CN111875943A - Carbon-containing high polymer material mixture for flame retardant for polyurethane foaming product - Google Patents
Carbon-containing high polymer material mixture for flame retardant for polyurethane foaming product Download PDFInfo
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Abstract
The invention discloses a carbon-containing high polymer material mixture for flame retardant of polyurethane foaming products, which adopts aromatic polycarbonate as a resin base, the molecular chain of the aromatic polycarbonate contains carbonate type high polymer of aryl, the carbon content of the polyurethane foaming products can be improved, sulfonate flame retardant, phosphate flame retardant and carbon type flame retardant are simultaneously added into the mixture, the flame retardant property of the mixture is improved, sodium ions with proper proportion are added into the phosphate flame retardant to react with phosphate radical to generate a refractory material bonding agent, the reaction temperature of condensation and hardening can be reduced, the mixture can meet the use requirement of the polyurethane foaming process in low-temperature environment, carbon nano tubes with the diameter of 10nm are added into the mixture, the mechanical property of the mixture is improved, and simultaneously, a large number of groups combined on the surface of the mixture can react with free groups of the aromatic polycarbonate, improving the fire resistance of the mixture.
Description
Technical Field
The invention relates to the technical field of macromolecules, in particular to a carbon-containing polymer material mixture for a flame retardant for a polyurethane foaming product.
Background
Polyurethane foam products are mainly used in the automobile, building and furniture industries as fillers or as shock absorbers, decorations and insulators, and can provide different characteristics in specific applications depending on the product, can be soft and elastic when used for seat cushions, and can be hard and durable when used for insulating materials, but the problem of improving the fire resistance of the polyurethane foam products is solved regardless of the application environment.
Most of the existing flame-retardant methods for foaming polyurethane foaming products adopt the mode that carbon fibers are added in a resin base to play a role in enhancing the fire resistance and the corrosion resistance of the products, the carbon fibers are expensive and not strong in economic practicability, most of the existing flame retardants for the polyurethane foaming products are halogen-free flame retardants, the flame-retardant effect is good, the price is low, but the carbon content in the halogen-free flame retardants is low, the mechanical property of the flame retardants can not be ensured, the application environment temperature is high, and the use requirements of the polyurethane foaming process in a low-temperature environment can not be met.
Disclosure of Invention
The invention aims to provide a carbon-containing high polymer material mixture for a flame retardant for a polyurethane foaming product, which can meet the use requirement of the polyurethane foaming process in a low-temperature environment and has better fire resistance, so as to solve the problems that carbon fibers proposed in the background art are expensive and have low economic practicability, most of the existing flame retardants for polyurethane foaming products are halogen-free flame retardants, the flame retardant effect is better, the price is low, but the carbon content in the halogen-free flame retardants is low, the mechanical property of the flame retardants cannot be ensured, the application environment temperature is higher, and the use requirement of the polyurethane foaming process in the low-temperature environment cannot be met.
In order to achieve the purpose, the invention adopts the following technical scheme:
the carbon-containing high polymer material mixture for the flame retardant for the polyurethane foaming product comprises the following components in parts by weight: 50-80 parts of aromatic polycarbonate, 1-7 parts of sulfonate flame retardant, 0.1-2 parts of sodium carbonate, 2-5 parts of phosphate flame retardant, 8-15 parts of carbon nano tube, 10-15 parts of carbon type flame retardant and 2-10 parts of skinning agent.
Preferably, the aromatic polycarbonate is produced by an ester interchange reaction between an aromatic dicarbonate, diphenyl carbonate and an aromatic dihydroxy compound.
Preferably, the sulfonate flame retardant is one or a mixture of two of potassium benzenesulfonyl benzene sulfonate, potassium perfluorobutyl sulfonate and potassium 2,4, 5-trichlorobenzene sulfonate.
Preferably, the sodium carbonate is mixed with a sulfonate flame retardant to form an alkali sulfonate containing mixture, the sodium carbonate content of the mixture being 10% of the sulfonate content.
Preferably, the phosphate flame retardant is a mixture of dimethyl methylphosphonate, diethyl ethylphosphate and tris (2-chloroethyl) phosphate, and the mixing ratio of dimethyl methylphosphonate, diethyl ethylphosphate and tris (2-chloroethyl) phosphate is 1:1-1.5: 0.5.
Preferably, the carbon nano tube is a multi-wall carbon nano tube subjected to graphitization treatment, and the tube diameter of the multi-wall carbon nano tube is 5-15 nm.
Preferably, the carbon-type flame retardant is a carbon-type compound polymerized by pentaerythritol dimer, melamine and lipid compounds.
The invention also provides a preparation method of the carbon-containing high polymer material mixture for the flame retardant for the polyurethane foaming product, which comprises the following steps:
s1, placing the aromatic dicarbonate, the diphenyl carbonate, the aromatic dihydroxy compound and the catalyst into a reaction kettle for reaction to form a mixture of a product fat (aromatic polycarbonate) and a product alcohol, and separating the product fat and the product alcohol by using a centrifuge to obtain pure aromatic polycarbonate;
s2, adding the aromatic polycarbonate obtained in the step S1 and the mixture containing alkali sulfonate into a reaction kettle, introducing nitrogen into the reaction kettle for protection, and uniformly stirring to obtain a primary flame retardant material mixture;
s3, discharging nitrogen, heating the primary flame-retardant material mixture to 180-230 ℃, adding part of the phosphate flame retardant and the cut carbon nano tubes into the reaction kettle, and continuously stirring to obtain a secondary flame-retardant material mixture;
and S4, closing the heating device, adding the carbon-type flame retardant into the secondary flame retardant material mixture after the temperature in the reaction kettle is reduced to be below 120 ℃, fully stirring to obtain a flame retardant material mixture raw material, adding the skinning agent into the flame retardant material mixture raw material, and stirring to obtain a flame retardant material mixture finished product.
Preferably, the primary flame retardant material mixture is heated to a temperature not exceeding 300 ℃.
The invention provides a carbon-containing high polymer material mixture for a flame retardant for a polyurethane foaming product, which adopts aromatic polycarbonate as a resin base to improve the chemical stability of the mixture, adopts a carbonate type high polymer containing aryl in a molecular chain to improve the carbon content in the polyurethane foaming product, simultaneously adds a sulfonate flame retardant, a phosphate type flame retardant and a carbon type flame retardant into the mixture to improve the flame retardant property of the mixture, adds sodium carbonate in a proper proportion into the phosphate type flame retardant, uses sodium ions as alkaline metal ions to react with phosphate radicals to generate a refractory material binding agent, can reduce the reaction temperature of condensation and hardening action, enables the mixture to meet the use requirement of the polyurethane foaming process in a low-temperature environment, adds carbon nano tubes with the diameter of 10nm into the mixture, improves the mechanical property of the mixture, a large number of groups bound to the surface of the polycarbonate can react with free groups of the aromatic polycarbonate, thereby improving the flame resistance of the mixture.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The carbon-containing high polymer material mixture for the flame retardant for the polyurethane foaming product comprises the following components in parts by weight: 70 parts of aromatic polycarbonate, 5 parts of sulfonate flame retardant, 0.5 part of sodium carbonate, 2.5 parts of phosphate flame retardant, 8 parts of carbon nano tube, 10 parts of carbon-type flame retardant and 4 parts of skinning agent, wherein the aromatic polycarbonate is prepared by carrying out ester exchange reaction on aromatic dicarbonate, diphenyl carbonate and aromatic dihydroxy compound, the sulfonate flame retardant is one or a mixture of potassium benzenesulfonyl benzenesulfonate, potassium perfluorobutylsulfonate and potassium 2,4, 5-trichlorobenzenesulfonate, sodium carbonate and the sulfonate flame retardant are mixed to form an alkali-containing sulfonate mixture, the content of sodium carbonate in the mixture accounts for 10% of the sulfonate content, the phosphate flame retardant is a mixture of dimethyl methylphosphonate, diethyl ethylphosphate and tris (2-chloroethyl) phosphate, the mixing ratio of dimethyl methylphosphonate, diethyl ethylphosphate and tris (2-chloroethyl) phosphate is 1:1:0.5, the carbon nano tube is a multi-wall carbon nano tube subjected to graphitization treatment, the tube diameter of the multi-wall carbon nano tube is 10nm, and the carbon type flame retardant is a carbon type compound polymerized by pentaerythritol dimer, melamine and lipid compounds.
Example 2
The carbon-containing high polymer material mixture for the flame retardant for the polyurethane foaming product comprises the following components in parts by weight: 70 parts of aromatic polycarbonate, 5 parts of sulfonate flame retardant, 0.5 part of sodium carbonate, 2.5 parts of phosphate flame retardant, 8 parts of carbon nano tube, 10 parts of carbon-type flame retardant and 4 parts of skinning agent, wherein the aromatic polycarbonate is prepared by carrying out ester exchange reaction on aromatic dicarbonate, diphenyl carbonate and aromatic dihydroxy compound, the sulfonate flame retardant is one or a mixture of potassium benzenesulfonyl benzenesulfonate, potassium perfluorobutylsulfonate and potassium 2,4, 5-trichlorobenzenesulfonate, sodium carbonate and the sulfonate flame retardant are mixed to form an alkali-containing sulfonate mixture, the content of sodium carbonate in the mixture accounts for 10% of the sulfonate content, the phosphate flame retardant is a mixture of dimethyl methylphosphonate, diethyl ethylphosphate and tris (2-chloroethyl) phosphate, the mixing ratio of dimethyl methylphosphonate, diethyl ethylphosphonate and tris (2-chloroethyl) phosphate is 1:1.5:0.5, the carbon nano tube is a multi-wall carbon nano tube subjected to graphitization treatment, the tube diameter of the multi-wall carbon nano tube is 10nm, and the carbon type flame retardant is a carbon type compound polymerized by pentaerythritol dimer, melamine and lipid compounds.
Example 3
The carbon-containing high polymer material mixture for the flame retardant for the polyurethane foaming product comprises the following components in parts by weight: 70 parts of aromatic polycarbonate, 5 parts of sulfonate flame retardant, 0.5 part of sodium carbonate, 5 parts of phosphate flame retardant, 8 parts of carbon nano tube, 7.5 parts of carbon type flame retardant and 4 parts of skinning agent, wherein the aromatic polycarbonate is prepared by carrying out ester exchange reaction on aromatic dicarbonate, diphenyl carbonate and aromatic dihydroxy compound, the sulfonate flame retardant is one or a mixture of potassium benzenesulfonyl benzenesulfonate, potassium perfluorobutylsulfonate and potassium 2,4, 5-trichlorobenzenesulfonate, the sodium carbonate and the sulfonate flame retardant are mixed to form an alkali-containing sulfonate mixture, the content of sodium carbonate in the mixture accounts for 10% of the sulfonate content, the phosphate flame retardant is a mixture of dimethyl methylphosphonate, diethyl ethylphosphate and tris (2-chloroethyl) phosphate, the mixing ratio of dimethyl methylphosphonate, diethyl ethylphosphate and tris (2-chloroethyl) phosphate is 1:1.5:0.5, the carbon nano tube is a multi-wall carbon nano tube subjected to graphitization treatment, the tube diameter of the multi-wall carbon nano tube is 10nm, and the carbon type flame retardant is a carbon type compound polymerized by pentaerythritol dimer, melamine and lipid compounds.
Example 4
The carbon-containing high polymer material mixture for the flame retardant for the polyurethane foaming product comprises the following components in parts by weight: 70 parts of aromatic polycarbonate, 2.5 parts of sulfonate flame retardant, 0.5 part of sodium carbonate, 5 parts of phosphate flame retardant, 8 parts of carbon nano tube, 10 parts of carbon-type flame retardant and 4 parts of skinning agent, wherein the aromatic polycarbonate is prepared by carrying out ester exchange reaction on aromatic dicarbonate, diphenyl carbonate and aromatic dihydroxy compound, the sulfonate flame retardant is one or a mixture of potassium benzenesulfonyl benzenesulfonate, potassium perfluorobutylsulfonate and potassium 2,4, 5-trichlorobenzenesulfonate, the sodium carbonate and the sulfonate flame retardant are mixed to form an alkali-containing sulfonate mixture, the content of sodium carbonate in the mixture accounts for 10% of the sulfonate content, the phosphate flame retardant is a mixture of dimethyl methylphosphonate, diethyl ethylphosphate and tris (2-chloroethyl) phosphate, and the mixing ratio of the dimethyl methylphosphonate, the diethyl ethylphosphonate and the tris (2-chloroethyl) phosphate is 1:1.5:0.5, the carbon nano tube is a multi-wall carbon nano tube subjected to graphitization treatment, the tube diameter of the multi-wall carbon nano tube is 10nm, and the carbon type flame retardant is a carbon type compound polymerized by pentaerythritol dimer, melamine and lipid compounds.
Example 5
The carbon-containing high polymer material mixture for the flame retardant for the polyurethane foaming product comprises the following components in parts by weight: 72.5 parts of aromatic polycarbonate, 5 parts of sulfonate flame retardant, 0.5 part of sodium carbonate, 5 parts of phosphate flame retardant, 8 parts of carbon nano tube, 5 parts of carbon-type flame retardant and 4 parts of skinning agent, wherein the aromatic polycarbonate is prepared by carrying out ester exchange reaction on aromatic dicarbonate, diphenyl carbonate and aromatic dihydroxy compound, the sulfonate flame retardant is one or a mixture of potassium benzenesulfonyl benzenesulfonate, potassium perfluorobutylsulfonate and potassium 2,4, 5-trichlorobenzenesulfonate, the sodium carbonate and the sulfonate flame retardant are mixed to form an alkali-containing sulfonate mixture, the content of sodium carbonate in the mixture accounts for 10% of the sulfonate content, the phosphate flame retardant is a mixture of dimethyl methylphosphonate, diethyl ethylphosphate and tris (2-chloroethyl) phosphate, the mixing ratio of the dimethyl methylphosphonate, the diethyl ethylphosphonate and the tris (2-chloroethyl) phosphate is 1:1.5:0.5, the carbon nano tube is a multi-wall carbon nano tube subjected to graphitization treatment, the tube diameter of the multi-wall carbon nano tube is 10nm, and the carbon type flame retardant is a carbon type compound polymerized by pentaerythritol dimer, melamine and lipid compounds.
The invention also provides a preparation method of the carbon-containing high polymer material mixture for the flame retardant for the polyurethane foaming product, which comprises the following steps:
s1, placing the aromatic dicarbonate, the diphenyl carbonate, the aromatic dihydroxy compound and the catalyst into a reaction kettle for reaction to form a mixture of a product fat (aromatic polycarbonate) and a product alcohol, and separating the product fat and the product alcohol by using a centrifuge to obtain pure aromatic polycarbonate;
s2, adding the aromatic polycarbonate obtained in the step S1 and the mixture containing alkali sulfonate into a reaction kettle, introducing nitrogen into the reaction kettle for protection, and uniformly stirring to obtain a primary flame retardant material mixture;
s3, discharging nitrogen, heating the primary flame-retardant material mixture to 180-230 ℃, wherein the heating temperature of the primary flame-retardant material mixture is not more than 300 ℃, adding part of the phosphate flame retardant and the cut carbon nano tubes into the reaction kettle, and continuously stirring to obtain a secondary flame-retardant material mixture;
and S4, closing the heating device, adding the carbon-type flame retardant into the secondary flame retardant material mixture after the temperature in the reaction kettle is reduced to be below 120 ℃, fully stirring to obtain a flame retardant material mixture raw material, adding the skinning agent into the flame retardant material mixture raw material, and stirring to obtain a flame retardant material mixture finished product.
In summary, the following steps: the carbon-containing high polymer material mixture for the flame retardant for the polyurethane foaming product adopts aromatic polycarbonate as a resin base to improve the chemical stability of the mixture, the carbonate type high polymer containing aryl in a molecular chain can improve the carbon content in the polyurethane foaming product, a sulfonate flame retardant, a phosphate flame retardant and a carbon type flame retardant are simultaneously added into the mixture to improve the flame retardant property of the mixture, sodium carbonate with proper proportion is added into the phosphate type flame retardant, sodium ions are used as alkaline metal ions to react with phosphate radicals to generate a refractory material bonding agent, the reaction temperature of condensation and hardening can be reduced, the mixture can meet the use requirement of the polyurethane foaming process in a low-temperature environment, carbon nano tubes with the diameter of 10nm are added into the mixture, and a large number of groups combined on the surface can react with free groups of the aromatic polycarbonate while the mechanical property of the mixture is improved, improving the fire resistance of the mixture.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A carbon-containing high polymer material mixture for a flame retardant for a polyurethane foaming product is characterized in that: the flame retardant for the polyurethane foaming product comprises the following carbon-containing high polymer material mixture according to the formula by weight: 50-80 parts of aromatic polycarbonate, 1-7 parts of sulfonate flame retardant, 0.1-2 parts of sodium carbonate, 2-5 parts of phosphate flame retardant, 8-15 parts of carbon nano tube, 10-15 parts of carbon type flame retardant and 2-10 parts of skinning agent.
2. The carbon-containing polymer material mixture for the flame retardant of the polyurethane foam product as claimed in claim 1, wherein: the aromatic polycarbonate is prepared by performing ester exchange reaction on aromatic dicarbonate, diphenyl carbonate and aromatic dihydroxy compound.
3. The carbon-containing polymer material mixture for the flame retardant of the polyurethane foam product as claimed in claim 1, wherein: the sulfonate flame retardant is one or a mixture of two of benzenesulfonyl potassium benzenesulfonate, perfluorobutyl potassium sulfonate and 2,4, 5-trichlorobenzene potassium sulfonate.
4. The carbon-containing polymer material mixture for the flame retardant of the polyurethane foam product as claimed in claim 1, wherein: the sodium carbonate is mixed with the sulfonate flame retardant to form an alkali-containing sulfonate mixture, and the content of the sodium carbonate in the mixture accounts for 10% of the sulfonate content.
5. The carbon-containing polymer material mixture for the flame retardant of the polyurethane foam product as claimed in claim 1, wherein: the phosphate flame retardant is a mixture of dimethyl methylphosphonate, diethyl ethylphosphate and tris (2-chloroethyl) phosphate, and the mixing ratio of the dimethyl methylphosphonate to the diethyl ethylphosphate to the tris (2-chloroethyl) phosphate is 1:1-1.5: 0.5.
6. The carbon-containing polymer material mixture for the flame retardant of the polyurethane foam product as claimed in claim 1, wherein: the carbon nano tube is a multi-wall carbon nano tube subjected to graphitization treatment, and the tube diameter of the multi-wall carbon nano tube is 5-15 nm.
7. The carbon-containing polymer material mixture for the flame retardant of the polyurethane foam product as claimed in claim 1, wherein: the carbon-type flame retardant is a carbon-type compound polymerized by pentaerythritol dimer, melamine and lipid compounds.
8. A method for preparing a carbon-containing polymer material mixture for a flame retardant of a polyurethane foam product according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
s1, placing the aromatic dicarbonate, the diphenyl carbonate, the aromatic dihydroxy compound and the catalyst into a reaction kettle for reaction to form a mixture of a product fat (aromatic polycarbonate) and a product alcohol, and separating the product fat and the product alcohol by using a centrifuge to obtain pure aromatic polycarbonate;
s2, adding the aromatic polycarbonate obtained in the step S1 and the mixture containing alkali sulfonate into a reaction kettle, introducing nitrogen into the reaction kettle for protection, and uniformly stirring to obtain a primary flame retardant material mixture;
s3, discharging nitrogen, heating the primary flame-retardant material mixture to 180-230 ℃, adding part of the phosphate flame retardant and the cut carbon nano tubes into the reaction kettle, and continuously stirring to obtain a secondary flame-retardant material mixture;
and S4, closing the heating device, adding the carbon-type flame retardant into the secondary flame retardant material mixture after the temperature in the reaction kettle is reduced to be below 120 ℃, fully stirring to obtain a flame retardant material mixture raw material, adding the skinning agent into the flame retardant material mixture raw material, and stirring to obtain a flame retardant material mixture finished product.
9. The method for preparing the carbon-containing polymer material mixture for the flame retardant of the polyurethane foam product as claimed in claim 8, wherein the method comprises the following steps: the heating temperature of the primary flame-retardant material mixture is not more than 300 ℃.
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| CN110144103A (en) * | 2018-02-10 | 2019-08-20 | 汉达精密电子(昆山)有限公司 | Halogen-free flame retardant PC conductive material and products thereof |
| CN110551378A (en) * | 2018-06-01 | 2019-12-10 | 汉达精密电子(昆山)有限公司 | Halogen-free flame-retardant PC/carbon nano tube conductive material and product thereof |
| CN110746756A (en) * | 2019-09-18 | 2020-02-04 | 金发科技股份有限公司 | Flame-retardant polycarbonate composite material and preparation method thereof |
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