CN109400839A - A kind of flame retardant combination polyethers, fire-retardant polyisocyanurate foam and preparation method thereof - Google Patents
A kind of flame retardant combination polyethers, fire-retardant polyisocyanurate foam and preparation method thereof Download PDFInfo
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- CN109400839A CN109400839A CN201811200972.XA CN201811200972A CN109400839A CN 109400839 A CN109400839 A CN 109400839A CN 201811200972 A CN201811200972 A CN 201811200972A CN 109400839 A CN109400839 A CN 109400839A
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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
-
- 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
- C08G18/4202—Two or more polyesters 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
-
- 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
- C08J9/142—Compounds containing oxygen but no halogen atom
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
Abstract
This application involves a kind of flame retardant combination polyethers, are counted on the basis of parts by weight, are made of following raw material components: 15-30 parts of polyether polyol, first 50-75 parts of polyester polyol, second 10-20 parts of polyester polyol, 3.0-5.0 parts of surfactant, the first 0.5-1.0 parts of catalyst, second 1.0-2.0 parts of catalyst, 1.0-2.0 parts of third catalyst, 25-40 parts of fire retardant, 1.0-1.5 parts of chemical foaming agent, 2.6-3.6 parts of additive, 13-18 parts of physical blowing agent；Wherein the sum of pure and mild second polyester polyol dosage of polyether polyol, the first polyester polyols is 100 parts；Wherein pure and mild second polyester polyol of first polyester polyols is the aromatic polyester polyol with flame retarding construction, and the additive is aliphatic ketone.The application also provides a kind of fire-retardant polyisocyanurate foam and preparation method thereof, and the fire-retardant polyisocyanurate foam is made of the first component and the second component, wherein the first component is mixed by the raw material components of flame retardant combination polyethers as described above；Second group is divided into poly methylene poly phenyl poly isocyanate.
Description
Technical field
This application involves chemosynthesis technical fields, and specifically, this application involves a kind of flame retardant combination polyethers, are originated from institute
State the fire-retardant polyisocyanurate foam of flame retardant combination polyethers and the preparation method of the fire-retardant polyisocyanurate foam.
Background technique
Polyurethane material is a kind of thermal insulation material haveing excellent performance, and thermal coefficient is low, good weatherability, caking property and corrosion resistant
Corrosion is superior to other thermal insulation materials, obtains very big popularization in field of thermal insulation such as China's household electrical appliances, building, chemical pipelines at present.
But the promotion with the country to thermal insulation material fire-protection rating, the low disadvantage of polyurethane material anti-flammability gradually embody, and make
For a kind of organic insulation material, flame retardant property only up to reach B2 grade, and the A grade compared to general inorganic heat insulation material is prevented fires
Performance differs greatly.
For this not high deficiency of polyurethane material flame retardant property, polyisocyanurate material is developed, is a kind of poly-
The modified material of urethane material, by introducing a large amount of benzene ring structure, flame retardant property can achieve B1 grades or more, then pass through steel
The Material claddings such as plate, Cement fibre cloth, also can achieve A grades or more.In this way, the advantage of polyisocyanurate material just gradually body
Reveal and, compare inorganic heat insulation material, reach same heat insulation effect, it is only necessary to the 1/2-1/3 of its insulation layer thickness, construction
Easier, waste of material is low, has begun large-scale popularization and use in the multiple provinces in China.
Mainstream foaming agent used in poly-isocyanurate has HCFC-141b, HFC-245fa, HFC-365mfc, penta at present
Alkane etc..HCFC-141b has been disabled since it has biggish destruction to ozone layer in the sector substantially.HFC-245fa and
The latent value (ODP) of the ozone-depleting of HFC-365mfc is 0, and global warming potential (GWP) is respectively 820 and 840, belongs to transition production
Product, the problem of also facing substitution.
At present the zero odp value of mainstream, in low GWP value foaming agent, for pentane since its own is inflammable and explosive, risk is high, and
Its thermal conductivity is high, foam poor flame retardant properties obtained, larger using limiting.The thermal conductivity of water is very high, and compares other uses
The system material quantity of physical blowing agent is more, only has use in individual industries.The LBA of forth generation foaming agent such as Honeywell Inc.
Or the Opteon1100 of Ke Mu company, current production scale very little, and it is expensive, also come without promoting.Formic acid first
The boiling point and solubility and HCFC-141b of ester are very close, and its is low in cost, and do not contain volatile organic matter (VOC), are
Foaming agent substitute ideal at present.
But influencing the greatest problem that methyl formate uses is that methyl formate easily hydrolyzes in combined polyether system, is generated
Formic acid and methanol, and irreversible chemical reaction occurs for formic acid and amines catalyst, causes raw material reactivity slack-off, product is close
Degree increases, and system storage time shortens.Even if it among article system, can also occur slowly to hydrolyze, hydrolysate formic acid
There is biggish solubility effect to foamed product with methanol, it is big to will appear foam contraction, product compressive strength within three months
The generation for phenomena such as width declines.Methyl formate hydrolysis and the solubility effect to foamed product are solved, is that methyl formate foaming agent is answered
Maximum difficult point.
For this purpose, there is an urgent need in the art to develop one kind can effectively inhibit the flame retardant combination polyethers of methyl formate hydrolysis, resistance
Fire polyisocyanurate foam and preparation method thereof.
Summary of the invention
In existing methyl formate foaming solution, the general dosage by special catalyst and reduction methyl formate
It solves the problems, such as methyl formate hydrolysis, but cannot be still fully solved in practical application, storage stability summer is at most 10
It or so still has rotten situation, and foamed product solubility effect still remains, using being very limited.
The application's is designed to provide a kind of flame retardant combination polyethers that can effectively inhibit methyl formate hydrolysis, to solve
Certainly the problems of the prior art.The application wherein by methyl formate dissolution, reduces its hydrolysis by introducing special additive
Situation has obtained good using effect, and the shelf-life can extend to 90 days or more, can be adapted for the life of most clients
It produces.Meanwhile the solubility effect in foamed product is there has also been sizable improvement, still retention property after product is at most placed 1 year
Substantially do not decline.Both of the aforesaid problem has the scheme of good solution, and methyl formate foaming agent is in poly-isocyanurate
Later period in system promotes will more smoothly.
The purpose of the application, which also resides in, provides a kind of fire-retardant polyisocyanurate foam from the flame retardant combination polyethers.
The purpose of the application, which also resides in, provides a kind of method for preparing fire-retardant polyisocyanurate foam.
To achieve the goals above, the application provides following technical proposals.
In the first aspect, the application provides a kind of flame retardant combination polyethers, is counted on the basis of parts by weight, by following originals
Material component is made:
Wherein the sum of pure and mild second polyester polyol dosage of polyether polyol, the first polyester polyols is 100 parts；
Wherein pure and mild second polyester polyol of first polyester polyols is that the aromatic polyester with flame retarding construction is polynary
Alcohol；
Wherein the additive includes aliphatic ketone.
In a kind of embodiment of first aspect, the additive is butanone.
In a kind of embodiment of first aspect, the polyether polyol is a kind of halogenated polyether polyalcohol, function
Degree is 3,320~340mgKOH/g of hydroxyl value, 6000~8000mPas of viscosity；
And/or first polyester polyol is a kind of aromatic polyester polyol with flame retarding construction, degree of functionality
For 2-2.5,280~310mgKOH/g of hydroxyl value, 5000~9000mPas of viscosity；
And/or second polyester polyol is a kind of aromatic polyester polyol with flame retarding construction, degree of functionality
For 2.5-3,390~420mgKOH/g of hydroxyl value, 6300~9300mPas of viscosity.
In a kind of embodiment of first aspect, the surfactant includes foam stabiliser；
And/or first catalyst is amines catalyst；
And/or second catalyst is metal-based catalysts；
And/or the third catalyst is three cluster catalyst；
And/or the fire retardant is the common chlorine-based flame retardant of polyurethane and/or phosphorus flame retardant；
And/or the chemical foaming agent is water；
And/or the physical blowing agent includes methyl formate.
In a kind of embodiment of first aspect, first polyether polyol is the production of Su Wei fluorine chemistry Co., Ltd
Polyether glycol I xol B251；
And/or first polyester polyol is the polyester polyol PS- of Nanjing Nanjing Si Taipan Chemical Co., Ltd.
3158；
And/or second polyester polyol is the polyester polyol PS- of Nanjing Nanjing Si Taipan Chemical Co., Ltd.
4027；
And/or first catalyst is the Polycat 15 of Air Prod & Chem's production；
And/or second catalyst is the Dabco K15 and/or Polycat 46 of Air Prod & Chem's production；
And/or the third catalyst is the Dabco TMR-30 of Air Prod & Chem's production；
And/or the foam stabiliser is L-6900 and/or the Jiangsu for stepping the production of figure new high-tech material (China) Co., Ltd
Beauty thinks the AK-8825 that limited liability company's production is learned in Dehua；
And/or the fire retardant is tricresyl phosphate (2- chloropropyl) ester and/or ethyl phosphonic acid diethylester；
And/or the water includes deionized water.
In second aspect, the application provides a kind of fire-retardant polyisocyanurate foam, the fire-retardant poly-isocyanurate
Foam is made of the first component and the second component, wherein raw material of first component by flame retardant combination polyethers as described in relation to the first aspect
Component mixes；Second group is divided into poly methylene poly phenyl poly isocyanate.
In a kind of embodiment of second aspect, described second group is divided into Yantai Wanhua Polyurethane Co., Ltd's life
PM200, PM400 of production；The 44V20 of Bayer AG's production, one or more of the M20S of BASF joint-stock company production.
In a kind of embodiment of second aspect, the weight ratio of first component and the second component is 1:1.5-
1.7。
In a kind of embodiment of second aspect, when according to national standard " GB/T 8624-2012 construction material and system
Product classification system for fire performance " when being tested, the flame retardant property of the fire-retardant polyisocyanurate foam reaches B1 grades.
In a third aspect, the application provides a kind of fire-retardant polyisocyanurate foam prepared as described in second aspect
Method obtains described fire-retardant the method includes mixing the first component and the second component of predetermined weight ratio after constant temperature foaming
Polyisocyanurate foam.
In a kind of embodiment of the third aspect, the blowing temperature of constant temperature foaming is 55 DEG C -65 DEG C.
Compared with prior art, gather the beneficial effects of the present application are as follows solving methyl formate in poly-isocyanurate combination
The hydrolysis situation occurred in ether system, shelf lives can be improved by 90 days or more, meanwhile, the foamed product produced does not have
Situations such as shrinking, deforming, flame retardant property reaches B1 grades, facilitates methyl formate pushing away in household electrical appliances combined polyether system
Extensively, safety and physical property are better than pentane system, and overall cost ratio HFC class and HFO class foaming agent are much lower, ODP,
GWP, VOC value are zero, and the feature of environmental protection is also optimal in all foaming agents.
Specific embodiment
Unless otherwise indicated, from context cues or belong to the convention of the prior art, otherwise number all in the application
It is all based on weight with percentage, and test and characterizing method used is all synchronous with the submission date of the application.It is being applicable in
In the case where, any patent, patent application or disclosure involved in the application are fully incorporated in this as reference, and its
Patent families of equal value are also introduced into as reference, about the synthetic technology in this field, product disclosed by these special documents
With the definition of fabrication design, polymer, comonomer, initiator or catalyst etc..If the specific art disclosed in the prior art
Defining for language is inconsistent with any definition provided herein, then term provided herein of being subject to defines.
Digital scope in the application is approximation, therefore unless otherwise stated, it may include the number other than range
Value.Numberical range include with the increased all numerical value from lower limit value to upper limit value of 1 unit, condition be any lower value with
There are the intervals of at least two unit between any high value.For example, if compositional, physics or other property (such as molecules
Amount, melt index (MI) etc.) it is 100 to 1000, it is meant that clearly list all single numbers, such as 100,101,102 etc., with
And all subranges, such as 100 to 166,155 to 170,198 to 200 etc..For comprising the numerical value less than 1 or comprising big
In the range of 1 score (such as 1.1,1.5 etc.), then suitably regard 1 unit as 0.0001,0.001,0.01 or 0.1.
For the range comprising the units less than 10 (such as 1 to 5), usually regard 1 unit as 0.1.These are only intended to table
The specific example of the content reached, and all possible combination of the numerical value between cited minimum and peak is all recognized
In this application for clear record.It is also pointed out that term " first " herein, " second " etc. do not limit sequencing, only
In order to distinguish the substance of different structure.
About chemical compound in use, unless explicitly stated otherwise, otherwise odd number includes all isomeric forms, otherwise also
So (for example, whole isomers that " hexane " either individually or collectively includes hexane).In addition, unless explicitly stated otherwise, otherwise using
"one", the noun that "an" or "the" are described also includes its plural form.
Term "comprising", " comprising ", " having " and their derivative are not excluded for any other component, step or mistake
The presence of journey, and whether disclose in this application with these other components, step or process unrelated.To eliminate any query,
Unless expressly stated, otherwise in the application it is all use term "comprising"s, " comprising ", or " having " composition may include appoint
What additional additive, auxiliary material or compound.On the contrary, in addition to necessary to operating characteristics those, term " substantially by ...
Composition " excludes any other component, step or process except the hereinafter described range of any term.Term " by ...
Composition " does not include any component, step or the process for not specifically describing or listing.Unless expressly stated, otherwise term "or" refers to
Separate member listed or any combination thereof.
In a specific embodiment, the application provides a kind of flame retardant combination polyethers.
The flame retardant combination polyethers of the application is made of following component, and the number is mass fraction, polyether polyol, first
Polyester polyol, the summation of the second polyester polyol are 100 parts:
In a specific embodiment, the flame retardant combination polyethers of the application includes polyether polyol.Suitable for this Shen
The polyether polyol of purpose please include but is not limited to by make epoxides (such as ethylene oxide, propylene oxide, epoxy butane or
Tetrahydrofuran) there is the product for being polymerize and being obtained in polyfunctionality initiator.Suitable initiator contains multiple reactive hydrogens
Atom, specific example include water, butanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, ethanol amine,
Diethanol amine, triethanolamine, toluenediamine, diethyl toluene diamine, aniline, diphenylmethanediamiand, ethylenediamine, hexamethylene two
Amine, cyclohexanedimethanol, resorcinol, bisphenol-A, glycerol, trimethylolpropane, 1,2,6- hexanetriol, pentaerythrite or they
Combination.
In a specific embodiment, polyether polyol is preferably a kind of halogenated polyether polyalcohol, and degree of functionality is
3,320~340mgKOH/g of hydroxyl value, 6000~8000mPas of viscosity, typical model Su Wei fluorine chemistry Co., Ltd gathers
Ethoxylated polyhydric alcohol Ixol B251.Ixol B251 is a kind of halogenated aliphatic polyether triol, and main component is a kind of epoxy chloropropionate
The mixture of alkyl polyols (solvay fluor company trade mark Ixol B350) and a small amount of triethyl phosphate.
In a specific embodiment, the flame retardant combination polyethers of the application further includes the fragrant adoption with flame retarding construction
Ester polyol.Aromatic polyester polyol refers to the polyester polyol containing phenyl ring, usually with aromatic acid (or acid anhydrides, ester)
It is the polyester polyol of Material synthesis with dihydric alcohol (and/or polyalcohol).The raw material of polyester is usually phthalic anhydride or right
Phthalic acid etc., common binary raw polyol are diglycol, trihydroxylic alcohol etc..
In a specific embodiment, herein described first polyester polyol is a kind of fragrance with flame retarding construction
Adoption ester polyol, degree of functionality 2-2.5,280~310mgKOH/g of hydroxyl value, 5000~9000mPas of viscosity are typical
The polyester polyol PS-3158 of model Nanjing Nanjing Si Taipan Chemical Co., Ltd..
In a specific embodiment, herein described second polyester polyol is a kind of fragrance with flame retarding construction
Adoption ester polyol, degree of functionality 2.5-3,390~420mgKOH/g of hydroxyl value, 6300~9300mPas of viscosity are typical
The polyester polyol PS-4027 of model Nanjing Nanjing Si Taipan Chemical Co., Ltd..
The flame retardant combination polyethers of the application further includes surfactant, and surfactant usually supports foaming agent and polyalcohol
Homogenization, and adjust polyisocyanurate foam pore structure.Surfactant may include any conjunction as known in the art
The mixture of suitable surfactant or surfactant.
In a specific embodiment, the surfactant of the application includes foam stabiliser.Herein described foam
Stabilizer is type siloxane foam stabiliser, preferably steps the L-6900 and/or Jiangsu of figure new high-tech material (China) Co., Ltd
Beauty thinks the AK-8825 that limited liability company is learned in Dehua.
In a specific embodiment, flame retardant combination polyethers as described herein further includes carbon monoxide-olefin polymeric.Catalyst
Commonly used in the reaction between catalysis isocyanates and polyalcohol, and it is not consumed in the reaction.In a kind of specific embodiment
In, the flame retardant combination polyethers of the application includes at least the first catalyst, the second catalyst and third catalyst.Herein described
One catalyst is the common amines catalyst of polyurethane field, preferably Polycat 15 (Air Prod & Chem's production).
Herein described second catalyst is the common metal-based catalysts of polyurethane, and (air chemical industry produces the preferred Dabco K15 of the application
The production of product company) and/or Polycat 46 (Air Prod & Chem's production).Herein described third catalyst is polyurethane
Common three clusters catalyst, the preferred Dabco TMR-30 of the application (Air Prod & Chem's production).
In a specific embodiment, the flame retardant combination polyethers of the application further includes fire retardant.It is herein described fire-retardant
Agent be the common chlorine-based flame retardant of polyurethane and/or phosphorus flame retardant, preferably tricresyl phosphate (2- chloropropyl) ester (TCPP) and/or
Ethyl phosphonic acid diethylester (DEEP).
In a specific embodiment, the flame retardant combination polyethers of the application further includes additive.The additive is available
Make solvent, for dissolving methyl formate, and inhibits the hydrolysis of methyl formate.In a specific embodiment, as described herein
Additive is aliphatic ketone comprising but be not limited to butanone, pentanone, new pentanone, cyclohexanone etc..Particularly preferably implement in one kind
In mode, additive described herein is butanone.
In a specific embodiment, the flame retardant combination polyethers of the application also optionally includes that other are routinely added
Agent, the conventional additives include but is not limited to chain extender, chain terminating agent, processing aid, adhesion promotor, antioxidant, disappear
Infusion, deicer, molecular sieve, UV light stabilizing agent, filler, thixotropic agent, colorant, inert diluent or their combination.
Flame retardant combination polyethers described herein may also include chemical foaming agent and physical blowing agent.Herein, term
" physical blowing agent " refers to the foaming agent that will not be chemically reacted with isocyanates or polyalcohol.Physical blowing agent can be gas
Body or liquid.Liquid physical blowing agent usually flashes to gas when heated, and usually reverts to liquid while cooling.In one kind
In specific embodiment, herein described physical blowing agent is methyl formate.
Herein, term " chemical foaming agent " refer to isocyanates, polyalcohol or other components occur chemical reaction and
Foaming agent of the release for the gas of foaming.In a specific embodiment, chemical foaming agent as described herein includes water, special
It is not deionized water.
The application also provides a kind of fire-retardant polyisocyanurate foam, and the fire-retardant polyisocyanurate foam is by the first component
With the second component with certain proportion after mechanical stirring mixes, pass through a series of chemical reaction synthesize.First component is logical
The raw material components for crossing flame retardant combination polyethers as described above mix.First component is by a certain proportion of polyether polyol, poly-
Ester polyol, surfactant, catalyst, additive, foaming agent etc. are formed by mechanical mixture；Second group is divided into more methylenes
Quito polyphenyl polyisocyanate (PAPI).
Herein described poly methylene poly phenyl poly isocyanate is that the common polymethylene polyphenyl of polyurethane field is more
Isocyanates, such as PM200, PM400 that Yantai Wanhua Polyurethane Co., Ltd produces, the 44V20 of Beyer Co., Ltd, BASF
The M20S etc. of joint-stock company.The PM400 of the preferred Yantai Wanhua Polyurethane Co., Ltd's production of the application.
The weight ratio of herein described first component and the second component is 1:1.5-1.7.
The application also provides a kind of method for preparing the fire-retardant polyisocyanurate foam as described in second aspect, the side
Method includes mixing the first component and the second component of predetermined weight ratio, obtains the fire-retardant poly-isocyanurate after constant temperature foaming
Foam.
Embodiment
Below in conjunction with embodiments herein, clear and complete description is carried out to the technical solution of the application.Such as nothing
It illustrates, reagent used and raw material can all be bought by commercial sources.Actual conditions are not specified in the following example
Experimental method according to conventional methods and conditions, or is selected according to product manual.
Embodiment 1-4 and comparative example 1-2
Firstly, according to the first component of the ingredient preparation embodiment 1-4 and comparative example 1-2 in following table, number shown in table 1
It is mass fraction.
The first component formula of table 1. embodiment 1-4 and comparative example 1-2
Other raw materials described in upper table in addition to PAPI are poured into reaction vessel according to regulation ratio, utilize electric mixer
It is uniformly mixed, the first component is made；The temperature of the first component and the second component is adjusted to 22 DEG C again, according to corresponding weight ratio
Example is poured into reaction vessel, is then stirred 10-15 seconds using electric mixer, liquid after mixing is poured into constant temperature
In 55-65 DEG C of thickness 12cm mold, mold is shut, opens mold after placing 25min under the conditions of 60 DEG C of constant temperature, it can get Ben Shen
It please the poly-isocyanurate insulating foam.
Embodiment 1-4 and comparative example 1-2 resulting materials are tested for the property, the table 2 that acquired results see below.Performance is surveyed
Test-object is quasi-:
Cream time, gel time, unsticking time: it is estimated using stopwatch；
Freely steep density, molding bubble density: the density measurement of GB/T 6343-95 polyurethane foam plastics；
Compressive strength: the measurement of GB/T 8813-2008 rigid foam compression performance；
Thermal coefficient: GB/T 10295-2008 Technology of Steady State Thermal Resistance of Thermal Insulating Material and the measurement heat-flow meter method in relation to characteristic；
Dimensional stability: the measurement of GB/T 6342-1996 foamed plastics and rubber linear dimension；
Flame retardant property: GB/T 8624-2012 construction material and classification of combustion properties of building materials and products.
2. embodiment 1-4 of table and comparative example 1-2 the performance test results
As known from Table 2, it after the application obtained flame-retardant combined polyether is placed 30 days, the reaction time and freely steeps density and does not have
Too big variation can be used with long term storage, and body after low temperature placement 180 days is made after fire-retardant polyisocyanurate foam product
Product change rate very little ensure that the long-term performance of product is stablized.It is carried out pair in the pentamethylene foaming system with existing market mainstream
Cyclopentane systems are superior to than, it has been found that physical properties such as its compressive strength, thermal coefficient, dimensional stability, anti-flammability, then plus
Its upper safety is higher, the value with large-scale promotion.Raw material used in this application is that sold raw material, raw material come on the market
Source is extensive, can be mass produced.
The above-mentioned description to embodiment is that this Shen can be understood and applied for the ease of those skilled in the art
Please.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without paying creative labor.Therefore, the application is not limited to implementation here
Example, those skilled in the art make according to herein disclosed content in the case where not departing from the application scope and spirit
It improves and modifies within all scope of the present application.
Claims (11)
1. a kind of flame retardant combination polyethers, is counted on the basis of parts by weight, is made of following raw material components:
Wherein the sum of pure and mild second polyester polyol dosage of polyether polyol, the first polyester polyols is 100 parts；
Wherein pure and mild second polyester polyol of first polyester polyols is the aromatic polyester polyol with flame retarding construction；
Wherein the additive includes aliphatic ketone.
2. flame retardant combination polyethers as described in claim 1, which is characterized in that the additive is butanone.
3. flame retardant combination polyethers as described in claim 1, which is characterized in that the polyether polyol is that a kind of halogenated polyether is more
First alcohol, degree of functionality 3,320~340mgKOH/g of hydroxyl value, 6000~8000mPas of viscosity；
And/or first polyester polyol is a kind of aromatic polyester polyol with flame retarding construction, degree of functionality 2-
2.5,280~310mgKOH/g of hydroxyl value, 5000~9000mPas of viscosity；
And/or second polyester polyol is a kind of aromatic polyester polyol with flame retarding construction, degree of functionality is
2.5-3,390~420mgKOH/g of hydroxyl value, 6300~9300mPas of viscosity.
4. flame retardant combination polyethers as described in claim 1, which is characterized in that the surfactant includes foam stabiliser；
And/or first catalyst is amines catalyst；
And/or second catalyst is metal-based catalysts；
And/or the third catalyst is three cluster catalyst；
And/or the fire retardant is the common chlorine-based flame retardant of polyurethane and/or phosphorus flame retardant；
And/or the chemical foaming agent is water；
And/or the physical blowing agent includes methyl formate.
5. flame retardant combination polyethers as claimed in claim 4, which is characterized in that first polyether polyol is Su Wei fluorine chemistry
The polyether glycol I xol B251 of Co., Ltd's production；
And/or first polyester polyol is the polyester polyol PS-3158 of Nanjing Nanjing Si Taipan Chemical Co., Ltd.；
And/or second polyester polyol is the polyester polyol PS-4027 of Nanjing Nanjing Si Taipan Chemical Co., Ltd.；
And/or first catalyst is the Polycat 15 of Air Prod & Chem's production；
And/or second catalyst is the Dabco K15 and/or Polycat46 of Air Prod & Chem's production；
And/or the third catalyst is the Dabco TMR-30 of Air Prod & Chem's production；
And/or the foam stabiliser is that the L-6900 for stepping the production of figure new high-tech material (China) Co., Ltd and/or Jiangsu beauty are thought
Learn the AK-8825 of limited liability company's production in Dehua；
And/or the fire retardant is tricresyl phosphate (2- chloropropyl) ester and/or ethyl phosphonic acid diethylester；
And/or the water includes deionized water.
6. a kind of fire-retardant polyisocyanurate foam, the fire-retardant polyisocyanurate foam is by the first component and the second component system
At wherein the first component is mixed by the raw material components of flame retardant combination polyethers according to any one of claims 1 to 5；The
Two groups are divided into poly methylene poly phenyl poly isocyanate.
7. fire-retardant polyisocyanurate foam as claimed in claim 6, which is characterized in that described second group is divided into Yantai Wanhua
PM200, PM400 of polyurethane limited liability company production；The 44V20 of Bayer AG's production, the production of BASF joint-stock company
One or more of M20S.
8. fire-retardant polyisocyanurate foam as claimed in claim 6, which is characterized in that first component and the second component
Weight ratio be 1:1.5-1.7.
9. fire-retardant polyisocyanurate foam as claimed in claim 6, which is characterized in that when according to national standard " GB/T
8624-2012 construction material and classification of combustion properties of building materials and products " when being tested, the fire-retardant polyisocyanurate foam it is fire-retardant
Performance reaches B1 grades.
10. a kind of method for preparing fire-retardant polyisocyanurate foam as claimed in claim 6, pre- the method includes mixing
Determine the first component and the second component of weight ratio, obtains the fire-retardant polyisocyanurate foam after constant temperature foaming.
11. preparing the method for fire-retardant polyisocyanurate foam as claimed in claim 10, which is characterized in that constant temperature foaming
Blowing temperature is 55 DEG C -65 DEG C.
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| CN110105536A (en) * | 2019-03-19 | 2019-08-09 | 广州朗腾聚氨酯有限公司 | A kind of low-smoke low-toxicity combined polyether and its polyurethane preparation method |
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| CN113698568A (en) * | 2021-07-20 | 2021-11-26 | 佳化化学科技发展（上海）有限公司 | Combined polyether, polyisocyanurate foam, preparation method and application thereof |
| CN115536801A (en) * | 2022-09-23 | 2022-12-30 | 上海玓墨节能科技有限公司 | Cold-insulation high-flame-retardant spraying type hard polyurethane foam and preparation method thereof |
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