Scratch-resistant master batch as well as preparation method and application thereof

Abstract

The invention relates to the field of functional master batches, and provides a scratch-resistant master batch as well as a preparation method and application thereof, and the scratch-resistant master batch comprises the following raw materials in parts by weight: 60-80 parts of ultra-high molecular weight polyethylene, 40-60 parts of modified nano barium sulfate and 5-10 parts of silicone master batch. The master batch provided by the invention has good scratch resistance while ensuring the glossiness, and can be widely applied to polypropylene resins.

Description

Technical Field

[0001] The present invention relates to the field of functional masterbatches, and in particular to a scratch-resistant masterbatch and a preparation method and application thereof. Background Art

[0002] Polypropylene (PP) is a general-purpose plastic that is relatively inexpensive and offers advantages such as lightweight, chemical resistance, excellent electrical insulation, and superior mechanical properties and processability. It is widely used in a variety of fields, including home appliances, automobiles, and electronic appliances. Amidst increasingly fierce market competition, PP resins are gradually replacing some higher-priced general-purpose plastics. However, with the development of society and the improvement of people's quality of life, higher and higher requirements are being placed on the materials used. Polypropylene resins suffer from poor surface scratch resistance, which not only significantly reduces the aesthetics of their products but also severely limits their scope of application.

[0003] Currently, the most common method for improving the scratch resistance of polypropylene resins is to fill the resin with inorganic fillers and small-molecule scratch-resistant agents, such as amides. However, while this method improves the scratch resistance of polypropylene resins, it often reduces their surface gloss and produces oil streaks on the surface of injection-molded parts. In other words, these methods are not ideal and effective in improving both the scratch resistance and surface gloss of polypropylene resins. Alternatively, while some materials, such as nano-iron oxide or nano-barium sulfate, can achieve both improved scratch resistance and high gloss when added to polypropylene resins, these nanomaterials still suffer from the problems of easy agglomeration and poor dispersion, resulting in less than ideal improvements in the scratch resistance of polypropylene resins.

[0004] Patent CN116218082A discloses a scratch-resistant PP masterbatch, its preparation method, and its application. The raw materials include a carrier resin, a pigment, an anti-aging additive, and a scratch-resistant agent. The scratch-resistant agent is a mixture of silicone masterbatch, erucamide, and polysiloxane. It has the characteristics of reducing the surface friction coefficient and improving the wear resistance of the material. However, erucamide affects the gloss of the resin, which may limit its application to a certain extent. Patent CN107793617 B discloses a scratch-resistant masterbatch, its preparation method and application, and a thermoplastic composite material composed of the scratch-resistant masterbatch. The scratch-resistant masterbatch disclosed in this application includes the following components: ultra-high molecular weight polyethylene, cubic boron nitride, polyethylene grafted with maleic anhydride, and a processing aid. Although the preferred particle size of the cubic boron nitride in this application is 1250-2000 mesh, which has a certain effect on improving dispersibility, the strong interaction between the cubic boron nitride particles makes them prone to self-agglomeration, so the improvement of the scratch resistance of the resin matrix may not be ideal.

[0005] Therefore, there is an urgent need on the market for a scratch-resistant masterbatch that can be added to polypropylene resin so that it can have good scratch resistance while ensuring gloss. Summary of the Invention

[0006] In response to the problems existing in the prior art, the present invention synthesizes a scratch-resistant masterbatch using ultra-high molecular weight polyethylene, modified nano-barium sulfate, silicone masterbatch and glass microbeads as raw materials. When added to polypropylene resin, it can ensure gloss while also having good scratch resistance.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] On one hand, the present invention provides a scratch-resistant masterbatch, which comprises the following raw materials in parts by weight: 60-80 parts of ultra-high molecular weight polyethylene, 40-60 parts of modified nano-barium sulfate, and 5-10 parts of silicone masterbatch.

[0009] In some embodiments of the present invention, the ultra-high molecular weight polyethylene has an average number average molecular weight of 4.5-5.5 million.

[0010] Preferably, the ultra-high molecular weight polyethylene has an average number average molecular weight of 5 million.

[0011] The applicant selected ultra-high molecular weight polyethylene (UHMWPE) of a specific molecular weight as the main component of the scratch-resistant masterbatch. Due to its long molecular chain and high molecular weight, it can better disperse and absorb stress when scratched, thereby reducing wear and scratching of the material, which is beneficial to improving the scratch resistance of polypropylene. In addition, the UHMWPE has a smooth surface and self-lubricating properties, which further reduces the surface damage caused by friction when the scratch-resistant masterbatch is added to polypropylene, thereby allowing the polypropylene to maintain a good gloss.

[0012] In some embodiments of the present invention, the method for preparing the modified nano-barium sulfate comprises the following steps:

[0013] (1) Potassium persulfate and potassium hydroxide are placed in a reaction vessel 1, deionized water is added, and the mixture is stirred to obtain a solution 1 for later use; barium chloride and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide are placed in a reaction vessel 2, deionized water is added, and the mixture is heated to 60-75° C. and stirred to obtain a solution 2 for later use;

[0014] (2) adding solution 1 of step (1) dropwise to solution 2 while stirring, maintaining a constant temperature of 60-75° C., sealing after completion of the addition, continuing to stir until neutral, centrifuging, washing, and drying to obtain nano-barium sulfate for use;

[0015] (3) Add the nano-barium sulfate obtained in step (2) to deionized water, ultrasonicate, heat to 70-80° C., add aluminate coupling agent UP-801 and palmitic acid, stir, filter, wash, and dry to obtain modified nano-barium sulfate.

[0016] In some embodiments of the present invention, in step (1), the mass ratio of barium chloride to potassium persulfate is 1:(0.3-0.7).

[0017] Preferably, in step (1), the mass ratio of barium chloride to potassium persulfate is 1:0.57.

[0018] In some embodiments of the present invention, in step (1), the mass ratio of barium chloride to [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide is 1:(0.4-0.8).

[0019] Preferably, in step (1), the mass ratio of barium chloride to [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide is 1:0.6.

[0020] In some embodiments of the present invention, in step (3), the mass ratio of nano-barium sulfate, aluminate coupling agent UP-801 and palmitic acid is 1: (0.05-0.15): (0.03-0.07).

[0021] Preferably, in step (3), the mass ratio of nano-barium sulfate, aluminate coupling agent UP-801 and palmitic acid is 1:0.1:0.05.

[0022] Nano-barium sulfate can effectively improve the surface hardness and strength of polypropylene, as well as its heat resistance and wear resistance, that is, it has a good effect on improving the scratch resistance of polypropylene. Compared with fillers such as talc powder and calcium carbonate, nano-barium sulfate has little effect on the gloss of polypropylene. It can effectively improve the scratch resistance of polypropylene while ensuring the gloss of polypropylene. However, due to the large specific surface area and high cohesive energy of particles, nano-calcium carbonate is prone to agglomeration and has poor dispersion.

[0023] On the one hand, the applicant uses potassium persulfate and barium chloride as precursors, utilizes the principle that potassium persulfate releases sulfate under heating conditions of an alkaline potassium hydroxide aqueous solution, and adds [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide as a surface modifier to regulate the nucleation and growth process of nano-barium sulfate, increase the steric effect of the nano-barium sulfate surface, and thus make the synthesized nano-barium sulfate particles uniform in size, have good dispersibility, and have good mechanical properties and biocompatibility; on the other hand, the applicant uses an aluminate coupling agent and palmitic acid to jointly modify the nano-barium sulfate. The surface modification of the nano-barium sulfate with the aluminate coupling agent and palmitic acid increases the hydrophobicity of the nano-barium sulfate surface, thereby effectively improving the compatibility and dispersibility of the nano-barium sulfate in the polypropylene matrix, and the successful bonding of the aluminate coupling agent to the barium sulfate surface can improve the heat resistance of the barium sulfate, which to a certain extent solves the problem of reduced activation and whiteness of the nano-barium sulfate due to poor heat resistance caused by palmitic acid modification.

[0024] In some embodiments of the present invention, 1-5 parts by weight of glass microspheres are further included.

[0025] In some embodiments of the present invention, the glass microspheres are solid glass microspheres with an average particle size of 30-60 μm.

[0026] The applicant added a certain amount of solid glass microbeads with a particle size range of 30-60 μm to the scratch-resistant masterbatch, which has good compatibility and dispersibility in polypropylene and can effectively improve the scratch resistance, mechanical properties and gloss.

[0027] Another aspect of the present invention further provides a method for preparing the scratch-resistant masterbatch described in the above technical solution, comprising the following steps:

[0028] Ultra-high molecular weight polyethylene, modified nano-barium sulfate, silicone masterbatch and glass microbeads are mixed, extruded, and granulated at 150-200°C to obtain the scratch-resistant masterbatch.

[0029] In another aspect, the present invention provides the use of the scratch-resistant masterbatch described in the above technical solution, which is used in polypropylene resin.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) The present invention uses ultra-high molecular weight polyethylene, modified nano-barium sulfate, silicone masterbatch and glass microbeads as raw materials to synthesize a scratch-resistant masterbatch. Through the synergistic effect of the various components, when added to a polypropylene resin, it can ensure gloss while also having good scratch resistance.

[0032] (2) The present invention uses potassium persulfate and barium chloride as precursors, adds [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl) ammonium hydroxide as a surface modifier, and synthesizes nano-barium sulfate with good dispersibility and mechanical properties. The nano-barium sulfate is jointly modified by an aluminate coupling agent and palmitic acid, so that the modified nano-barium sulfate has good compatibility and dispersibility in a polypropylene matrix, which can effectively improve the scratch resistance and gloss of polypropylene.

[0033] (3) The masterbatch prepared by the present invention has good scratch resistance while ensuring glossiness, can be widely used in polypropylene resins, and has good commercial application value. DETAILED DESCRIPTION

[0034] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following examples are illustrative of the present invention and are intended only to illustrate the present invention and are not intended to limit the present invention. Other combinations and various modifications within the scope of the present invention may be made without departing from the spirit or scope of the present invention.

[0035] In the following examples and comparative examples, except for the modified nano-barium sulfate, the other compound monomers and related reagents used can be purchased from the market. Among them, the average number average molecular weight of the ultra-high molecular weight polyethylene is 5 million; the glass microspheres are solid glass microspheres with an average particle size of 40 μm.

[0036] Preparation Example 1

[0037] The synthesis method of modified nano-barium sulfate A comprises the following steps:

[0038] (1) 0.85 g of potassium persulfate and 0.35 g of potassium hydroxide were placed in a reaction vessel 1, 200 ml of deionized water was added, and the mixture was stirred until completely dissolved to obtain a solution 1 for later use; 1.5 g of barium chloride and 0.9 g of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide were placed in a reaction vessel 2, 100 ml of deionized water was added, the mixture was heated to 70° C., and the mixture was stirred until completely dissolved to obtain a solution 2 for later use;

[0039] (2) adding the solution 1 of step (1) dropwise to the solution 2 at 4 mL / min while stirring at 400 r / min, maintaining a constant temperature of 70° C. After the addition is complete, sealing, stirring is continued until neutral, centrifuging, washing with deionized water 3 times, and drying at 60° C. for 4 h to obtain nano-barium sulfate for use;

[0040] (3) 2 g of the nano-barium sulfate obtained in step (2) was added to 120 ml of deionized water, ultrasonicated for 30 min, heated to 75 ° C, added with 0.2 g of aluminate coupling agent UP-801 and 0.1 g of palmitic acid, stirred for 50 min, filtered, washed with deionized water three times, and dried at 100 ° C for 4 h to obtain modified nano-barium sulfate A.

[0041] Preparation Example 2

[0042] The specific implementation method of modified nano-barium sulfate B is the same as that of modified nano-barium sulfate A, except that the mass of potassium persulfate in step (1) is replaced by 0.3 g.

[0043] Preparation Example 3

[0044] The specific implementation method of modified nano-barium sulfate C is the same as that of modified nano-barium sulfate A, except that in step (1), the mass of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide is replaced with 0.4g.

[0045] Preparation Example 4

[0046] The specific implementation method of modified nano-barium sulfate D is the same as that of modified nano-barium sulfate A, except that in step (3), the mass of aluminate coupling agent UP-801 is replaced with 0.08 g.

[0047] Preparation Example 5

[0048] The specific implementation method of modified nano-barium sulfate E is the same as that of modified nano-barium sulfate A, except that the mass of palmitic acid in step (3) is replaced by 0.04 g.

[0049] Example 1

[0050] A scratch-resistant masterbatch comprises the following raw materials, calculated by weight: 70 parts of ultra-high molecular weight polyethylene, 50 parts of modified nano-barium sulfate A, 8 parts of silicone masterbatch, and 3 parts of glass microbeads.

[0051] The preparation method of the scratch-resistant masterbatch in this embodiment includes the following steps:

[0052] Ultra-high molecular weight polyethylene, modified nano-barium sulfate A, silicone masterbatch and glass beads are mixed, extruded by a twin-screw extruder, and granulated at 180° C. to obtain the scratch-resistant masterbatch.

[0053] Example 2

[0054] A scratch-resistant masterbatch comprises the following raw materials, calculated by weight: 60 parts of ultra-high molecular weight polyethylene, 40 parts of modified nano-barium sulfate A, 5 parts of silicone masterbatch, and 1 part of glass microbeads.

[0055] The preparation method of the scratch-resistant masterbatch in this embodiment includes the following steps:

[0056] Ultra-high molecular weight polyethylene, modified nano-barium sulfate A, silicone masterbatch and glass microbeads are mixed, extruded by a twin-screw extruder, and granulated at 150° C. to obtain the scratch-resistant masterbatch.

[0057] Example 3

[0058] A scratch-resistant masterbatch comprises the following raw materials, calculated by weight: 80 parts of ultra-high molecular weight polyethylene, 60 parts of modified nano-barium sulfate A, 10 parts of silicone masterbatch, and 5 parts of glass microbeads.

[0059] The preparation method of the scratch-resistant masterbatch in this embodiment includes the following steps:

[0060] Ultra-high molecular weight polyethylene, modified nano-barium sulfate A, silicone masterbatch and glass microbeads are mixed, extruded by a twin-screw extruder, and granulated at 200° C. to obtain the scratch-resistant masterbatch.

[0061] Example 4

[0062] A scratch-resistant masterbatch comprises the following raw materials, calculated by weight: 70 parts of ultra-high molecular weight polyethylene, 50 parts of modified nano-barium sulfate A, and 8 parts of silicone masterbatch.

[0063] The preparation method of the scratch-resistant masterbatch in this embodiment includes the following steps:

[0064] Ultra-high molecular weight polyethylene, modified nano-barium sulfate A and silicone masterbatch are mixed, extruded by a twin-screw extruder, and granulated at 180° C. to obtain the scratch-resistant masterbatch.

[0065] Example 5

[0066] This embodiment provides a scratch-resistant masterbatch and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that modified nano-barium sulfate B replaces modified nano-barium sulfate A in equal amounts.

[0067] Example 6

[0068] This embodiment provides a scratch-resistant masterbatch and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that modified nano-barium sulfate C replaces modified nano-barium sulfate A in equal amounts.

[0069] Example 7

[0070] This embodiment provides a scratch-resistant masterbatch and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that modified nano-barium sulfate D replaces modified nano-barium sulfate A in equal amounts.

[0071] Example 8

[0072] This embodiment provides a scratch-resistant masterbatch and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that modified nano-barium sulfate E replaces modified nano-barium sulfate A in equal amounts.

[0073] Comparative Example 1

[0074] This comparative example provides a scratch-resistant masterbatch and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the modified nano-barium sulfate A is replaced by an equal amount of nano-barium sulfate.

[0075] Performance Testing

[0076] The scratch resistance and glossiness of the scratch-resistant masterbatch described in Examples 1-8 and Comparative Example 1 were tested, and the test results are shown in Table 1.

[0077] 5 g of the scratch-resistant masterbatch in Examples 1-8 and Comparative Example 1 was mixed with 150 g of polypropylene, mixed at 160 r / min for 6 min, melt-extruded and granulated in a twin-screw extruder, and molded into samples with a thickness of 3 mm and a diameter of 10 mm by an injection molding machine. The samples were tested for scratch resistance and glossiness.

[0078] (1) Scratch resistance

[0079] Referring to the standard GMW14688, the coating surface was scratched using a German ERICHSEN 430P-1 electric cross-hatch instrument. A 0.5mm scratching head was used. Under a pressure of 5N, 20 scratches with a spacing of 4mm and a length of 40mm were scratched on the coating at a speed of 1000mm / min. After scratching in one direction, the plastic plate was rotated 90° and scratched again. The scratch resistance of the sample surface was determined by comparing the change in gloss (△L) before and after scratching using a Dutch TQC GL0010 gloss meter. The smaller the change in gloss before and after scratching, the better the scratch resistance of the sample surface.

[0080] (2) Glossiness

[0081] Refer to standard GB / T 9754, the incident light angle is 60°.

[0082] Table 1

[0083] Group △L Glossiness / 60°(°) Example 1 0.50 95 Example 2 0.53 94 Example 3 0.55 92 Example 4 0.65 89 Example 5 0.85 85 Example 6 0.90 83 Example 7 0.92 81 Example 8 0.95 80 Comparative Example 1 1.05 75

[0084] It can be seen from the data in Table 1 that the scratch-resistant masterbatch in Examples 1-3 of the present invention has good scratch resistance and gloss as a whole, among which, in Example 4, no glass beads are added to the scratch-resistant masterbatch, which reduces the scratch resistance and gloss of the sample to a certain extent; Examples 5-8 change the addition ratio of potassium persulfate, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide, aluminate coupling agent UP-801 and palmitic acid in the synthesis process of modified nano-barium sulfate, so that the dispersibility of the modified nano-barium sulfate is not well improved, which leads to a significant decrease in the scratch resistance and gloss of the sample; Comparative Example 1 is an equal amount of nano-barium sulfate replacing modified nano-barium sulfate A, and the test found that the scratch resistance and gloss of the scratch-resistant masterbatch showed poor results.

[0085] The above embodiments are only for illustrating the technical concept and features of the present invention. Its purpose is to enable people familiar with this technology to understand the content of the present invention and implement it. It cannot be used to limit the scope of protection of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A scratch-resistant masterbatch, characterized in that: The scratch-resistant masterbatch comprises the following raw materials in parts by weight: 60-80 parts of ultra-high molecular weight polyethylene, 40-60 parts of modified nano-barium sulfate, and 5-10 parts of silicone masterbatch.

2. The scratch-resistant masterbatch according to claim 1, characterized in that The average number average molecular weight of the ultra-high molecular weight polyethylene is 4.5-5.5 million.

3. The scratch-resistant masterbatch according to claim 1, characterized in that The preparation method of the modified nano-barium sulfate comprises the following steps: (1) Potassium persulfate and potassium hydroxide are placed in a reaction vessel 1, deionized water is added, and the mixture is stirred to obtain a solution 1 for later use; barium chloride and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide are placed in a reaction vessel 2, deionized water is added, and the mixture is heated to 60-75° C. and stirred to obtain a solution 2 for later use; (2) adding solution 1 of step (1) dropwise to solution 2 while stirring, maintaining a constant temperature of 60-75° C., sealing after completion of the addition, continuing to stir until neutral, centrifuging, washing, and drying to obtain nano-barium sulfate for use; (3) Add the nano-barium sulfate obtained in step (2) to deionized water, ultrasonicate, heat to 70-80° C., add aluminate coupling agent UP-801 and palmitic acid, stir, filter, wash, and dry to obtain modified nano-barium sulfate.

4. The scratch-resistant masterbatch according to claim 3, characterized in that In the step (1), the mass ratio of barium chloride to potassium persulfate is 1:(0.3-0.7).

5. The scratch-resistant masterbatch according to claim 3, characterized in that In the step (1), the mass ratio of barium chloride to [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide is 1:(0.4-0.8).

6. The scratch-resistant masterbatch according to claim 3, characterized in that In the step (3), the mass ratio of nano-barium sulfate, aluminate coupling agent UP-801 and palmitic acid is 1: (0.05-0.15): (0.03-0.07).

7. The scratch-resistant masterbatch according to claim 1, characterized in that Calculated by weight, 1-5 parts of glass micro beads are also included.

8. The scratch-resistant masterbatch according to claim 7, characterized in that The glass microbeads are solid glass microbeads with an average particle size of 30-60 μm.

9. A method for preparing the scratch-resistant masterbatch according to any one of claims 7 to 8, characterized in that: The following steps are involved: Ultra-high molecular weight polyethylene, modified nano-barium sulfate, silicone masterbatch and glass microbeads are mixed, extruded, and granulated at 150-200°C to obtain the scratch-resistant masterbatch.

10. Use of the scratch-resistant masterbatch according to any one of claims 7 to 8, characterized in that: Used in polypropylene resins.