Low-smoke flame-retardant PVC floor film and preparation method thereof

Abstract

The invention relates to the technical field of polyvinyl chloride, and discloses a low-smoke flame-retardant PVC floor film and a preparation method thereof.The low-smoke flame-retardant PVC floor film is prepared from, by weight, 100 parts of polyvinyl chloride resin, 5-20 parts of epoxidized soybean oil antistatic flame retardant and the like. The epoxidized soybean oil antistatic flame retardant contains a large number of phosphate flame-retardant groups and a benzene ring structure with high char-forming property, combusted phosphate is pyrolyzed to generate phosphoric acid substances, dehydration of a floor film is promoted to form a carbon layer, oxygen can be isolated, smoke escape is inhibited, and good smoke suppression and flame retardant effects are achieved. The epoxidized soybean oil antistatic flame retardant contains hydrophilic carboxyl and quaternary ammonium salt groups, so that the water contact angle of a polyvinyl chloride film can be reduced, the surface resistivity is reduced, and the surface hydrophilicity and antistatic performance of a floor film are improved.

Description

Technical Field

[0001] The invention relates to the technical field of polyvinyl chloride, in particular to a low-smoke flame-retardant PVC floor film and a preparation method thereof. Background Art

[0002] Polyvinyl chloride has good mechanical properties, chemical resistance, corrosion resistance and other properties, and is widely used in building materials such as floor membranes, wood-plastic panels, pipes and tubes. In order to improve the flame retardancy, antistatic, surface hydrophilicity and other properties of polyvinyl chloride floor membranes and other building materials, flame retardants, antistatic agents, etc. need to be added, such as zinc borate, phosphate ester and other flame retardants, carbon black, quaternary ammonium salts and other antistatic agents. Compared with inorganic flame retardants and antistatic agents, organic flame retardants and antistatic agents have various preparation methods, better compatibility with high molecular weight polymer resins, and less effect on the mechanical properties of the materials.

[0003] Epoxidized soybean oil is inexpensive, readily available, non-toxic, and pollution-free. It contains active epoxy groups and can be used as a main agent in plasticizers, compatibilizers, flame retardants, and other additives. It is widely used in polymer materials such as polyvinyl chloride (PVC). Chinese patent CN113372220B discloses a polyester-hydrogenated rosin-modified epoxidized soybean oil, its preparation method, and its application. The polyester-hydrogenated rosin-modified epoxidized soybean oil is obtained by reacting hydrogenated rosin with epoxidized soybean oil. This oil can plasticize PVC. However, the modified epoxidized soybean oil in this patent does not improve the flame retardant or antistatic properties of PVC. Summary of the Invention

[0004] The invention solves the problem of poor hydrophilicity and antistatic performance of polyvinyl chloride materials used for floor membranes and improves flame retardancy.

[0005] Technical solution: A low-smoke flame-retardant PVC floor film and a preparation method thereof. The low-smoke flame-retardant PVC floor film includes, by weight, 100 parts of polyvinyl chloride resin, 5-20 parts of epoxy soybean oil antistatic flame retardant, 6-15 parts of filler, 15-30 parts of plasticizer, 3-4 parts of heat stabilizer, and 2.5-4 parts of additives.

[0006] The preparation method of low-smoke flame-retardant PVC floor film is as follows:

[0007] Step A: Add 112-128 parts of glycine and 150-168 parts of triethylamine to methanol by weight, stir, then add 100 parts of terephthalaldehyde, stir and react at 20-30°C for 40-60 minutes, then add 206-216 parts of diethyl phosphite, stir and react at 20-30°C for 12-18 hours, dilute with water, add hydrochloric acid solution dropwise to adjust the pH to 3-4, precipitate, filter the product, and recrystallize it in dichloromethane to obtain a phosphate flame retardant. The reaction formula is:

[0008]

[0009] Step B: Add 100 parts of epoxy soybean oil, 120-200 parts of phosphate flame retardant, and 4-6 parts of fluoroboric acid to isopropyl alcohol by weight, perform the reaction, distill under reduced pressure, wash with saturated sodium sulfate solution, and dry to obtain epoxy soybean oil flame retardant.

[0010] Step C: Add 100 parts by weight of epoxy soybean oil flame retardant and 60-75 parts by weight of alkyl bromide to N,N-dimethylformamide to react with the unreacted imino groups of the epoxy soybean oil flame retardant. Then, add 120-150 parts of alkyl bromide and stir to carry out quaternization reaction. Then, distill under reduced pressure, wash with petroleum ether, and dry to obtain epoxy soybean oil antistatic flame retardant. The reaction formula is:

[0011]

[0012] Step D: Add polyvinyl chloride resin, epoxy soybean oil antistatic flame retardant, filler, plasticizer, heat stabilizer, and additives into a mixer, mix at 80-90° C. for 10-30 minutes, then mix in an open mill at 165-175° C. for 10-20 minutes, and finally hot press at 170-180° C. for 8-10 minutes under a pressure of 10-15 MPa in a flat vulcanizer, and cold press at room temperature for 5-8 minutes to obtain a low-smoke flame-retardant PVC floor film.

[0013] Furthermore, the reaction temperature in step B is 70-80° C., and the reaction time is 24-36 h.

[0014] Furthermore, in step C, the temperature of the first reaction is 40-60° C. and the reaction time is 6-10 h, and the temperature of the second reaction is 110-130° C. and the reaction time is 24-48 h.

[0015] Furthermore, the structural formula of the alkyl bromide in step C is Br-C n H 2n+1 , n is any integer between 4 and 8.

[0016] Furthermore, the filler is calcium carbonate powder or silicon dioxide powder.

[0017] Furthermore, the plasticizer is dioctyl phthalate or dibutyl phthalate.

[0018] Furthermore, the heat stabilizer is a lead salt stabilizer, including any one or a combination of dibasic lead phosphite and tribasic lead sulfate.

[0019] Furthermore, the auxiliary agent is any one or a combination of stearic acid, calcium stearate, and zinc stearate.

[0020] The beneficial technical effects of the present invention are as follows: the imino group of the phosphate flame retardant is reacted with the epoxy group of the epoxy soybean oil to obtain the epoxy soybean oil flame retardant, which is further quaternized with 1-bromohexane or the like to obtain the epoxy soybean oil antistatic flame retardant, which is then blended with polyvinyl chloride, fillers, plasticizers, etc. to form a film to obtain a low-smoke flame-retardant PVC floor film.

[0021] The epoxy soybean oil antistatic flame retardant of the present invention contains a large number of phosphate flame retardant groups and a benzene ring structure with high carbonization property. The combustion of phosphate esters is pyrolyzed to generate phosphoric acid substances, which promote the dehydration of the floor film to form a carbon layer, can isolate oxygen, inhibit smoke escape, reduce the peak value of the combustion heat release rate and the total smoke production during combustion, and show good smoke suppression and flame retardant effects.

[0022] The epoxy soybean oil antistatic flame retardant contains hydrophilic carboxyl groups and quaternary ammonium salt groups, which can reduce the water contact angle of the polyvinyl chloride film, improve the surface hydrophilicity, and help reduce the surface resistivity. In addition, the quaternary ammonium salt cationic group can promote charge transfer, reduce the surface charge density of the PVC floor film, significantly reduce the surface resistivity, and improve the antistatic performance. DETAILED DESCRIPTION

[0023] To make the purpose, features, and advantages of the invention of this application more obvious and easy to understand, the technical solutions in the embodiments of this application are clearly and completely described below. Obviously, the embodiments described below are only part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0024] Polyvinyl chloride resin model HG-1000F is sourced from Wanhua Chemical (Yantai) Petrochemical Co., Ltd.

[0025] Example 1

[0026] (1) 56 g of glycine and 75 g of triethylamine were added to 3.7 L of methanol, and after stirring, 50 g of terephthalaldehyde was added, and the mixture was stirred at 30° C. for 40 min. Then, 103 g of diethyl phosphite was added, and the mixture was stirred at 30° C. for 12 h. 7 L of water was added to dilute the mixture, and hydrochloric acid solution was added dropwise to adjust the pH to 3. The precipitate was precipitated, and the product was filtered and recrystallized in dichloromethane to obtain a phosphate flame retardant.

[0027] (2) Add 200 g of epoxy soybean oil, 240 g of phosphate flame retardant, and 8 g of fluoroboric acid to 1 L of isopropanol, heat to 75°C, stir and react for 24 h, distill under reduced pressure, wash with saturated sodium sulfate solution, and dry to obtain epoxy soybean oil flame retardant.

[0028] (3) Add 300 g of epoxy soybean oil flame retardant and 206 g of 1-bromohexane to 3 L of N,N-dimethylformamide, heat to 60 ° C, stir and react for 6 h, then add 412 g of 1-bromohexane, heat to 120 ° C, stir and react for 36 h, distill under reduced pressure, wash with petroleum ether, and dry to obtain epoxy soybean oil antistatic flame retardant.

[0029] (4) Add 5 kg of polyvinyl chloride resin, 0.25 kg of epoxy soybean oil antistatic flame retardant, 600 g of filler calcium carbonate powder, 1.5 kg of plasticizer dioctyl phthalate, 55 g of dibasic lead phosphite, 95 g of tribasic lead sulfate, 72 g of stearic acid, and 128 g of calcium stearate into a mixer, mix at 80 ° C for 20 min, then mix at 175 ° C for 10 min in an open mill, and finally hot press at 175 ° C for 10 min under a pressure of 10 MPa in a flat vulcanizer, and cold press at room temperature for 5 min to obtain a low-smoke flame-retardant PVC floor film.

[0030] Example 2

[0031] (1) 64 g of glycine and 84 g of triethylamine were added to 4 L of methanol, and 50 g of terephthalaldehyde was added after stirring. The mixture was stirred at 20° C. for 60 min, and then 108 g of diethyl phosphite was added. The mixture was stirred at 20° C. for 18 h. 8 L of water was added to dilute the mixture, and hydrochloric acid solution was added dropwise to adjust the pH to 4. The precipitate was precipitated, and the product was filtered and recrystallized in dichloromethane to obtain a phosphate flame retardant.

[0032] (2) Add 200 g of epoxy soybean oil, 320 g of phosphate flame retardant, and 9.6 g of fluoroboric acid to 1.2 L of isopropanol, heat to 70°C, stir and react for 36 h, distill under reduced pressure, wash with saturated sodium sulfate solution, and dry to obtain epoxy soybean oil flame retardant.

[0033] (3) Add 300 g of epoxy soybean oil flame retardant and 225 g of 1-bromooctane to 3 L of N,N-dimethylformamide, heat to 40 ° C, stir and react for 10 h, then add 450 g of 1-bromooctane, heat to 130 ° C, stir and react for 24 h, distill under reduced pressure, wash with petroleum ether, and dry to obtain epoxy soybean oil antistatic flame retardant.

[0034] (4) Add 5 kg of polyvinyl chloride resin, 0.6 kg of epoxy soybean oil antistatic flame retardant, 750 g of filler calcium carbonate powder, 1.1 kg of plasticizer dibutyl phthalate, 70 g of dibasic lead phosphite, 130 g of tribasic lead sulfate, 50 g of stearic acid, and 75 g of calcium stearate into a mixer, mix at 90 ° C for 10 min, then mix at 165 ° C for 20 min in an open mill, and finally hot press at 180 ° C for 10 min under a pressure of 15 MPa in a flat vulcanizer, and cold press at room temperature for 8 min to obtain a low-smoke flame-retardant PVC floor film.

[0035] Example 3

[0036] (1) To 1.5 L of isopropanol were added 200 g of epoxy soybean oil, 400 g of a phosphate flame retardant (prepared in Example 1), and 12 g of fluoroboric acid. The mixture was heated to 80° C. and stirred for 24 h. The mixture was distilled under reduced pressure, washed with a saturated sodium sulfate solution, and dried to obtain an epoxy soybean oil flame retardant.

[0037] (2) Add 300 g of epoxy soybean oil flame retardant and 180 g of 1-bromobutane to 4 L of N,N-dimethylformamide, heat to 45 ° C, stir and react for 10 hours, then add 360 g of 1-bromobutane, heat to 110 ° C, stir and react for 48 hours, distill under reduced pressure, wash with petroleum ether, and dry to obtain epoxy soybean oil antistatic flame retardant.

[0038] (3) Add 5 kg of polyvinyl chloride resin, 1 kg of epoxy soybean oil antistatic flame retardant, 300 g of filler silica powder, 0.75 kg of plasticizer dioctyl phthalate, 60 g of dibasic lead phosphite, 110 g of tribasic lead sulfate, 60 g of stearic acid, and 100 g of zinc stearate into a mixer, mix at 80 ° C for 30 min, then mix at 170 ° C for 10 min in an open mill, and finally hot press at 170 ° C for 8 min under a pressure of 10 MPa in a flat vulcanizer, and cold press at room temperature for 5 min to obtain a low-smoke flame-retardant PVC floor film.

[0039] Comparative Example 1: The difference between this comparative example and Example 1 is that the epoxy soybean oil antistatic flame retardant is not added.

[0040] (1) 5 kg of polyvinyl chloride resin, 0.25 kg of epoxy soybean oil, 600 g of filler calcium carbonate powder, 1.5 kg of plasticizer dioctyl phthalate, 55 g of dibasic lead phosphite, 95 g of tribasic lead sulfate, 72 g of stearic acid, and 128 g of calcium stearate were added to a mixer and mixed at 80 ° C for 20 min, then mixed at 175 ° C for 10 min in an open mill, and finally hot pressed at 175 ° C for 10 min under a pressure of 10 MPa in a flat vulcanizer, and cold pressed at room temperature for 5 min to obtain a PVC floor film.

[0041] Comparative Example 2: The difference between this comparative example and Example 1 is that epoxy soybean oil is used instead of epoxy soybean oil antistatic flame retardant.

[0042] (1) 5 kg of polyvinyl chloride resin, 0.25 kg of epoxy soybean oil, 600 g of filler calcium carbonate powder, 1.5 kg of plasticizer dioctyl phthalate, 55 g of dibasic lead phosphite, 95 g of tribasic lead sulfate, 72 g of stearic acid, and 128 g of calcium stearate were added to a mixer and mixed at 80 ° C for 20 min, then mixed at 175 ° C for 10 min in an open mill, and finally hot pressed at 175 ° C for 10 min under a pressure of 10 MPa in a flat vulcanizer, and cold pressed at room temperature for 5 min to obtain a PVC floor film.

[0043] Comparative Example 3: The difference between this comparative example and Example 1 is that the epoxy soybean oil flame retardant is used instead of the epoxy soybean oil antistatic flame retardant.

[0044] (1) 5 kg of polyvinyl chloride resin, 0.25 kg of epoxy soybean oil flame retardant, 600 g of filler calcium carbonate powder, 1.5 kg of plasticizer dioctyl phthalate, 55 g of dibasic lead phosphite, 95 g of tribasic lead sulfate, 72 g of stearic acid, and 128 g of calcium stearate were added to a mixer and mixed at 80 ° C for 20 min, then mixed at 175 ° C for 10 min in an open mill, and finally hot pressed at 175 ° C for 10 min under a pressure of 10 MPa in a flat vulcanizer, and cold pressed at room temperature for 5 min to obtain a PVC floor film.

[0045] Comparative Example 4: The difference between this comparative example and Example 1 is that iminodiacetic acid is used instead of the phosphate flame retardant.

[0046] (1) Add 200 g of epoxy soybean oil, 240 g of iminodiacetic acid, and 8 g of fluoroboric acid to 1 L of isopropanol, heat to 75°C, stir and react for 24 h, distill under reduced pressure, wash with saturated sodium sulfate solution, and dry to obtain carboxyl-containing epoxy soybean oil.

[0047] (2) 5 kg of polyvinyl chloride resin, 0.25 kg of carboxyl-containing epoxy soybean oil, 600 g of filler calcium carbonate powder, 1.5 kg of plasticizer dioctyl phthalate, 55 g of dibasic lead phosphite, 95 g of tribasic lead sulfate, 72 g of stearic acid, and 128 g of calcium stearate were added to a mixer and mixed at 80°C for 20 min. Then, the mixture was mixed at 175°C for 10 min in an open mill. Finally, the mixture was hot pressed at 175°C for 10 min under a pressure of 10 MPa in a flat vulcanizer and cold pressed at room temperature for 5 min to obtain a PVC floor film.

[0048] The combustion performance of PVC floor membrane was tested using a cone calorimeter with a thermal radiation condition of 35kW / m 2 The surface resistivity of PVC flooring was tested using an insulation resistance tester at a temperature of 25°C and a relative humidity of 60%. The water contact angle was tested according to GB / T 30693-2014.

[0049] Table 1 PVC floor film performance test

[0050]

[0051]

[0052] After testing, compared with the PVC floor film of Comparative Example 1, Examples 1-3 added epoxy soybean oil anti-static flame retardant, which contains a large number of phosphate flame retardant groups and a highly char-forming benzene ring structure. The combustion of phosphate esters pyrolyzes to generate phosphoric acid substances, which promote the dehydration of the floor film to form a carbon layer, can isolate oxygen, inhibit smoke escape, reduce the peak combustion heat release rate and total smoke production during combustion, and show good smoke suppression and flame retardant effects. In addition, the epoxy soybean oil anti-static flame retardant contains hydrophilic carboxyl groups and quaternary ammonium salt groups, which can reduce the water contact angle of the polyvinyl chloride film, improve the surface hydrophilicity, and help reduce the surface resistivity. The quaternary ammonium salt cationic group can promote charge transfer and reduce the surface charge density of the PVC floor film, thereby significantly reducing the surface resistivity and improving the antistatic performance.

[0053] In Comparative Example 2, only epoxy soybean oil was added, which does not contain phosphate flame retardant groups and highly char-forming benzene ring structures, nor does it contain carboxyl groups and quaternary ammonium salt groups. As a result, the peak heat release rate and total smoke production of the PVC floor film are large, the smoke suppression and flame retardant properties are very poor, and the surface resistivity and water contact angle are large, and the antistatic and surface hydrophilicity are poor.

[0054] Comparative Example 3 added epoxy soybean oil flame retardant, which does not contain quaternary ammonium salt cationic groups, resulting in a large surface resistivity of the PVC floor film and poor antistatic performance.

[0055] In Comparative Example 4, iminodiacetic acid and epoxy soybean oil were reacted to obtain carboxyl-containing epoxy soybean oil, which did not contain phosphate flame retardant groups and highly char-forming benzene ring structures, nor did it contain quaternary ammonium salt cationic groups. As a result, the smoke suppression and flame retardant properties of the PVC floor film were very poor, and the surface resistivity was large and the antistatic performance was poor.

[0056] This specific embodiment is merely an explanation of the present invention and is not intended to limit the present invention. After reading this specification, those skilled in the art may make non-creative modifications to this embodiment as needed. However, as long as such modifications are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. A low-smoke flame-retardant PVC floor film, characterized in that: The low-smoke flame-retardant PVC floor film comprises, by weight, 100 parts of polyvinyl chloride resin, 5-20 parts of epoxy soybean oil antistatic flame retardant, 6-15 parts of filler, 15-30 parts of plasticizer, 3-4 parts of heat stabilizer, and 2.5-4 parts of additives; The preparation method of the epoxy soybean oil antistatic flame retardant is as follows: (1) adding 100 parts by weight of epoxy soybean oil, 120-200 parts of phosphate flame retardant, and 4-6 parts of fluoroboric acid to isopropyl alcohol, and performing the reaction by vacuum distillation, washing, and drying to obtain the epoxy soybean oil flame retardant; The structural formula of the phosphate flame retardant is (2) Add 100 parts by weight of epoxy soybean oil flame retardant and 60-75 parts of alkyl bromide to N,N-dimethylformamide, stir and react, then add 120-150 parts of alkyl bromide, continue stirring and react, distill under reduced pressure, wash with petroleum ether, and dry to obtain epoxy soybean oil antistatic flame retardant.

2. The low-smoke flame-retardant PVC floor membrane according to claim 1, characterized in that: The reaction temperature in (1) is 70-80°C and the reaction time is 24-36h.

3. The low-smoke flame-retardant PVC floor membrane according to claim 1, characterized in that: The temperature of the first reaction in (2) is 40-60°C and the reaction time is 6-10 hours, and the temperature of the second reaction is 110-130°C and the reaction time is 24-48 hours.

4. The low-smoke flame-retardant PVC floor membrane according to claim 1, characterized in that: The structural formula of the alkyl bromide in (2) is Br-C n H 2n+1 , n is any integer between 4 and 8.

5. The low-smoke flame-retardant PVC floor membrane according to claim 1, characterized in that: The filler is calcium carbonate micropowder or silicon dioxide micropowder.

6. The low-smoke flame-retardant PVC floor membrane according to claim 1, characterized in that: The plasticizer is dioctyl phthalate or dibutyl phthalate.

7. The low-smoke flame-retardant PVC floor membrane according to claim 1, characterized in that: The heat stabilizer is a lead salt stabilizer, including any one or a combination of dibasic lead phosphite and tribasic lead sulfate.

8. The low-smoke flame-retardant PVC floor membrane according to claim 1, characterized in that: The auxiliary agent is any one or a combination of stearic acid, calcium stearate and zinc stearate.

9. The low-smoke flame-retardant PVC floor membrane according to claim 1, characterized in that: The preparation method of the phosphate flame retardant comprises the following steps: adding 112-128 parts of glycine and 150-168 parts of triethylamine by weight to methanol, stirring, adding 100 parts of terephthalaldehyde, stirring and reacting at 20-30° C. for 40-60 minutes, then adding 206-216 parts of diethyl phosphite, stirring and reacting at 20-30° C. for 12-18 hours, adding water for dilution, dripping a hydrochloric acid solution to adjust the pH to 3-4, precipitating a precipitate, filtering the product, and recrystallizing it to obtain the phosphate flame retardant.

10. A method for preparing the low-smoke flame-retardant PVC floor film according to any one of claims 1 to 9, characterized in that: The preparation method comprises the following steps: adding polyvinyl chloride resin, epoxy soybean oil antistatic flame retardant, filler, plasticizer, heat stabilizer and auxiliary agent into a mixer, mixing at 80-90° C. for 10-30 minutes, then kneading in an open mill at 165-175° C. for 10-20 minutes, and finally hot pressing at 170-180° C. for 8-10 minutes under a pressure of 10-15 MPa in a flat vulcanizing press, and cold pressing at room temperature for 5-8 minutes to obtain a low-smoke flame-retardant PVC floor film.

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