CN113667293B - Flame-retardant polyurethane high-tenacity rubber prepolymer and preparation method thereof - Google Patents
Flame-retardant polyurethane high-tenacity rubber prepolymer and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of polyurethane products, and particularly discloses a flame-retardant polyurethane high-tenacity rubber prepolymer and a preparation method thereof. The flame-retardant polyurethane acrylic adhesive prepolymer comprises the following components in parts by weight: 30-50 parts of isocyanate, 50-70 parts of polyester polyol, 40-60 parts of phosphorus-containing cellulose fiber, 30-50 parts of coal gangue micro powder, 2.4-2.8 parts of catalyst and 4-8 parts of silane coupling agent. When the flame-retardant polyurethane acrylic rubber prepolymer is ignited by flame, phosphoric acid generated by decomposing the phosphorus-containing cellulose fiber can generate a carbonized film on the surface of the flame-retardant polyurethane acrylic rubber prepolymer, the phosphorus-containing cellulose fiber and the gangue micro powder increase the adhesive force of the carbonized film, reduce the possibility of falling of the carbonized film and improve the flame retardant property of the flame-retardant polyurethane acrylic rubber prepolymer.
Description
Technical Field
The application relates to the technical field of polyurethane products, in particular to a flame-retardant polyurethane high-tenacity rubber prepolymer and a preparation method thereof.
Background
The polyurethane high-tenacity rubber is also called polyurethane PU elastomer, and has good strength and small compression deformation. A new material between plastic and rubber. Polyurethane acrylic rubber has both the rigidity of plastics and the elasticity of rubber, so that the polyurethane acrylic rubber is widely applied to industrial production.
In the related art, a flame-retardant polyurethane high-tenacity rubber prepolymer comprises the following components in parts by weight: 30-50 parts of isocyanate, 50-70 parts of polyester polyol, 2.4-2.8 parts of catalyst and 10-14 parts of phosphate flame retardant, wherein the phosphate flame retardant is at least one of tricresyl phosphate, triisopropylphenyl phosphate and cresyldiphenyl phosphate. The preparation method of the flame-retardant polyurethane acrylic adhesive prepolymer comprises the following steps: (1) Mixing polyester polyol with a catalyst, preheating the mixture at 100-150 ℃, maintaining the vacuum degree at-0.08 to-0.1 MPa during preheating, and preheating for 2-3h to obtain a preheated mixture; (2) Adding phosphate flame retardant and isocyanate into the preheated mixture, uniformly mixing, reducing the temperature of a reaction system to 60-80 ℃, and continuously reacting for 2-2.5h to obtain the flame-retardant polyurethane acrylic adhesive prepolymer. When the flame-retardant polyurethane high-impact adhesive prepolymer is burnt by flame, the phosphate ester flame retardant is converted into phosphoric acid, and the phosphoric acid carbonizes the flame-retardant polyurethane high-impact adhesive prepolymer, so that a carbonized film is generated on the surface of a fire-starting part of the flame-retardant polyurethane high-impact adhesive prepolymer, and the carbonized film isolates the flame-retardant polyurethane high-impact adhesive prepolymer from air, thereby achieving the flame-retardant effect.
In view of the above-mentioned related technologies, the inventor believes that the carbonized film can play a flame retardant role, but the thermal expansion coefficients of the carbonized film and the flame retardant polyurethane high-impact adhesive prepolymer are not consistent, and when the flame retardant polyurethane high-impact adhesive prepolymer is continuously burned by flame, the carbonized film is easy to fall off from the surface of the flame retardant polyurethane high-impact adhesive prepolymer due to deformation, which easily causes the flame retardant effect of the flame retardant polyurethane high-impact adhesive prepolymer to be reduced.
Disclosure of Invention
In the related art, when the flame-retardant polyurethane acrylic rubber prepolymer is burnt for a long time, the carbonized film is easy to fall off, and the flame-retardant effect of the flame-retardant polyurethane acrylic rubber prepolymer is influenced. In order to overcome the defect, the application provides a flame-retardant polyurethane acrylic adhesive prepolymer and a preparation method thereof.
In a first aspect, the application provides a flame retardant polyurethane high-tenacity rubber prepolymer, which adopts the following technical scheme:
the flame-retardant polyurethane acrylic rubber prepolymer comprises the following components in parts by weight: 30-50 parts of isocyanate, 50-70 parts of polyester polyol, 40-60 parts of phosphorus-containing cellulose fiber, 30-50 parts of coal gangue micro powder, 2.4-2.8 parts of catalyst and 4-8 parts of silane coupling agent.
By adopting the technical scheme, compared with the related technology, on the basis of a polyurethane matrix generated by the reaction of isocyanate and polyester polyol, phosphorus-containing cellulose fiber and coal gangue micropowder are added, and the coal gangue micropowder is subjected to hydrophobic modification by using a silane coupling agent to prepare the flame-retardant polyurethane high-tenacity adhesive prepolymer.
The coal gangue micro powder consists of carbon particles and silicate particles, when the prepolymer of the flame-retardant polyurethane acrylic adhesive prepolymer is burnt, the carbon particles on the surface of the polyurethane matrix are burnt, oxygen is consumed in the burning process, and the external oxygen is isolated from the polyurethane matrix by carbon dioxide generated by burning, so that the spreading rate of flame is slowed down. While the carbon particles are combusted, the end of the phosphorus-containing cellulose fiber near the flame is decomposed into cellulose residues and phosphoric acid. The phosphoric acid has strong dehydration property, and simultaneously dehydrates the polyurethane matrix and the cellulose residue at the flame burning position, and finally forms a carbonized film on the surface of the polyurethane matrix. When the cellulose residue is carbonized, the end of the phosphorus-containing cellulose fiber far away from the carbonized film is still kept intact, so that the phosphorus-containing cellulose fiber has an anchoring effect on the carbonized film. Silicate particles in the coal gangue provide a large number of attachment sites for the carbonized film, and the contact area between the carbonized film and the polyurethane matrix is increased, so that the possibility of falling off of the carbonized film is reduced, and the flame retardant effect of the flame retardant polyurethane acrylic adhesive prepolymer is improved.
Preferably, the flame-retardant polyurethane acrylic rubber prepolymer comprises the following components in parts by weight: 45-55 parts of isocyanate, 45-55 parts of phosphorus-containing cellulose fiber, 35-45 parts of coal gangue micropowder, 2.5-2.7 parts of catalyst and 5-7 parts of silane coupling agent.
By adopting the technical scheme, the proportion of the flame-retardant polyurethane high-impact adhesive prepolymer is optimized, and the flame-retardant effect of the flame-retardant polyurethane high-impact adhesive prepolymer is favorably improved.
Preferably, the preparation method of the phosphorus-containing cellulose fiber comprises the following steps:
(1) Weighing cellulose fibers and phosphorus oxychloride, dissolving the phosphorus oxychloride and the cellulose fibers in dichloromethane, and uniformly stirring, wherein the weight ratio of the cellulose fibers to the phosphorus oxychloride is (2-2.4): 1;
(2) Heating dichloromethane in water bath at 32-38 deg.C for 3-5 hr, stopping heating, and distilling to remove dichloromethane to obtain phosphorus-containing cellulose fiber.
By adopting the technical scheme, chlorine atoms in the phosphorus oxychloride can capture hydrogen atoms in the cellulose fibers, and the phosphorus atoms are grafted to the cellulose fibers, so that the phosphorus-containing cellulose fibers can be obtained.
Preferably, the formula of the flame-retardant polyurethane acrylic rubber prepolymer also comprises 18-24 parts by weight of microcapsules, and the formula of the microcapsules comprises the following raw materials in parts by weight: 20-40 parts of persulfate, 40-60 parts of stearic acid and 30-50 parts of bentonite, wherein the stearic acid is used for coating the persulfate and the bentonite.
By adopting the technical scheme, when the flame-retardant polyurethane acrylic rubber prepolymer is prepared, the microcapsules are dispersed in a polyurethane matrix. When the polyurethane matrix is burned by flame, the stearic acid is heated and melted, and absorbs heat in the melting process, so that the heating speed of the polyurethane matrix is slowed down. After the stearic acid is melted, persulfate is diffused to the outside of the microcapsule, persulfate in the persulfate is heated and activated and decomposed to generate sulfate radical free radicals, and the sulfate radical free radicals can capture high-energy free radicals generated around flame, so that the possibility of damage of the high-energy free radicals to a carbonized film is reduced, and the flame retardant effect of the flame retardant polyurethane high-tenacity adhesive prepolymer is improved.
Preferably, the preparation method of the microcapsule comprises the following steps:
(1) Mixing stearic acid and absolute ethyl alcohol, and stirring at 50-60 ℃ until the stearic acid is dissolved to obtain a base solution;
(2) And adding persulfate and bentonite into the base solution, performing ultrasonic dispersion for 10-15min, cooling the base solution, and performing vacuum drying on the base solution at the temperature of lower than 35 ℃ to obtain persulfate microcapsules.
By adopting the technical scheme, firstly, ethanol is used as a solvent to disperse stearic acid, then bentonite is used as a carrier of persulfate, and then the stearic acid is solidified by cooling and drying, so that the bentonite can be coated, and the microcapsule is prepared.
Preferably, the bentonite has an average particle size of 6 to 10 μm.
By adopting the technical scheme, when the average particle size of the bentonite is too small, the microcapsules are easy to break in the processing process, so that the persulfate is lost. When the average particle size of the bentonite is too large, the rate of releasing persulfate by the microcapsule under the burning condition is slow, and the capture effect of persulfate on high-energy free radicals is influenced. When the average particle size of the bentonite is 16-20 microns, the persulfate is not easy to run off, and the microcapsule releases the persulfate faster under the burning condition, so that the flame-retardant polyurethane acrylic adhesive prepolymer has a better flame-retardant effect.
Preferably, the formula of the microcapsule also comprises 4-8 parts of embedding auxiliary agent, wherein the embedding auxiliary agent is pyrrole, and the embedding auxiliary agent is mixed with absolute ethyl alcohol in the step (1) of preparing the microcapsule.
Through adopting above-mentioned technical scheme, the persulfate is the initiator of pyrrole polymerization, and at microcapsule shaping in-process, pyrrole polymerization forms polypyrrole under the effect of persulfate, and polypyrrole carries out the shutoff to the hole on bentonite surface to strengthened the adsorption effect of bentonite to the persulfate, reduced the possibility that the persulfate takes place to run off, help improving the flame retardant efficiency of fire retardant polyurethane acrylic rubber prepolymer.
Preferably, the formula of the flame-retardant polyurethane acrylic rubber prepolymer also comprises 4-8 parts by weight of calcium citrate.
By adopting the technical scheme, when the flame-retardant polyurethane acrylic rubber prepolymer is burnt by flame, calcium ions in the calcium citrate are combined with phosphoric acid generated by decomposition of phosphorus-containing cellulose fibers, and calcium phosphate is formed in the carbonized film, so that the density of the carbonized film is increased, and the oxygen isolation effect of the carbonized film is improved. Meanwhile, carbon particles generated by thermal decomposition of the citrate are combined with the carbonized film, so that the thickness of the carbonized film is increased, and the flame-retardant effect of the flame-retardant polyurethane acrylic adhesive prepolymer is improved.
Preferably, the formula of the flame-retardant polyurethane acrylic rubber prepolymer also comprises 4-8 parts by weight of zirconium oxychloride.
By adopting the technical scheme, when the flame-retardant polyurethane acrylic rubber prepolymer is burned by flame, zirconium oxychloride is decomposed to generate zirconium dioxide and hydrogen chloride, the hydrogen chloride is adsorbed by a silicate component in coal gangue micropowder, and the zirconium dioxide reacts with a carbonized film to generate zirconium carbide and carbon dioxide. The defects of the carbonized film are repaired by the zirconium carbide, and the carbon dioxide is helpful for removing oxygen around the flame, so that the flame retardant effect of the flame retardant polyurethane acrylic adhesive prepolymer is improved.
In a second aspect, the application provides a preparation method of a flame-retardant polyurethane acrylic adhesive prepolymer, which adopts the following technical scheme.
A preparation method of a flame-retardant polyurethane acrylic adhesive prepolymer comprises the following steps:
(1) Mixing polyester polyol, a catalyst, coal gangue micropowder and a silane coupling agent under an anaerobic condition, preheating the mixture at 100-150 ℃, wherein the preheating time is 2-3h, and obtaining a preheated mixture after preheating is finished;
(2) Adding isocyanate and phosphorus-containing cellulose fiber into the preheated mixture, uniformly mixing, reducing the temperature of a reaction system to 60-80 ℃, and continuously reacting for 2-2.5h to obtain the flame-retardant polyurethane acrylic adhesive prepolymer.
By adopting the technical scheme, compared with the preparation method in the related technology, the preparation method does not need to dry the polyester polyol in the preheating process, but utilizes the moisture generated by the polyester polyol in the preheating process to activate the silane coupling agent, the activated silane coupling agent carries out hydrophobic modification on the surface of the coal gangue micro powder, the redundant moisture is converted into crystal water in the coal gangue micro powder, the moisture in the polyester polyol is consumed, and the silane coupling agent does not need to be separately activated, so that the processing efficiency is favorably improved.
In summary, the present application has the following beneficial effects:
1. when the flame-retardant polyurethane high-tenacity adhesive prepolymer is burnt by flame, carbon dioxide generated by burning carbon particles in coal gangue micro powder isolates oxygen, phosphoric acid generated by decomposing phosphorus-containing cellulose fiber enables polyurethane ester to form a carbonized film, the residual part of the phosphorus-containing cellulose fiber anchors the carbonized film, and silicate particles in the coal gangue micro powder provide attachment points for the carbonized film, so that the flame retardant property of the flame-retardant polyurethane high-tenacity adhesive prepolymer is improved.
2. In the application, calcium citrate is preferably selected as one of the raw materials of the flame-retardant polyurethane high-performance adhesive prepolymer, calcium ions in the calcium citrate can be combined with phosphoric acid to form calcium phosphate, the density of the carbonized film is increased, carbon particles generated by thermal decomposition of citrate increase the thickness of the carbonized film, and the flame retardant property of the flame-retardant polyurethane high-performance adhesive prepolymer is favorably improved.
3. According to the method, polyester polyol, a catalyst, coal gangue micro powder and a silane coupling agent are mixed and then preheated, the silane coupling agent is activated by water lost by the polyester polyol, the surface of the coal gangue micro powder is subjected to hydrophobic modification by the activated silane coupling agent, and the excessive water is converted into crystal water in the coal gangue micro powder, so that the water in the polyester polyol can be consumed, and the silane coupling agent does not need to be activated independently, so that the processing efficiency is improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation of phosphorus-containing cellulose fiber
Preparation example 1 is described below as an example.
Preparation example 1
The raw materials used in the preparation examples can be obtained commercially, wherein the cellulose fiber is the cellulose fiber sold by Shandong Xingmao engineering materials, the phosphorus oxychloride is the phosphorus oxychloride produced by Shandong' an Qianghua chemical industry, and the dichloromethane is the industrial dichloromethane produced by Jinan Xinkubai chemical industry, etc. The phosphorus-containing cellulose fiber is prepared according to the following method:
(1) Weighing cellulose fibers and phosphorus oxychloride, dissolving the phosphorus oxychloride and the cellulose fibers in dichloromethane, and uniformly stirring, wherein the weight ratio of the cellulose fibers to the phosphorus oxychloride is 1.8:1;
(2) And (3) heating the dichloromethane in water bath at the temperature of 35 ℃, stopping heating after heating for 4 hours, and distilling to remove the dichloromethane to obtain the phosphorus-containing cellulose fibers.
As shown in Table 1, production examples 1 to 5 were different in the weight ratio of the cellulose fibers to phosphorus oxychloride.
TABLE 1
Preparation example of microcapsules
Preparation example 6 is described below as an example.
Preparation example 6
The raw materials used in the preparation examples can be obtained from the market, wherein stearic acid is produced by Shandong Xin Chili chemical engineering Co., ltd, absolute ethyl alcohol is 99.9 absolute ethyl alcohol produced by Shandong Xin Heng chemical engineering Co., ltd, persulfate is sodium persulfate produced by Shandong Juxin Heng chemical trade Co., ltd, bentonite is natural bentonite sold by Yongshun mineral product processing factory in Lingshou county, and pyrrole is purchased from Jiangsu Qingquan chemical corporation Ltd. The phosphorus-containing cellulose fiber is prepared by the following method:
(1) Mixing 40kg of stearic acid and 120kg of absolute ethyl alcohol, and stirring at 55 ℃ until the stearic acid is dissolved to obtain a base solution;
(2) Adding 20kg of sodium persulfate and 30kg of bentonite into the base liquid, performing ultrasonic dispersion for 12min, then cooling the base liquid, and performing vacuum drying on the base liquid at the temperature of lower than 35 ℃ to obtain persulfate microcapsules, wherein the bentonite is subjected to grinding treatment, and the average particle size of the bentonite is 4 microns.
As shown in Table 2, the production examples 6 to 10 were different in the compounding ratio of the microcapsules.
TABLE 2
| Sample(s) | Sodium persulfate/kg | Bentonite/kg | Stearic acid/kg |
| Preparation example 6 | 20 | 30 | 40 |
| Preparation example 7 | 25 | 35 | 45 |
| Preparation example 8 | 30 | 40 | 50 |
| Preparation example 9 | 35 | 45 | 55 |
| Preparation example 10 | 40 | 50 | 60 |
As shown in Table 3, production examples 11 to 14 differ from production example 8 in the average particle size of bentonite.
TABLE 3
Preparation example 15
The difference between the preparation example and the preparation example 12 is that the microcapsule formula also comprises 4kg of embedding aid, the embedding aid is pyrrole, and the embedding aid is mixed with absolute ethyl alcohol in the step (1).
As shown in Table 3, production examples 15 to 19 differ in the amount of pyrrole used.
TABLE 4
| Sample(s) | Preparation example 15 | Preparation example 16 | Preparation example 17 | Preparation example 18 | Preparation example 19 |
| Pyrrole/kg | 4 | 5 | 6 | 7 | 8 |
Examples
The raw materials used in the embodiment of the application can be obtained commercially, the polyester polyol is industrial polyester polyol (EGPG) produced by Shandong Liang New Material science and technology Limited, the catalyst is CUCAT-RC10 polyurethane catalyst produced by Guangzhou Yoghun synthetic materials Limited, the coal gangue is coal gangue sold by Yongze Industrial and trade Limited, the silane coupling agent is silane coupling agent KH-602 produced by Nanjing Quanxi chemical industry Limited, the isocyanate is hexamethylene diisocyanate produced by Shandong Kepler Biotechnology Limited, the calcium citrate is purchased from Jinyue chemical industry Limited, and the zirconium oxychloride is purchased from Shanghangji Industrial chemical industry Limited.
Examples 1 to 5
The following description will be given by taking example 1 as an example.
Example 1
The flame-retardant polyurethane acrylic rubber prepolymer in the embodiment 1 is prepared according to the following steps:
(1) Mixing 50kg of polyester polyol, 2.4kg of catalyst, 30kg of coal gangue micro powder and 4kg of silane coupling agent under an anaerobic condition, preheating the mixture at 135 ℃, wherein the preheating time is 2.5h, and obtaining a preheated mixture after the preheating is finished, wherein the coal gangue micro powder is a crushed product of coal gangue, and the average particle size of the coal gangue micro powder is 3 mu m;
(2) And adding 30kg of isocyanate and 40kg of the phosphorus-containing cellulose fiber prepared in the preparation example 1 into the preheated mixture, uniformly mixing, cooling the temperature of a reaction system to 70 ℃, and continuously reacting for 2.2 hours to obtain the flame-retardant polyurethane acrylic adhesive prepolymer.
As shown in Table 5, examples 1 to 5 differ mainly in the ratio of raw materials
TABLE 5
As shown in Table 6, example 3 differs from examples 6 to 9 mainly in the preparation of the phosphorus-containing cellulose fibers.
TABLE 6
Example 10
The difference between this example and example 7 is that the formulation of the flame retardant polyurethane acrylic adhesive prepolymer further includes 18kg of microcapsules, and the microcapsules prepared in preparation example 6 are selected as the microcapsules.
As shown in Table 7, examples 10 to 23 differ mainly in the microcapsule preparation examples.
TABLE 7
As shown in Table 8, example 21 differs from examples 24 to 26 in the amount of the microcapsules used.
TABLE 8
| Sample(s) | Example 21 | Example 24 | Example 25 | Example 26 |
| Microcapsules/kg | 18 | 20 | 22 | 24 |
Example 27
The difference between this example and example 25 is that the formulation of the flame retardant polyurethane acrylic rubber prepolymer also includes 4kg of calcium citrate, and the calcium citrate is mixed with the preheated mixture in step (2) of preparing the flame retardant polyurethane acrylic rubber prepolymer.
As in Table 9, examples 27-31 differ in the amount of calcium citrate used.
TABLE 9
| Sample(s) | Example 27 | Example 28 | Example 29 | Example 30 | Example 31 |
| Calcium citrate/kg | 4 | 5 | 6 | 7 | 8 |
Example 32
The difference between the present example and example 29 is that the formulation of the flame retardant polyurethane acrylic rubber prepolymer further includes 4kg of zirconium oxychloride, and the zirconium oxychloride is mixed with the preheated mixture in the step (2) of preparing the flame retardant polyurethane acrylic rubber prepolymer.
As shown in Table 10, examples 32 to 36 were different in the amount of zirconium oxychloride used.
Watch 10
| Sample(s) | Example 32 | Example 33 | Example 34 | Example 35 | Example 36 |
| Zirconium oxychloride per kg | 4 | 5 | 6 | 7 | 8 |
Comparative example
Comparative example 1
A flame-retardant polyurethane high-tenacity rubber prepolymer is prepared by the following method: (1) Mixing 60kg of polyester polyol with 2.6kg of catalyst, preheating the mixture at 135 ℃, maintaining the vacuum degree at-0.09 MPa during preheating, and preheating for 2.5 hours to obtain a preheated mixture; (2) And adding 10kg of tricresyl phosphate and 40kg of isocyanate into the preheated mixture, uniformly mixing, cooling the temperature of a reaction system to 70 ℃, and continuously reacting for 2.3 hours to obtain the flame-retardant polyurethane acrylic adhesive prepolymer.
Comparative example 2
The difference between the comparative example and the example 3 is that the coal gangue micro powder is replaced by montmorillonite with the same weight, the montmorillonite is purchased from a Yongshui mineral processing factory in Lingshou county, and the average particle size of the montmorillonite is the same as that of the coal gangue micro powder.
Comparative example 3
This comparative example differs from example 3 in that the phosphorus-containing cellulose fibers are not included.
Performance test method
The flame retardant polyurethane high-performance rubber prepolymer was subjected to a combustion test according to the test method in GB/T2408-2008 determination of plastic combustion performance (horizontal and vertical methods), and the flame retardant effect of the flame retardant polyurethane high-performance rubber prepolymer was characterized by the oxygen index, with the test results shown in table 11.
TABLE 11
| Sample(s) | Oxygen index/% | Sample(s) | Oxygen index/% |
| Example 1 | 24.8 | Example 21 | 32.3 |
| Example 2 | 25.4 | Example 22 | 31.9 |
| Example 3 | 25.7 | Example 23 | 31.5 |
| Example 4 | 25.3 | Example 24 | 32.7 |
| Example 5 | 25.1 | Example 25 | 33.9 |
| Example 6 | 26.1 | Example 26 | 32.8 |
| Example 7 | 26.5 | Example 27 | 35.4 |
| Example 8 | 26.2 | Example 28 | 36.2 |
| Example 9 | 25.8 | Example 29 | 36.7 |
| Example 10 | 27.0 | Example 30 | 36.3 |
| Example 11 | 27.4 | Example 31 | 35.9 |
| Example 12 | 28.5 | Example 32 | 37.4 |
| Example 13 | 27.7 | Example 33 | 37.8 |
| Example 14 | 26.9 | Example 34 | 38.3 |
| Example 15 | 29.6 | Example 35 | 37.9 |
| Example 16 | 30.2 | Example 36 | 37.4 |
| Example 17 | 29.7 | Comparative example 1 | 18.5 |
| Example 18 | 29.1 | Comparative example 2 | 20.4 |
| Example 19 | 31.4 | Comparative example 3 | 21.2 |
| Example 20 | 31.8 | / | / |
As can be seen by combining examples 1-5 with comparative example 1 and by combining Table 11, the oxygen index measured for examples 1-5 is higher than that of comparative example 1, indicating that the minimum oxygen concentration required for combustion of the flame retardant polyurethane high tensile strength adhesive prepolymers of examples 1-5 is higher than that of comparative example 1. In examples 1 to 5, the flame retardant polyurethane acrylic adhesive prepolymer of example 3 had the best flame retardant effect.
It can be seen by combining example 3 and comparative example 2 and table 11 that the oxygen index measured in example 3 is higher than that in comparative example 2, which shows that the flame retardant effect of the flame retardant polyurethane acrylic rubber prepolymer is reduced when montmorillonite is used to replace coal gangue micropowder.
Combining example 3 and comparative example 3 and table 11, it can be seen that the oxygen index measured in example 3 is higher than that in comparative example 3, which shows that the phosphorus-containing cellulose fiber is helpful to improve the flame retardant effect of the flame retardant polyurethane acrylic rubber prepolymer.
As can be seen by combining example 3 with examples 6-9 and Table 11, the oxygen index measured in example 7 is the largest, which indicates that the phosphorus-containing cellulose prepared according to the formulation system of preparation example 3 is more helpful for improving the flame retardant effect of the flame retardant polyurethane acrylic rubber prepolymer.
By combining example 7 with examples 10-14 and table 11, it can be seen that the oxygen indexes measured in examples 10-14 are all higher than those in example 7, indicating that the microcapsules are helpful for improving the flame retardant effect of the flame retardant polyurethane high-impact adhesive prepolymer. In examples 10-14, the oxygen index measured in example 12 was the highest, indicating that the microcapsules prepared according to the formulation of preparation 8 are more useful for improving the flame retardant properties of the flame retardant polyurethane high impact adhesive prepolymer.
When the average particle size of bentonite used for preparing the microcapsules is 6 to 10 μm, the oxygen index is higher and the flame retardant property of the flame retardant polyurethane acrylic adhesive prepolymer is better as can be seen by combining the examples 12, 15 to 18 and the table 11.
In combination with example 16 and examples 19-23 and table 11, it can be seen that the oxygen indexes measured in examples 19-23 are all higher than those in example 16, which indicates that the microcapsules prepared by using pyrrole as the embedding aid are more helpful to improve the flame retardant property of the flame retardant polyurethane acrylic adhesive prepolymer. In examples 19-23, the oxygen index measured in example 21 was the highest, indicating that the microcapsules prepared in preparation 17 are more effective in improving the flame retardant properties of the flame retardant polyurethane acrylic adhesive prepolymer in the preparation with the addition of pyrrole.
It can be seen from the combination of example 21 and examples 24-26 that the oxygen index measured in example 25 is the highest among examples 21 and 24-26, which shows that the addition of the microcapsule according to the amount of example 25 is more helpful to improve the flame retardant property of the flame retardant polyurethane high-impact adhesive prepolymer.
In combination with example 25, examples 27-31 and Table 11, it can be seen that the oxygen indexes measured in examples 27-31 are all higher than those in example 25, which shows that calcium citrate is helpful for improving the flame retardant effect of the flame retardant polyurethane high-impact adhesive prepolymer. Among examples 27 to 31, example 29 showed the highest oxygen index.
In combination with example 29 and examples 32-36 and table 11, it can be seen that the oxygen indexes of examples 32-36 are all higher than example 29, which indicates that zirconium oxychloride is helpful for improving the flame retardant effect of the flame retardant polyurethane acrylic adhesive prepolymer. In examples 32-36, example 34 measured the highest oxygen index.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (7)
1. The flame-retardant polyurethane high-tenacity rubber prepolymer is characterized by comprising the following components in parts by weight: 30-50 parts of isocyanate, 50-70 parts of polyester polyol, 40-60 parts of phosphorus-containing cellulose fiber, 30-50 parts of coal gangue micro powder, 2.4-2.8 parts of catalyst, 4-8 parts of silane coupling agent and 4-8 parts of calcium citrate; the formula of the flame-retardant polyurethane acrylic rubber prepolymer also comprises 18-24 parts of microcapsules by weight, and the formula of the microcapsules comprises the following raw materials by weight: 20-40 parts of persulfate, 40-60 parts of stearic acid and 30-50 parts of bentonite, wherein the stearic acid is used for coating the persulfate and the bentonite; the preparation method of the microcapsule comprises the following steps:
(1) Mixing stearic acid and absolute ethyl alcohol, and stirring at 50-60 ℃ until the stearic acid is dissolved to obtain a base solution;
(2) Adding persulfate and bentonite into the base liquid, performing ultrasonic dispersion for 10-15min, cooling the base liquid, and performing vacuum drying on the base liquid at the temperature of lower than 35 ℃ to obtain persulfate microcapsules.
2. The flame-retardant polyurethane acrylic rubber prepolymer according to claim 1, wherein the flame-retardant polyurethane acrylic rubber prepolymer comprises the following components in parts by weight: 35-45 parts of isocyanate, 45-55 parts of phosphorus-containing cellulose fiber, 35-45 parts of coal gangue micropowder, 2.5-2.7 parts of catalyst and 5-7 parts of silane coupling agent.
3. The flame-retardant polyurethane acrylic adhesive prepolymer according to claim 1, wherein the preparation method of the phosphorus-containing cellulose fiber comprises the following steps:
(1) Weighing cellulose fibers and phosphorus oxychloride, dissolving the phosphorus oxychloride and the cellulose fibers in dichloromethane, and uniformly stirring, wherein the weight ratio of the cellulose fibers to the phosphorus oxychloride is (2-2.4): 1;
(2) Heating dichloromethane in water bath at 32-38 deg.C for 3-5 hr, stopping heating, and distilling to remove dichloromethane to obtain phosphorus-containing cellulose fiber.
4. The flame retardant polyurethane high-impact adhesive prepolymer according to claim 1, wherein the average particle size of the bentonite is 6-10 μm.
5. The flame-retardant polyurethane acrylic adhesive prepolymer according to claim 1, wherein the microcapsule further comprises 4-8 parts of an embedding aid, the embedding aid is pyrrole, and the embedding aid is mixed with absolute ethyl alcohol in the step (1) of preparing the microcapsule.
6. The flame-retardant polyurethane acrylic rubber prepolymer as claimed in claim 1, wherein the flame-retardant polyurethane acrylic rubber prepolymer further comprises 4-8 parts by weight of zirconium oxychloride.
7. The preparation method of the flame-retardant polyurethane acrylic rubber prepolymer according to any one of claims 1 to 6, which is characterized by comprising the following steps:
(1) Mixing polyester polyol, a catalyst, coal gangue micropowder and a silane coupling agent under an anaerobic condition, preheating the mixture at 100-150 ℃, wherein the preheating time is 2-3h, and obtaining a preheated mixture after preheating is finished;
(2) Adding isocyanate and phosphorus-containing cellulose fiber into the preheated mixture, uniformly mixing, reducing the temperature of a reaction system to 60-80 ℃, and continuously reacting for 2-2.5 hours to obtain a flame-retardant polyurethane acrylic adhesive prepolymer; and (3) mixing the calcium citrate with the preheated mixture in the step (2) of preparing the flame-retardant polyurethane acrylic adhesive prepolymer.
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| CN104356242A (en) * | 2014-10-17 | 2015-02-18 | 中国林业科学研究院林产化学工业研究所 | Halogen-free cellulose based phosphorus flame retardant and preparation method thereof |
| CN105949432A (en) * | 2016-01-30 | 2016-09-21 | 南京理工大学 | Composite thermal insulation material comprising modified coal gangue and rigid polyurethane foamed plastic |
| CN106810669A (en) * | 2017-01-17 | 2017-06-09 | 深圳市力信陆南橡塑五金有限公司 | A kind of excellent power glue performed polymer of flame retardant polyurethane and preparation method thereof |
| CN106866922A (en) * | 2015-12-10 | 2017-06-20 | 上海凯众材料科技股份有限公司 | The preparation method of microporous polyurethane elastomer |
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| CN104356242A (en) * | 2014-10-17 | 2015-02-18 | 中国林业科学研究院林产化学工业研究所 | Halogen-free cellulose based phosphorus flame retardant and preparation method thereof |
| CN106866922A (en) * | 2015-12-10 | 2017-06-20 | 上海凯众材料科技股份有限公司 | The preparation method of microporous polyurethane elastomer |
| CN105949432A (en) * | 2016-01-30 | 2016-09-21 | 南京理工大学 | Composite thermal insulation material comprising modified coal gangue and rigid polyurethane foamed plastic |
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