Preparation method of waste fluororubber reinforced chloroprene rubber

Abstract

The invention relates to the field of waste rubber recovery, in particular to a preparation method of waste fluororubber reinforced chloroprene rubber. In the invention, the waste fluororubber is pre-cooled, frozen at low temperature and crushed into particles by using an ultra-low temperature crusher, then the particles are added into a ball mill, the fluororubber micron particles are obtained through ball milling, and the particles can be used as a filler to be applied to chloroprene rubber. The product developed by the invention comprises the following components in parts by weight: 100 parts of raw chloroprene rubber (CR); 1-10 parts of fluororubber micron particles; 1-10 parts of a reinforcing agent; 4 parts of an acid acceptor; and 3 parts of a vulcanizing agent. The low-temperature brittleness of the fluororubber is utilized, the waste fluororubber is crushed into particles at low temperature, and the particle size requirement of ball milling is met. And grinding the fluororubber subjected to freeze grinding into micron-sized particles by a ball milling method, and adding the micron-sized particles into the chloroprene rubber. On one hand, the fluororubber micron particles have good compatibility, and on the other hand, the fluororubber micron particles retain a cross-linked structure of fluororubber, so that the chloroprene rubber can be endowed with better mechanical properties.

Description

Technical Field

[0001] The invention relates to the field of waste rubber recycling, in particular to a method for preparing waste fluororubber reinforced chloroprene rubber. Background Art

[0002] Fluororubber has excellent thermal stability, oil resistance, and solvent resistance, and is widely used in automotive parts, aerospace, equipment manufacturing, and other fields. However, due to the high cost of fluororubber, the current recycling solutions for fluororubber on the market have disadvantages such as high cost and low utilization rate of recycled products. The recycling of waste fluororubber has become an urgent problem to be solved.

[0003] Neoprene has many excellent properties such as durability, chemical resistance, oil resistance, heat resistance, weather resistance and ozone resistance. It also has high tensile strength, elongation and good adhesion, as well as certain flame retardancy and acid and alkali resistance, so it is widely used in industry and manufacturing. However, carbon black is usually used to strengthen neoprene, and the strength improvement is limited.

[0004] In summary, it is of great significance to develop a method for recycling waste fluororubber and using it to reinforce chloroprene rubber. Summary of the invention

[0005] In order to solve the current problem, the present invention provides a method for preparing waste fluororubber reinforced chloroprene rubber, which can meet the above requirements.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is: a waste fluororubber reinforced chloroprene rubber comprises the following components:

[0007] Neoprene rubber, 100 parts;

[0008] Fluororubber micron particles, 1 to 10 parts;

[0009] Enhancer, 1 to 10 parts;

[0010] Acid absorbent, 4 parts;

[0011] Vulcanizing agent, 3 parts.

[0012] Furthermore, the fluororubber micron particles are prepared from waste fluororubber, and the brand of the waste fluororubber is VITON A-201C.

[0013] Furthermore, the method for preparing the fluororubber micron particles comprises the following steps:

[0014] S1. Precool the waste fluororubber to -20-0°C with liquid nitrogen;

[0015] S2, using liquid refrigerant to further cool the pre-cooled waste fluororubber until the temperature reaches -40 to -35°C, then crushing it into particles with an ultra-low temperature crusher, and filtering and sieving particles of 16 to 20 mesh;

[0016] S3. Put the obtained particles into a ball mill, use a 500ml zirconia jar and zirconia beads, the ball-to-material ratio (mass ratio of zirconia beads to fluororubber particles) is 4:1, and the specifications of the zirconia beads used are 10mm and 5mm in diameter. At the same time, the mass ratio of 10mm zirconia beads to 5mm zirconia beads is 2:1. The rotation speed is 400rpm and the ball milling time is 8h to obtain fluororubber micron particles.

[0017] Furthermore, the reinforcing agent is carbon black sp5000.

[0018] Furthermore, the acid absorber is composed of zinc oxide and magnesium oxide, and the ratio of the two is 1:1 by weight.

[0019] Furthermore, the vulcanizing agent is a dipentadienyl vulcanizing agent.

[0020] A method for preparing waste fluororubber reinforced chloroprene rubber comprises the following steps:

[0021] S1. Use an open mill to plasticize the chloroprene rubber for 10 to 15 minutes;

[0022] S2, add acid absorbent, reinforcing agent, fluororubber micron particles in sequence, and pass through until fully mixed;

[0023] S3. Finally, add the vulcanizing agent and pass it through the tube again to obtain the desired chloroprene rubber.

[0024] Furthermore, the roller distance of the mixing mill is 1 mm, and the temperatures of the front and rear rollers are both 40°C.

[0025] (1) The present invention uses an ultra-low temperature freezing mill to destroy the original physical cross-linking structure of fluororubber in a low-temperature freezing state, thereby utilizing the cold brittleness of fluororubber and easily obtaining fluororubber micron particles that meet the ball milling particle size requirements.

[0026] (2) The present invention obtains fluororubber micron particles by ball milling. Compared with ordinary carbon black fillers and directly frozen and crushed fluororubber particles, the micron particles, when used as fillers in the preparation of chloroprene rubber, not only have better compatibility with chloroprene rubber, but also can give chloroprene rubber more superior mechanical properties. DETAILED DESCRIPTION

[0027] [Example 1]

[0028] The present embodiment provides a waste fluororubber-reinforced chloroprene rubber, which comprises the following components by weight: chloroprene rubber raw rubber, 100 parts; fluororubber micron particles, 1 part; reinforcing agent, 5 parts; acid absorbent, 4 parts; and vulcanizing agent, 3 parts.

[0029] In this embodiment, the preparation method of fluororubber micron particles includes the following steps:

[0030] S1. Precool the waste fluororubber to -20-0°C with liquid nitrogen;

[0031] S2, using liquid refrigerant to further cool the pre-cooled waste fluororubber until the temperature reaches -40 to -35°C, then crushing it into particles with an ultra-low temperature crusher, and filtering and sieving particles of 16 to 20 mesh;

[0032] S3. Put the obtained particles into a ball mill, use a 500ml zirconia jar and zirconia beads, the ball-to-material ratio (mass ratio of zirconia beads to fluororubber particles) is 4:1, and the specifications of the zirconia beads used are 10mm and 5mm in diameter. At the same time, the mass ratio of 10mm zirconia beads to 5mm zirconia beads is 2:1. The rotation speed is 400rpm and the ball milling time is 8h to obtain fluororubber micron particles.

[0033] In this embodiment, the preparation method of waste fluororubber reinforced chloroprene rubber comprises the following steps:

[0034] S1. Use an open mill to plasticize the chloroprene rubber for 10 to 15 minutes;

[0035] S2, add acid absorbent, reinforcing agent, fluororubber micron particles in sequence, and pass through until fully mixed;

[0036] S3. Finally, add the vulcanizing agent and pass it through the tube again to obtain the desired chloroprene rubber.

[0037] For the convenience of comparison, the experimental results are listed in Table 1.

[0038] [Example 2]

[0039] The present embodiment provides a waste fluororubber reinforced chloroprene rubber, which comprises the following components by weight: chloroprene rubber raw rubber, 100 parts; fluororubber micron particles, 5 parts; reinforcing agent, 5 parts; acid absorbent, 4 parts; and vulcanizing agent, 3 parts.

[0040] In this embodiment, the preparation method of fluororubber micron particles includes the following steps:

[0041] S1. Precool the waste fluororubber to -20-0°C with liquid nitrogen;

[0042] S2, using liquid refrigerant to further cool the pre-cooled waste fluororubber until the temperature reaches -40 to -35°C, then crushing it into particles with an ultra-low temperature crusher, and filtering and sieving particles of 16 to 20 mesh;

[0043] S3. Put the obtained particles into a ball mill, use a 500ml zirconia jar and zirconia beads, the ball-to-material ratio (mass ratio of zirconia beads to fluororubber particles) is 4:1, and the specifications of the zirconia beads used are 10mm and 5mm in diameter. At the same time, the mass ratio of 10mm zirconia beads to 5mm zirconia beads is 2:1. The rotation speed is 400rpm and the ball milling time is 8h to obtain fluororubber micron particles.

[0044] In this embodiment, the preparation method of waste fluororubber reinforced chloroprene rubber comprises the following steps:

[0045] S1. Use an open mill to plasticize the chloroprene rubber for 10 to 15 minutes;

[0046] S2, add acid absorbent, reinforcing agent, fluororubber micron particles in sequence, and pass through until fully mixed;

[0047] S3. Finally, add the vulcanizing agent and pass it through the tube again to obtain the desired chloroprene rubber.

[0048] For the convenience of comparison, the experimental results are listed in Table 1.

[0049] [Example 3]

[0050] The present embodiment provides a waste fluororubber reinforced chloroprene rubber, which comprises the following components by weight: chloroprene rubber raw rubber, 100 parts; fluororubber micron particles, 9 parts; reinforcing agent, 1 part; acid absorbent, 4 parts; and vulcanizing agent, 3 parts.

[0051] In this embodiment, the preparation method of fluororubber micron particles includes the following steps:

[0052] S1. Precool the waste fluororubber to -20-0°C with liquid nitrogen;

[0053] S2, using liquid refrigerant to further cool the pre-cooled waste fluororubber until the temperature reaches -40 to -35°C, then crushing it into particles with an ultra-low temperature crusher, and filtering and sieving particles of 16 to 20 mesh;

[0054] S3. Put the obtained particles into a ball mill, use a 500ml zirconia jar and zirconia beads, the ball-to-material ratio (mass ratio of zirconia beads to fluororubber particles) is 4:1, and the specifications of the zirconia beads used are 10mm and 5mm in diameter. At the same time, the mass ratio of the two beads is 2:1. The rotation speed is 400rpm and the ball milling time is 8h to obtain fluororubber micron particles.

[0055] In this embodiment, the preparation method of waste fluororubber reinforced chloroprene rubber comprises the following steps:

[0056] S1. Use an open mill to plasticize the chloroprene rubber for 10 to 15 minutes;

[0057] S2, add acid absorbent, reinforcing agent, fluororubber micron particles in sequence, and pass through until fully mixed;

[0058] S3. Finally, add the vulcanizing agent and pass it through the tube again to obtain the desired chloroprene rubber.

[0059] For easy comparison, the experimental results are listed in Table 1.

[0060] [Comparative Example 1]

[0061] The present embodiment provides a waste fluororubber-reinforced chloroprene rubber, which comprises the following components by weight: 100 parts of chloroprene rubber raw rubber; 10 parts of a reinforcing agent; 4 parts of an acid absorber; and 3 parts of a vulcanizing agent.

[0062] In this embodiment, the preparation method of waste fluororubber reinforced chloroprene rubber comprises the following steps:

[0063] S1. Use an open mill to plasticize the chloroprene rubber for 10 to 15 minutes;

[0064] S2, add acid absorbent and enhancer in sequence, and pass through until fully mixed;

[0065] S3. Finally, add the vulcanizing agent and pass it through the tube again to obtain the desired chloroprene rubber.

[0066] For easy comparison, the experimental results are listed in Table 1.

[0067] [Comparative Example 2]

[0068] The present embodiment provides a chloroprene rubber reinforced with waste fluororubber, which comprises the following components by weight: 100 parts of chloroprene rubber raw rubber; 5 parts of fluororubber frozen crushed particles; 5 parts of a reinforcing agent; 4 parts of an acid absorbent; and 3 parts of a vulcanizing agent.

[0069] In this embodiment, the preparation method of fluororubber frozen pulverized particles comprises the following steps:

[0070] S1. Precool the waste fluororubber to -20-0°C with liquid nitrogen;

[0071] S2, using liquid refrigerant to further cool the pre-cooled waste fluororubber until the temperature reaches -40 to -35°C, then crushing it into particles with an ultra-low temperature crusher, and filtering and sieving particles of 16 to 20 mesh;

[0072] In this embodiment, the preparation method of waste fluororubber reinforced chloroprene rubber comprises the following steps:

[0073] S1. Use an open mill to plasticize the chloroprene rubber for 10 to 15 minutes;

[0074] S2, add the acid absorbent, enhancer, and fluorine rubber frozen crushed particles in sequence, and pass them through a thin tube until they are fully mixed;

[0075] S3. Finally, add the vulcanizing agent and pass it through the tube again to obtain the desired chloroprene rubber.

[0076] For the convenience of comparison, the experimental results are listed in Table 1.

[0077] [Comparative Example 3]

[0078] The present embodiment provides a waste fluororubber reinforced chloroprene rubber, which comprises the following components by weight: chloroprene rubber raw rubber, 100 parts; fluororubber micron particles, 10 parts; acid absorbent, 4 parts; vulcanizing agent, 3 parts.

[0079] In this embodiment, the preparation method of fluororubber micron particles includes the following steps:

[0080] S1. Precool the waste fluororubber to -20-0°C with liquid nitrogen;

[0081] S2. Use liquid refrigerant to further cool the pre-cooled waste fluororubber until the temperature reaches -40 to -35°C, then use an ultra-low temperature crusher to break it into particles, and filter and sieve out particles of 16-20 mesh;

[0082] S3. Put the obtained particles into a ball mill, use a 500ml zirconia jar and zirconia beads, the ball-to-material ratio (mass ratio of zirconia beads to fluororubber particles) is 4:1, and the specifications of the zirconia beads used are 10mm and 5mm in diameter. At the same time, the mass ratio of the two beads is 2:1. The rotation speed is 400rpm and the ball milling time is 8h to obtain fluororubber micron particles.

[0083] In this embodiment, the method for preparing waste fluororubber reinforced chloroprene rubber comprises the following steps: S1, using an open mill to plasticize the chloroprene rubber for 10 to 15 minutes;

[0084] S2, add acid absorbent and fluororubber micron particles in sequence, and pass them through thin tubes until they are fully mixed;

[0085] S3. Finally, add the vulcanizing agent and pass it through the tube again to obtain the desired chloroprene rubber.

[0086] For the convenience of comparison, the experimental results are listed in Table 1.

[0087] Table 1: Effects of different contents of fluororubber-derived carbon materials on the mechanical properties of fluororubber

[0088]

[0089] It can be seen from Example 2 and Comparative Example 1 that when 5 parts of fluororubber micron particles and carbon black are added respectively, compared with using 10 parts of carbon black as a reinforcing agent, the tensile properties are improved by 2.3 MPa, an overall improvement of about 22.5%; the elongation at break is improved by 34.9%, an overall improvement of about 18.8%; the hardness is improved by 7.8 HB, an overall improvement of about 14.1%.

[0090] By comparing Example 2 and Comparative Example 2, it can be seen that compared with the particles broken by an ultra-low temperature freezing crusher after freezing, when the same number of fluororubber micron particles are used as fillers, the tensile properties are increased by 0.8 MPa, an overall increase of about 6.8%; the elongation at break is increased by 10.9%, an overall increase of about 5.2%; the hardness is increased by 2.7 HB, an overall increase of about 4.5%.

[0091] From the analysis of the above results, it can be seen that the fluororubber micron particles obtained by this method, when used as fillers, can significantly improve the mechanical properties of the material compared to traditional reinforcing materials such as carbon black. At appropriate proportions, they can significantly improve the mechanical properties of the material and have a broad application space.

[0092] It should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. For ordinary technicians in this technical field, several improvements and modifications can be made on the basis of the above embodiments without departing from the principles of the present invention. These improvements and modifications all fall within the scope of protection of the claims of the present invention.

Claims

1. A waste fluororubber reinforced chloroprene rubber, characterized in that: By weight, it includes the following components: Neoprene rubber, 100 parts; Fluororubber micron particles, 1 to 10 parts; Enhancer, 1 to 10 parts; Acid absorbent, 4 parts; Vulcanizing agent, 3 parts.

2. The waste fluororubber reinforced chloroprene rubber according to claim 1, characterized in that: The fluororubber micron particles are prepared from waste fluororubber, and the brand of the waste fluororubber is VITON A-201C.

3. The method for preparing fluororubber micron particles according to claim 2, characterized in that: The steps include: S1. Precool the waste fluororubber to -20-0°C with liquid nitrogen; S2, using liquid refrigerant to further cool the pre-cooled waste fluororubber until the temperature reaches -40 to -35°C, then crushing it into particles with an ultra-low temperature crusher, and filtering and sieving particles of 16 to 20 mesh; S3. Put the obtained particles into a ball mill, use a 500ml zirconia jar and zirconia beads, the ball-to-material ratio (mass ratio of zirconia beads to fluororubber particles) is 4:1, and the specifications of the zirconia beads used are 10mm and 5mm in diameter. At the same time, the mass ratio of 10mm zirconia beads to 5mm zirconia beads is 2:

1. The rotation speed is 400rpm and the ball milling time is 8h to obtain fluororubber micron particles.

4. The waste fluororubber reinforced chloroprene rubber according to claim 1, characterized in that: The reinforcing agent is carbon black sp5000.

5. The waste fluororubber reinforced chloroprene rubber according to claim 1, characterized in that: The acid absorber is composed of zinc oxide and magnesium oxide, and the weight ratio of the two is 1:

1.

6. The waste fluororubber reinforced chloroprene rubber according to claim 1, characterized in that: The vulcanizing agent is a dipentadienyl vulcanizing agent.

7. A method for preparing waste fluororubber reinforced chloroprene rubber, characterized in that: The steps include: S1. Use an open mill to plasticize the chloroprene rubber for 10 to 15 minutes; S2, add acid absorbent, reinforcement, fluororubber micron particles in sequence, and pass through until fully mixed; S3. Finally, add the vulcanizing agent and pass it through the tube again to obtain the desired chloroprene rubber.

8. The method for preparing waste fluororubber reinforced chloroprene rubber according to claim 7, characterized in that: The roller gap of the mixing mill was 1 mm, and the temperature of the front and rear rollers was 40 °C.

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