Polyurethane elastomer material for fender and preparation method thereof

Abstract

The embodiment of the invention provides a polyurethane elastomer material for a fender and a preparation method of the polyurethane elastomer material. The method comprises the following steps: mixing a polyurethane elastomer and a rubber body according to a ratio, adding the mixture into an internal mixer, and mixing for 2-10 minutes; adding a coupling agent and an auxiliary agent into the internal mixer, and continuously mixing for 5-8 minutes; the preparation method comprises the following steps: adding sulfur, mixing for 1-3 minutes, adding the obtained mixture into a screw machine, and extruding and granulating to obtain the polyurethane elastomer material, according to the polyurethane elastomer material disclosed by the invention, the fender polyurethane material has the characteristics of excellent elastic property, difficulty in tearing and the like.

Description

Technical Field

[0001] The present application relates to the technical field of polyurethane elastomer materials, and in particular to a polyurethane elastomer material for fenders and a preparation method thereof. Background Art

[0002] Fenders are inflatable or water-filled rubber cushioning products used on docks or ships. They are mainly used to reduce the impact between ships and docks or ships when docking or mooring, and protect ships and docks from damage. They are generally made of pure rubber or rubber and metal skeletons and cord layers. They are molded and vulcanized by laminating method, or molded first and then vulcanized in a vulcanizer. Fenders are widely used in ports, docks and ships.

[0003] At present, rubber is usually used as fender, mainly because the rubber fender can absorb energy when it is hit. However, since it mainly absorbs energy by the space formed by the rubber, its disadvantage is that the energy absorption is limited. In addition, the fender made of rubber is very easy to crack at its corners and stress concentration points, so its service life is short.

[0004] In view of this, how to obtain a polyurethane elastic material with high elasticity and not easy to tear for use as a fender becomes very meaningful. Summary of the invention

[0005] The present application provides a polyurethane elastomer material for fenders and a preparation method thereof, which are used to solve the technical problems of existing polyurethane fender materials, such as poor elasticity and easy tearing.

[0006] In a first aspect, the present application provides a polyurethane elastomer material for a fender, the polyurethane elastomer material comprising: a polyurethane elastomer and a rubber body;

[0007] The structural formula of the polyurethane elastomer is shown below:

[0008]

[0009] The R4 is Wherein, R is selected from any one of -H, -CH3, -CH2CH3, -CH2CH2CH3, -NH2 or -OH; m = 25 to 35, n = 15 to 25;

[0010] The R1, R2 and R3 are independently selected from any one of a connecting bond, a substituted or unsubstituted 6-membered saturated carbocyclic group, and a substituted or unsubstituted phenyl group.

[0011] In an optional embodiment, the rubber body includes natural rubber, butadiene rubber and styrene-butadiene rubber;

[0012] Wherein, the mass ratio of the natural rubber, butadiene rubber and styrene butadiene rubber is 1:(0.8-0.95):(0.8-0.95).

[0013] In an optional embodiment, R1, R2, and R3 are independently selected from any one of formula (1) to formula (3):

[0014]

[0015] In an optional implementation, the polyurethane elastomer material further comprises: a coupling agent, sulfur and an auxiliary agent; wherein the coupling agent is a silane coupling agent;

[0016] Calculated by weight, it comprises: 50-150 parts of polyurethane elastomer, 20-80 parts of rubber body, 0.1-10 parts of coupling agent, 0.5-8 parts of sulfur and 5-30 parts of auxiliary agent.

[0017] In an optional embodiment, the auxiliary agent includes 2 to 4 parts of zinc stearate, 10 to 25 parts of white carbon black, 1 to 10 parts of accelerator, 0.1 to 2 parts of antioxidant, and 0.1 to 1 part of antioxidant.

[0018] Wherein, the accelerator is accelerator MBT and accelerator MBTS in any proportion.

[0019] In an optional embodiment, the antioxidant includes at least one of N-phenyl-α-aniline, N-phenyl-β-naphthylamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine and N,N'-diphenyl-p-phenylenediamine.

[0020] In a second aspect, the present application provides a method for preparing a polyurethane elastomer material for a fender, the preparation method comprising:

[0021] The polyurethane elastomer and the rubber body are mixed in proportion and added into an internal mixer for mixing for 2 to 10 minutes;

[0022] Add the coupling agent and auxiliary agent into the internal mixer and continue mixing for 5 to 8 minutes;

[0023] After sulfur is added and kneaded for 1 to 3 minutes, the obtained mixture is added to a screw machine for extrusion and granulation to obtain the polyurethane elastomer material.

[0024] In an optional implementation manner, the mixing temperature of the internal mixer is 130-150°C.

[0025] In an optional implementation manner, the extrusion temperature of the screw machine is 140-180° C., and the rotation speed of the screw machine is 300-500 rpm.

[0026] In a third aspect, the present application provides a fender, comprising: the polyurethane elastomer material described in any one of the embodiments of the first aspect of the present application, or the polyurethane elastomer material prepared by any one of the preparation methods described in the second aspect of the present application.

[0027] The polyurethane elastomer material for fenders and the preparation method thereof provided in the present application have the following beneficial effects compared with the prior art:

[0028] 1. The polyurethane elastic material in the present application is obtained by mixing a polyurethane elastomer and a rubber body. The polyurethane elastomer and the rubber body have good compatibility, which can improve the comprehensive performance of the material to a certain extent.

[0029] 2. The polyurethane elastomer selected in the present application has a large number of cyclic molecules, which are prone to generate van der Waals forces, hydrogen bonds, etc. between the cyclic molecules and other molecules, thereby improving the compatibility of the polyurethane elastomer and other components, so that the prepared polyurethane elastic material has more excellent elastic properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and, together with the description, serve to explain the principles of the present application.

[0031] Figure 1 A process flow chart of a method for preparing a polyurethane elastomer material for fenders provided in an embodiment of the present application;

[0032] Figure 2 This is a process flow chart of a method for preparing a polyurethane elastomer for fenders provided in an embodiment of the present application.

[0033] The above drawings have shown clear embodiments of the present application, which will be described in more detail later. These drawings and text descriptions are not intended to limit the scope of the present application in any way, but to illustrate the concept of the present application to those skilled in the art by referring to specific embodiments. DETAILED DESCRIPTION

[0034] Exemplary embodiments will be described in detail herein, examples of which are shown in the accompanying drawings. When the following description refers to the drawings, the same numbers in different drawings represent the same or similar elements unless otherwise indicated. The implementations described in the following exemplary embodiments do not represent all implementations consistent with the present application. Instead, they are merely examples of devices and methods consistent with some aspects of the present application as detailed in the appended claims.

[0035] The present application provides a polyurethane elastomer material for fenders and a preparation method thereof, aiming to solve the above technical problems of the prior art.

[0036] The technical solution of the present application and how the technical solution of the present application solves the above-mentioned technical problems are described in detail below with specific embodiments. The following specific embodiments can be combined with each other, and the same or similar concepts or processes may not be repeated in some embodiments. The embodiments of the present application will be described below in conjunction with the accompanying drawings.

[0037] Figure 1 This is a process flow chart of a method for preparing a polyurethane elastomer material for fenders provided in an embodiment of the present application. Figure 1 As shown, the preparation method comprises:

[0038] S101, mixing the polyurethane elastomer and the rubber body according to a certain proportion, adding them into an internal mixer and kneading them for 2 to 10 minutes.

[0039] S102, adding the coupling agent and the auxiliary agent into the internal mixer, and continuing to mix for 5 to 8 minutes; wherein the mixing temperature of the internal mixer is 130 to 150°C.

[0040] S103, after adding sulfur and kneading for 1 to 3 minutes, adding the obtained mixture into a screw machine for extrusion granulation, the extrusion temperature of the screw machine is 140 to 180° C., and the speed of the screw machine is 300 to 500 rpm, to obtain a polyurethane elastomer material.

[0041] The polyurethane elastomer in this application is prepared by the following method:

[0042] S201, adding the first compound and the second compound into a solvent, reacting at 65° C. to 80° C. under a nitrogen atmosphere and adding a catalyst to obtain an intermediate product.

[0043] S202, adding the intermediate product and the third compound into a solvent, reacting at 35-50° C. under a nitrogen atmosphere to obtain a polyurethane elastomer.

[0044] The solvent may be selected from one or more of N-methyl-2-pyrrolidone, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc) and dimethyl sulfoxide.

[0045] The catalyst can be selected from an organic tin catalyst or a tertiary amine catalyst, for example, it can be selected from any one of dibutyltin dilaurate (DBTDL), stannous octoate, triethylenediamine, bis(dimethylaminoethyl) ether or N,N-dimethylcyclohexylamine; and the amount of the catalyst added is a conventional amount, which can be based on the first compound, and the mass ratio of the catalyst to the first compound is 1:200-400; the molar ratio of the first compound, the second compound and the third compound is 1:0.4-0.6:0.42-0.55; of course, those skilled in the art can understand that it includes but is not limited to the above ratios.

[0046] The first compound may be any one of the following formulas (1-1) to (1-4):

[0047]

[0048]

[0049] The second compound may be

[0050]

[0051] The third compound may be

[0052]

[0053] Specifically, the corresponding polyurethane elastomer materials were prepared by the following Examples 1 to 3 and Comparative Examples 1 to 4, wherein the polyurethane elastomer materials in Examples 1 to 3 were prepared by the above steps S101 to S103.

[0054] Example 1

[0055] S301, the polyurethane elastomer and the rubber body are mixed according to a certain proportion and added into an internal mixer for mixing for 10 minutes.

[0056] S302, adding the coupling agent and the auxiliary agent into the internal mixer, and continuing to mix for 5 minutes; wherein the mixing temperature of the internal mixer is 140°C.

[0057] S303, after adding sulfur and kneading for 3 minutes, adding the obtained mixture into a screw machine for extrusion granulation, the extrusion temperature of the screw machine is 160° C., and the speed of the screw machine is 500 rpm, to obtain a polyurethane elastomer material.

[0058] The components include: 120 parts of polyurethane elastomer, 70 parts of rubber body, 4 parts of coupling agent, 3 parts of sulfur and 30 parts of additives; the additives include: 3 parts of zinc stearate, 19 parts of white carbon black, 6 parts of accelerator, 1 part of antioxidant and 1 part of anti-aging agent.

[0059] The polyurethane elastomer is prepared by the above method, wherein the first compound selected in this embodiment is of formula (1-1); the structural formula of the polyurethane elastomer is R1 and R2 are of formula (3), R3 is the structural formula of the second compound, m=30, n=20.

[0060] Example 2

[0061] The only difference between this embodiment and embodiment 1 is that the first compound selected in this embodiment is of formula (1-2), and the structural formulas of the corresponding polyurethane elastomer are R1 and R2, which are also the same as formula (1-2).

[0062] Example 3

[0063] The only difference between this embodiment and embodiment 1 is that the structural formula of the polyurethane elastomer is that the structural formulas of R1 and R2 are selected from formula (2).

[0064] Comparative Example 1

[0065] The only difference between this comparative example and Example 1 is that the components do not contain polyurethane elastomer.

[0066] Comparative Example 2

[0067] The only difference between this comparative example and Example 1 is that the components do not contain a rubber body.

[0068] Comparative Example 3

[0069] The difference between this comparative example and Example 1 is that the polyurethane elastomer is prepared by the following method:

[0070] S401, mixing castor oil and isophorone diisocyanate, heating and stirring to react, and obtaining a prepolymer.

[0071] S402, mixing the prepolymer, polytetrahydrofuran, double-terminal hydroxyl-containing silicone oil and a catalyst, and performing a curing reaction to obtain a polyurethane elastic material.

[0072] Comparative Example 4

[0073] The only difference between this comparative example and Example 1 is that the polyurethane elastomer selected is thermoplastic polyurethane elastomer TPU purchased from the market.

[0074] Performance Test:

[0075] The tensile strength, elongation at break, hardness, tear strength and elasticity of the polyurethane elastomer materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were tested respectively. The test results are shown in Table 1.

[0076] Among them, the tensile strength and elongation at break are tested with reference to GB / T1040 standard; the hardness is tested with reference to GB / T2411 standard; the tear strength is tested with reference to GB / T529 standard; the elasticity is tested with reference to GB / T1681 standard; and the oxygen index is tested with reference to ASTMD2863 standard.

[0077] Table 1. Performance test results:

[0078]

[0079] It can be seen from Table 1 that the polyurethane elastic materials obtained in Examples 1 to 3 of the present application have excellent tensile strength and elongation at break compared with the polyurethane elastic materials in Comparative Examples 1 to 4.

[0080] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A polyurethane elastomer material for fenders, characterized in that: The polyurethane elastomer material comprises: a polyurethane elastomer and a rubber body; The structural formula of the polyurethane elastomer is shown below: The R4 is Wherein, R is selected from any one of -H, -CH3, -CH2CH3, -CH2CH2CH3, -NH2 or -OH; m = 25 to 35, n = 15 to 25; The R1, R2 and R3 are independently selected from any one of a connecting bond, a substituted or unsubstituted 6-membered saturated carbocyclic group, and a substituted or unsubstituted phenyl group.

2. The polyurethane elastomer material for fender according to claim 1, characterized in that: The rubber body includes natural rubber, butadiene rubber and styrene-butadiene rubber; Wherein, the mass ratio of the natural rubber, butadiene rubber and styrene butadiene rubber is 1:(0.8-0.95):(0.8-0.95).

3. The polyurethane elastomer material for fender according to claim 1, characterized in that: The R1, R2, and R3 are independently selected from any one of formula (1) to formula (3):

4. The polyurethane elastomer material for fender according to claim 1, characterized in that: The polyurethane elastomer material also includes: a coupling agent, sulfur and an auxiliary agent; Calculated by weight, it comprises 50-150 parts of polyurethane elastomer, 20-80 parts of rubber body, 0.1-10 parts of coupling agent, 0.5-8 parts of sulfur and 5-30 parts of auxiliary agent.

5. The polyurethane elastomer material for fender according to claim 4, characterized in that: The auxiliary agent comprises 2-4 parts of zinc stearate, 10-25 parts of white carbon black, 1-10 parts of accelerator, 0.1-2 parts of antioxidant and 0.1-1 part of anti-aging agent.

6. The polyurethane elastomer material for fender according to claim 4, characterized in that: The antioxidant comprises at least one of N-phenyl-α-aniline, N-phenyl-β-naphthylamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine and N,N'-diphenyl-p-phenylenediamine.

7. A method for preparing a polyurethane elastomer material for fenders, characterized in that: The preparation method comprises: The polyurethane elastomer and the rubber body are mixed in proportion and added into an internal mixer for mixing for 2 to 10 minutes; Add the coupling agent and auxiliary agent into the above internal mixer and continue mixing for 5 to 8 minutes; After sulfur is added and kneaded for 1 to 3 minutes, the obtained mixture is added to a screw machine for extrusion and granulation to obtain the polyurethane elastomer material.

8. The method for preparing a polyurethane elastomer material for fender according to claim 7, characterized in that: The mixing temperature of the internal mixer is 130-150°C.

9. The method for preparing a polyurethane elastomer material for fender according to claim 7, characterized in that: The extrusion temperature of the screw machine is 140-180° C., and the rotation speed of the screw machine is 300-500 rpm.

10. A fender, characterized in that: The fender comprises the polyurethane elastomer material according to any one of claims 1 to 6, or the polyurethane elastomer material prepared by the preparation method according to any one of claims 7 to 8.

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