Preparation method and application of nylon 12-color masterbatch with high color powder content

Abstract

The present invention discloses a method for preparing a nylon 12 masterbatch with a high toner content. The nylon masterbatch is prepared using a two-step method: first, a degradable material, a nylon 12 resin, toner and other additives are granulated; in a second step, the degradable material in the masterbatch is decomposed, thereby increasing the toner concentration in the masterbatch. By blending nylon 12, degradable materials, toner and other materials, the problem of low dispersion when PA12 resin is directly blended with toner in the traditional preparation method is overcome. Through the degradation process in the second step, the overall resin ratio is reduced, the toner ratio is increased, and the problem of poor compatibility between traditional masterbatches and PA12 plastic materials is solved. The method has the advantages of high toner content, uniform color dispersion, no solvent and small molecule precipitation, and environmental protection and mildness.

Description

Technical Field

[0001] The invention belongs to the technical field of modified plastics, and in particular relates to a preparation method and application of a nylon 12 color masterbatch with a high color powder content. Background Art

[0002] Masterbatch is a mixture of resin and pigment. It is widely used in the production process of plastic products. In industrial production, a certain amount of nylon 12 masterbatch products can be prepared by mixing carrier resin with colorant, dispersant and other components. In actual use, it is often expected that the coloring component content in the masterbatch is higher in order to save materials and reduce production costs.

[0003] Due to factors such as technical level and related raw material restrictions, domestic masterbatches are relatively single in type, generally dominated by general-purpose masterbatches, and there are few reports on high-content, ultra-high-content and multifunctional masterbatches.

[0004] Chinese patent CN 115260626A discloses a blue phase high content high pigment carbon black colored polyethylene masterbatch and its preparation method, which improves the color powder content by modifying the carbon black surface and improving the compatibility between the coloring component and the resin. However, this method of modifying the surface of the coloring component has two hidden dangers: first, some solvents are often contained in the preparation process, and it is easy for the solvent components to remain and be brought into the product, which brings certain hidden dangers; second, due to the natural structural differences between the color powder and the resin, this method cannot significantly increase the color powder content in the masterbatch.

[0005] Chinese patent CN 10292487808B discloses a method for preparing masterbatch with high color powder content, which increases the contact area between resin and color powder by mixing and grinding, and prepares a masterbatch with a color powder content of up to 60%. This method is suitable for the preparation of masterbatches with olefin resins such as PE, EVA, and PP as color powder carriers. In the actual production process, the resin with PA, especially PA12, as a carrier is difficult to achieve extreme extension due to its polarity, so the contact area between the resin and the color powder is limited, and the content of masterbatches based on PA is lower than 30% for a long time.

[0006] Degradable materials have been gaining popularity in recent years, and reports on the production of nylon 12 masterbatches using degradable materials as the matrix have also been frequently seen. Chinese patent CN102746629B discloses a degradable masterbatch and a method for preparing the same. A degradable nylon 12 masterbatch is prepared by blending and granulating color powder and PLA resin, and the feasibility of the degradable masterbatch is verified. Chinese patent CN113480750A discloses a process for preparing biodegradable masterbatch. This process realizes the application of PLA masterbatch in the spinning field by making PLA dyeing masterbatch. Chinese patent CN116836525B discloses an environmentally friendly degradable masterbatch and a method for preparing the same. This method realizes the mass production of degradable masterbatch using PBS material as the matrix. The nylon 12 masterbatches reported in the above patents are all masterbatch products prepared with degradable materials as carriers. In actual use, they can only be applied to degradable materials. Once used in non-degradable materials, the degradation characteristics of the degradable material matrix will cause performance degradation and surface defects, which greatly limits the use of degradable masterbatches. Summary of the invention

[0007] In order to overcome the shortcomings of the above-mentioned prior art, the present invention provides a nylon 12 masterbatch with a high toner content and a preparation method thereof. The present invention prepares a nylon 12 masterbatch with a relatively low toner content by co-extruding a degradable and non-degradable resin and other masterbatch components, and then promotes the degradation of the degradable material through certain process conditions, thereby realizing an increase in the relative content of toner in the masterbatch.

[0008] In order to achieve the above technical effects, the present invention adopts the following technical solutions:

[0009] A method for preparing nylon 12 color masterbatch with high color powder content, wherein the nylon 12 color masterbatch is prepared by two major steps of extrusion granulation and degradation treatment; comprising:

[0010] Step 1: All raw materials are melted and extruded to make original masterbatch;

[0011] Step 2: Eliminate the degradable materials from the original masterbatch prepared in step 1, thereby preparing a nylon 12 masterbatch with a high color powder content.

[0012] In the present invention, the sum of the weight percentages of the components in the original masterbatch is 100%, and the masterbatch is made from the following raw materials:

[0013]

[0014] In the present invention, the other additives include one or more of light stabilizers (such as UV532, UV944, UV326, etc.) and dispersing aids (such as EBS, polyethylene wax, PETS).

[0015] In the present invention, the degradable material includes but is not limited to one or more of biodegradable materials such as PBAT, PLA, and PBS;

[0016] Preferably, the melting temperature of the degradable material is 100-300°C, and the melt flow rate at 2.16kg and 190°C is 0.1-100g / 10min, preferably 1.5-25g / 10min, and more preferably 2-10g / 10min.

[0017] In the present invention, the toner includes one or more compounds of organic toner (such as azo pigments, phthalocyanine pigments, heterocyclic pigments, etc.) and inorganic toner (such as inorganic mineral pigments, oxidizing substances, inorganic iron ion pigments).

[0018] In the present invention, the PA12 resin includes one or more existing PA12 resins such as high viscosity, medium viscosity, low viscosity and nylon elastomer with nylon 12 as the main chain. Preferably, the melt flow rate of the PA12 resin at 2.26kg and 235°C is 3-35g / 10min, preferably 5-20g / 10min.

[0019] In the present invention, the antioxidant is selected from one or more of hindered phenol antioxidants or phosphite antioxidants and copolymers thereof.

[0020] In the present invention, the original masterbatch can be granulated by one or more of a twin-screw extruder, a single-screw extruder, an internal mixer, a continuous internal mixer, etc., and the granulation temperature is 100-300°C, preferably 180-250°C.

[0021] In the present invention, the original masterbatch can be biodegraded in a normal climate environment, a seawater high-salt environment, an industrial composting environment, etc., or degraded by one or more biological enzymes (keratinase, amylase, esterase, etc.), as long as the degradable materials can be eliminated.

[0022] In the present invention, the original masterbatch is preferably pre-degraded in a high temperature (30-80°C) and high humidity (relative humidity 30-90%) environment before degradation, preferably at a temperature of 50-60°C and a humidity of 50-70%; the pre-degradation time is 200-1000h, preferably 400-800h.

[0023] In the present invention, the masterbatch is dried in an oven to obtain a finished product, for example, at 60-100° C. for 2-8 hours.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] Due to the large difference in polarity between toner and PA resin, the active free radicals of the degradable resin material are cross-linked to drive the expansion of toner small molecules, thereby promoting the compatibility and dispersion of the two, solving the problem of poor compatibility and difficult processing between traditional PA resin and high-concentration toner.

[0026] The invention discloses a nylon 12 color masterbatch with a high color powder content, which has the advantages of good compatibility with PA resin, high concentration, easy processing, etc., and can be widely used in the fields of electronic appliances, sports shoes, food and medicine packaging, etc. DETAILED DESCRIPTION

[0027] The following are specific embodiments of the present invention, which further describe the technical solutions of the present invention, but the present invention includes but is not limited to these embodiments.

[0028] In the following examples and comparative examples of the present invention, some of the raw materials and their sources are shown in Table 1:

[0029] Materials not introduced here are all commercially available and will not be described in detail.

[0030] Masterbatch preparation:

[0031] Weigh the raw materials according to the components and dosage (weight parts) in Table 1 and Table 2, mix them in a high-speed mixer for 5 minutes, mix the raw materials evenly, and extrude the mixed blend through a twin-screw extruder for granulation at a speed of 500rpm and a temperature of 180-240°C to obtain the original masterbatch, which is a columnar particle with a diameter of 2-4mm and a length of 2-5mm. The obtained particles are placed in an environment of 80°C and 80% humidity for 300 hours, and then 2% of the original masterbatch is added to the cutinase at 50°C and 75% humidity for 700 hours, and then passed through an oven at 80°C and dried for 5 hours.

[0032] Table 1

[0033]

[0034] Table 2

[0035]

[0036] The granular material granulated according to the above method is injection molded on an injection molding machine to prepare samples.

[0037] According to the determination method of plastic ash content in national standard GB / T9345, the sample size is 80*6*4mm;

[0038] Simply supported beam impact strength is carried out according to ISO179, and the specimen size is 80*6*4mm;

[0039] The melt flow rate of the material is measured using an instrument designed and manufactured in accordance with JB / T5456 and ISO1133 standards for measuring the volume flow rate of thermoplastic melts.

[0040] Table 3 is the performance test results of Examples 1-5 and Comparative Examples 1-3:

[0041] Table 3

[0042]

[0043] Note: Processing levels are: (3) easy to process; (2) difficult to process; (1) very difficult to process; (0) cannot be formed;

[0044] According to Examples 1-5 and Comparative Examples 1-3 in Table 3, the blending of degradable resin, PA12 resin and color powder into granules has good fluidity, high strength and easy processing. After degradation treatment, the color powder content in the masterbatch is significantly increased compared with before.

[0045] It should be noted that the above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing nylon 12 color masterbatch, comprising: Step 1: All raw materials are melted and extruded to make original masterbatch; Step 2: Eliminate the degradable materials from the original masterbatch obtained in step 1, thereby obtaining the nylon 12 color masterbatch.

2. The preparation method according to claim 1, wherein The original masterbatch is made from raw materials containing the following components:

3. The preparation method according to claim 2, wherein The other additives include one or more of light stabilizers (eg, UV532, UV944, UV326) and dispersing aids (eg, EBS, polyethylene wax, PETS).

4. The preparation method according to claim 2, wherein The degradable material includes one or more of PBAT, PLA, and PBS.

5. The preparation method according to claim 4, wherein The melting temperature of the degradable material is 100-300° C., and the melt flow rate under the conditions of 2.16 kg and 190° C. is 0.1-100 g / 10 min, preferably 1.5-25 g / 10 min.

6. The preparation method according to claim 2, wherein: The toner includes one or more of organic toner (eg, azo pigments, phthalocyanine pigments, heterocyclic pigments) and inorganic toner (eg, inorganic mineral pigments, oxidizing pigments, inorganic iron ion pigments).

7. The preparation method according to claim 2, wherein: The PA12 resin includes one or more of a high-viscosity PA12 resin, a medium-viscosity PA12 resin, a low-viscosity PA12 resin, and a nylon elastomer with nylon 12 as the main chain; Preferably, the melt flow rate of PA12 resin at 2.26 kg and 235° C. is 3-35 g / 10 min, preferably 5-20 g / 10 min.

8. The preparation method according to claim 2, wherein: The antioxidant is selected from one or more of hindered phenol antioxidants or phosphite antioxidants and copolymers thereof.

9. The preparation method according to claim 2, wherein: The original masterbatch is biodegraded in a normal climate environment, a seawater high-salinity environment or an industrial composting environment, or is degraded using biological enzymes (such as keratinase, amylase, esterase) to eliminate the degradable materials.

10. The preparation method according to claim 2 or 9, wherein: The original masterbatch is pre-degraded in a high temperature (30-80°C) and high humidity (relative humidity 30-90%) environment before degradation, preferably at 50-60°C and 50-70% humidity; the pre-degradation time is 200-1000h, preferably 400-800h.

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