CN104592686B - For pvc material manufacturing table tennis and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of for pvc material manufacturing table tennis and preparation method thereof, described pvc material includes the raw material of following weight portion: polrvinyl chloride 50～150 parts；Nano-calcium carbonate 5～20 parts；Solid plasticizer 6～22 parts；Calcium-zinc composite stabilizing agent 3～12 parts；Toughener 10～30 parts；Pigment 0.01～0.1 part.This pvc material in mechanical property, especially in spring and resistance to impact performance with xylonite table tennis substantially close to, in outward appearance and touch, the most basically identical with xylonite table tennis.

Description

Polyvinyl chloride material for making table tennis and its preparation method

technical field

The invention relates to the technical field of table tennis manufacturing, in particular to a polyvinyl chloride material used for manufacturing table tennis and a preparation method thereof.

Background technique

Since 1935, the hard ball made of celluloid as the main raw material has been the official game ball of table tennis. However, there are many problems in the manufacture, storage and transportation of celluloid table tennis balls. Mainly: (1) long production cycle and high cost; (2) serious environmental pollution; (3) great potential safety hazards.

Both at home and abroad have been devoting themselves to the research and development of non-celluloid table tennis materials and table tennis manufacturing technology thereof. Chinese patent 90103206.9 discloses a modified polystyrene as the main body, and then adds auxiliary materials such as plasticizers to manufacture table tennis balls by means of vacuum suction; Chinese patent 01126885.9 discloses a modified polystyrene with low-pressure polyethylene and polycarbonate as the main raw material, using multiple pressure extrusion methods to manufacture seamless table tennis; Chinese patent 201210394317.9 discloses a butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer and cellulose acetate as the main raw material, using injection molding method to manufacture low-cost table tennis; Chinese patent 201310139356.9, Chinese patent 201210327507.9 and Chinese patent 201310069506.3 all disclose different technologies for manufacturing table tennis with cellulose acetate as the main raw material.

In the specific production process of the above-mentioned disclosed patented technology, either the performance of the table tennis ball is difficult to reach the standard or the production efficiency cannot be compared with the existing technology. Ball technology can replace celluloid as a new material for making table tennis balls. This material should not only be very close to celluloid in terms of mechanical properties to ensure the sports characteristics of table tennis balls, but also meet the requirements of existing table tennis technology equipment in terms of processing performance. To ensure the high-speed and efficient manufacturing process.

Contents of the invention

In view of this, the purpose of the present invention is to propose a polyvinyl chloride material for making table tennis and a preparation method thereof, so as to overcome the technical problems in the prior art.

Based on above-mentioned purpose, the present invention provides a kind of polyvinyl chloride material that is used to manufacture table tennis, comprises the raw material of following weight portion:

50-150 parts of polyvinyl chloride; 5-20 parts of nano-calcium carbonate;

6-22 parts of solid plasticizer; 3-12 parts of calcium-zinc composite stabilizer;

10-30 parts of toughening agent; 0.01-0.1 parts of pigment.

As an embodiment of the present invention, the polyvinyl chloride material includes the following raw materials in parts by mass:

80-120 parts of polyvinyl chloride; 11-16 parts of nano-calcium carbonate;

10-18 parts of solid plasticizer; 6-10 parts of calcium-zinc composite stabilizer;

15-25 parts of toughening agent; 0.03-0.08 parts of pigment.

As yet another embodiment of the present invention, the particle size of the nano-calcium carbonate is 100-1000 nm.

As yet another embodiment of the present invention, the nano-calcium carbonate is nano-calcium carbonate modified by a surfactant.

As another embodiment of the present invention, the surfactant is calcium stearate.

As yet another embodiment of the present invention, the step of described calcium stearate modified nanometer calcium carbonate comprises:

Mix calcium carbonate and water according to the solid-to-liquid ratio of 1:4~6g/g, heat up to 60~90°C, add calcium stearate, react for 40~80 minutes, then filter, vacuum dry, grind and sieve to obtain modified Nano-calcium carbonate; the quality of the calcium stearate is 0.5-3% of the quality of the nano-calcium carbonate.

As yet another embodiment of the present invention, the polyvinyl chloride is selected from a polyvinyl chloride resin with a degree of polymerization of 800-1500.

As yet another embodiment of the present invention, the solid plasticizer is at least one selected from camphor powder and dicyclohexyl terephthalate.

As another embodiment of the present invention, the toughening agent is selected from at least one of MBS resin, chlorinated polyethylene and vinyl acetate resin.

The present invention also provides a method for preparing the above-mentioned polyvinyl chloride material for making table tennis, the preparation method comprising the following steps:

Stir and mix the raw materials in a high-speed mixer according to their respective weight proportions, first mix at a low speed, then mix at a high speed, the mixing speed is 400-800 rpm, the temperature of the mixture is 115-120°C, and then the mixture is discharged Cool in a cooling mixer, wait until cooled to 45-30°C, and discharge;

Extrude the mixed raw materials with a single-screw extruder at a temperature of 135-160°C, and then introduce the extruded material into a two-roll machine for mixing at a temperature of 150-170°C;

Use a flat tractor to pull the sheet material to a six-roller machine, and shape it into a sheet with a thickness of 58-62 μm at 40-45 ° C. The sheet material is dropped to 40-25 ° C by the six-roller machine to obtain Polyvinyl chloride sheet used to make table tennis balls.

As can be seen from the above, the polyvinyl chloride material used to manufacture table tennis provided by the invention is made into a table tennis ball by stamping. The thickness of the sheet is uniform and controllable than injection molding, and the density is uniform. The material is easy to extend and has good processing performance, which is conducive to stamping and forming, so that the entire table tennis ball is more uniform and concentricity is better, so the pass rate of table tennis balls (eccentricity ≤ 60°) is higher.

The polyvinyl chloride material that is used to manufacture table tennis provided by the present invention takes polyvinyl chloride as the main raw material, and is assisted with nano-calcium carbonate, solid plasticizer, reinforcing toughening agent and thermal stabilizer etc., in the preparation sheet process, The flatness during extrusion is better; after being made into a table tennis ball, it is basically close to celluloid table tennis balls in terms of mechanical properties, especially in terms of bounce and impact resistance. Celluloid table tennis is basically the same.

Moreover, the production process of the polyvinyl chloride material does not use solvents at all, so there is no waste liquid discharge; the use of polyvinyl chloride instead of celluloid eliminates potential safety hazards in the production process; the use of polyvinyl chloride sheets instead of celluloid sheets Manufacture table tennis, can basically continue to use table tennis manufacturing process and not significantly increase equipment cost. Therefore, the preparation method of the polyvinyl chloride material is simple, safe, reliable and environmentally friendly, and the pollution in the preparation process of the celluloid sheet is completely abandoned.

Description of drawings

Fig. 1 is the process flow chart of the polyvinyl chloride material that the embodiment of the present invention is used to manufacture table tennis.

detailed description

In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be described in further detail below in conjunction with specific embodiments and with reference to the accompanying drawings.

Example 1

Referring to Fig. 1, as an embodiment of the present invention, the preparation method described for making the polyvinyl chloride material of table tennis comprises the following steps:

1) Take by weighing 100kg of polyvinyl chloride (polymerization degree 810), 15kg of calcium carbonate with a particle diameter of 200nm, 15kg of camphor powder, 7kg of calcium-zinc composite stabilizer, 20kg of MBS resin, and 10g of ultramarine blue.

2) Mix the raw materials obtained in step 1) in a high-speed mixer, first mix at a low speed, and then mix at a high speed. The material is discharged into the cooling mixer for cooling, and the material is discharged after being cooled to 40°C.

3) Extrude the mixed raw materials with a single-screw extruder at a temperature of 135 to 160°C; then introduce the extruded material into a two-roller machine for kneading and sheet production at a kneading temperature of 160°C.

4) Pull the sheet to a six-roll machine with a flat tractor, and shape it into a sheet with a thickness of 59 μm at 40° C., and the discharge temperature of the sheet is reduced to 35° C. through the six-roll machine.

5) Slice the shaped sheet (generally sliced into 1-meter-wide and 2-meter-long sheets, or the size of the sheet can be changed according to needs), then naturally cool to room temperature, and then flatten the sheet and store it in storage to obtain Polyvinyl chloride material used to make table tennis balls.

Among them, the MBS resin is a terpolymer of methyl methacrylate (M)-butadiene (B)-styrene (S).

Example 2

Referring to Fig. 1, as an embodiment of the present invention, the preparation method described for making the polyvinyl chloride material of table tennis comprises the following steps:

1) take polyvinyl chloride (polymerization degree 1020) 110kg, particle diameter is the calcium carbonate 12kg of 800nm, dicyclohexyl terephthalate 15kg, calcium-zinc composite stabilizer 8kg, MBS resin 10kg and chlorinated polyethylene 10kg, Lemon yellow 30g.

2) Mix the raw materials obtained in step 1) in a high-speed mixer, first mix at a low speed, and then mix at a high speed. The material is discharged into the cooling mixer for cooling, and the material is discharged after being cooled to 45°C.

3) Extrude the mixed raw materials with a single-screw extruder at a temperature of 135-160°C; then introduce the extruded material into a two-roller machine for kneading and extruding into sheets at a kneading temperature of 170°C.

4) Pull the sheet material to a six-roll machine with a flat tractor, and shape it into a sheet with a thickness of 60 μm at 45 ° C. The discharge temperature of the sheet material is dropped to room temperature through the six-roll machine.

5) Slicing the shaped sheet, then naturally cooling to room temperature, then flattening the sheet and putting it in storage to obtain the polyvinyl chloride material for making table tennis.

Example 3:

Referring to Fig. 1, as an embodiment of the present invention, the preparation method described for making the polyvinyl chloride material of table tennis comprises the following steps:

1) take polyvinyl chloride (polymerization degree 1200) 80kg, particle diameter is the calcium carbonate 15kg of 500nm, camphor powder 9kg and dicyclohexyl terephthalate 8kg, calcium-zinc composite stabilizer 10kg, chlorinated polyethylene 25kg, Titanium dioxide 200g.

2) Mix the raw materials obtained in step 1) in a high-speed mixer, first mix at a low speed, and then mix at a high speed. The material is discharged into the cooling mixer for cooling, and the material is discharged after being cooled to 38°C.

3) Extrude the mixed raw materials with a single-screw extruder at an extrusion temperature of 135-160°C; then introduce the extruded material into a two-roller machine for kneading and sheet production at a kneading temperature of 155°C.

4) Pull the sheet to a six-roll machine with a flat tractor, and shape it into a sheet with a thickness of 58 μm at 42° C., and the discharge temperature of the sheet is reduced to 28° C. through the six-roll machine.

5) Slicing the shaped sheet, then naturally cooling to room temperature, then flattening the sheet and putting it in storage to obtain the polyvinyl chloride material for making table tennis.

Example 4:

Referring to Fig. 1, as an embodiment of the present invention, the preparation method described for making the polyvinyl chloride material of table tennis comprises the following steps:

1) Take polyvinyl chloride (polymerization degree 1400) 100kg, particle diameter is the calcium carbonate 16kg of 400nm, camphor powder 6kg and dicyclohexyl terephthalate 6kg, calcium-zinc composite stabilizer 6kg, MBS resin 12kg and chlorinated vinegar Resin 10kg, Ultramarine 10g.

2) Mix the raw materials obtained in step 1) in a high-speed mixer, first mix at a low speed, and then mix at a high speed. The material is discharged into a cooling mixer for cooling, and the material is discharged after being cooled to 42°C.

3) Extrude the mixed raw materials with a single-screw extruder at a temperature of 135 to 160°C; then introduce the extruded material into a two-roller machine for kneading and sheet production at a kneading temperature of 150°C.

4) Pull the sheet to a six-roll machine with a flat tractor, and shape it into a sheet with a thickness of 59.5 μm at 43° C., and the discharge temperature of the sheet is reduced to 28° C. through the six-roll machine.

5) Slicing the shaped sheet, then naturally cooling to room temperature, then flattening the sheet and putting it in storage to obtain the polyvinyl chloride material for making table tennis.

Example 5:

Referring to Fig. 1, as an embodiment of the present invention, the preparation method described for making the polyvinyl chloride material of table tennis comprises the following steps:

1) Take by weighing polyvinyl chloride (polymerization degree 1500) 95kg, particle diameter is the calcium carbonate 11kg of 650nm, camphor powder 18kg, calcium-zinc composite stabilizer 7kg, MBS resin 7kg and chlorinated polyethylene 8kg, tartrazine 30g.

2) Mix the raw materials obtained in step 1) in a high-speed mixer, first mix at a low speed, and then mix at a high speed. The material is discharged into the cooling mixer for cooling, and the material is discharged after being cooled to 40°C.

3) Extrude the mixed raw materials with a single-screw extruder at a temperature of 135 to 160°C; then introduce the extruded material into a two-roller machine for kneading and sheet production at a kneading temperature of 160°C.

4) Pull the sheet to a six-roll machine with a flat tractor, and shape it into a sheet with a thickness of 60.5 μm at 42° C., and the discharge temperature of the sheet is reduced to 30° C. through the six-roll machine.

5) Slicing the shaped sheet, then naturally cooling to room temperature, then flattening the sheet and putting it in storage to obtain the polyvinyl chloride material for making table tennis.

Embodiment 6:

As an embodiment of the present invention, the nano-calcium carbonate may be nano-calcium carbonate modified by a surfactant. The modification steps are as follows:

Calcium carbonate with a particle diameter of 200nm is put into a container, water is added, the solid-to-liquid ratio is 1:5g/g, the temperature is raised, and until the temperature reaches 80°C, a modifier calcium stearate is added, and the stearic acid The mass of calcium is 1% of the mass of the nano-calcium carbonate, reacted for 60 minutes under stirring, then filtered, vacuum-dried, ground and sieved to obtain the modified nano-calcium carbonate.

The calcium carbonate in embodiment 1 is replaced by described modified nano-calcium carbonate, and other is the same as embodiment 1, obtains the polyvinyl chloride material that is used to make table tennis.

Embodiment 7:

As an embodiment of the present invention, the nano-calcium carbonate may be nano-calcium carbonate modified by a surfactant. The modification steps are as follows:

Calcium carbonate with a particle diameter of 800nm is put into a container, water is added, the solid-to-liquid ratio is 1:4.5g/g, the temperature is raised, and when the temperature reaches 85°C, a modifier calcium stearate is added, and the stearic acid The quality of the acid calcium is 1.5% of the quality of the nano-calcium carbonate, reacted for 50 minutes under stirring, then filtered, vacuum-dried, ground and sieved to obtain the modified nano-calcium carbonate.

The calcium carbonate in embodiment 2 is replaced with described modified nano-calcium carbonate, and other is the same as embodiment 2, obtains the polyvinyl chloride material that is used to make table tennis.

Embodiment 8:

As an embodiment of the present invention, the nano-calcium carbonate may be nano-calcium carbonate modified by a surfactant. The modification steps are as follows:

Calcium carbonate with a particle diameter of 500nm is put into a container, water is added, the solid-to-liquid ratio is 1:5.5g/g, the temperature is raised, and when the temperature reaches 73°C, a modifier calcium stearate is added, and the stearic acid The quality of the acid calcium is 0.8% of the quality of the nano-calcium carbonate, reacted for 65 minutes under stirring, then filtered, vacuum-dried, ground and sieved to obtain the modified nano-calcium carbonate.

The calcium carbonate in embodiment 3 is replaced by described modified nanometer calcium carbonate, other is with embodiment 3, obtains the polyvinyl chloride material that is used to make table tennis.

Cut the polyvinyl chloride material obtained in the above examples into discs with a diameter of 5.5 cm, then place the original sheet in a hemispherical mold, and punch it into two hemispheres, one male and one female, at 100-130 °C, and then The two hemispheres are dried, glued, chamfered, expanded into a ball in a water bath, dried, and polished to obtain a table tennis ball. Its performance test data is as follows:

It can be seen that the polyvinyl chloride material used to manufacture table tennis provided by the present invention is made into table tennis balls by stamping, the thickness of the sheet is uniform and controllable than injection molding, the density is uniform, the sheet is easy to extend during heating, and the processing performance is improved. Well, it is conducive to stamping and forming, so that the whole table tennis ball is more uniform and concentricity is better, so the qualified rate of table tennis balls (eccentricity ≤ 60°) is higher.

The polyvinyl chloride material that is used to manufacture table tennis provided by the present invention takes polyvinyl chloride as the main raw material, and is assisted with nano-calcium carbonate, solid plasticizer, reinforcing toughening agent and thermal stabilizer etc., in the preparation sheet process, The flatness during extrusion is better; after being made into a table tennis ball, it is basically close to celluloid table tennis balls in terms of mechanical properties, especially in terms of bounce and impact resistance. Celluloid table tennis is basically the same.

Moreover, the production process of the polyvinyl chloride material does not use solvents at all, so there is no waste liquid discharge; the use of polyvinyl chloride instead of celluloid eliminates potential safety hazards in the production process; the use of polyvinyl chloride sheets instead of celluloid sheets Manufacture table tennis, can basically continue to use table tennis manufacturing process and not significantly increase equipment cost. Therefore, the preparation method of the polyvinyl chloride material is simple, safe, reliable and environmentally friendly, and the pollution in the preparation process of the celluloid sheet is completely abandoned.

Those of ordinary skill in the art should understand that: the above descriptions are only specific embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principles of the present invention etc., should be included within the protection scope of the present invention.

Claims (9)

1. a polyvinyl chloride material for making table tennis, is characterized in that, described polyvinyl chloride material comprises the raw material of following weight portion: 50-150 parts of polyvinyl chloride; 5-20 parts of nano-calcium carbonate; 6-22 parts of solid plasticizer; 3-12 parts of calcium-zinc composite stabilizer; 10-30 parts of toughening agent; 0.01-0.1 parts of pigment; Wherein, the solid plasticizer is selected from at least one of camphor powder and dicyclohexyl terephthalate. 2. the polyvinyl chloride material that is used to manufacture table tennis according to claim 1, is characterized in that, described polyvinyl chloride material comprises the raw material of following mass parts: 80-120 parts of polyvinyl chloride; 11-16 parts of nano-calcium carbonate; 10-18 parts of solid plasticizer; 6-10 parts of calcium-zinc composite stabilizer; 15-25 parts of toughening agent; 0.03-0.08 parts of pigment. 3. the polyvinyl chloride material that is used to manufacture table tennis according to claim 1, is characterized in that, the particle diameter of described nano calcium carbonate is 100～1000nm. 4. the polyvinyl chloride material that is used to manufacture table tennis according to claim 1, is characterized in that, described nano-calcium carbonate is the nano-calcium carbonate through surfactant modification. 5. The polyvinyl chloride material for making table tennis balls according to claim 4, characterized in that, the surfactant is calcium stearate. 6. the polyvinyl chloride material that is used to make table tennis according to claim 5, is characterized in that, the step of described calcium stearate modified nano calcium carbonate comprises: Mix calcium carbonate and water according to the solid-to-liquid ratio of 1:4~6g/g, heat up to 60~90°C, add calcium stearate, react for 40~80 minutes, then filter, vacuum dry, grind and sieve to obtain modified Nano-calcium carbonate; the quality of the calcium stearate is 0.5-3% of the quality of the nano-calcium carbonate. 7. The polyvinyl chloride material for making table tennis balls according to claim 1, characterized in that the polyvinyl chloride is polyvinyl chloride resin with a degree of polymerization of 800-1500. 8. The polyvinyl chloride material for making table tennis balls according to claim 1, wherein the toughening agent is selected from at least one of MBS resin, chlorinated polyethylene and vinyl acetate resin. 9. according to the preparation method of the polyvinyl chloride material that is used to make table tennis described in any one in claim 1～8, it is characterized in that, described preparation method comprises the following steps: Stir and mix the raw materials in a high-speed mixer according to their respective weight proportions, first mix at a low speed, then mix at a high speed, the mixing speed is 400-800 rpm, the temperature of the mixture is 115-120°C, and then the mixture is discharged Cool in a cooling mixer, wait until cooled to 45-30°C, and discharge; Extrude the mixed raw materials with a single-screw extruder at a temperature of 135-160°C, and then introduce the extruded material into a two-roll machine for mixing at a temperature of 150-170°C; Use a flat tractor to pull the sheet material to a six-roller machine, and shape it into a sheet with a thickness of 58-62 μm at 40-45 ° C. The sheet material is dropped to 40-25 ° C by the six-roller machine to obtain Polyvinyl chloride sheet used to make table tennis balls.