CN108503767A - Combined polyether, hard polyurethane foams and preparation method thereof and water heater - Google Patents
Combined polyether, hard polyurethane foams and preparation method thereof and water heater Download PDFInfo
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- CN108503767A CN108503767A CN201710115446.2A CN201710115446A CN108503767A CN 108503767 A CN108503767 A CN 108503767A CN 201710115446 A CN201710115446 A CN 201710115446A CN 108503767 A CN108503767 A CN 108503767A
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/14—Manufacture of cellular products
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
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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
- C08J9/12—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
- C08J9/141—Hydrocarbons
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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
- C08J9/12—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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
- F24H9/00—Details
- F24H9/0005—Details for water heaters
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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
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
Abstract
The present invention discloses a kind of combined polyether, hard polyurethane foams and preparation method thereof and water heater, wherein combined polyether includes polyalcohol and foaming agent, and the polyalcohol includes polyether polyol and/or polyester polyol, and the foaming agent includes hexafluorobutene.Technical scheme of the present invention can make environmental-friendly and thermal coefficient is relatively low with the rigid polyurethane foam obtained by the combined polyether.
Description
Technical field
The present invention relates to field of water heaters, more particularly to a kind of combined polyether, hard polyurethane foams and preparation method thereof
And water heater.
Background technology
In water heater industry, hard polyurethane foams usually are coated in the outer surface of its liner, to reduce water in liner
Thermal loss, to improve the energy saving capability of water heater.However, currently used hard polyurethane foams are using including HCFC-
Prepared by the foaming agent of 141b (a fluorine dichloroethanes), and HCFC-141b (a fluorine dichloroethanes) has destruction to ozone layer
Effect, can not meet environmental requirement.
Invention content
The main object of the present invention is to propose a kind of combined polyether, it is intended to so that with the hard polyurethane obtained by the combined polyether
Ester foamed material environment is friendly.
To achieve the above object, combined polyether proposed by the present invention includes polyalcohol and foaming agent, and the polyalcohol includes
Polyether polyol and/or polyester polyol, the foaming agent include hexafluorobutene.
Preferably, the foaming agent further includes pentane and/or hydrofluorocarbon.
Preferably, the pentane includes at least one of pentamethylene, isopentane and pentane.
Preferably, the hydrofluorocarbon is one kind in pentafluoropropane, 3-pentafluorobutane and tetrafluoroethane.
Preferably, the polyether polyol includes at least the one of polyether polyol A, polyether polyol B and polyether polyol C
Kind, the polyester polyol is polyester polyol D, wherein：
The polyether polyol A is polymerized with propylene oxide using sorbierite as initiator, viscosity be 8000~
15000mpas, hydroxyl value are 360~500mgKOH/g, degree of functionality 6；
The polyether polyol B is polymerized with propylene oxide using glycerine as initiator, viscosity be 250~
600mpas, hydroxyl value are 150~350mgKOH/g；
The polyether polyol C is polymerized with propylene oxide using sucrose as initiator, viscosity be 5000~
12000mpas, hydroxyl value are 360~440mgKOH/g；
The polyester polyol D is phthalic anhydride polyester, 1000~2000mpas of viscosity, 200~350mgKOH/g of hydroxyl value, official
Energy degree is 2.7.
Preferably, the combined polyether further includes water, composite catalyst, foam stabiliser and fire retardant, wherein：
The composite catalyst includes pentamethyl-diethylenetriamine, Bis-dimethylamino ethylether, N- methyldicyclohexyls
Amine and 4-methyl hexamethylene diamine, dimethyl cyclohexyl amine, 1,2- methylimidazoles and dimethyl benzylamine, (2- hydroxypropyls) trimethyl first
At least one of sour ammonium, second quaternary ammonium salt and pungent quaternary ammonium salt；
The foam stabiliser is the silicone oil of Si-C structures；
The fire retardant includes three (2- chloroethyls) phosphates, tricresyl phosphate (2- chloropropyls) ester, tricresyl phosphate (2,3- dichloros third
Base) ester, neopentyl glycol ethylene glycol phosphate, dimethyl methyl phosphonate, resorcinol bis- (diphenyl phosphoesters), ethyl phosphonic acid two
At least one of ethyl ester and propyl dimethyl phosphate.
Preferably, the combined polyether includes：
The polyether polyol A of 30~60 parts by weight；
The polyether polyol B of 3~15 parts by weight；
The polyether polyol C of 15~40 parts by weight；
The polyester polyol D of 5~20 parts by weight；
The pentane of 0~15 parts by weight；
The hydrofluorocarbon of 0~20 parts by weight；
The hexafluorobutene of 1~30 parts by weight；
The water of 0.5~2.0 parts by weight；
The composite catalyst of 1~3.5 parts by weight；
The foam stabiliser of 1~5 parts by weight；And
The fire retardant of 1~15 parts by weight.
Preferably, the parts by weight of the polyether polyol A are 40~60, and the parts by weight of the polyether polyol B are 5
The parts by weight of~15, the polyether polyol C are 20~30, and the parts by weight of the polyester polyol D are 5~15, described
The parts by weight of fire retardant are 5~10.
The present invention also proposes a kind of preparation method of hard polyurethane foams, includes the following steps：
Organic isocyanate is uniformly mixed with combined polyether；Wherein, the combined polyether includes polyalcohol and foaming agent,
The polyalcohol includes polyether polyol and/or polyester polyol, and the foaming agent includes hexafluorobutene；
Composition injection foaming cavity after mixing is foamed.
Preferably, the organic isocyanate is multiple first class polyphenyl polyisocyanate.
Preferably, the weight ratio between the organic isocyanate and the combined polyether is 0.9~1.3.
Preferably, in described the step of composition injection foaming cavity after mixing is foamed, the hair
Ranging from 20~50 DEG C of the external temperature of cavity is steeped, internal temperature range is 20~50 DEG C.
Preferably, in described the step of composition injection foaming cavity after mixing is foamed, described group
The temperature range for closing object is 15~25 DEG C, operating pressure ranging from 12~14Mpa of the injection.
The present invention also proposes a kind of hard polyurethane foams, and the hard polyurethane foams are by aforementioned hard polyurethane foams
Preparation method prepared by.
The present invention also proposes a kind of water heater, including liner and hard polyurethane foams, the hard polyurethane foams
Prepared by preparation method by aforementioned hard polyurethane foams, and it is attached to the outer surface of the liner.
In technical scheme of the present invention, foaming agent used by combined polyether includes hexafluorobutene, which has
The advantages such as low thermal conductivity, zero ozone depletion potential and acceptable low global warming potential (being less than 10.0) therefore can make
It is able to that rigid polyurethane foam obtained by the combined polyether is environmental-friendly and thermal coefficient is relatively low, to may make by the hard
The water heater of polyurethane foamed material cladding liner can meet environmental requirement and have low energy consumption.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
The structure shown according to these attached drawings obtains other attached drawings.
Fig. 1 is the flow diagram of one embodiment of preparation method of hard polyurethane foams of the present invention.
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art obtained without creative efforts it is all its
His embodiment, shall fall within the protection scope of the present invention.
If, should " first ", " the it is to be appreciated that relate to the description of " first ", " second " etc. in the embodiment of the present invention
Two " etc. description is used for description purposes only, and is not understood to indicate or imply its relative importance or is implicitly indicated meaning
The quantity of the technical characteristic shown." first " is defined as a result, the feature of " second " can explicitly or implicitly include at least one
A this feature.In addition, the technical solution between each embodiment can be combined with each other, but must be with ordinary skill
Personnel can be implemented as basis, will be understood that this technical side when the combination of technical solution appearance is conflicting or cannot achieve
The combination of case is not present, also not the present invention claims protection domain within.
The present invention proposes a kind of combined polyether.
In an embodiment of the present invention, which includes polyalcohol and foaming agent.Wherein, polyalcohol includes that polyethers is more
First alcohol and polyester polyol, foaming agent include hexafluorobutene (abbreviation FEA-1100).In the present embodiment, FEA-1100 has low lead
The advantages such as hot coefficient, zero ozone depletion potential and acceptable low global warming potential (being less than 10.0), therefore, may make with
Rigid polyurethane foam is environmental-friendly obtained by combined polyether including FEA-1100 and thermal coefficient is relatively low, to may make
The water heater of liner is coated by the rigid polyurethane foam can meet environmental requirement and have low energy consumption.Right the design is unlimited
In this, in other embodiment, the polyalcohol in the combined polyether can only include also in polyether polyol and polyester polyol
One of them.
In the present embodiment, further, the foaming agent may also include at least one of pentane and hydrofluorocarbon, by
This, can it is environmental-friendly in the rigid polyurethane foam obtained by guarantee and with compared with low thermal conductivity while, reduce raw material
Cost.Specifically, pentane may include at least one of pentamethylene, isopentane and pentane, and preferably include pentamethylene；
Hydrofluorocarbon can be then in pentafluoropropane (HFC-245fa), 3-pentafluorobutane (HFC-365mfc) and tetrafluoroethane (HFC-134a)
One kind, and preferably pentafluoropropane.
In the present embodiment, further, the polyether polyol includes polyether polyol A, polyether polyol B and polyethers
At least one of polyalcohol C, polyester polyol are polyester polyol D, wherein：
Polyether polyol A is polymerized with propylene oxide using sorbierite as initiator, viscosity be 8000~
15000mpas, hydroxyl value are 360~500mgKOH/g, degree of functionality 6.Polyether polyol A can improve prepared hard
The intensity of polyurethane foam so that abscess is fine and smooth uniformly in prepared hard polyurethane foams, and can reduce thermal coefficient.
Polyether polyol B is polymerized with propylene oxide using glycerine as initiator, and viscosity is 250~600mpas,
Hydroxyl value is 150~350mgKOH/g.The mobility of combined polyether can be improved in polyether polyol B, improves prepared hard polyurethane
The caking property of ester foam.
Polyether polyol C is polymerized with propylene oxide using sucrose as initiator, and viscosity is 5000~12000mpa
S, hydroxyl value are 360~440mgKOH/g.During preparing hard polyurethane foams by the combined polyether, usually also need to add
Enter organic isocyanate；Polyether polyol C degrees of functionality are high, and being reacted with organic isocyanate has higher activity, after foaming
Curing rate is fast, can improve the easily crisp disadvantage of prepared hard polyurethane foams epidermis, improves prepared hard polyaminoester
The adhesion strength and mechanical strength of foam.
Polyester polyol D is phthalic anhydride polyester, 1000~2000mpas of viscosity, 200~350mgKOH/g of hydroxyl value, degree of functionality
2.7.Polyester polyol D contains phenyl ring, and the intensity of prepared hard polyurethane foams can be improved, and it is poly- to reduce prepared hard
The thermal coefficient of urethane foam；In addition, polyester polyol D viscosity is small, good fluidity is conducive to improve prepared hard polyurethane
The cementability of ester foam.
In the present embodiment, further, which further includes water, composite catalyst, foam stabiliser and fire-retardant
Agent, wherein：
Composite catalyst includes pentamethyl-diethylenetriamine, Bis-dimethylamino ethylether, N- methyldicyclohexyl amine
(PC-12) and 4-methyl hexamethylene diamine, dimethyl cyclohexyl amine (PC-8), 1,2- methylimidazoles and dimethyl benzylamine, (2- hydroxyls third
At least one of base) trimethyl ammonium formate (TMR-2), second quaternary ammonium salt and pungent quaternary ammonium salt；Such composite catalyst can improve
While reaction speed, the mobility of foam is improved, in order to fast demoulding.It should be noted that composite catalyst usually wraps
Include kicker, gel catalyst and polymerization catalyst.
Foam stabiliser is the silicone oil of Si-C structures, such as steps the L-6863, L-6988, L-6952 of figure；Mei Side's
AK8812, AK8809 etc., and preferably L-6988, AK8809；Such foam stabiliser can be improved combined polyether foaming when
Nucleating effect.
Fire retardant include three (2- chloroethyls) phosphates (TCEP), tricresyl phosphate (2- chloropropyls) ester (TCPP), tricresyl phosphate (2,
Bis- chloropropyls of 3-) ester (TDCPP), neopentyl glycol ethylene glycol phosphate, dimethyl methyl phosphonate (DMMP), resorcinol bis- (two
Phenyl phosphate ester) (RDP), at least one of ethyl phosphonic acid diethylester (DEEP) and propyl dimethyl phosphate (DMPP)；It is such
Fire retardant can reduce the combustibility of prepared hard polyurethane foams.Also, the fire retardant is preferably neopentyl glycol ethylene glycol
Phosphate, dimethyl methyl phosphonate (DMMP), resorcinol bis- (diphenyl phosphoesters) (RDP), ethyl phosphonic acid diethylester
(DEEP) and at least one of propyl dimethyl phosphate (DMPP), this based flame retardant are halogen-free flame retardants.
In the present embodiment, it is preferably included in the combined polyether：The polyether polyol A of 30~60 parts by weight；3~15 weight
The polyether polyol B of part；The polyether polyol C of 15~40 parts by weight；The polyester polyol D of 5~20 parts by weight；0~15 weight
The pentane of part；The hydrofluorocarbon of 0~20 parts by weight；The FEA-1100 of 1~30 parts by weight；The water of 0.5~2.0 parts by weight；1~3.5
The composite catalyst of parts by weight；The foam stabiliser of 1~5 parts by weight；And 1~15 parts by weight fire retardant.In view of hot water
The preparation process condition of device, the hard polyurethane foams being coated on outside its liner will usually carry out foaming system at relatively high temperatures
It is standby, and common expanded material is not appropriate for foaming at relatively high temperatures.However, using the combination under the present embodiment formula
Prepared by the expanded material of polyethers, the foaming being applicable under higher temperature, can meet the system of the hard polyurethane foams of water heater
It is standby to require.
It should be noted that in the present embodiment, the parts by weight of polyether polyol A can be more preferably 40~60,
So that the thermal coefficient of prepared hard polyurethane foams is relatively low.The parts by weight of polyether polyol B can be more preferably 5
~15, so that the combined polyether has compared with high fluidity.The parts by weight of polyether polyol C can be more preferably 20~
30, so that the adhesion strength of prepared hard polyurethane foams and mechanical strength are higher.The parts by weight of polyester polyol D can
Further preferably 5~15, since the degree of functionality of polyester polyol D is small, dosage should not be excessive, and it is poly- otherwise to influence prepared hard
The demolding performace of urethane foam.The parts by weight of fire retardant can be more preferably 5~10, so that prepared hard polyaminoester
The combustibility of foam is relatively low.
The present invention also proposes a kind of preparation method of hard polyurethane foams.
Referring to Fig.1, in an embodiment of the present invention, the preparation method of the hard polyurethane foams includes the following steps：
Step S10, organic isocyanate is uniformly mixed with combined polyether；
Step S20, composition injection foaming cavity after mixing is foamed.
In the present embodiment, the concrete structure of the combined polyether is with reference to above-described embodiment, and at least, which includes more
First alcohol and foaming agent, wherein polyalcohol includes polyether polyol and/or polyester polyol, and foaming agent includes hexafluorobutene.Such as
This, may make the preparation-obtained rigid polyurethane foam of preparation method using hard polyurethane foams of the present invention, ring
Border is friendly and thermal coefficient is relatively low, to may make the water heater for coating liner by the rigid polyurethane foam that can meet ring
Guaranteed request and have low energy consumption.Further include organic isocyanic acid in the composition to inject foaming cavity in addition, in the present embodiment
The mobility of foam can be improved in ester, the such as, but not limited to PM2010 of Yantai Wanhua, the organic isocyanate, and keeps foam
Higher intensity；Normally, which preferably uses multiple first class polyphenyl polyisocyanate.
If being appreciated that, the weight accounting of organic isocyanate is too low, can make the hard polyurethane foams for preparing gained
Intensity is small, poor dimensional stability；If the weight accounting of organic isocyanate is excessively high, it can make the rigid polyurethane foam for preparing gained
Foam is crisp and cementability is poor.In the present embodiment, the weight ratio between organic isocyanate and combined polyether is preferably 0.9~1.3,
To take into account the intensity and brittleness that prepare gained hard polyurethane foams.
In the present embodiment, normally, further include step before step S10：
S30, each component in the combined polyether is pre-mixed.
It is appreciated that be first pre-mixed each component in combined polyether, then will be after organic isocyanate and premixing
Combined polyether mixed, be conducive to the uniform mixing of the composition comprising the organic isocyanate and the combined polyether, from
And improve the overall performance consistency for the hard polyurethane foams for preparing gained.
It should be noted that for water heater, foaming cavity typically refers to outer surface of liner and table in outer cover of water heater
Between face between the cavity that is separated out.Preferably, in step S20, ranging from 20~50 DEG C of the external temperature of the foaming cavity,
Internal temperature range is 20~50 DEG C.In addition, in step S20, the temperature range of the composition is preferably 15~25 DEG C, institute
The operating pressure for stating injection ranges preferably from 12~14Mpa.
Below with reference to specific embodiment, present invention is described, it should be noted that following embodiment is only to describe
Property, without limiting the invention in any way.
Embodiment
Composition of raw materials：The polyether polyol A of 40 parts by weight, the polyether polyol B of 6 parts by weight, the polyethers of 30 parts by weight are more
First alcohol C, the polyester polyol of 10 parts by weight, 8.5 parts by weight composite flame-retardant agent (DEEP and DMPP weight ratios 1：1), 0.4 parts by weight
Kicker (PC-12), the gel catalysts (PC-8) of 1.9 parts by weight, 0.5 parts by weight polymerization catalyst (TMR-2),
The FEA- of the silicon class A foam A stabilizer of 2.0 parts by weight, the water of 0.7 parts by weight, the HFC-245fa of 5.5 parts by weight, 25 parts by weight
1100, the PM2010 (organic isocyanate) of the Yantai Wanhua of 126.69 parts by weight.
Preparation method：Component during above-mentioned raw materials are formulated in addition to organic isocyanate carries out in advance in stirring pressurized tank
It is uniformly mixed；After premixing uniformly, pre-composition is transferred to the white material work tank of foaming machine by pump, thus with mounted in black material
Organic isocyanate in work tank injected under the pressure of 12.5MPa by high-pressure mixing head at the top of the hot water with gas vent
Device water tank die for molding；The external temperature of foaming cavity mould is 28 DEG C, and internal temperature is 32 DEG C, the material in high pressure foaming machine
Temperature is 18 DEG C.
Comparative example
Composition of raw materials：The polyether polyol A of 40 parts by weight, the polyether polyol B of 10 parts by weight, the polyethers of 25 parts by weight are more
4 parts of first alcohol C, the polyester polyol of 15 parts by weight, composite flame-retardant agent (DEEP and DMPP weight ratios 1：1), the foaming of 0.5 parts by weight
Polymerization catalyst (TMR-2), 2.0 weights of catalyst (PC-12), the gel catalyst (PC-8) of 1.5 parts by weight, 0.5 parts by weight
Measure the Yantai Wanhua of the silicon class A foam A stabilizer of part, the water of 1.5 parts by weight, the HCFC-141b of 24 parts by weight, 130.20 parts by weight
PM2010 (organic isocyanate).
Preparation method：Same embodiment.
Performance measurement is carried out to the hard polyurethane foams obtained by embodiment and comparative example.Wherein, foam core density
Testing standard is carried out according to GB/T6343-2009, and foam thermal conductivity test is carried out according to standard GB/T10295-2008, the sun
Energy water heater efficiency test is carried out according to standard GB 18708-2002.
The parameters table specific as follows obtained by performance measurement：
| Performance parameter | Embodiment | Comparative example |
| Foam core density Kg/m3 | 35.72 | 37.80 |
| 22.5 DEG C of thermal coefficient | 18.70 | 18.60 |
| Water heater coefficient of energy dissipation | 0.670 | 0.660 |
As can be seen from the above table, the foam core density in embodiment can reduce hard in water heater compared with low in comparative example
The note bubble amount of polyurethane foam while reducing cost, reduces the total weight of product entirety；In addition, the heat conduction system in embodiment
Number and water heater coefficient of energy dissipation and being not much different in comparative example, therefore, technical scheme of the present invention can effectively solve hot water
Expanded material in device industry is using environmental issue caused by blowing agent H CFC-141b.
The present invention also proposes a kind of hard polyurethane foams, and the hard polyurethane foams are by above-mentioned hard polyurethane foams
Prepared by preparation method, the specific steps of the preparation method of the hard polyurethane foams are with reference to above-described embodiment, due to this hard
Polyurethane foam uses whole technical solutions of above-mentioned all embodiments, therefore at least technical solution with above-described embodiment
Caused all advantageous effects, this is no longer going to repeat them.
The present invention also proposes a kind of water heater, which includes liner and hard polyurethane foams, the hard polyurethane
The specific composition of ester foam is with reference to above-described embodiment, since this water heater uses whole technical sides of above-mentioned all embodiments
Case, therefore at least all advantageous effects caused by the technical solution with above-described embodiment, this is no longer going to repeat them.Its
In, hard polyurethane foams are attached to the outer surface of the liner by way of high-pressure foam.
The foregoing is merely the preferred embodiment of the present invention, are not intended to limit the scope of the invention, every at this
Under the inventive concept of invention, using equivalent structure transformation made by description of the invention and accompanying drawing content, or directly/use indirectly
In the scope of patent protection that other related technical areas are included in the present invention.
Claims (15)
1. a kind of combined polyether, which is characterized in that including polyalcohol and foaming agent, the polyalcohol include polyether polyol and/
Or polyester polyol, the foaming agent include hexafluorobutene.
2. combined polyether as described in claim 1, which is characterized in that the foaming agent further includes pentane and/or hydrofluorocarbon.
3. combined polyether as claimed in claim 2, which is characterized in that the pentane includes pentamethylene, isopentane and pentane
At least one of.
4. combined polyether as claimed in claim 2, which is characterized in that the hydrofluorocarbon is pentafluoropropane, 3-pentafluorobutane and four
One kind in fluoroethane.
5. such as claim 2 to 4 any one of them combined polyether, which is characterized in that the polyether polyol includes that polyethers is more
At least one of first alcohol A, polyether polyol B and polyether polyol C, the polyester polyol are polyester polyol D, wherein：
The polyether polyol A is polymerized with propylene oxide using sorbierite as initiator, viscosity be 8000~
15000mpas, hydroxyl value are 360~500mgKOH/g, degree of functionality 6；
The polyether polyol B is polymerized with propylene oxide using glycerine as initiator, and viscosity is 250~600mpas,
Hydroxyl value is 150~350mgKOH/g；
The polyether polyol C is polymerized with propylene oxide using sucrose as initiator, and viscosity is 5000~12000mpa
S, hydroxyl value are 360~440mgKOH/g；
The polyester polyol D is phthalic anhydride polyester, 1000~2000mpas of viscosity, 200~350mgKOH/g of hydroxyl value, degree of functionality
It is 2.7.
6. combined polyether as claimed in claim 5, which is characterized in that further include water, composite catalyst, foam stabiliser and resistance
Agent is fired, wherein：
The composite catalyst include pentamethyl-diethylenetriamine, Bis-dimethylamino ethylether, N- methyldicyclohexyls amine and
4-methyl hexamethylene diamine, dimethyl cyclohexyl amine, 1,2- methylimidazoles and dimethyl benzylamine, (2- hydroxypropyls) trimethyl formic acid
At least one of ammonium, second quaternary ammonium salt and pungent quaternary ammonium salt；
The foam stabiliser is the silicone oil of Si-C structures；
The fire retardant includes three (2- chloroethyls) phosphates, tricresyl phosphate (2- chloropropyls) ester, tricresyl phosphate (2,3- bis- chloropropyl)
Ester, neopentyl glycol ethylene glycol phosphate, dimethyl methyl phosphonate, resorcinol bis- (diphenyl phosphoesters), ethyl phosphonic acid diethyl
At least one of ester and propyl dimethyl phosphate.
7. combined polyether as claimed in claim 6, which is characterized in that the combined polyether includes：
The polyether polyol A of 30~60 parts by weight；
The polyether polyol B of 3~15 parts by weight；
The polyether polyol C of 15~40 parts by weight；
The polyester polyol D of 5~20 parts by weight；
The pentane of 0~15 parts by weight；
The hydrofluorocarbon of 0~20 parts by weight；
The hexafluorobutene of 1~30 parts by weight；
The water of 0.5~2.0 parts by weight；
The composite catalyst of 1~3.5 parts by weight；
The foam stabiliser of 1~5 parts by weight；And
The fire retardant of 1~15 parts by weight.
8. combined polyether as claimed in claim 7, which is characterized in that the parts by weight of the polyether polyol A are 40~60,
The parts by weight of the polyether polyol B are 5~15, and the parts by weight of the polyether polyol C are 20~30, and the polyester is more
The parts by weight of first alcohol D are 5~15, and the parts by weight of the fire retardant are 5~10.
9. a kind of preparation method of hard polyurethane foams, which is characterized in that include the following steps：
Organic isocyanate is uniformly mixed with such as claim 1 to 8 any one of them combined polyether；
Composition injection foaming cavity after mixing is foamed.
10. the preparation method of hard polyurethane foams as claimed in claim 9, which is characterized in that the organic isocyanate
For multiple first class polyphenyl polyisocyanate.
11. the preparation method of the hard polyurethane foams as described in claim 9 or 10, which is characterized in that organic isocyanide
Weight ratio between acid esters and the combined polyether is 0.9~1.3.
12. the preparation method of hard polyurethane foams as claimed in claim 9, which is characterized in that will be uniformly mixed described
In the step of composition injection foaming cavity afterwards is foamed, ranging from 20~50 DEG C of the external temperature of the foaming cavity,
Internal temperature range is 20~50 DEG C.
13. the preparation method of hard polyurethane foams as claimed in claim 12, which is characterized in that will be uniformly mixed described
In the step of composition injection foaming cavity afterwards is foamed, the temperature range of the composition is 15~25 DEG C, the note
The operating pressure entered ranging from 12~14Mpa.
14. a kind of hard polyurethane foams, which is characterized in that the hard polyurethane foams are any by such as claim 9 to 13
Prepared by the preparation method of hard polyurethane foams described in.
15. a kind of water heater, which is characterized in that including liner and hard polyurethane foams as claimed in claim 14, institute
State the outer surface that hard polyurethane foams are attached to the liner.
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| CN201710115446.2A CN108503767A (en) | 2017-02-28 | 2017-02-28 | Combined polyether, hard polyurethane foams and preparation method thereof and water heater |
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| CN201710115446.2A CN108503767A (en) | 2017-02-28 | 2017-02-28 | Combined polyether, hard polyurethane foams and preparation method thereof and water heater |
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| CN109294218A (en) * | 2018-09-28 | 2019-02-01 | 上海东大聚氨酯有限公司 | Combined polyether, polyurethane foam feedstock composition, from its polyurethane foam and its preparation method and application |
| CN109666116A (en) * | 2018-12-27 | 2019-04-23 | 广州拜尔冷链聚氨酯科技有限公司 | A kind of high intensity refrigerator carriage hard polyaminoester combined polyether |
| CN109749613A (en) * | 2018-12-20 | 2019-05-14 | 上海东大聚氨酯有限公司 | A kind of environmentally friendly spraying combined polyether, polyurethane foam and its feedstock composition and preparation method |
| CN112521569A (en) * | 2020-10-26 | 2021-03-19 | 中投(天津)智能管道股份有限公司 | Production process for low-point horizontal casting polyurethane for heat-insulating pipeline |
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| CN116262811A (en) * | 2021-12-13 | 2023-06-16 | 山东一诺威新材料有限公司 | Combined polyether and polyurethane foam for outdoor high-capacity heat-insulating kettle |
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Application publication date: 20180907 |