Polyurethane rubber compound for space beans as well as preparation method and application of polyurethane rubber compound

Abstract

The invention relates to the technical field of polyurethane rubber compounds, and discloses a polyurethane rubber compound for space beans as well as a preparation method and application of the polyurethane rubber compound. The formula of the polyurethane rubber compound comprises the following raw materials in parts by weight: 111 parts of raw polyurethane rubber UR601-10 containing 10% of fumed silica A200, 0.5-1.5 parts of stearic acid, 20-30 parts of white carbon black, 0.5-1.5 parts of a silane coupling agent, 0.4-1 part of an antioxidant, 0.5-1 part of an anti-yellowing agent and 2-6 parts of a vulcanizing agent. The preparation method comprises the following steps: firstly, carrying out pre-dispersion mixing and synthesis reaction to obtain polyether type polyurethane raw rubber UR601-10 containing 10% of fumed silica; the white carbon black and the raw rubber are promoted to be dispersed and combined through a two-stage mixing method, more combined rubber is formed, the polyurethane rubber compound is obtained, and the polyurethane rubber compound has better tensile strength and tearing strength and can bring better locking force and longer service life when being applied to space beans.

Description

Technical Field

[0001] The invention relates to the technical field of materials for fishing gear, and in particular to a polyurethane compound rubber for space beans, a preparation method and application thereof. Background Art

[0002] Space beans are an essential small accessory for Taiwan fishing. They are mainly used to fix floats and lead skins. In addition, they can help remember the water depth, prevent sub-line entanglement, and locate baits. In the early stage, space beans were generally black olive-shaped or cylindrical beans made of ordinary rubber, but ordinary rubber has poor aging resistance and low temperature resistance, which affects its service life. Later, in order to improve the service life and improve the requirements of color, it developed into silicone-based space beans, which can be made into various colored, translucent and transparent space beans. Although space beans have been developed and improved, silicone-based space beans still have obvious disadvantages. First, the strength of silicone is low, and it is easy to wear and tear. Secondly, the shrinkage of silicone is not good enough, which makes the float and lead skin easy to move. The key performance requirements that affect the use effect of space beans are locking force and tear resistance. If the locking force is not enough, the float and lead skin are prone to sliding, and the space beans cannot play a fixing role. Poor tear resistance makes it easy to be cut by the fishing line when adjusting the position of the float or lead skin, affecting the service life. The process of casting or lifting the rod will also produce a certain pulling force on the space bean. The space bean has poor strength performance and is prone to wear and cracking. At the same time, the glue used on the space bean is required to have a medium hardness (70-80A), because too high hardness is not easy to thread, and too low hardness will reduce the locking force and tear resistance. In addition, the transparency of the space bean has become another favorite of users, because adding some flashing or luminous materials to the space bean can not only improve the appearance, but also attract fish to take the bait.

[0003] Polyether polyurethane has high strength, good wear resistance, excellent elasticity, aging resistance, low temperature performance and water resistance. Peroxide vulcanization can obtain higher tensile strength, bring good locking force, and can be made transparent and in various colors. Using it to replace silicone as the material of space beans can improve the service life of space beans to a certain extent. However, the tear strength of peroxide-cured polyurethane material is relatively poor, which also limits the service life of space beans to a certain extent. Summary of the invention

[0004] In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a method for preparing a polyurethane compound for space beans.

[0005] Another object of the present invention is to provide a polyurethane rubber compound for space beans. The rubber compound has the advantages of high elasticity, excellent tensile strength and tear strength, and high transparency. When applied to space beans, it can provide excellent locking force and tear resistance, thereby further improving the service life of the space beans.

[0006] Another object of the present invention is to provide an application of the polyurethane rubber compound.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] A method for preparing a polyurethane compound for space beans, characterized in that:

[0009] The polyurethane rubber compound is composed of the following raw materials in parts by weight:

[0010] 111 parts of polyurethane raw rubber UR601-10 containing 10% fumed silica A200, 0.5-1.5 parts of stearic acid, 20-30 parts of silica, 0.5-1.5 parts of silane coupling agent, 0.4-1 parts of antioxidant, 0.5-1 parts of anti-yellowing agent, 2-6 parts of vulcanizing agent;

[0011] The preparation method of the polyurethane rubber compound comprises the following steps:

[0012] (1) Preparation of polyurethane raw rubber UR601-10 containing 10% fumed silica A200: fumed silica A200 and polyether diol are mixed, and a small molecule chain extender, diisocyanate, and a cross-linking reaction inhibitor are added to carry out a synthesis reaction;

[0013] (2) 111 parts of polyurethane raw rubber UR601-10 containing 10% fumed silica A200, 0.5-1.5 parts of stearic acid, 15-20 parts of white carbon black, 0.5-1.5 parts of silane coupling agent, 0.4-1 parts of antioxidant, and 0.5-1 parts of anti-yellowing agent are mixed in the order of “polyurethane raw rubber→stearic acid and antioxidant→white carbon black→silane coupling agent and anti-yellowing agent” to obtain a mixed rubber;

[0014] (3) Weigh the remaining 5 to 10 parts of white carbon black and 2 to 6 parts of vulcanizing agent, and mix them evenly in the order of "first-stage mixed rubber → white carbon black → vulcanizing agent" to obtain the polyurethane mixed rubber for space beans.

[0015] Preferably, the mass ratio of the polyether diol, fumed silica A200, small molecule chain extender, diisocyanate and cross-linking reaction inhibitor in step (1) is 100:(13-14):(3-5):(13-16):(0.001-0.003).

[0016] Preferably, the synthesis reaction temperature in step (1) is 70-80°C, the time is 15-20 min, and after the reaction is completed, it is baked at 100°C for 18 h.

[0017] Preferably, the polyether diol in step (1) is polytetramethylene ether diol; the small molecule chain extender is trimethylolpropane monoallyl ether; and the cross-linking reaction inhibitor is phosphoric acid.

[0018] Preferably, the Mooney viscosity (ML100℃1+4) of the polyurethane raw rubber UR601-10 containing 10% fumed silica A200 is 55±10.

[0019] Preferably, in the raw material composition, the white carbon black is white carbon black with good reinforcement and good compatibility, and is at least one of precipitated white carbon black H-160, precipitated white carbon black HT-203, fumed white carbon black A200 or fumed white carbon black HL-150.

[0020] Preferably, in the raw material composition, the silane coupling agent is a silane coupling agent suitable for enhancing the reinforcing effect of polyurethane and white carbon black, and is at least one of A-172, KH-540, and KH-550.

[0021] Preferably, in the raw material composition, the vulcanizing agent includes a peroxide vulcanizing agent and a crosslinking aid thereof, the peroxide vulcanizing agent is at least one of DCP, BIPB, and DBPH, and the crosslinking aid is at least one of TAIC, TMPTA, and TMPTMA;

[0022] The antioxidant is a compounding agent suitable for improving the antioxidant performance of polyurethane, and is at least one of antioxidant 1076 and antioxidant 245; the anti-yellowing agent is at least one of H120 and UV-N.

[0023] The polyurethane mixed rubber is prepared by the method of the invention.

[0024] The invention discloses an application of the polyurethane mixed rubber in space beans.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] The polyurethane rubber mix prepared by the invention is suitable for making space beans, and the basic physical properties of the rubber material can meet the following requirements: Shore hardness 70A-80A, tensile strength ≥20MPa, 100% modulus ≥3.5MPa, tear strength ≥50kN / m, and resilience ≥40%. The polyurethane raw rubber adopted by the invention is dispersed and mixed with 10% of fumed silica A200 during the synthesis reaction process, so that the combination of silica and raw rubber is more closely made, and the dispersion and combination of silica and raw rubber are further strengthened through a two-stage mixing method to form more combined rubber, thereby improving the tensile strength and tearing strength of the rubber mix, and the manufactured space beans can obtain better locking force and tearing resistance, and improve the service life of the space beans. In addition, the transparency of the space beans can also be better, and the space beans are suitable for being made into high transparency and various colors, and are worthy of popularization and application. DETAILED DESCRIPTION

[0027] The present invention will be described in more detail below by way of examples and comparative examples, which are merely illustrative and do not limit the scope of the present invention. Where specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer are used. Where the materials or equipment used do not specify the manufacturer, they are all conventional products that can be purchased commercially.

[0028] The invention provides a technical solution: a polyurethane rubber mix for space beans and a preparation method thereof. The polyurethane rubber mix is ​​composed of the following raw materials in parts by weight: 111 parts by weight of polyurethane raw rubber UR601-10 containing 10% fumed silica A200, 0.5 to 1.5 parts by weight of stearic acid, 20 to 30 parts by weight of silica, 0.5 to 1.5 parts by weight of a silane coupling agent, 0.4 to 1 parts by weight of an antioxidant, 0.5 to 1 parts by weight of an anti-yellowing agent, and 2 to 6 parts by weight of a vulcanizing agent.

[0029] The method for preparing the rubber compound comprises the following steps:

[0030] Step 1: Preparation of polyurethane raw rubber UR601-10 containing 10% fumed silica A200, firstly use a colloid mill to pre-disperse and mix the fumed silica A200 and polyether diol, then put it into a reactor with a small molecule chain extender trimethylolpropane monoallyl ether, diisocyanate, and a cross-linking reaction inhibitor for synthesis reaction, control the reaction temperature at 70-80°C, the reaction time at 15-20min, use a stainless steel plate to receive the material, place it in an oven at 100°C and bake it for 18 hours, and obtain polyurethane raw rubber UR601-10 containing 10% fumed silica A200;

[0031] The mass ratio of polyether diol, fumed silica A200, trimethylolpropane monoallyl ether, diisocyanate and cross-linking reaction inhibitor is: 100: (13-14): (3-5): (13-16); (0.001-0.003).

[0032] Step 2: Weigh 111 parts by mass of polyurethane raw rubber UR601-10, 0.5-1.5 parts by mass of stearic acid, 15-20 parts by mass of white carbon black, 0.5-1.5 parts by mass of silane coupling agent, 0.4-1 parts by mass of antioxidant, and 0.5-1 parts by mass of anti-yellowing agent, and mix them evenly in an open mill or internal mixer in the order of adding “polyurethane raw rubber→stearic acid and antioxidant→white carbon black→silane coupling agent and anti-yellowing agent” to obtain a mixed rubber;

[0033] Step 3: Weigh the remaining 5 to 10 parts by mass of white carbon black and 2 to 6 parts by mass of vulcanizing agent, and mix them evenly in an open mixer in the order of adding "first-stage mixed rubber → white carbon black → vulcanizing agent" to obtain the polyurethane mixed rubber for space beans.

[0034] Embodiment 1:

[0035] This embodiment uses an example of a polyurethane compound formulation, with the following weight parts: 111 parts of polyurethane raw rubber UR601-10 containing 10% fumed silica A200, 1 part of stearic acid, 20 parts of fumed silica A200, 1 part of coupling agent A-172, 0.8 parts of antioxidant 1076, 0.8 parts of anti-yellowing agent UV-N, 1 part of vulcanizing agent DCP, and 3 parts of crosslinking aid TMPTMA; a total of 138.6 parts.

[0036] The ingredients are prepared according to the above formula and mixed evenly according to the preparation method of the present invention to obtain a natural color (high transparency) polyurethane mixed rubber. The sample is vulcanized at 175° C.×5 min and various physical properties are tested after being left standing.

[0037] Embodiment 2:

[0038] This embodiment uses an example to produce a polyurethane compound formulation, with the following weight parts: 111 parts of polyurethane raw rubber UR601-10 containing 10% fumed silica A200, 1.2 parts of stearic acid, 26 parts of precipitated silica HT-203, 1.2 parts of coupling agent A-172, 2450.6 parts of antioxidant, 0.8 parts of anti-yellowing agent UV-N, 1.2 parts of vulcanizing agent DCP, and 3 parts of crosslinking aid TMPTMA; a total of 145 parts.

[0039] The ingredients are prepared according to the above formula and mixed evenly according to the preparation method of the present invention to obtain a natural color (high transparency) polyurethane mixed rubber. The sample is vulcanized at 175° C.×5 min and various physical properties are tested after being left standing.

[0040] Embodiment 3:

[0041] This embodiment uses an example to produce a polyurethane compound formulation, with the following weight parts: 111 parts of polyurethane raw rubber UR601-10 containing 10% fumed silica A200, 1.2 parts of stearic acid, 30 parts of precipitated silica HT-203, 1.5 parts of coupling agent A-172, 2450.6 parts of antioxidant, 0.8 parts of anti-yellowing agent UV-N, 1.5 parts of vulcanizing agent DCP, and 4 parts of crosslinking aid TMPTMA; a total of 150.6 parts.

[0042] The ingredients are prepared according to the above formula and mixed evenly according to the preparation method of the present invention to obtain a natural color (high transparency) polyurethane mixed rubber. The sample is vulcanized at 175° C.×5 min and various physical properties are tested after being left standing.

[0043] Comparative Example 1:

[0044] The formula of the rubber mix in this comparative example is the same as that in Example 1, except that the polyurethane raw rubber UR601-10 containing 10% fumed silica A200 is not prepared. The weight parts are as follows: 1100 parts of polyurethane raw rubber UR601, 1 part of stearic acid, 31 parts of fumed silica A200, 1 part of coupling agent A-172, 0.8 parts of antioxidant 1076, 0.8 parts of anti-yellowing agent UV-N, 1 part of vulcanizing agent DCP, and 3 parts of crosslinking aid TMPTMA; a total of 138.6 parts.

[0045] According to the above-mentioned formula, the conventional method of adding materials to the rubber mix is ​​"raw rubber → small materials (stearic acid, antioxidant) → white carbon black → other additives (coupling agent, anti-yellowing agent) → vulcanizing agent (including cross-linking additive)". After uniform mixing in an internal mixer or an open mixer, a natural color (high transparency) polyurethane rubber mix is ​​obtained. The sample is vulcanized at 175°C × 5min, and various physical properties are tested after standing.

[0046] Comparative Example 2:

[0047] The formula of the mixed rubber in this comparative example is the same as that in Example 2, except that the polyurethane raw rubber UR601-10 containing 10% fumed silica A200 is not prepared. The weight parts are as follows: 1100 parts of polyurethane raw rubber UR601, 1.2 parts of stearic acid, 11 parts of fumed silica A200, 26 parts of precipitated silica HT-203, 1.2 parts of coupling agent A-172, 0.6 parts of antioxidant 245, 0.8 parts of anti-yellowing agent UV-N, 1.2 parts of vulcanizing agent DCP, and 3 parts of crosslinking aid TMPTMA; a total of 145 parts.

[0048] According to the above-mentioned formula, the conventional method of adding materials to the rubber mix is ​​"raw rubber → small materials (stearic acid, antioxidant) → white carbon black → other additives (coupling agent, anti-yellowing agent) → vulcanizing agent (including cross-linking additive)". After uniform mixing in an internal mixer or an open mixer, a natural color (high transparency) polyurethane rubber mix is ​​obtained. The sample is vulcanized at 175°C × 5min, and various physical properties are tested after standing.

[0049] Comparative Example 3:

[0050] The formula of the mixed rubber in this comparative example is the same as that in Example 3, except that the polyurethane raw rubber UR601-10 containing 10% fumed silica A200 is not prepared. The weight parts are as follows: 1100 parts of polyurethane raw rubber UR601, 1.2 parts of stearic acid, 11 parts of fumed silica A200, 30 parts of precipitated silica HT-203, 1.5 parts of coupling agent A-172, 0.6 parts of antioxidant 245, 0.8 parts of anti-yellowing agent UV-N, 1.5 parts of vulcanizing agent DCP, and 4 parts of crosslinking aid TMPTMA; a total of 150.6 parts.

[0051] According to the above-mentioned formula, the conventional method of adding materials to the rubber mix is ​​"raw rubber → small materials (stearic acid, antioxidant) → white carbon black → other additives (coupling agent, anti-yellowing agent) → vulcanizing agent (including cross-linking additive)". After uniform mixing in an internal mixer or an open mixer, a natural color (high transparency) polyurethane rubber mix is ​​obtained. The sample is vulcanized at 175°C × 5min, and various physical properties are tested after standing.

[0052] From the performance results of the above-mentioned Examples 1 to 3 and Comparative Examples 1 to 3, the physical properties of the rubber mix are relatively good, but the tensile strength and tear strength of the examples are significantly higher than those of the comparative examples. This is mainly because the preparation method of the present invention can further improve its strength performance. This allows the rubber mix to be used in space beans, which can better meet the tear resistance requirements of fishing lines and greatly improve its service life. At the same time, the excellent tensile strength and elasticity give the space beans excellent locking force on the fishing lines, bringing a better user experience.

[0053] The test results are shown in the following table:

[0054]

[0055] The above is only a specific implementation of the present invention, but the protection scope of the present invention is not limited thereto. For those skilled in the art, it can be understood that various changes or substitutions to these embodiments without departing from the principle of the present invention should be included in the protection scope of the present invention. Matters not covered in the present invention belong to the common knowledge in the art.

Claims

1. A method for preparing a polyurethane rubber compound for space beans, characterized in that: The polyurethane rubber compound is composed of the following raw materials in parts by weight: 111 parts of polyurethane raw rubber UR601-10 containing 10% fumed silica A200, 0.5-1.5 parts of stearic acid, 20-30 parts of silica, 0.5-1.5 parts of silane coupling agent, 0.4-1 parts of antioxidant, 0.5-1 parts of anti-yellowing agent, 2-6 parts of vulcanizing agent; The preparation method of the polyurethane rubber compound comprises the following steps: (1) Preparation of polyurethane raw rubber UR601-10 containing 10% fumed silica A200: fumed silica A200 and polyether diol are mixed, and a small molecule chain extender, diisocyanate, and a cross-linking reaction inhibitor are added to carry out a synthesis reaction; (2) 111 parts of polyurethane raw rubber UR601-10 containing 10% fumed silica A200, 0.5-1.5 parts of stearic acid, 15-20 parts of white carbon black, 0.5-1.5 parts of silane coupling agent, 0.4-1 parts of antioxidant, and 0.5-1 parts of anti-yellowing agent are mixed in the order of "polyurethane raw rubber → stearic acid and antioxidant → white carbon black → silane coupling agent and anti-yellowing agent" to obtain a mixed rubber; (3) Weigh the remaining 5 to 10 parts of white carbon black and 2 to 6 parts of a vulcanizing agent, and mix them evenly in the order of "first-stage mixed rubber → white carbon black → vulcanizing agent" to obtain the polyurethane mixed rubber for space beans.

2. The preparation method according to claim 1, characterized in that: The mass ratio of the polyether diol, fumed silica A200, small molecule chain extender, diisocyanate and cross-linking reaction inhibitor in step (1) is 100:(13-14):(3-5):(13-16):(0.001-0.003).

3. The preparation method according to claim 2, characterized in that: The synthesis reaction temperature in step (1) is 70-80° C., the time is 15-20 min, and after the reaction is completed, it is baked at 100° C. for 18 h.

4. The preparation method according to claim 3, characterized in that: The polyether diol in step (1) is polytetramethylene ether diol; the small molecule chain extender is trimethylolpropane monoallyl ether; and the cross-linking reaction inhibitor is phosphoric acid.

5. The preparation method according to claim 4, characterized in that: The Mooney viscosity (ML100°C 1+4) of the polyurethane raw rubber UR601-10 containing 10% fumed silica A200 is 55±10.

6. The preparation method according to any one of claims 1 to 5, characterized in that: In the raw material composition, the white carbon black is white carbon black with good reinforcement and good compatibility, and is at least one of precipitated white carbon black H-160, precipitated white carbon black HT-203, fumed white carbon black A200 or fumed white carbon black HL-150.

7. The preparation method according to claim 6, characterized in that: In the raw material composition, the silane coupling agent is a silane coupling agent suitable for enhancing the reinforcing effect of polyurethane and white carbon black, and is at least one of A-172, KH-540, and KH-550.

8. The preparation method according to claim 7, characterized in that: In the raw material composition, the vulcanizing agent includes a peroxide vulcanizing agent and a crosslinking aid thereof, the peroxide vulcanizing agent is at least one of DCP, BIPB, and DBPH, and the crosslinking aid is at least one of TAIC, TMPTA, and TMPTMA; The antioxidant is a compounding agent suitable for improving the antioxidant performance of polyurethane, and is at least one of antioxidant 1076 and antioxidant 245; the anti-yellowing agent is at least one of H120 and UV-N.

9. The polyurethane rubber compound prepared by the method according to any one of claims 1 to 8.

10. Use of the polyurethane rubber compound according to claim 9 in space beans.

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