CN109422898A - Foaming agent comprising tertiary ammonium salt and ethanolamine salt and the purposes for polyurethane interval plate foam-body material - Google Patents
Foaming agent comprising tertiary ammonium salt and ethanolamine salt and the purposes for polyurethane interval plate foam-body material Download PDFInfo
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- CN109422898A CN109422898A CN201710734498.8A CN201710734498A CN109422898A CN 109422898 A CN109422898 A CN 109422898A CN 201710734498 A CN201710734498 A CN 201710734498A CN 109422898 A CN109422898 A CN 109422898A
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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
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- 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
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- 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
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- 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
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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Abstract
A kind of polyurethane foams comprising tertiary ammonium salt and ethanolamine salt is disclosed, which includes: the first compound mixture (M1) 1) comprising the trimethylamine salt compound class with following general formula (I): A‑[B+]p(I), wherein B+It is the cation of the trimethylamine B of+1 valence, A‑It is: CO3 2‑, HCO3 ‑Or CO3 2‑With HCO3 ‑Conjugate；2) comprising the mono- ethoxy-ammonium carbonate compound of N- with logical formula (II) and the N with logical formula (II), second of compound mixture of N'- bis- (ethoxy)-ammonium carbonate compound (M2): (RN+H3)(N+H4)CO3 2‑Or (RN (II),+H3)2CO3 2‑(III), in formula, R is ethoxy；The molar ratio of the compound of the compound and logical formula (III) of logical formula (II) is 1:0 to 1:2.5.Foaming agent is suitable for preparing polyurethane interval plate foam-body material.
Description
Technical field
The present invention relates to trimethylamine 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 trimethylamine as CO2 donor as catalysis base
Novel organic ammonium salt compounds and preparation method thereof of group and solubilizing group and preparing polyurethane interval plate foam-body material
In application.The present invention relates to the polyurethane foams comprising tertiary ammonium salt and ethanolamine salt and its for (preparation) polyurethane interval
The purposes of plate 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 conduct of machine tertiary amino group
The novel organic ammonium salt compounds of solubilizing group, and its answering in foamed material such as polyurethane interval plate 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 tertiary amine groups, the first compound mixture (M1) as foaming agent releases CO in decomposition2
Generated decomposition product is tertiary 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.
According to the first embodiment of the present invention, a kind of foaming agent comprising tertiary ammonium salt and ethanolamine salt is provided, it is used
In preparing polyurethane interval plate foam-body material.The foaming agent includes:
1) the first compound mixture (M1) comprising the trimethylamine salt compound class with following general formula (I):
A-[B+]p (I)
Wherein, B+It is the cation of the trimethylamine B of+1 valence, A-It is: CO3 2-, HCO3 -Or CO3 2-With HCO3 -Conjugate；
P is in A-For HCO3 -In the case where for 1, p in A-For CO3 2-In the case where be 2；
2) comprising the mono- ethoxy-ammonium carbonate compound of N- with logical formula (II) and N, N'- bis- with logical formula (III)
Second of compound mixture (M2) of (ethoxy)-ammonium carbonate compound, i.e., a kind of alcohol amine salt compound mixture,
(RN+H3)(N+H4)CO3 2-(II),
Or
(RN+H3)2CO3 2-(III),
In formula, R is ethoxy；
The molar ratio of the compound of the compound and logical formula (III) of logical formula (II) is 1:0 to 1:2.5.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 trimethylamine 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 1:1-5.5 (preferably 1:1.3-5), Xiang You according to the molar ratio of ammonium carbonate and/or aminoquinoxaline and ethylene oxide
Ammonium carbonate and/or aminoquinoxaline and water, which are formed by slurry or saturated solution, is added ethylene oxide to allow reaction to mix
Object is reacted, [then, optionally, from be formed by vacuumized in reaction mixture removing a part water and unreacted
Ethylene oxide], obtaining aqueous organic alcohol amine mixture, (general, its pH is 7.5-10, preferably pH 8-9.7, preferably
PH 8.3-9.6, preferably pH 8.2-9.6, more preferable pH 8.5-9.5, such as pH=9), i.e. second of compound mixture
(M2)。
In this application, " optionally " indicate carry out or without.
It is preferred that the first compound mixture (M1) and the weight ratio of second of compound mixture (M2) are 0.2-
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), trimethylamine compound B
In amido 50-100% 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 compound
The 75-90% of amido in 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 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 trimethylamine B is one or more among following: three (C1-C4Alkyl) amine；E.g. select
From in trimethylamine, triethylamine, tripropylamine, tri-butylamine, dimethylethyl amine, methyidiethylamine, dimethyl propyl amine and
One of methyl dipropylamine is 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 trimethylamine 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 trimethylamine 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 for (preparation) ice polyurethane interval plate 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- ethoxy, the compound and foaming raw material
(such as polyether polyol or polyester polyol) sufficiently dissolves each other, and can be homogeneously dispersed in composition, foam and equably foam, make
The polyurethane foam that must be prepared has highly uniform distribution of cells and abscess-size.
In addition, the compound of logical formula (II) of the invention and the compound of logical formula (III) contain hydroxyl and amido simultaneously,
That is it is organic alcohol amine carbonate.CO is released in decomposition2Generated decomposition product (i.e. alcohol amine compound) is still later
So contain hydroxyl and amino, can be used as the chain extender or crosslinking agent in foamable reaction.That is, logical formula (II) of the invention
Compound and the compound existing " foaming effect " of logical formula (III) have " chain extension " or " crosslinking " effect again, lead to polyurethane foam
Body has good dimensional stability, and especially long-term dimensional stability is placed 1 year under environmental condition indoors, do not sent out
Contracting is spoilt in the distinguishable deformation of raw meat eye.
Second of compound mixture (M2) of the invention, i.e. one kind comprising N- hydroxyethylation ammonium carbonate salts compound contain
Water organic alcohol amine mixture, by being heated to 70 DEG C of a large amount of carbon dioxide of release, then, remaining alcohol amine compound carries out gas
Analysis of hplc measures the mono- ethoxy-ammonium carbonate of N- and N, N'- bis- (ethoxy)-carbonic acid in reaction product (i.e. mixture M 2)
The molar ratio of ammonium compounds is in 1:0 to 1:2.5 range, preferably 1:0.3 to 1:2, preferably 1:0.5 to 1:1 range.
Above-described logical formula (I) compound is that have as CO2The organic amine salt compounds of the anion of donor.
It is preferred that the polyurethane foamed composite object further includes: foam stabiliser, catalyst etc..These auxiliary agents are
It is common in polyurethane interval plate 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 tertiary amine compounds)；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 interval plate foam-body material, this method is included in polyurethane preparation
Introduce the 1-10% for being based on urethane raw total weight (including isocyanates and polyalcohol), above-mentioned organic uncle of preferably 2-5%
Amine salt compound or trimethylamine salt compound mixture.
The present invention also provides above-mentioned trimethylamine salt compounds or trimethylamine salt compound mixture to send out for (preparation)
Purposes in foam material such as polyurethane interval plate 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 obtained are significantly enhanced
Foams have good dimensional stability, and polyurethane foam finished product naked eyes after placing some months, even 1 year almost do not have
Shrinkage phenomenon is observed, without collapse bubble or collapse phenomenon.Long period example is placed especially under higher temperature (such as 40-70 DEG C)
As still having good dimensional stability after (10 days).
4, it when logical formula (I) compound of the invention is the compound with tertiary amine group, decomposes and discharges in the compound (I)
CO out2Generated decomposition product, that is, tertiary 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 life of polyurethane interval plate 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, herein
In density 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 of N- dimethyl benzylamine, 70% bis- (dimethylamino ethyl) ethers
Glycol solution, 70% potassium octanoate 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 silicon
Alkane 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
1.5 mL/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 trimethylamine (molecular weight 59) and 3kg water of 3kg are added in transparent quartz glass reactor, stirred evenly,
Reactor is sealed, then under constant stirring, temperature is controlled between 40-65 DEG C, carbon dioxide is passed into reactor, control
Pressing pressure is not higher than 0.3MPa, and temperature control reacts 10 hours, and pressure is bled off after cooling to 40 DEG C or less, releases product.It obtains
Compound 1.PH >=7.5, decomposition temperature is at 42 DEG C -70 DEG C.
Preparation example 2
The triethylamine (molecular weight 101) and 3.5kg water of 3kg are added in transparent quartz glass reactor, stirring is equal
It is even, reactor is sealed, then under constant stirring, temperature is controlled 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 dimethylethyl amine (molecular weight 73) of 3kg, 2.5kg are added in transparent quartz glass reactor,
It stirs evenly, seals reactor, then under constant stirring, control temperature between 40-65 DEG C, carbon dioxide is passed into instead
It answers in device, 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
Methyidiethylamine (molecular weight 87), the 3kg water of 3kg are added in transparent quartz glass reactor, stirred
Uniformly, reactor is sealed, then under constant stirring, temperature is controlled 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
The ethylene oxide of 1.7kg is then added in slurry (ammonium carbonate is not completely dissolved) in sour ammonium, cools down in stirring, control pressure is not high
In 0.6MPa, slowly temperature reaction, control temperature is consistently lower than 60 DEG C and reacts 14 hours.After the reaction was completed, temperature is slowly reduced
To 50 DEG C hereinafter, slowly removing the water and unreacted ethylene oxide of a part under the vacuum degree of 600 millimetress of mercury or so, so
After discharge vacuum, cool to and reactants be discharged after 40 DEG C or less, obtain aqueous carbonate polyol amine salt compound mixture (abbreviationization
Close object 5), belong to one of second of compound mixture M2.About 376 centipoise of viscosity, pH=9.2, point of compound 5
Solving temperature is 58-63 DEG C.With atomic absorption spectrophotometer (Seiko Instruments, Inc.；SAS/727) measurement alkali gold
Belong to and the content of alkaline-earth metal ions is lower than detectable limit.
Gas chromatographic analysis shows that compound 5 is that the mixture comprising a variety of hydramine (is referred to as second of change in this application
Polymer mixtures M2), the wherein mono- ethoxy-ammonium carbonate of N- and N, N'- bis- (ethoxy)-carbon in reaction product (i.e. mixture M 2)
The molar ratio of sour ammonium compounds is about 1:0.36.
By infrared spectrum analysis, second of compound mixture obtained is reacted by ammonium carbonate and ethylene oxide
(M2) the N- hydroxyethylation ammonium carbonate salts compound (i.e. aqueous organic alcohol amine mix product) in has in 2928-2970cm-
The stretching vibration of the secondary amine salt N-H of 1 range is unimodal, in 1550-1565cm-1The bending vibration of the secondary amine salt N-H of range is unimodal, with
And in 3210-3405cm-1The OH stretching vibration peak of the Hydrogenbond of the Qiang Erkuan of range, these show N- ethoxy of the present invention
Changing ammonium carbonate salts compound has hydroxyl and secondary amine simultaneously, while wherein containing a small amount of water.Therefore, N- hydroxyl second of the invention
Base 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
The conduct of the parts by weight of compound 1 and 4.5 prepared by example 1 made above as foaming agent of 4 parts by weight is sent out
The compound 5 prepared by example 5 made above of infusion, 30 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 20 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 PT-303 of 1 parts by weight, the potassium acetate of 1.5 parts by weight and 5 parts by weight HCFC-141b obtain thoroughly after mixing
Then 83 parts of isocyanates MDI (PM200, the limited public affairs of Yantai Wanhua chemical groups share are added in bright composition, foam wherein
Department), polyurethane foamed material is made in agitated uniformly rear foam.The material is used as polyurethane interval plate 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 168KPa.
The foam product of embodiment 1 has good heat-insulating property, can satisfy polyurethane interval plate foam-body material
The requirement of the various performances in field.
Sample is taken, amplifies 100 times of observation abscesses using SEM after being sliced with blade.As shown in fig. 1, mean cell diameter
It is 201.4 microns.Cell size is uniform.
Embodiment 2
The conduct of the parts by weight of compound 2 and 5.0 prepared by example 2 made above as foaming agent of 3 parts by weight is sent out
The compound 5 prepared by example 5 made above of infusion, 30 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 20 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 PT-303 of 1 parts by weight, the A33 of 1 parts by weight, the potassium acetate of 1.5 parts by weight and 6 parts by weight HCFC-141b it is mixed
Transparent composition, foam is obtained after closing uniformly, 83 parts of isocyanates MDI (PM200, Yantai Wanhua chemistry are then added wherein
Group Plc), polyurethane foamed material is made in agitated uniformly rear foam.The material is steeped as polyurethane interval 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 163KPa.
Embodiment 3
The conduct of the parts by weight of compound 3 and 4.5 prepared by above embodiments 3 as foaming agent of 4 parts by weight is sent out
The compound 5 prepared by example 5 made above of infusion, 30 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 20 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 production), the PT-303 of 1 parts by weight, the A33 of 1 parts by weight, the potassium acetate of 1 parts by weight and 6 parts by weight HCFC-141b mixing
Transparent composition, foam is obtained after uniformly, and 83 parts of isocyanates MDI (PM200, Yantai Wanhua chemistry collection are then added wherein
Limited liability company, group), polyurethane foamed material is made in agitated uniformly rear foam.The material is used as polyurethane interval 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 165KPa.
Embodiment 4
The conduct of the parts by weight of compound 4 and 5.5 prepared by above embodiments 4 as foaming agent of 3 parts by weight is sent out
The compound 6 prepared by example 6 made above of infusion, 30 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 20 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), PT-303 (production of air chemical company, the U.S.), the potassium acetate 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 83 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
Interval 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 36Kg/m3, compressive strength is about 147KPa.
Claims (10)
1. including a kind of foaming agent of tertiary ammonium salt and ethanolamine salt, which includes:
1) the first compound mixture (M1) comprising the trimethylamine salt compound class with following general formula (I):
A-[B+]p (I)
Wherein, B+It is the cation of the trimethylamine B of+1 valence, A-It is: CO3 2-Or CO3 2-With HCO3 -Conjugate；P is in A-For
HCO3 -In the case where for 1, p in A-For CO3 2-In the case where be 2；
2) comprising the mono- ethoxy-ammonium carbonate compound of N- with logical formula (II) and the N with logical formula (II), (the hydroxyl second of N'- bis-
Base)-ammonium carbonate compound second of compound mixture (M2),
(RN+H3)(N+H4)CO3 2-(II),
Or
(RN+H3)2CO3 2-(III),
In formula, R is ethoxy；
The molar ratio of the compound of the compound and logical formula (III) of logical formula (II) is 1:0 to 1:2.5.
2. foaming agent according to claim 1, wherein the first compound mixture (M1) is by trimethylamine 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, the molar ratio according to ammonium carbonate and/or aminoquinoxaline and ethylene oxide is
1:1-5.5 (preferably 1:1.3-5) adds to being formed by slurry or saturated solution by ammonium carbonate and/or aminoquinoxaline and water
Enter ethylene oxide to allow reaction mixture to be reacted, obtaining aqueous organic alcohol amine mixture, (general, its pH is 7.5-
10, preferably pH 8-9.7, preferably pH 8.3-9.6, more preferable pH 8.5-9.5, such as pH=9), i.e. second of compound
Mixture (M2).
4. foaming agent described in any one of -3 according to claim 1, wherein the first compound mixture (M1) and second
The weight ratio of kind compound mixture (M2) is 0.2-0.9:1, 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), trimethylamine
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 trimethylamine B is among following
It is one or more: three (C1-C4Alkyl) amine；E.g. it is selected from trimethylamine, triethylamine, tripropylamine, tri-butylamine, diformazan
Base ethylamine, methyidiethylamine, one of dimethyl propyl amine and methyl dipropylamine or a variety of.
8. a kind of polyurethane foamed composite object, it includes: 0.5-100 weight % (more preferable 2-80wt%, more preferable 4-
60wt%, more preferable 6-40wt%, such as 8wt%, 10wt%, 15wt% or 20wt%) according to claim 1 any one in -7
Foaming agent described in；The physical blowing agent of 0-50 weight %；The water and 0.0-99.5 weight % of 0-5 weight % is (preferably
20.0-98.0 weight %, more preferable 40-96wt%, more preferable 60-94wt%, more preferable 70-88wt%, more preferable 75-
Polymer polyatomic alcohol 85wt%)；Wherein, total weight of the weight percent based on polyurethane foamed composite object.
9. polyurethane foamed composite object according to claim 8, wherein polymer polyatomic alcohol is selected from: polyether polyol is gathered
Ester polyol, polyether-polyester polyol, polycarbonate glycol, polycarbonate-polyester polyalcohol, polycarbonate-polyether polyols
Alcohol, polybutadiene polyol or polysiloxane polyhydric alcohol, and the average functionality of polymer polyatomic alcohol is generally 2-16, preferably
2.5-10 more preferable 3-8；And/or
The physical blowing agent at least one of is selected from the group: pentane, isopentane, pentamethylene, boiling point is in 0-100 DEG C of range
Interior other alkane, HCFC-141b, HFC-245fa, HFC-365mfc, LBA, FEA-1100, boiling point is within the scope of 0-100 DEG C
Other fluorochlorohydrocarbons or organosilane ester.
10. foaming agent described in any one of -7 is for the use in polyurethane interval plate foam-body material according to claim 1
On the way.
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|---|---|---|---|---|
| EP0419114A2 (en) * | 1989-09-19 | 1991-03-27 | Imperial Chemical Industries Plc | Novel chemical blowing agent |
| US5143945A (en) * | 1989-07-19 | 1992-09-01 | The Dow Chemical Company | Carboxylic acid modified carbon dioxide co-blown polyurethane-polyisocyanurate foams |
| CN1111187A (en) * | 1993-11-04 | 1995-11-08 | 拜尔公司 | A process for the CFC-free production of cellular polyurethane molded parts |
| CN101939350A (en) * | 2008-02-09 | 2011-01-05 | 拜尔材料科学股份公司 | Light-fast foamed polyurethane moldings |
| CN102803325A (en) * | 2009-04-24 | 2012-11-28 | 东曹株式会社 | Foaming additive for manufacturing polyurethane foam, and rigid polyurethane foam manufacturing method using said additive |
| CN103965470A (en) * | 2014-04-30 | 2014-08-06 | 四川大学 | Hydrophobically-modified polyethyleneimine foaming agent capable of releasing carbon dioxide, and application thereof |
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2017
- 2017-08-24 CN CN201710734498.8A patent/CN109422898B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5143945A (en) * | 1989-07-19 | 1992-09-01 | The Dow Chemical Company | Carboxylic acid modified carbon dioxide co-blown polyurethane-polyisocyanurate foams |
| EP0419114A2 (en) * | 1989-09-19 | 1991-03-27 | Imperial Chemical Industries Plc | Novel chemical blowing agent |
| CN1111187A (en) * | 1993-11-04 | 1995-11-08 | 拜尔公司 | A process for the CFC-free production of cellular polyurethane molded parts |
| CN101939350A (en) * | 2008-02-09 | 2011-01-05 | 拜尔材料科学股份公司 | Light-fast foamed polyurethane moldings |
| CN102803325A (en) * | 2009-04-24 | 2012-11-28 | 东曹株式会社 | Foaming additive for manufacturing polyurethane foam, and rigid polyurethane foam manufacturing method using said additive |
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