Antibacterial PVC (polyvinyl chloride) sheet as well as preparation method and application thereof

Abstract

The invention discloses an antibacterial PVC sheet and a preparation method and application thereof, and relates to the technical field of PVC materials.3-chloropropyl dimethyl vinyl silane and tetrakis (trimethylsiloxy) titanium are used as raw materials to prepare a novel stabilizer, the stabilizer is good in compatibility with PVC, the stability of the stabilizer is improved, and the anti-bacterial PVC sheet is suitable for being used as an anti-bacterial PVC sheet. The stabilizer can be uniformly dispersed in PVC (polyvinyl chloride) under the condition that a compatilizer is not added, so that the stabilizer gives full play to the action effect, and the stabilizer can remarkably improve the light stability and heat stability of PVC, thereby effectively prolonging the service life of a PVC material and widening the application range of the PVC material.

Description

Technical Field

[0001] The invention relates to the technical field of PVC materials, and in particular to an antibacterial PVC sheet material and a preparation method and application thereof. Background Art

[0002] Polyvinyl chloride (PVC) is the third largest synthetic polymer plastic in the world, second only to polyethylene and polypropylene. PVC is a polymer formed by free radical polymerization of vinyl chloride monomer under the action of initiators or light or heat.

[0003] PVC material has good plasticity and can be processed into products of various shapes and specifications through thermal processing, mechanical processing and chemical processing; PVC material has excellent corrosion resistance and can effectively resist the erosion of chemical substances; PVC material is an excellent electrical insulation material with high voltage resistance, suitable for use as an insulation material for electrical and electronic devices. However, PVC material also has disadvantages, such as poor light stability and thermal stability, low physical and mechanical properties, and insufficient flame retardancy. The glass transition temperature of PVC is 77-90℃, and it begins to decompose at around 170℃. At temperatures above 100℃ or after long-term exposure to sunlight, it will decompose to produce hydrogen chloride, and further autocatalytic decomposition will cause discoloration, degradation of physical and mechanical properties, and other problems. Therefore, in practical applications, stabilizers must be added to improve the light and heat stability of PVC. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a method for preparing an antibacterial PVC sheet, improve the stability (including light stability and thermal stability) of PVC by preparing a new stabilizer, and solve the problem of poor compatibility between the stabilizer and PVC.

[0005] The technical problem to be solved by the present invention is achieved by adopting the following technical solutions:

[0006] One of the purposes of the present invention is to provide a method for preparing an antibacterial PVC sheet, comprising the following steps:

[0007] (1) adding 3-chloropropyldimethylvinylsilane, an initiator and tetrakis(trimethylsilyl)titanium to an organic solvent, heating the mixture for reaction, removing the organic solvent after the reaction is completed, and vacuum drying to obtain a stabilizer;

[0008] (2) uniformly mixing PVC, a reinforcing agent, a plasticizer, a stabilizer, an antioxidant and an antibacterial agent to obtain a premix;

[0009] (3) The premix is ​​added into a twin-screw extruder, plasticized and extruded, and then calendered by a calender to obtain an antibacterial PVC sheet.

[0010] Further, the mass ratio of the 3-chloropropyldimethylvinylsilane to tetrakis(trimethylsiloxy)titanium is 10:(1-10). Preferably, the mass ratio of the 3-chloropropyldimethylvinylsilane to tetrakis(trimethylsiloxy)titanium is 10:(2-5).

[0011] Furthermore, the initiator is an azo initiator or an organic peroxide initiator.

[0012] Furthermore, the organic solvent is tetrahydrofuran. Of course, other organic solvents with good compatibility with the reaction raw materials can also be used, but tetrahydrofuran is soluble in water and has a low boiling point, and can be recovered and reused by vacuum distillation during post-treatment, or can be removed by water washing.

[0013] In the present invention, 3-chloropropyldimethylvinylsilane is subjected to homopolymerization reaction under the action of an initiator to generate a polymer, and tetrakis(trimethylsilyl)titanium is dispersed in the network structure of the polymer, which can not only improve the compatibility of the stabilizer with PVC without adding a compatibilizer, but also increase the chlorine content, thereby better improving the stability of the PVC material.

[0014] Furthermore, the reinforcing agent is one or more of white carbon black, calcium carbonate, wollastonite, kaolin, glass fiber, carbon fiber, and sepiolite fiber, but is not limited thereto. The physical and mechanical properties, processing properties, and durability of the PVC material can be improved by adding the reinforcing agent.

[0015] Furthermore, the plasticizer is one or more of phthalate plasticizers, phosphate plasticizers, epoxy plasticizers, polyol ester plasticizers, and citrate plasticizers, but is not limited thereto. The addition of plasticizers can increase the flexibility of PVC, improve processing performance, and improve the durability of PVC materials.

[0016] Furthermore, the antioxidant is a hindered phenol antioxidant and / or a phosphite antioxidant. The antioxidant is added to improve the antioxidant performance of PVC, delay the oxidation reaction of PVC materials, and thus extend its service life.

[0017] Furthermore, the antibacterial agent is an inorganic antibacterial agent and / or an organic antibacterial agent. The inorganic antibacterial agent includes but is not limited to one or more of silver ions, zinc oxide, and titanium dioxide; the organic antibacterial agent includes but is not limited to one or more of quaternary ammonium salt antibacterial agents, guanidine antibacterial agents, heterocyclic compound antibacterial agents, and aldehyde antibacterial agents. The addition of antibacterial agents can give PVC good antibacterial properties, thereby broadening the application range of PVC materials.

[0018] Furthermore, the mass ratio of the PVC, reinforcing agent, plasticizer, stabilizer, antioxidant and antibacterial agent is 100:(10-30):(5-20):(1-10):(0.1-1):(0.1-1).

[0019] Furthermore, the processing temperature of the twin-screw extruder is 130-170°C, the screw speed is 50-200rpm, and the screw aspect ratio is (15-25):1; the processing temperature of the calender is 180-190°C, and the calendering speed is 5-15m / min.

[0020] The second object of the present invention is to provide an antibacterial PVC sheet prepared by the above-mentioned preparation method.

[0021] The third object of the present invention is to provide the application of the antibacterial PVC sheet in daily necessities, floor coverings, pipes, packaging materials, sealing materials, wires and cables, building materials, etc.

[0022] The invention has the beneficial effects that: the invention uses 3-chloropropyldimethylvinylsilane and tetrakis(trimethylsiloxy)titanium as raw materials to prepare a novel stabilizer, the stabilizer has good compatibility with PVC, the stabilizer can be evenly dispersed in PVC without adding a compatibilizer, so that the stabilizer can fully exert its effect, and the stabilizer can significantly improve the light stability and thermal stability of PVC, thereby effectively extending the service life of the PVC material and widening the application range of the PVC material. DETAILED DESCRIPTION

[0023] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further described below in conjunction with specific embodiments.

[0024] Example 1

[0025] (1) Add 10 parts of 3-chloropropyldimethylvinylsilane, 0.5 parts of benzoyl peroxide and 2 parts of tetrakis(trimethylsilyl)titanium to tetrahydrofuran, raise the temperature to 80° C. and react until all the monomers are polymerized. After the reaction is completed, remove the tetrahydrofuran by vacuum distillation and dry in vacuo to obtain a stabilizer.

[0026] (2) 100 parts of PVC, 10 parts of white carbon black, 10 parts of tributyl phosphate, 3 parts of stabilizer, 0.5 parts of antioxidant 1010 and 1 part of zinc oxide were mixed uniformly to obtain a premix.

[0027] (3) adding the premix into a twin-screw extruder, plasticizing and extruding, and then calendering and molding through a calender, the processing temperature of the twin-screw extruder is 130-170° C., the screw speed is 180 rpm, and the screw aspect ratio is 25:1; the processing temperature of the calender is 180-190° C., and the calendering speed is 5 m / min, to obtain an antibacterial PVC sheet.

[0028] Example 2

[0029] (1) Add 10 parts of 3-chloropropyldimethylvinylsilane, 0.25 parts of azobisisobutyronitrile and 3 parts of tetrakis(trimethylsilyl)titanium to tetrahydrofuran, raise the temperature to 70° C. and react until all the monomers are polymerized. After the reaction is completed, remove the tetrahydrofuran by distillation under reduced pressure, and vacuum dry to obtain a stabilizer.

[0030] (2) 100 parts of PVC, 15 parts of calcium carbonate, 5 parts of tributyl citrate, 5 parts of stabilizer, 0.5 parts of antioxidant 1076 and 0.5 parts of nano silver were mixed to obtain a premix.

[0031] (3) adding the premix into a twin-screw extruder, plasticizing and extruding, and then calendering and molding through a calender, the processing temperature of the twin-screw extruder is 130-170° C., the screw speed is 200 rpm, and the screw length-diameter ratio is 20:1; the processing temperature of the calender is 180-190° C., and the calendering speed is 15 m / min, to obtain an antibacterial PVC sheet.

[0032] Example 3

[0033] (1) Add 10 parts of 3-chloropropyldimethylvinylsilane, 0.3 parts of benzoyl peroxide and 5 parts of tetrakis(trimethylsilyl)titanium to tetrahydrofuran, raise the temperature to 80° C. and react until all monomers are polymerized. After the reaction is completed, remove the tetrahydrofuran by vacuum distillation and dry in vacuo to obtain a stabilizer.

[0034] (2) 100 parts of PVC, 20 parts of wollastonite powder, 15 parts of dioctyl phthalate, 8 parts of stabilizer, 0.25 parts of antioxidant 168 and 0.6 parts of polyhexamethylene biguanide were mixed uniformly to obtain a premix.

[0035] (3) adding the premix into a twin-screw extruder, plasticizing and extruding, and then calendering and molding through a calender, the processing temperature of the twin-screw extruder is 130-170° C., the screw speed is 100 rpm, and the screw length-diameter ratio is 15:1; the processing temperature of the calender is 180-190° C., and the calendering speed is 10 m / min, to obtain an antibacterial PVC sheet.

[0036] Example 4

[0037] (1) Add 10 parts of 3-chloropropyldimethylvinylsilane, 0.4 parts of azobisisobutyronitrile and 5 parts of tetrakis(trimethylsilyl)titanium to tetrahydrofuran, raise the temperature to 60° C. and react until all the monomers are polymerized. After the reaction is completed, remove the tetrahydrofuran by distillation under reduced pressure, and vacuum dry to obtain a stabilizer.

[0038] (2) 100 parts of PVC, 25 parts of kaolin, 20 parts of tributyl phosphate, 10 parts of stabilizer, 0.4 parts of antioxidant 1010 and 0.3 parts of nano silver were mixed to obtain a premix.

[0039] (3) The premix is ​​added into a twin-screw extruder, plasticized and extruded, and then calendered by a calender. The processing temperature of the twin-screw extruder is 130-170° C., the screw speed is 120 rpm, and the screw length-diameter ratio is 25:1; the processing temperature of the calender is 180-190° C., and the calendering speed is 8 m / min, to obtain an antibacterial PVC sheet.

[0040] Example 5

[0041] (1) Add 10 parts of 3-chloropropyldimethylvinylsilane, 0.5 parts of benzoyl peroxide and 5 parts of tetrakis(trimethylsilyl)titanium to tetrahydrofuran, raise the temperature to 70° C. and react until all monomers are polymerized. After the reaction is completed, remove the tetrahydrofuran by vacuum distillation and dry in vacuo to obtain a stabilizer.

[0042] (2) 100 parts of PVC, 30 parts of sepiolite fiber, 10 parts of tributyl citrate, 10 parts of stabilizer, 0.6 parts of antioxidant 168 and 1 part of zinc oxide were mixed uniformly to obtain a premix.

[0043] (3) adding the premix into a twin-screw extruder, plasticizing and extruding, and then calendering and molding through a calender, the processing temperature of the twin-screw extruder is 130-170° C., the screw speed is 150 rpm, and the screw length-diameter ratio is 20:1; the processing temperature of the calender is 180-190° C., and the calendering speed is 12 m / min, to obtain an antibacterial PVC sheet.

[0044] Example 6

[0045] (1) Add 10 parts of 3-chloropropyldimethylvinylsilane, 0.5 parts of azobisisobutyronitrile and 5 parts of tetrakis(trimethylsilyl)titanium to tetrahydrofuran, raise the temperature to 80° C. and react until all the monomers are polymerized. After the reaction is completed, remove the tetrahydrofuran by distillation under reduced pressure, and vacuum dry to obtain a stabilizer.

[0046] (2) 100 parts of PVC, 18 parts of white carbon black, 10 parts of dioctyl phthalate, 10 parts of stabilizer, 0.25 parts of antioxidant 1010, 0.25 parts of antioxidant 168 and 0.3 parts of nano silver were mixed to obtain a premix.

[0047] (3) adding the premix into a twin-screw extruder, plasticizing and extruding, and then calendering and molding through a calender, the processing temperature of the twin-screw extruder is 130-170° C., the screw speed is 100 rpm, and the screw length-diameter ratio is 25:1; the processing temperature of the calender is 180-190° C., and the calendering speed is 10 m / min, to obtain an antibacterial PVC sheet.

[0048] Comparative Example 1

[0049] Comparative Example 1 is to replace the stabilizer in Example 1 with tetrakis(trimethylsilyl)titanium, and other conditions are the same as Example 1.

[0050] (1) 100 parts of PVC, 10 parts of white carbon black, 10 parts of tributyl phosphate, 3 parts of tetrakis(trimethylsilyl)titanium, 0.5 parts of antioxidant 1010 and 1 part of zinc oxide were mixed uniformly to obtain a premix.

[0051] (2) adding the premix into a twin-screw extruder, plasticizing and extruding, and then calendering and molding through a calender, the processing temperature of the twin-screw extruder is 130-170° C., the screw speed is 180 rpm, and the screw length-diameter ratio is 25:1; the processing temperature of the calender is 180-190° C., and the calendering speed is 5 m / min, to obtain an antibacterial PVC sheet.

[0052] Comparative Example 2

[0053] Comparative Example 2 is that the stabilizer in Example 1 is replaced by lead stearate, and the other conditions are the same as Example 1.

[0054] (1) 100 parts of PVC, 10 parts of white carbon black, 10 parts of tributyl phosphate, 3 parts of lead stearate, 0.5 parts of antioxidant 1010 and 1 part of zinc oxide were mixed uniformly to obtain a premix.

[0055] (2) adding the premix into a twin-screw extruder, plasticizing and extruding, and then calendering and molding through a calender, the processing temperature of the twin-screw extruder is 130-170° C., the screw speed is 180 rpm, and the screw length-diameter ratio is 25:1; the processing temperature of the calender is 180-190° C., and the calendering speed is 5 m / min, to obtain an antibacterial PVC sheet.

[0056] Comparative Example 3

[0057] Comparative Example 3 is that the stabilizer in Example 1 is replaced by dibutyltin dilaurate, and the other conditions are the same as Example 1.

[0058] (1) 100 parts of PVC, 10 parts of white carbon black, 10 parts of tributyl phosphate, 3 parts of dibutyltin dilaurate, 0.5 parts of antioxidant 1010 and 1 part of zinc oxide were mixed uniformly to obtain a premix.

[0059] (2) adding the premix into a twin-screw extruder, plasticizing and extruding, and then calendering and molding through a calender, the processing temperature of the twin-screw extruder is 130-170° C., the screw speed is 180 rpm, and the screw length-diameter ratio is 25:1; the processing temperature of the calender is 180-190° C., and the calendering speed is 5 m / min, to obtain an antibacterial PVC sheet.

[0060] The PVC sheets prepared in the above Examples 1 to 6 and Comparative Examples 1 to 3 were subjected to a Congo red test (170° C.) and an ultraviolet aging test (UVA-340, 0.76 W, 8 h, 60° C.) to measure the thermal stability time and weight loss rate. The measurement results are shown in Table 1.

[0061] Table 1

[0062]

[0063]

[0064] It can be seen from Table 1 that, compared with the commonly used PVC stabilizers (lead stearate and dibutyltin dilaurate) in the art, the stabilizers prepared in Examples 1 to 6 of the present invention can better improve the thermal stability and light stability of the PVC sheet.

[0065] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for preparing an antibacterial PVC sheet, characterized in that: The following steps are involved: (1) adding 3-chloropropyldimethylvinylsilane, an initiator and tetrakis(trimethylsilyl)titanium to an organic solvent, heating the mixture for reaction, removing the organic solvent after the reaction is completed, and vacuum drying to obtain a stabilizer; (2) uniformly mixing PVC, a reinforcing agent, a plasticizer, a stabilizer, an antioxidant and an antibacterial agent to obtain a premix; (3) The premix is ​​added into a twin-screw extruder, plasticized and extruded, and then calendered by a calender to obtain an antibacterial PVC sheet.

2. The preparation method according to claim 1, characterized in that: The mass ratio of the 3-chloropropyldimethylvinylsilane to tetrakis(trimethylsilyloxy)titanium is 10:(1-10).

3. The preparation method according to claim 1, characterized in that: The initiator is an azo initiator or an organic peroxide initiator.

4. The preparation method according to claim 1, characterized in that: The reinforcing agent is one or more of white carbon black, calcium carbonate, wollastonite, kaolin, glass fiber, carbon fiber, and sepiolite fiber.

5. The preparation method according to claim 1, characterized in that: The plasticizer is one or more of phthalate plasticizers, phosphate plasticizers, epoxy plasticizers, polyol ester plasticizers, and citrate plasticizers.

6. The preparation method according to claim 1, characterized in that: The antioxidant is a hindered phenol antioxidant and / or a phosphite antioxidant.

7. The preparation method according to claim 1, characterized in that: The antibacterial agent is an inorganic antibacterial agent and / or an organic antibacterial agent.

8. The preparation method according to claim 1, characterized in that: The mass ratio of the PVC, reinforcing agent, plasticizer, stabilizer, antioxidant and antibacterial agent is 100:(10-30):(5-20):(1-10):(0.1-1):(0.1-1).

9. An antibacterial PVC sheet prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the antibacterial PVC sheet according to claim 9 in daily necessities, floor coverings, pipes, packaging materials, sealing materials, wires and cables, building materials, etc.

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