Low-buckling-deformation PVC floor and preparation method thereof

Abstract

The invention discloses a low-buckling-deformation PVC floor and a preparation method thereof, and belongs to the technical field of floors. The preparation method comprises the following steps: adding 100-110 parts by weight of PVC resin, 20-30 parts by weight of a filler, 10-15 parts by weight of an auxiliary agent, 5-10 parts by weight of a plasticizer, 1-3 parts by weight of a coupling agent, 0.8-2 parts by weight of a stabilizer, 0.8-2 parts by weight of an antioxidant, 0.8-2 parts by weight of an ultraviolet light absorber and 0.05-0.1 part by weight of a cross-linking agent into a mixer for mixing, uniformly mixing, adding into an internal mixer for internal mixing, adding into a calender for pressing into sheets, and finally cutting to obtain the PVC floor. The auxiliary agent contains rich fluorine element and halogen-free flame-retardant elements nitrogen, phosphorus and silicon, and chemical action exists between the auxiliary agent and the polyvinyl chloride resin, so that the auxiliary agent is not easy to migrate and separate, can continuously play flame-retardant and moisture-proof roles and protect the PVC floor for a long time, so that the PVC floor is not easy to warp, deform and burn, and the service life of the PVC floor is greatly prolonged.

Description

Technical Field

[0001] The invention belongs to the technical field of flooring, and in particular relates to a low-warping and deformation PVC flooring and a preparation method thereof. Background Art

[0002] With the progress of society and the development of science and technology, people have higher and higher requirements for the living environment, especially the building and decoration materials used in residential places. There are many new energy-saving and environmentally friendly building materials on the market, among which polyvinyl chloride (PVC) flooring is widely used, such as hospitals, schools, office buildings and other places. PVC flooring refers to the floor decoration material made of polymer resin and additives through appropriate processes. PVC flooring has the advantages of anti-ultraviolet, acid and alkali corrosion resistance, anti-moth, and good anti-slip performance, safe and comfortable walking.

[0003] PVC floors are usually used in crowded places, so the flame retardancy of PVC floors is very high, otherwise the consequences of fire will be disastrous, and the flame retardancy of PVC floors in the prior art does not meet the requirements. In addition, the moisture resistance of PVC floors in the prior art is poor, so the floor is prone to warping and deformation as the use time increases. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a low-warping PVC floor and a preparation method thereof.

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

[0006] A low-warping PVC floor comprises the following raw materials in parts by weight: 100-110 parts of PVC resin, 20-30 parts of filler, 10-15 parts of additive, 5-10 parts of plasticizer, 1-3 parts of coupling agent, 0.8-2 parts of stabilizer, 0.8-2 parts of antioxidant, 0.8-2 parts of ultraviolet absorber and 0.05-0.1 parts of cross-linking agent.

[0007] Furthermore, the filler is one or more of kaolin, calcium carbonate, titanium dioxide, magnesium hydroxide, and aluminum hydroxide.

[0008] Furthermore, the auxiliary agent is prepared by the following steps:

[0009] S1. Add perfluorooctanoic acid, EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride), NHS (N-hydroxysuccinimide) and DMF (N,N-dimethylformamide) into a dry three-necked flask, stir and dissolve, then heat to 50°C, slowly add 2-chloro-4,6-diamino-1,3,5-triazine, keep warm and react for 6 hours, cool to room temperature after the reaction, and distill under reduced pressure to obtain intermediate 1; the dosage ratio of perfluorooctanoic acid, 2-chloro-4,6-diamino-1,3,5-triazine, EDC, NHS and DMF is 41.4g:15.7g:3.8g:2.3g:240mL;

[0010] The molar ratio of perfluorooctanoic acid to 2-chloro-4,6-diamino-1,3,5-triazine is controlled to be 1:1.05-1.1, and the -COOH of perfluorooctanoic acid and the -NH2 of 2-chloro-4,6-diamino-1,3,5-triazine undergo amidation reaction under the action of EDC and NHS. The reaction equation is as follows:

[0011]

[0012] S2. Add intermediate 1, pyridine and DMF to a dry three-necked flask under nitrogen protection, stir and dissolve, heat to 60°C, slowly add di-n-butyl chlorophosphate, and continue to react at 60°C for 3h after the addition is completed. After the reaction is completed, cool to room temperature and distill under reduced pressure to obtain intermediate 2; the amount ratio of intermediate 1, di-n-butyl chlorophosphate, pyridine and DMF is 51.5g:23.5g:9.2mL:240mL;

[0013] Pyridine is used as an acid binding agent, and the molar ratio of intermediate 1 and di-n-butyl chlorophosphate is controlled to be 1:1.05-1.1. Then, -NH2 of intermediate 1 and -Cl of di-n-butyl chlorophosphate undergo a substitution reaction under heating. The reaction process is as follows:

[0014]

[0015] S3, nitrogen was blown into a dry three-necked flask for 30 minutes to expel the air and moisture in the flask, and then 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, pyridine and dimethyl sulfoxide were added, stirred and dissolved, and the temperature was raised to 70°C, and then 4-chloro-1-butene was slowly added. After the addition was completed, the temperature was kept at 70°C for 3 hours. After the reaction was completed, the reaction was cooled to room temperature and distilled under reduced pressure to obtain intermediate 3; the amount ratio of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 4-chloro-1-butene, pyridine and dimethyl sulfoxide was 27.6mL:10.9mL:9.7mL:200mL;

[0016] Pyridine is used as an acid binding agent, and the molar ratio of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and 4-chloro-1-butene is controlled to be 1:1.05-1.1. The -NH2 of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and the -Cl of 4-chloro-1-butene undergo a substitution reaction under heating. The reaction process is shown below:

[0017]

[0018] S4. Blow nitrogen gas into a dry three-necked flask for 30 minutes to expel air and moisture from the flask, then add intermediate 2, triethylamine and DMF, stir to dissolve, then heat to 60°C, then slowly add intermediate 3, after adding, continue to keep warm at 60°C for 3 hours, cool to room temperature after the reaction is completed, and distill under reduced pressure to obtain an auxiliary agent; the usage ratio of intermediate 2, intermediate 3, triethylamine and DMF is 62.4g:27.8g:14.2mL:250mL.

[0019] Triethylamine is used as an acid binding agent to control the molar ratio of intermediate 2 and intermediate 3 to be 1:1.05-1.1. The -Cl of intermediate 2 and the -NH2 of intermediate 3 undergo a substitution reaction under heating. The reaction process is as follows:

[0020]

[0021] There is a large amount of fluorine in the additives. Fluorine is the most electronegative non-metallic element and has a strong electron affinity, which makes it difficult for fluorine atoms to be polarized in compounds. When additives containing fluorine are added to PVC floors, the surface free energy of the PVC floors can be significantly reduced, thereby reducing the contact ability of the PVC floors with other substances, making the PVC floors effectively moisture-proof.

[0022] The phosphorus element in the additive provides an acid source, reacts with the polymer resin, and promotes the formation of carbonized products; the nitrogen element provides a gas source, which can make the system expand and foam, and also promotes the formation of the carbonized layer to form porous foam carbon; the silicon element generates an inorganic heat-insulating and insulating protective layer containing -Si-O bonds and -Si-C- bonds during combustion, which not only prevents the decomposition products generated by combustion from escaping, but also inhibits the thermal decomposition of the polymer material, achieving the purpose of high flame retardancy, low smoke emission, and low harmfulness. The additive of the present invention exerts an efficient and safe flame retardant effect through the synergistic effect of nitrogen, phosphorus, and silicon halogen-free flame retardant elements, and thus the PVC floor of the present invention has excellent flame retardancy.

[0023] The additive contains terminal carbon-carbon double bonds, which can produce chemical reactions with the unreacted carbon-carbon double bonds at the end of the polyvinyl chloride resin under the action of trace cross-linking agents, and then the additive is grafted onto the macromolecular chain of the polyvinyl chloride resin. The additive is not easy to migrate and fall out, and can continue to play a flame retardant and moisture-proof role, protecting the PVC floor for a long time, making it not easy to warp and deform, not easy to burn, and greatly extending the service life of the PVC floor.

[0024] Furthermore, the plasticizer is one or more of epoxy soybean oil, di-2-ethylhexyl phthalate, di-n-octyl adipate, and dioctyl sebacate.

[0025] Furthermore, the coupling agent is one or more of vinyltrimethoxysilane, vinyltriethoxysilane, and 3-(methacryloyloxy)propyltrimethoxysilane.

[0026] Furthermore, the stabilizer is a calcium zinc stabilizer.

[0027] Furthermore, the antioxidant is one or more of antioxidant 1010, antioxidant 1098, antioxidant 245, antioxidant 168, antioxidant 1076, and antioxidant DLTP.

[0028] Furthermore, the ultraviolet absorber is one or more of the ultraviolet absorber UV-P, ultraviolet absorber UV-531, and ultraviolet absorber UVP-327.

[0029] Furthermore, the cross-linking agent is one or more of benzoyl peroxide, di-tert-butyl peroxide, and azobisisobutyronitrile.

[0030] A method for preparing a low-warping PVC floor comprises the following steps:

[0031] Weigh each raw material by weight, then add all the raw materials into a mixer for mixing, add them to an internal mixer for internal mixing after mixing evenly, then add them to a calender for pressing into sheets, and finally cut them to obtain a low warping PVC floor.

[0032] The beneficial effects of the present invention are as follows: the additive contains rich fluorine elements and halogen-free flame retardant elements such as nitrogen, phosphorus and silicon, and there is a chemical reaction between the additive and the polyvinyl chloride resin, so the additive is not easy to migrate and fall out, can continuously play a flame retardant and moisture-proof role, and protect the PVC floor for a long time, making it not easy to warp and deform, not easy to burn, and greatly extending the service life of the PVC floor. 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, preparation of auxiliary agent, the specific steps are as follows:

[0035] S1. Add 41.4 g of perfluorooctanoic acid, 3.8 g of EDC, 2.3 g of NHS and 240 mL of DMF into a 500 mL dry three-necked flask, stir to dissolve and then heat to 50°C, then slowly add 15.7 g of 2-chloro-4,6-diamino-1,3,5-triazine, keep warm for 6 h, cool to room temperature after the reaction is completed, and distill under reduced pressure to obtain intermediate 1;

[0036] S2. Under nitrogen protection, add 51.5 g of intermediate 1, 9.2 mL of pyridine and 240 mL of DMF to a 500 mL dry three-necked flask, stir to dissolve, then heat to 60°C, slowly add 23.5 g of di-n-butyl chlorophosphate, continue to keep the temperature at 60°C for 3 h after the addition, cool to room temperature after the reaction, and distill under reduced pressure to obtain intermediate 2;

[0037] S3, nitrogen was blown into a 500 mL dry three-necked flask for 30 min to expel the air and moisture in the flask, and then 27.6 mL of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 9.7 mL of pyridine and 200 mL of dimethyl sulfoxide were added, stirred and dissolved, and the temperature was raised to 70°C, and then 10.9 mL of 4-chloro-1-butene was slowly added. After the addition was completed, the reaction was continued at 70°C for 3 h. After the reaction was completed, the reaction was cooled to room temperature and distilled under reduced pressure to obtain intermediate 3;

[0038] S4. Blow nitrogen gas into a 500mL dry three-necked flask for 30 minutes to expel air and moisture in the flask, then add 62.4g of intermediate 2, 14.2mL of triethylamine and 250mL of DMF, stir to dissolve and heat to 60°C, then slowly add 27.8g of intermediate 3, continue to keep the temperature at 60°C for 3h after the addition is completed, cool to room temperature after the reaction is completed, and distill under reduced pressure to obtain an auxiliary agent.

[0039] Example 2, preparing PVC floor, the specific steps are as follows:

[0040] Each raw material was weighed by weight, and then 100 parts of PVC resin, 20 parts of kaolin, 10 parts of the auxiliary agent prepared in Example 1, 5 parts of epoxy soybean oil, 1 part of 3-(methacryloyloxy)propyltrimethoxysilane, 0.8 parts of calcium zinc stabilizer, 0.8 parts of antioxidant 1098, 0.8 parts of ultraviolet absorber UV-P, and 0.05 parts of azobisisobutyronitrile were added into a mixer for mixing. After mixing evenly, the mixture was added into an internal mixer for internal mixing, and then added into a calender for pressing into sheets, and finally cut to obtain a low warpage PVC floor.

[0041] Example 3, preparing PVC floor, the specific steps are as follows:

[0042] The raw materials were weighed in parts by weight, and then 105 parts of PVC resin, 10 parts of calcium carbonate, 5 parts of titanium dioxide, 13 parts of magnesium hydroxide, 14 parts of the additive prepared in Example 1, 4 parts of di-2-ethylhexyl phthalate, 4 parts of di-n-ethylhexyl adipate, 2 parts of vinyl trimethoxy silane, 1.5 parts of calcium zinc stabilizer, 1 part of antioxidant 1010, 0.2 parts of antioxidant 245, 0.2 parts of antioxidant 168, 1.5 parts of ultraviolet absorber UV-531, and 0.08 parts of benzoyl peroxide were added into a mixer for mixing. After mixing evenly, the mixture was added into an internal mixer for internal mixing, and then added into a calender for pressing into sheets, and finally cut to obtain a low warpage PVC floor.

[0043] Example 4, preparing PVC floor, the specific steps are as follows:

[0044] The raw materials were weighed in parts by weight, and then 110 parts of PVC resin, 10 parts of kaolin, 5 parts of calcium carbonate, 5 parts of titanium dioxide, 5 parts of magnesium hydroxide, 5 parts of aluminum hydroxide, 15 parts of the additive prepared in Example 1, 5 parts of epoxy soybean oil, 5 parts of dioctyl sebacate, 2 parts of vinyl triethoxysilane, 1 part of 3-(methacryloyloxy)propyl trimethoxysilane, 2 parts of calcium zinc stabilizer, 1.5 parts of antioxidant 1076, 0.5 parts of antioxidant DLTP, 1 part of ultraviolet absorber UV-531, 1 part of ultraviolet absorber UVP-327, and 0.1 part of di-tert-butyl peroxide were added into a mixer for mixing. After mixing evenly, the mixture was added into an internal mixer for internal mixing, and then added into a calender for pressing into sheets, and finally cut to obtain a low warpage PVC floor.

[0045] Comparative Example 1: Preparation of PVC floor, the specific steps are as follows:

[0046] The remaining steps remained unchanged, except that the auxiliary agent in Example 2 was replaced by 7 parts of melamine cyanurate and 3 parts of perfluorooctanoic acid to prepare the prepared PVC floor.

[0047] Comparative Example 2, preparing PVC floor, the specific steps are as follows:

[0048] The remaining steps remain unchanged, only the additive in Example 2 is removed to prepare the PVC floor.

[0049] Performance Testing

[0050] The PVC floors prepared in the above-mentioned Examples 2-4 and Comparative Examples 1-2 were subjected to performance tests, and the test results are shown in Table 1 below:

[0051] Table 1

[0052]

[0053] “ / ” indicates no flame retardant rating.

[0054] The PVC flooring prepared in Examples 2-4 and Comparative Examples 1-2 was cut into 2 cm 3 The small cubes were immersed in distilled water at 10℃ and 35℃ for 15 days respectively, and the changes in the morphology of the small cubes were observed. The test results are shown in Table 2 below:

[0055] Table 2

[0056] Test items 10℃ distilled water 35℃ distilled water Example 2 No change No change Example 3 No change No change Example 4 No change No change Comparative Example 1 Volume expansion rate 5.7% Volume expansion rate 13.8% Comparative Example 2 Volume expansion rate 9.4% Volume expansion rate 23.7%

[0057] It can be seen from the test results in Table 2 that the PVC floors prepared in Examples 2-4 of the present invention have excellent waterproof and moisture-proof properties and are not prone to warping or deformation.

[0058] 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.

[0059] 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 low warping PVC floor, characterized in that: The invention comprises the following raw materials in parts by weight: 100-110 parts of PVC resin, 20-30 parts of filler, 10-15 parts of auxiliary agent, 5-10 parts of plasticizer, 1-3 parts of coupling agent, 0.8-2 parts of stabilizer, 0.8-2 parts of antioxidant, 0.8-2 parts of ultraviolet absorber and 0.05-0.1 parts of cross-linking agent; Wherein, the auxiliary agent is prepared by the following steps: S1. Add perfluorooctanoic acid, EDC, NHS and DMF into a flask, stir and heat to 50°C, add 2-chloro-4,6-diamino-1,3,5-triazine, react for 6 hours, cool, and distill under reduced pressure to obtain intermediate 1; the dosage ratio of perfluorooctanoic acid, 2-chloro-4,6-diamino-1,3,5-triazine, EDC, NHS and DMF is 41.4g:15.7g:3.8g:2.3g:240mL; S2. Add intermediate 1, pyridine and DMF into a flask under nitrogen protection, stir and heat to 60°C, add di-n-butyl chlorophosphate, react for 3h, cool, and distill under reduced pressure to obtain intermediate 2; the amount ratio of intermediate 1, di-n-butyl chlorophosphate, pyridine and DMF is 51.5g:23.5g:9.2mL:240mL; S3. After nitrogen is blown into the flask, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, pyridine and dimethyl sulfoxide are added, the temperature is raised to 70°C with stirring, 4-chloro-1-butene is added, the reaction is continued for 3 hours, the reaction is cooled, and the reaction is carried out by distillation under reduced pressure to obtain intermediate 3; the dosage ratio of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 4-chloro-1-butene, pyridine and dimethyl sulfoxide is 27.6 mL:10.9 mL:9.7 mL:200 mL; S4. After nitrogen is purged into the flask, intermediate 2, triethylamine and DMF are added, the temperature is raised to 60°C with stirring, and intermediate 3 is added. The reaction is carried out for 3 hours, and the mixture is cooled and distilled under reduced pressure to obtain an auxiliary agent. The dosage ratio of intermediate 2, intermediate 3, triethylamine and DMF is 62.4 g: 27.8 g: 14.2 mL: 250 mL.

2. The low warping PVC floor according to claim 1, characterized in that: The filler is one or more of kaolin, calcium carbonate, titanium dioxide, magnesium hydroxide and aluminum hydroxide.

3. The low warping PVC floor according to claim 1, characterized in that: The plasticizer is one or more of epoxy soybean oil, di-2-ethylhexyl phthalate, di-n-octyl adipate, and di-octyl sebacate.

4. The low warping PVC floor according to claim 1, characterized in that: The coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane and 3-(methacryloyloxy)propyl trimethoxy silane.

5. The low warping PVC floor according to claim 1, characterized in that: The stabilizer is a calcium zinc stabilizer.

6. The low warping PVC floor according to claim 1, characterized in that: The antioxidant is one or more of antioxidant 1010, antioxidant 1098, antioxidant 245, antioxidant 168, antioxidant 1076, and antioxidant DLTP.

7. The low warping PVC floor according to claim 1, characterized in that: The ultraviolet absorber is one or more of the ultraviolet absorber UV-P, the ultraviolet absorber UV-531, and the ultraviolet absorber UVP-327.

8. The low warping PVC floor according to claim 1, characterized in that: The cross-linking agent is one or more of benzoyl peroxide, di-tert-butyl peroxide, and azobisisobutyronitrile.

9. The method for preparing a low warpage PVC floor according to claim 1, characterized in that: The steps include: Weigh each raw material by weight, then add all the raw materials into a mixer for mixing, add them to an internal mixer for internal mixing after mixing evenly, then add them to a calender for pressing into sheets, and finally cut them to obtain a low warping PVC floor.

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