CN109422906A - Ethanol amine alkalinity foaming agent and the purposes for being used to prepare polyurethane solar energy foam-body material - Google Patents

Ethanol amine alkalinity foaming agent and the purposes for being used to prepare polyurethane solar energy foam-body material Download PDF

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CN109422906A
CN109422906A CN201710734906.XA CN201710734906A CN109422906A CN 109422906 A CN109422906 A CN 109422906A CN 201710734906 A CN201710734906 A CN 201710734906A CN 109422906 A CN109422906 A CN 109422906A
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compound
amine
foaming agent
preferable
weight
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CN109422906B (en
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毕戈华
毕玉遂
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Sky New Material Technology Co Ltd
Shandong University of Technology
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Sky New Material Technology Co Ltd
Shandong University of Technology
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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Abstract

Ethanol amine alkalinity foaming agent and the purposes for being used to prepare polyurethane solar energy foam-body material.Disclose a kind of polyurethane alkalinity foaming agent comprising primary amine salt and ethanolamine salt, the pH value of the alkalinity foaming agent is between 8.5-9.5, which includes: the first compound mixture (M1) 1) comprising the organic primary amine salt compound class with following general formula (I): A‑[B+]p(I), wherein B+It is the cation of the organic primary amine B of+1 valence, A‑It is: CO3 2‑, HCO3 ‑Or CO3 2‑With HCO3 ‑Conjugate；2) comprising the mono- ethoxy-ammonium carbonate compound of N- with logical formula (II) and the N with logical formula (II), second of compound mixture of N'- bis- (ethoxy)-ammonium carbonate compound (M2): (RN+H3)(N+H4)CO3 2‑Or (RN (II),+H3)2CO3 2‑(III), in formula, R is ethoxy；The molar ratio of the compound of the compound and logical formula (III) of logical formula (II) is 1:0 to 1:1.0.Foaming agent is suitable for preparing polyurethane solar energy foam-body material.

Description

Ethanol amine alkalinity foaming agent and it is used to prepare polyurethane solar energy foam-body material Purposes
Technical field
The present invention relates to have to be used as CO2Purposes of the organic amine salt compound of the anion of donor as foaming agent, more CO is used as specifically, providing and not only having2The anion of donor and organic primary amine are as catalytic group and solubilizing group Novel organic ammonium salt compounds are preparing the application in polyurethane solar energy foam-body material.More specifically to alkalinity Ethanol amine foaming agent and the purposes for being used to prepare polyurethane solar energy foam-body material.
Technical background
For hard polyurethane foam as a kind of macromolecule new material, it is excellent that light weight, intensity are high and have extremely low thermal conductivity 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 vehicle, refrigerator ice cabinet.Most important raw material is foaming agent in hard polyurethane foam production.These foaming agents remove at present All be chlorofluorocarbon substance other than pentamethylene, due to they to the destruction of atmospheric ozone layer so national governments sign already The international convention of " Montreal Protocol book " limits and is phased out, forbids the production and use of such product, and China is also should 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 countries such as America and Europe are forbidden to use HCFC-141b already, and Chinese Government just freezes the consumption figure of HCFC-141b for 2013 Knot in 2009 and 2010 levels of consumption, 2015 eliminate freeze 20% consumption figure, and promise be advanced to 2025 Total ban production and use, the developed countries such as current America and Europe use third generation blowing agents pentafluoropropane (HFC-245fa) It is all very high with the GWP (chamber effect potential value) of 3-pentafluorobutane (HFC-365mfc), second and third generation foaming agent, to atmospheric ozone The destruction of layer is serious, therefore the American-European use that will forbid third generation blowing agents before 2017.U.S. Honeywell is public thus Department has developed forth generation physical blowing agent chlorotrifluoropropylene (LBA), but the valuable product again, and ODP is (to ozone layer The latent energy value of destruction) it is zero, it is more relatively environment-friendly than the third generation, it is single expensive.These physics hair other than pentamethylene in a word Chlorine fluorine element is directed in infusion itself and production process, environmental issue is still difficult to thoroughly solve, 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 polyester polyol and/or polyether polyol 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 effect and solubility of the water in polyester polyol and/or polyether polyol are 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 foamed material.If made with water For foaming agent, then includes more urea bond in polyurethane foamed material, largely effect on the intensity and heat-insulating property of foamed material. In addition, if the dosage of the water as foaming agent improves slightly, then the performance and size of polyurethane foam can be significantly impacted Stability.If polyurethane foam, which is known from experience, meets with asking for contraction, incipient scorch and poor insulation property using water as unique foaming agent It inscribes (shrinkage, scorching, inadequate heat insulation).
In short, foaming agent in the prior art can not be dispersed in composition, foam with molecular level, to cause to steep The size for being unevenly distributed uniform abscess in hole is uneven, eventually affects the strength character and thermal insulating properties of foamed material.
Summary of the invention
To overcome disadvantage existing in the 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.
The object of the present invention is to provide not only have to be used as CO2The anion of donor and have the group conduct of machine primary amine groups The novel organic ammonium salt compounds of solubilizing group, and its answering in foamed material such as polyurethane solar energy foam-body material With.
The novel organic ammonium salt compounds are suitable as foaming agent.It generates CO in foaming process2Gas.The application Inventor it was unexpectedly observed that as CO2The anion with-n valence of donor is easy to decompose at elevated temperatures to generate CO2 Gas, or even when being foamed at a lower temperature, it is described below to be used as CO2The anion with-n valence of donor can It is activated by isocyanate-monomer NCO group as contained by MDI and TDI, quick release goes out CO2Gas.In addition, due to having solubilising Group, enable foaming agent be substantially soluble in foaming raw material (such as polyether polyol or polyester polyol) or with foaming raw material it Between have a good intersolubility, foaming agent of the invention can be homogeneously dispersed in equably to foam in composition, foam, The distribution of abscess is also relatively uniform in polyurethane foam, and the size of abscess is relatively uniform.In addition, the first of the invention Compound mixture (M1) contains primary amine groups, the first compound mixture (M1) as foaming agent releases CO in decomposition2 Generated decomposition product is primary amino-compound later, they are suitable as catalysts for polyurethanes applied in material.Therefore, Based on above-mentioned two aspect, the present invention is completed.
In this application, " as CO2The anion of donor " refers in case of heating or can in foaming process It decomposes and releases CO2Anion.
According to the first embodiment of the present invention, a kind of alkaline hydramine foaming comprising primary amine salt and ethanolamine salt is provided Agent, the pH value of the alkalinity foaming agent are between 8.5-9.5.Due to having alkalinity, foaming activity is high, is suitable for fast foaming, Therefore it is suitble to foam while constructing outdoors suitable for polyurethane solar energy foam-body material is prepared.The foaming agent Include:
1) the first compound mixture (M1) comprising the organic primary amine salt compound class with following general formula (I):
A-[B+]p (I)
Wherein, B+It is the cation of the organic primary amine B of+1 valence, A-It is: CO3 2-, HCO3 -Or CO3 2-With HCO3 -Conjugate； P is in A-For HCO3 -In the case where for 1, p in A-For CO3 2-In the case where be 2；
2) comprising the mono- ethoxy-ammonium carbonate compound of N- with logical formula (II) and N, N'- bis- with logical formula (III) Second of compound mixture (M2) of (ethoxy)-ammonium carbonate compound, i.e., a kind of alcohol amine salt compound mixture,
(RN+H3)(N+H4)CO3 2-Or (RN (II),+H3)2CO3 2-(III),
In formula, R is ethoxy；
The molar ratio of the compound of the compound and logical formula (III) of logical formula (II) is 1:0 to 1:1.Preferably 1:0 to 1: 0.5, more preferably 1:0.1 to 1:0.3.
For compound mixture (M1), it is preferred that A-It is: CO3 2-Or CO3 2-With HCO3 -Conjugate；P is in A-For HCO3 -In the case where for 1, p in A-For CO3 2-In the case where be 2.
It is preferred that the first compound mixture (M1) be by organic primary amine B in presence of water with CO2Made from reaction； Still it is enough to avoid generating carbaminate it is further preferred that the amount of water is as few as possible in the reactive mixture.That is the dosage of water So that the first compound mixture (M1) obtained is rendered as slurry state or saturated solution state, preferably slurry state (i.e. some carbonate is undissolved).
Generally, second of compound mixture (M2) is obtained by the following method: adding or do not adding ammonium hydroxide In the case of, it is 1:1-5.5 (preferably 1:1.3-5), Xiang You according to the molar ratio of ammonium carbonate and/or aminoquinoxaline and ethylene oxide Ammonium carbonate and/or aminoquinoxaline and water, which are formed by slurry or saturated solution, is added ethylene oxide to allow reaction mixture It is reacted, [then, optionally, from being formed by the water and unreacted for vacuumizing removing a part in reaction mixture Ethylene oxide], obtaining aqueous organic alcohol amine mixture, (general, its pH is 7.5-10, preferably pH 8-9.7, preferably pH 8.3-9.6, preferably pH 8.2-9.6, more preferable pH 8.5-9.5, such as pH=9), i.e. second of compound mixture (M2)。
In this application, " optionally " indicate carry out or without.
It is preferred that the first compound mixture (M1) and the weight ratio of second of compound mixture (M2) are 0.3-1: 1, more preferable 0.5-0.8:1, more preferable 0.6-0.7:1.
It is preferred that in the compound of logical formula (I) or in the first compound mixture (M1), organic primary amine compound B In the 50-100% of amido neutralized by anion A-, the 65-100% of the amido in preferably organic amine compound B is by anion A- is neutralized；It is further preferred that the 75-100% of the amido in organic amine compound B is neutralized by anion A-；It is further preferred that organic amine chemical combination The 75-90% of amido in object B is neutralized by anion A-.
The first compound mixture (M1) or second of respective water content of compound mixture (M2) are (respective) independent Ground is 2-40wt%, preferably 5-35wt%, more preferable 10-30wt%, more preferable 15-25wt%.
It is preferred that the pH of the first compound mixture (M1) is 7.0-8.8, preferably pH 7.3-8.6, more preferable pH 7.5-8.5。
It is preferred that the pH of second of compound mixture (M2) is 8.6-10, preferably 8.7-9.5, more preferable pH 8.8-9.3.
It is preferred that organic primary amine B is one or more among following:
C1-C24Primary hydrocarbyl amine class.Such as organic primary amine B is to be selected from methylamine, ethamine, propylamine, butylamine, amylamine, oneself Base 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), unsubstituted or substituted (such as halogen takes Generation) benzyl amine, cyclo-hexylamine, methylcyclohexyl amine, cyclohexyl methyl amine, in N- methylcyclohexyl amine and N- methylbenzylamine It is one or more.
According to another aspect of the present invention, the first compound for providing the compound comprising above-mentioned logical formula (I) is mixed Close object (M1) preparation method, this method comprises: by organic primary amine in presence of water with CO2Reaction is made.Reaction temperature is logical It is often 40-65 DEG C, preferably 45-60 DEG C, reaction pressure is 0.3MPa hereinafter, such as 0.1-0.2MPa, reaction time 6-20 hour, It is preferred that 8-12 hours.The dosage of water makes the water content of the first compound mixture (M1) be 2-40wt%, preferably 5- 35wt%, more preferable 10-30wt%, more preferable 15-25wt%.
The organic primary amine is those as described above.
Preferably, in above-mentioned second of compound mixture (M2) (that is, aqueous organic alcohol amine mixture), general formula (II) the sum of both compounds of compound and logical formula (III) weight accounts for the total weight of second of compound mixture (M2) 56-96wt%, more preferable 63-90wt%, further preferred 70-86wt%.
It is preferred that the water content of second of compound mixture (M2) is 2-40wt%, preferably 6-35wt%, more preferable 10- 30wt%, more preferable 15-25wt%.
Generally, in the preparation method of above-mentioned second of compound mixture (M2), using ammonium hydroxide (such as concentration 20- 28wt%, such as 25wt%) it is used as catalyst.The dosage of the ammonium hydroxide is total weight (or the gross weight of all raw materials of reaction mixture Amount) 0.5-7wt%, preferably 0.8-5wt%, preferably 1.0-3wt%.
According to the third aspect of the invention we, the composition of polyurethane foam is provided, that is, polyurethane foamed composite object.
The composition includes: 0.5-100 weight % (more preferable 2-80wt%, more preferable 4-60wt%, more preferable 6- 40wt%, such as 8wt%, 10wt%, 15wt% or 20wt%) above-described foaming agent；The physical blowing of 0-50 weight % Agent；0-5 weight % water and 0.0-99.5 weight % (preferably 20.0-98.0 weight %, more preferable 40-96wt%, more preferably 60-94wt%, more preferable 70-88wt%, more preferable 75-85wt%) polymer polyatomic alcohol；Wherein, the weight percent Total weight based on polyurethane foamed composite object.
It is preferred that the polymer polyatomic alcohol is selected from: polyether polyol, polyester polyol, polyether-polyester polyol, poly- carbon Acid esters glycol, polycarbonate-polyester polyalcohol, polycarbonate-polyether polyol, polybutadiene polyol or polysiloxanes are polynary Alcohol, and the average functionality of polymer polyatomic alcohol is generally 2-16, preferably 2.5-10, more preferable 3-8.
It is preferred that the physical blowing agent at least one of is selected from the group: pentane, isopentane, pentamethylene, boiling point is in 0- Other alkane within the scope of 100 DEG C, HCFC-141b, HFC-245fa, HFC-365mfc, LBA, FEA-1100, boiling point is in 0-100 Other fluorochlorohydrocarbons or organosilane ester within the scope of DEG C.
According to the fourth aspect of the invention, above-mentioned alkaline foaming agent is provided for (preparation) polyurethane solar energy foams material Purposes in material.
Present inventor is it was unexpectedly observed that the compound of above-mentioned logical formula (II) and the compound of logical formula (III) have Suitable decomposition temperature (generally in 55-70 DEG C of range, preferably in 58-65 DEG C of range) is easy to decompose at elevated temperatures to produce It, can be by isocyanate-monomer NCO as contained by MDI and TDI when giving birth to CO2 gas, or even being foamed at a lower temperature Group activation, quick release go out CO2 gas.In addition, due to solubilizing group N- ethoxy, the compound and foaming raw material (such as polyether polyol or polyester polyol) sufficiently dissolves each other, and can be homogeneously dispersed in composition, foam and equably foam, make The polyurethane foam that must be prepared has highly uniform distribution of cells and abscess-size.
In addition, the compound of logical formula (II) of the invention and the compound of logical formula (III) contain hydroxyl and amido simultaneously, That is it is organic alcohol amine carbonate.CO is released in decomposition2Generated decomposition product (i.e. alcohol amine compound) is still later So contain hydroxyl and amino, can be used as the chain extender or crosslinking agent in foamable reaction.That is, logical formula (II) of the invention Compound and the compound existing " foaming effect " of logical formula (III) have " chain extension " or " crosslinking " effect again, lead to polyurethane foam Body has good dimensional stability, and especially long-term dimensional stability is placed 1 year under environmental condition indoors, do not sent out Contracting is spoilt in the distinguishable deformation of raw meat eye.
Second of compound mixture (M2) of the invention, i.e. one kind comprising N- hydroxyethylation ammonium carbonate salts compound contain Water organic alcohol amine mixture, by being heated to 70 DEG C of a large amount of carbon dioxide of release, then, remaining alcohol amine compound carries out gas Analysis of hplc measures the mono- ethoxy-ammonium carbonate of N- and N, N'- bis- (ethoxy)-carbonic acid in reaction product (i.e. mixture M 2) The molar ratio of ammonium compounds is in 1:0 to 1:2.5 range, preferably 1:0.3 to 1:2, preferably 1:0.5 to 1:1 range.
Above-described logical formula (I) compound is that have as CO2The organic amine salt compounds of the anion of donor.
It is preferred that the polyurethane foamed composite object further includes: foam stabiliser, catalyst etc..These auxiliary agents are It is common in polyurethane solar energy foam-body material or polyurethane refrigerator ice cabinet field, and with the use of common amount.
It is preferred that the physical blowing agent at least one of is selected from the group: pentane, isopentane, pentamethylene, boiling point is in 0- Other alkane within the scope of 100 DEG C, HCFC-141b, HFC-245fa, HFC-365mfc, LBA, FEA-1100, boiling point is in 0-100 Other fluorochlorohydrocarbons within the scope of DEG C, organosilane ester etc..
Present inventor is surprised to find that the compound of above-mentioned logical formula (II) and compound and the foaming of logical formula (III) Compatibility or compatibility between polyester polyol and/or polyether polyol is very good, forms clear and bright homogeneous system.Especially It is found surprisingly that, when the first mixture (M1) is separately as foaming agent it and polyester polyol and/or polyether polyol it Between compatibility or compatibility it is not satisfactory, still, mix acquisition with second of mixture (M2) in the first mixture (M1) Mixture as foaming agent when, which can have good between the polyester polyol and/or polyether polyol of foaming Therefore good compatibility or compatibility can equally ensure to form abscess of uniform size in polyurethane foam material.? A kind of mixture (M1) have catalytic action and itself there are also foaming effects.That is, in second of compound mixture (M2) under medium, compatibility of the first compound mixture (M1) in polyester polyol and/or polyether polyol or point Scattered property is significantly improved.
Generally, although hard polyurethane foam composition of the invention is transparent or clear or opaque equal Even.This shows foaming agent dissolution of the present invention or is dispersed in polyether polyol or polyester polyol.It is especially more with polyester First alcohol is compared, when Primary resins group timesharing of the polyether polyol as foaming, foaming agent of the invention and polyether polyol Compatibility is very good, and foaming agent can be scattered in polyether polyol with molecular level.
Polyurethane foamed composite object (being commonly called as " white material ") of the invention has the feature that 1, comprising amine salt compound (example Such as, the compound for leading to formula (I) discharges CO after pyrolysis2, while remaining primary amine compound)；2, transparent or clarification or cream White；3, it is released in the case where heating (such as 40-80 DEG C temperature) or in the case where adding sour (inorganic acid or organic acid) Release CO2, peak decomposition temperature is usually between 45-65 DEG C；4, when composition, foam (i.e. " white material ") and isocyanates or When polyisocyanates (such as MDI or TDI) contact or mixing, mixed material moment (such as 0.2-4 seconds, such as 1-2 seconds) becomes cream White.In the present invention, material becomes rapidly milky, is accompanied by volume rapid expanding phenomenon, but this process and non-foam real Starting, material just starts starting later.In contrast, using water, or when using water and physical blowing agent as foaming agent, foam Milky white and starting be carry out simultaneously and be all delay.
Although in the present invention, composition, foam (" white material ") may include a small amount of water as blowing promotor, due to Logical formula (I) of the invention, (II) and (III) compound preferentially decompose release CO2, i.e., preferential foaming, therefore, the addition of a small amount of water Foaming process is not influenced or does not influence polyurethane foam end properties；That is being in some cases can be mixed with water What conjunction used.
The present invention provides the method for preparing polyurethane solar energy foam-body material, this method is included in polyurethane preparation Introduce be based on urethane raw total weight (including isocyanates and polyalcohol) 1-10%, above-mentioned organic the primary of preferably 2-5% Amine salt compound or organic primary amine salt compound mixture.
The present invention also provides above-mentioned organic primary amine salt compounds or organic primary amine salt compound mixture to send out for (preparation) Purposes in foam material such as polyurethane solar energy foam-body material.
Advantageous effects or advantage of the invention
1, logical formula (I) of the invention, (II) or (III) compound or foaming agent of the present invention have suitable decomposition temperature (50-70 DEG C), or there is suitable decomposition temperature when touching isocyanates, on the one hand storage is stablized at room temperature, another Aspect during polyurethane foam when foamable reaction system heats up can with reasonable speed carbon dioxide gas, with So that foamed material has ideal performance, such as the distribution density of abscess, the dimensional homogeneity of abscess.Alkalinity is conducive to improve hair Bubble activity, fast foaming, therefore it is suitable for the construction foaming of field polyurethane.
2, logical formula (II) of the invention or (III) compound have solubilizing group, that is, alcohol amine groups, the compound (II) or (III) polymer polyatomic alcohol such as polyether polyol and/or polyester polyol can be equably dissolved or are distributed in molecular level, Ensure the uniformity to foam, local excessive is avoided to foam.
3, logical formula (I) compound of the invention is the carbonate of primary amino-compound, is released in the compound (I) decomposition CO2Generated decomposition product, that is, primary amino-compound still contains at least two reactive hydrogens, and logical formula (II) or (III) later Compound decomposition releases CO2Decomposition product alcohol amine compound is generated later, and primary amino-compound and alcohol amine compound are suitable for making For chain extender and/or crosslinking agent, logical formula (I) of the invention, (II) and (III) compound, which were not only used as " blow point " but also were used as, " to be expanded Chain point " and/or " crosslinking points " significantly enhance the mechanical strength and mechanical strength of abscess, polyurethane foam tool obtained Have a good dimensional stability, polyurethane foam finished product after placing some months, even 1 year naked eyes almost without observing Shrinkage phenomenon, without collapse bubble or collapse phenomenon.Long period such as (10 days) are placed especially under higher temperature (such as 40-70 DEG C) Still there is good dimensional stability later.
4, it when logical formula (I) compound of the invention is the compound with primary amine group, decomposes and discharges in the compound (I) CO out2Generated decomposition product, that is, primary amino-compound later, they are suitable as catalyst, logical formula (I) chemical combination of the invention Object was not only used as " blow point " but also as catalyst.
5, logical formula (I) compound of the invention is not allowed volatile, and (metal ion does not have corruption to metal base to metal ion 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.
6, when being used as foaming agent with chlorofluorocarbons such as HCFC-141b or HFC-365mfc mixing, with exclusive use chlorofluorocarbons Foaming agent is compared, and the heat-insulating property of foamed material can be significantly improved.Currently, usually being sent out around foaming agent or specific chlorofluorocarbons Infusion come select to related foaming agent intersolubility or the preferable special polyether polyalcohol of compatibility, and use foaming of the invention Agent, without selecting specific polyether polyol or polyester polyol, usage range is extensive, is able to use in composition, foam each The polyester polyol and/or polyether polyol of seed type.On the other hand, if selection is suitble to polyurethane foam prepared by the present invention The auxiliary agents such as the polyethers of agent can obtain better performance.
7, compared with prior art, polyurethane foams provided by the invention is free of chlorine fluorine element, and ODP is (to ozone layer The latent energy value of destruction) it is that 0, GWP (chamber effect potential value) is equal to 1, it is most environmentally friendly polyurethane foams, performance is more excellent Good, cryogenic property is extremely excellent, through detecting the existing best physical blowing of thermal conductivity ratio at subzero 160 degrees Celsius Agent low 20% or so, this excellent characteristic can be used for the heat preservation of natural gas long-distance transportation pipeline.Poly- ammonia provided by the invention The alternative existing all physical blowing agents containing halogens of ester foaming agent, meet the life of polyurethane solar energy foam-body material Produce application.
8, use foaming agent of the present invention or logical formula (I), (II) and (III) compound as polyurethane foam prepared by foaming agent The size changing rate or shrinking percentage of foam material (this foamed material is to be made in laboratory self-control Fang Mo of stirring by hand)≤ 10%, preferably≤5%, more preferably≤1% (according to chinese national standard GB/T 8811-2008, standing time can be according to the mark It is required in standard, or even, standing time is 5 months).In addition, for example in 34-42Kg/m3Density foam under, thermally conductive system Number w/mk (10 DEG C) is between 0.01900-0.02200, preferably between 0.01910-0.02150.In addition, close herein It spends in range, the compressive strength of foams of the present invention is in 110-220Kpa range.
Detailed description of the invention
Fig. 1 is the SEM of the polyurethane foamed material of embodiment 1.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
In this application, it is used to prepare polyurethane foam or pure and mild poly- for the common polyether polyols in composition, foam Ester polyol is selected from following kinds: polyethers 4110,450,400A, MN500, SU380, SA380,403, SA460, G350；Polyester CF6320,DM2003,YD6004,AKS7004,CF6255.Custom catalysts are selected from: 33LV (A-33): 33% triethylene diamine Dipropylene glycol solution, N, N- dimethylethanolamine, N, the dipropyl two of N- dimethyl benzylamine, 70% bis- (dimethylamino ethyl) ethers Alcoholic solution, 70% potassium octanoate are in diethylene glycol solution, dibutyl tin dilaurate, PT303, PT304, potassium acetate, PC-8 (N, N- Dimethyl cyclohexyl amine), PC-5, PC-41, triethanolamine, JXP-508, JXP-509, TMR-2, TMR-3, TMR-4.Common silane Surfactant: 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.
Below with reference to embodiment, the present invention will be further described.
In this application, it is used to prepare polyurethane foam or pure and mild poly- for the common polyether polyols in composition, foam Ester polyol is to be usually used in those of polyurethane foamed material in the prior art.For catalysts for polyurethanes and surfactant, Auxiliary agent commonly used in the prior art can be used.
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 coefficient 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.Apparently (core) density is tested according to GB/T 6343-2009.Compressive strength according to GB/T 8813-2008 into Row test.
For compound containing in second of compound mixture (M2) of logical formula (II) or (III) as foaming agent The measurement method of amount first passes through and mixture (M2) is heated to 70 DEG C or more discharges carbon dioxide, residue (i.e. alcohol amine compounds Object) use gas chromatography.Wherein gas chromatograph is furnished with flame ionization ditector (FID), the matter for the immunomodulator compounds that foam Measuring concentration is about 10mg/mL.GC conditions: HP-5 capillary chromatographic column (i.d. × 0.25 μm 30m × 0.32mm, 5%phenyl methyl-siloxane)；Column temperature is temperature programming, and initial temperature is 80 DEG C, with 25 DEG C/min after holding 3min Rate rise to 250 DEG C, 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 30mL/min；Combustion-supporting gas is air, flow velocity 300mL/min；Make-up gas is nitrogen Gas, flow velocity 25mL/min；Input mode is split sampling, split ratio: 30:1；Sample volume is 1 μ L.
Preparation example 1
40% methylamine water solution (molecular weight 31) of 3kg is added in transparent quartz glass reactor, stirring and dissolving, Reactor is sealed, then under constant stirring, temperature is controlled between 40-65 DEG C, carbon dioxide is passed into reactor, control Pressing pressure is not higher than 0.3MPa, and temperature control reacts 10 hours, and pressure is bled off after cooling to 40 DEG C or less, releases product.It obtains Compound 1.PH >=8.0, decomposition temperature is at 42 DEG C -70 DEG C.
Preparation example 2
70% ethylamine solution (molecular weight 45) of 3kg is added in transparent quartz glass reactor, stirring and dissolving, Reactor is sealed, then under constant stirring, temperature is controlled between 40-65 DEG C, carbon dioxide is passed into reactor, control Pressing pressure is not higher than 0.3MPa, and temperature control reacts 10 hours, and pressure is bled off after cooling to 40 DEG C or less, releases product.It obtains Compound 2.PH >=8.2, decomposition temperature is at 42 DEG C -70 DEG C.
Preparation example 3
The water of the hexyl amine (molecular weight 101) of 3kg, 1.6kg are added in transparent quartz glass reactor, stirred molten Solution seals reactor, then under constant stirring, controls temperature between 40-65 DEG C, carbon dioxide is passed into reactor In, control pressure is not higher than 0.3MPa, and temperature control reacts 10 hours, and pressure is bled off after cooling to 40 DEG C or less, releases product. Obtain compound 3.PH >=8.2, decomposition temperature is at 42 DEG C -70 DEG C.
Preparation example 4
Cyclohexylamine (molecular weight 99), the 1.6kg water of 3kg are added in transparent quartz glass reactor, stirring and dissolving, Reactor is sealed, then under constant stirring, temperature is controlled between 40-65 DEG C, carbon dioxide is passed into reactor, control Pressing pressure is not higher than 0.3MPa, and temperature control reacts 10 hours, and pressure is bled off after cooling to 40 DEG C or less, releases product.It obtains Compound 4.PH >=8.2, decomposition temperature is at 42 DEG C -70 DEG C.
Preparation example 5
The water of the ammonium carbonate (molecular weight 96) of 1.4kg, 1kg are added in stainless steel reactor, stirring is started, forms carbon The ethylene oxide of 1.7kg is then added in slurry (ammonium carbonate is not completely dissolved) in sour ammonium, cools down in stirring, control pressure is not high In 0.6MPa, slowly temperature reaction, control temperature is consistently lower than 60 DEG C and reacts 14 hours.After the reaction was completed, temperature is slowly reduced To 50 DEG C hereinafter, slowly removing the water and unreacted ethylene oxide of a part under the vacuum degree of 600 millimetress of mercury or so, so After discharge vacuum, cool to and reactants be discharged after 40 DEG C or less, obtain aqueous carbonate polyol amine salt compound mixture (abbreviationization Close object 5), belong to one of second of compound mixture M2.About 376 centipoise of viscosity, pH=9.2, the decomposition of compound 5 Temperature is 58-63 DEG C.With atomic absorption spectrophotometer (Seiko Instruments, Inc.；SAS/727 alkali metal) is measured Content with alkaline-earth metal ions is lower than detectable limit.
Gas chromatographic analysis shows that compound 5 is that the mixture comprising a variety of hydramine (is referred to as second of change in this application Polymer mixtures M2), the wherein mono- ethoxy-ammonium carbonate of N- and N, N'- bis- (ethoxy)-carbon in reaction product (i.e. mixture M 2) The molar ratio of sour ammonium compounds is about 1:0.36.
By infrared spectrum analysis, second of compound mixture obtained is reacted by ammonium carbonate and ethylene oxide (M2) the N- hydroxyethylation ammonium carbonate salts compound (i.e. aqueous organic alcohol amine mix product) in has in 2928-2970cm-1 The stretching vibration of the secondary amine salt N-H of range is unimodal, in 1550-1565cm-1The bending vibration of the secondary amine salt N-H of range is unimodal, with And in 3210-3405cm-1The OH stretching vibration peak of the Hydrogenbond of the Qiang Erkuan of range, these show N- hydroxyethylation of the present invention Ammonium carbonate salts compound has hydroxyl and secondary amine simultaneously, while wherein containing a small amount of water.Therefore, N- ethoxy of the invention Change ammonium carbonate salts compound to include one or more hydramine carbonate compounds and typically contain a small amount of water.
Preparation example 6
Preparation example 5 is repeated, only being made of the aminoquinoxaline and ammonium carbonate of 1:1 molar ratio using same mole Salt substitutes (same mole) ammonium carbonate.Obtain compound 6, pH=9.2.
Application Example:
Embodiment 1
By alkaline foaming agent (by the weight of compound 1 and 4.5 prepared by example 1 made above as foaming agent of 3 parts by weight The compound 5 prepared by example 5 made above as foaming agent of amount part forms, pH=8.8), the polyether polyols of 20 parts by weight Alcohol SA460 (being produced by the Bin Hua group of Shandong Province Accessories during Binzhou), the polyether polyol SA380 of 20 parts by weight are (by Shandong Province Binzhou The Bin Hua group in city produces), polyester polyol (by Shandong Lanxing Dongda Chemical Co., Ltd), 1 weight of 10 parts by weight Part foam stabiliser DC3201 (production of air chemical company, the U.S.), 0.3 parts by weight N, N- dimethyl cyclohexyl amine (US Air Gasification work), the potassium octanoate of 1.5 parts by weight and 6 parts by weight pentamethylene obtain transparent composition, foam after mixing, then exist 66 parts of isocyanates MDI (PM200, Yantai Wanhua chemical groups limited liability company), agitated uniformly rear foaming is wherein added Polyurethane foamed material is made.The material is used as polyurethane solar energy foam-body material.The size of gained polyurethane foamed material Change rate or shrinking percentage≤1% (according to chinese national standard GB/T 8811-2008,5 months standing times).In addition, foams Density is about 35Kg/m3, compressive strength is about 120KPa.
The foam product of embodiment 1 has good heat-insulating property, can satisfy polyurethane solar energy foam-body material The requirement of the various performances in field.
Sample is taken, amplifies 100 times of observation abscesses using SEM after being sliced with blade.As shown in fig. 1, mean cell diameter It is 210.2 microns.Cell size is uniform.
Embodiment 2
By alkaline foaming agent (by the compound 2 and 4.5 prepared by example 2 made above as foaming agent of 3.5 parts by weight The compound 5 prepared by example 5 made above as foaming agent of parts by weight forms, pH=8.7), the polyethers of 20 parts by weight it is more First alcohol SA460 (being produced by the Bin Hua group of Shandong Province Accessories during Binzhou), 20 parts by weight polyether polyol SA380 (by Shandong Province shore The Bin Hua group in state city produces), the polyester polyol (by Shandong Lanxing Dongda Chemical Co., Ltd) of 10 parts by weight, 1 weight Measure the foam stabiliser DC3201 (production of air chemical company, the U.S.) of part, the N of 0.3 parts by weight, the N- dimethyl cyclohexyl amine (U.S. Air chemical industry), the potassium octanoate of 1.5 parts by weight and 6 parts by weight pentamethylene obtain transparent composition, foam after mixing, then 66 parts of isocyanates MDI (PM200, Yantai Wanhua chemical groups limited liability company), agitated uniformly rear hair are added wherein It is brewed to obtain polyurethane foamed material.The material is used as polyurethane solar energy foam-body material.The ruler of gained polyurethane foamed material Very little change rate or shrinking percentage≤1% (according to chinese national standard GB/T 8811-2008,5 months standing times).In addition, foam Volume density is about 35Kg/m3, compressive strength is about 118KPa.
Embodiment 3
By alkaline foaming agent (by the compound 3 and 4.5 prepared by example 3 made above as foaming agent of 4.0 parts by weight The compound 5 prepared by example 5 made above as foaming agent of parts by weight forms, pH=8.8), the polyethers of 20 parts by weight it is more First alcohol SA460 (being produced by the Bin Hua group of Shandong Province Accessories during Binzhou), 20 parts by weight polyether polyol SA380 (by Shandong Province shore The Bin Hua group in state city produces), the polyester polyol (by Shandong Lanxing Dongda Chemical Co., Ltd) of 10 parts by weight, 1 weight Measure the foam stabiliser DC3201 (production of air chemical company, the U.S.) of part, the N of 0.3 parts by weight, the N- dimethyl cyclohexyl amine (U.S. Air chemical industry), the potassium octanoate of 1.5 parts by weight and 6 parts by weight pentamethylene obtain transparent composition, foam after mixing, then 67 parts of isocyanates MDI (PM200, Yantai Wanhua chemical groups limited liability company), agitated uniformly rear hair are added wherein It is brewed to obtain polyurethane foamed material.The material is used as polyurethane solar energy foam-body material.The ruler of gained polyurethane foamed material Very little change rate or shrinking percentage≤1% (according to chinese national standard GB/T 8811-2008,5 months standing times).In addition, foam Volume density is about 35Kg/m3, compressive strength is about 121KPa.
Embodiment 4
By alkaline foaming agent (by the compound 3 and 4.5 prepared by example 4 made above as foaming agent of 3.0 parts by weight The compound 6 prepared by example 6 made above as foaming agent of parts by weight forms, pH=8.9), the polyethers of 20 parts by weight it is more First alcohol SA460 (being produced by the Bin Hua group of Shandong Province Accessories during Binzhou), 20 parts by weight polyether polyol SA380 (by Shandong Province shore The Bin Hua group in state city produces), the polyester polyol (by Shandong Lanxing Dongda Chemical Co., Ltd) of 10 parts by weight, 1 weight Measure the foam stabiliser DC3201 (production of air chemical company, the U.S.) of part, the N of 0.3 parts by weight, the N- dimethyl cyclohexyl amine (U.S. Air chemical industry), the potassium octanoate of 1.5 parts by weight and 6 parts by weight pentamethylene obtain transparent composition, foam after mixing, then 67 parts of isocyanates MDI (PM200, Yantai Wanhua chemical groups limited liability company), agitated uniformly rear hair are added wherein It is brewed to obtain polyurethane foamed material.The material is used as polyurethane solar energy foam-body material.The ruler of gained polyurethane foamed material Very little change rate or shrinking percentage≤1% (according to chinese national standard GB/T 8811-2008,5 months standing times).In addition, foam Volume density is about 35Kg/m3, compressive strength is about 115KPa.

Claims (10)

1. a kind of alkaline hydramine foaming agent comprising primary amine salt and ethanolamine salt, the pH value of the alkalinity foaming agent is in 8.5-9.5 Between, which includes:
1) the first compound mixture (M1) comprising the organic primary amine salt compound class with following general formula (I):
A-[B+]p (I)
Wherein, B+It is the cation of the organic primary amine B of+1 valence, A-It is: CO3 2-Or CO3 2-With HCO3 -Conjugate；P is in A-For HCO3 -In the case where for 1, p in A-For CO3 2-In the case where be 2；
2) comprising the mono- ethoxy-ammonium carbonate compound of N- with logical formula (II) and the N with logical formula (II), (the hydroxyl second of N'- bis- Base)-ammonium carbonate compound second of compound mixture (M2),
(RN+H3)(N+H4)CO3 2-Or (RN (II),+H3)2CO3 2-(III),
In formula, R is ethoxy；
The molar ratio of the compound of the compound and logical formula (III) of logical formula (II) is 1:0 to 1:1.0.
2. foaming agent according to claim 1, wherein the first compound mixture (M1) is by organic primary amine B in water In the presence of with CO2Made from reaction；Preferably, the amount of water is as few as possible in the reactive mixture is still enough to avoid generating ammonia Base formates.
3. foaming agent according to claim 1 or 2, wherein second of compound mixture (M2) is to make by the following method : in the case where adding or not adding ammonium hydroxide, the molar ratio according to ammonium carbonate and/or aminoquinoxaline and ethylene oxide is 1:1-5.5 (preferably 1:1.3-5) adds to being formed by slurry or saturated solution by ammonium carbonate and/or aminoquinoxaline and water Enter ethylene oxide to allow reaction mixture to be reacted, obtaining aqueous organic alcohol amine mixture, (general, its pH is 7.5- 10, preferably pH 8-9.7, preferably pH 8.3-9.6, more preferable pH 8.5-9.5, such as pH=9), i.e. second of compound Mixture (M2).
4. foaming agent described in any one of -3 according to claim 1, wherein the first compound mixture (M1) and second The weight ratio of kind compound mixture (M2) is 0.3-1:1, more preferable 0.5-0.8:1.
5. foaming agent described in any one of -4 according to claim 1, wherein in the compound of logical formula (I), organic primary amine The 50-100% of amido in compound B is by anion A-It neutralizes, the 65-100% quilt of the amido in preferably organic amine compound B Anion A-It neutralizes；It is further preferred that the 75-100% of the amido in organic amine compound B is by anion A-It neutralizes；It is further preferred that organic The 75-90% of amido in amine compounds B is by anion A-It neutralizes；And/or
The first compound mixture (M1) or second of respective water content of compound mixture (M2) independently are 2- 40wt%, preferably 5-35wt%, more preferable 10-30wt%, more preferable 15-25wt%.
6. foaming agent described in any one of -5 according to claim 1, wherein the pH of the first compound mixture (M1) is 7.0-8.8, preferably pH 7.3-8.6, more preferable pH 7.5-8.5；And/or
The pH of second of compound mixture (M2) is 8.6-10, preferably 8.7-9.5, more preferable pH 8.8-9.3.
7. foaming agent described in any one of -6 according to claim 1, wherein organic primary amine B is among following It is one or more: C1-C24Primary hydrocarbyl amine class；E.g. it is selected from methylamine, ethamine, propylamine, butylamine, amylamine, hexyl amine, heptan Base amine, octyl amine, nonyl amine, decyl amine, lauryl amine, tetradecylamine, hexadecylamine, octadecylamine, eicosane Base amine, tetracosyl amine, the aniline of unsubstituted or substituted (such as halogen substitution), the benzyl of unsubstituted or substituted (such as halogen substitution) Base amine, cyclo-hexylamine, methylcyclohexyl amine, cyclohexyl methyl amine, one of N- methylcyclohexyl amine and N- methylbenzylamine or It is a variety of.
8. a kind of polyurethane foamed composite object, it includes: 0.5-100 weight % (more preferable 2-80wt%, more preferable 4- 60wt%, more preferable 6-40wt%, such as 8wt%, 10wt%, 15wt% or 20wt%) according to claim 1 any one in -7 Foaming agent described in；The physical blowing agent of 0-50 weight %；The water and 0.0-99.5 weight % of 0-5 weight % is (preferably 20.0-98.0 weight %, more preferable 40-96wt%, more preferable 60-94wt%, more preferable 70-88wt%, more preferable 75- Polymer polyatomic alcohol 85wt%)；Wherein, total weight of the weight percent based on polyurethane foamed composite object.
9. polyurethane foamed composite object according to claim 8, wherein polymer polyatomic alcohol is selected from: polyether polyol is gathered Ester polyol, polyether-polyester polyol, polycarbonate glycol, polycarbonate-polyester polyalcohol, polycarbonate-polyether polyols Alcohol, polybutadiene polyol or polysiloxane polyhydric alcohol, and the average functionality of polymer polyatomic alcohol is generally 2-16, preferably 2.5-10 more preferable 3-8；And/or
The physical blowing agent at least one of is selected from the group: pentane, isopentane, pentamethylene, boiling point is in 0-100 DEG C of range Interior other alkane, HCFC-141b, HFC-245fa, HFC-365mfc, LBA, FEA-1100, boiling point is within the scope of 0-100 DEG C Other fluorochlorohydrocarbons or organosilane ester.
10. foaming agent described in any one of -7 is for the use in polyurethane solar energy foam-body material according to claim 1 On the way.
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