CN102675851A - Liquid expanded graphite flame retardant and preparation method for flame-retardant polyurethane foam material - Google Patents
Liquid expanded graphite flame retardant and preparation method for flame-retardant polyurethane foam material Download PDFInfo
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- CN102675851A CN102675851A CN201210173694XA CN201210173694A CN102675851A CN 102675851 A CN102675851 A CN 102675851A CN 201210173694X A CN201210173694X A CN 201210173694XA CN 201210173694 A CN201210173694 A CN 201210173694A CN 102675851 A CN102675851 A CN 102675851A
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Abstract
The invention discloses an expanded-graphite-based liquid flame retardant. The expanded-graphite-based liquid flame retardant comprises 100 parts of expansible graphite and 100 to 900 parts of diluent, wherein the diluent is at least one of a phosphate modifier and polyol. The invention also discloses a method for preparing a flame-retardant polyurethane foam material from the expanded-graphite-based liquid flame retardant. The method comprises the following steps of: (a) adding the expanded-graphite-based liquid flame retardant into polyisocyanate, adding a polymerization catalyst and a foaming agent, mixing uniformly, and optionally adding the polyol; and (b) molding to obtain the polyurethane foam material. The expanded-graphite-based flame retardant is a liquid product and is convenient to process and measure, and common phenomena such as viscosity increase, demixing and precipitation when solid expansible graphite is directly mixed into a polyol component are avoided; meanwhile, the flame retardant is favorable for environment friendliness because halogen groups are not contained; and the polyurethane product prepared from the flame retardant has a wide density range and a wide application range.
Description
Technical field
The present invention relates to a kind of liquid combustion inhibitor, especially a kind of expanded graphite fire retardant of liquid state also relates to the preparation method of the polyurethane foamed material that contains this fire retardant and the urethane that makes with this fire retardant.
Background technology
Polyurethane foam is to be raw material with polyol and isocyanic ester, the foam materials that under the effect of for example catalyzer, whipping agent, forms through addition polymerization, foaming.This material has excellent physical and mechanical properties, electric property, acoustical behavior and chemical resistance.Because its thermal conductivity is low, density is little, intensity is high, water-absorbent is little, adiabatic, insulation, sound insulation, chemicalstability is good, the back response rate that is hit is high, so is widely used in fields such as oil, chemical industry, transportation, building.
Polyurethane foam without fire-retardant finish is a kind of inflammable substance.For example density is 0.25g/cm
3About the incendivity and the cotton of polyurethane foam close, run into burning things which may cause a fire disaster or high bake very easily burns.Therefore need to adopt the whole bag of tricks to improve Flame Retardancy of Polyurethane Foam property.Many countries have made laws and have formulated the flame-retardant standard of material of construction.In order to satisfy requirement, many methods have been developed at present to the polyurethane foam flame retardant resistance.
Chinese patent CN1330678A discloses a kind of generation method of hard polyurethane foams, it comprise make POLYMETHYLENE POLYPHENYLISOCYANATE, polyvalent alcohol and active halogenated compound whipping agent, catalyzer, expanded graphite and be selected from phosphonic acid ester, SULPHOSUCCINIC ACID ESTER, halogenated phosphate or its combination additional fire retardant in the presence of the reaction.This kind Flame Retardancy of Polyurethane Foam property is by expanded graphite, active halogenated compound and collaborative the providing of additional fire retardant that be selected from phosphonic acid ester, SULPHOSUCCINIC ACID ESTER, halogenated phosphate or its combination.Though the polyurethane foam that makes with this method has excellent flame-retardant performance; And the halogenated compound fire retardant can be well miscible with raw material such as polyvalent alcohol, but owing to use halide-containing, when polyurethane foam combustion; This based flame retardant can decompose, and produces a large amount of smog and corrosion irritant gas.Contain a large amount of halogenic molecules (chlorine, bromine etc.) in the corrosion irritant gas, they can be elegant to atmospheric layer stratosphere (stratosphere), destroys the ozonosphere in the stratosphere, has a strong impact on the earth surface weather.Therefore, the application of halogen-containing fire retardant receives very big restriction, even bans use of in some countries and regions, and halogen-free flame retardants more and more receives publicity.
In order to overcome above-mentioned defective, Chinese patent CN1724577A discloses a kind of preparation method of polyurethane foam, and it uses expansible black lead as fire retardant.This preparation method comprises adding catalyzer and whipping agent in polyether glycol, adds expansible black lead behind the uniform mixing; Add isocyanic ester afterwards, molded after stirring.Though this method can obtain having the polyurethane foam of good flame-retardance ability, its shortcoming is:
(1) it uses the solid expansible black lead as fire retardant, when it is sneaked into polyol component, can cause the viscosity of mixture sharply to rise, and produces layering, deposited phenomenon;
(2) employed solid expansible black lead is a powder, is unfavorable for accurate measurement and conveying in the mass automatic production process.
Summary of the invention
First purpose of the present invention provides a kind of liquid combustion inhibitor that is used for polyurethane material, can not cause rapid rising of viscosity or layering, deposited phenomenon in the time of in sneaking into polyvalent alcohol, and is adapted at accurate measurement and conveying in the mass automatic production process.
Second purpose of the present invention provides and adopts polyurethane foamed material that above-mentioned fire retardant makes and preparation method thereof.
Technical scheme of the present invention is following:
A kind of based on the expanded graphite liquid combustion inhibitor, comprise following component in weight part:
100 parts of expansible black leads;
100-900 part thinner.
Preferably, preferred 100-400 part of said thinner.
Preferably, said thinner is selected from phosphate modified dose of at least a with polyvalent alcohol.
Preferably, said polyvalent alcohol is selected from least a in polyether glycol and the polyester polyol.
Preferably, to be selected from at least a and quadrol in Ucar 35, terepthaloyl moietie, USP Kosher, TriMethylolPropane(TMP), tetramethylolmethane, sucrose, the sorbyl alcohol and tolylene diamine at least a be that the functionality that initiator forms is that 2-6, hydroxyl value are the polyether polyol of 18-800 to said polyether glycol;
Said polyester polyol is selected from least a and terepthaloyl moietie, Ucar 35, USP Kosher, the TriMethylolPropane(TMP), 1 that backbone structure adopts hexanodioic acid and Tetra hydro Phthalic anhydride; The functionality that at least a polycondensation of 4-butyleneglycol, 1,6 pinakon, pentanediol forms is that 2-4, hydroxyl value are the polyester polyol of 50-500.
Preferably, said phosphate modified dose is selected from least a of inferior ester, three (DPG) phosphorous acid ester of di(2-ethylhexyl)phosphate benzene toluene ester, three (polyoxygenated alkene) SULPHOSUCCINIC ACID ESTER, three (polyoxygenated alkene) phosphoric acid, methyl-phosphoric acid dimethyl ester, propyl group dimethyl phosphate, ethyl phosphonic acid diethyl ester, triethyl phosphate or Tritolyl Phosphate.
Preferably, the auxiliary agent that also comprises 0.5-60 part.
Preferably, said auxiliary agent is selected from high-molecular weight polymer type wetting agent, liquid auxiliary rheological agents, controlled flocculation type auxiliary agent, wax dispersion, at least a than the alkylammonium salt of small molecular weight polymer type dispersion agent and HMW interpolymer; The preferred 0.8-2.5 part of said auxiliary agent.
It is above-mentioned based on the application of expanded graphite liquid combustion inhibitor in fire retardant material that the present invention also provides.
A kind of use above-mentionedly prepares the method for resistance combustion polyurethane foam material based on the expanded graphite liquid combustion inhibitor, comprises the steps:
(a) will comprise and mixing with POLYMETHYLENE POLYPHENYLISOCYANATE of polyvalent alcohol form mixture based on the expanded graphite liquid combustion inhibitor; In expansible black lead 100 weight parts; The add-on of POLYMETHYLENE POLYPHENYLISOCYANATE is the 500-1500 weight part, and simultaneously to wherein add polymerizing catalyst, whipping agent mixes;
(b) molded, obtain polyurethane foamed material.
Preferably, in the said step (a), also can in said mixture, add polyvalent alcohol.
Preferably, the weight ratio of polyvalent alcohol and expansible black lead is preferably 135-300 in said step (a) mixture: 100.
A kind of use above-mentionedly prepares the method for resistance combustion polyurethane foam material based on the expanded graphite liquid combustion inhibitor, comprises the steps:
(a) will not comprise and mixing of polyvalent alcohol form mixture based on expanded graphite liquid combustion inhibitor, POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol; In expansible black lead 100 weight parts; The add-on of POLYMETHYLENE POLYPHENYLISOCYANATE is the 500-1500 weight part; The add-on of polyvalent alcohol is the 100-900 weight part, and simultaneously to wherein add polymerizing catalyst, whipping agent mixes;
(b) molded, obtain polyurethane foamed material.
Preferably, the preferred 500-700 of the add-on of said POLYMETHYLENE POLYPHENYLISOCYANATE, the preferred 300-500 of the add-on of said polyvalent alcohol.
Preferably, also comprise the adding additive in the said step (a), said additive is selected from least a of UV light stabilizing agent and fire retardant.
Compared with prior art, beneficial effect of the present invention is following:
1. fire retardant of the present invention is a liquid prod; Thereby phenomenons such as common viscosity rising when having avoided that effectively solid expandable graphite sneaked into polyol component, layering, deposition; Liquid combustion inhibitor mixes and is more stable simultaneously; Therefore it is convenient to processing, metering and carries, and is fit to extensive automatic continuous production;
2. fire retardant of the present invention is not with halogen group; The synergistic effect of only utilizing thinner and expansible black lead to produce, thus the ion that diminishes ozonosphere do not produced, zero odp value (Ozone Depletion potential after the burning; Consume the ozone latent energy value), help environmental protection;
3. the density range of the polyurethane products that make with fire retardant of the present invention is wide, can (density range is 0.2-1.2g/cm from the foam to the solid
3), thereby can be widely used as block rigid polyurethane foam, metal and nonmetal plane materiel hard polyurethane foam board material, reaction injection moulding material, coated with hard polyurethane foam material.
Embodiment
The main ingredient of fire retardant of the present invention is an expansible black lead.In the present invention, term " expansible black lead " is meant that expansion multiplying power is that the expandable layer of 100-400 is from graphite; Said expansible black lead forms liquid form mixt after SULPHOSUCCINIC ACID ESTER and/or polyethers or polyester polyol modification.Compare with solid graphite, liquid form mixt is accurate measurement and conveying more easily, thereby is fit to mass automatic production.
In liquid combustion inhibitor of the present invention, phosphate modified dose addition does not have special restriction, as long as it can carry out modification to expansible black lead, makes it to become liquid combustion inhibitor and gets final product.In better instance of the present invention, by said expansible black lead 100 weight parts, phosphate modified dose add-on is the 40-100 weight part.
Liquid combustion inhibitor of the present invention also can randomly comprise polyethers or polyester polyol.The polyvalent alcohol that said polyethers or polyester polyol can be adopted when being used for synthesis of polyurethane is identical or different.Be preferably, the polyvalent alcohol that said polyethers or polyester polyol adopt during with synthesis of polyurethane is identical.
The non-limiting example of the polyvalent alcohol that is suitable for has; Polyether glycol is that the functionality that initiator forms is that 2-6, hydroxyl value are the polyether polyol of 18-800 with Ucar 35, terepthaloyl moietie, USP Kosher, TriMethylolPropane(TMP), tetramethylolmethane, sucrose, sorbyl alcohol, quadrol and/or tolylene diamine for example; Polyester polyol; For example backbone structure is a hexanodioic acid or/and Tetra hydro Phthalic anhydride and terepthaloyl moietie, Ucar 35, USP Kosher, TriMethylolPropane(TMP), 1; The functionality that 4-butyleneglycol, 1,6 pinakon or pentanediol polycondensation form is that 2-4, hydroxyl value are the polyester polyol of 50-500.
The purpose that in liquid combustion inhibitor of the present invention, adds polyether glycol or polyester polyol is to reduce the viscosity of said liquid combustion inhibitor.Therefore, the add-on of said polyvalent alcohol depends on the viscosity of required liquid combustion inhibitor.Those of ordinary skill in the art is reading the required fire retardant viscosity of content combination disclosed by the invention, can easily confirm the add-on of said polyvalent alcohol.
Also alternative adds auxiliary agents such as wetting agent in liquid combustion inhibitor of the present invention, and the purpose that adds auxiliary agent is to make whole system be homogeneous phase, no demixing phenomenon in a long time.The add-on of auxiliary agent does not have special restriction, as long as can reach SULPHOSUCCINIC ACID ESTER/polyethers or polyester polyol modification expansible black lead fire retardant does not have demixing phenomenon.In the present invention, the effect of said auxiliary agent is:
The viscosity of-adjustment system;
-under constant viscosity, can allow higher expanded graphite capacity value;
-improve the expanded graphite wettability and shorten jitter time;
-prevent the expanded graphite reflocculation;
-improve the tinting strength of expanded graphite.
Liquid combustion inhibitor of the present invention can use conventional method to make.In a better instance of the present invention, said method of manufacture comprises with the expansible black lead of order adding arbitrarily, SULPHOSUCCINIC ACID ESTER, polyvalent alcohol and wetting agent, mixing then.
The invention still further relates to a kind of method of manufacture of polyurethane foamed material.This method of manufacture comprises the step with liquid combustion inhibitor of the present invention and POLYMETHYLENE POLYPHENYLISOCYANATE, polymerizing catalyst, whipping agent hybrid reaction, or with liquid combustion inhibitor of the present invention as the 3rd component in proportion with polyvalent alcohol and isocyanic ester, polymerizing catalyst, whipping agent hybrid reaction.Said POLYMETHYLENE POLYPHENYLISOCYANATE can be the conventional POLYMETHYLENE POLYPHENYLISOCYANATE that this area is used to make urethane.In an instance of the present invention; The non-limiting example of said POLYMETHYLENE POLYPHENYLISOCYANATE has 4; 4 '-'-diphenylmethane diisocyanate or the diphenylmethanediisocyanate modified product, 2 of being correlated with; 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, poly methylene poly phenyl poly isocyanate or its relevant modified product.In a better instance of the present invention, the NCO% content of said POLYMETHYLENE POLYPHENYLISOCYANATE is 18.0-36.0%.Those of ordinary skill in the art is according to concrete purposes and combine its expertise to be not difficult to confirm the kind of concrete polymerizing catalyst, whipping agent etc. and the add-on in reaction mixture thereof.
Different with the method for using solid expandable graphite, the amount of the liquid combustion inhibitor that the present invention adds in polyvalent alcohol and/or POLYMETHYLENE POLYPHENYLISOCYANATE depends on concrete purposes requirement, and can not produce too high viscosity rising, layering or the sedimentary problem of causing of flame retardant agent content.The polyvalent alcohol that is fit to manufacturing urethane of the present invention does not have special restriction, and it can be the conventional polyvalent alcohol that is used to make urethane.
Also can in said reaction mixture, add other additive, for example other fire retardants, UV light stabilizing agent etc.Those of ordinary skill in the art is according to concrete purposes and combine its expertise to be not difficult to confirm concrete UV light stabilizing agent, the kind of other fire retardants etc. and the add-on in reaction mixture thereof.
In a better instance of the present invention, the indefiniteness example of said polymerizing catalyst has 1,4-diazonium (2,2, the 2-cyclooctane) (triethyl diamines DABCO), N; N, N ', N ', N "-pentamethyl--diethyl triamine (PMDETA), N; N-dimethylcyclohexylamine (DMCHA), N, N-dimethyl benzylamine, N, N '-Tetramethyl Ethylene Diamine (TMEDA); dimethyl amido propyl group amine (DMAPA) AminZ, N, N-dimethylethanolamine (DMEA), 2,4; 6-three (dimethyl amine ylmethyl) phenol, N-ethylmorpholine (NEM), two N, N '-dimethyl amine benzyl ethyl ether, dibutyl tin dilaurate (DBTDL) etc.;
In a better instance of the present invention, the non-limiting example of said other composite flame-retardant agents has melamine cyanurate, trimeric cyanamide, and ammonium polyphosphate, tetrabromo phenol A, IXOL 251, the dried glycol of tetrabromo-benzene etc.;
The indefiniteness example of said whipping agent water, hydrocarbon polymer (for example Skellysolve A, pentamethylene), hydrogenation fluorocarbon (for example R-245fa, R-134a, R-365, hydrogenation freonll-11, R-141b) are arranged or between them with the mixture of arbitrary proportion.
Below in conjunction with specific embodiment, further set forth the present invention.Should be appreciated that these embodiment only are used to explain the present invention, and are not used in qualification protection scope of the present invention.Improvement that the technician makes according to the present invention in practical application and adjustment still belong to protection scope of the present invention.
Embodiment 1
Present embodiment comprises based on the expanded graphite liquid combustion inhibitor makes 3 of 3 of examples and application examples, and wherein application examples be based on liquid graphite resistance combustion polyurethane foam made example, comprises that in addition 1 resistance combustion polyurethane foam material contrast makes routine.The preparation of common said liquid combustion inhibitor and polyurethane foam is carried out at normal temperatures, but the present invention is also included within and is higher than under the normal temperature state preparation said product.
Make example 1 based on the expanded graphite liquid combustion inhibitor
In a three-necked flask that has an electric mixer, add 20 gram polyether glycol Arcol 3601; 10 gram polyether glycol Arcol 1011; 0.4 gram auxiliary agent (alkylammonium salt of HMW interpolymer)
9076; 20 gram methyl-phosphoric acid dimethyl esters and 50 gram leafing expansible black leads 100.Under the normal temperature said mixing of materials is obtained based on expanded graphite liquid combustion inhibitor FR1 after evenly.
Make example 2 based on the expanded graphite liquid combustion inhibitor
In a three-necked flask that has an electric mixer, add 20 gram polyether glycol VORANOL 360; 10 gram polyether glycol Arcol 1011; 1.0 gram auxiliary agent (alkylammonium salt of HMW interpolymer)
9077; 30 gram methyl-phosphoric acid dimethyl esters and 40 gram leafing expansible black leads 300.Under the normal temperature said mixing of materials is obtained based on expanded graphite liquid combustion inhibitor FR 2 after evenly.
Make example 3 based on the expanded graphite liquid combustion inhibitor
In a three-necked flask that has an electric mixer, add 20 gram polyether glycol Desmophen 4034; 10 gram polyether glycol DC210; 10 gram modified castor oils and 0.4 gram auxiliary agent (alkylammonium salt of HMW interpolymer)
9076; 20 gram methyl-phosphoric acid dimethyl esters and 50 gram leafing expansible black leads 300.Under the normal temperature said mixing of materials is obtained based on expanded graphite liquid combustion inhibitor FR 3 after evenly.
3 preparing methods based on liquid graphite resistance combustion polyurethane foam made example 2,3,4 comprise: with said comprise polyvalent alcohol sneak into polyvalent alcohol based on the expanded graphite liquid combustion inhibitor; And add tensio-active agent (glycerine), water, polymerizing catalyst, other fire retardant and whipping agent simultaneously, mix in the said mixture adding POLYMETHYLENE POLYPHENYLISOCYANATE; The normal temperature lower mould obtains polyurethane foamed material then.The preparation method of 1 resistance combustion polyurethane foam material contrast manufacturing example 1 and the difference of above-mentioned method of manufacture are: add reactive flame retardant tetrabromo-bisphenol and additive flame retardant trimeric cyanamide, do not add based on the expanded graphite liquid combustion inhibitor.3 are seen the following form 1 based on 2,3,4 and 1 resistance combustion polyurethane foam material contrast manufacturings example 1 employed raw materials of liquid graphite resistance combustion polyurethane foam made example and performance thereof.
Table 1
Can find out by last table data; Used polyurethane foamed material relatively only to use its flame retardant properties of polyurethane foamed material of conventional flame retardant to be improved in the present embodiment based on the expanded graphite liquid combustion inhibitor; Reduced density simultaneously, thermal conductivity and compressive strength remain in the more stable scope.
Embodiment 2
Present embodiment comprises based on the expanded graphite liquid combustion inhibitor makes 4 of 4 of examples and application examples, and wherein application examples be routine based on liquid graphite resistance combustion polyurethane foam made.The preparation of common said liquid combustion inhibitor and polyurethane foamed material is carried out at normal temperatures, but the present invention is also included within and is higher than under the normal temperature state preparation said product.
Make example 4 based on the expanded graphite liquid combustion inhibitor
In a three-necked flask that has an electric mixer, add 27.9 gram polyester polyols (DESMOPHEN 3607), 10 gram leafing expansible black leads 300.Under the normal temperature said mixing of materials is obtained liquid combustion inhibitor FR 4 after evenly.
Make example 5 based on the expanded graphite liquid combustion inhibitor
In a three-necked flask that has an electric mixer, add 27.9 gram polyester polyols (DESMOPHEN 3607), 10 gram tricresyl phosphate (2-chloropropyl) esters and 10 gram leafing expansible black leads 300.Under the normal temperature said mixing of materials is obtained liquid combustion inhibitor FR 5 after evenly.
Make example 6 based on the expanded graphite liquid combustion inhibitor
In a three-necked flask that has an electric mixer, add 27.9 gram polyester polyols (DESMOPHEN 3607), 10 gram methyl-phosphoric acid dimethyl esters and 10 gram leafing expansible black leads 300.Under the normal temperature said mixing of materials is obtained liquid combustion inhibitor FR 6 after evenly.
Make example 7 based on the expanded graphite liquid combustion inhibitor
In a three-necked flask that has an electric mixer, add 27.9 gram polyester polyols (DESMOPHEN 3607), 10 gram tricresyl phosphate second fat and 10 gram leafing expansible black leads 300.Under the normal temperature said mixing of materials is obtained liquid combustion inhibitor FR7 after evenly.
4 preparing methods based on liquid graphite resistance combustion polyurethane foam manufacturing example 5,6,7,8 comprise: will saidly comprise polyvalent alcohol based in the expanded graphite liquid combustion inhibitor adding POLYMETHYLENE POLYPHENYLISOCYANATE; And adding tensio-active agent (glycerine), polymerizing catalyst, other fire retardant and whipping agent simultaneously, said mixture mixes; The normal temperature lower mould obtains polyurethane foamed material then.4 are seen the following form 2 based on liquid graphite resistance combustion polyurethane foam manufacturing example 5,6,7,8 employed raw materials and flame retardant properties thereof.
Table 2
Can be found out that by above-mentioned data the Flame Retardancy of Polyurethane Foam performance of having added based on the expanded graphite liquid combustion inhibitor has obtained significantly promoting, and obviously is superior to the Comparative Examples 1 among the embodiment 1, thermal conductivity and compressive strength remain in the more stable scope simultaneously.
Embodiment 3
Present embodiment comprises based on the expanded graphite liquid combustion inhibitor makes 4 of 4 of examples and application examples, and wherein application examples be routine based on liquid graphite resistance combustion polyurethane foam made.The preparation of common said liquid combustion inhibitor and polyurethane foamed material is carried out at normal temperatures, but the present invention is also included within and is higher than under the normal temperature state preparation said product.
Make example 8 based on the expanded graphite liquid combustion inhibitor
In a three-necked flask that has an electric mixer, add 30 gram polyester polyol DESMOPHEN 3607,10 gram tricresyl phosphate (2-chloropropyl) esters and 10 gram leafing expansible black leads 300.Under the normal temperature said mixing of materials is obtained liquid combustion inhibitor FR 8 after evenly.
Make example 9 based on the expanded graphite liquid combustion inhibitor
In a three-necked flask that has an electric mixer, add 30 gram polyester polyol DESMOPHEN 3607,9 gram tricresyl phosphate (2-chloropropyl) esters and 11 gram leafing expansible black leads 300.Under the normal temperature said mixing of materials is obtained liquid combustion inhibitor FR 9 after evenly.
Make example 10 based on the expanded graphite liquid combustion inhibitor
In a three-necked flask that has an electric mixer, add 30 gram polyester polyol DESMOPHEN 3607,8 gram tricresyl phosphate (2-chloropropyl) esters and 12 gram leafing expansible black leads 300.Under the normal temperature said mixing of materials is obtained liquid combustion inhibitor FR 10 after evenly.
Make example 11 based on the expanded graphite liquid combustion inhibitor
In a three-necked flask that has an electric mixer, add 30 gram polyester polyol DESMOPHEN 3607,7 gram tricresyl phosphate (2-chloropropyl) esters and 13 gram leafing expansible black leads 300.Under the normal temperature said mixing of materials is obtained liquid combustion inhibitor FR 11 after evenly.
4 preparing methods based on liquid graphite resistance combustion polyurethane foam manufacturing example 9,10,11,12 comprise: will saidly comprise polyvalent alcohol based in the expanded graphite liquid combustion inhibitor adding POLYMETHYLENE POLYPHENYLISOCYANATE; And adding tensio-active agent (glycerine), polymerizing catalyst, other fire retardant and whipping agent simultaneously, said mixture mixes; The normal temperature lower mould obtains polyurethane foamed material then.4 are seen the following form 3 based on liquid graphite resistance combustion polyurethane foam manufacturing example 9,10,11,12 employed raw materials and flame retardant properties thereof.
Table 3
Can find out that by above-mentioned data (density is 36kg/m with Comparative Examples 1 among the embodiment 1
3Compressive strength is 0.161MPa; Thermal conductivity is 0.0210W/m*K) contrast, the Flame Retardancy of Polyurethane Foam performance of having added in the present embodiment based on the expanded graphite liquid combustion inhibitor has obtained significantly promoting, and thermal conductivity remains in the more stable scope simultaneously; Reduce density, significantly improved compressive strength.
Embodiment 4
Present embodiment comprises based on the expanded graphite liquid combustion inhibitor makes 3 of 1 of example and application examples, wherein application examples be make based on liquid graphite resistance combustion polyurethane foam routine.The preparation of common said liquid combustion inhibitor and polyurethane foam is carried out at normal temperatures, but the present invention is also included within and is higher than under the normal temperature state preparation said product.
Make example 12 based on the expanded graphite liquid combustion inhibitor
In a three-necked flask that has an electric mixer, add 20 gram methyl-phosphoric acid dimethyl esters (DMMP), 10 gram leafing expansible black leads 300 and 1g auxiliary rheological agents
430.Under the normal temperature said mixing of materials is obtained liquid combustion inhibitor FR12 after evenly.
3 preparing methods based on liquid graphite resistance combustion polyurethane foam manufacturing example 13,14,15 comprise: will saidly not comprise polyvalent alcohol based in expanded graphite liquid combustion inhibitor adding polyvalent alcohol and the POLYMETHYLENE POLYPHENYLISOCYANATE; And adding tensio-active agent (glycerine), polymerizing catalyst, other fire retardant and whipping agent simultaneously, said mixture mixes; Add POLYMETHYLENE POLYPHENYLISOCYANATE then, stir, the normal temperature lower mould obtains polyurethane foamed material.3 flame retardant propertiess of making example 13,14,15 employed raw materials and made resistance combustion polyurethane foam material based on liquid graphite resistance combustion polyurethane foam see the following form 4.
Table 4
Can find out that by above-mentioned data (density is 36kg/m with Comparative Examples 1 among the embodiment 1
3Compressive strength is 0.161MPa, and thermal conductivity is 0.0210W/m*K) contrast, the Flame Retardancy of Polyurethane Foam performance of having added in the present embodiment based on the expanded graphite liquid combustion inhibitor has obtained significantly promoting; Reduced density simultaneously, thermal conductivity and compressive strength remain in the more stable scope.
Claims (15)
1. one kind based on the expanded graphite liquid combustion inhibitor, it is characterized in that, comprises the following component in weight part:
100 parts of expansible black leads;
100-900 part thinner.
2. as claimed in claim 1ly it is characterized in that the preferred 100-400 part of said thinner based on the expanded graphite liquid combustion inhibitor.
3. as claimed in claim 2ly it is characterized in that said thinner is selected from phosphate modified dose of at least a with polyvalent alcohol based on the expanded graphite liquid combustion inhibitor.
4. as claimed in claim 3ly it is characterized in that said polyvalent alcohol is selected from least a in polyether glycol and the polyester polyol based on the expanded graphite liquid combustion inhibitor.
5. as claimed in claim 4 based on the expanded graphite liquid combustion inhibitor; It is characterized in that at least a functionality that is initiator forms that said polyether glycol is selected from at least a and quadrol in Ucar 35, terepthaloyl moietie, USP Kosher, TriMethylolPropane(TMP), tetramethylolmethane, sucrose, the sorbyl alcohol and tolylene diamine is that 2-6, hydroxyl value are the polyether polyol of 18-800;
Said polyester polyol is selected from least a and terepthaloyl moietie, Ucar 35, USP Kosher, the TriMethylolPropane(TMP), 1 that backbone structure adopts hexanodioic acid and Tetra hydro Phthalic anhydride; The functionality that at least a polycondensation of 4-butyleneglycol, 1,6 pinakon, pentanediol forms is that 2-4, hydroxyl value are the polyester polyol of 50-500.
6. as claimed in claim 3 based on the expanded graphite liquid combustion inhibitor; It is characterized in that said phosphate modified dose is selected from least a of inferior ester, three (DPG) phosphorous acid ester of di(2-ethylhexyl)phosphate benzene toluene ester, three (polyoxygenated alkene) SULPHOSUCCINIC ACID ESTER, three (polyoxygenated alkene) phosphoric acid, methyl-phosphoric acid dimethyl ester, propyl group dimethyl phosphate, ethyl phosphonic acid diethyl ester, triethyl phosphate or Tritolyl Phosphate.
7. as claimed in claim 1ly it is characterized in that, also comprise the auxiliary agent of 0.5-60 part based on the expanded graphite liquid combustion inhibitor.
8. as claimed in claim 7 based on the expanded graphite liquid combustion inhibitor; It is characterized in that said auxiliary agent is selected from high-molecular weight polymer type wetting agent, liquid auxiliary rheological agents, controlled flocculation type auxiliary agent, wax dispersion, at least a than the alkylammonium salt of small molecular weight polymer type dispersion agent and HMW interpolymer;
The preferred 0.8-2.5 part of said auxiliary agent.
9. as each is described based on the application of expanded graphite liquid combustion inhibitor in fire retardant material among the claim 1-8.
10. one kind is used among the claim 1-8 each describedly to prepare the method for resistance combustion polyurethane foam material based on the expanded graphite liquid combustion inhibitor, it is characterized in that, comprises the steps:
(a) will comprise and mixing with POLYMETHYLENE POLYPHENYLISOCYANATE of polyvalent alcohol form mixture based on the expanded graphite liquid combustion inhibitor; In expansible black lead 100 weight parts; The add-on of POLYMETHYLENE POLYPHENYLISOCYANATE is the 500-1500 weight part, and simultaneously to wherein add polymerizing catalyst, whipping agent mixes;
(b) molded, obtain polyurethane foamed material.
11. preparation method as claimed in claim 10 is characterized in that, in the said step (a), also can in said mixture, add polyvalent alcohol.
12., it is characterized in that the weight ratio of polyvalent alcohol and expansible black lead is preferably 135-300:100 in said step (a) mixture like claim 10 or 11 described preparing methods.
13. one kind is used among the claim 1-8 each describedly to prepare the method for resistance combustion polyurethane foam material based on the expanded graphite liquid combustion inhibitor, it is characterized in that, comprises the steps:
(a) will not comprise and mixing of polyvalent alcohol form mixture based on expanded graphite liquid combustion inhibitor, POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol; In expansible black lead 100 weight parts; The add-on of POLYMETHYLENE POLYPHENYLISOCYANATE is the 500-1500 weight part; The add-on of polyvalent alcohol is the 100-900 weight part, and simultaneously to wherein add polymerizing catalyst, whipping agent mixes;
(b) molded, obtain polyurethane foamed material.
14. preparation method as claimed in claim 13 is characterized in that, the preferred 500-700 of the add-on of said POLYMETHYLENE POLYPHENYLISOCYANATE, the preferred 300-500 of the add-on of said polyvalent alcohol.
15., it is characterized in that also comprise the adding additive in the said step (a), said additive is selected from least a of UV light stabilizing agent and fire retardant like claim 10 or 13 described preparing methods.
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| CN105829477A (en) * | 2013-12-10 | 2016-08-03 | 韩国建设技术研究院 | Heat-Foamable Coating Agent And Method For Preparing Same |
| WO2018060255A1 (en) * | 2016-09-30 | 2018-04-05 | Covestro Polymers (China) Co. Ltd. | Composite flame retardant and polyurethane materials comprising the same |
| CN109081899A (en) * | 2018-07-23 | 2018-12-25 | 德清顾舒家华高分子材料有限公司 | A kind of fire-retardant heat insulation polyurethane foam |
| CN111171270A (en) * | 2020-02-23 | 2020-05-19 | 郑州大学 | Flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol and preparation method thereof |
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| US20050222284A1 (en) * | 2002-05-07 | 2005-10-06 | Williams Barbara A | Synergistic flame retardant blends for polyurethane foams |
| CN102432917A (en) * | 2011-09-03 | 2012-05-02 | 四川大学 | Halogen-free flame retardant additive, and soft and hard polyurethane foams and elastic body retarding flame by using same |
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| US20050222284A1 (en) * | 2002-05-07 | 2005-10-06 | Williams Barbara A | Synergistic flame retardant blends for polyurethane foams |
| CN102432917A (en) * | 2011-09-03 | 2012-05-02 | 四川大学 | Halogen-free flame retardant additive, and soft and hard polyurethane foams and elastic body retarding flame by using same |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105829477A (en) * | 2013-12-10 | 2016-08-03 | 韩国建设技术研究院 | Heat-Foamable Coating Agent And Method For Preparing Same |
| CN105829477B (en) * | 2013-12-10 | 2018-02-09 | 韩国建设技术研究院 | Thermally foamable coating agent and its manufacture method |
| WO2018060255A1 (en) * | 2016-09-30 | 2018-04-05 | Covestro Polymers (China) Co. Ltd. | Composite flame retardant and polyurethane materials comprising the same |
| CN107880314A (en) * | 2016-09-30 | 2018-04-06 | 科思创聚合物（中国）有限公司 | Composite flame-retardant agent and the polyurethane material for including it |
| US20200181355A1 (en) * | 2016-09-30 | 2020-06-11 | Covestro Deutschland Ag | Composite flame retardant and polyurethane materials comprising the same |
| CN109081899A (en) * | 2018-07-23 | 2018-12-25 | 德清顾舒家华高分子材料有限公司 | A kind of fire-retardant heat insulation polyurethane foam |
| CN111171270A (en) * | 2020-02-23 | 2020-05-19 | 郑州大学 | Flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol and preparation method thereof |
| CN111171270B (en) * | 2020-02-23 | 2022-01-07 | 郑州大学 | Flame-retardant polyurethane thermal insulation material prepared from crude glycerol bio-based polyol and preparation method thereof |
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Application publication date: 20120919 |