CN114573785B - Preparation method of flame-retardant conductive dual-property flexible polyurethane foam - Google Patents

Preparation method of flame-retardant conductive dual-property flexible polyurethane foam Download PDF

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CN114573785B
CN114573785B CN202210258298.0A CN202210258298A CN114573785B CN 114573785 B CN114573785 B CN 114573785B CN 202210258298 A CN202210258298 A CN 202210258298A CN 114573785 B CN114573785 B CN 114573785B
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polyurethane foam
flame
flexible polyurethane
diisocyanate
polyether polyol
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CN114573785A (en
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程国君
周龙旋
丁国新
万祥龙
闵凡飞
刘令云
王庆平
王周锋
张宏艳
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Anhui University of Science and Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • 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
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    • C08K3/10—Metal compounds
    • C08K3/14—Carbides
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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/06—Flexible foams
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/324—Alkali metal phosphate
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives

Abstract

The invention discloses a preparation method of flame-retardant conductive dual-property flexible polyurethane foam, which takes double-effect baking powder as a foaming agent and passes through two-dimensional Ti 3 C 2 T x The material respectively has synergistic effect with the composite phosphate and the TCPP to improve the conductivity and the flame retardant property of the flexible polyurethane foam. The flame-retardant conductive double-property flexible polyurethane foam prepared by the invention has uniform foam holes; based on composite phosphate, baking powder and novel two-dimensional Ti 3 C 2 T x The material ensures that the flexible polyurethane foam has a good continuous conductive network; based on two-dimensional Ti 3 C 2 T x The material and TCPP cooperate to make the soft polyurethane foam have good flame-retardant effect.

Description

Preparation method of flame-retardant conductive dual-property flexible polyurethane foam
Technical Field
The invention relates to a preparation method of flame-retardant conductive double-nature flexible polyurethane foam, and belongs to the technical field of material preparation.
Background
Polyurethane is short for polyurethane, and foamed plastic is one of the main varieties of polyurethane synthetic materials. Because of its excellent wear resistance, corrosion resistance, etc., it has been widely used in automobile parts, electronics, industrial, mechanical transmission parts, home furnishing, cosmetics, etc. However, the insulating flammability of polyurethane and the release of a large amount of smoke during combustion limit its industrial production and use. Therefore, it is necessary to improve the flame retardancy and the electrical conductivity of polyurethane. So far, research has shown that the addition of nanofillers is one of the methods for effectively improving the flame retardancy of polyurethanes. Two-dimensional Ti 3 C 2 T x The material being Ti 3 Etching product of AlC, ti 3 C 2 T x Has excellent electric conduction, flame retardance, energy storage and other properties, so that Ti 3 C 2 T x The polymer nano composite material has good application prospect as a functional filler of the polymer nano composite material.
The polyether polyol is mainly used as a raw material of the polyol for the transportation field abroad, and the mechanical property of the polyether polyol is obviously superior to that of the polyester polyol because the polyether polyol contains an ether bond structure. The polyether polyol used in each field is mainly sucrose type, sorbitol type, glycerol type and the like, and the functionality of the polyether polyol produced in China is two, three, four and the like at present.
Disclosure of Invention
The invention aims to provide a flame-retardant conductive double-property flexible polyurethane foamPreparation method by two-dimensional Ti 3 C 2 T x The material respectively has synergistic effect with the composite phosphate and the TCPP to improve the conductivity and the flame retardant property of the flexible polyurethane foam.
The flame-retardant conductive double-property flexible polyurethane foam prepared by the invention has uniform foam holes; based on composite phosphate, baking powder and novel two-dimensional Ti 3 C 2 T x The material ensures that the flexible polyurethane foam has a good continuous conductive network; based on two-dimensional Ti 3 C 2 T x The material and TCPP cooperate to make the soft polyurethane foam have good flame-retardant effect.
The invention relates to a preparation method of flame-retardant conductive double-property flexible polyurethane foam, which comprises the following steps:
step 1: sequentially adding water and composite phosphate into etched Ti 3 C 2 T x Stirring uniformly to form mud; ti (Ti) 3 C 2 T x The etching process adopts a laboratory self-created etching method, and firstly two-dimensional MAX (Ti 3 AlC 2 ) The surface activity of a two-dimensional system is increased in an auxiliary way through ball milling, and MAX is etched by adopting hydrochloric acid and lithium fluoride, so that two-dimensional Ti is obtained 3 C 2 T x Materials, specific references: shen Tian, guojun Cheng, zhongfeng Tang et al Fabrication of two-dimensional Ti 3 C 2 T x MXenes by ball milling pretreatment and mild etchant and their microstructure[J].Ceramics International,2020,46:28949-28954。
Step 2: sequentially adding triethylene diamine (catalyst), dodecyl dimethyl siloxane (foam stabilizer), KH-550 (silane coupling agent), ethylene glycol (chain extender), baking powder (foaming agent), TCPP (flame retardant) and quantitative diisocyanate into polyether polyol, and uniformly stirring to obtain cream yellow;
step 3: the mud-like Ti obtained in the step 1 is treated 3 C 2 T x Adding the mixture into the cream yellow polyether polyol system obtained in the step 2, and uniformly stirring and mixing the mixture to form dark black;
step 4: and (3) adding diisocyanate into the system in the step (3), uniformly stirring, and foaming to obtain the flame-retardant conductive double-property flexible polyurethane foam.
Still further:
step 1: adding 1-5g of etched Ti into 1-6g of water and 1-6g of composite phosphate in sequence 3 C 2 T x Stirring uniformly to form mud;
step 2: sequentially adding 0.1-0.3g of triethylene diamine, 0.1-0.3g of dodecyl dimethyl siloxane, 0.1-0.3g of KH-550, 0.1-0.3g of ethylene glycol, 1-10g of TCPP, 1-2g of baking powder and 0.5-1.0g of diisocyanate into 5-10g of polyether polyol, and uniformly stirring to obtain a cream yellow color;
step 3: the mud-like Ti obtained in the step 1 is treated 3 C 2 T x Adding the mixture into the cream yellow polyether polyol system obtained in the step 2, and uniformly stirring and mixing the mixture to form dark black;
step 4: adding 5-10g of diisocyanate into the system in the step 3, setting the rotating speed to be 1000-2000r/min and the reaction time to be 5-30s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive dual-property flexible polyurethane foam.
In the present invention, the composite phosphate contains eight components, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium acid pyrophosphate, disodium dihydrogen pyrophosphate, etc. The complex phosphate used in the present invention was purchased from Xuzhou additive food additives. Wherein sodium tripolyphosphate (Na 5 P 3 O 10 ) Mainly used as a moisture retention agent, the reaction equation: na (Na) 5 P 3 O 10 +2H 2 O＝2Na 2 HPO 4 +NaH 2 PO 4 . When no composite phosphate is added, only Ti is added 3 C 2 T x At this time, the polyurethane cannot foam. Only the composite phosphate and Ti are added simultaneously 3 C 2 T x At this point, the polyurethane foams. Ti of different masses (1 g, 2g, 3g, 4 g) 3 C 2 T x Is dissolved in 3g of water and is in the form of solution, and the concentration of the solution is increased along with the increase of the mass of the composite phosphate. When the mass of the composite phosphate reaches 3g, ti 3 C 2 T x The solution is in a wet mud form, and the best effect is achieved at this time.
One of the main causes of foam molding of polyurethane is the generation of carbon dioxide. The invention firstly adopts the double-effect baking powder as the foaming agent to foam polyurethane, and the double-effect baking powder is purchased from the Leling food of the benefit condiment Co. The reason why the foaming powder is not adopted as the foaming agent in the prior art is that firstly, the foaming rate of the foaming powder can not be controlled. The foaming rate of the baking powder is related to the quality of the baking powder, and if the quality of the baking powder is small, a certain multiplying power can not be achieved, and a certain height is formed; if the quality of the baking powder is large, although the baking powder may form a certain height, the foam cells are coarse and fragile, and the desired effect cannot be achieved. Through the relationship between the proportion of the prepared powder and the content of other substances, a new formula is formed, so that a certain multiplying power can be ensured, and uniform foam holes can be ensured. Secondly, the baking powder can spontaneously react when meeting water, and carbon dioxide is generated. This requires the treatment of the relationship between the baking powder and water, and the method has two steps: the first method comprises the steps of adding foam powder, stirring, and adding water; in the second method, the baking powder and the moisture are opened, and then stirred. After comprehensive consideration, the present invention adopts a second method.
The main components of the baking powder are disodium dihydrogen pyrophosphate (35% by weight) and sodium bicarbonate (45% by weight), and after the baking powder is contacted with water, acidic (hydrogen ions ionized by disodium dihydrogen pyrophosphate) and alkaline powder (bicarbonate ions) are simultaneously dissolved in water to react, and carbon dioxide (CO) is released 2 ) The method comprises the steps of carrying out a first treatment on the surface of the On the other hand, sodium bicarbonate releases water and carbon dioxide during the exothermic reaction, and these gases can expand the polyurethane. The baking powder is double-effect baking powder, and the baking powder starts to act when being dissolved in water in the fast reaction, and starts to act in the heating process in the slow reaction. Thus, the baking powder acts as a foaming agent in the present invention.
Through detection, the dual-property flexible polyurethane foam prepared by the invention is black, the pure polyurethane is insulating material with the property and the resistivity more than 10 10 Omega cm, limiting oxygen meansThe number is 17.0. When Ti is 3 C 2 T x When the concentration of the polyurethane foam is 12.0% -17.0%, and the polyurethane foam is cooperated with TCPP, the limiting oxygen index of the polyurethane foam is 30.0%, and the vertical burning level reaches V-0; resistivity of 10 4 Omega cm, and the conductivity does not decrease with time.
Compared with other methods, the invention has the beneficial effects that:
1. the flame-retardant conductive double-property flexible polyurethane foam prepared by the invention has stable flame-retardant performance;
2. the resistivity of the flame-retardant conductive double-property flexible polyurethane foam prepared by the invention does not decrease with the extension of time.
Drawings
FIG. 1 is a photograph of the burning process of an alcohol burner (a is the foamed polyurethane as such, b is the foamed polyurethane containing 20.0% TCPP, c is the foamed polyurethane containing 10.0% Ti) 3 C 2 T x Foamed polyurethane).
FIG. 2 is a photograph of the burning course of an alcohol burner (a is a flame containing 5.0% Ti) 3 C 2 T x Foamed polyurethane, b is a polyurethane containing 7.5% Ti 3 C 2 T x Foamed polyurethane, c is a polyurethane containing 10.0% Ti 3 C 2 T x Foamed polyurethane, d is a polyurethane containing 12.5% Ti 3 C 2 T x Foamed polyurethane).
FIG. 3 contains 5.0% Ti 3 C 2 T x The burning photo of the foamed polyurethane at different foaming ratios (e foaming ratio is 11.5, f foaming ratio is 16.6).
FIG. 4 is a scanning electron micrograph (a 1 and a2 are pre-combustion expanded polyurethane, a3 and a4 are post-combustion expanded polyurethane, b1 and b2 are pre-combustion expanded polyurethane containing 20.0% TCPP, b3 and b4 are post-combustion expanded polyurethane containing 20.0% TCPP, c1 and c2 are polyurethane containing 10.0% Ti) 3 C 2 T x Pre-combustion expanded polyurethane c3 and c4 are a polyurethane containing 10.0% Ti 3 C 2 T x Post-combustion foamed polyurethane).
FIG. 5 thermogravimetric curve of expanded polyurethane (wherein TCPP content is 20.0%, ti) 3 C 2 T x The content is 10.0%).
Fig. 6 Total Smoke Release (TSR) and Total Heat Release (THR) curves for the foamed polyurethane.
Detailed Description
The invention relates to a preparation method of flame-retardant conductive double-property flexible polyurethane foam, which comprises the following steps:
step 1: adding 1-5g of etched Ti into 1-6g of water and 1-6g of composite phosphate in sequence 3 C 2 T x Stirring uniformly to form mud;
step 2: sequentially adding 0.1-0.3g of triethylene diamine, 0.1-0.3g of dodecyl dimethyl siloxane, 0.1-0.3g of KH-550, 0.1-0.3g of ethylene glycol, 1-10g of TCPP, 1-2g of baking powder and 0.5-1.0g of diisocyanate into 5-10g of polyether polyol, and uniformly stirring to obtain a cream yellow color;
step 3: the mud-like Ti obtained in the step 1 is treated 3 C 2 T x Adding the mixture into the cream yellow polyether polyol system obtained in the step 2, and uniformly stirring and mixing the mixture to form dark black;
step 4: adding 5-10g of diisocyanate into the system in the step 3, setting the rotating speed to be 1000-2000r/min and the reaction time to be 5-30s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive dual-property flexible polyurethane foam.
The technical scheme of the invention is further analyzed and illustrated by the following specific examples. The polyether polyol used in the examples was 4110 type polyether polyol available from Guangzhou Qihua chemical Co.
Example 1:
sequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain a cream yellow color; finally, adding 5g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the polyurethane foam.
Through detection, the polyurethane foam prepared by the invention is yellowish, is an insulating material, and has resistivity greater than 10 10 Omega cm, limiting oxygen index of 17.0%, expansion ratio of 25.0, compression strength of 62.2kPa.
Example 2:
sequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol, 0.5g of diisocyanate, 2.5g of TCPP and 1.0g of baking powder into 5.0g of polyether polyol, and uniformly stirring to obtain a milky yellow color; finally, adding 5.0g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant flexible polyurethane foam.
Through detection, the polyurethane foam prepared by the invention is creamy yellow, and the resistivity is more than 10 10 Omega cm. At a concentration of 17.0% TCPP, the limiting oxygen index was 23.0% and the expansion ratio was 21.0.
Example 3:
sequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol, 0.5g of diisocyanate, 3g of TCPP and 1.0g of baking powder into 5.0g of polyether polyol, and uniformly stirring to obtain a cream yellow color; finally, adding 5.0g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant flexible polyurethane foam.
Through detection, the polyurethane foam prepared by the invention is creamy yellow, and the resistivity is more than 10 10 Omega cm. At a concentration of 20.0% TCPP, the oxygen index was 25.0% and the expansion ratio was 21.0.
Example 4:
sequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol, 0.5g of diisocyanate, 3.5g of TCPP and 1.0g of baking powder into 5.0g of polyether polyol, and uniformly stirring to obtain a milky yellow color; finally, adding 5.0g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant flexible polyurethane foam.
Through detection, the polyurethane foam prepared by the invention is creamy yellow, and the resistivity is more than 10 10 Omega cm. At a concentration of TCPP of 22.5%, the oxygen index was 27.0% and the expansion ratio was 22.0.
Example 5:
firstly, 3.0g of water and 3.0g of composite phosphate are added to 1.0g of etched Ti in sequence 3 C 2 T x Stirring uniformly to form mud; sequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol, 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain a cream yellow color; then the mud-like Ti is added 3 C 2 T x Adding into cream yellow polyether polyol, stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive dual-property rigid polyurethane foam.
Through detection, the flame-retardant conductive dual-property flexible polyurethane foam prepared by the invention is black and is prepared from Ti 3 C 2 T x At a concentration of 5.0%, the resistivity was 1X 10 5 Omega cm, oxygen index of 22.0% and expansion ratio of 7.0.
Example 6:
firstly, 3.0g of water and 3.0g of composite phosphate are added to 1.5g of etched Ti in sequence 3 C 2 T x Stirring uniformly to form mud; sequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol, 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain a cream yellow color; then the mud-like Ti is added 3 C 2 T x Stirring in cream yellow polyether polyol to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive dual-property flexible polyurethane foam.
Through detection, the flame-retardant conductive dual-property flexible polyurethane foam prepared by the invention is black and is prepared from Ti 3 C 2 T x At a concentration of 7.5%, the resistivity was 8X 10 4 Omega cm, oxygen index of 22.5% and expansion ratio of 6.0.
Example 7:
first, 3.0g of water and 3.0g of complex phosphate are combinedAdding 2.0g of etched Ti 3 C 2 T x Stirring uniformly to form mud; sequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol, 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain a cream yellow color; then the mud-like Ti is added 3 C 2 T x Adding into cream yellow polyether polyol, stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive dual-property flexible polyurethane foam.
Through detection, the flame-retardant conductive dual-property flexible polyurethane foam prepared by the invention is black and is prepared from Ti 3 C 2 T x At a concentration of 10.0%, the resistivity was 5X 10 4 Omega cm, oxygen index was 23.0% and expansion ratio was 7.0.
Example 8:
firstly, 3.0g of water and 3.0g of composite phosphate are added to 3.0g of etched Ti in sequence 3 C 2 T x Stirring uniformly to form mud; sequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol, 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain a cream yellow color; then the mud-like Ti is added 3 C 2 T x Adding into cream yellow polyether polyol, stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive dual-property flexible polyurethane foam.
Through detection, the flame-retardant conductive dual-property flexible polyurethane foam prepared by the invention is black and is prepared from Ti 3 C 2 T x At a concentration of 12.5%, the resistivity was 2.2X10 4 Omega cm, oxygen index 25.0% and expansion ratio 7.0.
Example 9:
firstly, 3.0g of water and 3.0g of composite phosphate are added to 3.0g of etched Ti in sequence 3 C 2 T x Stirring uniformly to obtainA mud shape; sequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol, 5.0g of TCPP and 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain a cream yellow color; then the mud-like Ti is added 3 C 2 T x Adding into cream yellow polyether polyol, stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive dual-property flexible polyurethane foam.
Through detection, the flame-retardant conductive dual-property flexible polyurethane foam prepared by the invention is black and is prepared from Ti 3 C 2 T x At a concentration of 12.0%, the resistivity was 5.46×10 4 Omega cm, compressive strength 133.2kPa, oxygen index 30.0%, vertical combustion V-0.
Example 10:
firstly, 3.0g of water and 3.0g of composite phosphate are added to 3.5g of etched Ti in sequence 3 C 2 T x Stirring uniformly to form mud; sequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol, 5.0g of TCPP and 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain a cream yellow color; then the mud-like Ti is added 3 C 2 T x Adding into cream yellow polyether polyol, stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive dual-property flexible polyurethane foam.
Through detection, the flame-retardant conductive dual-property flexible polyurethane foam prepared by the invention is black and is prepared from Ti 3 C 2 T x At a concentration of 15.0%, the resistivity was 5.13×10 4 Omega cm, compressive strength 132.2kPa, oxygen index 30.0%, vertical combustion V-0.
Example 11:
firstly, adding 3.0g of water and 3.0g of composite phosphate to 4.0g of etched Ti in sequence 3 C 2 T x Stirring uniformly to form mud; at the position ofSequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol, 5.0g of TCPP and 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain a cream yellow color; then the mud-like Ti is added 3 C 2 T x Adding into cream yellow polyether polyol, stirring to obtain dark black; finally adding 5.0g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive dual-property flexible polyurethane foam.
Through detection, the flame-retardant conductive dual-property flexible polyurethane foam prepared by the invention is black and is prepared from Ti 3 C 2 T x At a concentration of 17.0%, the resistivity was 2.23×10 4 Omega cm, compressive strength 135.2kPa, oxygen index 30.0%, vertical combustion V-0.
In examples 9 to 11, we adjusted Ti with the TCPP addition (5 g) unchanged 3 C 2 T x Is contained in the composition.
In example 9, ti 3 C 2 T x The addition amount is 3g, and the influence of the parameter on the product performance is as follows: at Ti 3 C 2 T x At a concentration of 12.0%, the resistivity was 5.46×10 4 Omega cm, compressive strength 133.2kPa, oxygen index 30.0%, vertical combustion V-0. In example 10, ti 3 C 2 T x The amount of added (C) was 3.5g, and the effect of this parameter on the product properties was: at Ti 3 C 2 T x At a concentration of 15.0%, the resistivity was 5.13×10 4 Omega cm, compressive strength 132.2kPa, oxygen index 30.0%, vertical combustion V-0. In example 11, ti 3 C 2 T x The amount of added (C) was 4g, and the effect of this parameter on the product properties was: at Ti 3 C 2 T x At a concentration of 17.0%, the resistivity was 2.23×10 4 Omega cm, compressive strength 135.2kPa, oxygen index 30.0%, vertical combustion V-0.
Example 12:
firstly, 3.0g of water and 3.0g of composite phosphate are added to 1.0g of etched Ti in sequence 3 C 2 T x Stirring uniformly to form mud; sequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol, 5.0g of TCPP and 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain a cream yellow color; then the mud-like Ti is added 3 C 2 T x Adding into cream yellow polyether polyol, stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive dual-property flexible polyurethane foam.
Through detection, the flame-retardant conductive dual-property flexible polyurethane foam prepared by the invention is black and is prepared from Ti 3 C 2 T x At a concentration of 4.0%, the resistivity was 6.51X10% 7 Omega cm, compression strength 126.2kPa, oxygen index 24.0%, vertical combustion V-1.
Example 13:
firstly, 3.0g of water and 3.0g of composite phosphate are added to 1.5g of etched Ti in sequence 3 C 2 T x Stirring uniformly to form mud; sequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol, 5.0g of TCPP and 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain a cream yellow color; then the mud-like Ti is added 3 C 2 T x Adding into cream yellow polyether polyol, stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive dual-property flexible polyurethane foam.
Through detection, the flame-retardant conductive dual-property flexible polyurethane foam prepared by the invention is black and is prepared from Ti 3 C 2 T x At a concentration of 6.0%, the resistivity was 3.54×10 6 Omega cm, compressive strength 128.1kPa, oxygen index 25.0%, vertical combustion V-1.
Example 14:
firstly, 3.0g of water and 3.0g of composite phosphate are added to 2.0g of etched Ti in sequence 3 C 2 T x Stirring uniformly to form mud; sequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol, 5.0g of TCPP and 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain a cream yellow color; then the mud-like Ti is added 3 C 2 T x Adding into cream yellow polyether polyol, stirring to obtain dark black; finally adding 5.0g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive dual-property flexible polyurethane foam.
Through detection, the flame-retardant conductive dual-property flexible polyurethane foam prepared by the invention is black and is prepared from Ti 3 C 2 T x At a concentration of 8.0%, the resistivity was 1.32X10% 5 Omega cm, compressive strength 130.7kPa, oxygen index 26.0%, vertical combustion V-1.
Example 15:
firstly, 3.0g of water and 3.0g of composite phosphate are added to 2.5g of etched Ti in sequence 3 C 2 T x Stirring uniformly to form mud; sequentially adding 0.1g of triethylene diamine, 0.1g of dodecyl dimethyl siloxane, 0.1g of KH-550,0.1g of ethylene glycol, 5.0g of TCPP and 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain a cream yellow color; then the mud-like Ti is added 3 C 2 T x Adding into cream yellow polyether polyol, stirring to obtain dark black; finally adding 5.0g of diisocyanate, setting the rotating speed to 1000r/min and the reaction time to 10s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive dual-property flexible polyurethane foam.
Through detection, the flame-retardant conductive dual-property flexible polyurethane foam prepared by the invention is black and is prepared from Ti 3 C 2 T x At a concentration of 8.0%, the resistivity was 8.65X10% 4 Omega cm, compressive strength 131.4kPa, oxygen index 28.0%, vertical burning V-1.
TABLE 1Ti 3 C 2 T x Relation between content and resistance of (C)
Table 2 cone calorimeter data
* TTI is ignition time, PHRR is maximum heat release rate, THR is total heat release amount, PSPR is maximum smoke yield, TSR is total smoke release amount, PCOPR is maximum CO release rate, PCO 2 PR is CO 2 Maximum release rate.

Claims (3)

1. The preparation method of the flame-retardant conductive double-property flexible polyurethane foam is characterized by comprising the following steps:
step 1: sequentially adding water and composite phosphate into etched Ti 3 C 2 T x Uniformly stirring to form mud;
step 2: sequentially adding triethylene diamine, dodecyl dimethyl siloxane, a silane coupling agent KH-550, ethylene glycol, double-effect baking powder, TCPP and diisocyanate into polyether polyol, and uniformly stirring to obtain a cream yellow color;
step 3: the mud-like Ti obtained in the step 1 is treated 3 C 2 T x Adding the mixture into the cream yellow polyether polyol system obtained in the step 2, and uniformly stirring and mixing the mixture to form dark black;
step 4: adding diisocyanate into the system in the step 3, uniformly stirring, and foaming to obtain flame-retardant conductive double-nature flexible polyurethane foam;
in the step 1, the adding amount of water is 1-6g, the adding amount of composite phosphate is 1-6g, and etched Ti 3 C 2 T x The addition amount of (2) is 3-4g; the composite phosphate contains eight components, namely sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium acid pyrophosphate and disodium dihydrogen pyrophosphate;
in the step 2, the addition amount of each raw material is as follows: 0.1-0.3g of triethylene diamine, 0.1-0.3g of dodecyl dimethyl siloxane, 0.1-0.3g of KH-550, 0.1-0.3g of glycol, 5g of TCPP, 1-2g of double effect baking powder, 0.5-1.0g of diisocyanate and 5-10g of polyether polyol.
2. The method of manufacturing according to claim 1, characterized in that:
in step 4, the amount of diisocyanate added is 5-10g.
3. The method of manufacturing according to claim 1, characterized in that:
the limiting oxygen index of the obtained polyurethane foam is 30.0%, the vertical burning level reaches V-0, and the resistivity is 10 4 Ω·cm。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103421302A (en) * 2013-09-06 2013-12-04 泉州源利鞋材有限公司 Inflaming-retarding antistatic anti-microbial soft polyurethane foam and preparing method thereof
JP2014047274A (en) * 2012-08-31 2014-03-17 Inoac Corp Polyurethane foam
CN112300363A (en) * 2020-11-17 2021-02-02 吉林省一一科技有限公司 MXene composite foam constructed based on polyurethane foaming principle and preparation method thereof
CN113861500A (en) * 2021-10-20 2021-12-31 安徽理工大学环境友好材料与职业健康研究院(芜湖) Preparation method of conductive rigid polyurethane foam

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014047274A (en) * 2012-08-31 2014-03-17 Inoac Corp Polyurethane foam
CN103421302A (en) * 2013-09-06 2013-12-04 泉州源利鞋材有限公司 Inflaming-retarding antistatic anti-microbial soft polyurethane foam and preparing method thereof
CN112300363A (en) * 2020-11-17 2021-02-02 吉林省一一科技有限公司 MXene composite foam constructed based on polyurethane foaming principle and preparation method thereof
CN113861500A (en) * 2021-10-20 2021-12-31 安徽理工大学环境友好材料与职业健康研究院(芜湖) Preparation method of conductive rigid polyurethane foam

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Cleaner production to a multifunctional polyurethane sponge with high fire safety and low toxicity release;Jingyi Lu;Journal of Cleaner Production;第333卷;130172 *
纳米碳材料改性聚氨酯泡沫的研究进展;李业光;贾洪;;炭素(第03期);15-17+38 *
蒙脱石剥离二维纳米片及其功能化应用;白皓宇;赵云良;王伟;张婷婷;宋少先;;矿产保护与利用;第39卷(第06期);101-111 *

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