+2 or+trivalent^n-Can respectively with one or more B^m+Into salt.And, With multiple-N⁺R³R⁴H groups and/or-N⁺R³The single organic amine ion B of H- groups^m+Can be with one or more A^n-Into Salt.

For (c) HCOO^-For, ammonium formate, formic acid hydrazine or formic acid organic amine salt are more stable compound in itself, point Solution temperature is generally greater than 100 DEG C, and the fusing point of such as ammonium formate is up to 116 DEG C.However, working as has ammonium formate, formic acid hydrazine or formic acid When machine amine salt is used as polyurethane foams, it is found that they but become unstable when touching isocyanates (such as MDI), reason is Ammonium formate, formic acid hydrazine or formic acid organic amine salt and NCO group reaction generate labile acid anhydride group, and then rapid decompose is put Go out carbon dioxide, while also release carbon monoxide, therefore in actual applications it should be noted that ventilation, explosion-proof.

Similarly, following anion also becomes unstable when touching isocyanates (such as MDI)：(e)R^aO-COO^-；(f)^- OOC-N(R¹)-R^b-N(R²)-COO^-Or R^b'(-N(R¹)-COO^-)₃；Or (h)^-OOC-OR^cO-COO^-；

It is preferred that, (e) R^aO-COO^-It is the moon formed by bicarbonate hydrocarbyl carbonate (such as bicarbonate methyl esters or bicarbonate ethyl ester) Ion or acid group.

It is preferred that, (f)^-OOC-N(R¹)-R^b-N(R²)-COO^-Or R^b'(-N(R¹)-COO^-)₃It is by (the amino of alkylene two respectively Formic acid) or alkylene three (carbamic acid) anion or acid group that are formed.

It is preferred that, (h)^-OOC-OR^cO-COO^-, it is by the carbonic acid of alkylene two (such as ethylene ammonium carbonate NH₄OOC- OCH₂CH₂O-COONH₄) anion or acid group that are formed.

It is preferred that, for example, when logical formula (I) compound is used to prepare the polyurethane foamed material of heat insulation-type as foaming agent, Especially the polyurethane foamed material of obturator-type when, from bubbling efficiency, the smell of foaming agent, heat-insulating property and abscess-size stability And the dimensional stability of polyurethane foam finished product considers that q=1-5, more preferably q=1-4, more preferably q=1-3 are especially excellent Q=1-2.5 is selected, particularly preferred q=1.5-2.0, by q mean value calculation.It is preferable, therefore, that B is two or moreization The mixture of compound.It is further preferred that including at least one N-H group (N-H covalent bonds, i.e. the H being connected with N) in B.

R¹,R²,R³And R⁴Independently selected from：H, R, the C optionally replaced by hydroxyl or amino or halogen₁-C₄Aliphatic alkyl (such as methyl or ethyl or propyl group), the cyclobutyl or cyclohexyl optionally replaced by hydroxyl or amino or halogen, or, optionally by hydroxyl Base or the phenyl or aminomethyl phenyl of the substitution of amino or halogen.

It is preferred that, R_1a、R_2a、R_3aOr R_4aIt is each independently selected from：H, the C optionally replaced by hydroxyl or amino or halogen₁-C₃ Aliphatic alkyl, the C optionally replaced by hydroxyl or amino or halogen₃-C₆Cyclic aliphatic alkyl, or, optionally by hydroxyl or amino or halogen The C of element substitution₆-C₇Aromatic hydrocarbyl (such as phenyl or aminomethyl phenyl).

It is further preferred that R_1a、R_2a、R_3aOr R_4aIt is each independently selected from：H, methyl or is optionally replaced by hydroxyl or amino or halogen Ethyl, or the propyl group or isopropyl optionally replaced by hydroxyl or amino or halogen optionally take by hydroxyl or amino or halogen The cyclohexyl in generation, or, the phenyl or aminomethyl phenyl optionally replaced by hydroxyl or amino or halogen.

It is further preferred that R_1a、R_2a、R_3aOr R_4aIt is each independently selected from：H, methyl, chloromethyl, bromomethyl, ethyl, cyclohexyl, Or, phenyl.

In general, the organic amine salt compound for leading to formula (I) contains alcohol amine compound or alcohol amine compound residue.Namely Say, the organic amine salt compound of logical formula (I) is that have as CO₂The anion A of donor^n-And contain alcohol amine compound or hydramine One or more organic amine salt compounds of compounds residues.

It is preferred that, A^n-It is the one or more in following anion：

(b)CO₃ ^2-；

(c)HCOO^-；

(d)HO-COO^-；Or

(g)(i.e. HC (OR ') O₂ ^2-), or(i.e. HCO₃ ^3-),

In formula, R ' is H, the C optionally replaced by hydroxyl or amino or halogen₁-C₂₆Alkyl (preferably C₁-C₁₀Alkyl, more preferably Methyl, ethyl, propyl group), C₁-C₂₆Acyl group (preferably C₁-C₁₀Acyl group, more preferably formoxyl, acetyl group or propiono).

In this application, " optionally " represent to carry out or without representing substitution or not replacing." optional " indicate or No.

Typically, in the compound of logical formula (I), ammonia, hydrazine or amino and/or amido (i.e.-N in organic amine compound B⁺ R³R⁴H groups and/or-N⁺R³H- groups) 50-100% by anion A^n-Neutralize, that is to say, that amino and/or amido into Salt rate is 50-100%.It is preferred that, ammonia, hydrazine or amino and/or the 65-100% of amido in organic amine compound B are by anion A^n- Neutralize.It is further preferred that ammonia, hydrazine or amino and/or the 75-100% of amido in organic amine compound B are by anion A^n-Neutralize.More It is preferred that, ammonia, hydrazine or amino and/or the 75-90% of amido in organic amine compound B are by anion A^n-Neutralize.

Except wherein A^n-Be formate (c) logical formula (I) compound (pH=5.5-6.5) outside, the logical formula (I)s of others The pH of compound is generally 7.5-10, it is preferable that be pH 7.8-9.5, more preferably pH 8-9.For example, when ammonia, hydrazine or organic amine chemical combination Amino and/or amido (i.e.-N in thing B⁺R³R⁴H groups and/or-N⁺R³H- groups) 50-95% by anion A^n-During neutralization, Now formula (1) compound is metastable.

When the amino and/or the 100% of amido in ammonia, hydrazine or organic amine compound B is by anion A^n-During neutralization, then formula (I) below general formula is become：

In this application, for simplicity, with m (wherein m=1-10, such as 1,2,3,4,5,6,7,8,9 or 10 It is individual)-N⁺R³R⁴H groups and/or-N⁺R³The organic amine ion of H- groups may be considered the organic amine ion of+m valencys.

It is preferred that, for m (such as m=1 or m=2-10, such as 3,4,5)-N⁺R³R⁴H groups and/or-N⁺R³H- Organic amine ion (the B of group^m+), wherein compound B is by (having with least one (preferably at least two) N-H covalent bond Have at least one reactive hydrogen bonded with N) organic amine compound (M), ammonia and/or hydrazine formed as initiation material. That is, in B or B^m+In N-R groups be by each molecule in the organic amine compound (M), ammonia and/or hydrazine extremely Formed by being replaced on a few N atom by said one or multiple R groups.That is, compound B is with N-R groups (or N- H covalent bonds) organic amine compound.It is preferred that, the organic amine compound B with N-R groups is by the organic amine Replaced at least one N atom of each molecule of class compound (M), ammonia and/or hydrazine by said one or multiple R groups Formed by.

Preferably, R¹And R²In at least one be H, more preferably R¹It is H and R²It is H or R group (such as ethoxy or hydroxyl Propyl group).

It is preferred that, organic amine compound (M), i.e. with least one N-H (that is, N-H covalent bonds or with least one The bonded H with N, is reactive hydrogen) organic amine compound (M), be selected from following organic amine compound in these：

C₁-C₂₄Alkyl amine (primary amine class), such as methylamine, ethamine, propylamine, butylamine, amylamine, hexyl amine, heptyl amine, Octyl amine, nonyl amine, decyl amine, lauryl amine, tetradecylamine, hexadecylamine, octadecylamine, eicosyl amine, Tetracosyl amine, the aniline of unsubstituted or substituted (such as halogen substitution), the benzyl amine of unsubstituted or substituted (such as halogen substitution), Cyclo-hexylamine, methylcyclohexyl amine, cyclohexyl methyl amine, N- methylcyclohexyls amine or N- methylbenzylamines, etc.；

Two (C₁-C₁₆Alkyl) amine (secondary amine class, the i.e. monoamine with a secondary amine), such as dimethylamine, diethyl Amine, Methylethyl amine, dipropylamine, methyl-propyl amine, ethyl propyl amine, dibutylamine, N-Ethylbutylamine, diamyl amine, two Hexyl amine, diheptyl amine, dioctylamine, dinonyl amine, didecylamine, two (dodecyl) amine, two (myristyl) amine, two (cetyl) amine, two (octadecyl) amine, two (eicosyl) amine or two (tetracosyl) amine, etc.；

Optionally in C₂-C₁₄The C being optionally substituted by a hydroxyl group on alkylene₂-C₁₄(two of which amido is each independent for alkylene Diamines Ground is primary amine groups or secondary amine), such as ethylenediamine, N- methyl ethylenediamines, N, N '-dimethyl ethylenediamine, 1,3- propane diamine, N- first Base, N ' ethyl -1,3- propane diamine, butanediamine (including various isomers, such as 1,2 or 1,3- or Putriscine), pentanediamine (bag Include various isomers), hexamethylene diamine (including various isomers), 3- methylols-hexamethylene diamine, heptamethylene diamine (including various isomers), 3- methylols-heptamethylene diamine, octamethylenediamine (including various isomers), 3,5- dihydroxy octamethylenediamines, nonamethylene diamine (including various isomeries Body), decamethylene diamine (including various isomers), 3,6- dihydroxy decamethylene diamines, dodecamethylene diamine, tetradecane diamines, p or m- benzene two Amine, 3,3 '-two chloro- 4,4 '-diphenylmethanediamiand (MOCA), or piperazine, etc.；

Optionally in C₂-C₁₄The C being optionally substituted by a hydroxyl group on alkylidene₄-C₁₆Polyalkylenepolyamines class, such as diethylenetriamines, Trien, tetren, penten, dipropylenetriamine, tri propylidene tetramine, four propylidene five Amine, five inferior propyl hexamine, two butylidene triamines, three butylidene tetramines, the amine of four butylidene five, triethylenediamine, dimethyl two Ethyl triamine, three (2- hydroxyls -1,3- propylidene) tetramines or four (2- hydroxyls -1,3- propylidene) five amine；Deng；

The C being optionally optionally substituted by a hydroxyl group with three primary amine groups₃-C₁₈Organic three amine is optional with four primary amine groups The C being optionally substituted by a hydroxyl group₅-C₁₈Organic tetraamine, such as 1,3,5- triamidos-hexamethylene, 1,3,5- tri- (amino-ethyl)-hexamethylene Alkane, 1,3,5- tri- (aminopropyl) -1,3,5- hexahydrotriazines, 1,3,5- tri- (methyl amine propyl group) -1,3,5- hexahydrotriazines, Or, melamine, season penta tetramine, etc.；Or

C₂-C₁₀Alcamines, such as monoethanolamine, diethanol amine, monopropylene glycol amine, dipropanolamine, monoisopropanolamine, diisopropyl Hydramine, monobutanolamine, or two butanolamines, etc..

It is further preferred that (M) is selected from：

Methylamine, ethamine, propylamine, butylamine, amylamine, hexyl amine, the aniline of unsubstituted or substituted (such as halogen substitution), not Substitution or the benzyl amine of substitution (such as halogen substitution), cyclo-hexylamine, or methylcyclohexyl amine；

Dimethylamine, diethylamide, Methylethyl amine, dipropylamine, or methyl-propyl amine；

Ethylenediamine, N- methyl-ethylenediamine, N, N '-dimethyl ethylenediamine, 1,3- propane diamine, N- methyl, N ' ethyls -1,3- Propane diamine, butanediamine (including various isomers, such as 1,2 or 1,3- or Putriscine), pentanediamine (including various isomers), Hexamethylene diamine (including various isomers), 3- methylols-hexamethylene diamine, p or m- phenylenediamines, 3,3 '-two chloro- 4,4 '-diphenyl methane Diamines (MOCA), or piperazine；

Diethylenetriamines, trien, or tetren；

1,3,5- triamido-hexamethylene, 1,3,5- tri- (amino-ethyl)-hexamethylene, 1,3,5- tri- (aminopropyl) -1,3, 5- hexahydrotriazines, 1,3,5- tri- (methyl amine propyl group) -1,3,5- hexahydrotriazines, or, melamine, season penta tetramine；

Or

Monoethanolamine, monopropylene glycol amine, monoisopropanolamine, or monobutanolamine.

In general, B is worked as^m+Be except+1 valency ammonium ion (⁺NH₄) or hydrazine ion outside have m (such as 2-10, Such as 3,4,5)-N⁺R³R⁴H groups and/or-N⁺R³(that is, B during the organic amine ion of H- groups^m+Be not +1 valency ammonium ion (⁺ NH₄) or hydrazine ion, i.e. when B is not ammonia or hydrazine), compound B is made by above-mentioned organic amine compound (M), ammonia and/or hydrazine For initiation material or it is used as initiator and epoxides (such as oxirane, expoxy propane, epoxychloropropane, epoxy bromopropane, ring Oxygen butane or epoxy chlorobutane or styrene oxide, and any two or a variety of mixtures in them) reacted institute's shape Into.

More specifically, compound B and A^n-The salt of formation, or B and A salt, or briefly, compound B is by upper State one or more in organic amine compound (M), ammonia and/or hydrazine and (a), (b), (c), (d), (e), (f) or (h) it is cloudy from The salt that son is formed is as initiation material or as initiator, with epoxides (such as oxirane, expoxy propane, epoxy chloropropionate Alkane, epoxy bromopropane, epoxy butane or epoxy chlorobutane or styrene oxide, and any two or a variety of mixed in them Compound) reacted what is formed.

In addition, working as A^n-It is any one of (a), (b), (c), (d), (e), (f) or (h) and B^m+It is with m (such as 1 or 2-10, such as 3,4,5)-N⁺R³R⁴H groups and/or-N⁺R³(that is, B during the organic amine ion of H- groups^m+No Be+1 valency ammonium ion (⁺NH₄) or hydrazine ion, i.e. when B is not ammonia or hydrazine), the compound (I) is in solvent (preferred matter Sub- property solvent, alcohols solvent or DMF, such as water) in, optionally in catalyst (such as ammoniacal liquor, or organic amine, such as ethamine, two Ethamine or triethylamine) in the presence of, by one or more anion in (a), (b), (c), (d), (e), (f) or (h) With ammonium salt or hydrazonium salt [such as aminoquinoxaline of aminoquinoxaline, hydroxyalkyl or the substitution of hydroxyalkyl alkoxy of ammonia or hydrazine formation (R¹R²N-COO^-+NH₄), carbamic acid hydrazine, carbazic acid ammonium, carbazic acid hydrazine, ammonium carbonate (CO₃ ^2-(⁺NH₄)₂), carbonic acid hydrazine, carbon Sour ammonium hydrazine, ammonium hydrogen carbonate, bicarbonate hydrazine, formic acid hydrazine or ammonium formate, and two or more in them mixture] or described the moon Organic amine salt (such as carbamic acid organic amine salt, hydroxyalkyl that ion is formed with above-mentioned one or more organic amine compounds (M) Or the carbamic acid organic amine salt of hydroxyalkyl alkoxy substitution, carbazic acid organic amine salt, N- hydroxyalkyls or N- hydroxyalkyl alcoxyls The carbazic acid organic amine salt of base substitution, carbonic acid organic amine salt, bicarbonate organic amine salt, formic acid organic amine salt, and in them The mixture of two or more), with epoxides (such as oxirane, expoxy propane, epoxychloropropane, epoxy bromopropane, epoxy Butane or styrene oxide, and any two or a variety of mixtures in them) reacted what is formed.Typically, here Described solvent is not limited to selected from following one or more in these：Methanol, ethanol, ethylene glycol, ethylene glycol, molecular weight Polyethylene glycol, molecular weight less than 400 are less than 300 polypropylene glycol, glycerine, formic acid glyceride or water.

In addition, working as A^n-It is (a) R¹R²N-COO^-Anion and B^m+Be+1 valency ammonium ion (⁺NH₄) or hydrazine ion [that is ,+1 Hydrazine ion (the H of valency₃ ⁺N-NH₂) or+divalent hydrazine ion (H₃ ⁺N-NH₃ ⁺)] when, the compound (I) is R¹R²N-COO^-+NH₄Or R¹R²N-COO^-H₃ ⁺N-NH₂Or (R¹R²N-COO^-)₂(H₃ ⁺N-NH₃ ⁺), wherein R¹Or R²One or both of be above-mentioned R group. These compound Rs¹R²N-COO^-+NH₄Or R¹R²N-COO^-H₃ ⁺N-NH₂Or (R¹R²N-COO^-)₂(H₃ ⁺N-NH₃ ⁺) there is R bases Group, therefore, can also be directly used as logical formula (I) compound or as foaming agent, certainly, these compound Rs¹R²N-COO^-+NH₄Or R¹R²N-COO^-H₃ ⁺N-NH₂Or (R¹R²N-COO^-)₂(H₃ ⁺N-NH₃ ⁺) further can also be reacted with above-mentioned epoxides, obtain There is the logical formula (I) compound of alcohol amine compound or hydramine residue in cationic moiety.Work as A^n-It is (a) R¹R²N-NH-COO^-It is cloudy Ion and B^m+Be+1 valency ammonium ion (⁺NH₄) or hydrazine ion [that is, the hydrazine ion (H of+1 valency₃ ⁺N-NH₂) or+divalent hydrazine ion (H₃ ⁺N-NH₃ ⁺)] when, the compound (I) is R¹R²N-NH-COO^-+NH₄Or R¹R²N-NH-COO^-H₃ ⁺N-NH₂Or (R¹R²N-NH- COO^-)₂(H₃ ⁺N-NH₃ ⁺), wherein R¹Or R²One or both of be above-mentioned R group.These compound Rs¹R²N-NH-COO^-+NH₄ Or R¹R²N-NH-COO^-H₃ ⁺N-NH₂Or (R¹R²N-NH-COO^-)₂(H₃ ⁺N-NH₃ ⁺) there is R group, therefore, also can directly it use Make logical formula (I) compound or as foaming agent, certainly, these compound Rs¹R²N-NH-COO^-+NH₄Or R¹R²N-NH-COO^-H₃ ⁺N- NH₂Or (R¹R²N-NH-COO^-)₂(H₃ ⁺N-NH₃ ⁺) further can also be reacted with above-mentioned epoxides, obtain in cation portion There is the logical formula (I) compound of alcohol amine compound or hydramine residue in point.

Typically, A is worked as^n-It is (g) anion and B^m+Be with m (such as 2-10, such as 3,4,5)-N⁺R³R⁴H groups And/or-N⁺R³(that is, B during the organic amine ion of H- groups^m+Be not +1 valency ammonium ion (⁺NH₄) or hydrazine ion, i.e. when B is not When ammonia or hydrazine), the compound (I) be by orthoformic acid ester type compound solvent (preferably protonic solvent, alcohols solvent or DMF in), optionally in the presence of catalyst (such as ammoniacal liquor, or organic amine, such as ethamine, diethylamine or triethylamine), and Belong to the organic amine M of Organic Alcohol amine or the compound B and water that belong to Organic Alcohol amine with least one above-mentioned N-R group In the presence of reaction be hydrolyzed formed.Preferably, the amount of the water is sufficient so that orthoformic acid ester type compound At least two ester group hydrolyses, it is further preferred that the amount of water be sufficient so that orthoformic acid ester type compound three ester groups hair Unboiled water solution.The hydrolyst of orthoformate is usually alkali compounds, preferably organic amine.It is preferred that, it is above-mentioned with least one The organic amine compound B of N-R groups (that is, at least one R group bonded with N) is by ammonia, hydrazine and/or above-described had Machine amines (M) and above-described epoxides (such as oxirane, expoxy propane, epoxychloropropane, epoxy bromine third Alkane, epoxy butane (including various isomers such as 1,2- epoxy butanes, 2,3- epoxy butanes), epoxy chlorobutane are (including various different Structure body such as 1,2- epoxy -4- chlorobutanes, 2,3- epoxies -1-chlorobutane) or styrene oxide, and any two or many in them Kind mixture) reacted prepared by.In the R group, q average value (i.e. the degree of polymerization of epoxides) is such as above institute Definition.Q average value can be selected according to the concrete application of polyurethane foamed material.It is preferred that, when for preparing heat insulation-type During polyurethane foamed material, especially the polyurethane foamed material of obturator-type when, from bubbling efficiency, the smell of foaming agent, thermal insulation Can and the dimensional stability of abscess-size stability and polyurethane foam finished product consider, or when being used for perforate or half perforate During polyurethane foamed material, from the size of bubbling efficiency, the smell of foaming agent, abscess sophistication and polyurethane foam finished product Stability consideration, more preferably q=1-5, more preferably q=1.2-4.5, q=1.3-4, particularly preferred q=1.5-3.5, by the flat of q Mean value computation.

Preferably, orthoformic acid ester type compound is the one or more in these following compounds：(the C of primitive nail three₁- C₈) alkyl esters, the preferably (C of primitive nail three₁-C₇) alkyl esters, for example, trimethyl orthoformate, triethyl orthoformate, orthoformic acid first Base diethyl ester, tripropyl orthoformate, primitive nail acid methyl dipropyl, tributyl orthoformate, orthoformic acid triphen base ester, orthoformic acid Tribenzyl ester, acetyl group orthoformic acid diethyl ester, acetyl group orthoformic acid ethyl-methyl ester, orthoformic acid three (ethylene glycol) ester, primitive nail Sour three (diethylene glycol) esters, orthoformic acid three (triethylene glycol) ester, orthoformic acid three (tetraethylene glycol) ester, (polyethylene glycol of orthoformic acid three (degree of polymerization=5-10)) ester, orthoformic acid three (propane diols) ester, orthoformic acid three (DPG) ester, orthoformic acid three (tripropylene glycol) Ester, orthoformic acid three (four propane diols) ester, orthoformic acid three (polypropylene glycol (degree of polymerization=5-10)) ester.

It is preferred that, solvent used in the hydrolytic process of orthoformate is not selected from following one or more in these, but not It is limited to：Methanol, ethanol, ethylene glycol, ethylene glycol, molecular weight be less than 400 polyethylene glycol, molecular weight be less than 300 polypropylene glycol, Glycerine, formic acid glyceride or water.

In order to prepare the compound of above-mentioned logical formula (I), them can be prepared using a variety of preparation methods.As just act Example, describes several representational preparation methods separately below.

According to another embodiment of the invention, the present invention, which also provides to prepare to have, is used as CO₂The anion of donor The method of organic amine salt compounds, or prepare wherein A^n-It is any one of (a), (b), (c), (d), (e), (f) or (h) Or the method for the compound of the logical formula (I) described above of a variety of anion, this method includes the first raw material and the second raw material exists In solvent (preferably protonic solvent or alcohols solvent), optionally in catalyst (such as ammoniacal liquor, or organic amine, such as ethamine, two Ethamine or triethylamine) in the presence of, reacted, wherein the first raw material is one kind or many in these following compounds Kind：

R¹R²N-COONH₄, R¹R²N-COOH organic amine compound (M) salt, R¹R²N-COOH hydrazonium salt (such as amino Formic acid hydrazine), R¹R²N-NH-COONH₄(such as carbazic acid ammonium), R¹R²N-NH-COOH hydrazonium salt (such as carbazic acid hydrazine), or R¹R²N-NH-COOH organic amine compound (M) salt, wherein R¹Or R²Independently selected from：H, optionally by hydroxyl or amino or halogen The C of element substitution₁-C₇Aliphatic alkyl (preferably C₁-C₄Alkyl), the C optionally replaced by hydroxyl or amino or halogen₃-C₇Cyclic aliphatic Alkyl (such as cyclobutyl or cyclohexyl), or, the C optionally replaced by hydroxyl or amino or halogen₆-C₁₀Aromatic hydrocarbyl (preferred phenyl Or aminomethyl phenyl)；

HO-COONH₄The bicarbonate of (i.e. ammonium hydrogen carbonate), bicarbonate hydrazine, or organic amine compound (M)；

R^aO-COONH₄, R^aO-COOH hydrazonium salt, or R^aO-COOH organic amine compound (M) salt；

NH₄OOC-N(R¹)-R^b-N(R²)-COONH₄, R^b'(-N(R¹)-COO)₃(NH₄)₃, HOOC-N (R¹)-R^b-N(R²)- COOH hydrazonium salt, HOOC-N (R¹)-R^b-N(R²)-COOH organic amine compound (M) salt, R^b'(-N(R¹)-COOH)₃Hydrazine Salt, or R^b'(-N(R¹)-COOH)₃Organic amine compound (M) salt；Or

Second raw material is the one or more in these following compounds：

Or benzene Ethylene oxide (styrene oxide)；

Wherein R¹, R², R^a, R^b, R^b', R^cAs defined above, R_1a、R_2a、R_3aOr R_4aAs defined above, and organic amine Compound (M) is as defined above.

It is preferred that, preparing wherein A^n-Be (a)-(f) or (h) logical formula (I) the reaction of compound in, the first raw material and The mol ratio of two raw materials is usually 1:1.3-5, preferably 1:1.5-4.5, more preferably 1:1.6-4, such as 1:1.5 to 1:3.

It is preferred that, the first raw material is the one or more in these following compounds：

Aminoquinoxaline, carbamic acid organic amine M (abbreviation carbamic acid amine), carbamic acid hydrazine, carbazic acid ammonium, diazanyl Formic acid hydrazine, H₂N-NH-COOH organic amine compound (M) salt, N- substituted amido ammonium formates (R¹R²N-COO^-+NH₄, Huo Chengzuo R¹R²N-COOH ammonium salt, R¹And R²It is asynchronously H), N- substituted amido formic acid organic amine M salt (that is, R¹R²N-COOH is formed with M Salt, abbreviation amidocarbonic acid amine, R¹And R²It is asynchronously H), ammonium carbonate, carbonic acid organic amine M salt (that is, H₂CO₃The salt formed with M, Abbreviation amine carbonate), carbonic acid hydrazine, ammonium carbonate hydrazine, ammonium formate, formic acid organic amine M salt (that is, formic acid and the salt of M formation, abbreviation formic acid Amine), formic acid hydrazine, ammonium hydrogen carbonate, bicarbonate organic amine M salt (that is, M bicarbonate, abbreviation Ammonium bicarbonate food grade), bicarbonate hydrazine, R^aO-COONH₄, R^aO-COOH M salt, R^aO-COOH hydrazonium salt, NH₄OOC-N(R¹)-R^b-N(R²)-COONH₄, R^b'(-N(R¹)- COONH₄)₃, HOOC-N (R¹)-R^b-N(R²)-COOH M salt, HOOC-N (R¹)-R^b-N(R²)-COOH hydrazonium salt, R^b'(-N (R¹)-COOH)₃M salt, R^b'(-N(R¹)-COOH)₃Hydrazonium salt, NH₄OOC-OR^cO-COONH₄, HOOC-OR^cO-COOH's is organic Amine M salt, or HOOC-OR^cO-COOH hydrazonium salt, wherein M are above-described organic amine compound (M).

In this application,⁺MH refers to organic amine M and one or more hydrogen ion (H⁺) it is combined formed cation.

It is preferred that, the second raw material is the one or more in these following compounds：

Oxirane, expoxy propane, epoxychloropropane, epoxy bromopropane, epoxy butane (including various isomers such as 1,2- Epoxy butane, 2,3- epoxy butanes), epoxy chlorobutane (including various isomers such as 1,2- epoxy -4- chlorobutanes, 2,3- epoxies - 1-chlorobutane) or styrene oxide.

It is preferred that, the present invention also provides and prepares wherein A^n-It is any one of (a), (b), (c), (d), (e), (f) or (h) Or the method for the compound of the logical formula (I) of a variety of anion, this method includes：Solvent (preferably protonic solvent or DMF, Such as water) in, optionally in the presence of catalyst (such as ammoniacal liquor, or organic amine, such as ethamine, diethylamine or triethylamine), by The ammonium salt or hydrazine of one or more anion and ammonia or hydrazine formation in (a), (b), (c), (d), (e), (f) or (h) Salt (such as aminoquinoxaline, the aminoquinoxaline replaced on amino by hydroxyalkyl or hydroxyalkyl alkoxy, carbamic acid hydrazine, Carbazic acid ammonium, carbazic acid hydrazine, ammonium carbonate, carbonic acid hydrazine, ammonium carbonate hydrazine, formic acid hydrazine, ammonium formate, bicarbonate hydrazine, or bicarbonate Ammonium, and two or more in them mixture) or the anion and above-mentioned one or more organic amine compound (M) shapes Into organic amine salt (such as carbamic acid organic amine M salt, the amino first replaced on amino by hydroxyalkyl or hydroxyalkyl alkoxy The carbazic acid organic amine M of sour organic amine M salt, carbazic acid organic amine M salt, N- hydroxyalkyls or the substitution of N- hydroxyalkyls alkoxy The mixture of salt, carbonic acid organic amine M salt, formic acid organic amine M salt or bicarbonate organic amine M salt, and two or more in them) As the first raw material, with epoxides described above (such as oxirane, expoxy propane, the epoxy chloropropionate as the second raw material Alkane, epoxy bromopropane, epoxy butane (including various isomers such as 1,2- epoxy butanes, 2,3- epoxy butanes), epoxy chlorobutane (including various isomers such as 1,2- epoxy -4- chlorobutanes, 2,3- epoxies -1-chlorobutane) or styrene oxide, and in them Any two or a variety of mixtures) reacted.Or, alternatively (it is less preferred scheme), can Using including advance addition and the rear method for neutralizing two steps, i.e. the method bag of the compound of the logical formula (I) of above-mentioned preparation Include：First, ammonia, hydrazine or above-mentioned one or more organic amine compounds (M), with the epoxides described above as the second raw material (such as oxirane, expoxy propane, epoxychloropropane, epoxy bromopropane, epoxy butane (including various isomers such as 1,2- rings Oxygen butane, 2,3- epoxy butanes), epoxy chlorobutane (including various isomers such as 1,2- epoxy -4- chlorobutanes, 2,3- epoxy -1- Chlorobutane) or styrene oxide, and any two or a variety of mixtures in them) reacted, then, gained compound With belonging to anion A^n-The respective acids of presoma (that is, one or more anion in (a)-(g) can be generated One or more acid compound or acid compound (such as CO₂, carbamic acid, or formic acid) carry out neutralization reaction.It is preferred that, neutralize It is not less than 7.5, more desirably not less than 7.8, more desirably not less than 8 to pH.Ammonium formate (116 DEG C of fusing point), formic acid hydrazine or formic acid have The pH value of machine amine M salt foaming agents is more typically in 5.5-6.0 scopes in 5.5-6.5 scopes.Wherein A^n-It is the formula of formate (c) (I) pH of compound is more typically in 5.5-6.0 scopes in 5.5-6.5 scopes.

According to another embodiment of the invention, the present invention, which also provides to prepare to have, is used as CO₂The anion of donor The method of orthoformic acid organic amine salt compounds, or prepare wherein A^n-It is the compound of the logical formula (I) for the anion that (g) is represented Method, this method includes：Orthoformic acid ester type compound is in solvent (preferably protonic solvent, alcohols solvent, such as water), optionally Ground is belonging to Organic Alcohol in the presence of catalyst (such as ammoniacal liquor, or organic amine, such as ethamine, diethylamine or triethylamine) Enter in the presence of the organic amine M of amine or the compound B and water that belong to Organic Alcohol amine with least one above-mentioned N-R group Row hydrolysis.Preferably, the amount of the water is sufficient so that at least two ester groups generation of orthoformic acid ester type compound Hydrolysis, it is further preferred that the amount of water is sufficient so that three ester group hydrolyses of orthoformic acid ester type compound.

Typically, when preparing the diazanyl alcohol amine salt compound of logical formula (I), organic amine compound B is hydrazine and optional ammonia Reacted what is formed as initiation material or as initiator and epoxides, the epoxides is selected from these following rings One or more in oxide：

Or benzene Ethylene oxide.

In this application, it is preferred that when logical formula (I) compound is diazanyl alcohol amine salt compound, A^n-Or B^m+In extremely Few one kind includes diazanyl or substitution diazanyl.In the method for preparing the diazanyl alcohol amine salt compound of logical formula (I), in the first raw material At least one is comprising hydrazine or contains diazanyl.Preparing wherein A^n-It is the diazanyl hydramine of the logical formula (I) by (g) anion represented In the method for salt compound, at least one of Organic Alcohol aminated compounds B includes diazanyl or substitution diazanyl.

In this application, it is preferable that with least one above-mentioned N-R group (that is, at least one R group bonded with N) The compound B for belonging to organic amine is by ammonia, hydrazine and/or above-described organic amine compound (M) and epoxides (such as ring Oxidative ethane, expoxy propane, epoxychloropropane, epoxy bromopropane, epoxy butane (including various isomers such as 1,2- epoxy butanes, 2,3- epoxy butanes), epoxy chlorobutane (including various isomers such as 1,2- epoxy -4- chlorobutanes, 2,3- epoxies -1-chlorobutane) Or styrene oxide, and any two or a variety of mixtures in them) reacted prepared by.In the R group, q It is average value (i.e. the degree of polymerization of epoxides), as defined above.Preparing wherein A^n-It is the formula for the anion that (g) is represented (I) during compound, the mol ratio of ammonia or organic amine compound (M) and epoxides is preferably 1.3-7, more preferably 1.5-4, more It is preferred that 1.5-3.Wherein A^n-It is that compound of the logical formula (I) of (g) is suitable as the polyurethane that foaming agent is used to prepare heat insulation-type Foamed material.That is, the present invention, which is also provided, prepares wherein A^n-It is the compound of the logical formula (I) for the anion that (g) is represented Method, this method includes：Ammonia or above-mentioned one or more organic amine compounds (M), enter with the epoxides as the second raw material Row reaction, prepares the organic amine compound with least one above-mentioned N-R group (that is, at least one R group bonded with N) B；Then, orthoformic acid ester type compound is in solvent (preferably protonic solvent, alcohols solvent, such as water), optionally in catalysis In the presence of agent (such as ammoniacal liquor, or organic amine, such as ethamine, diethylamine or triethylamine), and belonging to having for Organic Alcohol amine It is hydrolyzed in the presence of the machine amine M or compound B and water that belong to Organic Alcohol amine with least one above-mentioned N-R group anti- Should.Preferably, the amount of the water is sufficient so that at least two ester group hydrolyses of orthoformic acid ester type compound, more excellent Choosing, the amount of water is sufficient so that three ester group hydrolyses of orthoformic acid ester type compound.

Preferably, orthoformic acid ester type compound is the one or more in these following compounds：(the C of primitive nail three₁- C₈) alkyl esters, the preferably (C of primitive nail three₁-C₇) alkyl esters, for example, trimethyl orthoformate, triethyl orthoformate, orthoformic acid first Base diethyl ester, tripropyl orthoformate, primitive nail acid methyl dipropyl, tributyl orthoformate, orthoformic acid triphen base ester, orthoformic acid Tribenzyl ester, acetyl group orthoformic acid diethyl ester, acetyl group orthoformic acid ethyl-methyl ester, orthoformic acid binaryglycol ester, orthoformic acid R group in propylene glycol ester, orthoformic acid macrogol ester or orthoformate meets (1a), (2a) or (3a) feature.

It is preferred that, in this application, solvent is selected from following one or more in these：Methanol, ethanol, ethylene glycol, the third two Alcohol, molecular weight are less than polypropylene glycol, glycerine, glyceride or the water that 400 polyethylene glycol, molecular weight are less than 300.

When preparing diazanyl alcohol amine salt, the first raw material is comprising hydrazine or contains diazanyl, or, in the first raw material at least One kind is comprising hydrazine or contains diazanyl.Hydrazine is a kind of poisonous inflammable and explosive compound, therefore conscientiously to be read when in use Read knowledge used in connection with, the related requirement of strict implement and regulation.

Had according to another embodiment of the invention there is provided what is obtained by above-mentioned preparation method as CO₂Donor Anion organic amine salt compounds or compound mixture.It is preferred that, the compound or the compound mixture contain 25- 95wt%, preferably 27-90wt%, preferably 30-85wt%, preferably 40-80wt%, more preferably 45-75wt% single methanol amine are (for example MEA and/or single Propanolamine) salt and glycol amine (such as diethanol amine and/or dipropanolamine) salt (i.e. two kinds salt Weight sum), the gross weight based on compound or compound mixture.Or, it is preferred that the compound or the compound are mixed Compound contains 15-90wt%, preferably 17-88wt%'s, preferably 20-85wt%, preferably 25-80wt%, more preferably 30-70wt% Single methanol amine (such as MEA and/or single Propanolamine) and glycol amine (such as diethanol amine and/or dipropanolamine) (i.e. two kinds alcohol The weight sum of amine), the gross weight based on compound or compound mixture.

According to another embodiment of the invention there is provided the organic amine salt compound with logical formula (I), and by preparation side What method was obtained has as CO₂The organic amine salt compounds of the anion of donor, as the purposes of foaming agent, especially as The purposes of polyurethane foams, foamed polystyrene agent or foam polyvinyl chloride agent.These above-mentioned compounds in this application may be used With the referred to as foaming agent of the present invention or the polyurethane foams of the present invention.

In addition, the invention provides use of the foaming agent of the present invention as foamed polystyrene agent or foam polyvinyl chloride agent On the way, wherein A^n-It is the one or more in following anion：

(a)R¹R²N-COO^-Or R¹R²N-NH-COO^-；Wherein R¹And R²It is hydrogen, methyl, ethyl, H independently of one another (OCH₂CH₂)_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 (OCH₂CH(CBr₃))_q-；

(b)CO₃ ^2-；Or

(d)HO-COO^-。

In addition, in view of the decomposition temperature of ammonium formate (116 DEG C of fusing point) or formic acid organic amine M salt is higher, it is conventionally believed that They are not suitable for polyurethane foam.But, present inventor is by substantial amounts of research work it was unexpectedly observed that working as first Sour ammonium (116 DEG C of fusing point) or formic acid organic amine M salt can generate unstable with NCO group reaction when touching isocyanate groups Acid anhydrides, then decomposes to give off rapidly carbon dioxide and carbon monoxide, therefore should take necessary measure in actual applications Be aerated with it is explosion-proof.In addition, formic acid hydrazine has similar performance.

In this application, when preparing logical formula (I) compound using ammonium formate and epoxides, it is preferred that first by Formic acid carries out reaction with ammoniacal liquor and obtains formic acid aqueous ammonium, then adds a small amount of organic amine (such as methylamine, dimethylamine or front three Amine, ethylamine or diethylamide), thermal dehydration or it is concentrated under reduced pressure or is concentrated in vacuo (such as so that water content is 7-15wt% is Only, such as 10wt% or so), then pass to epoxides (such as oxirane and/or expoxy propane) and reacted, obtain formic acid Alcohol amine salt (I).Here, the addition of a small amount of organic amine (such as methylamine, dimethylamine or trimethylamine, ethylamine or diethylamide), Enable to prevent when formic acid alcohol amine salt (I) is used for and prepares composition, foam (" white material ") in composition, foam (" white material ") hair Raw crystallization, deposited phenomenon.When preparing logical formula (I) compound using formic acid hydrazine and epoxides, obtain and use formic acid with working as Ammonium and epoxides prepare performance or application effect similar or suitable during logical formula (I) compound.Alternatively, it is also possible to use first Acid directly reacts the compound for preparing logical formula (I) with alcamine compound.

In this application, logical formula (I) chemical combination is prepared when ammonium hydrogencarbonate is reacted as the first raw material and the second raw material During thing, usable catalyst, such as methylamine, dimethylamine, alcamines, other amines catalysts, bimetallic catalyst class (class), or Using pressurized, heated.

In addition, by selected from least one of these following alcamine compounds alcohol amine compound, (they are that have extremely Few N-H organic amine compound (M))：

C₂-C₁₂Alcamines, such as monoethanolamine, diethanol amine, triethanolamine, monopropylene glycol amine, dipropanolamine, three propyl alcohol Amine, monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, monobutanolamine, two butanolamines, or three butanolamines,

With belonging to anion A^n-Presoma respective acids (such as CO₂) neutralized formed below general formula (Ia) Organic amine salt compound

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

Also can be directly as foaming agent, especially as polyurethane foams, foamed polystyrene agent or foam polyvinyl chloride Agent, although these are not preferred.Selection used using formic acid or formates as foaming agent when due to reaction in can produce CO, thus should take necessary measure be aerated with it is explosion-proof, isocyanates is deposited when formic acid amine salt is used as foaming agent It is being necessary, because it could release carbon dioxide and carbon monoxide with isocyanates reaction..These above-mentioned compounds are at this Can foaming agent referred to as of the present invention in application.Polyurethane foams or in polyurethane foamed composite thing.Certainly, formula (Ia) These compound blowing agents be not preferred because it or they pH value is generally below 8, even below 7.5, more even Less than 7.1, even up to pH=6-7.When the polyurethane foamed material for preparing heat insulation-type, the especially polyurethane of obturator-type During foamed material, from bubbling efficiency, the smell of foaming agent, heat-insulating property and abscess-size stability and polyurethane foam Dimensional stability considers, or when the polyurethane foamed material for perforate or half perforate, from bubbling efficiency, foaming agent The dimensional stability consideration of smell, abscess sophistication and polyurethane foam finished product, these organic amine salt compound (Ia) (they Be not on the spot (insitu) by organic amine compound (M) with prepared by epoxide reaction) be not preferred.

If that is, first hydramine is prepared by ammonia, hydrazine and/or organic amine and epoxide reaction, then again with (a) acidic materials or acid compound that, the anion of (b), (c), (d), (e), (f), (g) and/or (h) is corresponded to are (for example Carbon dioxide or carbamic acid) neutralized, the organic amine salt compound of logical formula (I) is obtained, then gained organic amine salt compound PH (the usual pH of (i.e. alcohol amine salt)<7)、CO₂Precursor content is (with CO₂Burst size is related) and activity in foamable reaction is not Energy satisfactory (unless advantageous in terms of safety or cost for a few compounds such as orthoformate or hydrazine).Cause This, it is preferred that is by anion and ammonia, the hydrazine and/or organic amine of (a), (b), (c), (d), (e), (f), (g) and/or (h) (M) salt formed is directly reacted to obtain logical formula (I) compound with epoxides.

In addition, carbonic acid two (ethylol amine) salt, carbonic acid two (hydroxypropyl amine) salt, bicarbonate (ethylol amine) salt, bicarbonate (hydroxypropyl amine) salt, which is particularly suitable as foaming agent, to be used in foamed polystyrene or foam polyvinyl chloride.These compounds belong to Above-mentioned logical formula (I) compound.In addition, being not belonging to the carbonate of the polyalkylenepolyamines of above-mentioned logical formula (I) compound, such as two is sub- The carbonate of ethyl triamine, the carbonate of trien, the carbonate of tetramethylene pentamine, the carbonic acid of dipropylenetriamine Salt, the carbonate of tri propylidene tetramine, the carbonate of 4 sub-propyl-5-amine, also being suitable as foaming agent is used for foamed polystyrene Or in foam polyvinyl chloride.

In general, the formic acid amine salt foaming agent containing (c) formate cannot be directly used to foamed polystyrene agent or Foam polyvinyl chloride agent.

In addition, present inventor is it was unexpectedly observed that the compatibility ratio of ammonium formate or formic acid hydrazine and polymer polyatomic alcohol Preferably, i.e. ammonium formate or formic acid hydrazine can be directly dissolved in polymer polyatomic alcohol, therefore ammonium formate or formic acid hydrazine can be used directly Make polyurethane foams, therefore, present invention also provides purposes of the ammonium formate as foaming agent, especially as polyurethane foam Agent.When in the aqueous solution of ammonium formate or the aqueous solution of formic acid hydrazine containing it is a small amount of (such as 0.5-15wt%, such as 1-8wt%, more preferably When such as methylamine, dimethylamine, trimethylamine or the monoethanolamine of organic amine 2-6wt%), formic acid aqueous ammonium is not crystallized, sunk Form sediment.

Foaming agent of the present invention (that is, lead to the compound of formula (I), or by the method for above-mentioned 5th or the 6th embodiment What is obtained has as CO₂The organic amine salt compounds of the anion of donor) there are following characteristics：1) not in addition or not In the case of extra addition alkali compounds, in addition to ammonium formate, formic acid hydrazonium salt or formic acid organic amine M salt compounds, the present invention The pH value of foaming agent (i.e. compound of Formula I) is in 7.5-10, it is preferable that be ammonium formate between pH 7.8-9.5, more preferably pH 8-9 The pH value of (116 DEG C of fusing point), formic acid hydrazine or formic acid organic amine M salt foaming agents is in 5.5-6 scopes, or wherein A^n-It is formate (c) Logical formula (I) compound pH in 5.5-6.0 scopes；2) content of alkali metal or alkaline-earth metal is 0-200ppm (quality), excellent Choosing is less than 150ppm, more preferably less than more preferably less than 100ppm, more preferably less than 50ppm, 20ppm, more preferably less than 10ppm, more preferably less than 5ppm, most preferably below detectable limit or for 0ppm；3) content of water or exist as solvent Water content be 0-40wt%, more preferably preferably 5-35wt%, more preferably 10-30wt%, 15-25wt%；4) temperature is thermally decomposed Degree is to discharge CO between 36-120 DEG C and when decomposing₂Gas；Wherein higher certain form of hair of decomposition temperature Bright foaming agent thing becomes less stable when touching NCO group, can be decomposed between 45-70 DEG C and discharge CO₂；5) it is excellent Choosing, each molecule of foaming agent of the present invention contains at least one R group, and the R group is, for example, HOCH₂CH₂-、HOCH₂CH (CH₃)-、HOCH(CH₃)CH₂-、HOCH₂CH(C₆H₅)-、HOCH(C₆H₅)CH₂-、HOCH₂CH(CH₂Cl)-、HOCH(CH₂Cl) CH₂-、HOCH₂CH(CBr₃)-or HOCH (CBr₃)CH₂-；Further preferably, foaming agent of the present invention comprising it is a variety of (preferred 2-5 kinds, As 2 or 3 kind) there is the compound of logical formula (I) and average per molecule contains 1.5-5 R group, the R group is, for example, HOCH₂CH₂-、HOCH₂CH(CH₃)-、HOCH(CH₃)CH₂-、HOCH₂CH(C₆H₅)-、HOCH(C₆H₅)CH₂-、HOCH₂CH (CH₂Cl)-、HOCH(CH₂Cl)CH₂-、HOCH₂CH(CBr₃)-or HOCH (CBr₃)CH₂-；6) all N in foaming agent of the present invention There is 30-100%, preferably 50%-100%, more preferably 70%-100%, more preferably 85%-100% among atom N-H to be total to Valence link；7) in foaming agent of the present invention, the total content for leading to formula (I) compound and water is the 70-100% based on gross weight, more one As be 80-99.999%, be more typically 85-99.0% (containing solvent, and allowing containing a small amount of nonmetallic inclusion)；8th, with red External spectrum is analyzed, and some foaming agents of the present invention have in 2932-2970cm^-1The secondary amine salt N-H of scope stretching vibration is unimodal, 1555-1566cm^-1The secondary amine salt N-H of scope flexural vibrations are unimodal, in addition, in 3200-3400cm^-1Scope it is strong and wide The OH stretching vibration peaks of Hydrogenbond, show both there is hydroxyl in foaming agent, and secondary amine contains water simultaneously.Therefore, present invention hair Infusion includes one or more alcohol amine compounds and typically contains water.

It is further preferred that the compound average per molecule of logical formula (I) contains 1.5-5 R group.

In this application, it is preferable that the R group is HOCH₂CH₂-、HOCH₂CH(CH₃)-、HOCH(CH₃)CH₂-、HOCH₂CH (C₆H₅)-、HOCH(C₆H₅)CH₂-、HOCH₂CH(CH₂Cl)-、HOCH(CH₂Cl)CH₂-、HOCH₂CH(CBr₃)-or HOCH (CBr₃) CH₂-。

According to the 9th embodiment of the present invention, the present invention also provides polyurethane foamed composite thing, and it is included：0.01- 100 weight % above-described logical formula (I) compound (or is obtained by the method for above-mentioned second and the 3rd embodiment Have be used as CO₂The organic amine salt compounds of the anion of donor)；0-50 weight % physical blowing agent；0-5 weight % Water, and 0.0-99.99 weight % polymer polyatomic alcohol；Wherein, the percentage by weight is based on polyurethane foamed composite thing Gross weight.It is preferred that, it is included：0.1-80 weight % (more preferably 1-70wt%, more preferably 3-60wt%, more preferably 5- 50wt%, more preferably 7-40wt%, such as 10wt%, 15wt%) above-described logical formula (I) compound；0-40 weight %'s Physical blowing agent；0-4 weight % water, and 20.0-99.9 weight % (more preferably 30-99wt%, more preferably 40-97wt%, more It is preferred that 50-95wt%, more preferably 60-93wt%, such as 90wt% or 85wt%) polymer polyatomic alcohol；Wherein, the weight hundred Divide gross weight of the ratio based on polyurethane foamed composite thing.Preferably, composition, foam of the invention contains 0.5-4wt% altogether Water, more preferably 0.8-2.5wt%, more preferably 1-2.2wt% water.

It is preferred that, described composition, foam is further included：Foam stabiliser, catalyst and fire retardant etc..These auxiliary agents It is to commonly use in polyurethane field.

It is preferred that, polymer polyatomic alcohol is selected from：PPG, PEPA, polyether-polyester polyol, makrolon Glycol, polycarbonate-polyester polyalcohol, makrolon-PPG, polybutadiene polyol or polysiloxane polyhydric alcohol. The average functionality of polymer polyatomic alcohol is generally 2-16, more preferably preferably 2.5-10,3-8.

At least one of it is preferred that, the physical blowing agent is selected from the group：Pentane, isopentane, pentamethylene, boiling point is in 0- Other alkane in the range of 100 DEG C, HCFC-141b, HFC-245fa, HFC-365mfc, LBA, FEA-1100, boiling point is in 0-100 Other fluorochlorohydrocarbons in the range of DEG C, esters such as methyl formate.

Typically, composition, foam of the invention is transparent or clarification；Preferably, hard polyurethane foam composition, foam It is transparent or clarification or translucent or milky but uniform, or, soft polyurethane foam composition, foam is transparent Or milky uniform liquid.This shows foaming agent dissolving of the present invention or is dispersed in polymer polyatomic alcohol.Typically, this hair Bright foaming agent or foaming agent forms transparent or clarification system after being mixed with the PPG of the overwhelming majority.One As, foaming agent or foaming agent of the invention forms transparent or clarification system after being mixed with PEPA, still, have It is possible that after it is mixed with the PEPA of a few species, forming milky but uniform system.

The polyurethane foamed composite thing (being commonly called as " white material ") of the present invention has following characteristics：1st, comprising alcohol amine salt or alcohol amination Compound is (for example, the compound of logical formula (I) discharges CO after pyrolysis₂, while remaining alcamine compound)；2nd, it is transparent or clear Clear or translucent or milky but uniform liquid；3rd, in the case where heating (such as 40-80 DEG C of temperature) or in addition acid CO is discharged in the case of (inorganic acid more stronger than carbonic acid or organic acid)₂, peak decomposition temperature be usually 45-65 DEG C it Between；4th, when composition, foam (i.e. " white material ") is contacted or mixed with isocyanates or polyisocyanates (such as MDI or TDI), (such as 0.2-4 seconds, such as 1-2 seconds) the material moment of mixing becomes milky.In the present invention, material becomes rapidly milky, is accompanied by Volume rapid expanding phenomenon, but this process and it is non-foam it is real rise, material just starts to rise afterwards.Comparatively, use Water, or during using water and physical blowing agent as foaming agent, foam is milky white and to rise be while carrying out and being all delay hair Raw.

Although in the present invention, composition, foam (" white material ") can include a small amount of water as blowing promotor, due to The logical formula (I) compound of the present invention preferentially decomposes release CO₂, i.e., preferential foaming, therefore, the addition of a small amount of water does not influence to foam Journey does not influence polyurethane foam end properties.That is, being in some cases foaming agent in logical formula (I) compound Middle to there is a small amount of water, these water are present in the form of the individual molecule for being combined or being associated with logical formula (I) compound phase, or Be conducive to foaming, or be not involved in foaming, i.e., do not consume NCO group.Present inventor has found by research, in formula (I) compound is a small amount of water (i.e. associated water) present in foaming agent or even is not involved in reaction, i.e., do not consume NCO group.This It is the discovery that beyond expectation.

When including wherein A in the polyurethane foamed composite thing (be commonly called as " white material ") of the present invention^n-It is (f) HCOO^-(formate) Logical formula (I) compound when, it is preferred that polyurethane foamed composite thing of the invention (being commonly called as " white material ") is comprising 1-5 weight Water.Purpose is to reduce the amount of the carbon monoxide (CO) discharged in foaming process.

The present invention also provides polyurethane foamed material, and it passes through above-described polyurethane foamed composite thing and polyisocyanic acid Ester monomer (such as MDI and/or TDI) and/or isocyanate-terminated prepolymer react and formed after being mixed.Typically, The weight ratio of the polyurethane foamed composite thing and polyisocynate monomer and/or isocyanate-terminated prepolymer is, for example 0.5:1-2:In the range of 1, preferably 0.5:1-1:Exist in the range of 1 (for rigid polyurethane alveolitoid composition, foam) or preferably 1:1-2:(for flexible polyurethane alveolitoid composition, foam) in the range of 1.It is preferred that, described weight ratio should cause foaming to combine The reactive hydrogen of thing and the equivalent proportion of contained-NCO group in polyisocynate monomer and/or isocyanate-terminated prepolymer are 0.6-1.2:1, more preferably 0.7-0.9:1, i.e. NCO are slightly excessive relative to reactive hydrogen.

The present invention also provides the purposes of polyurethane foamed material, and it is used for polyurethane coating, refrigerator and refrigerator-freezer insulation, packaging Case insulation, insulating board for building, color steel, cold storage plate, the insulation of pipeline, LNG conveyings insulation, high rebound foam, low-resilience foam Deng.

It is preferred that, leading to the organic amine salt compound of formula (I) has at least two reactive hydrogens, such as 2-10, preferably 3-6. The reactive hydrogen is present in the form of primary amine groups, secondary amine or hydroxyl.Therefore, the organic amine salt compound for leading to formula (I) can Enough discharge CO₂To participate in foaming, chain extension and/or crosslinking are participated in again, strengthen intensity (the i.e. mechanical strength and/or machinery of abscess Intensity) so that the polyurethane foam obtained (this foams is to be made using stirring by hand in laboratory self-control Fang Mo) With good dimensional stability.Especially, when the density of polyurethane foam<25kg/m³When, it is considered that, prior art is only The polyurethane foam obtained only with water as foaming agent has serious shrinkage phenomenon, still, with the logical formula (I) of the present invention (this foams is to be made by oneself using stirring by hand in laboratory in Fang Mo to the polyurethane foam that compound is obtained as foaming agent Make) then there is excellent dimensional stability, the feelings of the time of at least five month are placed especially under environmental condition or room temperature condition Almost without macroscopic shrinkage phenomenon under condition.For example, according to chinese national standard GB/T 8811-2008, when simply placing Between change, the finished foam material (density for preparing of the present invention<25kg/m³) 5 are placed under the conditions of room temperature (23 ± 2 DEG C) Month, shrinkage factor (the length dimension rate of change ε of polyurethane foam_LOr width dimensions rate of change ε_wOr thickness rate of change ε r) Generally below 7%, it is more preferably less than 5%, even more preferably below 3%, even more preferably less than 1%.

The organic amine salt compound of the logical formula (I) of the present invention, can be according to each of polyurethane foamed material to be prepared Application field is planted specifically to be designed.

For example, being used as refrigerator, refrigerator, frozen products insulated container when the composition, foam (being commonly called as " white material ") of the present invention is used to prepare The heat-insulating material of refrigerator car polyurethane foamed material or for preparing the flexible polyurethane foams such as high resilience, low resilience When, preparing wherein A^n-Be (a)-(f) or (h) logical formula (I) the reaction of compound in, the first raw material rubs with the second raw material That ratio usually 1:1.3-3.5, preferably 1:1.5-3.In addition, when the composition, foam (being commonly called as " white material ") of the present invention is used to spray Spread man-hour, the mol ratio of the first raw material and the second raw material is usually 1:2.8-5, preferably 1:3-4.5, more preferably 1:3.3- 4。

Preferably, the reaction temperature for preparing logical formula (I) compound be between 0-200 DEG C, such as 10 DEG C, 20 DEG C, 30 DEG C, 40℃、50℃、60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃、130℃、150℃、160℃、170 DEG C, 180 DEG C and 190 DEG C.The pressure of reaction is such as 0.3MPa, 0.6MPa, 0.9MPa and 1.2MPa between 0.1-1.5MPa. Reaction time is such as 0.5 hour between 0.5-20 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, it is 7 small When, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours.

The decomposition temperature of the logical formula (I) compound of the present invention is usually between 45-120 DEG C, between preferably 50-70 DEG C, Or, when touching isocyanates, its decomposition temperature is between 45-70 DEG C.

The advantageous effects or advantage of the present invention

1st, the compound (such as diazanyl alcohol amine salt compound) or foaming agent of the present invention of logical formula (I) of the invention have suitable Decomposition temperature, or there is when touching isocyanates suitable decomposition temperature, on the one hand store stable at room temperature, it is another Aspect during polyurethane foam when foamable reaction system heats up can with rational speed carbon dioxide gas, with So that expanded material has preferable performance, the distribution density of such as abscess, the dimensional homogeneity of abscess.In the present invention most preferably Foaming agent is carbaminate and/or carbonate with logical formula (I), and this is attributed to their suitable decomposition temperature, properly Carbon dioxide rate of release, the distribution density of excellent abscess, the dimensional homogeneity of excellent abscess foams in identical and joins Several lower abscess apertures for forming foams are significantly less than abscess quantity in the physical blowing agents such as water, pentamethylene, unit volume much More than other foaming agents, so as to assign foamed material good heat-insulating property.The foaming agent of the present invention is (particularly with carbamic acid For salt and/or carbonate) there is higher pH value (pH>7.5), high (or the CO2 of its acid group content for Unit Weight Burst size is big), and with higher reactivity during as foaming agent, especially as polyurethane foams.Especially, diazanyl alcohol Amine salt compound is compared with the organic alcohol amine salt compound without diazanyl, because a diazanyl has two amino so that diazanyl Compound has higher alkalescence than amino-compound, and therefore, Unit Weight can combine more anion, i.e. acid group contains Amount is high (or CO2 burst sizes are bigger).

2nd, there is the compound (such as diazanyl alcohol amine salt compound) of logical formula (I) of the invention solubilizing group to be R group, should Compound (I) can equably be dissolved with molecular level or be distributed in polymer polyatomic alcohol such as PPG and/or polyester is more In first alcohol, or polyvinyl chloride (PVC) resin or polystyrene (PS) resin, it is ensured that the uniformity of foaming, it is to avoid local excessive is sent out Bubble.

3rd, the compound (such as diazanyl alcohol amine salt compound) of logical formula (I) of the invention has hydramine residue or with hydramine Compound, decomposes in the foaming agent (I) and discharges CO₂Catabolite produced afterwards is alcohol amine compound still containing at least Two reactive hydrogens, they are suitable as chain extender and/or crosslinking agent, and logical formula (I) compound of the invention was both used as " blow point " " chain extension point " and/or " crosslinking points " are used as again, significantly enhance the mechanical strength and mechanical strength of abscess, the polyurethane obtained Foams have good dimensional stability, and polyurethane foam finished product naked eyes after some months, even 1 year is placed almost do not have Have and observe shrinkage phenomenon, without bubble or the collapse phenomenon of collapsing.Especially in higher (such as 40-60 DEG C, or even 40-70 DEG C) decentralization of temperature Put the long period such as (10 days) still has good dimensional stability afterwards.

4th, the compound (such as diazanyl alcohol amine salt compound) of logical formula (I) of the invention do not allow it is volatile, without metal from Sub (metal ion is corrosive to metal base), and chlorofluorocarbon blowing agent is wholly or largely substituted, therefore, for environment Have great importance for protection, and the effect foamed is substantially better than foaming when using other foaming agents in the prior art Effect.

5th, when being mixed with pentamethylene as foaming agent, compared with pentamethylene is used alone, foam material can be significantly improved The heat-insulating property of material.When being mixed with CFC such as HCFC-141b or HFC-365mfc as foaming agent, with chlorine fluorine is used alone Hydrocarbon is compared, and can significantly improve the heat-insulating property of foamed material.At present, foaming agent or specific chlorofluorocarbon blowing agent are generally surrounded Come select to related foaming agent intersolubility or the preferable special polyether polyalcohol of compatibility, and use the present invention foaming agent, nothing Specific PPG or PEPA need to be selected, usage range extensively, can be used various types of in composition, foam The PEPA and/or PPG of type.

6th, foaming agent of the invention has amido, and itself has self-catalysis function, can reduce polyurethane foaming catalyst Use, can at least reduce the use of early stage catalyst or can even save early stage catalyst.

7th, compared with prior art, the polyurethane foams that provides of the present invention not chlorofluorocarbon or not chloride fluorine element, ODP (to the latent energy value of the destruction of ozone layer) is equal to 1 for 0, GWP (chamber effect potential value), is most environmentally friendly polyurethane foams, Performance comparision is excellent, and cryogenic property is extremely excellent, and the thermal conductivity ratio in the case of subzero 160 degrees Celsius is existing best after testing Physical blowing agent it is low by 20% or so, this excellent characteristic can be used for natural gas long-distance transportation pipeline insulation, Ling Yite Property is to be used in mixed way that the thermal conductivity factor of foamed material can be greatly lowered with pentamethylene, and this excellent heat-insulating property can be big The power consumption of the equipment such as amplitude reduction refrigerator ice cabinet.The polyurethane foams that the present invention is provided is alternative existing all containing halocarbon The physical blowing agent of (containing halogen), meets the production application of polyurethane material.

8th, it is made as foaming agent with the compound (such as diazanyl alcohol amine salt compound) of foaming agent of the present invention or logical formula (I) The size changing rate of standby polyurethane foamed material (this foams is to make by oneself in Fang Mo to make in laboratory using stirring by hand) Or shrinkage factor≤4.5%, preferably≤1.5%, more preferably≤0.5% (according to chinese national standard GB/T 8811-2008, place Time can be according to required in the standard, or even, standing time is 5 months).In addition, for example in 34-42Kg/m³Foam Under volume density, thermal conductivity factor w/mk (10 DEG C) is between 0.01900-0.02200, preferably in 0.01910-0.02150 Between.

9th, a small amount of water is contained in logical formula (I) compound of the invention or mixture (such as diazanyl alcohol amine salt compound), These water are combined or associated with the molecule of the alcohol amine salt compound of logical formula (I) with individual molecule, therefore, individual molecule form The water of presence is very beneficial for foaming, is conducive to improving the performance of foam product.Although same using a small amount of in the prior art Water be used as foaming agent or auxiliary blowing agent, still, these water be typically in the form of water cluster or water clusters (i.e. micro- water The form of drop) exist, especially each water cluster is of different sizes, and the foaming of composition, foam can be caused uneven, especially It causes the part of foams to be collapsed, and influences the various performances of foam product.

Brief description of the drawings

Fig. 1 is the infrared spectrogram of embodiment A-3 product.

Fig. 2 is the infrared spectrogram of embodiment A-4 product.

Fig. 3 is the infrared spectrogram of embodiment B-6 product.

Fig. 4 is the electron scanning micrograph (SEM) of the foams of embodiment 4.

Fig. 5 is the SEM for the contrast foams 4-1 for repeating embodiment 4.

Fig. 6 is the SEM for the reference foams 4-2 for repeating embodiment 4.

Fig. 7 is the SEM for the contrast foams 4-3 for repeating embodiment 4.

Fig. 8 is the SEM for the reference foams 4-4 for repeating embodiment 4.

Fig. 9 is the SEM of the foams of embodiment 16.

Figure 10, Figure 12 and Figure 14 are the outward appearance of use compound A-4 of the invention as the polyurethane foam of foaming agent Photo.

Figure 11, Figure 13 and Figure 15 are the outward appearance photo of the contrast polyurethane foam with Water blown.

Figure 16 is the SEM of the polystyrene foamed material of embodiment 34.

Figure 17 is the infrared spectrogram of the compound (diazanyl alcohol amine salt) of embodiment 36.

Embodiment

With reference to embodiment, the present invention will be further described.

In this application, for preparing polyurethane foam or for the conventional PPG in composition, foam and poly- Ester polyol is selected from following kinds：Polyethers 4110,450,400A, MN500, SU380, SA380,403, SA460, G350；Polyester CF6320、DM2003、YD6004、AKS7004、CF6255.Custom catalystses are selected from：33LV(A-33)：33% triethylene diamine DPG solution, N, N- dimethylethanolamines, N, N- dimethyl benzylamines, the dipropyl two of 70% pair of (dimethylamino ethyl) ether Alcoholic solution, 70% potassium octanoate are in diethylene glycol solution, dibutyl tin laurate, PT303, PT304, potassium acetate, PC-8 (N, N- Dimethyl cyclohexyl amine), PC-5, PC-41, monoethanolamine, diethanol amine, triethanolamine, JXP-508, JXP-509, TMR-2, TMR-3、TMR-4.Conventional fire retardant：TCPP, TCEP, DMMP, ammonium chloride, aluminium-hydroxide powder, DM1201, DM1301, tetrabromo Phthalic anhydride glycol.Conventional silane surface active agent：DC8545、AK-158、AK-8805、AK-8812、AK-8809、AK-8818、AK- 8860、DCI990、DC5188、DC6070、DC3042、DC3201.Non- silane surface active agent：LK-221,LK-443.

Safety instruction：The situation for being directed to use with epoxide every in the present invention, for the sake of security, will react Thing has to pass through before and after adding reactor to be reacted under inert gas (such as nitrogen or argon gas) processing and protection, is prevented Blast.In addition, when adding oxirane, for the sake of security, be preferably added portionwise in reactor, and epoxy Propane can be added disposably in reactor, can also be in batches.Reactor is generally the pressure reactor equipped with cooling device, removes It is non-to be otherwise noted.Epoxide will be slowly added in reactor in batches, and for those comparatively safe epoxidations Compound will be also slowly added in reactor by several times in batches, the reaction condition such as control reaction speed, it is ensured that safety.Hydrazine hydrate It is also inflammable and explosive poisonous compound, therefore must be also carried out when in use according to related request and regulation.

According to chinese national standard GB/T 26689-2011, (refrigerator, refrigerator-freezer are moulded with hard polyurethane foams in embodiment Material) test foams properties.The size of sample is generally 10*10*2.5cm.

Thermal conductivity factor is carried out according to GB/T 10294-2008 or GB/T 10295-2008.Mean temperature is 10 DEG C, cold and hot 15~20 DEG C of the plate temperature difference.Apparent (core) density is tested according to GB/T 6343-2009.Low-Temperature Size stability is according to GB/T 8811-2008, is tested at -30 DEG C ± 2 DEG C.Compressive strength is tested according to GB/T 8813-2008.Rate of closed hole (i.e. closed pore Percentage by volume) tested according to GB/T 10799-2008.

Various hydramine (such as MEA, diethanol amine, three in compound or compound mixture for leading to formula (I) Monoethanolamine, single Propanolamine, dipropanolamine or tripropanol amine) content measuring method, gas chromatography can be used.Wherein gas phase Chromatograph is furnished with flame ionization ditector (FID), and the mass concentration for leading to formula (I) compound is about 10mg/mL, is standard Solution.GC conditions：HP-5 capillary chromatographic columns (30m × 0.32mm i.d. × 0.25 μm, 5%phenyl methyl- siloxane)；Column temperature is temperature programming, and initial temperature is 80 DEG C, and 250 DEG C are risen to 25 DEG C/min speed after keeping 3min, Keep 5min；250 DEG C of injector temperature；260 DEG C of detector temperature；Carrier gas is High Purity Nitrogen, and flow velocity is 1.5mL/min；Combustion gas is Hydrogen, flow velocity is 30mL/min；Combustion-supporting gas is air, and flow velocity is 300mL/min；Make-up gas is nitrogen, and flow velocity is 25mL/min； Input mode is split sampling, split ratio：30:1；Sample size is 1 μ L.

A) logical formula (I) compound is prepared from amino acid ammonium salt or carbamic acid organic amine (M) salt

Embodiment A-1

1.4 tons of aminoquinoxalines (molecular weight 78.07), 0.7 ton of ethylene glycol, 0.9 ton of water are added to cold But in the stainless steel autoclave (the abbreviation reactor in following other embodiments) of water leg, agitator is started so that Aminoquinoxaline slowly dissolves and (is not necessarily completely dissolved), uses nitrogen purge, then closed reactor and starts stirring, 1.7 tons altogether of expoxy propane (molecular weight 58.08,34 DEG C of boiling point) is passed through, controls the charging rate of expoxy propane to control Pressure in reactor is not higher than 0.6MPa, is slowly heated up in the case where being stirred continuously, and temperature control reacts 15 hours below 70 DEG C, reaction Complete, slowly reduce the temperature to after 50 DEG C and control vacuum (preferably shorter than 500mmHg) below 600 millimetress of mercury slowly to remove Unnecessary water (for example reaching the water content less than 20wt%) and unreacted expoxy propane, then bleed off vacuum, cool to Reactant is released after less than 40 DEG C, compound A-1 is obtained.The centipoise of viscosity 200, pH=9, compound A-1 decomposition temperature is 45- 70 DEG C (extremely slowly being decomposed since 45 DEG C, peak decomposition temperature is 57-62 DEG C).Use atomic absorption spectrophotometer (Seiko Instruments,Inc.；SAS/727 the content for) determining alkali and alkaline earth metal ions ion is less than detectable limit. The mol ratio of gas chromatographic analysis, single Propanolamine and dipropanolamine is 1:0.06.Compound A-1 contains about 75wt% single propyl alcohol The salt of both amine and dipropanolamine.Also contain the water of some.In addition, compound A-1 contain about 55wt% single Propanolamine and Dipropanolamine (in heating compound A-1 to discharge carbon dioxide after).

Compound A-1 is a kind of at room temperature or in the more stable transparent or supernatant liquid of environmental condition, is suitable as Polyurethane foams, it and HFC-245fa, LBA, the fundamental characteristics of 3-pentafluorobutane contrast such as following table：

	Compound A-1	HFC245fa	3-pentafluorobutane	LBA
					ODP	0	0	0	0
GWP	1	1030.01	793.98	5.00
					Boiling point (DEG C)	45 DEG C start slow decompose	15.3	40.2	19.3

As can be seen from the above table, compound A-1 GWP (chamber effect potential value) is equal to 1, and decomposition temperature is higher, gram Many shortcomings of some low boilings (being less than 20 DEG C) physical blowing agent such as HFC-245fa, LBA, 3-pentafluorobutane etc. are taken, such as GWP is much larger than 1, boiling point than relatively low, volatile, and to be equal to 1, boiling point higher, not volatile by the compounds of this invention A-1 GWP, And ODP (to latent energy value of the destruction of ozone layer) is 0, will not destroy atmospheric ozone layer；It is not volatile to be readily transported and store.

Embodiment A-2

1.4 tons of aminoquinoxaline, 0.7 ton of ethylene glycol, 0.9 ton of water are added to the stainless steel with cooling jacket In reactor, start stirring so that aminoquinoxaline slowly dissolves and (is not necessarily completely dissolved), reaction system through nitrogen treatment and Heat temperature raising after protection, it is 45-70 DEG C to control temperature, and control pressure is no more than 0.6MPa, is then slowly added in batches total The oxirane (molecular weight 44.05) of 1.3 tons of meter, controls 45-70 DEG C of temperature, pressure is in 0.6MPa reactions stirred below after adding 5 hours, 50 DEG C are then cooled to, the unnecessary water (for example reaching the water content less than 30wt%) of lower removing is depressurized under 600mHg With unreacted oxirane, cool to and product is released after less than 40 DEG C, obtain compound A-2.Viscosity about 250, pH=9, Compound A-2 decomposition temperature is in 45-70 DEG C of scope.

Embodiment A-3 (present invention is preferably)

1kg aminoquinoxaline, 1kg water are added in reactor, dissolving under agitation (allows to exist undissolved Aminoquinoxaline), nitrogen purge is used, 2kg expoxy propane is then added into transparent quartz glass reactor, opens Dynamic stirring, slowly heats up, temperature control is between 50-60 DEG C, and pressure is reacted under the conditions of being not higher than 0.6MPa in the case where being stirred continuously, Marvellous phenomenon is occurred in that suddenly when reaction proceeds to about 2 hours：Muddy, opaque mixture moment become it is transparent or Clear solution, continues to react 8 hours, then cools to 50 DEG C, is that below 600 millimetress of mercury deviate from unnecessary water in vacuum With unreacted expoxy propane, cool to and product is released after less than 40 DEG C.Reaction time ensures that reaction is completed according to mol ratio.Obtain Obtain compound A-3.The centipoise of viscosity 200, pH=9.1, decomposition temperature is in 45-70 DEG C of scope.Liquid-phase chromatographic analysis and gas phase color Analysis of spectrum, it is the mixture for including a variety of hydramine to show compound A-3.Water content is 21.5wt%.Infrared spectrogram such as Fig. 1 institutes Show.

Embodiment A-4 (present invention is preferably)

1 ton of aminoquinoxaline, 1 ton of water are added in the stainless steel pressure reactor with cooling water jecket, The lower dissolving (allowing the presence of undissolved aminoquinoxaline) of stirring, uses nitrogen purge, 2.2 tons of ring is then added portionwise Ethylene Oxide is into reactor, and then closed reactor, starts stirring, slowly heated up in the case where being stirred continuously, temperature control 45-70 DEG C it Between, pressure reacts 10 hours under the conditions of being not higher than 0.6MPa, then cools to 50 DEG C, is below 600 millimetress of mercury in vacuum The unnecessary water of abjection, cools to and product is released after less than 40 DEG C.Obtain compound A-4.The centipoise of viscosity 200, pH=9 is decomposed Temperature is in 45-70 DEG C of scope.Liquid-phase chromatographic analysis and gas chromatographic analysis, it is to include a variety of hydramine to show compound A-4 Mixture.Infrared spectrogram is as shown in Figure 2.

Embodiment A-5 (present invention is preferably)

7kg ammonium carbonate and 7kg aminoquinoxaline, 12kg water are added in reactor, dissolving under agitation (is permitted Permitted the presence of undissolved aminoquinoxaline and ammonium carbonate), nitrogen purge is used, 30kg epoxy third is then added portionwise again Alkane, slowly heats up in the case where being stirred continuously, and temperature control is between 45-70 DEG C, and control pressure is not higher than 0.6MPa, reacts 10 hours, so After cool to 50 DEG C, temperature control below 50 DEG C, vacuum be 600 millimetress of mercury below deviate from unnecessary water and unreacted ring Ethylene Oxide, cools to and vacuum is bled off after less than 40 DEG C, product is released, that is, obtain compound A-5.The centipoise of viscosity about 200, pH= 9, decomposition temperature is in 45-70 DEG C of scope.

Embodiment A-6 (present invention is preferably)

16kg carbamic acid monoethanolamine salt, 10kg water are added in reactor, nitrogen purge reactor is used, stirs Dissolving is mixed, 12kg expoxy propane is added portionwise into reactor, stirring is started, control pressure is not higher than 0.6MPa, continuous Slowly heated up under stirring, when temperature control reaction 5 is small when temperature is increased to 70 DEG C, then reduce the temperature to less than 50 DEG C, control is true Unnecessary water and unreacted expoxy propane is removed below the millimetres of mercury of reciprocal of duty cycle 600, cool to bled off after less than 40 DEG C vacuum, Release product, you can obtain compound A-6.The centipoise of viscosity 230.PH=9.Decomposition temperature is in 45-70 DEG C of scope.

Embodiment A-7

20kg carbamic acid diethylenetriamines salt, 10kg water are added in reactor, stirring and dissolving uses nitrogen Purge, under agitation, control pressure are not higher than 0.6MPa, and 15kg epoxy is added portionwise between 45-70 DEG C in temperature Propane adds temperature control after expoxy propane and reacted 5 hours, then cool at 50 DEG C, vacuum is in 600 millimeters of mercury into reactor Lower removing unnecessary water and unreacted expoxy propane are depressurized below post, cools to and vacuum is bled off after less than 40 DEG C, production is released Thing can obtain compound A-7.The centipoise of viscosity about 350.PH=9, decomposition temperature is in 45-70 DEG C of scope.

Embodiment A-8

1 ton of aminoquinoxaline (molecular weight 78.07), 1 ton of water are added in reactor, dissolving under agitation (is permitted Permitted the presence of undissolved aminoquinoxaline), nitrogen purge is used, 2.8 tons of epoxychloropropane (that is, table chlorine is then added Alcohol or chloro- 1, the 2- expoxy propane of 3-, molecular weight 92.52,117.9 DEG C of boiling point) into reactor, stirring is started, is being stirred continuously Under slowly heat up, temperature control is between 45-70 DEG C, and pressure, which is not higher than under the conditions of 0.6MPa, to react 10 hours, then cools to 50 DEG C, It is that below 600 millimetress of mercury deviate from unnecessary water and unreacted epoxychloropropane in vacuum, cools to after less than 40 DEG C Release product.Obtain compound A-8.The centipoise of viscosity 450, pH=9, decomposition temperature is in 45-70 DEG C of scope.

Embodiment A-9

0.65 ton of ammonium carbonate and 0.65 ton of aminoquinoxaline, 1.2 tons of water are added in reactor, under agitation Dissolve (allowing the presence of undissolved aminoquinoxaline and ammonium carbonate), use nitrogen purge, then add 3.6 tons of benzene Ethylene oxide (styrene oxide, molecular weight 120.15), slowly heats up in the case where being stirred continuously, temperature control 45-70 DEG C it Between, control pressure is not higher than 0.6MPa, reacts 10 hours, then cools to 50 DEG C, temperature control is below 50 DEG C, and vacuum is 600 Deviate from unnecessary water below millimetres of mercury, cool to and vacuum is bled off after less than 40 DEG C, product is released, that is, obtain compound A-9. The centipoise of viscosity about 460, pH=9, decomposition temperature is in 45-70 DEG C of scope.

Embodiment A-10

1kg carbamic acid hydrazine, 0.9kg water are added in reactor, dissolving under agitation 30 minutes (allows to exist A small amount of undissolved carbamic acid hydrazine), nitrogen purge is used, 1.8kg expoxy propane is then added portionwise to transparent In quartz glass reactor, stirring is started, is slowly heated up in the case where being stirred continuously, temperature control is between 50-70 DEG C, and pressure is not higher than Reacted under the conditions of 0.6MPa, when reaction proceed to about 2 it is small when or so return back out now marvellous phenomenon：It is muddy, opaque Mixture moment becomes transparent or clear solution, continues to react 5 hours, then cools to 50 DEG C, is 600 millimeters of mercury in vacuum Deviate from the water and unreacted expoxy propane of a part below post, cool to and product is released after less than 40 DEG C.Reaction time is enough Ensure that reaction is completed according to mol ratio.Obtain compound A-10.PH=8.9, decomposition temperature is in 45-70 DEG C of scope.Gas-chromatography Analysis, compound A-10 contains the salt of both about 76wt% single Propanolamine and dipropanolamine.Also contain the water of some.Separately Outside, compound A-10 contains about 56wt% single Propanolamine and dipropanolamine are (in heating compound A-10 to discharge carbon dioxide Afterwards).

B) preparing has CO₃ ^2-The logical formula (I) compound of anion

Embodiment B-1

14kg ammonium carbonate (molecular weight 96), 6kg ethylene glycol and 8kg water are added in reactor, stirring is started, So that ammonium carbonate slowly dissolves and (is not necessarily completely dissolved), nitrogen purge is used, 20kg expoxy propane is added, starts and stir Mix, control pressure is not higher than 0.6MPa, slowly heated up in the case where being stirred continuously, temperature control reacts 12 hours below 70 DEG C, has reacted Into, slowly reduce the temperature to after 50 DEG C control vacuum unnecessary water and unreacted is slowly removed below 600 millimetress of mercury Expoxy propane, then bleed off vacuum, cool to and reactants are released after less than 40 DEG C, obtain compound and obtain compound B-1.It is viscous About 300 centipoises of degree, pH=9, compound B-1 decomposition temperature is 45-70 DEG C.Liquid-phase chromatographic analysis and gas-chromatography point Analysis, it is the mixture for including a variety of hydramine to show compound B-1.With atomic absorption spectrophotometer (Seiko Instruments,Inc.；SAS/727 the content for) determining alkali and alkaline earth metal ions ion is less than detectable limit.Gas phase color The mol ratio of analysis of spectrum, single Propanolamine and dipropanolamine is 1:0.22.Compound B-1 contains about 78wt% single Propanolamine and two The salt of both Propanolamines.Compound B-1 contains about 56wt% single Propanolamine and dipropanolamine.

Embodiment B-2

1.4 tons of ammonium carbonate, 1 ton of water are added in the stainless steel pressure reactor with cooling jacket, stirred molten Solve (allowing the presence of undissolved ammonium carbonate), purged with nitrogen, then seal reactor, in the case where being stirred continuously, control temperature exists Between 45-70 DEG C, control pressure is not higher than 0.6MPa, and 1.3 tons of oxirane is added portionwise in reactor, is controlled after adding Temperature reaction 4 hours, then cools to 50 DEG C, and control vacuum removes unnecessary water and unreacted under below 600mHg decompressions Oxirane, cools to and vacuum is bled off after less than 40 DEG C, product is released.Obtain compound B-2.The centipoise of viscosity 300.PH= 9.1.Decomposition temperature is at 45-70 DEG C.Liquid-phase chromatographic analysis and gas chromatographic analysis, it is to include a variety of alcohol to show compound B-2 The mixture of amine.

Embodiment B-3

The water of 20kg ammonium carbonate, 18kg is added in transparent quartz glass reactor, stirring and dissolving (allows to exist Undissolved ammonium carbonate), nitrogen purge is used, in the case where being stirred continuously, control temperature is between 45-70 DEG C, control pressure Not higher than 0.6MPa, 45kg expoxy propane is added in reactor, rear temperature control reaction is added, when reaction proceeds to about 2 Marvellous phenomenon is occurred in that suddenly during or so hour：Muddy, opaque mixture moment becomes transparent or clear solution, continues Reaction 8 hours, then cools to 50 DEG C, control vacuum removes unnecessary water and unreacted ring under below 600mHg decompressions Ethylene Oxide, cools to and vacuum is bled off after less than 40 DEG C, product is released.Obtain compound B-3.Viscosity is about 250 centipoises. PH=9.1.Decomposition temperature is at 45-70 DEG C.

Embodiment B-4

20kg ammoniacal liquor (concentration 25wt%) is added in reactor, nitrogen purge is used, stirring is started, controlled Pressure is not higher than 0.6MPa, and temperature is no more than 120 DEG C, 16kg oxirane is added portionwise, and adds rear temperature control and reacts 1 hour. Cooled to after the completion of reaction and remove unnecessary water and unreacted oxirane after room temperature under reduced pressure, be passed through 4kg carbon dioxide (molecular weight 44) to pH value is 8 or so, and temperature control cools to room temperature below 80 DEG C after the completion of reaction.Obtain compound B- 4.Viscosity is about 400 centipoises.Decomposition temperature is in 45-75 DEG C of scope.

Embodiment B-5

20kg ammoniacal liquor (concentration 25wt%), 5kg ethylene glycol are added in reactor, nitrogen purge is used, Stirring is started, control pressure is not higher than 0.6MPa, and temperature is no more than 120 DEG C, 20kg expoxy propane is added portionwise, and is controlled after adding Temperature reaction 2 hours.Cooled to after the completion of reaction and remove unnecessary water and unreacted expoxy propane after room temperature under reduced pressure, be passed through 5kg carbon dioxide to pH value is 8 or so, and temperature control cools to room temperature below 80 DEG C after the completion of reaction.Obtain compound B-5.Viscosity is about 450 centipoises.Decomposition temperature is in 45-75 DEG C of scope.

Embodiment B-6

The diethylenetriamine (molecular weight 103.17) of 10kg parts by weight, 15kg water are added in reactor, nitrogen is used Gas purge, starts stirring, and control pressure is not higher than 0.6MPa, and temperature is no more than 120 DEG C, 15kg epoxy is added portionwise Propane, adds rear temperature control and reacts 1 hour.Cooled to after the completion of reaction and remove unnecessary water and unreacted ring after room temperature under reduced pressure Ethylene Oxide, carbon dioxide to the pH value for being passed through 6kg is 8 or so, and temperature control cools to room temperature i.e. below 80 DEG C, after the completion of reaction Can.Obtain compound B-6.Viscosity is about 500 centipoises.Decomposition temperature is in 45-70 DEG C of scope.Infrared spectrum is as shown in Figure 3.

Embodiment B-7

10kg ethylenediamine (molecular weight 60.12), 15kg water are added in reactor, nitrogen purge is used, Stirring is started, control pressure is not higher than 0.6MPa, and temperature is no more than 120 DEG C, 10kg oxirane (molecular weight is added portionwise 44.05) rear temperature control, is added to react 1 hour.Cooled to after the completion of reaction and remove unnecessary water after room temperature under reduced pressure and unreacted Oxirane, is passed through 5kg carbon dioxide untill pH value is 8, temperature control cools to room temperature i.e. below 80 DEG C, after the completion of reaction Can.Obtain compound B-7.Viscosity is about 500 centipoises.Decomposition temperature is in 45-70 DEG C of scope.

Embodiment B-8

The liquefied ammonia of 6kg ethylenediamine (molecular weight 60.12), 3.4kg is added in special pressure-resistant blending tank and mixes equal It is even, then it is added to by the certain flow of pipe control in mixing reactor, control pressure is in 0.6MPa, and it is 60 to control temperature Below DEG C, slowly mixed with 9kg carbon dioxides, room temperature reduced the temperature to after the completion of reaction, by all over products of acquisition and 10kg water is added in reactor together slowly dissolves (allowing with the presence of not tolerant) under agitation, uses nitrogen purge, Control pressure is not higher than 0.6MPa, and temperature is no more than under the conditions of 70 DEG C, 35kg expoxy propane is added portionwise, rear temperature control is added anti- Answer 5 hours.The water and unreacted expoxy propane for removing a part after room temperature under reduced pressure are cooled to after the completion of reaction.Obtain compound B-8.PH=9.1, decomposition temperature is in 45-70 DEG C of scope.

Embodiment B-9

By 6kg diethylenetriamine (molecular weight：103.17), 3kg liquefied ammonia be added in special pressure-resistant blending tank mix Close uniform, be then added to by the certain flow of pipe control in mixing reactor, control pressure controls temperature in 0.6MPa For less than 60 DEG C, slowly mixed with 7.6kg carbon dioxides, room temperature is reduced the temperature to after the completion of reaction, by the whole of acquisition Product and 10kg water are added in reactor together slowly dissolves (allowing with the presence of not tolerant) under agitation, is purged with nitrogen anti- Device is answered, control pressure is not higher than 0.6MPa, and temperature is no more than under the conditions of 70 DEG C, 22kg oxirane is added portionwise, after adding Temperature control reacts 5 hours.The water and unreacted oxirane for removing a part after room temperature under reduced pressure are cooled to after the completion of reaction.Obtain Compound B-9.PH=8.8, decomposition temperature is in 45-70 DEG C of scope.

Embodiment B-10

By 6kg diethylenetriamine (molecular weight：103.17), 3kg liquefied ammonia is added in special pressure-resistant blending tank and mixed Close uniform, be then added to by the certain flow of pipe control in mixing reactor, control pressure controls temperature in 0.6MPa For less than 60 DEG C, with 7.6kg carbon dioxides slowly hybrid reaction, room temperature is reduced the temperature to after the completion of reaction, by acquisition All over products and 10kg water are added in reactor together slowly dissolves (allowing with the presence of not tolerant) under agitation, is blown with nitrogen Sweep reactor, control pressure is not higher than 0.6MPa, temperature is no more than under the conditions of 70 DEG C, be added portionwise 9kg oxirane and 14kg expoxy propane, adds rear temperature control and reacts 5 hours.The water and not for removing a part after room temperature under reduced pressure is cooled to after the completion of reaction The oxirane and expoxy propane of reaction.Obtain compound B-10.PH=9.0, decomposition temperature is in 45-70 DEG C of scope.

Embodiment B-11

By 6kg ethylenediamine (molecular weight 60.12), 3kg methylamine (molecular weight：31.10), 1.7kg liquefied ammonia is added to spy It is well mixed, is then added to by the certain flow of pipe control in mixing reactor in the pressure-resistant blending tank of system, control pressure Power is in 0.6MPa, and it is less than 60 DEG C to control temperature, is slowly mixed with 8.5kg carbon dioxides, temperature is reduced after the completion of reaction To room temperature, all over products of acquisition and 10kg water are added in reactor together slowly to dissolve under agitation (allows to have and does not allow Thing presence), nitrogen purge is used, control pressure is not higher than 0.6MPa, and temperature is no more than under the conditions of 70 DEG C, is added portionwise 31kg expoxy propane, adds rear temperature control and reacts 5 hours.Cooled to after the completion of reaction removed under reduced pressure after room temperature a part water and Unreacted expoxy propane.Obtain compound B-11.PH=9.0, decomposition temperature is in 45-70 DEG C of scope.

Embodiment B-12

0.9kg carbonic acid hydrazine, 0.8kg water are added in reactor, dissolving under agitation 30 minutes (allows to exist not The aminoquinoxaline of dissolving), nitrogen purge is used, 1.8kg expoxy propane is then added portionwise to transparent quartzy glass In glass reactor, stirring is started, is slowly heated up in the case where being stirred continuously, temperature control is between 50-70 DEG C, and pressure is not higher than 0.6MPa bars Reacted under part, when reaction proceed to about 2 it is small when or so return back out now marvellous phenomenon：Muddy, opaque mixture wink Between become transparent or clear solution, continue to react 5 hours, then cool to 50 DEG C, be that below 600 millimetress of mercury take off in vacuum Go out the water and unreacted expoxy propane of a part, cool to and product is released after less than 40 DEG C.Reaction time ensure reaction according to Mol ratio is completed.Obtain compound B-12.PH=8.9, decomposition temperature is in 45-70 DEG C of scope.Gas chromatographic analysis, compound B- The salt of both 12 single Propanolamines containing about 77wt% and dipropanolamine.Also contain the water of some.In addition, compound B-12 contains There are about 56wt% single Propanolamine and dipropanolamine (in heating compound B-12 to discharge carbon dioxide after).

Embodiment B-13

0.9kg carbonic acid hydrazine, 0.8kg water are added in reactor, dissolving under agitation 30 minutes (allows to exist not The aminoquinoxaline of dissolving), nitrogen purge is used, 1.3kg oxirane is then added portionwise to transparent quartzy glass In glass reactor, stirring is started, is slowly heated up in the case where being stirred continuously, temperature control is between 50-70 DEG C, and pressure is not higher than 0.6MPa bars Reacted under part, when reaction proceed to about 2 it is small when or so return back out now marvellous phenomenon：Muddy, opaque mixture wink Between become transparent or clear solution, continue to react 5 hours, then cool to 50 DEG C, be that below 600 millimetress of mercury take off in vacuum Go out the water and unreacted oxirane of a part, cool to and product is released after less than 40 DEG C.Reaction time ensure reaction according to Mol ratio is completed.Obtain compound B-13.PH=8.8, decomposition temperature is in 45-70 DEG C of scope.

C) preparing has formate (HCOO^-) logical formula (I) compound

Embodiment C-1

By 15kg ammonium formate, 1kg methylamine catalyst, 10kg water, 5kg ethylene glycol are added in reactor, opened Dynamic stirring, uses nitrogen purge, control pressure is not higher than 0.5MPa, temperature control is below 120 DEG C, by 12kg oxirane It is added portionwise in reactor, reacts 5 hours.After the completion of reaction cool, then control vacuum be 600 millimetress of mercury below, Removed under reduced pressure below 100 DEG C of temperature unnecessary water and unreacted oxirane, remove vacuum, are put after cooling to less than 50 DEG C Go out product.Obtain compound C-1.Viscosity is about 200 centipoises, and pH=8.5, decomposition temperature is higher than 100 DEG C.

Embodiment C-2

Embodiment C-1 is repeated, simply 12kg oxirane is replaced using 15kg expoxy propane, and expoxy propane is not It is to add in batches in reactor, but is disposably added thereto.Obtain compound C-2.Viscosity is about 350 centipoises, pH= 8.6, decomposition temperature is higher than 100 DEG C.

Embodiment C-3

By 10kg methyl formate, 10kg Ethyl formate, 13kg ammoniacal liquor (concentration 25wt%), 35kg diethanol amine It is added in reactor, starts stirring, control pressure is not higher than 0.5MPa, is slowly heated up in the case where being stirred continuously, when temperature rise Reacted 15 hours to temperature control at 100 DEG C.Cool after the completion of reaction, it is temperature below 600 millimetress of mercury then to control vacuum Less than 100 DEG C removed under reduced pressure methanol and ethanol, remove vacuum, cool to less than 50 DEG C and release after product.Obtain compound C-3. Viscosity is about 400 centipoises, and pH=9, decomposition temperature is higher than 100 DEG C.

Above-claimed cpd C-1, C-2 and C-3 release carbon dioxide immediately when being contacted with isocyanates, while also putting Go out a small amount of CO gas, overcome the shortcoming of general physical blowing agent such as methyl formate.

Implement row C-4 (being not belonging to logical formula (I) compound)

24kg ammoniacal liquor (concentration 25wt%) is added in reactor, control temperature is being stirred continuously below 100 DEG C It is lower to be slowly added drop-wise to 20kg formic acid (concentration 85wt%) in ammoniacal liquor, add rear insulation reaction 1 hour, then control vacuum Below 600 millimetress of mercury, the unnecessary water of removed under reduced pressure below 100 DEG C of temperature.Obtain compound C-4.Viscosity is about 150 Centipoise, pH=9.5, decomposition temperature is higher than 100 DEG C.

Embodiment C-5 (is not belonging to logical formula (I) compound)

23kg ammoniacal liquor (concentration 25wt%), 1.5kg dimethylamine are added in reactor, control temperature is at 100 DEG C Hereinafter, be stirred continuously it is lower 20kg formic acid (concentration 85wt%) is slowly added drop-wise in ammoniacal liquor, add rear insulation reaction 1 small When, vacuum is then controlled for below 600 millimetress of mercury, the unnecessary water of removed under reduced pressure, removes vacuum below 100 DEG C of temperature, Cool to after less than 50 DEG C and release product acquisition compound C-5.Viscosity is about 150 centipoises, and pH=9.2, decomposition temperature is higher than 100℃。

Embodiment C-6 (is not belonging to logical formula (I) compound)

23kg ammoniacal liquor (concentration 25wt%), 1.5kg methylamine are added in reactor, control temperature 100 DEG C with Under, be stirred continuously it is lower 20kg formic acid (concentration 85wt%) is slowly added drop-wise in ammoniacal liquor, add rear insulation reaction 1 hour, Then vacuum is controlled for below 600 millimetress of mercury, the unnecessary water of removed under reduced pressure below 100 DEG C of temperature (such as can reach 10wt% or so water content), remove vacuum, cool to and product is released after less than 50 DEG C.Compound C-6 is obtained, is not tied It is brilliant, it may be possible to which that the methylamine added disturbs its crystallization.Viscosity is about 150 centipoises, and pH=9, decomposition temperature is higher than 100 DEG C.

Compound C-4, C-5 or C-6 send carbon dioxide immediately when being contacted with isocyanates, while also releasing few CO gas is measured, the shortcoming of general physical blowing agent is overcome.

Although compound C-1 to C-6 is not decomposed even at higher than 110 DEG C, inventor has found by experiment, These can easily decompose and discharge CO during polyurethane foam₂, reason is probably to work as to touch isocyanates chemical combination React the carbonic anhydride for generating less stable during thing with NCO group first.

D)Preparing has bicarbonate radical (HO-COO^-) logical formula (I) compound

Embodiment D-1

10kg ammonium hydrogen carbonate (molecular weight 79.06), 9.0kg water and 1kg ethylenediamines are added to transparent quartzy glass In glass reactor, stirring and dissolving (allows the presence of undissolved ammonium hydrogen carbonate), uses nitrogen purge, seals reactor, so Afterwards in the case where being stirred continuously, control temperature is between 45-65 DEG C, and control pressure is not higher than 0.6MPa, by 20kg expoxy propane point Criticize and be added in reactor, add rear temperature control and react 10 hours, then cool to 50 DEG C, control vacuum is depressurized in below 600mHg Lower removing unnecessary water and unreacted expoxy propane, cool to and vacuum are bled off after less than 40 DEG C, product is released.Obtain Compound D-1.Viscosity is about 250 centipoises.PH=8, decomposition temperature is at 36-42 DEG C.

Inventor it was unexpectedly observed that when compound D-1 be mixed with PPG and/or PEPA, for example with During composition, foam (" white material ") processed, the decomposition temperature for the compound D-1 being dissolved in white material can be improved to 45-65 DEG C.This So that compound D-1 has suitable decomposition temperature, therefore, be suitable for polyurethane foam.

E)Preparing has carbonic acid list hydrocarbyl carbonate (R^bO-COO^-) anion logical formula (I) compound

Embodiment E-1

Ammonium salt (molecular weight 93), 9.0kg water and the 1kg ethylenediamines of 10kg bicarbonate methyl esters are added to transparent stone In English glass reactor, stirring and dissolving (allows the presence of undissolved ammonium salt), uses nitrogen purge, seals reactor, so Afterwards in the case where being stirred continuously, control temperature is between 45-65 DEG C, and control pressure is not higher than 0.6MPa, by 20kg expoxy propane point Criticize and be added in reactor, add rear temperature control and react 10 hours, then cool to 50 DEG C, control vacuum is depressurized in below 600mHg Lower removing unnecessary water and unreacted expoxy propane, cool to and vacuum are bled off after less than 40 DEG C, product is released.Obtain Compound E-1.Viscosity is about 350 centipoises.PH=8, decomposition temperature is at 42 DEG C -60 DEG C.

F)Preparing has-OOC-N (R¹)-R^a-N(R²)-COO^-Or R^a'(-N(R¹)-COO^-)₃The logical formula (I) chemical combination of anion Thing

Embodiment F-1

By 10kg NH₄OOC-NH-(CH₂)₅-NH-COO NH₄(molecular weight 182), 9.0kg water are added to transparent stone In English glass reactor, stirring and dissolving (allows the presence of undissolved ammonium salt), uses nitrogen purge, seals reactor, so Afterwards in the case where being stirred continuously, control temperature is between 45-55 DEG C, and control pressure is not higher than 0.6MPa, by 20kg expoxy propane point Criticize and be added in reactor, add rear temperature control and react 10 hours, then cool to 50 DEG C, control vacuum is depressurized in below 600mHg Lower removing unnecessary water and unreacted expoxy propane, cool to and vacuum are bled off after less than 40 DEG C, product is released.Obtain Compound F-1.Viscosity is about 600 centipoises.PH=9, decomposition temperature is at 45 DEG C -70 DEG C.

Embodiment F-2

By the 12kg benzene -1,3,5- three (aminoquinoxaline) (molecular weight 306) with following formula：

It is added to 9.0kg water in transparent quartz glass reactor, stirring and dissolving (allows the presence of undissolved ammonium Salt), nitrogen purge is used, reactor is sealed, then in the case where being stirred continuously, control temperature is between 45-60 DEG C, control pressure Power is not higher than 0.6MPa, and 20kg expoxy propane is added portionwise in reactor, adds rear temperature control and reacts 10 hours, then drops Temperature is to 50 DEG C, and control vacuum removes unnecessary water and unreacted expoxy propane under below 600mHg decompressions, cools to 40 Vacuum is bled off after below DEG C, product is released.Obtain compound F-2.Viscosity is about 510 centipoises.PH=9.6.Decompose temperature Degree is at 45 DEG C -70 DEG C.

G)Prepare the logical formula (I) compound with primitive nail acid radical anion

Embodiment G-1

15kg triethyl orthoformate, 20kg diethanol amine, 10kg water are added in reactor, stirring is started, Control pressure is not higher than 0.1MPa, is slowly heated up in the case where being stirred continuously, when when temperature is increased to 80 DEG C, temperature control reaction 10 is small.Instead 50 DEG C are cooled to after the completion of answering, it is the following removed under reduced pressure ethanol of temperature 50 C below 600 millimetress of mercury then to control vacuum, Cool to less than 40 DEG C release products after produce compound G-1, viscosity is about 500 centipoises, pH=8.0, and decomposition temperature is in 45- 70℃。

Embodiment G-2

15kg trimethyl orthoformate, 2.0kg ethylene glycol, 10kg water, 6.0kg ethylenediamine are added to reactor In, stirring is started, control pressure is not higher than 0.1MPa, is slowly heated up in the case where being stirred continuously, the temperature control when temperature is increased to 70 DEG C Reaction 5 hours.Cool after the completion of reaction, then control vacuum below 600 millimetress of mercury, piptonychia is depressurized below temperature 50 C Alcohol, removes vacuum, and compound G-2, about warm 250 centipoise of viscosity, pH=can be obtained after cooling to less than 40 DEG C releasing products 8.3,45-70 DEG C of decomposition temperature.

Embodiment G-3

15kg triethyl orthoformate, 13kg monoethanolamine, 7.0kg water are added in reactor, stirring is started, Slowly heated up in the case where being stirred continuously, temperature control reacts 8 hours below 100 DEG C.Cool after the completion of reaction, then control the vacuum to be Below 600 millimetress of mercury, the following removed under reduced pressure ethanol of temperature 50 C removes vacuum, cools to less than 50 DEG C and releases after product i.e. The compound G-3 of two ester group hydrolyses of wherein triethyl orthoformate is obtained.The centipoise of viscosity about 300, pH=8.1, 45-70 DEG C of decomposition temperature.

Embodiment G-4

The ammoniacal liquor of 20kg orthoformic acid glycol ester, 11kg diethanol amine, 10kg is added in reactor, starts and stirs Mix, slowly heated up in the case where being stirred continuously, temperature control, which is no more than at 100 DEG C, to react 8 hours.Cool after the completion of reaction, then control true Reciprocal of duty cycle is that the unnecessary water of the following removed under reduced pressure of temperature 50 C removes vacuum, cools to less than 40 DEG C below 600 millimetress of mercury Compound G-4 can be obtained after releasing product.The centipoise of viscosity about 500, pH=8,45-70 DEG C of decomposition temperature.

Application Example

Embodiment 1

It regard 8 parts by weight as the compound A-1 that is prepared by above example A-1 of foaming agent, the polyethers of 50 parts by weight Foam stabiliser DC3201 (the US Air gasifications of polyalcohol 4110 (being produced by the Bin Hua groups of Shandong Province Accessories during Binzhou), 1 parts by weight Work company produce), the fire retardant TCPP (Jiangsu Yoke Chemical Co., Ltd.'s production) and 2 part by weight of catalyst of 12.5 parts by weight Transparent composition, foam is obtained after A33 (33LV, the production of air chemical company of the U.S.) is well mixed, is then added wherein 95.5 parts of isocyanates MDI (PM200, Yantai Wanhua chemical groups limited company), agitated uniform rear foaming is made poly- Urethane foamed material.

Embodiment 2

It regard 8 parts by weight as the compound A-2 that is prepared by above example A-2 of foaming agent, the polyethers of 30 parts by weight The PEPA CF6320 (Jiangsu Fu Sheng new materials Co., Ltd) and the foam of 1 parts by weight of polyalcohol 4110,20 parts by weight Transparent foaming is obtained after stabilizer DC3201, the fire retardant TCPP of 12.5 parts by weight and 2 part by weight of catalyst A33 are well mixed Composition, then adds 95.5 parts of isocyanates MDI (PM200) wherein, and polyurethane foam is made in agitated uniform rear foaming.

Embodiment 3

The compound A-3's, the foam stabiliser DC3201 of 2 parts by weight, 0.5 parts by weight as foaming agent of 20 parts by weight The catalyst PC-5 (US Air gasification work) of catalyst dibutyltin dilaurylate, 0.5 parts by weight, the catalyst PC- of 1 parts by weight 8 (US Air gasification works), the catalyst PT304 (US Air gasification work) of 1 parts by weight, the catalyst A33 of 1 parts by weight, 40 weight The fire retardant TCPP, the PPG 4110 of 20 parts by weight, the AKS7004 (AEKYUNG of 10 parts by weight of part PETROCHEMICAL CO., LTD KOREA), MN500 (Shandong Lanxing Dongda Chemical Co., Ltd, hydroxyl of 10 parts by weight Value mgKOH/g：It is uniform mixed 330-350) with the PEPA CF6320 (Jiangsu Fu Sheng new materials Co., Ltd) of 10 parts by weight With 50kg consumptions after conjunction, through flush coater and isocyanates MDI (PM200) according to volume ratio 1:(i.e. " white material " is with MDI's by 1-1.6 Volume ratio) spraying prepares polyurethane foamed material.

Embodiment 4

It regard 7 parts by weight as the compound A-4 of foaming agent, the catalyst PC-41 (US Air gasification work) of 1 parts by weight, 0.5 The catalyst PC-8 (US Air gasification work) of parts by weight, the parts by weight of pentamethylene 13, the foam stabiliser DC8545 of 2 parts by weight are (beautiful State's air chemical industry) it is added to PPG 2010 (Jiangsu Hai'an Petrochemical Plant produces), 25 parts by weight of 50 parts by weight PPG SA380 (Shandong Inov Polyurethane Co., Ltd.) and 25 parts by weight PPG SA460 (mountains An eastern Nowe polyurethane limited company) mixture in be well mixed, obtain transparent composition, foam (referred to as " white Material "), the system that foamed in 148.2 parts of isocyanates MDI (PM200), agitated uniform rear injection foaming mould is then added wherein Obtain belt leather polyurethane foamed material.

Sample is taken, 100 times of observation abscesses are amplified using SEM after being cut into slices with blade.As shown in Figure 4, cell diameter is 205 Micron.

As a comparison, the present embodiment 4 is repeated, simply 5 parts by weight water and the pentamethylene (1 of 12 parts by weight:2.4 weight ratios) use Make foaming agent, obtain contrast foams 4-1；As shown in Figure 5, cell diameter is 396 microns.

In addition, repeating the present embodiment 4, simply the compounds of this invention A-4 and pentamethylene (1:1.5 weight ratios) it is used as foaming Agent, is obtained with reference to foams 4-2；As shown in Figure 6, cell diameter is 306 microns.As a comparison, the present embodiment 4 is repeated, only It is water+LBA+ pentamethylene (1:1:1 weight ratio) it is used as foaming agent, obtain contrast foams 4-3, as shown in Figure 7, cell diameter For 495 microns.The present embodiment 4 is repeated, simply the compounds of this invention A-4, LBA and pentamethylene (1:1.2:1.3 weight ratios) it is used as Foaming agent, obtains and refers to foams 4-4, as shown in Figure 8, cell diameter is 335 microns.

As can be seen that foams seem fine and smooth, uniform, fine and close from Fig. 4, Fig. 6 and Fig. 8, abscess quantity in unit area It is obvious many.As can be seen that the diameter of abscess is substantially uneven from Fig. 5, Fig. 7, abscess quantity is substantially on the low side in unit area.

Embodiment 5

Using 6 parts by weight, as the foam stabiliser DC3201 of the compound A-5 of foaming agent, 1 parts by weight, (US Air gasifies Work) PPGs 4110 (Binzhou City, Shandong Province Bin Hua groups) of 30 parts by weight, the PEPA CF6320 (rivers of 20 parts by weight Su Fusheng new materials Co., Ltd), 0.5 part by weight of catalyst PC-41 (US Air gasification work), be well mixed after obtain foaming group Compound, then adds 85 parts by weight isocyanates MDI (PM200) wherein, and polyurethane foam is made in agitated uniform rear foaming.

Embodiment 6

It regard 20 parts by weight as the compound A-6 of foaming agent, PPG 2010 (Jiangsu Province Hai'an of 50 parts by weight Petrochemical plant produce), the PPG SA380 (Shandong Inov Polyurethane Co., Ltd.'s production) of 25 parts by weight and PPG SA460 (Shandong Inov Polyurethane Co., Ltd.), the catalyst PC- of 0.5 parts by weight of 25 parts by weight 41 (US Air gasification works), the catalyst PC-8 (US Air gasification work) of 0.5 parts by weight obtain transparent foaming after being well mixed Composition, then adds 175 parts of isocyanates MDI (PM200) wherein, and polyurethane foam material is made in agitated uniform rear foaming Material.

Embodiment 7

Using the compound A-7 as foaming agent, the 10 parts by weight HFC-365mfc of 4 parts by weight, the polyethers of 11 parts by weight is more First alcohol 4110 (Shandong Binzhou Bin Hua groups), PEPA DM2003 (the limited public affairs of Guangdong dolantin fine chemistry industry of 39 parts by weight Department), the foam stabiliser DC3201 (US Air gasification work) of 1.5 parts by weight and the catalyst JXP-508 (US Airs of 1 parts by weight Gasify work), the catalyst JXP-509 (US Air gasification work) of 0.6 parts by weight, catalyst K-15 (U.S.'s air of 1.5 mass point Chemical industry) it is well mixed after obtain composition, foam, the fire retardant TCPP of 25 parts by weight and then add the different of 155 parts by weight wherein Polyurethane foam is made in cyanate MDI (PM200), agitated uniform rear foaming.

Embodiment 8

Using the compound A-1 as foaming agent, the 10 parts by weight HFC-365mfc of 4 parts by weight, the polyethers of 15 parts by weight is more First alcohol 4110 (Shandong Binzhou Bin Hua groups), PEPA DM2003 (the limited public affairs of Guangdong dolantin fine chemistry industry of 35 parts by weight Department), catalyst PC-8 (US Air gasification work), 0.5 weight of the foam stabiliser DC3201 of 1.5 parts by weight and 0.5 parts by weight Composition, foam, the fire retardant TCPP of 25 parts by weight are obtained after the catalyst PC-41 (US Air gasification work) of part is well mixed, so Add 160 parts of isocyanates MDI (PM200) wherein afterwards, it is agitated it is uniform after foaming polyurethane foamed material is made.

Embodiment 9

Using 7 parts by weight as the compound A-3 of foaming agent, the catalyst PC-41 (US Air gasification work) of 1 parts by weight, The catalyst PC-8 (US Air gasification work) of 0.5 parts by weight, the parts by weight of pentamethylene 13, the foam stabiliser DC8545 of 2 parts by weight (US Air gasification work) is added to the PPG 2010 (Jiangsu Hai'an Petrochemical Plant's production) of 50 parts by weight, 25 weight (the Nowe polyurethane share of Shandong one is limited by the PPG SA380 (Shandong) of part and the PPG SA460 of 25 parts by weight Company) mixture in be well mixed, then add 150 parts of isocyanates MDI (PM200) wherein, it is agitated it is uniform after send out It is brewed to obtain polyurethane foam.

Embodiment 10

Using the compound A-2,8 parts by weight HFC-365mfc, 30 parts by weight as foaming agent of 5 parts by weight polyether polyols Alcohol 4110 (Shandong Binzhou Bin Hua groups), the PEPA CF6320 (Jiangsu Fu Sheng new materials Co., Ltd) of 20 parts by weight and The foam stabiliser DC3201 (US Air gasification work) of 1 parts by weight, (refined gram of Jiangsu chemical industry has the fire retardant TCPP of 12.5 parts by weight Limit company) and 1 part by weight of catalyst A33 (33LV, US Air gasification work), catalyst PC-41 (the US Air gasifications of 1 parts by weight Work) it is well mixed after obtain composition, foam, 102 parts of isocyanates MDI (PM200) are then added wherein, it is agitated uniform Foam afterwards and polyurethane foam is made.

Table 1：The performance of polyurethane foam

Explanation：Detection data in list above are the foam samples prepared using conventional foam box and self-control foaming model The detection data done, be by hand prepare freely steep sample.

Wherein shrinkage factor (size changing rate) is measured according to chinese national standard GB/T 8811-2008, simply standing time For 5 months.Similarly hereinafter.

The product of wherein embodiment 4 seems fine and smooth, uniform, fine and close, as shown in figure 4, with good heat-insulating property, can Meet the requirement of the various performances in refrigerator and refrigerator-freezer field.The product of embodiment 5 disclosure satisfy that various in polyurethane pipe insulation The requirement of performance.The product of embodiment 6 seems very fine and smooth, uniform, densification, disclosure satisfy that LNG (liquefied natural gas) conveying guarantors The requirement of the cold various performances of application.The product of embodiment 7 disclosure satisfy that the requirement of the various performances of polyurethane heated board.Embodiment 8 product disclosure satisfy that polyurethane colorful steel plate, the requirement of the various performances of cold storage plate.

Embodiment 11

It regard 7 parts by weight as the compound B-1 that is prepared by above example B-1 of foaming agent, the polyethers of 50 parts by weight Foam stabiliser DC3201 (US Air gasification work), 12.5 weights of polyalcohol 4110 (Binzhou City, Shandong Province Bin Hua groups), 1 parts by weight The fire retardant TCPP (Jiangsu Yoke Chemical Co., Ltd.) and 2 part by weight of catalyst A33 (33LV, US Air gasification work) for measuring part are mixed Transparent composition, foam is obtained after conjunction is uniform, 95.5 parts of isocyanates MDI (PM200) are then added wherein, it is agitated equal Polyurethane foamed material is made in foaming after even.

Embodiment 12-20

Embodiment 12-20 repeats embodiment 2-10 respectively, and simply foaming agent is as shown in table 2.

Table 2：The performance of polyurethane foam

Explanation：The detection data in each list are using conventional foam box and make foam prepared by the model that foams by oneself above The detection data that sample is done, be by hand prepare freely steep sample.

The product of wherein embodiment 14 has good heat-insulating property, disclosure satisfy that the various performances in refrigerator and refrigerator-freezer field Requirement.The product of embodiment 15 disclosure satisfy that the requirement of various performances in polyurethane pipe insulation.The foam production of embodiment 16 Product seem finer and smoother, uniform, densification, as shown in figure 9, therefore, it disclosure satisfy that LNG (liquefied natural gas) conveys cold insulation application The requirement of various performances.The product of embodiment 17 disclosure satisfy that the requirement of the various performances of polyurethane heated board.Embodiment 18 Product disclosure satisfy that polyurethane colorful steel plate, the requirement of the various performances of cold storage plate.

Embodiment 21

It regard 4 parts by weight as the compound C-1 that is prepared by above example C-1 of foaming agent, the polyethers of 50 parts by weight Polyalcohol 4110, the foam stabiliser DC3201 of 1 parts by weight, (refined gram of Jiangsu chemical industry is limited by the fire retardant TCPP of 12.5 parts by weight Company) and 1 part by weight of catalyst A33 (33LV, US Air gasification work), the catalyst PC-41 (US Air gasification work) of 1 parts by weight Transparent composition, foam is obtained after well mixed, 104.5 parts of isocyanates MDI (PM200) are then added wherein, it is agitated Polyurethane foam is made in foaming after uniform.

Embodiment 22

It regard 4 parts by weight as the compound C-2 that is prepared by above example C-2 of foaming agent, the polyethers of 30 parts by weight Polyalcohol 4110, the PEPA CF6320 (Jiangsu Fu Sheng new materials Co., Ltd) of 20 parts by weight, the resistance of 12.5 parts by weight Fire agent TCPP (Jiangsu Yoke Chemical Co., Ltd.), foam stabiliser DC3201 (US Air gasification work), 0.5 weight of 1 parts by weight Measure and obtain saturating after part catalyst PC-8 (US Air gasification work), 1 part by weight of catalyst PC-41 (US Air gasification work) are well mixed Bright composition, foam, then adds part isocyanates MDI (PM200) wherein, and polyurethane is made in agitated uniform rear foaming Foam.

Embodiment 23

By the compound C-3 prepared by above example C-3 of 3.5 parts by weight, the foam stabiliser DC3201 of 2 parts by weight (US Air gasifies by (US Air gasification work), 1 part by weight of catalyst PC-8 (US Air gasification work), 1 part by weight of catalyst PC-41 Work), 13 parts by weight pentamethylene, PPG 2010 (Jiangsu Hai'an Petrochemical Plant), 25 weights for being added to 50 parts by weight Measure the PPG SA380 (Shandong Inov Polyurethane Co., Ltd.'s production) of part and the PPG of 25 parts by weight Obtained after being well mixed in SA460 (production of Shandong Inov Polyurethane Co., Ltd. of manufacturer) mixture Transparent composition, foam is obtained, 145 parts of isocyanates MDI (PM200) are then added wherein, agitated uniform rear injection is foamed Foamed in mould and belt leather polyurethane foam is made.

Embodiment 24-26

Embodiment 24-26 repeats embodiment 21-23 respectively, and simply foaming agent is as shown in table 2.Rate of closed hole is equal>97%.

Table 3：The performance of polyurethane foam

Embodiment 27

Using 17 parts by weight as the compound D-1 that is prepared by above example D-1 of foaming agent, 100 parts by weight it is poly- Ethoxylated polyhydric alcohol 4110 (Shandong Binzhou Bin Hua groups), the foam stabiliser DC3201 (US Air gasification work) of 2 parts by weight and 2 weight Part catalyst A33 (33LV), the catalyst PC-41 (US Air gasification work) of 2 parts by weight obtain transparent foaming after being well mixed Composition, then adds 160 parts of isocyanates MDI (PM200) wherein, and polyurethane foam is made in agitated uniform rear foaming.

Embodiment 28

By the PPG 2010 of the compound E-1 of 25 parts by weight, 50 parts by weight, (Jiangsu Hai'an Petrochemical Plant gives birth to Production), the PPG SA380 (Shandong Inov Polyurethane Co., Ltd.'s production) of 25 parts by weight and 25 parts by weight gather Ethoxylated polyhydric alcohol SA460 (Shandong Inov Polyurethane Co., Ltd.), 2 parts by weight foam stabiliser DC3201 (US Airs Gasify work), 0.5 part by weight of catalyst PC-8 (US Air gasification work), 1 part by weight of catalyst PC-41 (US Air gasification work) mix The transparent composition, foam of uniform rear acquisition is closed, 155 parts of isocyanates MDI (PM200) are then added wherein, it is agitated uniform Foam afterwards and polyurethane foam is made.

Embodiment 29

By the compound F-1 of 15 parts by weight, 10 parts by weight pentamethylene, 2 parts by weight foam stabiliser DC3201 (US Airs Gasify work), 1 part by weight of catalyst PC-8 (US Air gasification work), 1.5 part by weight of catalyst PC-41 (US Air gasification work) plus Enter PPG 2010 (Jiangsu Hai'an Petrochemical Plant), the PPG SA380 of 25 parts by weight to 50 parts by weight (Shandong Inov Polyurethane Co., Ltd.'s production) and PPG SA460 (the manufacturer Shandong one of 25 parts by weight Nowe polyurethane limited company produce) in be well mixed after obtain transparent composition, foam, 150 are then added wherein Foam obtained belt leather polyurethane foam in part isocyanates MDI (PM200), agitated uniform rear injection foaming mould.

Comparative example 1

Embodiment 28 is repeated, simply foaming agent is used as only with the pentamethylene of 15 parts by weight.

Table 4：The performance of polyurethane foam

Embodiment 30

It regard 12 parts by weight as the compound G-1 that is prepared by above example G-1 of foaming agent, the polyethers of 50 parts by weight Polyalcohol 4110, the foam stabiliser DC3201 of 1 parts by weight, (refined gram of Jiangsu chemical industry is limited by the fire retardant TCPP of 12.5 parts by weight Company) and 1 part by weight of catalyst A33 (33LV, US Air gasification work), the catalyst PC-41 (US Air gasification work) of 1 parts by weight Obtain composition, foam after well mixed, then add 104.5 parts of isocyanates MDI (PM200) wherein, it is agitated it is uniform after Polyurethane foam is made in foaming.

Embodiment 31

Using 7.5 parts by weight as the compound G-2 that is prepared by above example G-2 of foaming agent, 30 parts by weight it is poly- Ethoxylated polyhydric alcohol 4110, the PEPA CF6320 (Jiangsu Fu Sheng new materials Co., Ltd) of 20 parts by weight, 12.5 parts by weight Fire retardant TCPP (Jiangsu Yoke Chemical Co., Ltd.), the foam stabiliser DC3201 (US Air gasification work) of 1 parts by weight, 0.5 Obtained after part by weight of catalyst PC-8 (US Air gasification work), 1 part by weight of catalyst PC-41 (US Air gasification work) are well mixed Composition, foam, then adds part isocyanates MDI (PM200) wherein, and polyurethane foam is made in agitated uniform rear foaming.

Embodiment 32

By the compound G-3 prepared by above example G-3 of 9 parts by weight, the foam stabiliser DC3201 of 2 parts by weight (US Air gasifies by (US Air gasification work), 1 part by weight of catalyst PC-8 (US Air gasification work), 1 part by weight of catalyst PC-41 Work), 13 parts by weight pentamethylene, PPG 2010 (Jiangsu Hai'an Petrochemical Plant), 25 weights for being added to 50 parts by weight Measure the PPG SA380 (Shandong Inov Polyurethane Co., Ltd.'s production) of part and the PPG of 25 parts by weight Obtained after being well mixed in SA460 (production of Shandong Inov Polyurethane Co., Ltd. of manufacturer) mixture Composition, foam is obtained, is then added wherein in 145 parts of isocyanates MDI (PM200), agitated uniform rear injection foaming mould Belt leather polyurethane foam is made in foaming.

Embodiment 33

By the compound G-4 prepared by above example G-4 of 9.5 parts by weight, the foam stabiliser DC3201 of 2 parts by weight (US Air gasifies by (US Air gasification work), 1 part by weight of catalyst PC-8 (US Air gasification work), 1 part by weight of catalyst PC-41 Work), 13 parts by weight pentamethylene, PPG 2010 (Jiangsu Hai'an Petrochemical Plant), 25 weights for being added to 50 parts by weight Measure the PPG SA380 (Shandong Inov Polyurethane Co., Ltd.'s production) of part and the PPG of 25 parts by weight Obtained after being well mixed in SA460 (production of Shandong Inov Polyurethane Co., Ltd. of manufacturer) mixture Composition, foam is obtained, is then added wherein in 145 parts of isocyanates MDI (PM200), agitated uniform rear injection foaming mould Belt leather polyurethane foam is made in foaming.

Table 5：The performance of polyurethane foam

The performance of the CBA (abbreviation CFA) of the present invention

1st, the bin stability of composition, foam (referred to as white material) and foam performance test

1. .CFA-CP (abbreviation of pentamethylene) is used in mixed way the stability test for preparing and expecting in vain

We are according to the white material of the parameter configuration CFA-CP mixed systems of white material for refrigerator (in above example 9 White material), expect to determine white material activity after placing in 50 DEG C of baking ovens in vain, the reactivity expected in vain be measured by sampling every several days, it is real Test result such as table 5 below：

Table 5：The reactivity expected in vain

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 refers to rise time in table；GT refers to the wire drawing time.

As seen from the above table, the reactivity that changes of the CFA-CP in above-mentioned white material system over time is expected in vain is substantially not Become, it is generally acknowledged that can place more than half a year at normal temperatures after being placed 51 days at 50 DEG C.

In addition to reactivity, the foamed material thermal conductivity value prepared after CFA-CP mixing is also stabilization, the following is Foamed material (condition in the same manner as in Example 9) is prepared into after being sampled according to different time interval and to foamed material thermal conductivity factor It is tested etc. index, it is as a result as follows：

Date	Density kg/m³	Thermal conductivity factor (10 DEG C) λ w/mk
			2015.8.28	35	0.01917
2015.9.12	35	0.01923
			2015.9.24	35	0.01906
2015.10.15	35	0.01911

It can be seen from the table, although same white material standing time is different, the density of foaming does not change, and illustrates foaming effect Rate is constant, and thermal conductivity factor does not also change substantially.

2. CFA is only used only as the stability experiment of the white material prepared by foaming agent in

In the same manner as in Example 5, we are configured with the white material prepared completely using CFA in room temperature according to conventional white material formula It is lower to place 3 months, white material activity and the thermal conductivity factor of foam are measured by sampling every other month, measurement result is as follows：

Date	Reaction time	Thermal conductivity factor (10 DEG C) λ w/mk
			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

TFT refers to the skinning unsticking time in table.

As can be seen from the above table, reacting condition activity and heat conduction of the CFA of the present invention more than in white material system over time Coefficient keeps stable.

3. CFA is freely steeped under low-density and the stability of Water blown is contrasted

Above example 5 is repeated, but the consumption of foaming agent changes into the compound A-4 of 15 parts by weight, meanwhile, as right Than repeating above example 5, but only with water as foaming agent, respective white material and respective foam material are prepared respectively Material, in the case of the density identical of the foamed material obtained observe two kinds of foamed materials change with time stability whether Change.Preparation time is on April 16th, 2015, and density is all 22kg/m³, Figure 10 and Figure 12 are the initial outer of foams of the present invention See, Figure 11 and Figure 13 are the initial appearance for using water as the foams prepared by foaming agent.It is placed into September in 2015 29, Five totally months, the outward appearance of foam is observed, Figure 14 is product of the present invention, and outward appearance and size have almost no change, and Figure 15 is contrast Expert thinks in sample atrophy, polyurethane row, when foam density is in 25kg/m³Contract bubble during left and right in the case of Water blown Problem is inevitable, and this is the maximum difference of CFA and water.In other words, Water blown is used for the fields such as external wall spraying Change foamed material over time is shunk, thermal conductivity factor degenerates.

Other application

1st, the application of foaming agent of the invention in the preparation of polystyrol foam material

Embodiment 34

By the polystyrene resin powder of 100 parts by weight, the foaming agent B-1 of the present invention of 6 parts by weight, particle mean size 175 is micro- The calcium carbonate of rice, the zinc stearate of 0.3 parts by weight, toner (the big prosperous board, Wei Chang pigment Co., Ltd of Shenzhen of 0.3 parts by weight Production) input mixer mixed at a temperature of 30-40 DEG C of scope, acquisition foamed polystyrene composition, then utilize (draw ratio of screw rod is 28 for single screw extrusion machine:1) extrusion molding, each section of temperature of extruder be：One section 85 DEG C~95 DEG C, two 95 DEG C~105 DEG C, three sections, 105 DEG C~115 DEG C, four sections 115 DEG C~125 DEG C of section；125 DEG C~130 DEG C of mold temperature；Screw rod turns Speed is 5rpm~9rpm.The apparent density of the section bar obtained is 587kg/m³.SEM photograph is as shown in figure 16 (100 times of amplification). From photo as can be seen that the diameter of abscess is than more uniform.

2nd, the application of foaming agent of the invention in the preparation of polyvinyl-chloride foam material

Embodiment 35

By the polyvinyl chloride resin of 85 parts by weight, the foaming agent A-1 of the present invention of 5 parts by weight, the Tissuemat E of 0.5 parts by weight is average The calcium carbonate that 175 microns of granularity, the zinc stearate of 0.3 parts by weight, toner (the big prosperous board, the big prosperous pigment in Shenzhen of 0.3 parts by weight Co., Ltd produce) input mixer mixed at a temperature of 30-40 DEG C of scope, acquisition foam polyvinyl chloride composition, Then using single screw extrusion machine, (draw ratio of screw rod is 28:1) extrusion molding, each section of temperature of extruder be：One section 145 DEG C ~150 DEG C, two sections 155 DEG C~165 DEG C, three sections, 175 DEG C~185 DEG C, four sections 180 DEG C~195 DEG C；195 DEG C of mold temperature~ 205℃；Screw speed is 5rpm~9rpm.The proportion of the section bar obtained is 0.55g/cm³。

3、The preparation of diazanyl alcohol amine salt compound and its it is used as the application of foaming agent

Embodiment 36 (preparation example)

730g 80% hydrazine hydrate, 450g water are added in the stainless steel cauldron with cooling jacket, started Stirring so that hydrazine hydrate is sufficiently mixed with water, reaction system heat temperature raising after nitrogen treatment and protection, it is 45- to control temperature 70 DEG C, control pressure is no more than 0.3MPa, and the expoxy propane (molecular weight for amounting to 1200g is then slowly added in batches 58.08) 45-70 DEG C of temperature is controlled after, adding, then pressure cooled to 50 DEG C in 0.3MPa reactions stirred below 1 hour, Lower removing unnecessary water and unreacted expoxy propane are depressurized under 600mHg, stirring is opened, titanium dioxide is passed through into reactor Carbon 800-1200g, it is 45-60 DEG C to control temperature, and control pressure is reacted 4-8 hours no more than 0.3MPa, cools to less than 40 DEG C After release product, obtain compound, i.e. diazanyl alcohol amine salt compound.PH=8.9.The decomposition temperature of compound is in 45-70 DEG C of model Enclose.It is heated to quick release after 55 DEG C and goes out carbon dioxide.The infrared spectrum of compound is as shown in figure 17.

Embodiment 37 (Application Example)

It regard 20 parts by weight as the compound prepared by above example 36 of foaming agent, the polyether polyols of 30 parts by weight PEPA CF6320 (Jiangsu Fu Sheng new materials Co., Ltd), the fire retardant of 12.5 parts by weight of alcohol 4110,20 parts by weight TCPP (Jiangsu Yoke Chemical Co., Ltd.), the foam stabiliser DC3201 (US Air gasification work) of 1 parts by weight, 0.5 parts by weight Obtain transparent after catalyst PC-8 (US Air gasification work), 1 part by weight of catalyst PC-41 (US Air gasification work) are well mixed Composition, foam, then adds part isocyanates MDI (PM200) wherein, and polyurethane foam is made in agitated uniform rear foaming Material.The size of abscess is highly uniform, and the average diameter of abscess is bigger, illustrates that the amount of carbon dioxide gas is more.

Embodiment 38 (preparation example)

730g 80% hydrazine hydrate, 450g water are added in the stainless steel cauldron with cooling jacket, started Stirring so that hydrazine hydrate is sufficiently mixed with water, reaction system heat temperature raising after nitrogen treatment and protection, it is 45- to control temperature 70 DEG C, control pressure is no more than 0.3MPa, and the oxirane (molecular weight for amounting to 910g is then slowly added in batches 58.08) 45-70 DEG C of temperature is controlled after, adding, then pressure cooled to 50 DEG C in 0.3MPa reactions stirred below 1 hour, Lower removing unnecessary water and unreacted oxirane are depressurized under 600mHg, stirring is opened, 800- is passed through into reactor 1200g carbon dioxide, it is 45-60 DEG C to control temperature, and control pressure is reacted 4 hours no more than 0.3MPa, cool to less than 40 DEG C After release product, obtain compound.PH=8.8, the decomposition temperature of compound is in 45-70 DEG C of scope.It is heated to after 56 DEG C quick Discharge carbon dioxide.

Embodiment 39 (Application Example)

It regard 17 parts by weight as the compound prepared by above example 38 of foaming agent, the polyether polyols of 30 parts by weight PEPA CF6320 (Jiangsu Fu Sheng new materials Co., Ltd), the fire retardant of 12.5 parts by weight of alcohol 4110,20 parts by weight TCPP (Jiangsu Yoke Chemical Co., Ltd.), the foam stabiliser DC3201 (US Air gasification work) of 1 parts by weight, 0.5 parts by weight Obtain transparent after catalyst PC-8 (US Air gasification work), 1 part by weight of catalyst PC-41 (US Air gasification work) are well mixed Composition, foam, then adds part isocyanates MDI (PM200) wherein, and polyurethane foam is made in agitated uniform rear foaming Material.

Claims

1. the diazanyl alcohol amine salt compound with below general formula (I)：

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

Wherein m=1-10, preferably m=1-5；More preferably m=1-2；With

Wherein A^n-It is the one or more in following anion：

(b) carbonate：CO₃ ^2-；

(c) formate：HCOO^-；

(d) bicarbonate radical：HO-COO^-；

(e) organic single carbon acid group：R^aO-COO^-, wherein R^aIt is the C optionally replaced by hydroxyl or amino or halogen₁-C₂₆Alkyl is (excellent Select C₁-C₁₀Alkyl, more preferably C₁-C₃Alkyl), or C₁-C₂₆Acyl group (preferably C₁-C₁₀Acyl group, more preferably C₁-C₂Acyl group)；

In formula, R^bIt is the C optionally replaced by hydroxyl or amino or halogen₁-C₁₆Alkylene (preferably C₂-C₁₀Alkylene, more preferably C₂- C₆Alkylene), R^b' it is the trivalent C optionally replaced by hydroxyl or amino or halogen₂-C₂₀Alkyl (more preferably trivalent C₃-C₁₅Sub- hydrocarbon Base)；

(g)

In formula, R ' is H, the C optionally replaced by hydroxyl or amino or halogen₁-C₂₆Alkyl (preferably C₁-C₁₀Alkyl, more preferably C₁-C₃ Alkyl), or C₁-C₂₆Acyl group (preferably C₁-C₁₀Acyl group, more preferably C₁-C₇Acyl group)；Or

(h) organic many carbonates：^-OOC-OR^cO-COO^-,

In formula, R^cIt is the C optionally replaced by hydroxyl or amino or halogen₁-C₂₆Alkylene (preferably C₂-C₁₀Alkylene, more preferably C₂- C₆Alkylene)；

Wherein, R¹,R²,R³Or R⁴Independently selected from：H, R, the C optionally replaced by hydroxyl or amino or halogen₁-C₇Aliphatic alkyl (preferably C₁-C₄Alkyl), the C optionally replaced by hydroxyl or amino or halogen₃-C₇Cyclic aliphatic alkyl (such as cyclobutyl or cyclohexyl), Or, the C optionally replaced by hydroxyl or amino or halogen₆-C₁₀Aromatic hydrocarbyl (preferably phenyl or aminomethyl phenyl)；

Precondition is：The R in the compound of above-mentioned logical formula (I)¹,R²,R³Or R⁴In at least one be the R bases being connected with N atoms Group, or the compound of the logical formula (I) have at least one R group bonded with N；

Wherein one or more of the R group in following groups：

(1a)H[OCH(R_1a)CH(R_2a)]_q-, such as H (OCH₂CH₂)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 (OCH₂CH (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 q value or average value are q=1-3, preferably q=1-2.5, more preferably q=1.5-2.0, by q mean value calculation； R_1a、R_2a、R_3aOr R_4aIt is each independently selected from：H, the C optionally replaced by hydroxyl or amino or halogen₁-C₇Aliphatic alkyl, appoints Select the C replaced by hydroxyl or amino or halogen₃-C₇Cyclic aliphatic alkyl, or, the C optionally replaced by hydroxyl or amino or halogen₆-C₁₀ Aromatic hydrocarbyl.

2. compound according to claim 1, wherein organic amine B have primary amine, secondary amine and/or the tertiary amine groups of m to m+3 Group, and optionally there is quaternary ammonium group.

3. compound according to claim 1 or 2, wherein A^n-Be be selected from (a)-(h) it is two or more it is described it is cloudy from The combination of son or mixture, and/or B^m+It is combination or the mixture of two or more above-mentioned organic amine cations.

4. the compound according to any one of claim 1-3, wherein R¹,R²,R³Or R⁴Independently selected from：H, R, optionally The C replaced by hydroxyl or amino or halogen₁-C₄Aliphatic alkyl, the cyclobutyl optionally replaced by hydroxyl or amino or halogen or ring Hexyl, or, the phenyl or aminomethyl phenyl optionally replaced by hydroxyl or amino or halogen；It is further preferred that R_1a、R_2a、R_3aOr R_4aEach solely On the spot it is selected from：H, methyl or the ethyl optionally replaced by hydroxyl or amino or halogen, or optionally by hydroxyl or amino or halogen Substituted propyl group or isopropyl, the cyclohexyl optionally replaced by hydroxyl or amino or halogen, or, optionally by hydroxyl or amino or halogen The phenyl or aminomethyl phenyl of element substitution.

5. compound according to claim 4, wherein R_1a、R_2a、R_3aOr R_4aIt is each independently selected from：H, methyl, chloromethane Base, bromomethyl, ethyl, cyclohexyl, or, phenyl.

6. the compound according to any one of claim 1-5, wherein A^n-It is one kind in following anion Or it is a variety of：

(a)R¹R²N-COO^-Or R¹R²N-NH-COO^-；Wherein R¹And R²It is hydrogen, methyl, ethyl, methylol, hydroxyl second independently of one another Base or hydroxypropyl；

(b)CO₃ ^2-；

(c)HCOO^-；

(d)HO-COO^-；Or

(g)(i.e. HC (OR ') O₂ ^2-), or(i.e. HCO₃ ^3-),

In formula, R ' is H, the C optionally replaced by hydroxyl or amino or halogen₁-C₁₀Alkyl (more preferably methyl, ethyl, propyl group) or C₁-C₁₀Acyl group (more preferably formoxyl, acetyl group or propiono).

7. the compound according to any one of claim 1-6, wherein R¹And R²In at least one be H, more preferably R¹ It is H and R²It is H or R group.

8. the compound according to any one of claim 1-7, the content of its water is 0-40wt%, preferably 5- 35wt%, more preferably 10-30wt%, more preferably 15-25wt%；And/or, the compound average per molecule of logical formula (I) contains 1.5-5 R group.

9. the compound according to any one of claim 1-8, wherein, except wherein A^n-It is the logical formula (I) of formate Outside compound, the pH for leading to other compounds of formula (I) is 7.5-10, preferably 7.8-9.5, more preferably pH 8-9；And/or, its The content of the alkali and alkaline earth metal ions of formula of (I) compound be 0-200ppm (quality), more preferably less than 100ppm, it is more excellent Choosing is less than 10ppm, most preferably below detectable limit or for 0ppm.

10. the compound according to any one of claim 1-9, wherein, the compound or compound for leading to formula (I) are mixed Compound contains 25-95wt%, preferably 27-90wt%'s, preferably 30-85wt%, preferably 40-80wt%, more preferably 45-75wt% The salt of single methanol amine (such as MEA and/or single Propanolamine) and the salt of glycol amine (such as diethanol amine and/or dipropanolamine), The gross weight of compound or compound mixture based on logical formula (I)；And/or

In the compound or compound mixture of logical formula (I), logical formula (I) compound (such as single methanol amine with a R group Salt) with the mol ratio of the logical formula (I) compound (such as glycol amine salt) with two R groups it is 1:0 to 1:2.5, preferably 1:0.3 To 1:2, preferably 1:0.5 to 1:1.

11. the compound according to any one of claim 1-10, wherein,

The compound or compound mixture of logical formula (I) contain 15-90wt%, preferably preferably 17-88wt%, 20-85wt%, excellent Select 25-80wt%, more preferably 30-70wt% single methanol amine (such as MEA and/or single Propanolamine) and glycol amine (such as two Monoethanolamine and/or dipropanolamine), the gross weight of compound or compound mixture based on logical formula (I).

12. prepare the method for the compound of the logical formula (I) of any one in claim 1-11, wherein A^n-Be (a), (b), (c), (d), the anion of any one or more of (e), (f) or (h), this method includes the first raw material and the second raw material in solvent In (such as water), optionally in the presence of a catalyst, reacted, wherein the first raw material is in these following compounds One or more：

NH₄OOC-N(R¹)-R^b-N(R²)-COONH₄, R^b'(-N(R¹)-COO)₃(NH₄)₃, HOOC-N (R¹)-R^b-N(R²)-COOH Organic amine compound (M) salt, HOOC-N (R¹)-R^b-N(R²)-COOH hydrazonium salt, R^b'(-N(R¹)-COOH)₃Hydrazonium salt, or R^b'(-N(R¹)-COOH)₃Organic amine compound (M) salt；Or

NH₄OOC-OR^cO-COONH₄, HOOC-OR^cO-COOH hydrazonium salt, or HOOC-OR^cO-COOH organic amine compound (M) Salt；

Second raw material is the one or more in these following epoxides：

Or styrene oxide；

C₁-C₂₄Alkyl amine；

Two (C₁-C₁₆Alkyl) amine；

The C being optionally optionally substituted by a hydroxyl group with three primary amine groups₃-C₁₈Organic three amine is optional by hydroxyl with four primary amine groups The C of base substitution₅-C₁₈Organic tetraamine；Or

C₂-C₁₀Alcamines,

13. method according to claim 12, the wherein epoxides are：Oxirane, expoxy propane, epoxy chloropropionate Alkane, epoxy bromopropane, epoxy butane or epoxy chlorobutane or styrene oxide, and any two or a variety of mixed in them Compound；And/or

In the reaction when using water as solvent, the consumption of water is the 70- calculated based on the weight of the first raw material 250wt%, preferably 85-200wt%, more preferably 100-170wt%.

14. prepare the method for the compound of the logical formula (I) of any one in claim 1-11, wherein A^n-It is anion (g), should Method includes：Orthoformic acid ester type compound in a solvent, optionally in the presence of a catalyst, and is belonging to Organic Alcohol amine It is hydrolyzed in the presence of organic amine M or the compound B and water that belong to Organic Alcohol amine with least one above-mentioned N-R group Reaction；Wherein, the amount of the water is sufficient so that at least two ester group hydrolyses of orthoformic acid ester type compound, more excellent Choosing, the amount of water is sufficient so that three ester group hydrolyses of orthoformic acid ester type compound；

Wherein organic amine compound B is hydrazine and optional ammonia is carried out instead as initiation material or as initiator and epoxides Answer what is formed, one or more of the epoxides in these following epoxides：

Or styrene oxide.

15. method according to claim 14, wherein the epoxides is：Oxirane, expoxy propane, epoxy chloropropionate Alkane, epoxy bromopropane, epoxy butane or epoxy chlorobutane or styrene oxide, and any two or a variety of mixed in them Compound.

16. the compound prepared as the method described in claim 12 or 13；Preferably, the compound contains 25-95wt%, It is preferred that 27-90wt%, preferably 30-85wt%, preferably 40-80wt%, more preferably 45-75wt% single methanol amine (such as monoethanol Amine and/or single Propanolamine) salt and glycol amine (such as diethanol amine and/or dipropanolamine) salt, the gross weight based on compound Amount, or, the compound contains 15-90wt%, preferably preferably 17-88wt%, preferably 20-85wt%, 25-80wt%, more excellent Select 30-70wt% single methanol amine (such as MEA and/or single Propanolamine) and glycol amine (such as diethanol amine and/or dipropyl Hydramine), the gross weight based on compound.

17. the compound prepared as the method described in claims 14 or 15；Preferably, the compound contains 25-95wt%, It is preferred that 27-90wt%, preferably 30-85wt%, preferably 40-80wt%, more preferably 45-75wt% single methanol amine (such as monoethanol Amine and/or single Propanolamine) salt and glycol amine (such as diethanol amine and/or dipropanolamine) salt, the gross weight based on compound Amount, or, the compound contains 15-90wt%, preferably preferably 17-88wt%, preferably 20-85wt%, 25-80wt%, more excellent Select 30-70wt% single methanol amine (such as MEA and/or single Propanolamine) and glycol amine (such as diethanol amine and/or dipropyl Hydramine), the gross weight based on compound.

18. a kind of foaming agent, it includes the diazanyl hydramine with logical formula (I) according to any one of claim 1-11 Salt compound or diazanyl alcohol amine salt compound mixture, or as there is formula according to any one of claim 1-11 (I) diazanyl alcohol amine salt compound or diazanyl alcohol amine salt compound mixture is constituted；It is preferred that, the foaming agent is sent out as polyurethane Infusion, foamed polystyrene agent or foam polyvinyl chloride agent.

19. foaming agent according to claim 18, wherein A^n-It is the one or more in following anion：

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

20. a kind of foaming agent, wherein it includes compound according to claim 16 and/or compound according to claim 17 And it is used as polyurethane foams, foamed polystyrene agent or foam polyvinyl chloride agent.

21. formic acid hydrazine is used as the purposes of polyurethane foams.

22. purposes according to claim 21, wherein formic acid hydrazine are the form of the aqueous solution and (excellent containing 0.5-15wt% Select 1-8wt%) organic amine, the latter includes but is not limited to：Methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine or one Monoethanolamine.

23. polyurethane foamed composite thing, it is included：

The 0.01-100 weight % diazanyl hydramine salinization with logical formula (I) according to any one of claim 1-11 Compound or diazanyl alcohol amine salt compound mixture, or compound according to claim 16 or chemical combination according to claim 17 Thing；

0-50 weight % physical blowing agent；

0-5 weight % water, and

0.0-99.99 weight % polymer polyatomic alcohol；Wherein, the percentage by weight is based on the total of polyurethane foamed composite thing Weight.

24. polyurethane foamed composite thing according to claim 23, it is included：

0.1-80 weight % (more preferably 1-70wt%, more preferably 3-60wt%, more preferably 5-50wt%, more preferably 7-40wt%, Such as 10wt%, 15wt%) the diazanyl hydramine salt chemical combination with logical formula (I) according to any one of claim 1-11 Thing or diazanyl alcohol amine salt compound mixture, or compound according to claim 16 or compound according to claim 17；

0-40 weight % physical blowing agent；

0-4 weight % water, and

20.0-99.9 weight % (more preferably 30-99wt%, more preferably 40-97wt%, more preferably 50-95wt%, more preferably 60- 93wt%, such as 90wt% or 85wt%) polymer polyatomic alcohol；Wherein, the percentage by weight is based on polyurethane foamed composite The gross weight of thing.

25. the polyurethane foamed composite thing according to claim 23 or 24, it contains the water of 0.5-4wt% altogether, more excellent Select 0.8-2.5wt%, more preferably 1-2.2wt% water.

26. the polyurethane foamed composite thing according to any one of claim 23-25, wherein polymer polyatomic alcohol are selected From：It is PPG, PEPA, polyether-polyester polyol, PCDL, polycarbonate-polyester polyalcohol, poly- Carbonic ester-PPG, polybutadiene polyol or polysiloxane polyhydric alcohol.

27. the polyurethane foamed composite thing according to any one of claim 23-26, wherein composition, foam are transparent Or clarification；Preferably, hard polyurethane foam composition, foam be transparent or clarification or translucent or milky but It is uniform, or, soft polyurethane foam composition, foam is transparent or milky.

28. the polyurethane foamed composite thing according to any one of claim 23-27, it has following characteristics：1) wrap Containing alcohol amine salt or alcohol amine compound；2) transparent or clarification or translucent or milky uniform liquid；3) in case of heating or CO is discharged in the case of the addition organic acid more stronger than carbonic acid or inorganic acid₂；4) when composition, foam and isocyanates Or when polyisocyanates contact or mixing, the material being mixed to form becomes milky in 0.2-4 seconds (preferably 1-2 seconds).

29. polyurethane foamed composite thing according to claim 28, causes mixing when wherein it is mixed with polyisocyanates The material of formation becomes milky, with volume rapid expanding phenomenon, but this process and it is non-foam it is real rise, material afterwards Just start to rise.

30. polyurethane foamed material, it passes through the polyurethane foamed composite thing and polyisocyanates any one of 23-29 Monomer and/or isocyanate-terminated prepolymer react and formed after being mixed.