CN114573785A - Preparation method of flame-retardant conductive double-property soft polyurethane foam - Google Patents

Preparation method of flame-retardant conductive double-property soft polyurethane foam Download PDF

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CN114573785A
CN114573785A CN202210258298.0A CN202210258298A CN114573785A CN 114573785 A CN114573785 A CN 114573785A CN 202210258298 A CN202210258298 A CN 202210258298A CN 114573785 A CN114573785 A CN 114573785A
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polyurethane foam
flame
diisocyanate
tcpp
baking powder
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CN114573785B (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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Abstract

The invention discloses a preparation method of flame-retardant conductive double-property soft polyurethane foam, which takes double-effect baking powder as a foaming agentTwo-dimensional Ti3C2TxThe material respectively has synergistic effect with the composite phosphate and TCPP to improve the conductivity and flame retardant property of the soft polyurethane foam. The flame-retardant conductive double-property soft polyurethane foam prepared by the invention has uniform foam pores; based on composite phosphate, baking powder and novel two-dimensional Ti3C2TxMaterials, which make the flexible polyurethane foam have a good continuous conductive network; based on two-dimensional Ti3C2TxThe material and TCPP have synergistic effect, so that the flexible polyurethane foam has good flame retardant effect.

Description

Preparation method of flame-retardant conductive double-property soft polyurethane foam
Technical Field
The invention relates to a preparation method of flame-retardant conductive double-property soft polyurethane foam, belonging to the technical field of material preparation.
Background
Polyurethane is short for polyurethane, and foam 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, industry, mechanical transmission parts, home furnishing, cosmetics, etc. However, the insulating flammability and the release of a large amount of smoke during combustion of polyurethane limit its industrial production and application. Therefore, it is necessary to improve flame retardancy and electrical conductivity of polyurethane. To date, research has shown that the addition of nanofillers is one of the effective ways to improve the flame retardancy of polyurethanes. Two-dimensional Ti3C2TxThe material being Ti3Etching products of AlC, Ti3C2TxHas excellent conductive, flame retardant, energy storage and other properties, so that Ti is obtained3C2TxHas good application prospect as the functional filler of polymer nano composite material。
The raw material of the polyol which is used in the transportation field at home and abroad is mainly polyether polyol, because the polyether polyol contains an ether bond structure, the mechanical property of the polyether polyol is obviously superior to that of the polyester polyol. The polyether polyols used in various fields are mainly sucrose type, sorbitol type, glycerin type and the like, and the functionality of the currently produced polyether polyols in China is two, three, four and the like.
Disclosure of Invention
The invention aims to provide a preparation method of flame-retardant conductive double-property soft polyurethane foam, which is prepared by two-dimensional Ti3C2TxThe material respectively has synergistic effect with the composite phosphate and TCPP to improve the conductivity and flame retardant property of the soft polyurethane foam.
The flame-retardant conductive double-property soft polyurethane foam prepared by the invention has uniform foam pores; based on composite phosphate, baking powder and novel two-dimensional Ti3C2TxMaterials, which make the flexible polyurethane foam have a good continuous conductive network; based on two-dimensional Ti3C2TxThe material and TCPP have synergistic effect, so that the flexible polyurethane foam has good flame retardant effect.
The preparation method of the flame-retardant conductive double-property soft polyurethane foam comprises the following steps:
step 1: adding water and composite phosphate into the etched Ti in sequence3C2TxStirring uniformly to form a mud shape; ti3C2TxThe etching process adopts a laboratory self-created etching method, and firstly, two-dimensional MAX (Ti)3AlC2) The surface activity of a two-dimensional system is improved in an auxiliary mode through ball milling, and MAX is etched by hydrochloric acid and lithium fluoride, so that two-dimensional Ti is obtained3C2TxMaterials, specific references: shen Tian, Guojun Cheng, Zhongfeng Tang, et al3C2TxMXenes 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), foaming powder (foaming agent), TCPP (flame retardant) and a certain amount of diisocyanate into polyether polyol, and uniformly stirring to obtain a milky yellow color;
and step 3: the muddy Ti obtained in the step 13C2TxAdding the obtained product into the cream yellow polyether polyol system obtained in the step (2), and stirring and mixing the obtained product uniformly to obtain dark black;
and 4, step 4: and (3) adding diisocyanate into the system obtained in the step (3), uniformly stirring, and foaming to obtain the flame-retardant conductive double-property soft polyurethane foam.
Further:
step 1: sequentially adding 1-5g of etched Ti into 1-6g of water and 1-6g of composite phosphate3C2TxStirring 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 cream yellow;
and step 3: the muddy Ti obtained in the step 13C2TxAdding the obtained product into the cream yellow polyether polyol system obtained in the step (2), and stirring and mixing the obtained product uniformly to obtain dark black;
and 4, step 4: 5-10g of diisocyanate is added into the system in the step 3, the set rotation speed is 1000-2000r/min, and the reaction time is 5-30 s; and pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive double-property soft 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, and the like. The composite phosphate used in the present invention was purchased from xu zhou tianan food additives limited. Wherein the sodium tripolyphosphate (Na)5P3O10) Mainly used as a moisture retention agent, the reaction equation: na (Na)5P3O10+2H2O＝2Na2HPO4+NaH2PO4. When no complex phosphate is added, only Ti is added3C2TxIn this case, the polyurethane cannot be foamed. Only adding composite phosphate and Ti simultaneously3C2TxIn the meantime, the polyurethane can be foamed. Ti of different masses (1g, 2g, 3g, 4g)3C2TxDissolved in 3g of water to form a 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, Ti3C2TxThe solution is in the form of a wet paste, which is the most effective.
One of the main causes of foam molding of polyurethane is the generation of carbon dioxide. The invention adopts the double-effect baking powder as the foaming agent to foam the polyurethane for the first time, and the used double-effect baking powder is purchased from a flavouring-benefiting company Limited in Leling. The prior art does not adopt the baking powder as the foaming agent, namely, the foaming rate of the baking powder can not be controlled. The foaming rate of the baking powder is related to the mass of the baking powder, and if the baking powder has small mass, a certain multiplying power cannot be achieved to form a certain height; if the mass of the baking powder is larger, although the baking powder may form a certain height, the foam holes are coarse and fragile, and the desired effect cannot be achieved. A new formula is formed by the relationship between the proportion of the foaming powder and the content of other substances, so that a certain multiplying power can be ensured, and uniform foam holes can also be ensured. Secondly, the baking powder can react spontaneously when meeting water to generate carbon dioxide. This requires the disposal of the baking powder and water relationship, and the method has two methods: the first method can be to add the baking powder, stir and then add water; in the second method, baking powder and water are opened, and then stirring is performed. Taken together, the present invention employs a second approach.
The baking powder mainly comprises disodium dihydrogen pyrophosphate (35%) and sodium bicarbonate (45%), and is contacted with water, and then acidic powder (hydrogen ions ionized from disodium dihydrogen pyrophosphate) and alkaline powder (bicarbonate ions) are dissolved in water and react to release carbon dioxide (CO)2) (ii) a On the other hand, during the exothermic reaction, carbonic acidThe sodium bicarbonate releases water and carbon dioxide, which cause the polyurethane to expand. The baking powder is double-effect baking powder, and in the quick reaction, the baking powder starts to act when dissolved in water, and in the slow reaction, the baking powder starts to act in the heating process. Therefore, the baking powder functions as a foaming agent in the present invention.
Through detection, the prepared double-property soft polyurethane foam is black, pure polyurethane is the property of an insulating material, and the resistivity is more than 1010Ω · cm, limiting oxygen index 17.0. When Ti is present3C2TxWhen the concentration of the polyurethane foam is 12.0-17.0%, the polyurethane foam has a limit oxygen index of 30.0% and a vertical combustion level of V-0 under the synergistic effect with TCPP; resistivity of 104Omega cm or so, and the conductivity does not decrease with time.
Compared with other methods, the method has the beneficial effects that:
1. the flame-retardant conductive double-property soft 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 can not be reduced along with the prolonging of time.
Drawings
FIG. 1 photograph of the alcohol burner burning process (a is the original form of the foamed polyurethane, b is the foamed polyurethane containing 20.0% TCPP, c is the foamed polyurethane containing 10.0% Ti3C2TxA foamed polyurethane).
FIG. 2 photograph showing the burning process of alcohol burner (a is 5.0% Ti content)3C2TxA foamed polyurethane, b is a polyurethane containing 7.5% Ti3C2TxA foamed polyurethane, c is a polyurethane containing 10.0% of Ti3C2TxFoamed polyurethane, d is 12.5% Ti3C2TxA foamed polyurethane).
FIG. 3 contains 5.0% Ti3C2TxThe photographs of the foamed polyurethane of (2) were taken for combustion at different expansion ratios (the expansion ratio of e was 11.5, and the expansion ratio of f was 16.6).
FIG. 4 scanning Electron micrographs (a1 and a2 for polyurethane foams before combustion)A3 and a4 are post-combustion foaming polyurethanes; b1 and b2 are pre-combustion foamed polyurethanes containing 20.0% TCPP, and b3 and b4 are post-combustion foamed polyurethanes containing 20.0% TCPP; c1 and c2 are 10.0% Ti3C2TxPre-combustion foamed polyurethane, c3 and c4 being 10.0% Ti3C2TxPost-combustion foamed polyurethane).
FIG. 5 thermogravimetric curve of foamed polyurethane (in which the TCPP content is 20.0%, Ti)3C2TxContent 10.0%).
FIG. 6 Total Smoke Release (TSR) and Total Heat Release (THR) curves for foamed polyurethane.
Detailed Description
The preparation method of the flame-retardant conductive double-property soft polyurethane foam comprises the following steps:
step 1: sequentially adding 1-5g of etched Ti into 1-6g of water and 1-6g of composite phosphate3C2TxStirring 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 cream yellow;
and 3, step 3: the muddy Ti obtained in the step 13C2TxAdding the obtained product into the cream yellow polyether polyol system obtained in the step (2), and stirring and mixing the obtained product uniformly to obtain dark black;
and 4, step 4: adding 5-10g of diisocyanate into the system in the step 3, setting the rotating speed to be 1000-2000r/min, and setting the reaction time to be 5-30 s; and pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive double-property soft polyurethane foam.
The technical solution of the present invention is further illustrated by the following specific examples. The polyether polyol used in the examples was a 4110 type polyether polyol available from Kyowa chemical Co., Ltd.
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 milky yellow product; finally, adding 5g of diisocyanate, setting the rotating speed to be 1000r/min, and setting the reaction time to be 10 s; and 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 light yellow, is an insulating material, and has the resistivity of more than 1010Omega cm, a limiting oxygen index of 17.0%, an expansion ratio of 25.0, and a compressive strength of 62.2 kPa.
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 product; finally, adding 5.0g of diisocyanate, setting the rotating speed to be 1000r/min and the reaction time to be 10 s; and 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 1010Omega cm. At a TCPP concentration of 17.0%, 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 cream yellow; finally, adding 5.0g of diisocyanate, setting the rotating speed to be 1000r/min and the reaction time to be 10 s; and pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant flexible polyurethane foam.
The polyurethane foam prepared by the invention is creamy yellow and has the resistivity larger than 1010Omega cm. When the concentration of TCPP was 20.0%, 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 be 1000r/min and the reaction time to be 10 s; and 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 1010Omega cm. When the concentration of TCPP was 22.5%, the oxygen index was 27.0% and the expansion ratio was 22.0.
Example 5:
first, 3.0g of water and 3.0g of composite phosphate were added to 1.0g of etched Ti in this order3C2TxStirring 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 creamy yellow; then adding the mud-like Ti3C2TxAdding into cream yellow polyether polyol, and stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to be 1000r/min and the reaction time to be 10 s; and pouring the obtained material into a mould, curing and demoulding to obtain the flame-retardant conductive dual-property hard polyurethane foam.
Through detection, the flame-retardant conductive double-property soft polyurethane foam prepared by the invention is black, and is coated on Ti3C2TxAt a concentration of 5.0%, the resistivity was 1X 105Omega cm, oxygen index of 22.0%, foaming ratio of 7.0.
Example 6:
first, 3.0g of water and 3.0g of composite phosphate were added to 1.5g of etched Ti in this order3C2TxStirring 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 cream yellow; then adding the mud-like Ti3C2TxPutting into cream yellow polyether polyol, and stirring to obtain dark black; finally, 5.0g of diisocyanate is added, the set rotating speed is 1000r/min,the reaction time is 10 s; and pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive double-property soft polyurethane foam.
Through detection, the flame-retardant conductive double-property soft polyurethane foam prepared by the invention is black, and is coated on Ti3C2TxAt a concentration of 7.5%, the resistivity was 8X 104Omega cm, oxygen index of 22.5%, foaming ratio of 6.0.
Example 7:
first, 3.0g of water and 3.0g of composite phosphate were added to 2.0g of etched Ti in this order3C2TxStirring 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 cream yellow; then adding the mud-like Ti3C2TxAdding into cream yellow polyether polyol, and stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to be 1000r/min and the reaction time to be 10 s; and pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive double-property soft polyurethane foam.
Through detection, the flame-retardant conductive double-property soft polyurethane foam prepared by the invention is black, and is coated on Ti3C2TxAt a concentration of 10.0%, the resistivity was 5X 104Omega cm, an oxygen index of 23.0%, and an expansion ratio of 7.0.
Example 8:
first, 3.0g of water and 3.0g of composite phosphate were added to 3.0g of etched Ti in this order3C2TxStirring 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 cream yellow; then the muddy Ti3C2TxAdding into cream yellow polyether polyol, and stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to be 1000r/min and the reaction time to be 10 s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive double-layerFlexible polyurethane foams.
Through detection, the flame-retardant conductive double-property soft polyurethane foam prepared by the invention is black, and is coated on Ti3C2TxAt a concentration of 12.5%, the resistivity was 2.2X 104Omega cm, an oxygen index of 25.0%, and an expansion ratio of 7.0.
Example 9:
first, 3.0g of water and 3.0g of composite phosphate were added to 3.0g of etched Ti in this order3C2TxStirring 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, 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain cream yellow; then adding the mud-like Ti3C2TxAdding into cream yellow polyether polyol, and stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to be 1000r/min and the reaction time to be 10 s; and pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive double-property soft polyurethane foam.
Through detection, the flame-retardant conductive double-property soft polyurethane foam prepared by the invention is black, and is coated on Ti3C2TxAt a concentration of 12.0%, the resistivity was 5.46X 104Omega cm, compressive strength 133.2kPa, oxygen index 30.0%, vertical burning V-0.
Example 10:
first, 3.0g of water and 3.0g of composite phosphate were added to 3.5g of etched Ti in this order3C2TxStirring uniformly into 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, 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain cream yellow; then the muddy Ti3C2TxAdding into cream yellow polyether polyol, and stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to be 1000r/min and the reaction time to be 10 s; and pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive double-property soft polyurethane foam.
Through detection, the flame-retardant conductive double-property soft polyurethane foam prepared by the invention is black, and is coated on Ti3C2TxAt a concentration of 15.0%, the resistivity was 5.13X 104Omega cm, compressive strength 132.2kPa, oxygen index of 30.0%, vertical burning is V-0.
Example 11:
first, 3.0g of water and 3.0g of composite phosphate were added to 4.0g of etched Ti in this order3C2TxStirring 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, 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain cream yellow; then adding the mud-like Ti3C2TxAdding into cream yellow polyether polyol, and stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to be 1000r/min and the reaction time to be 10 s; and pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive double-property soft polyurethane foam.
The flame-retardant conductive double-property soft polyurethane foam prepared by the invention is black through detection, and is coated on Ti3C2TxAt a concentration of 17.0%, the resistivity was 2.23X 104Omega cm, a compressive strength of 135.2kPa, an oxygen index of 30.0%, and a vertical burning of V-0.
In examples 9 to 11, Ti was adjusted without changing the amount of TCPP added (5g)3C2TxThe content of (a).
In example 9, Ti3C2TxThe addition amount is 3g, and the influence of the parameters on the product performance is as follows: at Ti3C2TxAt a concentration of 12.0%, the resistivity was 5.46X 104Omega cm, compressive strength 133.2kPa, oxygen index 30.0%, vertical burning V-0. In example 10, Ti3C2TxIs 3.5g, the influence of this parameter on the product properties is: at Ti3C2TxAt a concentration of 15.0%, the resistivity was 5.13X 104Omega cm, compressive strength 132.2kPa, oxygen index of30.0%, and the vertical combustion is V-0. In example 11, Ti3C2TxIs 4g, the influence of the parameters on the product performance is as follows: at Ti3C2TxAt a concentration of 17.0%, the resistivity was 2.23X 104Omega cm, a compressive strength of 135.2kPa, an oxygen index of 30.0%, and a vertical burning of V-0.
Example 12:
first, 3.0g of water and 3.0g of composite phosphate were added to 1.0g of etched Ti in this order3C2TxStirring 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, 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain cream yellow; then adding the mud-like Ti3C2TxAdding into cream yellow polyether polyol, and stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to be 1000r/min and the reaction time to be 10 s; and pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive double-property soft polyurethane foam.
Through detection, the flame-retardant conductive double-property soft polyurethane foam prepared by the invention is black, and is coated on Ti3C2TxAt a concentration of 4.0%, the resistivity was 6.51X 107Omega cm, compressive strength 126.2kPa, oxygen index 24.0%, vertical burning V-1.
Example 13:
first, 3.0g of water and 3.0g of composite phosphate were added to 1.5g of etched Ti in this order3C2TxStirring 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, 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain cream yellow; then adding the mud-like Ti3C2TxAdding into cream yellow polyether polyol, and stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to be 1000r/min and the reaction time to be 10 s; pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive double-soft materialA polyurethane foam.
Through detection, the flame-retardant conductive double-property soft polyurethane foam prepared by the invention is black, and is coated on Ti3C2TxAt a concentration of 6.0%, the resistivity was 3.54X 106Omega cm, compressive strength 128.1kPa, oxygen index 25.0%, vertical burning V-1.
Example 14:
first, 3.0g of water and 3.0g of composite phosphate were added to 2.0g of etched Ti in this order3C2TxStirring 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, 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain cream yellow; then adding the mud-like Ti3C2TxAdding into cream yellow polyether polyol, and stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to be 1000r/min and the reaction time to be 10 s; and pouring the obtained material into a mold, curing and demolding to obtain the flame-retardant conductive double-property soft polyurethane foam.
Through detection, the flame-retardant conductive double-property soft polyurethane foam prepared by the invention is black, and is coated on Ti3C2TxAt a concentration of 8.0%, the resistivity was 1.32X 105Omega cm, compressive strength 130.7kPa, oxygen index 26.0%, vertical burning V-1.
Example 15:
first, 3.0g of water and 3.0g of composite phosphate were added to 2.5g of etched Ti in this order3C2TxStirring 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, 1.0g of baking powder and 0.5g of diisocyanate into 5.0g of polyether polyol, and uniformly stirring to obtain cream yellow; then adding the mud-like Ti3C2TxAdding into cream yellow polyether polyol, and stirring to obtain dark black; finally, adding 5.0g of diisocyanate, setting the rotating speed to be 1000r/min and the reaction time to be 10 s; pouring the obtained material into a mould, curing and demoulding to prepare the flame-retardant conductive double-property soft polyurethane foam。
The flame-retardant conductive double-property soft polyurethane foam prepared by the invention is black through detection, and is coated on Ti3C2TxAt a concentration of 8.0%, the resistivity was 8.65X 104Omega cm, compressive strength 131.4kPa, oxygen index 28.0%, vertical burning V-1.
TABLE 1Ti3C2TxContent of (2) in relation to the resistance
Figure BDA0003549256930000091
TABLE 2 Cone calorimeter data
Figure BDA0003549256930000092
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, PCO2PR is CO2The maximum release rate.

Claims (7)

1. A preparation method of flame-retardant conductive double-property flexible polyurethane foam is characterized by comprising the following steps:
double-effect baking powder is used as a foaming agent and passes through two-dimensional Ti3C2TxThe material respectively has synergistic effect with the composite phosphate and TCPP to improve the conductivity and flame retardant property of the soft polyurethane foam.
2. The method of claim 1, comprising the steps of:
step 1: adding water and composite phosphate into the etched Ti in sequence3C2TxStirring uniformly to form a mud shape;
step 2: sequentially adding triethylene diamine, dodecyl dimethyl siloxane, a silane coupling agent KH-550, ethylene glycol, baking powder, TCPP and diisocyanate into polyether polyol, and uniformly stirring to obtain a milky yellow color;
and step 3: the muddy Ti obtained in the step 13C2TxAdding the obtained product into the cream yellow polyether polyol system obtained in the step (2), and stirring and mixing the obtained product uniformly to obtain dark black;
and 4, step 4: and (3) adding diisocyanate into the system obtained in the step (3), uniformly stirring, and foaming to obtain the flame-retardant conductive double-property soft polyurethane foam.
3. The method of claim 2, wherein:
in the step 1, the addition amount of water is 1-6g, the addition amount of composite phosphate is 1-6g, and etched Ti3C2TxThe amount of (B) is 1-5 g.
4. The method of claim 2, wherein:
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-5500.1, 0.1-0.3g of glycol, 1-10g of TCPP, 1-2g of baking powder, 0.5-1.0g of diisocyanate and 5-10g of polyether polyol.
5. The method of claim 2, wherein:
in step 4, the amount of diisocyanate added is 5 to 10 g.
6. The production method according to claim 2, 3, 4 or 5, characterized in that:
the amount of TCPP added was 5g, and etched Ti3C2TxThe amount of (B) is 3-4 g.
7. The method of manufacturing according to claim 6, characterized in that:
the prepared polyurethane foam has the limiting oxygen index of 30.0 percent, the vertical combustion level of V-0 and the resistivity of 104Ω·cm。
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