Preparation method of multifunctional flame-retardant novel non-slip mat

Abstract

The invention relates to a preparation method of a multifunctional flame-retardant novel non-slip mat, and belongs to the technical field of non-slip mats. Natural rubber, solution polymerized styrene-butadiene rubber, zinc oxide, stearic acid, an anti-aging agent, paraffin, activated calcium carbonate, titanium dioxide, white carbon black, 50 # engine oil, sulfur, an accelerant, a flame retardant, phthalocyanine blue, lithopone and coumarone are fed into a rubber mixing mill to be mixed, and after batching-out, the mixture returns to the rubber mixing mill to be continuously mixed to obtain a semi-finished product; and pouring the semi-finished product into a mold, and carrying out compression molding by using a vulcanizing machine to obtain the multifunctional flame-retardant novel non-slip mat. The flame retardant disclosed by the invention is prepared from mercaptoethyl guanidine (MEG) dihydrobromide, magnesium thioglycolate, methylbenzene, a 1, 2-vinyl diphosphonic acid / yttrium complex and a photoinitiator. The prepared multifunctional flame-retardant novel non-slip mat is soft, comfortable, moderate in hardness and good in flame retardant property.

Description

Technical Field

[0001] The invention relates to the technical field of anti-skid pads, in particular to a method for preparing a multifunctional flame-retardant novel anti-skid pad. Background Art

[0002] As people's living standards continue to improve, people's requirements for bathrooms and kitchens, which are indispensable in their daily lives, are also increasing. Accidents of slipping and falling in bathrooms and kitchens happen from time to time. In order to prevent accidents, anti-slip mats came into being.

[0003] Chinese patent CN106750609A: Provides a high-strength wear-resistant anti-skid pad and its preparation method. The preparation method is as follows: (1) weighing ingredients: natural rubber, chloroprene rubber, zinc oxide, stearic acid, white carbon black, zinc borate, sulfur, accelerator DM, antioxidant 4010, dioctyl sebacate, silicon nitride, cerium oxide, modified kaolin; (2) paper cup modified kaolin; (3) mixing rubber and pressing into sheets; (4) vulcanization treatment.

[0004] Chinese patent CN101747629A: relates to an anti-skid pad or sheet, which is characterized in that it is based on silicone rubber, chemical powder that can generate negative ions is added, and after being evenly mixed, a molding or injection molding process is used to make a sheet-shaped anti-skid pad or sheet.

[0005] Chinese patent CN113736155A: Provides an anti-slip rubber composition, a mixing method and an application thereof. The anti-slip rubber composition includes, by weight, 137.5 parts of oil-extended solution-polymerized styrene-butadiene rubber, 30 to 60 parts of carbon black, 30 to 60 parts of high specific surface area white carbon black, 30 to 60 parts of low specific surface area white carbon black, 2 to 6 parts of silane coupling agent, 40 to 90 parts of environmentally friendly oil, 5 to 20 parts of functional resin, 2 to 5 parts of zinc oxide, 1 to 3 parts of stearic acid, 4 to 9 parts of antioxidant, 1 to 2.5 parts of sulfur and 2 to 5 parts of accelerator.

[0006] The anti-skid mats prepared by the above patents and prior art have too little friction with the ground, causing the anti-skid mats to slide easily; some anti-skid mats are made of hard materials, and their watertight properties make it impossible to clear the sewage washed down, affecting the discharge of indoor sewage. Summary of the invention

[0007] In order to solve the above problems, the present invention provides a method for preparing a multifunctional flame-retardant novel anti-slip mat, and the operating steps are as follows: S1: weigh 30-100 parts of natural rubber, 70-100 parts of solution polymerized styrene-butadiene rubber, 2-5 parts of zinc oxide, 1-2 parts of stearic acid, 1-2 parts of antioxidant, 1-1.5 parts of paraffin, 50-80 parts of activated calcium carbonate, 5-10 parts of titanium dioxide, 15-25 parts of white carbon black, 15-25 parts of 50# engine oil, 1-2 parts of sulfur, 0.5-2.5 parts of accelerator, 0.05-0.5 parts of flame retardant, 0.5-1.5 parts of phthalocyanine blue, 5-10 parts of lithopone, and 3-8 parts of coumarone, and send them into a rubber mixer and mix them for 20-30 minutes. After unloading, return them to the rubber mixer and continue mixing for 10-20 minutes to obtain a semi-finished product; S2: Pour the semi-finished product into a mold and use a vulcanizer to perform compression molding to obtain a multifunctional flame-retardant new anti-slip mat.

[0008] The mixing temperature of the rubber mixer is 100-120°C.

[0009] The temperature of the vulcanizing machine is 170-190°C, the pressure is 5-10MPa, and the time is 15-25min.

[0010] The accelerator is one of accelerator M, accelerator TT, accelerator CZ and accelerator DM.

[0011] The antioxidant is one of antioxidant AW, antioxidant A, antioxidant D and antioxidant RD.

[0012] The multifunctional flame-retardant novel anti-skid mat has nipple-like protrusions on its surface for anti-skid and massage functions, a plurality of supporting ribs and anti-skid suckers on its bottom surface, and a drainage channel and water-permeable holes.

[0013] The flame retardant preparation method is: A1: Under nitrogen protection, 20-40 parts of mercaptoethylguanidine (MEG) dihydrobromide (CAS No.: 32665-11-5), 3-6 parts of magnesium thioglycolate (CAS No.: 63592-16-5), 200-300 parts of toluene, 4-7 parts of 1,2-vinyl diphosphonic acid / yttrium complex, and 0.02-0.05 parts of photoinitiator were stirred and mixed uniformly, and reacted at 60-70°C for 30-60 minutes; A2: After the reaction is completed, ultraviolet light irradiation is performed: click chemistry reaction is performed using ultraviolet light with a maximum absorption wavelength of 365 nm; A3: After the reaction is completed, toluene is removed by distillation to obtain a flame retardant.

[0014] The preparation method of the 1,2-vinyl diphosphonic acid / yttrium complex is as follows: K1: 20-40 parts of 1,2-vinyl diphosphonic acid, 3-6 parts of yttrium nitrate, and 200-300 parts of water are stirred and reacted at 60-70°C for 30-60 minutes; K2: After the reaction is complete, water is removed by distillation to obtain a 1,2-vinyldiphosphonic acid / yttrium complex.

[0015] Reaction mechanism Thiol click chemistry is a highly efficient and selective type of chemical reaction that proceeds through the addition reaction between thiol (-SH) groups and double bonds (such as vinyl groups). Under UV light irradiation, these reactions can generate the target products with high selectivity and efficiency.

[0016] The specific operation steps include mixing mercaptoethylguanidine (MEG) dihydrobromide and magnesium thioglycolate with 1,2-vinyldiphosphonic acid / yttrium complex respectively, heating and stirring under nitrogen protection and irradiating with ultraviolet light, and finally obtaining a flame retardant containing dihydrobromide, diphosphonic acid / yttrium complex and magnesium acetate.

[0017] Technical effects and application prospects 1. Improve flame retardant properties: By introducing a variety of active ingredients, the new flame retardant can release non-flammable gases during the combustion process, forming an insulation layer to prevent the spread of flames.

[0018] 2. Enhance the thermal stability of materials: These ingredients not only improve the flame retardant properties, but also enhance the thermal stability and mechanical strength of the materials.

[0019] 3. Environmental advantages: Compared with traditional halogen flame retardants, phosphonate-based flame retardants are more environmentally friendly and reduce the emission of harmful smoke and gases.

[0020] 4. Application prospects: It is suitable for polymer materials, textiles, electronic equipment and other fields, especially in occasions requiring high fire safety.

[0021] In general, the new flame retardant prepared by thiol click chemistry reaction combines the advantages of mercaptoethylguanidine (MEG) dihydrobromide, magnesium thioglycolate and 1,2-vinyl diphosphonic acid / yttrium complex, thereby significantly improving the flame retardant properties and environmental friendliness of the material. This new flame retardant is not only innovative in technology, but also shows broad prospects in practical applications. DETAILED DESCRIPTION

[0022] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following is a detailed description in combination with embodiments and comparative examples: 1. Static friction coefficient: Tested on water-wetted glass surface according to GB / T10006-1988; 2. Shore A hardness: Tested in accordance with GB / T531.1-2008; 3. Oxygen index: Tested in accordance with GB / T 2406.2-2009 "Determination of combustion behavior by oxygen index method Part 2: Room temperature test".

[0023] Example 1 A method for preparing a multifunctional flame-retardant novel anti-slip mat, the operating steps of which are as follows: S1: Weigh 30g natural rubber, 70g solution polymerized styrene-butadiene rubber, 2g zinc oxide, 1g stearic acid, 1g antioxidant, 1g paraffin, 50g activated calcium carbonate, 5g titanium dioxide, 15g white carbon black, 15g 50# engine oil, 1g sulfur, 0.5g accelerator, 0.05g flame retardant, 0.5g phthalocyanine blue, 5g lithopone, 3g coumarone, send to rubber mixer and mix for 20min, after unloading, return to rubber mixer and continue mixing for 10min to obtain semi-finished product; S2: Pour the semi-finished product into a mold and use a vulcanizer to perform compression molding to obtain a multifunctional flame-retardant new anti-slip mat.

[0024] The mixing temperature of the rubber mixer is 100°C.

[0025] The temperature of the vulcanizing machine is 170° C., the pressure is 5 MPa, and the time is 15 minutes.

[0026] The accelerator is accelerator M.

[0027] The antioxidant is antioxidant AW.

[0028] The multifunctional flame-retardant novel anti-skid mat has nipple-like protrusions on its surface for anti-skid and massage functions, a plurality of supporting ribs and anti-skid suckers on its bottom surface, and a drainage channel and water-permeable holes.

[0029] The flame retardant preparation method is: A1: Under nitrogen protection, 20g of mercaptoethylguanidine (MEG) dihydrobromide (CAS No.: 32665-11-5), 3g of magnesium thioglycolate (CAS No.: 63592-16-5), 200g of toluene, 4g of 1,2-vinyl diphosphonic acid / yttrium complex, and 0.02g of photoinitiator were stirred and mixed uniformly, and reacted at 60°C for 30 minutes; A2: After the reaction is completed, ultraviolet light irradiation is performed: click chemistry reaction is performed using ultraviolet light with a maximum absorption wavelength of 365 nm; A3: After the reaction is completed, toluene is removed by distillation to obtain a flame retardant.

[0030] The preparation method of the 1,2-vinyl diphosphonic acid / yttrium complex is as follows: K1: 20 g 1,2-vinyl diphosphonic acid, 3 g yttrium nitrate, and 200 g water were stirred at 60°C for 30 minutes; K2: After the reaction is complete, water is removed by distillation to obtain a 1,2-vinyldiphosphonic acid / yttrium complex.

[0031] Example 2 A method for preparing a multifunctional flame-retardant novel anti-slip mat, the operating steps of which are as follows: S1: Weigh 50g natural rubber, 80g solution polymerized styrene-butadiene rubber, 3g zinc oxide, 1.5g stearic acid, 1.5g antioxidant, 1.1g paraffin, 60g activated calcium carbonate, 6g titanium dioxide, 18g white carbon black, 18g 50# engine oil, 1.5g sulfur, 1g accelerator, 0.2g flame retardant, 0.8g phthalocyanine blue, 6g lithopone, 5g coumarone, send to rubber mixer and mix for 25min, after unloading, return to rubber mixer and continue mixing for 15min to obtain semi-finished product; S2: Pour the semi-finished product into a mold and use a vulcanizer to perform compression molding to obtain a multifunctional flame-retardant new anti-slip mat.

[0032] The mixing temperature of the rubber mixer is 105°C.

[0033] The temperature of the vulcanizing machine is 175° C., the pressure is 6 MPa, and the time is 18 minutes.

[0034] The accelerator is accelerator TT.

[0035] The antioxidant is antioxidant A.

[0036] The multifunctional flame-retardant novel anti-skid mat has nipple-like protrusions on its surface for anti-skid and massage functions, a plurality of supporting ribs and anti-skid suckers on its bottom surface, and a drainage channel and water-permeable holes.

[0037] The flame retardant preparation method is: A1: Under nitrogen protection, 25g of mercaptoethylguanidine (MEG) dihydrobromide (CAS No.: 32665-11-5), 4g of magnesium thioglycolate (CAS No.: 63592-16-5), 240g of toluene, 5g of 1,2-vinyl diphosphonic acid / yttrium complex, and 0.2g of photoinitiator were stirred and mixed uniformly, and reacted at 65°C for 40 minutes; A2: After the reaction is completed, ultraviolet light irradiation is performed: click chemistry reaction is performed using ultraviolet light with a maximum absorption wavelength of 365 nm; A3: After the reaction is completed, toluene is removed by distillation to obtain a flame retardant.

[0038] The preparation method of the 1,2-vinyl diphosphonic acid / yttrium complex is as follows: K1: 25 g of 1,2-vinyl diphosphonic acid, 4 g of yttrium nitrate, and 240 g of water were stirred and reacted at 65°C for 40 minutes; K2: After the reaction is complete, water is removed by distillation to obtain a 1,2-vinyldiphosphonic acid / yttrium complex.

[0039] Example 3 A method for preparing a multifunctional flame-retardant novel anti-slip mat, the operating steps of which are as follows: S1: Weigh 80g natural rubber, 90g solution polymerized styrene butadiene rubber, 4g zinc oxide, 1.5g stearic acid, 1.5g antioxidant, 1.4g paraffin, 70g activated calcium carbonate, 8g titanium dioxide, 23g white carbon black, 23g 50# engine oil, 1.5g sulfur, 2g accelerator, 0.4g flame retardant, 1.3g phthalocyanine blue, 8g lithopone, 7g coumarone, send to rubber mixer and mix for 25min, after unloading, return to rubber mixer and continue mixing for 15min to obtain semi-finished product; S2: Pour the semi-finished product into a mold and use a vulcanizer to perform compression molding to obtain a multifunctional flame-retardant new anti-slip mat.

[0040] The mixing temperature of the rubber mixer is 115°C.

[0041] The temperature of the vulcanizing machine is 185° C., the pressure is 8 MPa, and the time is 23 minutes.

[0042] The accelerator is accelerator CZ.

[0043] The antioxidant is antioxidant D.

[0044] The multifunctional flame-retardant novel anti-skid mat has nipple-like protrusions on its surface for anti-skid and massage functions, a plurality of supporting ribs and anti-skid suckers on its bottom surface, and a drainage channel and water-permeable holes.

[0045] The flame retardant preparation method is: A1: Under nitrogen protection, 35 g of mercaptoethylguanidine (MEG) dihydrobromide (CAS No.: 32665-11-5), 5 g of magnesium thioglycolate (CAS No.: 63592-16-5), 280 g of toluene, 6 g of 1,2-vinyl diphosphonic acid / yttrium complex, and 0.04 g of photoinitiator were stirred and mixed uniformly, and reacted at 65°C for 50 minutes; A2: After the reaction is completed, ultraviolet light irradiation is performed: click chemistry reaction is performed using ultraviolet light with a maximum absorption wavelength of 365 nm; A3: After the reaction is completed, toluene is removed by distillation to obtain a flame retardant.

[0046] The preparation method of the 1,2-vinyl diphosphonic acid / yttrium complex is as follows: K1: 35 g of 1,2-vinyl diphosphonic acid, 5 g of yttrium nitrate, and 280 g of water were stirred and reacted at 65°C for 50 minutes; K2: After the reaction is complete, water is removed by distillation to obtain a 1,2-vinyldiphosphonic acid / yttrium complex.

[0047] Example 4 A method for preparing a multifunctional flame-retardant novel anti-slip mat, the operating steps of which are as follows: S1: Weigh 100g natural rubber, 100g solution polymerized styrene butadiene rubber, 5g zinc oxide, 2g stearic acid, 2g antioxidant, 1.5g paraffin, 80g activated calcium carbonate, 10g titanium dioxide, 25g white carbon black, 25g 50# engine oil, 2g sulfur, 2.5g accelerator, 0.5g flame retardant, 1.5g phthalocyanine blue, 10g lithopone, 8g coumarone, send to a rubber mixer and mix for 30min, after unloading, return to the rubber mixer and continue mixing for 20min to obtain a semi-finished product; S2: Pour the semi-finished product into a mold and use a vulcanizer to perform compression molding to obtain a multifunctional flame-retardant new anti-slip mat.

[0048] The mixing temperature of the rubber mixer is 120°C.

[0049] The temperature of the vulcanizing machine is 190° C., the pressure is 10 MPa, and the time is 25 minutes.

[0050] The accelerator is accelerator DM.

[0051] The antioxidant is antioxidant RD.

[0052] The multifunctional flame-retardant novel anti-skid mat has nipple-like protrusions on its surface for anti-skid and massage functions, a plurality of supporting ribs and anti-skid suckers on its bottom surface, and a drainage channel and water-permeable holes.

[0053] The flame retardant preparation method is: A1: Under nitrogen protection, 40g of mercaptoethylguanidine (MEG) dihydrobromide (CAS No.: 32665-11-5), 6g of magnesium thioglycolate (CAS No.: 63592-16-5), 300g of toluene, 7g of 1,2-vinyl diphosphonic acid / yttrium complex, and 0.05g of photoinitiator were stirred and mixed uniformly, and reacted at 70°C for 60 minutes; A2: After the reaction is completed, ultraviolet light irradiation is performed: click chemistry reaction is performed using ultraviolet light with a maximum absorption wavelength of 365 nm; A3: After the reaction is completed, toluene is removed by distillation to obtain a flame retardant.

[0054] The preparation method of the 1,2-vinyl diphosphonic acid / yttrium complex is as follows: K1: 40 g of 1,2-vinyl diphosphonic acid, 6 g of yttrium nitrate, and 300 g of water were stirred and reacted at 70°C for 60 minutes; K2: After the reaction is complete, water is removed by distillation to obtain a 1,2-vinyldiphosphonic acid / yttrium complex.

[0055] Comparative Example 1 No flame retardant was added, and the rest was the same as in Example 1.

[0056] Comparative Example 2 The 1,2-vinyldiphosphonic acid / yttrium complex was not added, and the other steps were the same as in Example 1.

[0057] Comparative Example 3 The other steps were the same as in Example 1 except that mercaptoethylguanidine (MEG) dihydrobromide was not added.

[0058] The test results of the above embodiments are shown in Table 1.

[0059] Table 1 Static friction coefficient Shore A hardness Oxygen index / % Example 1 0.67 56 34.3 Example 2 0.68 55 34.7 Example 3 0.70 54 34.9 Example 4 0.71 53 35.2 Comparative Example 1 0.45 65 25.8 Comparative Example 2 0.59 63 29.3 Comparative Example 3 0.62 61 30.6 Through the data analysis of the above embodiments and comparative examples, the multifunctional flame-retardant novel anti-skid mat prepared by the present invention has moderate hardness, good anti-skid performance and good flame-retardant performance.

[0060] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for preparing a multifunctional flame-retardant novel anti-slip mat, the operating steps of which are: S1: weigh 30-100 parts of natural rubber, 70-100 parts of solution polymerized styrene-butadiene rubber, 2-5 parts of zinc oxide, 1-2 parts of stearic acid, 1-2 parts of antioxidant, 1-1.5 parts of paraffin, 50-80 parts of activated calcium carbonate, 5-10 parts of titanium dioxide, 15-25 parts of white carbon black, 15-25 parts of 50# engine oil, 1-2 parts of sulfur, 0.5-2.5 parts of accelerator, 0.05-0.5 parts of flame retardant, 0.5-1.5 parts of phthalocyanine blue, 5-10 parts of lithopone, and 3-8 parts of coumarone, and send them into a rubber mixer and mix them for 20-30 minutes. After unloading, return them to the rubber mixer and continue mixing for 10-20 minutes to obtain a semi-finished product; S2: pour the semi-finished product into a mold and use a vulcanizer to perform compression molding to obtain a multifunctional flame-retardant new anti-slip mat; The flame retardant is prepared by reacting mercaptoethylguanidine (MEG) dihydrobromide, magnesium thioglycolate, 200-300 parts of toluene and 1,2-vinyl diphosphonic acid / yttrium complex.

2. The method for preparing a multifunctional flame-retardant novel anti-slip mat according to claim 1, characterized in that: The mixing temperature of the rubber mixer is 100-120°C.

3. The method for preparing a multifunctional flame-retardant novel anti-slip mat according to claim 1, characterized in that: The temperature of the vulcanizing machine is 170-190°C, the pressure is 5-10MPa, and the time is 15-25min.

4. The method for preparing a multifunctional flame-retardant novel anti-slip mat according to claim 1, characterized in that: The accelerator is one of accelerator M, accelerator TT, accelerator CZ and accelerator DM.

5. The method for preparing a multifunctional flame-retardant novel anti-slip mat according to claim 1, characterized in that: The antioxidant is one of antioxidant AW, antioxidant A, antioxidant D and antioxidant RD.

6. The method for preparing a multifunctional flame-retardant novel anti-slip mat according to claim 1, characterized in that: The multifunctional flame-retardant novel anti-skid mat has nipple-like protrusions on its surface for anti-skid and massage functions, a plurality of supporting ribs and anti-skid suckers on its bottom surface, and a drainage channel and water-permeable holes.

7. The method for preparing a multifunctional flame-retardant novel anti-slip mat according to claim 1, characterized in that: The flame retardant preparation method is: A1: Under nitrogen protection, 20-40 parts of mercaptoethylguanidine (MEG) dihydrobromide, 3-6 parts of magnesium thioglycolate, 200-300 parts of toluene, 4-7 parts of 1,2-vinyl diphosphonic acid / yttrium complex, and 0.02-0.05 parts of photoinitiator are stirred and mixed uniformly, and reacted at 60-70°C for 30-60 minutes; A2: After the reaction is completed, ultraviolet light irradiation is performed: click chemistry reaction is performed using ultraviolet light with a maximum absorption wavelength of 365 nm; A3: After the reaction is completed, toluene is removed by distillation to obtain a flame retardant.

8. The method for preparing a multifunctional flame-retardant novel anti-slip mat according to claim 7, characterized in that: The preparation method of the 1,2-vinyl diphosphonic acid / yttrium complex is as follows: K1: 20-40 parts of 1,2-vinyl diphosphonic acid, 3-6 parts of yttrium nitrate, and 200-300 parts of water are stirred and reacted at 60-70°C for 30-60 minutes; K2: After the reaction is complete, water is removed by distillation to obtain a 1,2-vinyldiphosphonic acid / yttrium complex.