CN107312192A

CN107312192A - Organic alcohol amine salt compounds and its purposes as foaming agent

Info

Publication number: CN107312192A
Application number: CN201710523673.9A
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: 2017-06-30
Publication date: 2017-11-03
Anticipated expiration: 2037-06-30
Also published as: CN107312192B

Abstract

Organic 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, this leads to the salt and the salt of glycol amine for the single methanol amine that formula (I) compound contains 25 95wt%.They can be as polyurethane foams, and most foaming agent can be used as foamed polystyrene agent or foam polyvinyl chloride agent.

Description

Organic alcohol amine salt compounds and its purposes as foaming agent

Technical field

The present invention relates to being used as CO₂The organic alcohol amine salt compounds of the anion of donor and its it is used as foaming agent Purposes, more specifically there is provided not only have to be used as CO₂The anion of donor and with hydroxyalkyl or hydroxyalkyl alkoxy base Group is used as the new organic of solubilizing group as solubilizing group or C2-C14 alkyl (such as 2- chloroethyls, 3- chloropropyls or phenethyl) Amine compoundses, and its in expanded material such as polyurethane foam or PVC foam material or foamed polystyrene material Application.

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 organic 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；

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, particularly preferred q=1-2.5, particularly preferred q=1.5-2.0, by q's 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-C₇Fat Fat race alkyl, the C optionally replaced by hydroxyl or amino or halogen₃-C₇Cyclic aliphatic alkyl, or, optionally by hydroxyl or amino or halogen Substituted C₆-C₁₀Aromatic hydrocarbyl；

Wherein, single methanol amine (such as MEA that the compound or compound mixture of formula (I) contain 25-95wt% is led to And/or single Propanolamine) salt and glycol amine (such as diethanol amine, ethanol propanol amine and/or dipropanolamine) salt, based on formula (I) compound or the gross weight of compound mixture.

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

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

B^m+Be or comprising：The ammonium ion of+1 valency and/or with m-⁺NR³R⁴H groups and/or-⁺NR³The one of H- groups The cation of kind or a variety of organic amine B；

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：R¹R²N-COO^-；

(b) carbonate：CO₃ ^2-；

(c) formate：HCOO^-；

(d) bicarbonate radical：HO-COO^-；

(g)Or

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

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, single methanol amine (such as MEA that the compound or compound mixture of formula (I) contain 25-95wt% is led to And/or single Propanolamine) salt and glycol amine (such as diethanol amine, ethanol propanol amine and/or dipropanolamine) salt, based on logical The compound of formula (I) or the gross weight of compound mixture.

It is preferred that, 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 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 (such as ethoxy, hydroxypropyl And/or hydroxyl chloropropyl).

Typically, the water content of the logical 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.

It is preferred that, 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.

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.

It is preferred that, R group is hydroxypropyl, i.e. HO-CH₂-CH₂(CH₃)-or HO-CH₂(CH₃)-CH₂-, ethoxy, and/or, hydroxyl Base chloropropyl.

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

(b) carbonate：CO₃ ^2-；Or

(d) bicarbonate radical：HO-COO^-；

And/or

Wherein

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

The method for preparing the compound of formula above (I) there is provided one kind according to the third embodiment the present invention, wherein A^n-It is the anion of any one or more of (a), (b), (c), (d), (e), (f) or (h), this method includes the first raw material With the second raw material in water, optionally in the presence of a catalyst, reacted, the consumption of water is using the weight of the first raw material as base The 70-250wt%, preferably 85-200wt%, more preferably 100-170wt%, more preferably 110-160wt% that plinth is calculated；

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

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)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 chemical combination Thing (M) salt；

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

Or styrene 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.

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

It is preferred that, A^n-And B^m+At least one of comprising hydrazine and/or include diazanyl or substitution diazanyl.

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.

The method for preparing the compound of formula above (I) there is provided one kind according to the 4th embodiment of the present invention, wherein A^n-It is anion (g), this method includes：Orthoformic acid ester type compound in a solvent, optionally in the presence of a catalyst, 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 is hydrolyzed；Wherein, the consumption of water is the 90- calculated based on the weight of orthoformic acid ester type compound 250wt%, preferably 100-220wt%, more preferably 110-200wt%, more preferably 120-180wt%；

Wherein organic amine compound B is that organic amine compound (M), ammonia and/or hydrazine draw as initiation material or conduct Hair agent is reacted what is formed with epoxides, the one kind or many of the epoxides in these following epoxides Kind：

Or styrene oxide.

It is preferred that, in above-mentioned preparation method, the epoxides is：Oxirane, expoxy propane, epoxychloropropane, ring Oxygen N-Propyl Bromide, epoxy butane or epoxy chlorobutane or styrene oxide, and any two or a variety of mixtures in them.

Chemical combination according to prepared by the 5th embodiment of the present invention there is provided the preparation method as the 3rd embodiment Thing；Preferably, the compound contains 25-95wt%, preferably preferably 27-90wt%, preferably 30-85wt%, 40-80wt%, More preferably 45-75wt% single methanol amine (such as MEA and/or single Propanolamine) salt and glycol amine (such as diethanol amine, Ethanol propanol amine and/or dipropanolamine) salt, the gross weight based on compound, or, the compound contains 15-90wt%, excellent Select 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, ethanol propanol amine and/or dipropanolamine), the gross weight based on compound Amount.

Chemical combination according to prepared by the 6th embodiment of the present invention there is provided the preparation method as the 4th embodiment Thing；Preferably, the compound contains 25-95wt%, preferably preferably 27-90wt%, preferably 30-85wt%, 40-80wt%, More preferably 45-75wt% single methanol amine (such as MEA and/or single Propanolamine) salt and glycol amine (such as diethanol amine, Ethanol propanol amine and/or dipropanolamine) salt, the gross weight based on compound, or, the compound contains 15-90wt%, excellent Select 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, ethanol propanol amine and/or dipropanolamine), the gross weight based on compound Amount.

According to the present invention there is provided a kind of foaming agent, it includes according to the organic alcohol amine salt compound with logical formula (I) or had Machine alcohol amine salt compound mixture, or mixed by the organic amine alkoxide cpd with logical formula (I) or organic alcohol amine salt compound Thing is constituted.

According to the present invention there is provided a kind of foaming agent, it includes the 5th embodiment or the 6th reality according to the present invention Apply the compound of scheme.

Above-mentioned foaming agent is suitable as polyurethane foams, foamed polystyrene agent or foam polyvinyl chloride agent.

According to the present invention, the organic alcohol amine salt compound with logical formula (I) or the mixing of organic alcohol amine salt compound are also provided Thing as polyurethane foams, foamed polystyrene agent or foam polyvinyl chloride agent purposes.It is preferred that, A^n-It is to be selected from following the moon One or more in ion：

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

According to the present invention, polyurethane foamed composite thing is also provided, it is included：

0.01-100 weight % organic alcohol amine salt compound or the mixing of organic alcohol amine salt compound with logical formula (I) Thing, or according to the compound or the compound of the 6th embodiment of the 5th embodiment of the invention；

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, 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%) organic alcohol amine salt compound or the mixing of organic alcohol amine salt compound with logical formula (I) Thing, or according to the compound or the compound of the 6th embodiment of the 5th embodiment of the invention；

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.

Typically, above-mentioned composition, foam is transparent or clarification；Preferably, hard polyurethane foam composition, foam is Bright or clarification or translucent or milky is still uniform, or, soft polyurethane foam composition, foam is transparent or newborn White.

Typically, polyurethane foamed composite thing has following characteristics：1) alcohol amine salt or alcohol amine compound are included；2) it is transparent or clear Clear or translucent or milky uniform liquid；3) in case of heating or in the addition organic acid or inorganic more stronger than carbonic acid CO is discharged in the case of acid₂；4) when composition, foam is contacted or mixed with isocyanates or polyisocyanates, it is mixed to form Material become milky in 0.2-4 seconds (preferably 1-2 seconds).

Typically, the material being mixed to form is caused to become milky, companion when polyurethane foamed composite thing is mixed with polyisocyanates With there is a volume rapid expanding phenomenon, but this process and it is non-foam it is real rise, material just starts to rise afterwards.

The present invention also provides a kind of polyurethane foamed material, and it passes through above-mentioned polyurethane foamed composite thing and polyisocyanates Monomer and/or isocyanate-terminated prepolymer react and formed after being mixed.

The present invention especially also provides carbonic acid two (ethylol amine) salt, carbonic acid two (hydroxypropyl amine) salt, bicarbonate (ethoxy Amine) salt, bicarbonate (hydroxypropyl amine) salt, the carbonate of diethylenetriamines, the carbonate of trien, tetramethylene five The carbonate of amine, the carbonate of dipropylenetriamine, the carbonate of tri propylidene tetramine and the carbonate of 4 sub-propyl-5-amine are made For the purposes of foaming agent, they are used for foamed polystyrene or foam polyvinyl chloride.

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.

In this application, it is preferred that R is hydroxypropyl, i.e. HO-CH₂-CH₂(CH₃)-or HO-CH₂(CH₃)-CH₂-, hydroxyl second Base 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 22-96wt%, preferably preferably 25-95wt%, preferably 27-90wt%, preferably 30-85wt%, 40- The salt and glycol amine (such as two of 80wt%, more preferably 45-75wt% single methanol amine (such as MEA and/or single Propanolamine) Monoethanolamine, ethanol propanol amine and/or dipropanolamine) salt (i.e. both sums：The salt of salt+glycol amine of single methanol amine), based on logical The compound of formula (I) or the gross weight of compound mixture.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 are (for example MEA and/or single Propanolamine) and glycol amine (such as diethanol amine, ethanol propanol amine and/or dipropanolamine) (both i.e. it With：Single methanol amine+glycol amine), the gross weight of compound or compound mixture based on logical formula (I).

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 or hydroxyl chloropropyl).

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 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.Prepare the side of the diazanyl alcohol amine salt compound with primitive nail acid group (g) of logical formula (I) In method, 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.

In addition, being used as foamed polystyrene agent or poly- the invention provides the foaming immunomodulator compounds of the logical formula (I) of the present invention The purposes of vinyl chloride foaming agent, 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.

When selection is used using formic acid or formates as foaming agent due to reaction in can produce CO, therefore should take must The measure wanted be aerated with it is explosion-proof, formic acid amine salt be used as foaming agent when isocyanates presence be necessary because It could release carbon dioxide and carbon monoxide with isocyanates reaction.These above-mentioned compounds in this application can referred to as originally Invention foaming agent.Polyurethane foams or in polyurethane foamed composite thing.Certainly, these compounds foaming of formula (Ia) Agent is not preferred, because it or they pH value is generally below 8, even below 7.5, more even below 7.1, even up to PH=6-7.When the polyurethane foamed material for preparing heat insulation-type, especially the polyurethane foamed material of obturator-type when, from hair Steep efficiency, the smell of foaming agent, heat-insulating property and abscess-size stability and the dimensional stability of polyurethane foam is integrated Consider, or when the polyurethane foamed material for perforate or half perforate, it is fine and smooth from bubbling efficiency, the smell of foaming agent, abscess The dimensional stability of degree and polyurethane foam finished product considers, (they are not (on the spot for these organic amine salt compounds (Ia) Situ) 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 tetren, 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.

Therefore, the application also provides carbonic acid two (ethylol amine) salt, carbonic acid two (hydroxypropyl amine) salt, bicarbonate (ethoxy Amine) salt, bicarbonate (hydroxypropyl amine) salt, carbonic acid (ethylol amine) (hydroxypropyl amine) salt, the carbonate of diethylenetriamines, Sanya The carbonate of tetramine, the carbonate of tetren, the carbonate of dipropylenetriamine, the carbonic acid of tri propylidene tetramine One or more mixtures in the carbonate of salt or 4 sub-propyl-5-amine are as the purposes of foaming agent, and they are used for polyphenyl second Alkene foams or foam polyvinyl chloride.

Although in addition, being not preferred, present inventor also found one in the alkyl carbonate amine salt of below general formula Plant or a variety of mixtures is as the purposes of foaming agent, they are used for foamed polystyrene or foam polyvinyl chloride：

(R¹NH₂)₂CO₃,

(R¹R²NH)₂CO₃,

(R¹NH₂)(R¹R²NH)₂CO₃,

(R¹NH₂)HCO₃, or

(R¹R²NH)HCO₃,

In formula, R¹Or R²It may be the same or different, and be methyl, ethyl, propyl group, butyl, hexyl, ring third independently of one another Base or cyclohexyl.

More specifically, one or more mixtures in above-mentioned alkyl carbonate amine salt refer to：Carbonic acid two (methyl amine) Salt, carbonic acid two (dimethyl amine) salt, carbonic acid (methyl amine) (dimethyl amine) salt, carbonic acid two (ethylamine) salt, (diethyl of carbonic acid two Amine) salt, carbonic acid (ethylamine) (diethylamide) salt, carbonic acid two (propyl group amine) salt, carbonic acid two (dipropylamine) salt, carbonic acid (propyl group Amine) (dipropylamine) salt, bicarbonate (methyl amine) salt, bicarbonate (ethylamine) salt, bicarbonate (propyl group amine) salt, carbonic acid (methyl Amine) (ethylamine) salt, carbonic acid (methyl amine) (propyl group amine) salt, carbonic acid (ethylamine) (propyl group amine) salt, carbonic acid (methyl amine) (diethyl Base amine) salt, carbonic acid (ethylamine) (dimethyl amine) salt, carbonic acid (methyl amine) (dipropylamine) salt, carbonic acid (propyl group amine) (dimethyl Amine) salt, carbonic acid (ethylamine) (dipropylamine) salt, carbonic acid (propyl group amine) (diethylamide) salt, carbonic acid (dimethyl amine) (diethyl Amine) salt, it is one or more in carbonic acid (dimethyl amine) (dipropylamine) salt or carbonic acid (diethylamide) (dipropylamine) salt Mixture.

Simply, the styrofoam or the abscess-size of polyvinyl chloride foam body formed is not as using the present invention The abscess-size for the foamed material that other foaming agents are obtained is uniform like that, and waving because of the catabolite produced after foaming Hair property is higher, and ammonia taste is given out in foamed material.So, these alkyl carbonate amine salt compounds are not preferred as foaming agent 's.

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 that ammonium formate is the aqueous solution or 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, leads to the compound of formula (I), or the organic alcohol amine salt obtained by above-mentioned preparation method Compound has following characteristics：1) in the case where additionally not adding alkali compounds in addition or not, except ammonium formate, formic acid hydrazonium salt Or outside formic acid organic amine M salt compounds, the pH value of foaming agent (i.e. compound of Formula I) of the present invention is in 7.5-10, it is preferable that be pH Between 7.8-9.5, more preferably pH 8-9, the pH value of ammonium formate (116 DEG C of fusing point), formic acid hydrazine or formic acid organic amine M salt foaming agents In 5.5-6 scopes, or wherein A^n-It is the pH of logical formula (I) compound of formate (c) in 5.5-6.0 scopes；2) alkali metal or alkali The content of earth metal be 0-200ppm (quality), more preferably less than preferably shorter than 150ppm, more preferably less than 100ppm, 50ppm, More preferably less than 20ppm, more preferably less than 10ppm, more preferably less than 5ppm, most preferably below detectable limit or for 0ppm； 3) content of water or the content of the water existed as solvent are 0-40wt%, more preferably preferably 5-35wt%, 10-30wt%, More preferably 15-25wt%；4) heat decomposition temperature is to discharge CO between 36-120 DEG C and when decomposing₂Gas；Wherein divide The higher certain form of foaming agent thing of the present invention of solution temperature becomes less stable when touching NCO group, can be in 45-70 Decomposed between DEG C and discharge CO₂；5) 30-100%, preferably 50%- among all N atoms in foaming agent of the present invention 100%th, more preferably 70%-100%, more preferably 85%-100% has N-H covalent bonds；6) in foaming agent of the present invention, formula (I) total content of compound and water is the 70-100% based on gross weight, is more typically 80-99.999%, is more typically 85- 99.0% (containing solvent, and allowing containing a small amount of nonmetallic inclusion)；7), with infrared spectrum analysis, some present invention foaming Agent has in 2932-2970cm^-1The secondary amine salt N-H of scope stretching vibration is unimodal, in 1555-1566cm^-1The secondary amine salt of scope N-H flexural vibrations are unimodal, in addition, in 3200-3400cm^-1The OH stretching vibration peaks of the strong and wide Hydrogenbond of scope, table Both there is hydroxyl, secondary amine contains water simultaneously in bright foaming agent.Therefore, foaming agent of the present invention includes one or more alcohol aminations Compound and typically contain water.

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-。

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, logical formula (I) compound or foaming agent of the present invention of the invention have the single methanol amine salt and glycol amine of certain content Salt, has suitable reactivity when being used for as foaming agent and preparing polyurethane foamed material, and have in foaming process There is suitable decomposition temperature, or there is suitable decomposition temperature when touching isocyanates, on the one hand store at room temperature steady It is fixed, on the other hand carbon dioxide can discharged with rational speed when foamable reaction system heats up during polyurethane foam Gas, to cause expanded material that there is preferable performance, the distribution density of such as abscess, the dimensional homogeneity of abscess.In the present invention Most preferred foaming agent is carbaminate and/or carbonate with logical formula (I), and this is attributed to their suitable decomposition temperature Degree, suitable carbon dioxide rate of release, the distribution density of excellent abscess, the dimensional homogeneity of excellent abscess, identical Foaming parameter under form the abscess aperture of foam and be significantly less than abscess in the physical blowing agents such as water, pentamethylene, unit volume Quantity is far more than other foaming agents, so as to assign foamed material good heat-insulating property.The present invention foaming agent (particularly with For carbaminate and/or carbonate) there is higher pH value (pH>7.5), its acid group content for Unit Weight High (or CO2 burst sizes are big), and with higher reactivity during as foaming agent, especially as polyurethane foams.Especially Its, diazanyl alcohol amine salt compound is compared with the organic alcohol amine salt compound without diazanyl, because a diazanyl has two amino, So that hydrazo compound has higher alkalescence than amino-compound, therefore, Unit Weight can combine more anion, That is, acid group content is high (or CO2 burst sizes are bigger).

2nd, logical formula (I) compound of the invention has solubilizing group i.e. R group, and the compound (I) can be with molecular level Equably dissolve or be distributed in polymer polyatomic alcohol such as PPG and/or PEPA, or polyvinyl chloride (PVC) resin Or in polystyrene (PS) resin, it is ensured that the uniformity of foaming, it is to avoid local excessive foams.

3rd, logical formula (I) compound of the invention has hydramine residue or with alcohol amine compound, is decomposed in the foaming agent (I) Discharge CO₂Catabolite produced afterwards is that alcohol amine compound still contains at least two reactive hydrogens, and they are suitable as Chain extender and/or crosslinking agent, logical formula (I) compound of the invention not only as " blow point " but also were used as " chain extension point " and/or " were crosslinked Point ", significantly enhances the mechanical strength and mechanical strength of abscess, and the polyurethane foam obtained has good dimensionally stable Property, shrinkage phenomenon is almost not observed in polyurethane foam finished product naked eyes after some months, even 1 year is placed, without the bubble that collapses Or collapse phenomenon.Especially at higher temperature (such as 40-60 DEG C, or even 40-70 DEG C) place the long period for example (10 days) it Still there is good dimensional stability afterwards.

4th, logical formula (I) compound of the invention is not allowed volatile, and (metal ion does not have corruption to metal ion to metal base Corrosion), and chlorofluorocarbon blowing agent is wholly or largely substituted, therefore, have great importance for environmental protection, and And the effect of foaming is substantially better than foaming effect when using other foaming agents in the prior art.

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, with foaming agent of the present invention or logical formula (I) compound, as the polyurethane foamed material prepared by foaming agent, (this steeps Foam body be using by hand stirring laboratory make by oneself Fang Mo in make) size changing rate or shrinkage factor≤4.5%, preferably≤ 1.5%, more preferably≤0.5% (according to chinese national standard GB/T 8811-2008, standing time can be according to wanting in the standard Ask, or even, standing time is 5 months).In addition, for example in 34-42Kg/m³Density foam under, thermal conductivity factor w/mk (10 DEG C) are between 0.01900-0.02200, preferably between 0.01910-0.02150.

9th, a small amount of water is contained in logical formula (I) compound of the invention or mixture, these water are with leading to individual molecule The molecule of the alcohol amine salt compound of formula (I) is combined or associated, therefore, and the water that individual molecule form is present is very beneficial for hair Bubble, is conducive to improving the performance of foam product.Although equally using a small amount of water in the prior art as foaming agent or auxiliary Foaming agent, still, these water are typically to exist in the form of water cluster or water clusters (i.e. in the form of water droplet), especially respectively Individual water cluster is of different sizes, and the foaming of composition, foam can be caused uneven, especially causes the part of foams to be collapsed Contracting, influences the various performances of foam product.

Brief description of the drawings

Fig. 1 is the infrared spectrogram of embodiment A-4 product.

Fig. 2 is the infrared spectrogram of the product of embodiment 8.

Fig. 3 is the electron scanning micrograph (SEM) of the foams of embodiment 2.

Fig. 4 is the SEM of the foams of comparative example 1.

Fig. 5 is the SEM of the foams of embodiment 6.

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), 1.2 tons of water are added to the stainless of cooling water jecket In steel autoclave (the abbreviation reactor in following other embodiments), agitator is started so that aminoquinoxaline dissolves, Nitrogen purge is used, then closed reactor and stirring is started, is passed through 1.90 tons altogether of expoxy propane (molecular weight 58.08,34 DEG C of boiling point), the charging rate of expoxy propane is controlled to control the not higher than 0.6MPa of the pressure in reactor, not Slowly heated up under disconnected stirring, temperature control reacts 15 hours below 70 DEG C, reaction is completed, slowly reduce the temperature to control after 50 DEG C true Reciprocal of duty cycle (preferably shorter than 500mmHg) below 600 millimetress of mercury slowly removes unnecessary water and (for example reached less than 20wt%'s Water content) and unreacted expoxy propane, vacuum is then bled off, cools to and reactant is released after less than 40 DEG C, compound is obtained A-1.The centipoise of viscosity 200, pH=9, compound A-1 decomposition temperature for 45-70 DEG C (extremely slowly decomposed since 45 DEG C, Peak decomposition temperature is 57-62 DEG C).With atomic absorption spectrophotometer (Seiko Instruments, Inc.；SAS/727) survey The content for determining alkali and alkaline earth metal ions ion is less than detectable limit.Gas chromatographic analysis, single Propanolamine and dipropanolamine Mol ratio is 1:0.18.Compound A-1 contains the salt of both about 74wt% single Propanolamine and dipropanolamine.Also contain some Water.In addition, single Propanolamine and dipropanolamine that compound A-1 contains about 55wt% (in heating compound A-1 to discharge dioxy Residue is analyzed after change carbon), the gross weight based on the compound A-1 before heat resolve.

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

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-2.PH=9.2, decomposition temperature is in 45-70 DEG C of scope.

Embodiment A-3

1.4 tons of aminoquinoxaline, 0.8 ton of ethylene glycol, 1.0 tons 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 1.25 tons of meter, controls 45-70 DEG C of temperature after adding, pressure is stirred below anti-in 0.6MPa Answer 5 hours, then cool to 50 DEG C, the unnecessary water of lower removing is depressurized under 600mHg and (for example reaches that the water less than 30wt% contains Amount) and unreacted oxirane, cool to and product is released after less than 40 DEG C, obtain compound A-3.Viscosity about 245, pH= 9, compound A-3 decomposition temperature are in 45-70 DEG C of scope.

Embodiment A-4

1kg aminoquinoxaline, 1.1kg water are added in reactor, dissolved under agitation, is purged and reacted with nitrogen Device, then adds 2.1kg expoxy propane into transparent quartz glass reactor, starts stirring, in the case where being stirred continuously slowly Heating, temperature control is between 50-60 DEG C, and pressure is reacted under the conditions of being not higher than 0.6MPa, when reaction proceeds to about 2 hours Marvellous phenomenon is occurred in that suddenly：Muddy, opaque mixture moment becomes transparent or clear solution, continues to react 8 hours, Then 50 DEG C are cooled to, is that below 600 millimetress of mercury deviate from unnecessary water and unreacted expoxy propane in vacuum, cools Product is released after to less than 40 DEG C.Reaction time ensures that reaction is completed according to mol ratio.Obtain compound A-4.200 lis of viscosity Pool, pH=9.1, decomposition temperature is in 45-70 DEG C of scope.Liquid-phase chromatographic analysis and gas chromatographic analysis, show that compound A-4 is Include the mixture of a variety of hydramine.Water content is 20.5wt%.Infrared spectrogram is as shown in Figure 1.

Embodiment A-5

1.1 tons of aminoquinoxaline, 1.2 tons of water are added to the stainless steel pressure reactor with cooling water jecket In, dissolve under agitation, use nitrogen purge, 2.3 tons of expoxy propane is then added portionwise into reactor, Ran Houfeng Reactor is closed, stirring is started, is slowly heated up in the case where being stirred continuously, temperature control is between 45-70 DEG C, and pressure is not higher than 0.6MPa conditions Lower reaction 10 hours, then cools to 50 DEG C, is that below 600 millimetress of mercury deviate from unnecessary water in vacuum, cools to 40 Product is released after below DEG C.Obtain compound A-5.The centipoise of viscosity 200, pH=9, decomposition temperature is in 45-70 DEG C of scope.Liquid phase color Analysis of spectrum and gas chromatographic analysis, it is the mixture for including a variety of hydramine to show compound A-5.

Embodiment A-6

7kg ammonium carbonate and 7kg aminoquinoxaline, 15kg water are added in reactor, dissolved under agitation, is used Nitrogen purge, is then added portionwise 32kg expoxy propane, is slowly heated up in the case where being stirred continuously, temperature control is in 45-70 again Between DEG C, 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 Deviate from unnecessary water and unreacted expoxy propane below 600 millimetress of mercury, cool to and vacuum, releasing are bled off after less than 40 DEG C Product, that is, obtain compound A-6.The centipoise of viscosity about 250, pH=9, decomposition temperature is in 45-70 DEG C of scope.

Embodiment A-7

16kg carbamic acid monoethanolamine salt, 18kg water are added in reactor, nitrogen purge reactor is used, stirs Dissolving is mixed, 13kg 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-7.The centipoise of viscosity 280.PH=9.Decomposition temperature is in 45-70 DEG C of scope.

Embodiment A-8

21kg carbamic acid diethylenetriamines salt, 15kg water are added in reactor, stirring and dissolving uses nitrogen Purge, under agitation, control pressure are not higher than 0.6MPa, and 16kg 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-8.The centipoise of viscosity about 350.PH=9, decomposition temperature is in 45-70 DEG C of scope.

Embodiment A-9

1.2kg ammonium carbonate and 1.2kg aminoquinoxaline, 2.7kg water are added in reactor, it is molten under agitation Solution, uses nitrogen purge, then adds 7.1kg styrene oxide (styrene oxide, molecular weight 120.15), slowly heated up in the case where being stirred continuously, temperature control is between 45-70 DEG C, and control pressure is not higher than 0.6MPa, and reaction 10 is small When, 50 DEG C are then cooled to, temperature control is below 50 DEG C, and vacuum is to deviate from unnecessary water below 600 millimetress of mercury, is cooled to Vacuum is bled off after less than 40 DEG C, product is released, that is, obtains compound A-9.The centipoise of viscosity about 460, pH=9, decomposition temperature exists 45-70 DEG C of scope.

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

Embodiment B-1

The water of 16kg ammonium carbonate (molecular weight 96) and 15.5kg is added in reactor, stirring is started so that carbonic acid Ammonium dissolves, and uses nitrogen purge, adds 28kg expoxy propane, starts stirring, control pressure is not higher than 0.6MPa, not Slowly heated up under disconnected stirring, temperature control reacts 12 hours below 70 DEG C, reaction is completed, slowly reduce the temperature to control after 50 DEG C true Reciprocal of duty cycle slowly removes unnecessary water and unreacted expoxy propane below 600 millimetress of mercury, then bleeds off vacuum, cools to Reactant is released after less than 40 DEG C, compound is obtained and obtains compound B-1.The centipoise of viscosity about 300, pH=8.9, compound B- 1 decomposition temperature is 45-70 DEG C.Liquid-phase chromatographic analysis and gas chromatographic analysis, it is to include a variety of hydramine to show compound B-1 Mixture.With atomic absorption spectrophotometer (Seiko Instruments, Inc.；SAS/727 alkali metal and alkaline earth) are determined The content of metal ion is less than detectable limit.The mol ratio of gas chromatographic analysis, single Propanolamine and dipropanolamine is 1:0.28. Compound B-1 contains the salt of both about 79wt% single Propanolamine and dipropanolamine.Compound B-1 contains single the third of about 59wt% Hydramine and dipropanolamine (are analyzed residue after carbon dioxide) in heating compound A-1 with discharging, based on heating point The gross weight of compound B-1 before solution.

Embodiment B-2

0.95kg carbonic acid hydrazine, 0.8kg water are added in reactor, dissolving under agitation 30 minutes (allows to exist Undissolved aminoquinoxaline), nitrogen purge is used, 1.8kg expoxy propane is then added portionwise to transparent quartz 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 Under the conditions of reacted, when reaction proceed to about 2 it is small when or so return back out now marvellous phenomenon：Muddy, opaque mixture Moment becomes transparent or clear solution, continues to react 5 hours, then cools to 50 DEG C, is below 600 millimetress of mercury in vacuum Deviate from 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 by Completed according to mol ratio.Obtain compound B-2.PH=9.1, decomposition temperature is in 45-70 DEG C of scope.

Embodiment B-3

0.95kg carbonic acid hydrazine, 0.8kg water are added in reactor, dissolving under agitation 30 minutes (allows to exist Undissolved aminoquinoxaline), nitrogen purge is used, 1.3kg oxirane is then added portionwise to transparent quartz 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 Under the conditions of reacted, when reaction proceed to about 2 it is small when or so return back out now marvellous phenomenon：Muddy, opaque mixture Moment becomes transparent or clear solution, continues to react 5 hours, then cools to 50 DEG C, is below 600 millimetress of mercury in vacuum Deviate from the water and unreacted oxirane of a part, cool to and product is released after less than 40 DEG C.Reaction time ensure reaction by Completed according to mol ratio.Obtain compound B-3.PH=9.1, decomposition temperature is in 45-70 DEG C of scope.

Embodiment B-4

The water of 10kg ammonium carbonate, 11kg is added in transparent quartz glass reactor, stirring and dissolving is blown with nitrogen Reactor is swept, in the case where being stirred continuously, control temperature is between 45-70 DEG C, and control pressure is not higher than 0.6MPa, by 22kg epoxy Propane is added in reactor, adds the reaction of rear temperature control, when reaction proceed to about 2 it is small when or so when occur in that suddenly it is marvellous Phenomenon：Muddy, opaque mixture moment becomes transparent or clear solution, continues to react 8 hours, then cools to 50 DEG C, Control vacuum removes unnecessary water and unreacted expoxy propane under below 600mHg decompressions, is put after cooling to less than 40 DEG C Fall vacuum, release product.Obtain compound B-4.Viscosity is about 340 centipoises.PH=9.1.Decomposition temperature is in 45-70 ℃。

Embodiment B-5

10kg 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, 8.5kg 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 4.2kg titanium dioxide Carbon (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-5.Viscosity is about 360 centipoises.Decomposition temperature is in 45-75 DEG C of scope.

Embodiment B-6

10kg ammoniacal liquor (concentration 25wt%), 2.6kg ethylene glycol are added in reactor, is purged and reacted with nitrogen Device, starts stirring, and control pressure is not higher than 0.6MPa, and temperature is no more than 120 DEG C, 11.5kg expoxy propane is added portionwise, plus Complete rear temperature control reacts 2 hours.Cooled to after the completion of reaction and remove unnecessary water and unreacted expoxy propane after room temperature under reduced pressure, Carbon dioxide to the pH value for being passed through 3kg is 7.3 or so, and temperature control cools to room temperature below 80 DEG C after the completion of reaction.Obtain Compound B-6.Viscosity is about 420 centipoises.Decomposition temperature is in 45-75 DEG C of scope.

Embodiment B-7

The diethylenetriamine (molecular weight 103.17) of 12kg parts by weight, 16kg 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, 19kg 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 7kg is 7.5 or so, and 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 4kg ethylenediamine (molecular weight 60.12), 5.4kg 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 8kg carbon dioxides, room temperature reduced the temperature to after the completion of reaction, by all over products of acquisition and 11kg water is added in reactor together slowly to be dissolved under agitation, uses nitrogen purge, and control pressure is not higher than 0.6MPa, temperature is no more than under the conditions of 70 DEG C, and 30kg expoxy propane is added portionwise, and is added rear temperature control and is reacted 5 hours.React The water and unreacted expoxy propane for removing a part after room temperature under reduced pressure are cooled to after.Obtain compound B-8.PH=9.0, point Temperature is solved in 45-70 DEG C of scope.

Embodiment B-9

By 6.5kg diethylenetriamine (molecular weight：103.17), 2.5kg liquefied ammonia is added to special pressure-resistant blending tank In be well mixed, be then added to by the certain flow of pipe control in mixing reactor, control pressure is in 0.6MPa, control Temperature is less than 60 DEG C, is slowly mixed with 7.9kg carbon dioxides, room temperature is reduced the temperature to after the completion of reaction, by acquisition All over products and 12kg water are added in reactor slowly dissolve under agitation together, use nitrogen purge, control pressure Not higher than 0.6MPa, temperature is no more than under the conditions of 70 DEG C, and 24kg oxirane is added portionwise, and is added rear temperature control and is reacted 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 9kg diethylenetriamine (molecular weight：103.17), 4.5kg liquefied ammonia is added in special pressure-resistant blending tank It is well mixed, then it is added to by the certain flow of pipe control in mixing reactor, control pressure is in 0.6MPa, control temperature Spend for less than 60 DEG C, with 11kg carbon dioxides slowly hybrid reaction, room temperature is reduced the temperature to after the completion of reaction, by acquisition All over products and 18kg water are added in reactor slowly dissolve under agitation together, use nitrogen purge, control pressure Not higher than 0.6MPa, temperature is no more than under the conditions of 70 DEG C, 12kg oxirane and 20kg expoxy propane is added portionwise, after adding Temperature control reacts 5 hours.The water and unreacted oxirane and ring for removing a part after room temperature under reduced pressure are cooled to after the completion of reaction Ethylene Oxide.Obtain compound B-10.PH=9.0, decomposition temperature is in 45-70 DEG C of scope.

Embodiment B-11

By 8kg ethylenediamine (molecular weight 60.12), 4kg methylamine (molecular weight：31.10), 1.5kg 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, slowly mixes, is reduced the temperature to after the completion of reaction with 12kg carbon dioxides Room temperature, all over products of acquisition and 15kg water are added in reactor together and slowly dissolved under agitation, are 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, 32kg expoxy propane is added portionwise, after adding Temperature control reacts 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-11.PH=9.0, 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)Preparation 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.

Sample is taken, 100 times of observation abscesses are amplified using SEM after being cut into slices with blade.As shown in Figure 3, cell diameter is 208 Micron.

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 2 seems fine and smooth, uniform, fine and close, with good heat-insulating property, disclosure satisfy that refrigerator and The requirement of the various performances in refrigerator-freezer field.The product of embodiment 1 disclosure satisfy that the requirement of various performances in polyurethane pipe insulation.

Embodiment 3

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 4

Embodiment 4 repeats embodiment 2, 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 3 disclosure satisfy that the requirement of various performances in polyurethane pipe insulation.The product of embodiment 4 With good heat-insulating property, the requirement of the various performances in refrigerator and refrigerator-freezer field disclosure satisfy that.

Embodiment 5

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.

Comparative example 1

Embodiment 4 is repeated, simply foaming agent is used as only with the pentamethylene of 15 parts by weight.SEM photograph is as shown in Figure 4.

Table 4：The performance of polyurethane foam

Other application

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

Embodiment 6

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 5 (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 7

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 8 (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 2.

Embodiment 9 (Application Example)

It regard 20 parts by weight as the compound prepared by above example 8 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, compared with the foams of above-mentioned other embodiments, the abscess of the product of the present embodiment it is flat Equal diameter is bigger, illustrates that the amount of carbon dioxide gas is more.

Embodiment 10 (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, cools 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 11 (Application Example)

It regard 17 parts by weight as the compound prepared by above example 10 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.

4th, application of the carbonic acid polyalkylenepolyamines salt as foaming agent in the preparation of polystyrol foam material

Embodiment 12

By the polystyrene resin powder of 100 parts by weight, the diethylenetriamines carbonate of 6 parts by weight, particle mean size 175 The calcium carbonate of micron, the zinc stearate of 0.3 parts by weight, toner (the big prosperous board, the big prosperous limited public affairs of pigment in Shenzhen of 0.3 parts by weight Department production) input mixer mixed at a temperature of 30-40 DEG C of scope, acquisition foamed polystyrene composition, Ran Houli With single screw extrusion machine, (draw ratio of screw rod is 28:1) extrusion molding, each section of temperature of extruder be：One section 85 DEG C~95 DEG C, Two sections 95 DEG C~105 DEG C, three sections, 105 DEG C~115 DEG C, four sections 115 DEG C~125 DEG C；125 DEG C~130 DEG C of mold temperature；Screw rod Rotating speed is 5rpm~9rpm.The apparent density of the section bar obtained is 536kg/m³.It is identical with the product of embodiment 6, shone from SEM Piece (100 times of amplification) is as can be seen that the diameter of abscess is also than more uniform.

5th, application of the carbonic acid polyalkylenepolyamines salt as foaming agent in the preparation of polyvinyl-chloride foam material

Embodiment 13

By the polyvinyl chloride resin of 85 parts by weight, the carbonate of the dipropylenetriamine of 5 parts by weight, the polyethylene of 0.5 parts by weight Wax, the calcium carbonate that 175 microns of particle mean size, the zinc stearate of 0.3 parts by weight, toner (the big prosperous board, Shenzhen of 0.3 parts by weight Wei Chang pigment 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 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 of section；Mold temperature 195 DEG C~205 DEG C；Screw speed is 5rpm~9rpm.The proportion of the section bar obtained is 0.53g/cm³。

6th, application of the alkyl carbonate amine salt as foaming agent in the preparation of polystyrol foam material

Embodiment 14

By the polystyrene resin powder of 100 parts by weight, carbonic acid two (methyl amine) salt 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 25-35 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 498kg/m³.It is identical with the product of embodiment 6, from SEM photograph (amplification 100 times) it can be seen that, although abscess is relatively large in diameter, but the size of abscess is less uniform.Meanwhile, foam material One light ammonia taste is given out in material.This shows, although alkyl carbonate amine salt also can be used in foamed polystyrene, The uniformity of the size of abscess and the ammonia taste distributed determine alkyl carbonate amine salt to a certain extent in foamed material It is not preferred foaming agent.

Claims

1. the organic 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)；

(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-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, particularly preferred q=1-2.5, particularly preferred q=1.5-2.0, by being averaged for q Value is calculated；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, optionally replaced by hydroxyl or amino or halogen C₆-C₁₀Aromatic hydrocarbyl；

Wherein, lead to formula (I) compound or compound mixture contain 25-95wt% single methanol amine (for example MEA and/or Single Propanolamine) salt and glycol amine (such as diethanol amine, ethanol propanol amine and/or dipropanolamine) salt, based on logical formula (I) The gross weight of compound or compound mixture.

2. the organic alcohol amine salt compound with below general formula (I)：

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

B^m+Be or comprising：The ammonium ion of+1 valency and/or with m-⁺NR³R⁴H groups and/or-⁺NR³One kind of H- groups is more Plant organic amine B cation；

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

Wherein Aⁿ- it is the one or more in following anion：

(a) carbamic acid root：R¹R²N-COO^-；

(b) carbonate：CO₃ ^2-；

(c) formate：HCOO^-；

(d) bicarbonate radical：HO-COO^-；

(g)

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

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-；

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

4. the compound according to any one of claim 1-3, wherein A^n-It is two or more in (a)-(h) The combination of the anion or mixture, and/or B^m+It is combination or the mixture of two or more above-mentioned organic amine cations.

5. the compound according to any one of claim 1-4, 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.

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

7. the compound according to any one of claim 1-6, 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).

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

The water content of the logical formula (I) compound be 0-40wt%, more preferably preferably 5-35wt%, 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, the alkali metal and alkaline earth of its formula of (I) compound The content of metal is 0-200ppm (quality), and more preferably less than 100ppm, more preferably less than 10ppm are most preferably below detected The limit is 0ppm；And/or, wherein, except wherein Aⁿ- be formate logical formula (I) compound outside, lead to formula (I) it is other The pH of compound is 7.5-10, preferably 7.8-9.5, more preferably pH 8-9.

10. the compound according to any one of claim 1-9, wherein R are hydroxypropyls, i.e.,

HO-CH₂-CH₂(CH₃)-or HO-CH₂(CH₃)-CH₂-, ethoxy, and/or, hydroxyl chloropropyl.

11. the compound according to any one of claim 1-10, wherein A^n-It is one in following anion Plant or a variety of：

(b) carbonate：CO₃ ^2-；Or

(d) bicarbonate radical：HO-COO^-；

And/or

Wherein

12. the compound according to any one of claim 1-11, wherein, the compound or compound for leading to formula (I) are mixed Compound contains 27-90wt%, and preferably 30-85wt%, preferably 40-80wt%, more preferably 45-75wt% single methanol amine are (such as single Monoethanolamine and/or single Propanolamine) salt and glycol amine (such as diethanol amine, ethanol propanol amine and/or dipropanolamine) salt, base In the compound or the gross weight of compound mixture of 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；And/or

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, ethanol propanol amine and/or dipropanolamine), the gross weight of compound or compound mixture based on logical formula (I).

13. prepare the method for the compound of the logical formula (I) of any one in claim 1-12, 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 water In, optionally in the presence of a catalyst, reacted, 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%, more preferably 110-160wt%；

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 hydrazine 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.

14. method according to claim 13, 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.

15. prepare the method for the compound of the logical formula (I) of any one in claim 1-12, 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 consumption of water is the 90-250wt%, preferably 100- calculated based on the weight of orthoformic acid ester type compound 220wt%, more preferably 110-200wt%, more preferably 120-180wt%；

Wherein organic amine compound B is organic amine compound (M), ammonia and/or hydrazine as initiation material or as initiator Reacted what is formed with epoxides, one or more of the epoxides in these following epoxides：

Or styrene oxide.

16. method according to claim 15, 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.

17. the compound prepared as the method described in claim 13 or 14；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, ethanol propanol amine and/or dipropanolamine) salt, based on change The gross weight of compound, 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, ethanol propanol amine and/or dipropanolamine), the gross weight based on compound.

18. the compound prepared as the method described in claim 15 or 16；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, ethanol propanol amine and/or dipropanolamine) salt, based on change The gross weight of compound, 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, ethanol propanol amine and/or dipropanolamine), the gross weight based on compound.

19. a kind of foaming agent, it includes the organic alcohol amine with logical formula (I) according to any one of claim 1-12 Salt compound or organic alcohol amine salt compound mixture, or as there is formula according to any one of claim 1-12 (I) organic amine alkoxide cpd or organic alcohol amine salt compound mixture is constituted.

20. a kind of foaming agent, it includes compound according to claim 17 and/or compound according to claim 18.

21. the foaming agent according to claim 19 or 20, it is used as polyurethane foams, foamed polystyrene agent or polychlorostyrene Ethene foaming agent.

22. the organic alcohol amine salt compound or Organic Alcohol with logical formula (I) according to any one of claim 1-12 Amine salt compound mixture as polyurethane foams, foamed polystyrene agent or foam polyvinyl chloride agent purposes.

23. the organic amine alkoxide cpd or Organic Alcohol with logical formula (I) according to any one of claim 1-12 Amine salt compound mixture is used as the purposes of foamed polystyrene agent or foam polyvinyl chloride agent, wherein Aⁿ- it is selected from following One or more in anion：

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

24. polyurethane foamed composite thing, it is included：

The 0.01-100 weight % organic alcohol amine salinization with logical formula (I) according to any one of claim 1-12 Compound or organic alcohol amine salt compound mixture, or compound according to claim 17 or chemical combination according to claim 18 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.

25. polyurethane foamed composite thing according to claim 24, 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 organic alcohol amine salt chemical combination with logical formula (I) according to any one of claim 1-12 Thing or organic alcohol amine salt compound mixture, or compound according to claim 17 or compound according to claim 18；

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.

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

27. the polyurethane foamed composite thing according to any one of claim 24-26, 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 24-27, 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 24-29 Monomer and/or isocyanate-terminated prepolymer react and formed after being mixed.

Carbonic acid two 31. (ethylol amine) salt, carbonic acid two (hydroxypropyl amine) salt, bicarbonate (ethylol amine) salt, bicarbonate (hydroxypropyl Amine) salt, carbonic acid (ethylol amine) (hydroxypropyl amine) salt, the carbonate of diethylenetriamines, the carbonate of trien, four The carbonate of the amine of ethylidene five, the carbonate of dipropylenetriamine, the carbonate of tri propylidene tetramine or 4 sub-propyl-5-amine One or more mixtures in carbonate are as the purposes of foaming agent, and they are used for foamed polystyrene or polyvinyl chloride is sent out Bubble.

32. one or more mixtures in the alkyl carbonate amine salt of below general formula are as the purposes of foaming agent, they are used for Foamed polystyrene or foam polyvinyl chloride：

(R¹NH₂)₂CO₃,

(R¹R²NH)₂CO₃,

(R¹NH₂)(R¹R²NH)₂CO₃,

(R¹NH₂)HCO₃, or

(R¹R²NH)HCO₃,

In formula, R¹Or R²May be the same or different, and be independently of one another methyl, ethyl, propyl group, butyl, hexyl, cyclopropyl or Cyclohexyl.

Carbonic acid two 33. (methyl amine) salt, carbonic acid two (dimethyl amine) salt, carbonic acid (methyl amine) (dimethyl amine) salt, (second of carbonic acid two Base amine) salt, carbonic acid two (diethylamide) salt, carbonic acid (ethylamine) (diethylamide) salt, carbonic acid two (propyl group amine) salt, carbonic acid two (dipropylamine) salt, carbonic acid (propyl group amine) (dipropylamine) salt, bicarbonate (methyl amine) salt, bicarbonate (ethylamine) salt, carbonic acid Hydrogen (propyl group amine) salt, carbonic acid (methyl amine) (ethylamine) salt, carbonic acid (methyl amine) (propyl group amine) salt, carbonic acid (ethylamine) (propyl group Amine) salt, carbonic acid (methyl amine) (diethylamide) salt, carbonic acid (ethylamine) (dimethyl amine) salt, carbonic acid (methyl amine) (dipropyl Amine) salt, carbonic acid (propyl group amine) (dimethyl amine) salt, carbonic acid (ethylamine) (dipropylamine) salt, carbonic acid (propyl group amine) (diethyl Amine) salt, carbonic acid (dimethyl amine) (diethylamide) salt, carbonic acid (dimethyl amine) (dipropylamine) salt or carbonic acid (diethylamide) One or more mixtures in (dipropylamine) salt are as the purposes of foaming agent, and they are used for foamed polystyrene or polychlorostyrene Ethene foams.