CN109021281A - A kind of composite foamable agent and its purposes for preparing polyurethane foam - Google Patents
A kind of composite foamable agent and its purposes for preparing polyurethane foam Download PDFInfo
- Publication number
- CN109021281A CN109021281A CN201810721437.2A CN201810721437A CN109021281A CN 109021281 A CN109021281 A CN 109021281A CN 201810721437 A CN201810721437 A CN 201810721437A CN 109021281 A CN109021281 A CN 109021281A
- Authority
- CN
- China
- Prior art keywords
- component
- parts
- composite foamable
- added
- carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- 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
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/16—Unsaturated hydrocarbons
- C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
-
- 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
- C08J2375/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of composite foamable agent comprising component A and component B, by weight, component A include following component: (A1) includes 100 parts of polyether polyol of 10-20 parts of modified polyoxyethylene polyoxypropylene polylols；(A2) 5-10 parts of modified ester polyols；(A3) 10-30 parts of phenyl amines carbonate-ethanolamines bicarbonate mixtures as carbon dioxide donor；Component B includes following component: (B1) 5-20 parts of butene compounds replaced by 4,5 or 6 fluorine atoms；(B2) 1-25 parts of other physical blowing agents and 0.5-10 parts of deionized waters；(B3) 0.5-10 parts of auxiliary agents.Further relate to purposes of the composite foamable agent in preparation polyurethane foam, the composite foamable agent passes through unique component modified and selection, to have very excellent foam performance, it can make polyurethane foam that there is good heat preservation and mechanical strength, and then have a good application prospect and be worth in multiple technical fields.
Description
Technical field
The present invention relates to a kind of foaming agents and application thereof, more particularly, to a kind of composite foamable agent and its prepare polyurethane foam
The purposes of foam belongs to foaming agent technical field.
Background technique
In technical field of macromolecules, polyurethane foam is presently the most common macromolecule heat-insulating material, has
Many advantages, such as light weight, intensity height, thermal conductivity, it is widely used to energy-saving building materials, automobile interior decoration, cold-storage insulation material
The specific fields such as material, refrigerator-freezer.
Measuring a whether excellent important parameter of polyurethane foam heat-insulating property is thermal coefficient.And polyurethane foam material
The heat transfer of material relies primarily on three kinds of approach: the solid phase conduction and heat radiation of vapor, foamed bulk in abscess.Work as temperature
When spending lower, minimum, influence of the vapor in bubble to thermal coefficient to account for about foam volume 90% of heat radiation heat transfer
Maximum, the i.e. type and dosage for depending mainly on the size of foaming agent of foam thermal conductivity.Currently, these foaming agents are in addition to ring penta
Most of other than alkane is chlorofluorocarbon substance, and since they can destroy atmospheric ozone layer, national governments, which have signed, " is covered special
The international convention of Lear memorandum of agreement " limits and is phased out, forbids the production and use of such product.
Currently, the material more friendly to ozone layer, such as hydro fluorocarbons (HFC) are instead of Chlorofluorocarbons.Chlorofluorocarbons
Compound has proved to be the maximum arch-criminal of greenhouse gases, causes global warming and by the protocol about climate change
It is limited.The currently used foaming agent for thermosetting foams mainly includes HCFC-141b, and pentane class isomers have can
Combustion property and have low-yield efficiency.Therefore, finding new alternative foaming agent is inexorable trend.
Third generation blowing agents pentafluoropropane (HFC-245fa) and 3-pentafluorobutane that the developed countries such as America and Europe use at present
(HFC-365), both substances are still more serious to the destruction of atmospheric ozone layer.Therefore, American-European countries gradually forbids
The use of third generation blowing agents.Honeywell Inc. has developed forth generation physical blowing agent chlorotrifluoropropylene (LBA), but should
Valuable product, ODP (to the latent energy value of the destruction of ozone layer) is although be zero, to the chamber effect potential value of atmosphere
(GWP) still higher.
CN106750490 discloses a kind of foaming agent for thermosetting foams.This foaming agent is individual or and hydrogen
The 2,4,4,4- tetrafluoro butene-1 that fluoroolefins (HFO), hydrofluoroalkane (HFC), hydro-chloro fluoroolefin (HCFO) or hydrocarbon combine.The foaming
Agent is effective as one of manufacture of thermosetting foams foaming agent.But the foaming agent is not still avoided that chlorine fluoroolefins
It uses.
In addition, additionally using carbon dioxide in the prior art as polyurethane foams.But, it is contemplated that gas titanium dioxide
The fugacity of carbon and its solubility in raw material MDI and polyester polyol and/or polyether polyol are simultaneously bad, to make
Obtaining carbon dioxide can not be uniformly dispersed in composition, foam, and foaming process is not easy to control.Therefore, titanium dioxide is directly used
There are still certain defects for carbon.
In addition, there are also the prior art using water as polyurethane foams.But due to hydrogen bond very strong in hydrone
Effect, solubility of the hydrone in polyester polyol and/or polyether polyol and bad, so as to cause hydrone usually with micro-
The form of drop is present in polyether polyatomic alcohol component, typically results in local excessive foaming, and then affect the strong of final material
Degree and heat-insulating property.
Outside removing carbon dioxide and water, with hexafluorobutene substance such as 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene are the halogen of representative
Belong to liquid blowing agent for alkene, have many advantages, such as following: ODP is close to 0, GWP value less than under 7, small toxicity, normal temperature and pressure
It is nonflammable, thermal coefficient is small (for 10.2mW/ (mK)) at 25 DEG C, be preferable forth generation foaming agent, more and more
Applied in foaming agent.
By a large amount of further investigations of researcher, more foaming agents have also been developed, such as:
CN 102597035A discloses the combination of a kind of anti-form-1-chloro- 3,3,3- trifluoro propene and polyol blends
Object；
CN 102498237B, which is disclosed, prepares polyurethane foam by foaming agent of the chloro- 3,3,3- trifluoro propene of 1-；
CN 103881131 discloses the foaming agent group containing 1- chloro- 3,3,3- trifluoro propene and 1,1,1,3,3- pentafluoropropene
Object is closed, it is lower with the polyurethane foam thermal coefficient that it is prepared.
But there are still some defects for above-mentioned foaming agent and thus obtained product, such as drop is easy in reaction process
Activity, the storage stability of low catalyst are shorter etc., significantly limit its extent of spreading amd application.
Therefore, seek novel foaming agent, foaming method and thus obtained polyurethane foam, be still that current polyurethane produces
Industry technical problem in the urgent need to address.
Summary of the invention
For the disadvantages mentioned above and deficiency for overcoming the prior art, the present invention provides a kind of novel composite foamable agent system, with
And the composite foamable agent is used to prepare the purposes of polyurethane foam.
It should be noted that in the present invention, term "comprising" used, " comprising ", " having ", " containing " or its it is any its
It is deformed, it is intended that covers the " comprising " of non-exclusionism.For example, composition, step, method, product or dress comprising listed elements
Set and be not necessarily limited to those elements, but may include not expressly listed other elements or such composition, step, method,
Product or the intrinsic element of device.
Specifically, technical scheme is as follows.
The first purpose of this invention, provides a kind of composite foamable agent, and the composite foamable agent includes component A and component B,
By weight, in which:
The component A includes following component:
(A1) comprising 100 parts of polyether polyol of 10-20 parts of modified polyoxyethylene polyoxypropylene polylols；
(A2) 5-10 parts of modified ester polyols；
(A3) 10-30 parts of phenyl amines carbonate-ethanolamines bicarbonate mixtures as carbon dioxide donor,
In, the mass ratio of the phenyl amines carbonate and ethanolamines bicarbonate is 2-5:1, and phenyl amines carbonate-ethyl alcohol
Amine bicarbonate mixture has 15wt% water content below；
The component B includes following component:
(B1) the 5-20 parts of butene compounds replaced by 4,5 or 6 fluorine atoms；
(B2) 1-25 parts of other physical blowing agents and 0.5-10 parts of deionized waters；
(B3) 0.5-10 parts of auxiliary agents, the auxiliary agent include catalyst, surfactant and optional other additives.
It explains in more detail, in the composite foamable agent, the dosage of each component in component A and B is exactly above-mentioned
Respective parts by weight.
In component (A1), the 10-20 parts by weight in the 100 parts by weight polyether polyol are modified polyoxypropylene polyoxy
Vinyl polyols, and remaining 80-90 parts by weight are then conventional polyether polyol, it can be directly commercially available, or by initiator
It is prepared with oxyalkylene reaction, oxyalkylene is selected from propylene oxide and/or ethylene oxide.
For example, the conventional polyether polyol can be GP-725, GP-4520, TEAP-265, GP- of CARPOL company
4000 etc. perhaps SD-360, AD-310, SG-361, SD-522, S-490 of JEFFOL company etc. or a Nowe polyurethane are public
SA380, polyether polyol 2100 of Jiangsu Hai'an petrochemical industry of department etc..Those skilled in the art can carry out suitably select and
It determines, is no longer described in detail herein.
In component (A1), the modified polyoxyethylene polyoxypropylene polylol is made by the steps to obtain:
Polyoxyethylene polyoxypropylene polyalcohol and methyl hexahydrophthalic anhydride are added in reactor, proper catalyst is added,
Air in logical nitrogen metathesis reactor, is then heated to 125-130 DEG C, insulation reaction 0.5 hour；Then to reaction mixture
Middle addition hydroquinone and glycidyl methacrylate, and it is cooled to 100-105 DEG C, continue insulation reaction at such a temperature
1-2 hours, when detecting the content of epoxides less than 1wt%, it is initially added into 2-methylimidazole, and is warming up to 120 DEG C and continues instead
It answers 1-2 hours, until reaction was completed after resulting resin viscosity is steady, cooled to room temperature is to get arriving the modified polyoxy third
Alkene polyoxyethylene polylol.
Wherein, the polyoxyethylene polyoxypropylene polyalcohol is a kind of very well known substance, can pass through a variety of business canals
Road and buy acquisition, may be, for example, the Specflex-NC630 etc. of Dow Co. company, be no longer described in detail herein.
Wherein, the mass ratio of the polyoxyethylene polyoxypropylene polyalcohol and methyl hexahydrophthalic anhydride can be 15-25:1, such as
It can be 15:1,20:1 or 25:1.
Wherein, the catalyst is ethyl (triphenylphosphine) acetic acid esters, and those skilled in the art can close its dosage
Suitable selection, such as its dosage can be the 0.1-0.2% of the polyoxyethylene polyoxypropylene polyol quality.
Wherein, the quality of the polyoxyethylene polyoxypropylene polyalcohol and hydroquinone, glycidyl methacrylate
Than being respectively 1000:2-3 (such as 1000:2,1000:2.5 or 1000:3) and 20-25:1 (such as 20:1,22:1 or 25:1).
Wherein, the mass ratio of the polyoxyethylene polyoxypropylene polyalcohol and 2-methylimidazole is 40-50:1, be may be, for example,
40:1,45:1 or 50:1.
In component (A2), the modified ester polyol is made by the steps to obtain:
Reactor is added in ethylene oxide mono acrylic ester, N- methylimidazole and lower alkyl alcohol, leads to nitrogen metathesis reactor
In air, be stirred to react at 30 DEG C 15-30 minutes, oil bath is warming up to 42-45 DEG C after solution becomes transparent, and the reaction was continued
Terminate after being substantially free of imidazole radicals into reaction mixture, evaporating solvent under reduced pressure, concentrated reaction mixture is to get the modified ester
Polyalcohol.
Wherein, the mass ratio of the ethylene oxide mono acrylic ester and N- methylimidazole is 4-5:1, may be, for example, 4:1,
4.5:1 or 5:1；The ethylene oxide mono acrylic ester is a kind of very well known compound, is no longer described in detail herein.
Wherein, the mass ratio of the ethylene oxide mono acrylic ester and lower alkyl alcohol be 1-2:1, may be, for example, 1:1,
1.5:1 or 2:1；The lower alkyl alcohol may be, for example, methanol, ethyl alcohol or normal propyl alcohol.
In component (A3), the phenyl amines carbonate is made by the steps to obtain:
By 1-2 amino on phenyl ring by alkylidene acid ammonium substituent group (i.e.-(CH2)nCOONH4) replace phenyl amines chemical combination
Object and suitable water-ethylene glycol mixed solvent are added in reactor, and wherein ethylene glycol weight is the 10-30% of water weight；It fills
Divide stirring and dissolving complete, after leading to the air in nitrogen metathesis reactor, catalyst ethamine is added, and be warming up to 50-55 DEG C, stirs
The lower epoxyalkane being added selected from propylene oxide or ethylene oxide, isothermal reaction 8-10 hours under 0.15-0.3MPa pressure, instead
It removes excess of solvent after answering under reduced pressure, and controls products therefrom water content lower than 15wt%, viscosity is 300-500 centipoise, i.e.,
Obtain the phenyl amines carbonate.
Wherein, the integer of n=0-2 may be, for example, 0,1 or 2.
Wherein, the phenyl amines (hereinafter referred to as " amino benzenes compounds ") replaced by alkylidene acid ammonium substituent group embodies
Close object may be, for example, carbanilic acid ammonium, amino phenyl acetate ammonium, o-dihydroxy ammon base ammonium formate, 1,3- diamino acid ammonium benzene or
Three (aminoquinoxaline) benzene etc..
Wherein, there is no stringent restrictions for the dosage of water-ethylene glycol mixed solvent, as long as it facilitates reaction and subsequent operation
, can suitably be selected according to actual needs.
Wherein, the mass ratio of the amino benzenes compounds and catalyst ethamine is 10-20:1, may be, for example, 10:1,15:1
Or 20:1.
Wherein, the mass ratio of the amino benzenes compounds and epoxyalkane be 1:1-1.4, may be, for example, 1:1,1:1.2 or
1:1.4。
In component (A3), the ethanolamines bicarbonate is made by the steps to obtain:
The mixture of ammonium hydrogen carbonate, water, ethylene glycol amine and ethanol amine is added in reactor, and propyl formate is added,
Stirring and dissolving is led to the air in nitrogen metathesis reactor, is then sealed, by the ring selected from propylene oxide or ethylene oxide under stirring
Oxygen alkane is added in reactor, controls 50-60 DEG C of reaction temperature, pressure 0.1-0.3MPa, is kept for thermotonus 6-10 hours, from
It so cools, removed under reduced pressure solvent and unreacted alkane to obtain ethanolamines bicarbonate mixture, and control institute
The water content for obtaining product is lower than 10wt%, and product viscosity is 200-300 centipoise.
Wherein, the mass ratio of ammonium hydrogen carbonate, water, ethylene glycol amine and ethanol amine is 1:1-1.4:0.1-0.15:0.05-
0.08。
Wherein, the mass ratio of ammonium hydrogen carbonate and propyl formate is 45-55:1, may be, for example, 45:1,50:1 or 55:1.
Wherein, the mass ratio of ammonium hydrogen carbonate and epoxyalkane is 1:2.
It, can be in polyurethane foam by using the above-mentioned phenyl amines carbonate and ethanolamines bicarbonate being prepared
In the preparation of foam, when it is contacted with isocyanates, carbon dioxide gas can be quickly released, while also releasing an a small amount of oxidation
Carbon gas, the quick excellent foam performance not having with other Typical physical foaming agent such as methyl formates not only, and can be with
Other components when preparing polyurethane produce certain crosslinked action, and decomposition temperature can be improved to a certain extent, into
One step improves the applicability of obtained polyurethane foam, practicability and high temperatures, has better universality.
In component (B1), the butene compounds that described 4,5 or 6 fluorine atoms replace can be commercially available, such as
Can be cis-1,1,1,4,4,4-hexafluoro-2-butene, anti-form-1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene or 2,4,4,4- tetra- is fluoro-
Any one in 1- butylene etc. or any a variety of, with arbitrary proportion mixing mixtures.
In component (B2), the physical blowing agent is selected from other routines in addition to alkenyl halide, well known in the art
Physical blowing agent, including hydrocarbon and/or volatile organic matter matter, for example, alkane, fluoric ether, carbon dioxide, aldehyde,
The compounds such as ester, alkoxy methane, ether, ketone.
More specifically, may be, for example, HFC-125, carbon dioxide, pentane, 1- fluorine pentane, methyl formate, normal butane,
Iso-butane, HFC-227ea, dimethyl ether, dimethoxymethane, in acetone any one or it is any several.
In component (B3), the auxiliary agent is the different demands according to polyurethane foam and the auxiliary agent accordingly added.
Wherein, it includes the functional group that can be chemically reacted with the isocyanates in later step that catalyst, which may be, for example,
The compounds such as aminoalkyl urea, amine, amino ethers, or be organic catalyst or metal tin catalyst.
More specifically, the catalyst can be dimethylaminoethyl ether, N, N, the double amino second of N- trimethyl-N '-ethoxy
It is any one in base ether, (3- dimethyl-amino propylamine) urea or dibutyltin oxide, dibutyl tin dilaurate, tin octoate etc.
Kind or any a variety of mixture.
Wherein, the surfactant can be to guarantee stabilization when polyurethane foam and use regular activated dose, can quotient
Purchase is obtained or is prepared according to this field conventional method.
More specifically, the surfactant can be organosiloxane-oxyalkylene hydrocarbon copolymer class activating agent, may be, for example,
DC193, DC-197 and DC- of B8404, B8407, B8409 and B8462 of Goldschmidt company, Air Products company
In L-5130, L-5180, L-5340, L-5440, L-6100 of 5582 or Momentive company etc. any one or it is any
A variety of mixtures.
Wherein, other additives may be, for example, pigment, age resister, light stabilizer, fire retardant, sticker, plasticizer, resist
Electrostatic agent, bacteriostatic agent, antioxidant or filler etc., these can be commercially available, and can choose in polyurethane foam field
Common specific substance, be no longer described in detail herein.
As described above, the present invention provides a kind of novel composite foamable agent systems, are selected by unique component
With use so that obtained polyurethane has good multiple performance, have in polyurethane preparation field and good answer
With and promotional value.
The second aspect, the present invention relates to purposes of the composite foamable agent in polyurethane foam preparation method.
More specifically, the polyurethane foam preparation method includes the following steps:
Step S1: the composite foamable agent is prepared；
Step S2: preparation polyether polyol carbonate products；
Step S3: blocked isocyanate prepolymer is prepared by the polyether polyol carbonate products；
Step S4: the composite foamable agent and the blocked isocyanate prepolymer being mixed, foamed, to be made
Polyurethane foam.
More specifically, the step S1 is as follows:
Step S1: each component of said components A and B are weighed respectively, first mixes each component in component B
Uniformly, (A1) and (A2) that component A is added adds (A3) of component A, stirs evenly after mixing, until obtaining transparent
Or clear foaming mixture, to obtain composite foamable agent.
Wherein, as described above, the parts by weight of component A and B are exactly to form the respective parts by weight of each component of A and B.
Wherein, all restrictions of component (A1), (A2), (A3), (B1), (B2) and (B3) are homogeneously same as above-mentioned composite foamed
Restriction in agent is not repeated to list herein for the sake of saving length.
More specifically, the step S2 is specific as follows:
Step S2: preparation polyether polyol ester compounds, the polyether polyol ester compounds have 50-100mg KOH/
The OH value of g, preferably with the OH value of 55-75mg KOH/g.
In the step S2, the polyether polyol carbonic ester is made by the steps to obtain:
In a high pressure reaction kettle, in the presence of double metal cyanide catalyst and auxiliary agent, polyether polyol is added, leads to
Nitrogen displacement, is heated to 130 DEG C, is passed through enough carbon dioxide pressurizations, add propylene oxide, while according to 1 DEG C/min of drop
Temperature is down to 105 DEG C from 130 DEG C by warm rate, continues stirring 0.5-1 hours after propylene oxide addition, then natural
It is cooling, and removing volatile components are evaporated, obtain polyether polyol carbonic ester.
Wherein, the double metal cyanide catalyst is well-known catalysts used in synthesizing polyether glycol ester,
It is found in more periodicals in the prior art and/or patent application, is no longer described in detail herein.
Wherein, the auxiliary agent is p-tert-Butylcatechol.
Wherein, the polyether polyol is also a very well known substance, may be, for example, polypropylene oxide trihydroxylic alcohol, gathers
Propylene oxide dihydric alcohol etc..
Wherein, the mass ratio of the polyether polyol and double metal cyanide catalyst is 800-1000:1, such as
It can be 800:1,900:1 or 1000:1.
Wherein, the mass ratio of the polyether polyol and auxiliary agent be 100-200:1, may be, for example, 100:1,150:1 or
200:1。
Wherein, the dosage of carbon dioxide is at least the dosage that can be all esterified the hydroxyl of the polyether polyol, this
Field technical staff suitably can be determined and be selected, and be no longer described in detail herein.
Wherein, the mass ratio of the polyether polyol and propylene oxide is 1:3-4, may be, for example, 1:3,1:3.5 or 1:4.
More specifically, the step S3 specifically comprises the following steps:
(1) prewired isocyanate mixture: the mixture include 65-75wt% diphenyl-methane-group diisocyanate and
25-35wt% polyphenyl polymethylene polyisocyanates, wherein diphenyl-methane-group diisocyanate is selected from 4,4'- diphenylmethane group
Diisocyanate or 2,4'- '-diphenylmethane diisocyanate, the polyphenyl polymethylene polyisocyanates have 30-35wt%
NCO base content；
(2) in the reactor, the polyether polyol for being 38-40mg KOH/g by the isocyanate mixture and OH value,
With polyether polyol carbonic ester made from step S2, mix 2-5 minutes under agitation, then 30-35 DEG C of temperature strip
Stewing process 12-16 hours under part, then by the prepolymer mixing of generation 3-5 minutes to get the blocked isocyanate pre-polymerization
Object.
Wherein, in step (1), polyphenyl polymethylene polyisocyanates are a kind of known substance, commonly referred to as PAPI
Or thick MDI, acquisition can be bought by commercial channel, may be, for example, the M20S of BASF；MR200, MR100 of three wells；Yantai ten thousand
PM2010, PM200 of Hua company；44V-10L, 44V-20L, 44V-40L of Bayer；The Suprasec5005 of Huntsman,
Suprasec2085,Suprasec 5000；And PAPI27 or PAPI135 of Dow company etc..It is no longer retouched in detail herein
It states.
Wherein, in the step (1), the concrete operations of the prewired isocyanate mixture are to limit above-mentioned content
Diphenyl-methane-group diisocyanate is uniformly mixed with polyphenyl polymethylene polyisocyanates.
Wherein, it in step (2), as described above, the polyether polyol is a very well known substance, may be, for example,
Polypropylene oxide trihydroxylic alcohol, Polyoxypropylene diol etc. can also be 28:72's as primer and weight ratio by using glycerol
Oxypropylene-oxyethylene mixture carries out addition reaction and is prepared, this be found in it is much more in the prior art, no longer into
Row detailed description.
Wherein, in step (2), the mass ratio of the isocyanate mixture and polyether polyol is 100:1-2, such as
It can be 100:1,100:1.5 or 100:2.
Wherein, in step (2), the mass ratio of the isocyanate mixture and polyether polyol carbonate products is
10-15:1 may be, for example, 10:1,12:1 or 15:1.
More specifically, the step S4 is specific as follows:
By the blocked isocyanate prepolymer of the composite foamable agent of step S1 and step S3 according to 1:0.8-1.4
Mass ratio be sufficiently mixed, and foam, to obtain polyurethane foam.
Wherein, the technological means such as the concrete operation step of foaming, temperature are all that the very well known routine in foaming field is known
Know, composite foamable agent can such as be mixed in foaming pipette tips with blocked isocyanate prepolymer, be injected in closed foaming mould
Hard polyurethane foams are made, operation, technological parameter so etc. is all that known to those skilled in the art and can carry out
General adjustment is no longer described in detail herein.
The inventors discovered that in the present invention, by using the novel composite foamable agent and above-mentioned unique preparation
Method, so that polyurethane foam obtained has excellent many performances, thus may be used in heat-insulating material, it can be extensive
For in many concrete applications such as low-temperature insulation, insulation, to there is good application potential and use value.
In conclusion the present invention provides a kind of novel composite foamable agent and its being used to prepare the purposes of polyurethane, make
With the composite foamable agent and unique polyurethane preparation method, so that obtained polyurethane has many excellent properties,
Such as:
1, polyurethane foam of the invention has ideal mechanical performance and uniform foam cell distribution density, especially in low temperature
There is down significant low thermal conductivity and dimensional stability.
2, polyurethane foam of the present invention is by using modified polyoxyethylene polyoxypropylene polylol, modified ester polyol
Deng, the furthermore use of composite foamed system, there is good mechanical strength, can be used as the good compatible material of the liners such as refrigerator-freezer.
3, by the present invention in that with unique composite foamable agent, especially with the use of modified polyoxyethylene polyoxypropylene base
Polyalcohol, modified ester polyol and blocked isocyanate prepolymer etc., to significantly enhance the mechanical strength and machinery of abscess
Intensity, and make hole bubble that there is reasonable aperture.
4, the present invention does not use chlorofluorocarbon blowing agent, and the latent energy value to the destruction of ozone layer is 0, GWP (greenhouse effects potential
Value) less than 2, the feature of environmental protection is high.
5, phenyl amines carbonate-ethanolamines bicarbonate component used in the present invention does not allow volatile, decomposition temperature
Height avoids Typical physical foaming agent especially summer is volatile at a lower temperature, brings the defect of peculiar smell.
6, foam mechanical function admirable of the invention, dimensional stability is high, and material structure is stablized, and can steadily be used for low
In warm environment.
In conclusion composite foamable agent of the invention has a good application prospect and market value.
Specific embodiment
Below by specific preparation example and embodiment, the present invention is described in detail, but these exemplary embodiments
Purposes and purpose be only used to enumerate the present invention, any type of any limit not is constituted to real protection scope of the invention
It is fixed, it is more non-that protection scope of the present invention is confined to this.
It should be noted that unless otherwise defined, all technical terms and scientific terms used herein have and this hair
The identical meanings that bright one skilled in the art understand and grasp, difference or difference if it exists then should be according to this explanations
Definition in book is understood and is defined.Preparation example 1: the preparation of modified polyoxyethylene polyoxypropylene polylol
By polyoxyethylene polyoxypropylene polyalcohol (for the Specflex-NC630 of Dow Co. company) and methyl hexahydrophthalic anhydride
Be added in reactor, be added catalyst ethyl (triphenylphosphine) acetic acid esters, lead to nitrogen metathesis reactor in air, then plus
Heat is to 128 DEG C, insulation reaction 0.5 hour；Then to addition hydroquinone and methyl propenoic acid glycidyl in reaction mixture
Ester, and 102 DEG C are cooled to, continue insulation reaction 1.5 hours at such a temperature, when detecting the content of epoxides less than 1wt%,
It is initially added into 2-methylimidazole, and is warming up to 120 DEG C the reaction was continued 1.5 hours, until terminating after resulting resin viscosity is steady anti-
It answers, cooled to room temperature is to get to modified polyoxyethylene polyoxypropylene polylol, and viscosity is 4.5Pa.s at room temperature.
Wherein, the mass ratio of polyoxyethylene polyoxypropylene polyalcohol and methyl hexahydrophthalic anhydride is 20:1；Catalyst amount is
The 0.15% of polyoxyethylene polyoxypropylene polyol quality；Polyoxyethylene polyoxypropylene polyalcohol and hydroquinone, metering system
The mass ratio of acid glycidyl ester is respectively 1000:2.5 and 22:1；Polyoxyethylene polyoxypropylene polyalcohol and 2-methylimidazole
Mass ratio is 45:1.
Preparation example 2: the preparation of modified ester polyol
Reactor is added in ethylene oxide mono acrylic ester, N- methylimidazole and methanol, leads to the sky in nitrogen metathesis reactor
Gas is stirred to react 23 minutes at 30 DEG C, and oil bath is warming up to 43 DEG C after solution becomes transparent, and the reaction was continued to reaction mixture
In be substantially free of imidazole radicals after terminate, evaporating solvent under reduced pressure, concentrated reaction mixture is to get the modified ester polyol.
Wherein, the mass ratio of ethylene oxide mono acrylic ester and N- methylimidazole is 4.5:1；Epoxy acrylate and methanol
Mass ratio be 1.5:1.
Preparation example 3: the preparation of phenyl amines carbonate
By 1,3- diamino acid ammonium benzene (namely meta phenylene diamine base ammonium formate) and suitable water-ethylene glycol mixed solvent
It is added in reactor, wherein ethylene glycol weight is the 20% of water weight；Dissolution is sufficiently stirred completely, leads to nitrogen metathesis reactor
In air after, catalyst ethamine is added, and is warming up to 52 DEG C, is added with stirring propylene oxide, the constant temperature under 0.22MPa pressure
Reaction 9 hours, removes excess of solvent under reduced pressure after reaction to get phenyl amines carbonate, products therefrom water content is lower than
15wt%, and make its 400 centipoise of viscosity.
Wherein, the mass ratio of 1,3- diamino acid ammonium benzene and ethamine is 15:1；1,3- diamino acid ammonium benzene with
The mass ratio of propylene oxide is 1:1.2.
At room temperature, which is presented stable sticky clear liquid shape, slowly decomposes since 55 DEG C after heating, but
Peak decomposition temperature is 69-71 DEG C.It can be seen that its decomposition temperature is higher than general foaming agent, avoid volatile equal scarce
It falls into.And the ODP value of the compound is 0, GWP value 1.5 does not destroy atmospheric ozone layer, is also convenient for transporting and store.
Preparation example 4: the preparation of ethanolamines bicarbonate
The mixture of ammonium hydrogen carbonate, water, ethylene glycol amine and ethanol amine is added in reactor, and propyl formate is added,
Stirring and dissolving is led to the air in nitrogen metathesis reactor, is then sealed, and ethylene oxide is added in reactor under stirring, control
It 55 DEG C of reaction temperature, pressure 0.2MPa, is kept for thermotonus 8 hours, natural cooling cooling, removed under reduced pressure solvent and unreacted
Alkane, to obtain ethanolamines bicarbonate, and the water content for controlling products therefrom is lower than 10wt%, and makes its viscosity
250 centipoises.
Wherein, the mass ratio of ammonium hydrogen carbonate, water, ethylene glycol amine and ethanol amine is 1:1.2:0.13:0.065；Ammonium hydrogen carbonate
Mass ratio with propyl formate is 50:1；The mass ratio of ammonium hydrogen carbonate and ethylene oxide is 1:2.
Preparation example 5: the preparation of polyether polyol carbonic ester
In a high pressure reaction kettle, double metal cyanide catalyst and p-tert-Butylcatechol is first added, adds
Dry polypropylene oxide trihydroxylic alcohol (its OH value is 230-250mg KOH/g), leads to nitrogen displacement, is heated to 130 DEG C, is passed through foot
The carbon dioxide of amount pressurizes, and propylene oxide is added, while according to 1 DEG C/min of rate of temperature fall, by temperature from 130 DEG C
105 DEG C are down to, continues stirring 45 minutes after propylene oxide addition, then natural cooling, and evaporate volatile group of removing
Point, polyether polyol carbonic ester is obtained, OH value is 60mg KOH/g, the CO in product2Content is 14wt%.
Wherein, the mass ratio of polypropylene oxide trihydroxylic alcohol and double metal cyanide catalyst is 900:1；Polyoxygenated third
The mass ratio of alkene trihydroxylic alcohol and p-tert-Butylcatechol is 150:1；Polypropylene oxide trihydroxylic alcohol and the quality with propylene oxide
Than for 1:3.5.
Preparation example 6: the preparation of blocked isocyanate prepolymer
(1) prewired isocyanate mixture: by the more of the 4,4'- diphenyl-methane-group diisocyanate of 70wt% and 30wt%
Phenyl polymethylene polyisocyanates (for the PM2010 of Yantai Wanhua company, the NCO base content with 30-35wt%) mixing
Uniformly, to obtain prewired isocyanate mixture；
(2) in the reactor, the polypropylene oxide two for being 38-40mg KOH/g by the isocyanate mixture and OH value
The polyether polyol carbonic ester made from first alcohol and the preparation example 5 mixes 4 minutes, then 32 DEG C of temperature under agitation
Stewing process 14 hours under the conditions of degree, then by the prepolymer of generation be sufficiently mixed 4 minutes it is pre- to get the blocked isocyanate
Polymers.
Wherein, the mass ratio of the isocyanate mixture and Polyoxypropylene diol is 100:1.5, the isocyanic acid
The mass ratio of ester admixture and polyether polyol carbonic ester is 12.5:1.
It should be noted that it is unless otherwise prescribed or specified, otherwise in following all embodiment and comparative examples, made
Modification polyoxyethylene polyoxypropylene polylol, modified ester polyol, phenyl amines carbonate, ethanolamines bicarbonate,
Polyether polyol carbonic ester and blocked isocyanate prepolymer are the respective sets being prepared in above-mentioned corresponding preparation example 1-6
Part.
Embodiment 1
Step S1: preparing composite foamable agent, specifically:
By weight, following each component of following component A and B is weighed respectively, first by each component in component B
It is uniformly mixed, (A1) and (A2) that component A is added adds (A3) of component A, stir evenly after mixing, until obtaining
Transparent or clear foaming mixture is named as F1 to obtain composite foamable agent；
By weight, in which:
The component A includes following component:
(A1) (remaining 90 parts are 100 parts of polyether polyol comprising 10 parts of modified polyoxyethylene polyoxypropylene polylols
The SD-360 of EFFOL company)；
(A2) 10 parts of modified ester polyols；
(A3) 12 parts of phenyl amines carbonate-ethanolamines bicarbonate mixtures as carbon dioxide donor, wherein institute
The mass ratio of phenyl amines carbonate and ethanolamines bicarbonate is stated as 2:1, and phenyl amines carbonate-ethanolamines carbonic acid
Hydrogen salt mixture has 15wt% water content below；
The component B includes following component:
(B1) 5 parts of fluoro- 1- butylene of 2,4,4,4- tetra-；
(B2) 25 parts of 1- fluorine pentanes and 0.5 part of deionized water；
(B3) 0.5 part of auxiliary agent is (by 0.1 part of dibutyl tin dilaurate, the DC193 and 0.15 of 0.25 part of Products company
Part fire retardant triethyl phosphate composition)；
Step S2: preparation polyether polyol carbonate products, specially preparation example 5；
Step S3: blocked isocyanate prepolymer is prepared by the polyether polyol carbonate products, is specially prepared
Example 6；
Step S4: the composite foamable agent and the blocked isocyanate prepolymer being mixed, foamed, to be made
Polyurethane foam, specific as follows:
By the blocked isocyanate prepolymer of the composite foamable agent of step S1 and step S3 according to the matter of 1:0.8
Amount ratio is sufficiently mixed, and is injected in polyurethane blowing mold and foamed, so that polyurethane foam be made, is named as J1.
It is tested according to GB/T 10799-2008 standard, it is found that foam rate of closed hole > 97%, the cell diameter of J1 is
180-200 μm, quality is fine and smooth, uniform foam cell is fine and close.
Embodiment 2
Step S1: preparing composite foamable agent, specifically:
By weight, following each component of following component A and B is weighed respectively, first by each component in component B
It is uniformly mixed, (A1) and (A2) that component A is added adds (A3) of component A, stir evenly after mixing, until obtaining
Transparent or clear foaming mixture is named as F2 to obtain composite foamable agent；
By weight, in which:
The component A includes following component:
(A1) (remaining 80 parts are 100 parts of polyether polyol comprising 20 parts of modified polyoxyethylene polyoxypropylene polylols
The GP-4000 of CARPOL company)；
(A2) 5 parts of modified ester polyols；
(A3) 30 parts of phenyl amines carbonate-ethanolamines bicarbonate mixtures as carbon dioxide donor, wherein institute
The mass ratio of phenyl amines carbonate and ethanolamines bicarbonate is stated as 5:1, and phenyl amines carbonate-ethanolamines carbonic acid
Hydrogen salt mixture has 15wt% water content below；
The component B includes following component:
(B1) 20 parts of cis- -1,1,1,4,4,4- hexafluoro -2- butylene；
(B2) 1 part of HFC-125 and 10 part of deionized water；
(B3) 10 parts of auxiliary agents are (by 1 part of dimethylaminoethyl ether, B8404, the 2 parts of fire retardants of 3 parts of Goldschmidt companies
Diethyl ethyl phosphonic acid ester, 1 part of light stabilizer and 3 parts of plasticizer compositions)；
Step S2: preparation polyether polyol carbonate products, specially preparation example 5；
Step S3: blocked isocyanate prepolymer is prepared by the polyether polyol carbonate products, is specially prepared
Example 6；
Step S4: the composite foamable agent and the blocked isocyanate prepolymer being mixed, foamed, to be made
Polyurethane foam, specific as follows:
By the blocked isocyanate prepolymer of the composite foamable agent of step S1 and step S3 according to the matter of 1:1.4
Amount ratio is sufficiently mixed, and is injected in polyurethane blowing mold and foamed, so that polyurethane foam be made, is named as J2.
It is tested according to GB/T 10799-2008 standard, it is found that foam rate of closed hole > 98%, the cell diameter of J2 is
190-205 μm, quality is fine and smooth, uniform foam cell is fine and close.
Embodiment 3
Step S1: preparing composite foamable agent, specifically:
By weight, following each component of following component A and B is weighed respectively, first by each component in component B
It is uniformly mixed, (A1) and (A2) that component A is added adds (A3) of component A, stir evenly after mixing, until obtaining
Transparent or clear foaming mixture is named as F3 to obtain composite foamable agent；
By weight, in which:
The component A includes following component:
(A1) (remaining 85 parts are 100 parts of polyether polyol comprising 15 parts of modified polyoxyethylene polyoxypropylene polylols
The polyether polyol 2100 of Jiangsu Hai'an petrochemical industry)；
(A2) 7.5 parts of modified ester polyols；
(A3) 21.6 parts of phenyl amines carbonate-ethanolamines bicarbonate mixtures as carbon dioxide donor, wherein
The mass ratio of the phenyl amines carbonate and ethanolamines bicarbonate is 3.5:1, and phenyl amines carbonate-ethanolamines
Bicarbonate mixture has 15wt% water content below；
The component B includes following component:
(B1) 12.5 parts of anti-form-1s, 1,1,4,4,4- hexafluoro -2- butylene；
(B2) 13 parts of HFC-227ea and 5 part of deionized waters；
(B3) 5 parts of auxiliary agents (by 1.5 parts of (3- dimethyl-amino propylamine) ureas, 1 part of Air Products company DC193,
0.5 part of barium sulfate, 2 parts of age resister compositions)；
Step S2: preparation polyether polyol carbonate products, specially preparation example 5；
Step S3: blocked isocyanate prepolymer is prepared by the polyether polyol carbonate products, is specially prepared
Example 6；
Step S4: the composite foamable agent and the blocked isocyanate prepolymer being mixed, foamed, to be made
Polyurethane foam, specific as follows:
By the blocked isocyanate prepolymer of the composite foamable agent of step S1 and step S3 according to the matter of 1:1.1
Amount ratio is sufficiently mixed, and is injected in polyurethane blowing mold and foamed, so that polyurethane foam be made, is named as J3.
It is tested according to GB/T 10799-2008 standard, it is found that foam rate of closed hole > 98%, the cell diameter of J3 is
185-200 μm, quality is fine and smooth, uniform foam cell is fine and close.
It can be seen that composite foamable agent F1-F3 has good foaming effect, can make in the preparation of polyurethane foam
Final polyurethane foam has very narrow and small cell diameter, and foaming effect is excellent.
Comparative example 1-4
Comparative example 1: the modification polyoxyethylene polyoxypropylene polylol in example 1 group point (A1) is deleted,
It is homogeneously same as embodiment 1, and obtained polyurethane foam is named as D1.
It is tested according to GB/T 10799-2008 standard, it is found that foam rate of closed hole > 97%, the cell diameter of D1 is
200-230 μm (cell diameter is become larger), quality exquisiteness (because cell diameter becomes larger, sophistication is in a slight decrease), abscess are equal
Even densification.
Comparative example 2: the modification ester polyol in 2 component of embodiment (A2) is deleted, other to be homogeneously same as embodiment
2, obtained polyurethane foam is named as D2.
It is tested according to GB/T 10799-2008 standard, it is found that foam rate of closed hole > 96%, the cell diameter of D2 is
215-250 μm (cell diameter is become larger), quality exquisiteness (because cell diameter becomes larger, sophistication is in a slight decrease), abscess are equal
Even densification.
Comparative example 3: the phenyl amines carbonate in 3 component of embodiment (A2) is deleted, other to be homogeneously same as embodiment
3, obtained polyurethane foam is named as D3.
It is tested according to GB/T 10799-2008 standard, it is found that foam rate of closed hole > 91%, the cell diameter of D3 is
240-285 μm (cell diameter significantly becomes larger), quality sophistication decreases, but distribution of cells is uneven, consistency and
Even property is substantially reduced.
Comparative example 4: the ethanolamines bicarbonate in example 1 group point (A2) is deleted, other to be homogeneously same as reality
Example 1 is applied, obtained polyurethane foam is named as D4.
It is tested according to GB/T 10799-2008 standard, it is found that foam rate of closed hole > 92%, the cell diameter of D4 is
250-325 μm (cell diameter significantly becomes larger), quality shows slightly coarse, and distribution of cells is seriously uneven, consistency and uniformity
There is apparent reduction.
As above as it can be seen that when modified polyoxyethylene polyoxypropylene polylol, modified ester polyol, phenyl amines carbonate and second
When alcamines bicarbonate lacks any one, the mode of appearance that all will lead to gained foam is decreased or is deteriorated, especially
When lacking ethanolamines bicarbonate, appearance characterization has reduction the most significant, this proves only while using these components, institute
Obtained composite foamable agent could generate best foaming effect and technical effect in the preparation of polyurethane foam.
Performance test
It is tested according to national standards to urethane foam sample obtained in above-described embodiment and comparative example (having a size of 10 × 10
× 2cm) multiple performance tests are carried out, test index, unit (or test condition) and corresponding standard are as follows:
Density: kg/m3, GB/T 6343-2009；
Room temperature thermal coefficient: 20 DEG C, mw/ (mk), GB/T 10294-2008；
Measurement of Low Temperature Thermal Conductivity: -50 DEG C, mw/ (mk), GB/T 10294-2008；
Compressive strength: KPa, GB/T 8813-2008；
Dimensional contraction rate: %, GB/T 8811-2008；
High temperature deformation rate: %, 80 DEG C, 72h, GB/T 8811-2008；
Low-temperature deformation rate: %, -80 DEG C, 72h, GB/T 8811-2008.
Test result see the table below 1.
Table 1
By in table it can be seen that 1, polyurethane foam of the invention have lower density and lower thermal coefficient,
Especially thermal coefficient is substantially less than room temperature thermal coefficient under cryogenic；2, polyurethane foam of the invention has higher
Mechanical strength (compressive strength) and good dimensional stability (high temperature deformation rate and low-temperature deformation rate) are suitable for building heat preservation
Plate, freezer refrigerator plate.This is because the phenyl amines carbonate and ethanolamines bicarbonate compound in foaming agent are in addition to supplying
It is participated in except foaming to gas, amine therein itself may participate in modified polyoxyethylene polyoxypropylene polylol and/or modification again
The chain extension of ester polyol and crosslinking, and in modified polyoxyethylene polyoxypropylene polylol, modified ester polyol, sealing end isocyanic acid
Ester etc. rationally under the collocation of component, enhances the mechanical strength of foam, and further such that polyurethane foam have it is good
Dimensional stability.3, when lacking modified ester polyol in composite foamable agent, each performance of D2, which will be significantly smaller than, lacks modification
The D1 of polyoxyethylene polyoxypropylene polylol, this is proved for the improvement ability of comprehensive performance, and modified ester polyol is wanted
Better than modified polyoxyethylene polyoxypropylene polylol.4, composite foamed for similarly, for the improvement ability of comprehensive performance
Ethanolamines bicarbonate in agent is better than phenyl amines carbonate.
As described above, the present invention provides a kind of novel composite foamable agent and its use in preparation polyurethane foam
On the way, the composite foamable agent, to have very excellent foam performance, can make institute by unique component modified and selection
Obtained polyurethane foam has good heat preservation and mechanical strength, and then in multiple technical fields such as low temperature plate, insulation
The multiple fields such as heat preservation have a good application prospect and are worth.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of composite foamable agent, the composite foamable agent includes component A and component B, by weight, in which:
The component A includes following component:
(A1) comprising 100 parts of polyether polyol of 10-20 parts of modified polyoxyethylene polyoxypropylene polylols；
(A2) 5-10 parts of modified ester polyols；
(A3) 10-30 parts of phenyl amines carbonate-ethanolamines bicarbonate mixtures as carbon dioxide donor, wherein institute
The mass ratio of phenyl amines carbonate and ethanolamines bicarbonate is stated as 2-5:1, and phenyl amines carbonate-ethanolamines carbon
Sour hydrogen salt mixture has 15wt% water content below；
The component B includes following component:
(B1) the 5-20 parts of butene compounds replaced by 4,5 or 6 fluorine atoms；
(B2) 1-25 parts of other physical blowing agents and 0.5-10 parts of deionized waters；
(B3) 0.5-10 parts of auxiliary agents, the auxiliary agent include catalyst, surfactant and optional other additives.
2. composite foamable agent as described in claim 1, it is characterised in that: in component (A1), the modified polyoxypropylene is poly-
Oxyethylene group polyalcohol is made by the steps to obtain:
Polyoxyethylene polyoxypropylene polyalcohol and methyl hexahydrophthalic anhydride are added in reactor, proper catalyst is added, leads to nitrogen
Air in gas metathesis reactor is then heated to 125-130 DEG C, insulation reaction 0.5 hour；Add then in reaction mixture
Enter hydroquinone and glycidyl methacrylate, and be cooled to 100-105 DEG C, continues insulation reaction 1-2 at such a temperature
Hour, when detecting the content of epoxides and being less than 1wt%, it is initially added into 2-methylimidazole, and be warming up to 120 DEG C the reaction was continued 1-
2 hours, until reaction was completed after resulting resin viscosity is steady, cooled to room temperature was to get poly- to the modified polyoxypropylene
Oxyethylene group polyalcohol.
3. composite foamable agent as claimed in claim 1 or 2, it is characterised in that: in component (A2), the modified ester polyol
It is made by the steps to obtain:
Reactor is added in ethylene oxide mono acrylic ester, N- methylimidazole and lower alkyl alcohol, is led in nitrogen metathesis reactor
Air is stirred to react 15-30 minutes at 30 DEG C, and oil bath is warming up to 42-45 DEG C after solution becomes transparent, and the reaction was continued to anti-
Answering terminates after being substantially free of imidazole radicals in mixture, evaporating solvent under reduced pressure, and concentrated reaction mixture is polynary to get the modified ester
Alcohol.
4. composite foamable agent as described in any one of claims 1-3, it is characterised in that: in component (A3), the phenyl amines
Carbonate is made by the steps to obtain:
By 1-2 amino on phenyl ring by alkylidene acid ammonium substituent group (i.e.-(CH2)nCOONH4) replace amino benzenes compounds and
Suitable water-ethylene glycol mixed solvent is added in reactor, and wherein ethylene glycol weight is the 10-30% of water weight；Sufficiently stir
Mix dissolution completely, after leading to the air in nitrogen metathesis reactor, catalyst ethamine be added, and is warming up to 50-55 DEG C, stirring it is lower plus
Enter the epoxyalkane selected from propylene oxide or ethylene oxide, isothermal reaction 8-10 hours under 0.15-0.3MPa pressure, reaction knot
It removes excess of solvent after beam under reduced pressure, and controls products therefrom water content lower than 15wt%, viscosity is 300-500 centipoise to get institute
State phenyl amines carbonate.
5. composite foamable agent according to any one of claims 1-4, it is characterised in that: in component (A3), the ethanol amine
Class bicarbonate is made by the steps to obtain:
The mixture of ammonium hydrogen carbonate, water, ethylene glycol amine and ethanol amine is added in reactor, and propyl formate is added, is stirred
Dissolution is led to the air in nitrogen metathesis reactor, is then sealed, by the alkylene oxide selected from propylene oxide or ethylene oxide under stirring
Hydrocarbon is added in reactor, controls 50-60 DEG C of reaction temperature, pressure 0.1-0.3MPa, is kept for thermotonus 6-10 hours, naturally cold
But cool down, removed under reduced pressure solvent and unreacted alkane to obtain ethanolamines bicarbonate mixture, and control gained and produce
The water content of object is lower than 10wt%, and product viscosity is 200-300 centipoise.
6. purposes of the described in any item composite foamable agents of claim 1-5 in polyurethane foam preparation method.
7. purposes as claimed in claim 6, it is characterised in that: the polyurethane foam preparation method includes the following steps:
Step S1: the composite foamable agent is prepared；
Step S2: preparation polyether polyol carbonate products；
Step S3: blocked isocyanate prepolymer is prepared by the polyether polyol carbonate products；
Step S4: the composite foamable agent and the blocked isocyanate prepolymer are mixed, foamed, so that poly- ammonia be made
Ester foam.
8. purposes as claimed in claim 7, it is characterised in that: the step S1 is as follows:
Step S1: weighing each component of said components A and B respectively, first mixes each component in component B equal
It is even, be added component A (A1) and (A2) add (A3) of component A after mixing, stir evenly, until acquisition it is transparent or
Clear foaming mixture, to obtain composite foamable agent.
9. purposes as claimed in claim 7 or 8, it is characterised in that: in the step S2, the polyether polyol carbonic ester is logical
Following steps are crossed to be prepared:
In a high pressure reaction kettle, in the presence of double metal cyanide catalyst and auxiliary agent, polyether polyol is added, leads to nitrogen
Displacement, is heated to 130 DEG C, is passed through enough carbon dioxide pressurizations, adds propylene oxide, while according to 1 DEG C/min of cooling speed
Temperature is down to 105 DEG C from 130 DEG C by rate, continues stirring 0.5-1 hours after propylene oxide addition, then natural cooling,
And removing volatile components are evaporated, obtain polyether polyol carbonic ester.
10. such as the described in any item purposes of claim 7-9, it is characterised in that: the step S3 specifically comprises the following steps:
(1) prewired isocyanate mixture: the mixture includes 65-75wt% diphenyl-methane-group diisocyanate and 25-
35wt% polyphenyl polymethylene polyisocyanates, wherein diphenyl-methane-group diisocyanate is selected from 4,4'- diphenylmethane group two
Isocyanates or 2,4'- '-diphenylmethane diisocyanate, the polyphenyl polymethylene polyisocyanates are with 30-35wt%'s
NCO base content；
(2) in the reactor, the polyether polyol for being 38-40mg KOH/g by the isocyanate mixture and OH value, and step
The polyether polyol carbonic ester made from rapid S2, mixes 2-5 minutes, under agitation then under the conditions of 30-35 DEG C of temperature
Stewing process 12-16 hours, then by the prepolymer mixing of generation 3-5 minutes to get the blocked isocyanate prepolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810721437.2A CN109021281B (en) | 2018-07-04 | 2018-07-04 | Composite foaming agent and application thereof in preparation of polyurethane foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810721437.2A CN109021281B (en) | 2018-07-04 | 2018-07-04 | Composite foaming agent and application thereof in preparation of polyurethane foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109021281A true CN109021281A (en) | 2018-12-18 |
| CN109021281B CN109021281B (en) | 2021-11-26 |
Family
ID=65521833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810721437.2A Expired - Fee Related CN109021281B (en) | 2018-07-04 | 2018-07-04 | Composite foaming agent and application thereof in preparation of polyurethane foam |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109021281B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762136A (en) * | 2019-01-25 | 2019-05-17 | 海信容声(广东)冰箱有限公司 | A kind of polyurethane foamed composite object, polyurethane foam and its preparation method and application |
| CN114106283A (en) * | 2021-11-04 | 2022-03-01 | 滁州凯凯建筑节能有限公司 | Polyurethane composite material and preparation method and system thereof |
| CN114423833A (en) * | 2019-07-09 | 2022-04-29 | 赢创运营有限公司 | Polyol ether based foam additives for polyurethane dispersions with high filler content |
| CN116285306A (en) * | 2023-05-24 | 2023-06-23 | 北京宇极科技发展有限公司 | Foaming composition, polyurethane foam and preparation method thereof |
| CN116410440A (en) * | 2023-04-03 | 2023-07-11 | 佛山市惠安家居用品有限公司 | Hydrophilic antibacterial sponge and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1898289A (en) * | 2003-12-23 | 2007-01-17 | 陶氏环球技术公司 | Process for producing polyurethane products autocatalytic using tertiary amine capped polyether polyols |
| CN103764703A (en) * | 2011-03-28 | 2014-04-30 | 拜耳知识产权有限责任公司 | Method for producing flexible polyurethane foam materials |
| US20150141542A1 (en) * | 2012-05-22 | 2015-05-21 | Bayer Materialscience Ag | Method for producing flame-protected polyurethane foams having low bulk densities |
| CN105968291A (en) * | 2015-03-11 | 2016-09-28 | 赢创德固赛有限公司 | Production of polyurethane systems using polyether polycarbonate polyols |
| CN107089910A (en) * | 2016-06-02 | 2017-08-25 | 山东理工大学 | Carbonic acid organic amine salt compounds and its purposes as foaming agent |
| CN107089927A (en) * | 2016-06-02 | 2017-08-25 | 山东理工大学 | With being used as CO2The organic amine salt compounds and its purposes as foaming agent of the anion of donor |
-
2018
- 2018-07-04 CN CN201810721437.2A patent/CN109021281B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1898289A (en) * | 2003-12-23 | 2007-01-17 | 陶氏环球技术公司 | Process for producing polyurethane products autocatalytic using tertiary amine capped polyether polyols |
| CN103764703A (en) * | 2011-03-28 | 2014-04-30 | 拜耳知识产权有限责任公司 | Method for producing flexible polyurethane foam materials |
| US20150141542A1 (en) * | 2012-05-22 | 2015-05-21 | Bayer Materialscience Ag | Method for producing flame-protected polyurethane foams having low bulk densities |
| CN105968291A (en) * | 2015-03-11 | 2016-09-28 | 赢创德固赛有限公司 | Production of polyurethane systems using polyether polycarbonate polyols |
| CN107089910A (en) * | 2016-06-02 | 2017-08-25 | 山东理工大学 | Carbonic acid organic amine salt compounds and its purposes as foaming agent |
| CN107089927A (en) * | 2016-06-02 | 2017-08-25 | 山东理工大学 | With being used as CO2The organic amine salt compounds and its purposes as foaming agent of the anion of donor |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762136A (en) * | 2019-01-25 | 2019-05-17 | 海信容声(广东)冰箱有限公司 | A kind of polyurethane foamed composite object, polyurethane foam and its preparation method and application |
| CN114423833A (en) * | 2019-07-09 | 2022-04-29 | 赢创运营有限公司 | Polyol ether based foam additives for polyurethane dispersions with high filler content |
| CN114106283A (en) * | 2021-11-04 | 2022-03-01 | 滁州凯凯建筑节能有限公司 | Polyurethane composite material and preparation method and system thereof |
| CN116410440A (en) * | 2023-04-03 | 2023-07-11 | 佛山市惠安家居用品有限公司 | Hydrophilic antibacterial sponge and preparation method thereof |
| CN116285306A (en) * | 2023-05-24 | 2023-06-23 | 北京宇极科技发展有限公司 | Foaming composition, polyurethane foam and preparation method thereof |
| CN116285306B (en) * | 2023-05-24 | 2023-08-18 | 北京宇极科技发展有限公司 | Foaming composition, polyurethane foam and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109021281B (en) | 2021-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109021281A (en) | A kind of composite foamable agent and its purposes for preparing polyurethane foam | |
| KR102120908B1 (en) | Mixtures containing 1,1,1,4,4,4-hexafluorobutene and 1-chloro-3,3,3-trifluoropropene | |
| CN105601978B (en) | A kind of hard polyurethane foams | |
| JP2018168377A (en) | Storage stable foamable compositions containing 1,1,1,4,4,4-hexafluoro-2-butene | |
| JP2017197768A (en) | Foamed body, and article produced from foamed body containing hcfo or hfo foaming agent | |
| JP7474290B2 (en) | Polyester polyol composition containing HF0-1336MZZM(Z) | |
| US20220112349A1 (en) | Compositions and methods comprising vinylidene fluoride | |
| JP2001506291A (en) | Mixture containing 1,1,1,3,3-pentafluorobutane | |
| JPH08509512A (en) | Method for producing rigid polyurethane foam | |
| JP2013500386A (en) | Composition of HCFO-1233zd and polyol blend for use in polyurethane foam | |
| CN110105520A (en) | A kind of heat preservation hard polyurethane foams and preparation method thereof | |
| JP2004285321A (en) | Rigid polyurethane foam composition and low-temperature insulator using the same | |
| WO2020078329A1 (en) | Flame retardant combination polyether, and thermal insulating material for polyisocyanurate sheet material and preparation method therefor | |
| JP2004285319A (en) | Rigid polyurethane foam composition and low-temperature insulator using the same | |
| WO2006002043A1 (en) | Process for making polyurethane and polyisocyanurate foams using mixtures of a hydrofluorocarbon and methyl formate as a blowing agent | |
| CN109021280A (en) | A kind of preparation method and polyurethane foam of polyurethane foam | |
| CN109535688A (en) | A kind of polyurethane foam heat insulation material and preparation method thereof | |
| CN108586792A (en) | The new application of hexafluoro-isobutene | |
| JP2002047326A (en) | Production method for rigid urethane spray foam used as building thermal insulation material | |
| Lee et al. | Properties of Polyurethane Foam Blown by Environment Friendly Blowing Agent | |
| CN109422904B (en) | Blowing agents comprising secondary amines and alkanolamine salts and use in polyurethane continuous panel foam materials | |
| CN109422899B (en) | Blowing agents comprising tertiary amines and alkanolamine salts and use in polyurethane continuous panel foam materials | |
| CN109422894B (en) | Blowing agent comprising tertiary amine salt and propanol amine salt and use for polyurethane refrigerator-freezer foam material | |
| CN109422903B (en) | Blowing agents comprising secondary amine salts and propanolamine salts and use for polyurethane refrigerator-freezer foam materials | |
| CN109422916B (en) | Blowing agents comprising secondary amine salts and ethanolamine salts and use for polyurethane slabstock foam materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210915 Address after: 462000 No. 328, group 14, Xiazhuang village, Wanjin Town, Zhaoling District, Luohe City, Henan Province Applicant after: Xu Yuting Address before: 100027 room 8320, 8 / F, Xinzhong building, building 2, Xinzhong West Street, Dongcheng District, Beijing Applicant before: BEIJING JINGDA LYUYE INTELLECTUAL PROPERTY AGENCY Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20211105 Address after: 543000 building 4, No.1 Xingyu Road, Wuzhou Industrial Park, Guangxi Zhuang Autonomous Region Applicant after: Guangxi sibaixiang Technology Industry Co.,Ltd. Address before: 462000 No. 328, group 14, Xiazhuang village, Wanjin Town, Zhaoling District, Luohe City, Henan Province Applicant before: Xu Yuting |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20211126 |