CN109422912A - Alkaline polyamines hydramine foaming agent and the purposes for being used to prepare polyurethane coating foam-body material - Google Patents
Alkaline polyamines hydramine foaming agent and the purposes for being used to prepare polyurethane coating foam-body material Download PDFInfo
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- CN109422912A CN109422912A CN201710736824.9A CN201710736824A CN109422912A CN 109422912 A CN109422912 A CN 109422912A CN 201710736824 A CN201710736824 A CN 201710736824A CN 109422912 A CN109422912 A CN 109422912A
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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
- C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
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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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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
Disclose a kind of polyurethane alkalinity foaming agent comprising polyamines salt and propyl alcohol amine salt, the pH value of the alkalinity foaming agent is between 8.5-9.5, which includes: the first compound mixture (M1) 1) comprising the organic polyamine salt compound class with following general formula (I): A‑B+(I), wherein B+It is the cation of organic polyamine B, A‑It is: CO3 2‑, HCO3 ‑Or CO3 2‑With HCO3 ‑Conjugate；2) comprising the mono- hydroxypropyl-ammonium carbonate compound of N- with logical formula (II) and the N with logical formula (II), second of compound mixture of N'- bis- (hydroxypropyl)-ammonium carbonate compound (M2): (RN+H3)(N+H4)CO3 2‑Or (RN (II),+H3)2CO3 2‑(III), in formula, R is hydroxypropyl；The molar ratio of the compound of the compound and logical formula (III) of logical formula (II) is 1:0 to 1:1.0.Foaming agent is suitable for preparing polyurethane coating foam-body material.
Description
Technical field
The present invention relates to have to be used as CO2Purposes of the organic amine salt compound of the anion of donor as foaming agent, more
CO is used as specifically, providing and not only having2The anion and organic polyamine of donor are as catalytic group and solubilizing group
Novel organic ammonium salt compounds are preparing the application in polyurethane coating foam-body material.More specifically to alkaline alcohol
Amine foaming agent and the purposes for being used to prepare polyurethane coating foam-body material.
Technical background
For hard polyurethane foam as a kind of macromolecule new material, it is excellent that light weight, intensity are high and have extremely low thermal conductivity
The heat-insulating material of matter is widely used in cold-storage insulation, especially chemical weapons cold-storage insulation, building energy conservation, solar energy, vapour
The industries such as the household electrical appliances such as vehicle, refrigerator ice cabinet.Most important raw material is foaming agent in hard polyurethane foam production.These foaming agents remove at present
All be chlorofluorocarbon substance other than pentamethylene, due to they to the destruction of atmospheric ozone layer so national governments sign already
The international convention of " Montreal Protocol book " limits and is phased out, forbids the production and use of such product, and China is also should
The signatories to a treaty of memorandum of agreement.
China is also using second generation chlorofluorocarbon blowing agent H CFC-141b (a fluorine dichloroethanes) and ring penta at present
Alkane, the developed countries such as America and Europe are forbidden to use HCFC-141b already, and Chinese Government just freezes the consumption figure of HCFC-141b for 2013
Knot in 2009 and 2010 levels of consumption, 2015 eliminate freeze 20% consumption figure, and promise be advanced to 2025
Total ban production and use, the developed countries such as current America and Europe use third generation blowing agents pentafluoropropane (HFC-245fa)
It is all very high with the GWP (chamber effect potential value) of 3-pentafluorobutane (HFC-365mfc), second and third generation foaming agent, to atmospheric ozone
The destruction of layer is serious, therefore the American-European use that will forbid third generation blowing agents before 2017.U.S. Honeywell is public thus
Department has developed forth generation physical blowing agent chlorotrifluoropropylene (LBA), but the valuable product again, and ODP is (to ozone layer
The latent energy value of destruction) it is zero, it is more relatively environment-friendly than the third generation, it is single expensive.These physics hair other than pentamethylene in a word
Chlorine fluorine element is directed in infusion itself and production process, environmental issue is still difficult to thoroughly solve, will all be eliminated.
Prior art discloses directly by CO2As polyurethane foams, still, in view of CO2The escape of gas is with it in original
Expect that the solubility in MDI and polyester polyol and/or polyether polyol is bad, so that CO2Gas can not in composition, foam
It is uniformly dispersed, and foaming process is not easily controlled.
In addition, prior art discloses directly using a small amount of water as polyurethane foams, still, in view of the hydrogen of hydrone
Key effect and solubility of the water in polyester polyol and/or polyether polyol are bad, and hydrone is present in the form of droplet
In composition, foam (such as polyether polyatomic alcohol component), local excessive is caused to react and foam in foamed material.If made with water
For foaming agent, then includes more urea bond in polyurethane foamed material, largely effect on the intensity and heat-insulating property of foamed material.
In addition, if the dosage of the water as foaming agent improves slightly, then the performance and size of polyurethane foam can be significantly impacted
Stability.If polyurethane foam, which is known from experience, meets with asking for contraction, incipient scorch and poor insulation property using water as unique foaming agent
It inscribes (shrinkage, scorching, inadequate heat insulation).
In short, foaming agent in the prior art can not be dispersed in composition, foam with molecular level, to cause to steep
The size for being unevenly distributed uniform abscess in hole is uneven, eventually affects the strength character and thermal insulating properties of foamed material.
Summary of the invention
To overcome disadvantage existing in the prior art, goal of the invention of the invention be to provide a kind of polyurethane foams and its
Preparation method, chlorofluorocarbon, will not destroy atmospheric ozone layer.
The object of the present invention is to provide not only have to be used as CO2The anion of donor and tool organic polyamine base group conduct
The novel organic ammonium salt compounds of solubilizing group, and its application in foamed material such as polyurethane coating foam-body material.
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 polyamines base, the first compound mixture (M1) as foaming agent releases CO in decomposition2
Generated decomposition product is polyamine compounds later, they are suitable as catalysts for polyurethanes applied in material.Therefore,
Based on above-mentioned two aspect, the present invention is completed.
In this application, " as CO2The anion of donor " refers in case of heating or can in foaming process
It decomposes and releases CO2Anion.
According to the first embodiment of the present invention, a kind of alkaline hydramine foaming comprising polyamines salt and propyl alcohol amine salt is provided
Agent, the pH value of the alkalinity foaming agent are between 8.5-9.5.Due to having alkalinity, foaming activity is high, is suitable for fast foaming,
Therefore it foams while spraying suitable for polyurethane coating foam-body material is prepared.The foaming agent includes:
1) the first compound mixture (M1) comprising the organic polyamine salt compound class with following general formula (I):
A- B+ (I)
Wherein, B+It is the cation of organic polyamine B, A-It is: CO3 2-Or CO3 2-With HCO3 -Conjugate；
2) comprising the mono- hydroxypropyl-ammonium carbonate compound of N- with logical formula (II) and N, N'- bis- with logical formula (III)
Second of compound mixture (M2) of (hydroxypropyl)-ammonium carbonate compound, i.e., a kind of alcohol amine salt compound mixture,
(RN+H3)(N+H4)CO3 2-(II),
Or
(RN+H3)2CO3 2-(III),
In formula, R is hydroxypropyl, it may be assumed that HO-CH2-CH2(CH3)-or HO-CH2(CH3)-CH2-；
The molar ratio of the compound of the compound and logical formula (III) of logical formula (II) is 1:0 to 1:1.Preferably 1:0 to 1:
0.5, more preferably 1:0.1 to 1:0.3.
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 polyamine B in presence of water with CO2Made from reaction；
Still it is enough to avoid generating carbaminate it is further preferred that the amount of water is as few as possible in the reactive mixture.That is the dosage of water
So that the first compound mixture (M1) obtained is rendered as slurry state or saturated solution state, preferably slurry state
(i.e. some carbonate is undissolved).
Generally, second of compound mixture (M2) is obtained by the following method: adding or do not adding ammonium hydroxide
In the case of, it is 1:1-5.5 (preferably 1:1.3-5), Xiang You according to the molar ratio of ammonium carbonate and/or aminoquinoxaline and propylene oxide
Ammonium carbonate and/or aminoquinoxaline and water, which are formed by slurry or saturated solution, is added propylene oxide to allow reaction mixture
It is reacted, [then, optionally, from being formed by the water and unreacted for vacuumizing removing a part in reaction mixture
Propylene oxide], obtaining aqueous organic alcohol amine mixture, (general, its pH is 7.5-10, preferably pH 8-9.7, preferably pH
8.3-9.6, preferably pH 8.2-9.6, more preferable pH 8.5-9.5, such as pH=9), i.e. second of compound mixture
(M2)。
In this application, " optionally " indicate carry out or without.
It is preferred that the first compound mixture (M1) and the weight ratio of second of compound mixture (M2) are 0.3-1:
1, more preferable 0.5-0.8:1, more preferable 0.6-0.7:1.
It is preferred that in the compound of logical formula (I) or in the first compound mixture (M1), organic polyamine 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 7.0-8.8, preferably pH 7.3-8.6, more preferable pH
7.5-8.5。
It is preferred that the pH of second of compound mixture (M2) is 8.6-10, preferably 8.7-9.5, more preferable pH 8.8-9.3.
It is preferred that organic polyamine B is one or more among following: C2-C16Polyamines class；It is further preferred that organic more
Amine B is one or more among following: C2-C6Alkylenediamine class (such as ethylenediamine, propane diamine, butanediamine, penta
Diamines or hexamethylene diamine) or C4-C16Polyalkylenepolyamines class；Further preferably, organic polyamine B is selected from ethylenediamine the third two
Amine, butanediamine, pentanediamine, hexamethylene diamine, diethylenetriamines, trien, tetren, penten,
Dipropylenetriamine, tri propylidene tetramine, 4 sub-propyl-5-amine, five inferior propyl hexamine, two butylidene triamines, three butylidenes four
Amine, one of four butylidenes, five amine or triethylenediamine or a variety of.In general, there is n nitrogen-atoms, then polyamines B
Salt-forming ion is the cation with n valence.
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 polyamine 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 polyamine is those as described above.
Preferably, in above-mentioned second of compound mixture (M2) (that is, aqueous organic alcohol amine mixture), general formula
(II) the sum of both compounds of compound and logical formula (III) weight accounts for the total weight of second of compound mixture (M2)
56-96wt%, more preferable 63-90wt%, further preferred 70-86wt%.
It is preferred that the water content of second of compound mixture (M2) is 2-40wt%, preferably 6-35wt%, more preferable 10-
30wt%, more preferable 15-25wt%.
Generally, in the preparation method of above-mentioned second of compound mixture (M2), using ammonium hydroxide (such as concentration 20-
28wt%, such as 25wt%) it is used as catalyst.The dosage of the ammonium hydroxide is total weight (or the gross weight of all raw materials of reaction mixture
Amount) 0.5-7wt%, preferably 0.8-5wt%, preferably 1.0-3wt%.
According to the third aspect of the invention we, the composition of polyurethane foam is provided, that is, polyurethane foamed composite object.
The composition includes: 0.5-100 weight % (more preferable 2-80wt%, more preferable 4-60wt%, more preferable 6-
40wt%, such as 8wt%, 10wt%, 15wt% or 20wt%) above-described foaming agent；The physical blowing of 0-50 weight %
Agent；0-5 weight % water and 0.0-99.5 weight % (preferably 20.0-98.0 weight %, more preferable 40-96wt%, more preferably
60-94wt%, more preferable 70-88wt%, more preferable 75-85wt%) polymer polyatomic alcohol；Wherein, the weight percent
Total weight based on polyurethane foamed composite object.
It is preferred that the polymer polyatomic alcohol is selected from: polyether polyol, polyester polyol, polyether-polyester polyol, poly- carbon
Acid esters glycol, polycarbonate-polyester polyalcohol, polycarbonate-polyether polyol, polybutadiene polyol or polysiloxanes are polynary
Alcohol, and the average functionality of polymer polyatomic alcohol is generally 2-16, preferably 2.5-10, more preferable 3-8.
It is preferred that the physical blowing agent at least one of is selected from the group: pentane, isopentane, pentamethylene, boiling point is in 0-
Other alkane within the scope of 100 DEG C, HCFC-141b, HFC-245fa, HFC-365mfc, LBA, FEA-1100, boiling point is in 0-100
Other fluorochlorohydrocarbons or organosilane ester within the scope of DEG C.
According to the fourth aspect of the invention, above-mentioned alkaline foaming agent is provided for (preparation) polyurethane coating foam-body material
In purposes.
Present inventor is it was unexpectedly observed that the compound of above-mentioned logical formula (II) and the compound of logical formula (III) have
Suitable decomposition temperature (generally in 55-70 DEG C of range, preferably in 58-65 DEG C of range) is easy to decompose at elevated temperatures to produce
It, can be by isocyanate-monomer NCO as contained by MDI and TDI when giving birth to CO2 gas, or even being foamed at a lower temperature
Group activation, quick release go out CO2 gas.In addition, due to solubilizing group N- hydroxypropyl, the compound and foaming raw material
(such as polyether polyol or polyester polyol) sufficiently dissolves each other, and can be homogeneously dispersed in composition, foam and equably foam, make
The polyurethane foam that must be prepared has highly uniform distribution of cells and abscess-size.
In addition, the compound of logical formula (II) of the invention and the compound of logical formula (III) contain hydroxyl and amido simultaneously,
That is it is organic alcohol amine carbonate.CO is released in decomposition2Generated decomposition product (i.e. alcohol amine compound) is still later
So contain hydroxyl and amino, can be used as the chain extender or crosslinking agent in foamable reaction.That is, logical formula (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- hydroxypropylation ammonium carbonate salts compound contain
Water organic alcohol amine mixture, by being heated to 70 DEG C of a large amount of carbon dioxide of release, then, remaining alcohol amine compound carries out gas
Analysis of hplc measures the mono- hydroxypropyl-ammonium carbonate of N- and N, N'- bis- (hydroxypropyl)-carbonic acid in reaction product (i.e. mixture M 2)
The molar ratio of ammonium compounds is in 1:0 to 1:2.5 range, preferably 1:0.3 to 1:2, preferably 1:0.5 to 1:1 range.
Above-described logical formula (I) compound is that have as CO2The organic amine salt compounds of the anion of donor.
It is preferred that the polyurethane foamed composite object further includes: foam stabiliser, catalyst etc..These auxiliary agents are
It is common in polyurethane coating foam-body material or polyurethane refrigerator ice cabinet field, and with the use of common amount.
It is preferred that the physical blowing agent at least one of is selected from the group: pentane, isopentane, pentamethylene, boiling point is in 0-
Other alkane within the scope of 100 DEG C, HCFC-141b, HFC-245fa, HFC-365mfc, LBA, FEA-1100, boiling point is in 0-100
Other fluorochlorohydrocarbons within the scope of DEG C, organosilane ester etc..
Present inventor is surprised to find that the compound 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 the first 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 polyamine 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 coating foam-body material, this method is included in polyurethane preparation and draws
Enter to be based on the 1-10% of urethane raw total weight (including isocyanates and polyalcohol), the above-mentioned organic polyamine of preferably 2-5%
Salt compound or organic polyamine salt compound mixture.
The present invention also provides above-mentioned organic polyamine salt compounds or organic polyamine salt compound mixture to send out for (preparation)
Purposes in foam material such as polyurethane coating foam-body material.
Advantageous effects or advantage of the invention
1, logical formula (I) of the invention, (II) or (III) compound or foaming agent of the present invention have suitable decomposition temperature
(50-70 DEG C), or there is suitable decomposition temperature when touching isocyanates, on the one hand storage is stablized at room temperature, another
Aspect during polyurethane foam when foamable reaction system heats up can with reasonable speed carbon dioxide gas, with
So that foamed material has ideal performance, such as the distribution density of abscess, the dimensional homogeneity of abscess.Alkalinity is conducive to improve hair
Bubble activity, fast foaming, therefore it is suitable for polyurethane coating foaming.
2, logical formula (II) of the invention or (III) compound have solubilizing group, that is, alcohol amine groups, the compound (II) or
(III) polymer polyatomic alcohol such as polyether polyol and/or polyester polyol can be equably dissolved or are distributed in molecular level,
Ensure the uniformity to foam, local excessive is avoided to foam.
3, logical formula (I) compound of the invention is the carbonate of polyamine compounds, is released in the compound (I) decomposition
CO2Generated decomposition product, that is, polyamine compounds still contain at least two reactive hydrogens, and logical formula (II) or (III) later
Compound decomposition releases CO2Decomposition product alcohol amine compound is generated later, and polyamine compounds and alcohol amine compound are suitable for making
For chain extender and/or crosslinking agent, logical formula (I) of the invention, (II) and (III) compound, which were not only used as " blow point " but also were used as, " to be expanded
Chain point " and/or " crosslinking points " significantly enhance the mechanical strength and mechanical strength of abscess, polyurethane foam tool obtained
Have a good dimensional stability, polyurethane foam finished product after placing some months, even 1 year naked eyes almost without observing
Shrinkage phenomenon, without collapse bubble or collapse phenomenon.Long period such as (10 days) are placed especially under higher temperature (such as 40-70 DEG C)
Still there is good dimensional stability later.
4, it when logical formula (I) compound of the invention is the compound with polyamine group, decomposes and discharges in the compound (I)
CO out2Generated decomposition product, that is, polyamine compounds 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 production of polyurethane coating foam-body material
Using.
8, use foaming agent of the present invention or logical formula (I), (II) and (III) compound as polyurethane foam prepared by foaming agent
The size changing rate or shrinking percentage of foam material (this foamed material is to be made in laboratory self-control Fang Mo of stirring by hand)≤
10%, preferably≤5%, more preferably≤1% (according to chinese national standard GB/T 8811-2008, standing time can be according to the mark
It is required in standard, or even, standing time is 5 months).In addition, for example in 34-42Kg/m3Density foam under, thermally conductive system
Number w/mk (10 DEG C) is between 0.01900-0.02200, preferably between 0.01910-0.02150.In addition, close herein
It spends in range, the compressive strength of foams of the present invention is in 110-220Kpa range.
Detailed description of the invention
Fig. 1 is the SEM of the polyurethane foamed material of embodiment 1.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
In this application, it is used to prepare polyurethane foam or pure and mild poly- for the common polyether polyols in composition, foam
Ester polyol is selected from following kinds: polyethers 4110,450,400A, MN500, SU380, SA380,403, SA460, G350；Polyester
CF6320,DM2003,YD6004,AKS7004,CF6255.Custom catalysts are selected from: 33LV (A-33): 33% triethylene diamine
Dipropylene glycol solution, N, N- dimethylethanolamine, N, the dipropyl two of N- dimethyl benzylamine, 70% bis- (dimethylamino ethyl) ethers
Alcoholic solution, 70% potassium octanoate are in diethylene glycol solution, dibutyl tin dilaurate, PT303, PT304, potassium acetate, PC-8 (N, N-
Dimethyl cyclohexyl amine), PC-5, PC-41, triethanolamine, JXP-508, JXP-509, TMR-2, TMR-3, TMR-4.Common silane
Surfactant: DC8545, AK-158, AK-8805, AK-8812, AK-8809, AK-8818, AK-8860, DCI990,
DC5188,DC6070,DC3042,DC3201.Non- silane surface active agent: LK-221, LK-443.
Below with reference to embodiment, the present invention will be further described.
In this application, it is used to prepare polyurethane foam or pure and mild poly- for the common polyether polyols in composition, foam
Ester polyol is to be usually used in those of polyurethane foamed material in the prior art.For catalysts for polyurethanes and surfactant,
Auxiliary agent commonly used in the prior art can be used.
According to chinese national standard GB/T 26689-2011, (refrigerator, refrigerator-freezer are moulded with hard polyurethane foams in embodiment
Material) test foams properties.The size of sample is generally 10*10*2.5cm.
Thermal coefficient is carried out according to GB/T 10294-2008 or GB/T 10295-2008.Mean temperature is 10 DEG C, cold and hot
15-20 DEG C of the plate temperature difference.Apparently (core) density is tested according to GB/T 6343-2009.Compressive strength according to GB/T 8813-2008 into
Row test.
For compound containing in second of compound mixture (M2) of logical formula (II) or (III) as foaming agent
The measurement method of amount first passes through and mixture (M2) is heated to 70 DEG C or more discharges carbon dioxide, residue (i.e. alcohol amine compounds
Object) use gas chromatography.Wherein gas chromatograph is furnished with flame ionization ditector (FID), the matter for the immunomodulator compounds that foam
Measuring concentration is about 10mg/mL.GC conditions: HP-5 capillary chromatographic column (i.d. × 0.25 μm 30m × 0.32mm,
5%phenyl methyl-siloxane)；Column temperature is temperature programming, and initial temperature is 80 DEG C, with 25 DEG C/min after holding 3min
Rate rise to 250 DEG C, keep 5min；250 DEG C of injector temperature；260 DEG C of detector temperature；Carrier gas is High Purity Nitrogen, and flow velocity is
1.5mL/min；Combustion gas is hydrogen, flow velocity 30mL/min；Combustion-supporting gas is air, flow velocity 300mL/min；Make-up gas is nitrogen
Gas, flow velocity 25mL/min；Input mode is split sampling, split ratio: 30:1；Sample volume is 1 μ L.
Preparation example 1
40% ethylenediamine solution (molecular weight 60) 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
The 50% diethylenetriamines aqueous solution (molecular weight 103) of 3kg is added in transparent quartz glass reactor,
Stirring and dissolving seals reactor, then under constant stirring, controls 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 2.PH >=7.5, decomposition temperature is at 42 DEG C -70 DEG C.
Preparation example 3
The water of the trien (molecular weight 146) of 3kg, 1.8kg are added in transparent quartz glass reactor,
Stirring and dissolving seals reactor, then under constant stirring, controls 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
Tetren (molecular weight 189), the 1.8kg water of 3kg are added in transparent quartz glass reactor, stirred
Dissolution is mixed, reactor is sealed, then under constant stirring, temperature is controlled between 40-65 DEG C, carbon dioxide is passed into reaction
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 i.e.
It can.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 propylene oxide of 2.0kg is then added in slurry (ammonium carbonate is not completely dissolved) in sour ammonium, cools down in stirring, control pressure is not high
In 0.6MPa, slowly temperature reaction, control temperature is consistently lower than 60 DEG C and reacts 14 hours.After the reaction was completed, temperature is slowly reduced
To 50 DEG C hereinafter, slowly removing the water and unreacted propylene oxide of a part under the vacuum degree of 600 millimetress of mercury or so, so
After discharge vacuum, cool to and reactants be discharged after 40 DEG C or less, obtain aqueous carbonate polyol amine salt compound mixture (abbreviationization
Close object 5), belong to one of second of compound mixture M2.About 400 centipoise of viscosity, pH=9.1, the decomposition of compound 5
Temperature is 58-63 DEG C.With atomic absorption spectrophotometer (Seiko Instruments, Inc.；SAS/727 alkali metal) is measured
Content with alkaline-earth metal ions is lower than detectable limit.
Gas chromatographic analysis shows that compound 5 is that the mixture comprising a variety of hydramine (is referred to as second of change in this application
Polymer mixtures M2), the wherein mono- hydroxypropyl-ammonium carbonate of N- and N, N'- bis- (hydroxypropyl)-carbon in reaction product (i.e. mixture M 2)
The molar ratio of sour ammonium compounds is about 1:0.35.
By infrared spectrum analysis, second of compound mixture obtained is reacted by ammonium carbonate and propylene oxide
(M2) the N- hydroxypropylation ammonium carbonate salts compound (i.e.) (i.e. aqueous organic alcohol amine mix product) in has in 2930-
The stretching vibration of the secondary amine salt N-H of 2975cm-1 range is unimodal, in 1554-1567cm-1The bending vibration of the secondary amine salt N-H of range
It is unimodal, and in 3200-3400cm-1The OH stretching vibration peak of the Hydrogenbond of the Qiang Erkuan of range, these show N- of the present invention
Hydroxypropylation ammonium carbonate salts compound has hydroxyl and secondary amine simultaneously, while wherein containing a small amount of water.Therefore, of the invention
N- hydroxypropylation ammonium carbonate salts compound includes one or more hydramine carbonate compounds and typically contains a small amount of water.
Preparation example 6
Preparation example 5 is repeated, only being made of the aminoquinoxaline and ammonium carbonate of 1:1 molar ratio using same mole
Salt substitutes (same mole) ammonium carbonate.Obtain compound 6, pH=9.2.
Application Example:
Embodiment 1
By alkaline foaming agent (by the weight of compound 1 and 4.5 prepared by example 1 made above as foaming agent of 4 parts by weight
The compound 5 prepared by example 5 made above as foaming agent of amount part forms, pH=8.8), the polyether polyols of 30 parts by weight
Alcohol 4110 (being produced by the Bin Hua group of Shandong Province Accessories during Binzhou), the polyester polyol of 20 parts by weight are (by the big chemical industry in Shandong blue star east
Co., Ltd), the foam stabiliser DC3201 (production of air chemical company, the U.S.) of 1 parts by weight, the resistance of 12.5 parts by weight
Fire agent TCPP (Jiangsu Yoke Chemical Co., Ltd.'s production), the PT-303 of 1 parts by weight, the potassium acetate of 1.5 parts by weight and 5 parts by weight
HCFC-141b obtains transparent composition, foam after mixing, be then added wherein 83 parts of isocyanates MDI (PM200,
Yantai Wanhua chemical groups limited liability company), polyurethane foamed material is made in agitated uniformly rear foam.The material is used as poly-
Urethane spray foam body material.The size changing rate or shrinking percentage≤1% of gained polyurethane foamed material are (according to China national mark
Quasi- GB/T 8811-2008,5 months standing times).In addition, density foam is about 37Kg/m3, compressive strength is about
160KPa。
The foam product of embodiment 1 has good heat-insulating property, can satisfy polyurethane coating foamed material field
Various performances requirement.
Sample is taken, amplifies 100 times of observation abscesses using SEM after being sliced with blade.As shown in fig. 1, mean cell diameter
It is 207.2 microns.Cell size is uniform.
Embodiment 2
By alkaline foaming agent (by the compound 2 and 4.5 prepared by example 2 made above as foaming agent of 3.5 parts by weight
The compound 5 prepared by example 5 made above as foaming agent of parts by weight forms, pH=8.7), the polyethers of 30 parts by weight it is more
First alcohol 4110 (being produced by the Bin Hua group of Shandong Province Accessories during Binzhou), 20 parts by weight polyester polyol (by eastern bigization of Shandong blue star
Work Co., Ltd), the foam stabiliser DC3201 (production of air chemical company, the U.S.) of 1 parts by weight, 12.5 parts by weight
Fire retardant TCPP (Jiangsu Yoke Chemical Co., Ltd.'s production), the PT-303 of 1 parts by weight, the A33 of 1 parts by weight, 1.5 parts by weight
Potassium acetate and 6 parts by weight HCFC-141b obtain transparent composition, foam after mixing, and 83 parts of isocyanides are then added wherein
Polyurethane foam material is made in acid esters MDI (PM200, Yantai Wanhua chemical groups limited liability company), agitated uniformly rear foam
Material.The material is used as polyurethane coating foam-body material.The size changing rate or shrinking percentage≤1% of gained polyurethane foamed material
(according to chinese national standard GB/T 8811-2008,5 months standing times).In addition, density foam is about 39Kg/m3, pressure
Contracting intensity is about 170KPa.
Embodiment 3
By alkaline foaming agent (by the compound 3 and 4.5 prepared by example 3 made above as foaming agent of 4.0 parts by weight
The compound 5 prepared by example 5 made above as foaming agent of parts by weight forms, pH=8.7), the polyethers of 30 parts by weight it is more
First alcohol 4110 (being produced by the Bin Hua group of Shandong Province Accessories during Binzhou), 20 parts by weight polyester polyol (by eastern bigization of Shandong blue star
Work Co., Ltd), the foam stabiliser DC3201 (production of air chemical company, the U.S.) of 1 parts by weight, 12.5 parts by weight
Fire retardant TCPP (Jiangsu Yoke Chemical Co., Ltd.'s production), the PT-303 of 1 parts by weight, the A33 of 1 parts by weight, 1 parts by weight vinegar
Sour potassium and 6 parts by weight HCFC-141b obtain transparent composition, foam after mixing, and 83 parts of isocyanic acids are then added wherein
Polyurethane foamed material is made in ester MDI (PM200, Yantai Wanhua chemical groups limited liability company), agitated uniformly rear foam.
The material is used as polyurethane coating foam-body material.The size changing rate or shrinking percentage≤1% of gained polyurethane foamed material (are pressed
According to chinese national standard GB/T 8811-2008,5 months standing times).In addition, density foam is about 37Kg/m3, compression is by force
Degree is about 162KPa.
Embodiment 4
By alkaline foaming agent (by the compound 3 and 4.5 prepared by example 4 made above as foaming agent of 3.0 parts by weight
The compound 6 prepared by example 6 made above as foaming agent of parts by weight forms, pH=8.8), the polyethers of 30 parts by weight it is more
First alcohol 4110 (being produced by the Bin Hua group of Shandong Province Accessories during Binzhou), 20 parts by weight polyester polyol (by eastern bigization of Shandong blue star
Work Co., Ltd), the foam stabiliser DC3201 (production of air chemical company, the U.S.) of 1 parts by weight, 12.5 parts by weight
Fire retardant TCPP (Jiangsu Yoke Chemical Co., Ltd.'s production), the PT-303 (production of air chemical company, the U.S.) of 1 parts by weight, 1
The potassium acetate of parts by weight and 6 parts by weight HCFC-141b obtain transparent composition, foam after mixing, are then added wherein
Poly- ammonia is made in 83 parts of isocyanates MDI (PM200, Yantai Wanhua chemical groups limited liability company), agitated uniformly rear foaming
Ester foamed material.The material is used as polyurethane coating foam-body material.The size changing rate or receipts of gained polyurethane foamed material
Shrinkage≤1% (according to chinese national standard GB/T 8811-2008,5 months standing times).In addition, density foam is about
39Kg/m3, compressive strength is about 168KPa.
Claims (10)
1. a kind of alkaline hydramine foaming agent comprising polyamines salt and propyl alcohol amine salt, the pH value of the alkalinity foaming agent is in 8.5-9.5
Between, which includes:
1) the first compound mixture (M1) comprising the organic polyamine salt compound class with following general formula (I):
A- B+ (I)
Wherein, B+It is the cation of organic polyamine B, A-It is: CO3 2-Or CO3 2-With HCO3 -Conjugate；
2) comprising the mono- hydroxypropyl-ammonium carbonate compound of N- with logical formula (II) and the N with logical formula (II), bis- (hydroxypropyl of N'-
Base)-ammonium carbonate compound second of compound mixture (M2),
(RN+H3)(N+H4)CO3 2-(II),
Or
(RN+H3)2CO3 2-(III),
In formula, R is hydroxypropyl, it may be assumed that HO-CH2-CH2(CH3)-or HO-CH2(CH3)-CH2-；
The molar ratio of the compound of the compound and logical formula (III) of logical formula (II) is 1:0 to 1:1.0.
2. foaming agent according to claim 1, wherein the first compound mixture (M1) is by organic polyamine B in water
In the presence of with CO2Made from reaction；Preferably, the amount of water is as few as possible in the reactive mixture is still enough to avoid generating ammonia
Base formates.
3. foaming agent according to claim 1 or 2, wherein second of compound mixture (M2) is to make by the following method
: in the case where adding or not adding ammonium hydroxide, the molar ratio according to ammonium carbonate and/or aminoquinoxaline and propylene oxide is
1:1-5.5 (preferably 1:1.3-5) adds to being formed by slurry or saturated solution by ammonium carbonate and/or aminoquinoxaline and water
Enter propylene oxide to allow reaction mixture to be reacted, obtaining aqueous organic alcohol amine mixture, (general, its pH is 7.5-
10, preferably pH 8-9.7, preferably pH 8.3-9.6, more preferable pH 8.5-9.5, such as pH=9), i.e. second of compound
Mixture (M2).
4. foaming agent described in any one of -3 according to claim 1, wherein the first compound mixture (M1) and second
The weight ratio of kind compound mixture (M2) is 0.3-1:1, more preferable 0.5-0.8:1.
5. foaming agent described in any one of -4 according to claim 1, wherein in the compound of logical formula (I), organic polyamine
The 50-100% of amido in compound B is by anion A-It neutralizes, the 65-100% quilt of the amido in preferably organic amine compound B
Anion A-It neutralizes；It is further preferred that the 75-100% of the amido in organic amine compound B is by anion A-It neutralizes；It is further preferred that organic
The 75-90% of amido in amine compounds B is by anion A-It neutralizes；And/or
The first compound mixture (M1) or second of respective water content of compound mixture (M2) independently are 2-
40wt%, preferably 5-35wt%, more preferable 10-30wt%, more preferable 15-25wt%.
6. foaming agent described in any one of -5 according to claim 1, wherein the pH of the first compound mixture (M1) is
7.0-8.8, preferably pH 7.3-8.6, more preferable pH 7.5-8.5；And/or
The pH of second of compound mixture (M2) is 8.6-10, preferably 8.7-9.5, more preferable pH 8.8-9.3.
7. foaming agent described in any one of -6 according to claim 1, wherein organic polyamine B is among following
It is one or more: C2-C16Polyamines class；It is further preferred that organic polyamine B is one or more among following: C2-C6Alkylene
Base Diamines (such as ethylenediamine, propane diamine, butanediamine, pentanediamine or hexamethylene diamine) or C4-C16Polyalkylenepolyamines class；Into one
Preferably, organic polyamine B is selected from ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, diethylenetriamines, Sanya to step
Tetramine, tetren, penten, dipropylenetriamine, tri propylidene tetramine, 4 sub-propyl-5-amine, five
Propylidene hexamine, two butylidene triamines, three butylidene tetramines, one of four butylidenes, five amine or triethylenediamine 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 purposes in polyurethane coating foam-body material according to claim 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022160439A1 (en) * | 2021-01-27 | 2022-08-04 | 山东理工大学 | Alkanolamine carbonate foaming agent composition for polyurethane rigid foam |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59191743A (en) * | 1983-04-14 | 1984-10-30 | Sanabotsuto Kk | Production of urethane foam |
| EP0909770A1 (en) * | 1997-10-15 | 1999-04-21 | Tosoh Corporation | Amine catalyst for producing polyurethane and polyisocyanurate |
| CN101939350A (en) * | 2008-02-09 | 2011-01-05 | 拜尔材料科学股份公司 | Light-fast foamed polyurethane moldings |
| CN102190811A (en) * | 2011-03-16 | 2011-09-21 | 杭州海虹精细化工有限公司 | Foaming agent subjected to surface modification by fluorosilane and preparation method thereof |
| CN104945599A (en) * | 2015-06-18 | 2015-09-30 | 常州大学 | Latent epoxy resin curing-foaming agent and method for preparing the same |
-
2017
- 2017-08-24 CN CN201710736824.9A patent/CN109422912B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59191743A (en) * | 1983-04-14 | 1984-10-30 | Sanabotsuto Kk | Production of urethane foam |
| EP0909770A1 (en) * | 1997-10-15 | 1999-04-21 | Tosoh Corporation | Amine catalyst for producing polyurethane and polyisocyanurate |
| CN101939350A (en) * | 2008-02-09 | 2011-01-05 | 拜尔材料科学股份公司 | Light-fast foamed polyurethane moldings |
| CN102190811A (en) * | 2011-03-16 | 2011-09-21 | 杭州海虹精细化工有限公司 | Foaming agent subjected to surface modification by fluorosilane and preparation method thereof |
| CN104945599A (en) * | 2015-06-18 | 2015-09-30 | 常州大学 | Latent epoxy resin curing-foaming agent and method for preparing the same |
Non-Patent Citations (1)
| Title |
|---|
| 刘惠明等: "副产己基胺聚醚多元醇的开发与应用", 《化工时刊》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022160439A1 (en) * | 2021-01-27 | 2022-08-04 | 山东理工大学 | Alkanolamine carbonate foaming agent composition for polyurethane rigid foam |
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