CN109422909A - Orthoformic acid alcohol amine salt and carbonate polyol amine salt alkalinity foaming agent and the purposes for being used to prepare polyurethane coating foam-body material - Google Patents

Orthoformic acid alcohol amine salt and carbonate polyol amine salt alkalinity foaming agent and the purposes for being used to prepare polyurethane coating foam-body material Download PDF

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CN109422909A
CN109422909A CN201710736192.6A CN201710736192A CN109422909A CN 109422909 A CN109422909 A CN 109422909A CN 201710736192 A CN201710736192 A CN 201710736192A CN 109422909 A CN109422909 A CN 109422909A
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compound
foaming agent
preferable
weight
mixture
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CN109422909B (en
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毕玉遂
毕戈华
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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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    • C08G18/08—Processes
    • C08G18/16—Catalysts
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    • C08J9/14—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 physical blowing agent organic
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    • C08J2203/00—Foams characterized by the expanding agent
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Abstract

Disclose a kind of polyurethane alkalinity foaming agent comprising orthoformic acid alcohol amine salt and carbonic acid propyl alcohol amine 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 orthoformic acid alcohol amine compound class with following general formula (I): A‑B+(I), wherein B+It is the cation of organic alcohol amine B, A‑It is primitive nail acid group；2) comprising the mono- hydroxypropyl-ammonium carbonate compound of N- with logical formula (II) and the N with logical formula (II), second of compound mixture of N'- bis- (hydroxypropyl)-ammonium carbonate compound (M2): (RN+H3)(N+H4)CO3 2‑Or (RN (II),+H3)2CO3 2‑(III), in formula, R is hydroxypropyl；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 coating foam-body material.

Description

Orthoformic acid alcohol amine salt and carbonate polyol amine salt alkalinity foaming agent and it is used to prepare polyurethane spray Apply the purposes of foam-body material
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 and orthoformic acid hydramine of donor are as catalytic group and solubilizing group Novel organic ammonium salt compounds preparing the application in polyurethane coating foam-body material.More specifically to primitive nail Acid alcohol amine/carbonate polyol amine base foaming agent and the purposes for being used to prepare polyurethane coating 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 and tool orthoformic acid alcohol amine groups of donor are made For the novel organic ammonium salt compounds of solubilizing group, and its answering in foamed material such as polyurethane coating 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 orthoformic acid hydramine, the first compound mixture (M1) as foaming agent is released in decomposition CO2Generated decomposition product is alcohol amine compound later, they are suitable as catalysts for polyurethanes applied in material.Cause This, is based on above-mentioned two aspect, completes the present invention.
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 alkali comprising orthoformic acid alcohol amine salt and carbonic acid propyl alcohol amine salt is provided Property hydramine foaming agent, the pH value of the alkalinity foaming agent is between 8.5-9.5.Due to having alkalinity, foaming activity is high, is suitable for Fast foaming, therefore it foams while spraying suitable for polyurethane coating foam-body material is prepared.The foaming agent packet It includes:
1) the first compound mixture (M1) comprising the orthoformic acid alcohol amine salt compound class with following general formula (I):
A-B+ (I)
Wherein, A-It is primitive nail acid groupB+It is the cation of organic alcohol amine B；
2) comprising the mono- hydroxypropyl-ammonium carbonate compound of N- with logical formula (II) and N, N'- bis- with logical formula (III) Second of compound mixture (M2) of (hydroxypropyl)-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 hydroxypropyl, it may be assumed that HO-CH2-CH2(CH3)-or HO-CH2(CH3)-CH2-；
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.
It is preferred that the first compound mixture (M1) is that hydrolysis occurs in the presence of hydramine B and water by orthoformate instead It answers prepared by (and at salt)；Preferably, the amount of water is sufficient to make orthoformate complete hydrolysis in the reactive mixture.
It is preferred that orthoformate compound is to be selected from one of these following compounds or a variety of: orthoformic acid three (C1-C8) Alkyl esters, preferably orthoformic acid three (C1-C7) alkyl esters；It is preferred that orthoformate be selected from it is following these one of or It is a variety of: trimethyl orthoformate, triethyl orthoformate, primitive nail acid methyl diethyl ester, tripropyl orthoformate, primitive nail acid methyl dipropyl Base ester, tributyl orthoformate, three amyl ester of orthoformic acid, three hexyl ester of orthoformic acid, 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, orthoformic acid three (two Ethylene glycol) ester, orthoformic acid three (triethylene glycol) ester, orthoformic acid three (tetraethylene glycol) ester, the (polyethylene glycol (degree of polymerization of orthoformic acid three =5-10)) ester, orthoformic acid three (propylene glycol) ester, orthoformic acid three (dipropylene glycol) ester, orthoformic acid three (tripropylene glycol) ester, primitive nail Sour three (four propylene glycol) esters, orthoformic acid three (polypropylene glycol (degree of polymerization=5-10)) ester.
It is further preferred that orthoformate compound is to be selected from one of these following compounds or a variety of: three (C of formic acid1-C6Alkane Base) ester.It is further preferred that being selected from orthoformic acid front three base ester, orthoformic acid triethyl group ester, orthoformic acid tripropyl ester, three fourth of orthoformic acid Base ester is one or more in three amyl ester of orthoformic acid or three hexyl ester of orthoformic acid.
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 propylene oxide Ammonium carbonate and/or aminoquinoxaline and water be formed by slurry (not being completely dissolved) or saturated solution be added propylene oxide with Just allow reaction mixture to be reacted, [then, optionally, from be formed by vacuumized in reaction mixture removing a part Water and unreacted propylene 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 change Polymer mixtures (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), orthoformic acid alcohol amine compound The 50-100% of amido in B is by anion A-It neutralizes, the 65-100% of the amido in preferably organic amine compound B is by 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 amine chemical combination The 75-90% of amido in object B is by anion A-It neutralizes.
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 alcohol amine B is one or more among following: C2-C12Alcamines；It is preferred that organic alcohol amine B It is selected from monoethanolamine, diethanol amine, triethanolamine, monopropylene glycol amine, dipropanolamine, tripropanol amine, monoisopropanolamine, two is different Propanolamine, triisopropanolamine, monobutanolamine, one of two butanolamines or three butanolamines or a variety of.
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 coating foam-body material In purposes.
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- hydroxypropyl, 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 (I) of the invention The compound existing " foaming effect " of compound, the compound of logical formula (II) and logical formula (III) has " chain extension " or " crosslinking " work again With, cause polyurethane foam have good dimensional stability, especially long-term dimensional stability, environmental condition indoors It is lower to place 1 year, there is no the distinguishable deformation of naked eyes or spoil contracting.
Second of compound mixture (M2) of the invention, i.e. one kind comprising N- hydroxypropylation 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- hydroxypropyl-ammonium carbonate of N- and N, N'- bis- (hydroxypropyl)-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 coating 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 and general formula of the compound of above-mentioned logical formula (I), logical formula (II) (III) compatibility or compatibility between the polyester polyol and/or polyether polyol of compound and foaming are very good, shape At clear and bright homogeneous system.Homogeneous foaming system can ensure to form abscess of uniform size in polyurethane foam material.? The first mixture (M1) has catalytic action and there are also foaming effects in itself.
It was unexpectedly observed that the compound of the compound and logical formula (III) of the compound of above-mentioned logical formula (I) and logical formula (II) The decomposition temperature that foams is variant, this difference is conducive to foaming process and is carried out in a manner of steady, continuous.
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 alcamine 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 coating foam-body material, this method is included in polyurethane preparation and draws Enter to be based on the 1-10% of urethane raw total weight (including isocyanates and polyalcohol), the above-mentioned primitive nail acid alcohol of preferably 2-5% Amine salt compound or orthoformic acid alcohol amine salt compound mixture.
The present invention also provides above-mentioned orthoformic acid alcohol amine salt compounds or orthoformic acid alcohol amine salt compound mixture for (system It is standby) purposes in foamed material such as polyurethane coating 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 polyurethane coating foaming.The compound of above-mentioned logical formula (I) and the chemical combination of logical formula (II) Foaming decomposition temperature between object and the compound of logical formula (III) is variant, this difference is conducive to foaming process with relatively more flat Surely, continuously mode carries out.
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, lead to formula (II) or the decomposition of (III) compound releases CO2Decomposition product alcohol amine compound, alcohol amination are generated later Close object and be suitable as chain extender and/or crosslinking agent, logical formula (II) of the invention and (III) compound be not only used as " blow point " but also As " chain extension point " and/or " crosslinking points ", the mechanical strength and mechanical strength of abscess, polyurethane foam obtained are significantly enhanced Foam body have good dimensional stability, polyurethane foam finished product place some months, even 1 year after naked eyes almost without Shrinkage phenomenon is observed, without collapse bubble or collapse phenomenon.The long period is placed for example especially under higher temperature (such as 40-70 DEG C) Still there is good dimensional stability after (10 days).
4, logical formula (I) compound of the invention decomposition releases CO2Generated decomposition product, that is, alcohol amine compound later, They are suitable 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 production of polyurethane coating foam-body material Using.
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
The water of the triethyl orthoformate of 15kg, the diethanol amine of 20kg, 10kg are added in reactor, stirring is started, It controls pressure and is not higher than 0.1MPa, slowly heat up under constant stirring, when temperature control reaction 10 is small when temperature is increased to 80 DEG C.Instead Should after the completion of cool to 50 DEG C, then controlling vacuum degree is 600 millimetress of mercury hereinafter, the following removed under reduced pressure ethyl alcohol of temperature 50 C, It cools to up to compound 1 after 40 DEG C or less releasing products, pH >=7.8, decomposition temperature is at 45-70 DEG C.
Preparation example 2
The water of the triethyl orthoformate of 15kg, the monoethanolamine of 13kg, 7.0kg are added in reactor, stirring is started, It slowly heats up under constant stirring, temperature control reacts 8 hours at 100 DEG C or less.Cool down after the reaction was completed, then controlling vacuum degree is 600 millimetress of mercury remove vacuum hereinafter, the following removed under reduced pressure ethyl alcohol of temperature 50 C, cool to after 50 DEG C or less releasing products i.e. The compound 2 of two ester group hydrolyses of wherein triethyl orthoformate is obtained.PH >=7.8,45-70 DEG C of decomposition temperature.
Preparation example 3
The ammonium hydroxide of the orthoformic acid tripropyl ester of 20kg, the diethanol amine of 11kg, 10kg are added in reactor, starts and stirs It mixes, slowly heats up under constant stirring, temperature control, which is no more than at 100 DEG C, to react 8 hours.Cool down after the reaction was completed, then control is true Reciprocal of duty cycle is 600 millimetress of mercury hereinafter, the unnecessary water of the following removed under reduced pressure of temperature 50 C, removes vacuum, cools to 40 DEG C or less Compound 3 can be obtained after releasing product.PH >=7.8,45-70 DEG C of decomposition temperature.
Preparation example 4
The ethanol amine of the trimethyl orthoformate of 15kg, the ethylene glycol of 2.0kg, the water of 10kg, 10.0kg are added to reaction In device, stirring is started, control pressure is not higher than 0.1MPa, slowly heats up under constant stirring, when temperature is increased to 70 DEG C of time controls Temperature reaction 5 hours.Cool down after the reaction was completed, then controlling vacuum degree is 600 millimetress of mercury hereinafter, depressurizing below temperature 50 C de- Methanol removes vacuum, and compound 4 can be obtained by cooling to after 40 DEG C or less releasing products, pH >=7.8, and 45-70 DEG C of decomposition temperature.
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 propylene oxide of 2.0kg 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 propylene 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 400 centipoise of viscosity, pH=9.1, 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- hydroxypropyl-ammonium carbonate of N- and N, N'- bis- (hydroxypropyl)-carbon in reaction product (i.e. mixture M 2) The molar ratio of sour ammonium compounds is about 1:0.35.
By infrared spectrum analysis, second of compound mixture obtained is reacted by ammonium carbonate and propylene oxide (M2) the N- hydroxypropylation ammonium carbonate salts compound (i.e.) (i.e. aqueous organic alcohol amine mix product) in has in 2930- The stretching vibration of the secondary amine salt N-H of 2975cm-1 range is unimodal, in 1554-1567cm-1The bending vibration of the secondary amine salt N-H of range It is unimodal, and in 3200-3400cm-1The OH stretching vibration peak of the Hydrogenbond of the Qiang Erkuan of range, these show N- of the present invention Hydroxypropylation ammonium carbonate salts compound has hydroxyl and secondary amine simultaneously, while wherein containing a small amount of water.Therefore, of the invention N- hydroxypropylation ammonium carbonate salts compound includes one or more hydramine carbonate compounds and typically contains 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 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 4 parts by weight The compound 5 prepared by example 5 made above as foaming agent of amount part forms, pH=8.9), the polyether polyols of 30 parts by weight Alcohol 4110 (being produced by the Bin Hua group of Shandong Province Accessories during Binzhou), the polyester polyol of 20 parts by weight are (by the big chemical industry in Shandong blue star east Co., Ltd), the foam stabiliser DC3201 (production of air chemical company, the U.S.) of 1 parts by weight, the resistance of 12.5 parts by weight Fire agent TCPP (Jiangsu Yoke Chemical Co., Ltd.'s production), the PT-303 of 1 parts by weight, the potassium acetate of 1.5 parts by weight and 5 parts by weight HCFC-141b obtains transparent composition, foam after mixing, be then added wherein 83 parts of isocyanates MDI (PM200, Yantai Wanhua chemical groups limited liability company), polyurethane foamed material is made in agitated uniformly rear foam.The material is used as poly- Urethane spray foam body material.The size changing rate or shrinking percentage≤1% of gained polyurethane foamed material are (according to China national mark Quasi- GB/T 8811-2008,5 months standing times).In addition, density foam is about 33Kg/m3, compressive strength is about 135KPa。
The foam product of embodiment 1 has good heat-insulating property, can satisfy polyurethane coating foamed material field Various performances requirement.
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 225.7 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 30 parts by weight it is more First alcohol 4110 (being produced by the Bin Hua group of Shandong Province Accessories during Binzhou), 20 parts by weight polyester polyol (by eastern bigization of Shandong blue star Work Co., Ltd), the foam stabiliser DC3201 (production of air chemical company, the U.S.) of 1 parts by weight, 12.5 parts by weight Fire retardant TCPP (Jiangsu Yoke Chemical Co., Ltd.'s production), the PT-303 of 1 parts by weight, the A33 of 1 parts by weight, 1.5 parts by weight Potassium acetate and 6 parts by weight HCFC-141b obtain transparent composition, foam after mixing, and 83 parts of isocyanides are then added wherein Polyurethane foam material is made in acid esters MDI (PM200, Yantai Wanhua chemical groups limited liability company), agitated uniformly rear foam Material.The material is used as polyurethane coating foam-body material.The size changing rate or shrinking percentage≤1% of gained polyurethane foamed material (according to chinese national standard GB/T 8811-2008,5 months standing times).In addition, density foam is about 34Kg/m3, pressure Contracting intensity is about 139KPa.
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=8.7), the polyethers of 30 parts by weight it is more First alcohol 4110 (being produced by the Bin Hua group of Shandong Province Accessories during Binzhou), 20 parts by weight polyester polyol (by eastern bigization of Shandong blue star Work Co., Ltd), the foam stabiliser DC3201 (production of air chemical company, the U.S.) of 1 parts by weight, 12.5 parts by weight Fire retardant TCPP (Jiangsu Yoke Chemical Co., Ltd.'s production), the PT-303 of 1 parts by weight, the A33 of 1 parts by weight, 1 parts by weight vinegar Sour potassium and 6 parts by weight HCFC-141b obtain transparent composition, foam after mixing, and 83 parts of isocyanic acids are then added wherein Polyurethane foamed material is made in ester MDI (PM200, Yantai Wanhua chemical groups limited liability company), agitated uniformly rear foam. The material is used as polyurethane coating foam-body material.The size changing rate or shrinking percentage≤1% of gained polyurethane foamed material (are pressed According to chinese national standard GB/T 8811-2008,5 months standing times).In addition, density foam is about 34Kg/m3, compression is by force Degree is about 138KPa.
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=8.8), the polyethers of 30 parts by weight it is more First alcohol 4110 (being produced by the Bin Hua group of Shandong Province Accessories during Binzhou), 20 parts by weight polyester polyol (by eastern bigization of Shandong blue star Work Co., Ltd), the foam stabiliser DC3201 (production of air chemical company, the U.S.) of 1 parts by weight, 12.5 parts by weight Fire retardant TCPP (Jiangsu Yoke Chemical Co., Ltd.'s production), the PT-303 (production of air chemical company, the U.S.) of 1 parts by weight, 1 The potassium acetate of parts by weight and 6 parts by weight HCFC-141b obtain transparent composition, foam after mixing, are then added wherein Poly- ammonia is made in 83 parts of isocyanates MDI (PM200, Yantai Wanhua chemical groups limited liability company), agitated uniformly rear foaming Ester foamed material.The material is used as polyurethane coating foam-body material.The size changing rate or receipts of gained polyurethane foamed material Shrinkage≤1% (according to chinese national standard GB/T 8811-2008,5 months standing times).In addition, density foam is about 36Kg/m3, compressive strength is about 156KPa.

Claims (10)

1. a kind of alkaline hydramine foaming agent comprising orthoformic acid alcohol amine salt and carbonic acid propyl alcohol amine salt, the pH value of the alkalinity foaming agent are Between 8.5-9.5, which includes:
1) the first compound mixture (M1) comprising the orthoformic acid alcohol amine salt compound class with following general formula (I):
A- B+ (I)
Wherein, A-It is primitive nail acid groupB+It is the cation of organic alcohol amine B；
2) comprising the mono- hydroxypropyl-ammonium carbonate compound of N- with logical formula (II) and the N with logical formula (II), bis- (hydroxypropyl of N'- 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 hydroxypropyl, it may be assumed that HO-CH2-CH2(CH3)-or HO-CH2(CH3)-CH2-；
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 orthoformate in hydramine B Occur prepared by hydrolysis in the presence of water；Preferably, the amount of water is sufficient to make orthoformic acid in the reactive mixture Ester complete hydrolysis.
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 propylene 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 propylene 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), primitive nail acid alcohol The 50-100% of amido in amine compounds B is by anion A-It neutralizes, the 65-100% of the amido in preferably organic amine compound B By 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 having The 75-90% of amido in machine 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 alcohol amine B is among following It is one or more: C2-C12Alcamines；It is preferred that organic alcohol amine B is to be selected from monoethanolamine, and diethanol amine, triethanolamine, one third Hydramine, dipropanolamine, tripropanol amine, monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, monobutanolamine, two butanolamines, or One of three butanolamines are a variety of；And/or
Orthoformate compound is to be selected from one of these following compounds or a variety of: three (C of orthoformic acid1-C8) alkyl esters.
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 purposes in polyurethane coating foam-body material according to claim 1.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61138616A (en) * 1984-12-10 1986-06-26 Kikusui Kagaku Kogyo Kk Foamable inorganic and organic composite composition
JPH07149945A (en) * 1993-10-05 1995-06-13 Sumitomo Chem Co Ltd Blowing agent and expandable composition
CN104945599A (en) * 2015-06-18 2015-09-30 常州大学 Latent epoxy resin curing-foaming agent and method for preparing the same
WO2016094859A1 (en) * 2013-12-16 2016-06-16 Ramani Narayan Polyols from protein biomass
CN106279607A (en) * 2016-08-08 2017-01-04 常州大学 A kind of with polyurethane foamed material that carbon dioxide is environmentally friendly latency foaming agent and preparation method thereof
CN106573881A (en) * 2014-04-11 2017-04-19 科思创德国股份有限公司 Method for producing xylylene diisocyanates in the gaseous phase

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61138616A (en) * 1984-12-10 1986-06-26 Kikusui Kagaku Kogyo Kk Foamable inorganic and organic composite composition
JPH07149945A (en) * 1993-10-05 1995-06-13 Sumitomo Chem Co Ltd Blowing agent and expandable composition
WO2016094859A1 (en) * 2013-12-16 2016-06-16 Ramani Narayan Polyols from protein biomass
CN106573881A (en) * 2014-04-11 2017-04-19 科思创德国股份有限公司 Method for producing xylylene diisocyanates in the gaseous phase
CN104945599A (en) * 2015-06-18 2015-09-30 常州大学 Latent epoxy resin curing-foaming agent and method for preparing the same
CN106279607A (en) * 2016-08-08 2017-01-04 常州大学 A kind of with polyurethane foamed material that carbon dioxide is environmentally friendly latency foaming agent and preparation method thereof

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