CN104540885A - Thermosetting foam with improved thermal insulation and flame retardancy, and preparation method therefor - Google Patents
Thermosetting foam with improved thermal insulation and flame retardancy, and preparation method therefor Download PDFInfo
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- CN104540885A CN104540885A CN201280075251.5A CN201280075251A CN104540885A CN 104540885 A CN104540885 A CN 104540885A CN 201280075251 A CN201280075251 A CN 201280075251A CN 104540885 A CN104540885 A CN 104540885A
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- thermocurable
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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
- C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
- C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
-
- 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
-
- 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
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
-
- 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
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
Abstract
Provided is a thermosetting foam comprising: a polyisocyanurate foam formed by polymerizing a polyol-based compound and an isocyanate-based compound; a nucleating agent; and a flame retardant, wherein the thermal decomposition initiation temperature of the thermosetting foam measured by thermogravimetric analysis is 310 DEG C or higher. In addition, provided is a method for preparing a thermosetting foam having the thermal decomposition initiation temperature measured by thermogravimetric analysis of 310 DEG C or higher, comprising the steps of: mixing a polyol-based compound and a nucleating agent; adding a flame retardant to the mixture of the polyol-based compound and the nucleating agent; and stirring an isocyanate-based compound with the mixture obtained by adding the flame retardant thereto to polymerize a polyisocyanurate.
Description
Technical field
The present invention relates to Thermocurable foam and preparation method thereof, relate to Thermocurable whipping agent that thermal insulation and flame retardant resistance be improved and preparation method thereof in more detail.
Background technology
Thermocurable foam is mainly used as the lagging material of various buildings, warehouse, refrigerator.Now, lagging material as intercept or reduce building inside and outside portion between heat exchange to increase the material of cooling and warming efficiency, be used in the various field such as building slab and panel, liquified natural gas carrier (LNGC) (LNG ship) cold insulation material, household electrical appliance wrapping material or automotive interior material widely, for the Thermocurable whipping agent of lagging material in order to improve heat-proof quality, can be formed with the foaming cell structure filling foamed gas.
Relative to another synthetic resins, above-mentioned Thermocurable whipping agent has outstanding heat-proof quality and processibility, physical property change based on temperature deviation is little, thus used widely, but, the reinforcement of the regulation of being correlated with along with the flame retardant resistance about lagging material recently, is carrying out adding in the Thermocurable whipping agent in the past used the research that fire retardant uses.
Record in No. 10-0610392nd, Korean granted patent after comprising mixing thermoplastic resin and fire retardant and in above-mentioned thermoplastic resin, dissolve thermopnore whipping agent continuously, thus the preparation method of the type thermoplastic resin flame-retardant intumescent agent of the step that foamed cell is grown up, but interpolation fire retardant, this is relative to the increase of flame retardant resistance, and the physical property of Thermocurable foam and heat-proof quality may reduce.
Summary of the invention
the technical problem to be solved in the present invention
An example of the present invention provides Thermocurable foam, introduces nucleator and fire retardant, thus have not only little but also uniform foamed cell while above-mentioned Thermocurable foam uses poly-isocyanurate.
The preparation method of the Thermocurable foam that an example more of the present invention provides thermal insulation and flame retardant resistance to be improved.
technical scheme
An example of the present invention provides Thermocurable foam, above-mentioned Thermocurable foam comprises and is polymerized by multicomponent alcoholics compound and isocyanate ester compound the polyisocyanurate foam, nucleator and the fire retardant that are formed, and to start temperature according to the thermolysis of thermogravimetry be more than 310 DEG C.
Above-mentioned fire retardant can be liquid phase or powder morphology.
Above-mentioned fire retardant can for being selected from least one in the group that is made up of phosphorus type flame retardant, metal hydride based flame retardant, halogen fire retardant, flame retardant and their mixture.
Above-mentioned phosphorus type flame retardant can for being selected from least one in the group that is made up of triphenylphosphate, phosphate toluene diphenyl ester, p isopropylbenzoic acid base benzene diphenyl ester and their mixture.
Above-mentioned halogen fire retardant can be decabromodiphynly oxide (decabromodiphenyl oxide) or octabromodiphenyl base oxide (octabromodiphenyl oxide).
Above-mentioned flame retardant can be ANTIMONY TRIOXIDE SB 203 99.8 PCT.
Above-mentioned nucleator can comprise silane compound or siloxane compound.
The mean diameter being formed in the foamed cell (cell) of above-mentioned polyisocyanurate foam can be about 50 μm to about 200 μm.
Relative to the above-mentioned multicomponent alcoholics compound of 100 weight parts, the content of above-mentioned fire retardant can be that about 1 weight part is to about 20 weight parts.
Relative to the above-mentioned multicomponent alcoholics compound of 100 weight parts, the content of above-mentioned nucleator can be that about 1 weight part is to about 10 weight parts.
Polymerizing catalyst, tensio-active agent and whipping agent can also be comprised in above-mentioned Thermocurable foam.
The thermal conductivity of above-mentioned Thermocurable foam can be about below 0.025W/mk.
The separated foam rate of above-mentioned Thermocurable foam can be about more than 80%.
The density of above-mentioned Thermocurable whipping agent can be about 10kg/m
3to about 150kg/m
3.
An example more of the present invention provides the preparation method of Thermocurable foam, the preparation method of above-mentioned Thermocurable foam comprises: the step of polyol blend compounds and nucleator, the step of fire retardant is added in the mixture of above-mentioned multicomponent alcoholics compound and nucleator, and stir isocyanate ester compound, to the step that poly-isocyanurate is polymerized in the mixture obtained after adding above-mentioned fire retardant; Be more than 310 DEG C of temperature according to the beginning temperature of thermogravimetry.
beneficial effect
The Thermocurable foam of an example of the present invention has lower thermal conductivity, and the mechanical properties such as compressive strength and flexural strength has outstanding flame retardant resistance while being improved.
Further, utilize the preparation method of the Thermocurable foam of an example more of the present invention, can utilize while influential environment-friendly foaming agent is not had to the destruction of ozonosphere and can obtain not only little but also uniform foamed cell by adding nucleator.
Embodiment
Below, example of the present invention is described in detail.But this just illustratively to propose, and the present invention is not limited thereto, the present invention only defines according to the category of the claimed scope of appended invention.
Thermocurable foam
An example of the present invention provides Thermocurable foam, above-mentioned Thermocurable foam comprises and is polymerized by multicomponent alcoholics compound and isocyanate ester compound the polyisocyanurate foam, nucleator and the fire retardant that are formed, and to start temperature according to the thermolysis of thermogravimetry be more than 310 DEG C.
Foam is as the plastic material of little hole comprising higher volume percent, Thermocurable foam carries out chemical reaction by heating, thus hardening, and cooling after again heat the heat-curing resin that also can not soften melting be made into foam form use.Above-mentioned Thermocurable foam can guarantee the thermal insulation of more than constant level, and can be used in the lagging material etc. of various buildings, warehouse, refrigerator.
When generally for the flame retardant resistance that improves and guarantee the Thermocurable foam of constant level and add fire retardant, when reacting with polyisocyanurate foam etc., surface tension increases and the size of foamed cell that formed may become large or burst.But one embodiment of the invention, for the above-mentioned counter productive occurred because adding fire retardant, can be carried out control surface tension force by the limited nucleator of mean particle size, thus can make up these effects.
Above-mentioned thermosetting foam comprises fire retardant, thus start temperature according to the thermolysis of thermogravimetry can for more than about 310 DEG C.As previously mentioned, also comprise nucleator while above-mentioned Thermocurable foam comprises fire retardant, thus the counter productive because fire retardant occurs can not occur, and comprise fire retardant, therefore, it is possible to the Thermocurable foam that while providing thermal insulation outstanding, flame retardant resistance is also outstanding.
Above-mentioned thermogravimetry refers to the analysis measuring and add the changes in weight hankering occurring in material, has been generally Knowing material and has measured for the stability of heat.Substantially, start at normal temperatures to be measured to about 600 DEG C, per minute respectively heats up the Simultaneously test of about 10 DEG C, and produces 5% in measuring with the interval of reducing fast of improving quality, and above-mentioned interval starts temperature or Mass lost temperature thermolysis.Comprise above-mentioned fire retardant, therefore start temperature according to the thermolysis of the thermogravimetry of above-mentioned Thermocurable foam and be measured as more than about 310 DEG C, and comprise nucleator and fire retardant simultaneously, the thermolysis higher than existing Thermocurable foam can be had and start temperature.
The polyisocyanurate foam that above-mentioned Thermocurable foam comprises can be polymerized by multicomponent alcoholics compound and isocyanate ester compound and be formed.Polyisocyanurate foam comprises with the material of ring structure in conjunction with the isocyanurate group of 3 isocyanate group forms in the polyurethane foam being in the past widely used as lagging material.Polyisocyanurate foam has very outstanding performance due to above-mentioned ring structure in thermostability and physical strength.Conventional art prepare polyurethane foam time, introduce additive in polyvalent alcohol, both as the material of clay or gaseous solvents and so on, thus reduce foamed cell size and by its obtain heat-proof quality raising effect.
But, when introducing above-mentioned additive in polyvalent alcohol, the problem of dispersiveness or stability in storage may be there is, therefore, in one embodiment of the invention, introduce nucleator, can dense, the foamed cell that is formed uniformly polyisocyanurate foam.The less effect of heat insulation of size being formed in the foamed cell of lagging material is more outstanding, and physical strength is also higher, therefore, the material of the nucleation that can contribute to the initial stage except whipping agent is added in polymeric material, reduce the size of foamed cell, and increase the density of foamed cell, thus the physical property of lagging material can be improved.
Above-mentioned multicomponent alcoholics compound, as the material comprising multiple hydroxyl in a molecule, reacts with isocyanate ester compound and generates urethane bonds and be polymerized.Above-mentioned multicomponent alcoholics compound can be polyester polyol (polyester polyol) or polyether glycol (polyether polyol).Polyester polyol can be by Tetra hydro Phthalic anhydride (phthalic anhydride) or adipic acid (adipic acid) and ethylene oxide (ethylene oxide), propylene oxide (propylene oxide) or their mixture carry out reacting to be polymerized preparing, and polyether glycol to be selected from ethylene glycol (ethylene glycol), 1,2-PD (1,2-propane glycol), butyleneglycol (butylenesglycol), 1,6-hexylene glycol (1,6-hexanediol), 1,8-ethohexadiol (1,8-oxtanediol), neopentyl glycol (neopentyl glycol), 2-methyl isophthalic acid, ammediol (2-methyl-1,3-propanediol), glycol (glycol), TriMethylolPropane(TMP) (trimethylolpropane), 1,2,3-hexanetriol (1,2,3-hexanetriol), BT (1,2,4-butanetriol), Pehanorm (trimethylolmethane), tetramethylolmethane (pentaerythriol), Diethylene Glycol (diethylene glycol), triethylene glycol (triethylene glycol), polyoxyethylene glycol (polyethyleneglycol), tripropylene glycol (tripropylene glycol), polypropylene glycol (polypropylene glycol), dibutylene glycol (dibutylene glycol), polytetramethylene glycol (polybutylene glycol), Sorbitol Powder (sorbitol), sucrose (sucrose), quinhydrones (hydroquinone), Resorcinol (resorcinol), catechol (catechol), at least one in the group that bis-phenol (bisphenol) forms and ethylene oxide, propylene oxide or their mixture carry out reacting be polymerized and prepare.
Above-mentioned isocyanate ester compound is as the material comprising isocyanic ester in molecule, the hydroxyl reaction of isocyanate group and multicomponent alcoholics compound and generate urethane bonds, and 3 isocyanate group carry out reaction and trimerizing, thus perform the effect forming isocyanuric acid ester.In order to form above-mentioned isocyanuric acid ester, the material that the quantity of general isocyanate group is many is more favourable than the isocyanate ester compound being used for polymerizable polyurethane, therefore, it is possible to the index using NCO is about 250 high diisocyanate cpds.
In one embodiment of the invention, be selected from by polyethylene diphenylmethane vulcabond (polymeric MDI, polymericmethylene diphenyl diisocyanate) monomeric mdi (monomeric MDI, monomeric methylene diphenyl diisocyanate) polymethyl benzene vulcabond (polymeric TDI, polymeric toluene diisocyanat) and monomer tolylene diisocyanate (monomeric TDI, monomerictoluene diisocyanate) at least one in the group that forms can use with isocyanate ester compound.
The fire retardant that above-mentioned Thermocurable foam comprises can be liquid phase form or powder morphology.When fire retardant is liquid phase form, dispersed outstanding, and with in the aspect of polyisocyanurate foam or nucleator or their mixture coagulated not there is favourable effect.
And, above-mentioned fire retardant can be powder morphology, when using the fire retardant of powder morphology particularly, above-mentioned fire retardant maintains the average particle diameter of about 1 μm to about 100 μm, thus the dispersiveness of fire retardant can be guaranteed, and the destruction of the foamed cell being formed at polyisocyanurate foam can be prevented.
Above-mentioned fire retardant can be selected from least one in the group that is made up of phosphorus type flame retardant, metal hydride based flame retardant, halogen fire retardant, flame retardant and their mixture.As the resistance to flame improving plastics, the additive that adds has the function hindering burning to fire retardant, and increases flame retardant resistance, thus can widen the availability for Thermocurable foam.
Particularly, above-mentioned phosphorus type flame retardant comprises at least one in the group being selected from and being made up of triphenylphosphate, phosphate toluene diphenyl ester, p isopropylbenzoic acid base benzene diphenyl ester and their mixture.Further, above-mentioned halogen fire retardant can comprise decabromodiphynly oxide or octabromodiphenyl base oxide, and above-mentioned flame retardant can comprise ANTIMONY TRIOXIDE SB 203 99.8 PCT.
Above-mentioned nucleator can comprise silane compound or siloxane compound.Comprise the thermal conductivity that nucleator can suppress inevitably to rise because adding fire retardant to a certain extent, and also can suppress surface tension.
The kind of above-mentioned nucleator is not particularly limited, and can use silicane nucleator, type siloxane nucleator or perfluoro alkane nucleator etc.Particularly, surface tension can be used low, and the silane compound outstanding with the consistency of methylenediphenyl diisocyanates or polyvalent alcohol and siloxane compound, and the mixture that can mix above-mentioned more than a kind uses.Compound as hexamethyldisilazane and dimethoxydimethylsilane can be used as above-mentioned silane compound to use, and hexamethyldisilane can be used as above-mentioned siloxane compound to use.
The mean diameter being formed in the foamed cell of above-mentioned polyisocyanurate foam can be about 50 μm to about 200 μm.Mean diameter refers to the mean diameter of the foamed cell of formation or represents diameter, when the mean diameter of above-mentioned foamed cell is less than about 50 μm, become large according to the contribution of conduction in thermal conductivity, there is the worry that thermal conductivity rises on the contrary, when being greater than about 200 μm, the size of the foamed cell formed becomes very large, therefore there is the problem generating uneven foamed cell.So the content of above-mentioned foamed cell maintains above-mentioned scope, thus has the advantage that can generate not only even but also little foamed cell.
Relative to the above-mentioned multicomponent alcoholics compound of 100 weight parts, the content of above-mentioned fire retardant can be about 1 weight part to 20 weight part.When comprising the above-mentioned fire retardant being less than about 1 weight part, flame retardant resistance may become bad, comprise be greater than about 20 weight part when, there is the worry that workability is bad.So the content of above-mentioned fire retardant maintains above-mentioned scope, thus have to play and maintain workability and improve the advantage of the effect of flame retardant resistance.
Relative to the above-mentioned multicomponent alcoholics compound of 100 weight parts, the content of above-mentioned nucleator can be that about 1 weight part is to about 20 weight parts.When comprising the above-mentioned nucleator being less than about 1 weight part, cause the effect as nucleator to play insignificant because of the nucleator added on a small quantity, and be greater than about 10 weight part when, uneven foamed cell may be formed because of plastic effect.Therefore, the content of above-mentioned nucleator maintains above-mentioned scope, thus has no matter add the advantage that fire retardant also can generate not only little but also uniform foamed cell.
Above-mentioned Thermocurable foam can also comprise polymerizing catalyst, tensio-active agent and whipping agent.Particularly, polymerizing catalyst can promote that the trimerizing between isocyanic ester reacts (trimerization), and improves speed of response, plays the effect contributing to forming isocyanurate group.Above-mentioned polymerizing catalyst can be selected from by acetic acid (aceticacid), sad (octanoicacid), 2,4,6-tri-(dimethylamino methyl) phenol (2,4,6-tris [(dimethylamino) methyl] phenol), 1,3,5-tri-(dimethylin-propylhexahydrotriazare (1,3,5-tris3-dimethylamine-propylhexahydrotrizine) and the group that forms of caproic acid potassium (potassium hexanoate) at least one.
Above-mentioned whipping agent produces gas in the course of the polymerization process, thus performs the effect forming foamed cell in the inside of lagging material.Whipping agent is present in unit after forming polyisocyanurate foam, and the material that the Simultaneous Stabilization that therefore use thermal conductivity is low is high is more favourable.Above-mentioned whipping agent can be selected from least one in the group that is made up of pentamethylene (cyclopentne), Chlorofluorocarbons (CFCs) (chlorofluorocarbon), iso-pentane (isopentane), Skellysolve A (n-pentane), Hydrochlorofluorocarbons (hydrochlorofluorocarbon), HFC (hydrofluorocarbon) and water, especially, favourable in environment as the pentamethylene of not chloride whipping agent, water or their mixture.
When forming foamed cell, above-mentioned tensio-active agent reconciliation statement surface tension, and the phenomenon suppressing the size of foamed cell excessive, and the effect performing that stabilization forms foamed cell.The kind of above-mentioned tensio-active agent can use known various kind in this area.
The thermal conductivity of above-mentioned Thermocurable foam can be about below 0.025W/mk.Thermal conductivity refers to the material property representing thermal conduction size, can class to release the lower heat-proof quality of thermal conductivity more outstanding.Above-mentioned Thermocurable foam comprises polyisocyanurate foam, nucleator and fire retardant simultaneously, not only there is flame retardant resistance but also there is outstanding thermal insulation, low thermal conductivity can be guaranteed, and above-mentioned thermal conductivity maintains about below 0.025W/mk, thus for building, household electrical appliance use, automobile use etc. availability can be improved.
The separated foam rate of above-mentioned Thermocurable foam can be about more than 80%.Above-mentioned Thermocurable foam is made up of the unit of alveolus shape, and in said units, the per-cent of closed cell is called separated foam rate.The higher thermal insulation of separated foam rate improves, and when therefore above-mentioned separated foam rate is less than about 80%, can not guarantee the thermal insulation of constant level.The upper limit of separated foam rate does not limit, but, when separated foam rate is too high, the situation that air permeability declines, elasticity reduces, degradation physical property reduces under weather resistance of Thermocurable foam may be there is, therefore, it is possible to will about 95% as the upper limit.
The density of above-mentioned Thermocurable foam is about 10kg/m
3to about 150kg/m
3, can be about 20kg/m particularly
3to about 100kg/m
3.The density of above-mentioned Thermocurable foam maintains above-mentioned scope, thus can provide Thermocurable foam light comparatively speaking.
The preparation method of Thermocurable foam
An example more of the present invention provides the preparation method of Thermocurable foam, the preparation method of above-mentioned Thermocurable foam comprises: the step of polyol blend compounds and nucleator, the step of fire retardant is added in the mixture of above-mentioned multicomponent alcoholics compound and nucleator, and stir isocyanate ester compound, to the step that poly-isocyanurate is polymerized in the mixture obtained after adding above-mentioned fire retardant; It is more than 310 DEG C according to the beginning temperature of thermogravimetry.Thermolysis starts temperature can be more than about 310 DEG C, and it is as aforementioned.
In the step of above-mentioned polyol blend compounds and nucleator, the speed of polyol blend compounds and nucleator can be about 500rpm to about 5000rpm.In order to the mixing initial stage that is dispersed in of multicomponent alcoholics compound, nucleator was with the low speed mixing of about about 500rpm about 30 seconds to about 60 seconds, and gather way gradually, the mixing later stage can be increased to the mixing velocity of about 5000rpm.On the contrary, when the initial stage mixes by too low speed, the viscosity of multicomponent alcoholics compound is high, and the viscosity of nucleator is low, and therefore the problem that nucleator disperses insufficient may occur.
Further, the step of polyol blend compounds and nucleator can be carried out at the temperature of about 0 DEG C to about 30 DEG C.Carry out temperature when being less than about 0 DEG C, the dispersion between multicomponent alcoholics compound and nucleator is insufficient, and on the contrary, carry out temperature when being greater than about 30 DEG C, the volatilization point because of nucleator is low and nucleator may evaporate.
The stirring velocity adding the step of fire retardant in the mixture of above-mentioned multicomponent alcoholics compound and nucleator can be about 500rpm to about 5000rpm.It is the speed that can mix fire retardant equably and set, and when exceeding this scope, each species distribution obtains uneven, thus the physical property of polyisocyanurate foam may reduce.
Further, the step adding fire retardant in the mixture of above-mentioned multicomponent alcoholics compound and nucleator can perform at the temperature of about 0 DEG C to about 40 DEG C.The characteristic of flame retardant resistance can be changed when exceeding this scope.Particularly, when adding fire retardant after adding tensio-active agent, in the multicomponent alcoholics compound of surface tension reduction and the mixture of nucleator, fire retardant can more effectively be admixed.
Stirring isocyanate ester compound in the mixture obtained after adding above-mentioned fire retardant, can be about 3000rpm to about 5000rpm to the stirring velocity of the step that poly-isocyanurate is polymerized.It to react and the speed set by the trimerizing carried out within the time faster fully between the reaction of multicomponent alcoholics compound and isocyanate ester compound and isocyanic ester.Occur when being stirred by the speed being less than about 3000rpm multicomponent alcoholics compound and isocyanate compound reaction can not smooth and easy degree of carrying out fully by the problem admixed, on the contrary, when being greater than about 5000rpm, the duration of contact of multicomponent alcoholics compound and isocyanate compound is short, and therefore reaction may be carried out insufficient.
Further, stir isocyanate ester compound in the mixture obtained after adding above-mentioned fire retardant, the step that poly-isocyanurate is polymerized can be performed in the temperature range of about 0 DEG C to about 20 DEG C.If, when execution temperature is less than 0 DEG C of temperature, polyreaction between multicomponent alcoholics compound and isocyanate ester compound and the reaction of the trimerizing between isocyanic ester are not easy to carry out, on the contrary, when execution temperature is greater than 20 DEG C of temperature, can induce too fast reaction, thus the stabilization of generating unit is hindered or the problem of reactive material volatilization.
Below, specific embodiments of the invention are provided.But the embodiment below recorded is just as illustrating particularly or the present invention being described, the present invention is not limited to this.
< embodiment and comparative example >
embodiment 1
Tetramethylsilane (the TMS as nucleator is added in the polyvalent alcohol of 100g weight, Tetramethyl silane) 3.0g, cumyl diphenyl phosphoester (IPPP, IsoPropylPhenyl DiphenylPhosphate) 1.0g as fire retardant.Use using the mixture of the weight ratio admixtured polyether polyvalent alcohol (polyether polyol) of 4:6 and polyester polyol (polyester polyol) as above-mentioned polyvalent alcohol.Relative to the tetramethylsilane as nucleator, the viscosity of the polyvalent alcohol used is high, therefore, insert well between polyol compound to enable tetramethylsilane, utilize mechanical stirring device (mechanical stirrer), initial reaction stage is with the stirring at low speed 30 seconds (first step stirring) of 500rpm, subsequently, stir (second step stirring) respectively with the speed of 1000rpm, 2000rpm, 3000rpm, 4000rpm, 5000rpm respectively and prepare mixed solution in 30 seconds.
Add cumyl diphenyl phosphoester (IPPP, the IsoPropylPhenylDiphenyl Phosphate) 1.0g as fire retardant in above-mentioned mixed solution, at 20 DEG C, stir 10 seconds to prepare polyisocyanurate foam with the speed of 3000rpm.Further, in order to above-mentioned polyol compound and vulcabond reaction and utilize mechanical stirring device, after stirring 20 seconds with 5000rpm speed, prepare Thermocurable foam in a mold.
embodiment 2
Except being increased to beyond 3.0g using the addition of the cumyl diphenyl phosphoester (IPPP, IsoPropylPhenyl DiphenylPhosphate) as fire retardant, prepare thermofixation foam with the method same with above-described embodiment 1.
embodiment 3
Except being increased to beyond 5.0g using the addition of the cumyl diphenyl phosphoester (IPPP, IsoPropylPhenyl DiphenylPhosphate) as fire retardant, prepare thermofixation foam with the method same with above-described embodiment 1.
embodiment 4
Except using phosphate toluene diphenyl ester (CDP, Cresyl Diphenyl Phosphate) replace cumyl diphenyl phosphoester (IPPP, IsoPropylPhenyl Diphenyl Phosphate) use as fire retardant, and addition is beyond 1.0g, prepares thermofixation foam with the method same with above-described embodiment 1.
embodiment 5
Except being increased to beyond 3.0g using the addition of the phosphate toluene diphenyl ester (CDP, Cresyl Diphenyl Phosphate) as fire retardant, prepare thermofixation foam with method similarly to Example 4.
embodiment 6
Except being increased to beyond 5.0g using the addition of the phosphate toluene diphenyl ester (CDP, Cresyl Diphenyl Phosphate) as fire retardant, prepare thermofixation foam with method similarly to Example 4.
comparative example 1
In order to the moisture that the inside removing the organic clay (30B clay, Southern Clay product (southern Clay Co.)) comprising hydroxyl comprises, drying 24 hours in vacuum drying oven.Poly-4 of 160g are added in the polyvalent alcohol of the 100g then used in embodiment 1,4-'-diphenylmethane diisocyanate (M50, BASF AG) and the above-mentioned organic clay (30Bclay) of 3.0g, and in the thermostatic oil bath of the temperature of reaction of maintenance 60 DEG C heavy soup reacting.In order to mix above-mentioned M50 and 30Bclay equably, reaction can carry out utilizing mechanical stirring device (mechanical stirrer) to stir 2 hours to prepare mixed solution with the speed of 3000rpm smoothly.
Add catalyzer and tensio-active agent in above-mentioned mixed solution, and carry out reaction at normal temperatures to prepare clay-poly-isocyanurate nano complex.Comprise poly-4 of above-mentioned organic clay, 4 '-'-diphenylmethane diisocyanate utilizes mechanical stirring device to carry out reacting, and stirs 10 seconds, and prepare Thermocurable foam in a mold with the speed of 5000rpm.
comparative example 2
Except not adding the nucleator as tetramethylsilane, and the cumyl diphenyl phosphoester (IPPP added as fire retardant, IsoPropylPhenyl Diphenyl Phosphate) beyond 5.0g, prepare Thermocurable foam with the method same with above-described embodiment 1.
comparative example 3
Except not adding as the nucleator of tetramethylsilane and as cumyl diphenyl phosphoester (IPPP, IsoPropylPhenyl Diphenyl Phosphate) fire retardant beyond, prepare Thermocurable foam with the method same with above-described embodiment 1.
Table 1
| Nucleator | Fire retardant | Fire retardant form | |
| Embodiment 1 | Tetramethylsilane 3.0g | Cumyl diphenyl phosphoester 1.0g | Liquid phase |
| Embodiment 2 | Tetramethylsilane 3.0g | Cumyl diphenyl phosphoester 3.0g | Liquid phase |
| Embodiment 3 | Tetramethylsilane 3.0g | Cumyl diphenyl phosphoester 5.0g | Liquid phase |
| Embodiment 4 | Tetramethylsilane 3.0g | Phosphate toluene diphenyl ester 1.0g | Liquid phase |
| Embodiment 5 | Tetramethylsilane 3.0g | Phosphate toluene diphenyl ester 3.0g | Liquid phase |
| Embodiment 6 | Tetramethylsilane 3.0g | Phosphate toluene diphenyl ester 5.0g | Liquid phase |
| Comparative example 1 | Organic clay 3.0g | - | - |
| Comparative example 2 | - | Cumyl diphenyl phosphoester 1.0g | Liquid phase |
| Comparative example 3 | - | - | - |
The physical property of < experimental example >-Thermocurable foam
Measure the thermal conductivity of above-described embodiment and comparative example, compressive strength, flexural strength and thermolysis and start temperature, first, in order to compare the heat-proof quality of the Thermocurable foam prepared according to above-described embodiment and comparative example, after measuring thermal conductivity according to ASTM C518, measure compressive strength according to ASTM D1621.
Further, measure flexural strength according to ASTM D790, thermolysis when measuring the changes in weight of Thermocurable foam by thermogravimetry starts temperature.
Table 2
Can determine that thermal conductivity is low according to the thermofixation foam of embodiment 1 to embodiment 6 compared with the thermofixation foam of comparative example 1 to comparative example 3 by above-mentioned experimental example.This be thermofixation foam be used as lagging material when, the physical property relevant with the heat-proof quality of most important physical property, it can thus be appreciated that silane compound be used as nucleator when, the heat-proof quality of lagging material is improved.When comparative example 1, although organic clay mixes as nucleator, the reductions such as stability in storage, finally represent heat-proof quality also disadvantageous result.
From the measurement result of compressive strength and flexural strength, embodiment is compared with comparative example, favourable substantially, and compressive strength and flexural strength play the auxiliary function of Thermocurable foam, embodiment is all expressed as follows result thus, can present the physical property being fully used as lagging material.
And, when embodiment 1 to embodiment 6, comprise nucleator and fire retardant simultaneously, thus show outstanding heat-proof quality and flame retardant properties, thermolysis is started at temperature more than about 310 DEG C, but in contrast, when comparative example 1, do not comprise fire retardant, and start thermolysis being less than at the temperature of about 310 DEG C.Although comprise fire retardant when comparative example 2, do not comprise nucleator, it is higher that thermolysis starts temperature, but measuring thermal conductivity is 0.029W/mK, confirms heat-proof quality thus and decline.All nucleator and fire retardant is not comprised, it can thus be appreciated that heat-proof quality and flame retardant properties all significantly reduce when comparative example 3.
Further, the average particle diameter being formed in the foamed cell of polyisocyanurate foam is determined as about 50 μm to about 200 μm in the case of the embodiment, by contrast, the average particle diameter of the foamed cell of comparative example is all determined as more than about 200 μm, when fire retardant and nucleator do not comprise, can determine to be difficult to form not only even but also little foamed cell.
Result can be known, the Thermocurable foam of one embodiment of the invention comprises fire retardant in polyisocyanurate foam, thus guarantee flame retardant resistance, meanwhile, also comprise nucleator, thus the surface tension of Thermocurable foam can be suppressed maintain the constant size of the foamed cell be formed in polyisocyanurate foam and can thermal conductivity be guaranteed.
Claims (15)
1. a Thermocurable foam, it is characterized in that, comprise polyisocyanurate foam that multicomponent alcoholics compound and isocyanate ester compound polymerization formed, nucleator and fire retardant, and to start temperature according to the thermolysis of thermogravimetry be more than 310 DEG C.
2. Thermocurable foam according to claim 1, is characterized in that, described fire retardant is liquid phase form or powder morphology.
3. Thermocurable foam according to claim 1, is characterized in that, described fire retardant is be selected from least one in the group that is made up of phosphorus type flame retardant, metal hydride based flame retardant, halogen fire retardant, flame retardant and their mixture.
4. Thermocurable foam according to claim 3, is characterized in that, described phosphorus type flame retardant is be selected from least one in the group that is made up of triphenylphosphate, phosphate toluene diphenyl ester, p isopropylbenzoic acid base benzene diphenyl ester and their mixture.
5. Thermocurable foam according to claim 3, is characterized in that, described halogen fire retardant is decabromodiphynly oxide or octabromodiphenyl base oxide.
6. Thermocurable foam according to claim 3, is characterized in that, described flame retardant is ANTIMONY TRIOXIDE SB 203 99.8 PCT.
7. Thermocurable foam according to claim 1, is characterized in that, described nucleator comprises silane compound or siloxane compound.
8. Thermocurable foam according to claim 1, is characterized in that, the mean diameter being formed in the foamed cell of described polyisocyanurate foam is 50 μm to 200 μm.
9. Thermocurable foam according to claim 1, is characterized in that, relative to the described multicomponent alcoholics compound of 100 weight parts, the content of described fire retardant is 1 weight part to 20 weight part.
10. Thermocurable foam according to claim 1, is characterized in that, relative to the described multicomponent alcoholics compound of 100 weight parts, the content of described nucleator is 1 weight part to 10 weight part.
11. Thermocurable foaies according to claim 1, is characterized in that, also comprise polymerizing catalyst, tensio-active agent and whipping agent in described Thermocurable foam.
12. Thermocurable foaies according to claim 1, is characterized in that, the thermal conductivity of described Thermocurable foam is below 0.025W/mk.
13. Thermocurable foaies according to claim 1, is characterized in that, the separated foam rate of described Thermocurable foam is more than 80%.
14. Thermocurable foaies according to claim 1, is characterized in that, the density of described Thermocurable foam is 10kg/m
3to 150kg/m
3.
The preparation method of 15. 1 kinds of Thermocurable foaies, is characterized in that, comprising:
The step of polyol blend compounds and nucleator,
The step of fire retardant is added in the mixture of described multicomponent alcoholics compound and nucleator, and
Isocyanate ester compound is stirred, to the step that poly-isocyanurate is polymerized in the mixture obtained after adding described fire retardant;
Be more than 310 DEG C of temperature according to the beginning temperature of thermogravimetry.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2012-0089610 | 2012-08-16 | ||
| KR1020120089610A KR20140023581A (en) | 2012-08-16 | 2012-08-16 | Thermosetting foaming body with superior adiabatic and flameproof effect and method for manufacturing the same |
| PCT/KR2012/011229 WO2014027726A1 (en) | 2012-08-16 | 2012-12-21 | Thermosetting foam with improved thermal insulation and flame retardancy, and preparation method therefor |
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| Publication Number | Publication Date |
|---|---|
| CN104540885A true CN104540885A (en) | 2015-04-22 |
| CN104540885B CN104540885B (en) | 2017-10-24 |
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| CN201280075251.5A Expired - Fee Related CN104540885B (en) | 2012-08-16 | 2012-12-21 | Thermocurable foaming body that thermal insulation and anti-flammability are improved and preparation method thereof |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20140023581A (en) |
| CN (1) | CN104540885B (en) |
| WO (1) | WO2014027726A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108137845A (en) * | 2015-10-20 | 2018-06-08 | 巴斯夫欧洲公司 | For producing cast-in-place foamed system and method |
| CN113490705A (en) * | 2018-12-07 | 2021-10-08 | 乐金华奥斯有限公司 | Thermosetting foam, method for producing same, and heat insulating material comprising same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020117029A1 (en) * | 2018-12-07 | 2020-06-11 | (주)엘지하우시스 | Thermosetting foam, manufacturing method therefor, and insulator comprising same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041371A (en) * | 1988-09-22 | 1990-04-18 | 石油部施工技术研究所 | The constituent of heat resist modification poly-isocyanurate |
| WO2010150955A1 (en) * | 2009-06-23 | 2010-12-29 | Korea University Industrial & Academic Collaboration Foundation | Method for preparing polyisocyanurate foam by using liquid nucleating agent and polyisocyanurate foam prepared by the same |
| US20110064938A1 (en) * | 2003-11-26 | 2011-03-17 | Breindel Raymond M | Thermoplastic foams and method of forming them using nano-graphite |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3567092A1 (en) * | 2005-11-01 | 2019-11-13 | The Chemours Company FC, LLC | Solvent compositions comprising unsaturated fluorinated hydrocarbons |
| KR20100119709A (en) * | 2009-10-13 | 2010-11-10 | 최정헌 | Polyurethane form and manufacturing method thereof |
-
2012
- 2012-08-16 KR KR1020120089610A patent/KR20140023581A/en active Application Filing
- 2012-12-21 CN CN201280075251.5A patent/CN104540885B/en not_active Expired - Fee Related
- 2012-12-21 WO PCT/KR2012/011229 patent/WO2014027726A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041371A (en) * | 1988-09-22 | 1990-04-18 | 石油部施工技术研究所 | The constituent of heat resist modification poly-isocyanurate |
| US20110064938A1 (en) * | 2003-11-26 | 2011-03-17 | Breindel Raymond M | Thermoplastic foams and method of forming them using nano-graphite |
| WO2010150955A1 (en) * | 2009-06-23 | 2010-12-29 | Korea University Industrial & Academic Collaboration Foundation | Method for preparing polyisocyanurate foam by using liquid nucleating agent and polyisocyanurate foam prepared by the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108137845A (en) * | 2015-10-20 | 2018-06-08 | 巴斯夫欧洲公司 | For producing cast-in-place foamed system and method |
| CN108137845B (en) * | 2015-10-20 | 2021-08-17 | 巴斯夫欧洲公司 | System and method for producing cast-in-place foam |
| CN113490705A (en) * | 2018-12-07 | 2021-10-08 | 乐金华奥斯有限公司 | Thermosetting foam, method for producing same, and heat insulating material comprising same |
| CN113490705B (en) * | 2018-12-07 | 2023-03-03 | 乐金华奥斯有限公司 | Thermosetting foam, method for producing same, and heat insulating material comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104540885B (en) | 2017-10-24 |
| WO2014027726A1 (en) | 2014-02-20 |
| KR20140023581A (en) | 2014-02-27 |
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