High-thermal-efficiency ground heating floor and preparation method thereof

Abstract

The invention discloses a high-thermal-efficiency ground heating floor and a preparation method thereof, and belongs to the technical field of floors. The high-thermal-efficiency floor heating floor is prepared from the following raw materials in parts by weight: 100 to 110 parts of polypropylene resin, 50 to 60 parts of filler, 10 to 20 parts of auxiliaries, 5 to 6 parts of coupling agent, 2 to 3 parts of barium stearate, 1.5 to 3 parts of zinc borate, 1 to 2 parts of polyethylene wax, 1 to 2 parts of anti-aging agent and 0.05 to 0.1 part of initiator. The auxiliary agent contains a heterocyclic ring and an amide structure with antibacterial activity, rich fluorine element and tourmaline, chemical action exists between every two of the auxiliary agent, the filler and the polypropylene resin, and the raw materials are good in compatibility and can fully and stably exert self-action, so that the auxiliary agent has a good antibacterial effect. The floor heating floor is high in heat conductivity coefficient and good in moisture-proof effect, can release negative ions to improve body health, meanwhile, has efficient, safe and lasting antibacterial property, and is excellent in comprehensive performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of flooring, and in particular, relates to a high-thermal-efficiency floor heating floor and a preparation method thereof. Background Art

[0002] Floors have been widely used in building decoration, and according to different uses, floors are divided into many types, and floor heating floor is one of them. Floor heating floor refers to the floor suitable for low-temperature hot water floor heating (referred to as floor heating), which must have good air permeability, heat dissipation function, heat resistance and environmental protection.

[0003] The best paving material for floor heating is solid wood composite flooring, but the production process of this flooring requires a lot of adhesives and paints, and these two materials will release a lot of formaldehyde. Although the formaldehyde content of the flooring made of ordinary wood-plastic materials is far lower than the national standard requirements, when used as floor heating flooring, its thermal conductivity, moisture resistance and antibacterial properties are insufficient. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a high thermal efficiency floor heating floor and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A high thermal efficiency floor heating floor comprises the following raw materials in parts by weight: 100-110 parts of polypropylene resin, 50-60 parts of filler, 10-20 parts of additive, 5-6 parts of coupling agent, 2-3 parts of barium stearate, 1.5-3 parts of zinc borate, 1-2 parts of polyethylene wax, 1-2 parts of anti-aging agent and 0.05-0.1 parts of initiator.

[0007] Furthermore, the filler is one or more of aluminum hydroxide, magnesium hydroxide, nano titanium dioxide, silicon powder, and graphene.

[0008] Furthermore, the coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, 3-(methacryloyloxy)propyl trimethoxy silane, and vinyl tri(2-methoxyethoxy) silane.

[0009] The addition of coupling agent can reduce the surface energy of filler and introduce carbon-carbon double bonds on the surface of filler, so that filler can not only be evenly dispersed in the floor heating floor, but also can produce chemical reaction with polypropylene resin or additives under the action of initiator, further improve the dispersion, so as to maximize its own role and improve the thermal conductivity, wear resistance, weather resistance and flame retardancy of floor heating floor.

[0010] Furthermore, the auxiliary agent is prepared by the following steps:

[0011] S1, under nitrogen protection, 2-aminobenzothiazole, triethylamine and carbon tetrachloride were added to a dry round-bottom flask, and the mixed solution of chloroacetyl chloride and carbon tetrachloride in the constant pressure dropping funnel was slowly added to the round-bottom flask under ice-water bath conditions. After the addition was completed, the reaction was continued under ice-water bath conditions for 30 minutes. After the reaction was completed, the reaction was distilled under reduced pressure to obtain intermediate 1; the amount ratio of 2-aminobenzothiazole, chloroacetyl chloride, triethylamine and carbon tetrachloride was 12g:7.1mL:14.5mL:120mL;

[0012] The molar ratio of 2-aminobenzothiazole to chloroacetyl chloride is controlled to be 1:1.1-1.15, then -NH2 of 2-aminobenzothiazole and acyl chloride of chloroacetyl chloride undergo amidation reaction under the condition of ice water bath, and the reaction process is as follows:

[0013]

[0014] S2. Add 3-perfluorooctyl-1,2-epoxypropane, 3-bis(methylamino)propane and chloroform into a dry three-necked flask, stir evenly and heat to 65°C. Keep warm for 3 hours. After the reaction, distill under reduced pressure, purify by column chromatography (a mixed solution of chloroform and ether is selected as the eluent, and the volume ratio of chloroform to ether is 9:1), and distill under reduced pressure to obtain intermediate 2; the dosage ratio of 3-perfluorooctyl-1,2-epoxypropane, 3-bis(methylamino)propane and chloroform is 22.2mL:11.8mL:130mL;

[0015] The molar ratio of 3-perfluorooctyl-1,2-epoxypropane to 3-bis(methylamino)propane is controlled to be 1:1.1-1.2, and then 3-perfluorooctyl-1,2-epoxypropane and 3-bis(methylamino)propane undergo a ring-opening reaction under heating conditions. The reaction process is as follows:

[0016]

[0017] S3, nitrogen was blown into a dry three-necked flask for 30 minutes to expel air and moisture in the flask, then intermediate 1, intermediate 2 and DMSO (dimethyl sulfoxide) were added, mixed evenly, and pyridine was slowly added, the temperature was raised to 70°C and stirred for reaction for 4 hours, after the reaction was completed, it was cooled to room temperature, and then distilled under reduced pressure to obtain intermediate 3; the amount ratio of intermediate 1, intermediate 2, pyridine and DMSO was 15.9 g:43.7 g:7.9 mL:180 mL;

[0018] The molar ratio of intermediate 1 to intermediate 2 is controlled to be 1:1 and intermediate 2 is slightly excessive. Under heating, -Cl of intermediate 1 and -NH- of intermediate 2 undergo nucleophilic substitution reaction, and pyridine is used as an acid binding agent. The reaction process is as follows:

[0019]

[0020] S4. Add intermediate 3, maleic anhydride, DMAP (4-dimethylaminopyridine) and DMSO to a three-necked flask under nitrogen protection, stir and heat to 50°C for reaction for 12 hours, and distill under reduced pressure after the reaction. Purify by column chromatography (the eluent is a mixed solution of methanol, ethyl acetate and petroleum ether, and the volume ratio of methanol, ethyl acetate and petroleum ether is 1:1:7), and distill under reduced pressure to obtain intermediate 4; the dosage ratio of intermediate 3, maleic anhydride, DMAP and DMSO is 38.4 g:5.8 g:0.18 g:200 mL;

[0021] The molar ratio of intermediate 3 to maleic anhydride is controlled to be 1:1.1-1.2, and then intermediate 3 and maleic anhydride undergo esterification reaction under the catalysis of DMAP. The reaction process is as follows:

[0022]

[0023] S5. Under nitrogen protection, add intermediate 4, tourmaline and DMF (N,N-dimethylformamide) into a three-necked flask, mix thoroughly and then slowly add concentrated sulfuric acid. After the addition is complete, heat to 110°C and keep warm for 5 hours. After the reaction is completed, cool to room temperature, filter, wash with deionized water until the filtrate is neutral, and dry at 100°C for 12 hours to obtain an auxiliary agent; the mass ratio of tourmaline to intermediate 4 is 10:1.

[0024] Under the catalytic action of concentrated sulfuric acid, the hydroxyl groups on the intermediate 4 react with the abundant hydroxyl groups on the surface of tourmaline to undergo esterification reaction. The reaction process is as follows:

[0025]

[0026] The additive contains amide groups and heterocycles, which are found to have good antibacterial biological activity; the additive is rich in fluorine elements, and adding the additive rich in fluorine elements as a raw material to the floor heating floor can significantly reduce the surface free energy of the floor, so that the floor heating floor of the present invention has excellent hydrophobic and oleophobic properties; the additive also contains tourmaline, which is a kind of ore that can generate electrostatic fields with permanent electron flow in a natural state, and can generate alkaline negative ions in air and water in a passive state. Tourmaline has the characteristic of radiating far infrared rays with a wavelength of 4-18μm. Tourmaline absorbs human body heat and converts it into negative ions and far infrared rays to react to the human body, improve blood circulation, promote metabolism, and enhance cell vitality.

[0027] In addition, the additive of the present invention contains carbon-carbon double bonds, which can react chemically with the double bonds on the surface of the filler under the action of the initiator, and can also react chemically with the carbon-carbon double bonds at the end of the polypropylene resin that have not reacted completely, which not only makes the additive highly dispersed and stably present in the floor heating floor, so as to give full play to the antibacterial effect, hydrophobic and oleophobic effect, release of negative ions to improve the health of the body, but also can further improve the dispersion of the filler. Therefore, the floor heating floor of the present invention not only has excellent and stable antibacterial properties, hydrophobic and oleophobic properties, wear resistance and weather resistance, but also has efficient and safe heat conduction function, flame retardant effect, and negative ion release function.

[0028] Furthermore, the antioxidant is one or more of antioxidant 1076, antioxidant 1010, ultraviolet absorber UV-531, light stabilizer AM-101, and light stabilizer 744.

[0029] Furthermore, the initiator is one or both of dibenzoyl peroxide and dicumyl peroxide.

[0030] A method for preparing a high thermal efficiency floor heating floor comprises the following steps:

[0031] Weigh each raw material by weight, and add polypropylene resin, filler, coupling agent, barium stearate, anti-aging agent and additives into a mixer in turn and mix evenly, then add zinc borate, polyethylene wax and initiator in turn, continue stirring, add to a granulator for granulation after sufficient mixing, and then extrude through an extrusion production line to prepare a high thermal efficiency floor heating floor.

[0032] The beneficial effects of the present invention are as follows: the additive of the present invention contains heterocyclic and amide structures with antibacterial activity, rich fluorine elements and tourmaline, and there is a chemical reaction between the additive, filler and polypropylene resin. The various raw materials have good compatibility and can fully and stably play their own roles. Therefore, the floor heating floor of the present invention has high thermal conductivity, good moisture-proof effect, can release negative ions to improve health, and also has efficient, safe and lasting antibacterial properties, and excellent comprehensive performance. DETAILED DESCRIPTION

[0033] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] Example 1

[0035] Preparation of auxiliary agent, the specific steps are as follows:

[0036] S1. Under nitrogen protection, 12 g of 2-aminobenzothiazole, 14.5 mL of triethylamine and 110 mL of carbon tetrachloride were added to a 250 mL dry round-bottom flask. A mixed solution of 7.1 mL of chloroacetyl chloride and 10 mL of carbon tetrachloride in a constant pressure dropping funnel was slowly added to the round-bottom flask under ice-water bath conditions. After the addition was completed, the reaction was continued under ice-water bath conditions for 30 min. After the reaction was completed, it was distilled under reduced pressure to obtain intermediate 1.

[0037] S2, add 22.2 mL of 3-perfluorooctyl-1,2-propylene oxide, 11.8 mL of 3-bis(methylamino)propane, and 130 mL of chloroform into a 250 mL dry three-necked flask, stir evenly, heat to 65°C, and keep warm for 3 hours. After the reaction is completed, distill under reduced pressure, purify by column chromatography (a mixed solution of chloroform and ether is selected as the eluent, and the volume ratio of chloroform to ether is 9:1), and distill under reduced pressure to obtain intermediate 2;

[0038] S3, nitrogen was blown into a 500 mL dry three-necked flask for 30 min to expel air and moisture in the flask, then 15.9 g of intermediate 1, 43.7 g of intermediate 2 and 180 mL of DMSO were added, and after mixing evenly, 7.9 mL of pyridine was slowly added, and the temperature was raised to 70 ° C and stirred for 4 h. After the reaction was completed, it was cooled to room temperature and then distilled under reduced pressure to obtain intermediate 3;

[0039] S4, under nitrogen protection, 38.4 g of intermediate 3, 5.8 g of maleic anhydride, 0.18 g of DMAP and 200 mL of DMSO were added to a 500 mL three-necked flask, and the mixture was heated to 50° C. with stirring for 12 h. After the reaction, the mixture was distilled under reduced pressure, purified by column chromatography (the eluent was a mixed solution of methanol, ethyl acetate and petroleum ether, and the volume ratio of methanol, ethyl acetate and petroleum ether was 1:1:7), and distilled under reduced pressure to obtain intermediate 4;

[0040] S5. Under nitrogen protection, add 4.5 g of intermediate 4, 45 g of tourmaline and 200 mL of DMF into a 500 mL three-necked flask, mix thoroughly and then slowly add 0.3 mL of concentrated sulfuric acid. After the addition is complete, heat to 110°C and keep warm for 5 hours. After the reaction is completed, cool to room temperature, filter, wash with deionized water until the filtrate is neutral, and dry at 100°C for 12 hours to obtain an auxiliary agent.

[0041] Example 2

[0042] To prepare the floor heating floor, the specific steps are as follows:

[0043] Weigh each raw material by weight, and add 100 parts of polypropylene resin, 30 parts of aluminum hydroxide, 5 parts of nano-titanium dioxide, 10 parts of silicon powder, 5 parts of graphene, 5 parts of vinyltrimethoxysilane, 2 parts of barium stearate, 0.5 parts of antioxidant 1076, 0.5 parts of ultraviolet absorber UV-531 and 10 parts of the additive prepared in Example 1 into a blender in sequence and mix evenly, then add 1.5 parts of zinc borate, 1 part of polyethylene wax and 0.05 parts of dibenzoyl peroxide in sequence, continue stirring, add to a granulator for granulation after sufficient mixing, and then extrude through an extrusion production line to prepare a floor heating floor.

[0044] Example 3

[0045] To prepare the floor heating floor, the specific steps are as follows:

[0046] Weigh each raw material by weight, and add 105 parts of polypropylene resin, 50 parts of magnesium hydroxide, 6 parts of graphene, 5.5 parts of 3-(methacryloyloxy)propyltrimethoxysilane, 2.6 parts of barium stearate, 0.9 parts of antioxidant 1010, 0.5 parts of ultraviolet absorber UV-531, 0.4 parts of light stabilizer AM-101 and 18 parts of the additives prepared in Example 1 into a blender in sequence and mix evenly, then add 2.7 parts of zinc borate, 1.6 parts of polyethylene wax and 0.08 parts of diisopropyl peroxide in sequence, continue stirring, add to a granulator for granulation after sufficient mixing, and then extrude through an extrusion production line to prepare a floor heating floor.

[0047] Example 4

[0048] To prepare the floor heating floor, the specific steps are as follows:

[0049] Weigh each raw material by weight, and add 110 parts of polypropylene resin, 30 parts of magnesium hydroxide, 10 parts of nano-titanium dioxide, 10 parts of silicon powder, 10 parts of graphene, 6 parts of vinyl tri(2-methoxyethoxy)silane, 3 parts of barium stearate, 0.5 parts of antioxidant 1076, 0.5 parts of antioxidant 1010, 0.5 parts of ultraviolet absorber UV-531, 0.5 parts of light stabilizer 744 and 20 parts of the additives prepared in Example 1 into a blender in sequence and mix evenly, then add 3 parts of zinc borate, 2 parts of polyethylene wax and 0.1 parts of dibenzoyl peroxide in sequence, continue stirring, add to a granulator for granulation after sufficient mixing, and then extrude through an extrusion production line to prepare a floor heating floor.

[0050] Comparative Example 1

[0051] To prepare the floor heating floor, the specific steps are as follows:

[0052] The remaining steps remained unchanged, and the auxiliary agent in Example 2 was replaced by 9.1 parts of tourmaline, 0.45 parts of 3-perfluorooctyl-1,2-propylene oxide and 0.45 parts of nano-silver antibacterial agent from Beijing Fulaisibo Technology Development Co., Ltd. to prepare a floor heating floor.

[0053] Comparative Example 2

[0054] To prepare the floor heating floor, the specific steps are as follows:

[0055] The remaining steps remain unchanged, and the additives in Example 2 are removed to prepare the floor heating floor.

[0056] Performance Testing

[0057] The antibacterial performance of the floor heating floor of Examples 2-4 and Comparative Examples 1-2 was tested with reference to GB / T 31402-2015, Escherichia coli ATYCC 25922 and Staphylococcus aureus ATCC 6538. The specific test results are shown in Table 1:

[0058] Table 1

[0059]

[0060] The floor heating floors prepared in Examples 2-4 and Comparative Examples 1-2 were subjected to the following performance tests, and the test results are shown in Table 2 below:

[0061] Table 2

[0062]

[0063] The floor heating floors prepared in Examples 2-4 and Comparative Examples 1-2 were cut into small cubes of the same size and immersed in distilled water at 10°C and 40°C for 15 days, respectively, to observe the changes in the morphology of the small cubes. The test results are shown in Table 3 below:

[0064] Table 3

[0065]

[0066] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0067] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A high thermal efficiency floor heating floor, characterized in that: The invention comprises the following raw materials in parts by weight: 100-110 parts of polypropylene resin, 50-60 parts of filler, 10-20 parts of auxiliary agent, 5-6 parts of coupling agent, 2-3 parts of barium stearate, 1.5-3 parts of zinc borate, 1-2 parts of polyethylene wax, 1-2 parts of anti-aging agent and 0.05-0.1 parts of initiator; Wherein, the auxiliary agent is prepared by the following steps: S1. Add 2-aminobenzothiazole, triethylamine and carbon tetrachloride into a flask under nitrogen protection, then add chloroacetyl chloride and carbon tetrachloride in an ice-water bath, react for 30 minutes, and distill under reduced pressure to obtain intermediate 1; S2, adding 3-perfluorooctyl-1,2-epoxypropane, 3-bis(methylamino)propane and chloroform into a flask, reacting at 65° C. for 3 h, distilling under reduced pressure, purifying by column chromatography, and distilling under reduced pressure to obtain intermediate 2; S3, nitrogen was blown into the flask, intermediate 1, intermediate 2 and DMSO were added, mixed, and pyridine was added, reacted at 70°C for 4h, cooled, and distilled under reduced pressure to obtain intermediate 3; S4, under nitrogen protection, add intermediate 3, maleic anhydride, DMAP and DMSO to a flask, react at 50°C for 12 hours, distill under reduced pressure, purify by column chromatography, and distill under reduced pressure to obtain intermediate 4; S5. Under nitrogen protection, add intermediate 4, tourmaline and DMF into a flask, mix, add concentrated sulfuric acid, react at 110° C. for 5 h, cool, filter, wash and dry to obtain an auxiliary agent.

2. A high thermal efficiency floor heating floor according to claim 1, characterized in that: The usage ratio of 2-aminobenzothiazole, chloroacetyl chloride, triethylamine and carbon tetrachloride in step S1 is 12g:7.1mL:14.5mL:120mL; the usage ratio of 3-perfluorooctyl-1,2-propylene oxide, 3-bis(methylamino)propane and chloroform in step S2 is 22.2mL:11.8mL:130mL; the usage ratio of intermediate 1, intermediate 2, pyridine and DMSO in step S3 is 15.9g:43.7g:7.9mL:180mL; the usage ratio of intermediate 3, maleic anhydride, DMAP and DMSO in step S4 is 38.4g:5.8g:0.18g:200mL; the mass ratio of tourmaline and intermediate 4 in step S5 is 10:

1.

3. The high thermal efficiency floor heating floor according to claim 1, characterized in that: The filler is one or more of aluminum hydroxide, magnesium hydroxide, nano titanium dioxide, silicon powder, and graphene.

4. The high thermal efficiency floor heating floor according to claim 1, characterized in that: The coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, 3-(methacryloyloxy)propyl trimethoxy silane and vinyl tri(2-methoxyethoxy) silane.

5. The high thermal efficiency floor heating floor according to claim 1, characterized in that: The anti-aging agent is one or more of antioxidant 1076, antioxidant 1010, ultraviolet absorber UV-531, light stabilizer AM-101, and light stabilizer 744.

6. The high thermal efficiency floor heating floor according to claim 1, characterized in that: The initiator is one or both of dibenzoyl peroxide and dicumyl peroxide.

7. The method for preparing a high thermal efficiency floor heating floor according to claim 1, characterized in that: The following steps are involved: Weigh each raw material by weight, and add polypropylene resin, filler, coupling agent, barium stearate, anti-aging agent and additives into a mixer in turn and mix evenly, then add zinc borate, polyethylene wax and initiator in turn, continue stirring, add to a granulator for granulation after sufficient mixing, and then extrude through an extrusion production line to prepare a high thermal efficiency floor heating floor.

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