CN109422904A - Foaming agent comprising secondary amine and alcohol amine salt and for the purposes in polyurethane continuous slab foam-body material - Google Patents

Foaming agent comprising secondary amine and alcohol amine salt and for the purposes in polyurethane continuous slab foam-body material Download PDF

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Publication number
CN109422904A
CN109422904A CN201710734841.9A CN201710734841A CN109422904A CN 109422904 A CN109422904 A CN 109422904A CN 201710734841 A CN201710734841 A CN 201710734841A CN 109422904 A CN109422904 A CN 109422904A
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compound
foaming agent
preferable
amine
weight
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CN109422904B (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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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J9/08—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 developing carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Foaming agent comprising secondary amine and alcohol amine salt and for the purposes in polyurethane continuous slab foam-body material.A kind of polyurethane foams comprising secondary amine salt and alcohol amine salt is disclosed, which includes: the first compound mixture (M1) 1) comprising the organic secondary salt compound class with following general formula (I): A‑[B+]p(I), wherein B+It is the cation of the organic secondary B of+1 valence, A‑It is: CO3 2‑, HCO3 ‑Or CO3 2‑With HCO3 ‑Conjugate；2) comprising the mono- hydroxypropyl of N-/mono- ethoxy-ammonium carbonate compound with logical formula (II) and the N with logical formula (II), second of compound mixture (M2) of N'- bis- (hydroxypropyl/ethoxy)-ammonium carbonate compound: (RN+H3)(N+H4)CO3 2‑Or (RN (II),+H3)2CO3 2‑(III), in formula, R is the conjugate of hydroxypropyl and ethoxy；The molar ratio of the glycol amine compounds of the single methanol amine compounds and logical formula (III) of logical formula (II) is 1:0 to 1:2.5.Foaming agent is suitable for preparing polyurethane continuous slab foam-body material.

Description

Foaming agent comprising secondary amine and alcohol amine salt and be used for polyurethane continuous slab foam-body material In purposes
Technical field
The present invention relates to organic secondary salt compound of anion having as CO2 donor and preparation method thereof and conducts The purposes of foaming agent, more specifically, providing not only has anion but also organic secondary as CO2 donor as catalysis base Novel organic ammonium salt compounds and preparation method thereof of group and solubilizing group and preparing polyurethane continuous slab foam-body material In application.The present invention relates to the polyurethane foams comprising secondary amine salt and alcohol amine salt and its it is used for (preparation) polyurethane continuous slab The purposes of 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 secondary amine The novel organic ammonium salt compounds of solubilizing group, and its answering in foamed material such as polyurethane continuous slab 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 secondary amine, the first compound mixture (M1) as foaming agent releases CO in decomposition2 Generated decomposition product is secondary amine 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.In this application, " hydroxypropyl/ethoxy " indicates the conjugate of hydroxypropyl and ethoxy Or mixed group.
According to the first embodiment of the present invention, the foaming agent comprising alcohol amine salt is provided, more specifically offer includes A kind of foaming agent of secondary amine salt and alcohol amine salt, it is used for polyurethane continuous slab foam-body material.The foaming agent includes:
1) the first compound mixture (M1) comprising the organic secondary salt compound class with following general formula (I):
A-[B+]p(I)
Wherein, B+It is the cation of the organic secondary 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- hydroxypropyl-ammonium carbonate compound of the N- as single methanol amine compounds and/or N- with logical formula (II) Single ethoxy-ammonium carbonate compound and the N as glycol amine compounds, N'- bis- (hydroxypropyl)-carbonic acid with logical formula (III) Ammonium compounds and/or N, second of compound mixture of N'- bis- (ethoxy)-ammonium carbonate compound (M2), that is, comprising having The mono- hydroxypropyl of the N-/mono- ethoxy-ammonium carbonate compound and the (hydroxypropyl/hydroxyl of the N with logical formula (III), N'- bis- of logical formula (II) Ethyl)-ammonium carbonate compound second of compound mixture (M2), belong to 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 (that is: HO-CH2-CH2(CH3)-or HO-CH2(CH3)-CH2) with the conjugate of ethoxy；
The molar ratio of the compound of the compound and logical formula (III) of logical formula (II) is 1:0 to 1:2.5.Preferably 1:0.3 is extremely 1:2, more preferably 1:0.5 are to 1:1.
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 secondary B in presence of water with CO2Made from reaction. The dosage of water makes the first compound mixture (M1) obtained be 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- according to ammonium carbonate and/or aminoquinoxaline and two kinds of epoxy epoxy propane/ethylene oxide molar ratios Ring is added to being formed by slurry or saturated solution by ammonium carbonate and/or aminoquinoxaline and water in 5.5 (preferably 1:1.3-5) Ethylene Oxide/ethylene oxide mixture to allow reaction mixture to be reacted, [and then from be formed by reaction mixture take out it is true The water and unreacted propylene oxide and ethylene oxide of sky removing a part], obtain aqueous organic alcohol amine mixture (one As, 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).In addition, two kinds of epoxy epoxy propane/ethylene oxide dosage molar ratios are as follows: 0.3-3:1, preferably 0.5-2:1, more preferable 0.8-1.2:1.
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 0.2- 0.9:1, preferably 0.25-0.85:1, more preferable 0.3-0.8:1, more preferable 0.5-0.75:1, more preferable 0.6-0.75:1.
It is preferred that in the compound of logical formula (I) or in the first compound mixture (M1), organic secondary 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 6.5-8.1, preferably pH 6.7-8.0, more preferable pH 7- 7.5。
It is preferred that the pH of second of compound mixture (M2) is 8.3-10, preferably 8.5-9.5, more preferable pH 8.8-9.2.
It is preferred that organic secondary B is one or more among following: two (C1-C4Alkyl) amine；E.g. select From in dimethylamine, diethylamine, dipropylamine, dibutylamine, Methylethyl amine, methyl-propyl amine, ethyl propyl amine, methyl butyl Amine, one of N-Ethylbutylamine or propylbutylamine or a variety of.
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 secondary 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 secondary 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 foaming agent is provided in (preparation) polyurethane continuous slab foam-body material 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 and N- ethoxy, the compound It sufficiently dissolves each other, can be homogeneously dispersed in composition, foam uniformly with foaming raw material (such as polyether polyol or polyester polyol) Ground foaming, so that the polyurethane foam of preparation 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 includes N- hydroxypropylation/hydroxyethylation ammonium carbonate salts chemical combination A kind of aqueous organic alcohol amine mixture of object, by being heated to 70 DEG C of a large amount of carbon dioxide of release, then, remaining alcohol amination It closes object and carries out gas chromatographic analysis, measure the mono- hydroxypropyl of N- in reaction product (mixture M 2)/mono- ethoxy-ammonium carbonate and N, The molar ratio of N'- bis- (hydroxypropyl/hydroxypropyl)-ammonium carbonate compound be in 1:0 to 1:2.5 range, preferably 1:0.3 to 1:2, it is excellent Select 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 continuous slab 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 secondary-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 continuous slab foam-body material, this method is included in polyurethane preparation The 1-10% for being based on urethane raw total weight (including isocyanates and polyalcohol) is introduced, preferably 2-5%'s is above-mentioned organic secondary Amine salt compound or organic secondary salt compound mixture.
The present invention also provides above-mentioned organic secondary salt compounds or organic secondary salt compound mixture to send out for (preparation) Purposes in foam material such as polyurethane continuous slab 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.
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, it when logical formula (I) compound of the invention is the compound with secondary amine group, decomposes and discharges in the compound (I) CO out2Generated decomposition product, that is, secondary amine 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 continuous slab 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% dimethylamine agueous solution (molecular weight 45) of 3kg is added in transparent quartz glass reactor, is 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 1.PH >=7.5, decomposition temperature is at 42 DEG C -70 DEG C.
Preparation example 2
30% diethylamine aqueous solution (molecular weight 73) of 3kg is added in transparent quartz glass reactor, is 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 2.PH >=7.5, decomposition temperature is at 42 DEG C -70 DEG C.
Preparation example 3
The water of the dipropylamine (molecular weight 101) of 3kg, 1.6kg are added in transparent quartz glass reactor, stirred Dissolution 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 >=7.5, decomposition temperature is at 42 DEG C -70 DEG C.
Preparation example 4
Methylethyl amine (molecular weight 59), the 1.6kg water of 3kg are added in transparent quartz glass reactor, stirred Dissolution 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 4.PH >=7.5, 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 Then the propylene oxide of 1.2kg and the ethylene oxide of 0.8kg is added in slurry (ammonium carbonate is not completely dissolved) in sour ammonium, while stirring, while Cooling, control pressure is not higher than 0.6MPa, slowly temperature reaction, and control temperature is consistently lower than 60 DEG C and reacts 14 hours.It has reacted Cheng Hou slowly reduces the temperature to 50 DEG C hereinafter, slowly removing the water and not of a part under the vacuum degree of 600 millimetress of mercury or so The propylene oxide and ethylene oxide of reaction, then discharge vacuum, and reactant is discharged after cooling to 40 DEG C or less, obtains aqueous carbon Acid alcohol amine salt compound mixture (abbreviation compound 5), belongs to one of second of compound mixture M2.Viscosity is about 420 centipoises, pH=9.1, the decomposition temperature of compound 5 are 58-63 DEG C.With atomic absorption spectrophotometer (Seiko Instruments,Inc.；SAS/727 the content for) measuring alkali and alkaline earth metal ions ion 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 of N-/mono- ethoxy-ammonium carbonate and N, N'- bis- in reaction product (i.e. mixture M 2) The molar ratio of (hydroxypropyl/ethoxy)-ammonium carbonate compound is about 1:0.25.
By infrared spectrum analysis, second of chemical combination obtained is reacted with propylene oxide/ethylene oxide by ammonium carbonate N- hydroxypropylation/hydroxyethylation ammonium carbonate salts compound (i.e.) (i.e. aqueous organic alcohol amine mixing produce in object mixture (M2) Product) have 2920-2978cm-1 range secondary amine salt N-H stretching vibration it is unimodal, in 1551-1568cm-1The secondary amine of range The bending vibration of salt N-H is unimodal, and in 3202-3405cm-1The OH stretching vibration peak of the Hydrogenbond of the Qiang Erkuan of range, this Show N- hydroxypropylation/hydroxyethylation ammonium carbonate salts compound of the present invention while there is hydroxyl and secondary amine, while wherein containing There is a small amount of water.Therefore, N- of the invention hydroxypropylation/hydroxyethylation ammonium carbonate salts compound includes one or more hydramine carbon Phosphate 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 ammonium carbonate.Obtain compound 6, pH=9.2.
Application Example:
Embodiment 1
The conduct of the parts by weight of compound 1 and 4.5 prepared by example 1 made above as foaming agent of 2 parts by weight is sent out The compound 5 prepared by example 5 made above of infusion, 40 parts by weight polyether polyol 4110 (by the shore of Shandong Province Accessories during Binzhou Change group's production), the bubble of the polyester polyol (by Shandong Lanxing Dongda Chemical Co., Ltd) of 10 parts by weight, 1 parts by weight Foam stabilizers DC3201 (production of air chemical company, the U.S.), 12.5 parts by weight fire retardant TCPP (refined gram of Jiangsu chemical industry is limited Company's production), the N of 1 parts by weight, N- dimethyl cyclohexyl amine (US Air gasification work), the potassium octanoate of 1.5 parts by weight and 6 parts by weight HCFC-141b obtains transparent composition, foam after mixing, be then added wherein 110 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 continuous slab foam-body material.The size changing rate or shrinking percentage≤1% of gained polyurethane foamed material are (according to China national Standard GB/T 8811-2008,5 months standing times).In addition, density foam is about 40Kg/m3, compressive strength is about 170KPa。
The foam product of embodiment 1 has good heat-insulating property, equally can satisfy each of refrigerator and refrigerator-freezer field The requirement of kind performance.
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 207.5 microns.Cell size is uniform.
Embodiment 2
The conduct of the parts by weight of compound 2 and 4.5 prepared by example 2 made above as foaming agent of 2 parts by weight is sent out The compound 5 prepared by example 5 made above of infusion, 40 parts by weight polyether polyol 4110 (by the shore of Shandong Province Accessories during Binzhou Change group's production), the bubble of the polyester polyol (by Shandong Lanxing Dongda Chemical Co., Ltd) of 10 parts by weight, 1 parts by weight Foam stabilizers DC3201 (production of air chemical company, the U.S.), 12.5 parts by weight fire retardant TCPP (refined gram of Jiangsu chemical industry is limited Company's production), the PC-41 of 1 parts by weight, the potassium octanoate of 1 parts by weight and 6 parts by weight HCFC-141b obtain after mixing it is transparent Composition, foam, then wherein be added 110 parts of isocyanates MDI (PM200, the limited public affairs of Yantai Wanhua chemical groups share Department), polyurethane foamed material is made in agitated uniformly rear foam.The material is used as polyurethane continuous slab foam-body material.Gained The size changing rate or shrinking percentage≤1% of polyurethane foamed material are (according to chinese national standard GB/T 8811-2008, when placement Between 5 months).In addition, density foam is about 40Kg/m3, compressive strength is about 165KPa.
Embodiment 3
The conduct of the parts by weight of compound 3 and 4.0 prepared by example 3 made above as foaming agent of 3 parts by weight is sent out The compound 5 prepared by example 5 made above of infusion, 40 parts by weight polyether polyol 4110 (by the shore of Shandong Province Accessories during Binzhou Change group's production), the bubble of the polyester polyol (by Shandong Lanxing Dongda Chemical Co., Ltd) of 10 parts by weight, 1 parts by weight Foam stabilizers DC3201 (production of air chemical company, the U.S.), 12.5 parts by weight fire retardant TCPP (refined gram of Jiangsu chemical industry is limited Company's production), PC-41 (US Air gas Chemical Manufacture), the potassium octanoate of 1 parts by weight and the 6 parts by weight HCFC-141b of 1 parts by weight Transparent composition, foam is obtained after mixing, and 112 parts of isocyanates MDI (PM200, Yantai Wanhuas are then added wherein Chemical groups limited liability company), polyurethane foamed material is made in agitated uniformly rear foam.It is continuous that the material is used as polyurethane Plate foam-body material.The size changing rate or shrinking percentage≤1% of gained polyurethane foamed material are (according to chinese national standard GB/T 8811-2008,5 months standing times).In addition, density foam is about 40Kg/m3, compressive strength is about 164KPa.
Embodiment 4
The conduct of the parts by weight of compound 4 and 4.5 prepared by example 4 made above as foaming agent of 3 parts by weight is sent out The compound 6 prepared by example 6 made above of infusion, 40 parts by weight polyether polyol 4110 (by the shore of Shandong Province Accessories during Binzhou Change group's production), the bubble of the polyester polyol (by Shandong Lanxing Dongda Chemical Co., Ltd) of 10 parts by weight, 1 parts by weight Foam stabilizers DC3201 (production of air chemical company, the U.S.), 12.5 parts by weight fire retardant TCPP (refined gram of Jiangsu chemical industry is limited Company's production), PC-41 (production of air chemical company, the U.S.), the potassium octanoate of 1 parts by weight and the 6 parts by weight HCFC- of 1 parts by weight 141b obtains transparent composition, foam after mixing, and 112 parts of isocyanates MDI (PM200, Yantai are then added wherein Wanhua Chemical Group Co., Ltd.), polyurethane foamed material is made in agitated uniformly rear foam.The material is used as polyurethane Continuous slab foam-body material.The size changing rate or shrinking percentage≤1% of gained polyurethane foamed material are (according to chinese national standard GB/T 8811-2008,5 months standing times).In addition, density foam is about 40Kg/m3, compressive strength is about 166KPa.

Claims (10)

1. including a kind of foaming agent of secondary amine salt and alcohol amine salt, which includes:
1) the first compound mixture (M1) comprising the organic secondary salt compound class with following general formula (I):
A-[B+]p (I)
Wherein, B+It is the cation of the organic secondary 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 with logical formula (II) the mono- hydroxypropyl of the N- as single methanol amine compounds/mono- ethoxy-ammonium carbonate compound with Second of change of the N as glycol amine compounds with logical formula (II), N'- bis- (hydroxypropyl/ethoxy)-ammonium carbonate compound Polymer mixtures (M2),
(RN+H3)(N+H4)CO3 2-(II),
Or
(RN+H3)2CO3 2-(III),
In formula, R is the conjugate of hydroxypropyl and ethoxy；
The molar ratio of the compound of the compound and logical formula (III) of logical formula (II) is 1:0 to 1:2.5.
2. foaming agent according to claim 1, wherein the first compound mixture (M1) is by organic secondary B in water In the presence of with CO2Made from reaction.
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, according to ammonium carbonate and/or aminoquinoxaline and two kinds of epoxy epoxies third Alkane/ethylene oxide molar ratio is 1:1-5.5 (preferably 1:1.3-5), is formed to by ammonium carbonate and/or aminoquinoxaline and water Slurry or saturated solution in be added propylene oxide/ethylene oxide mixture to allow reaction mixture to be reacted, contained (general, its pH is 7.5-10, preferably pH 8-9.7, preferably pH 8.3-9.6 to the organic alcohol amine mixture of water, more preferably 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 0.2-0.9:1, and preferably 0.25-0.85:1, more preferable 0.3-0.8:1 are more excellent Select 0.5-0.75:1.
5. foaming agent described in any one of -4 according to claim 1, wherein in the compound of logical formula (I), organic secondary 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 6.5-8.1, preferably pH 6.7-8.0, more preferable pH 7-7.5；And/or
The pH of second of compound mixture (M2) is 8.3-10, preferably 8.5-9.5, more preferable pH 8.8-9.2.
7. foaming agent described in any one of -6 according to claim 1, wherein organic secondary B is among following It is one or more: two (C1-C4Alkyl) amine；E.g. it is selected from dimethylamine, diethylamine, dipropylamine, dibutylamine, methyl Ethylamine, methyl-propyl amine, ethyl propyl amine, methyl butyl amine, one of N-Ethylbutylamine or propylbutylamine or more Kind.
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 continuous slab foam-body material according to claim 1 On the way.
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