Polyethylene color master batch and preparation method thereof
By introducing functional additives into polyethylene masterbatch and crosslinking them with the polyethylene matrix, the instability of polyethylene masterbatch under high-temperature oxidative environment is solved, and the long-term antioxidant and heat-oxidative aging resistance properties are improved.
Patent Information
- Application Number
- CN202511491463.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-18
- Publication Date
- 2025-12-16
AI Technical Summary
Polyethylene masterbatch is unstable in high-temperature oxidizing environments, and the migration and volatilization of existing small-molecule antioxidants cannot guarantee long-term antioxidant performance.
By using functional additives, polyethylene masterbatches containing hindered phenolic structures and silicon-oxygen bonds are prepared through cross-linking with the polyethylene matrix via chemical bonds. The stability and high bond energy of these chemical bonds are utilized to improve the high-temperature resistance and mechanical strength of the masterbatches.
It achieves long-lasting antioxidant effect and heat and oxygen aging resistance of color masterbatch, broadening its application range, and the functional additives are not easy to migrate, maintaining good mechanical properties.
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Figure CN121136244A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of color masterbatch, and particularly relates to a polyethylene color masterbatch and a preparation method thereof. BACKGROUND
[0002] As an indispensable pigment additive in the plastic processing industry, the polyethylene color masterbatch is widely used in packaging materials, household supplies, electronic appliances and medical devices and other fields due to its stable color, good dispersibility and easy processability. However, although the polyethylene color masterbatch has excellent performance, its performance in a high-temperature oxidation environment is not satisfactory, which is mainly due to the fact that the hydrogen atoms on the molecular chain of the polyethylene are easily attacked by free radicals to form free radicals. In a high-temperature or oxidation environment, these free radicals can further induce chain scission or crosslinking reactions, resulting in denaturation and rupture of the polyethylene. In addition, the amorphous part of the polyethylene molecular chain is easy to absorb oxygen and play a catalytic role of free radicals, further aggravating the occurrence of oxidation reaction. This characteristic of the molecular structure fundamentally determines the instability of the polyethylene color masterbatch in a high-temperature oxidation environment.
[0003] At present, the main method for modifying the oxidation resistance of polyethylene is to add small-molecule antibacterial agents, such as antioxidant GM and antioxidant 1010. These small-molecule antioxidants with hindered phenol structure can react with peroxide radicals, stabilize these radicals by providing hydrogen atoms, interrupt the radical chain reaction, and thus improve the oxidation resistance of polyethylene. However, this type of small-molecule antioxidant has a serious migration and volatilization phenomenon, which leads to the fact that the long-term oxidation resistance of the color masterbatch cannot be guaranteed, and thus there is a great defect in actual application. SUMMARY
[0004] (I) Technical problems solved In view of the deficiencies of the prior art, the present application provides a polyethylene color masterbatch and a preparation method thereof.
[0005] (II) Technical solutions A preparation method of a polyethylene color masterbatch, the polyethylene color masterbatch is made of the following components in parts by weight: 32-35 parts of high-density polyethylene, 40-42 parts of low-density polyethylene, 0.5-1.2 parts of a functional additive, 10-15 parts of pink powder, 3-4 parts of a processing aid, and 0.1-0.4 parts of an initiator. The preparation method comprises the following steps: In the first step, the raw materials are weighed according to the weight parts, and then placed in a mixer, the stirring speed is controlled to be 1000-1200 r / min, and the mechanical stirring is mixed for 20-40 min to form a mixture. Second step, the mixture is fed into the twin-screw extruder, control the temperature of each zone of the extruder in turn: 160±5℃, 170±5℃, 170±5℃, 180±5℃, 190±5℃, 180±5℃, 170±5℃, after melting extrusion, granulation, polyethylene color masterbatch can be prepared.
[0006] As a further scheme of the present application, the preparation method of the functional additive is as follows: 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and di(7-octenyl) dichlorosilane are added to toluene, stirring is started, and after a uniform reaction solution is formed, the temperature is gradually increased to 60-70℃, and after stirring for 1-2h, a Friedel-Crafts agent is added, and after the addition is completed, the temperature is maintained for 3-6h, the solvent is evaporated, the temperature is lowered to discharge the product, and after a post-treatment process, the functional additive is obtained, and the whole process is carried out under nitrogen protection.
[0007] As a further scheme of the present application, the molar ratio of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and di(7-octenyl) dichlorosilane is 1-2:1.
[0008] As a further scheme of the present application, the Friedel-Crafts agent is triethylamine, and the amount of triethylamine added is 10-15% of the total mass of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and di(7-octenyl) dichlorosilane.
[0009] Specifically, under the action of the Friedel-Crafts agent, the active benzyl alcohol in the structure of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol can be substituted with the silicon-chlorine group in the structure of di(7-octenyl) dichlorosilane, and by controlling the molar ratio, a functional additive containing two equivalents of unsaturated alkyl substituents and containing a hindered phenol structure and a silicon-oxygen bond in the structure can be prepared, and in the subsequent melt extrusion process, the unsaturated alkyl substituents in the structure can be crosslinked and polymerized with high-density polyethylene and low-density polyethylene under the action of an initiator, so as to enter the matrix molecular chain in the form of a chemical bond.
[0010] As a further scheme of the present application, the toner is at least one of titanium dioxide, azo compounds, naphthalene ring ketone compounds, phthalocyanine compounds, or anthracene ketone compounds.
[0011] As a further scheme of the present application, the processing aid is at least one of polyethylene wax, zinc stearate, stearic acid, or calcium stearate.
[0012] As a further scheme of the present application, the initiator is any one of benzoyl peroxide, dicumyl peroxide, or dibenzoyl peroxide.
[0013] A polyethylene color masterbatch according to claim 1 is prepared by the above preparation method.
[0014] (III) Beneficial technical effects The functional additive prepared by the application can be connected with the polyethylene matrix in the form of chemical bonds. On the one hand, the functional additive connected by chemical bonds can exist in the matrix structure for a long time and cannot volatilize and migrate, so the hindered phenol antioxidant groups in the structure can be retained for a long time, thereby guaranteeing the long-acting antioxidant effect of the color master batch. In addition, the siloxane bond contained in the structure of the functional additive has high bond energy, which can improve the high-temperature resistance of the color master batch, thereby producing a synergistic improvement in the heat-oxidative aging resistance of the color master batch. In addition, since the functional additive can crosslink the molecular chains of the polyethylene matrix, the mechanical strength of the color master batch can also be improved, thereby further widening the application range thereof. BRIEF DESCRIPTION OF DRAWINGS
[0015] In order to more clearly illustrate the technical solutions of the embodiments of the application, the following will briefly introduce the drawings needed to be used in the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the application, and other drawings can also be obtained by those skilled in the art without any creative effort on the basis of these drawings.
[0016] Figure 1 It is an infrared analysis test graph of the functional additive. DETAILED DESCRIPTION
[0017] In order to facilitate the understanding of the application, the following will give a more comprehensive description of the application. The following gives the preferred embodiments of the application. However, the application can be realized in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the application more thorough and comprehensive.
[0018] Preparation Example 1 Preparation of the functional additive: 0.8g of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and 0.6g of bis(7-octenyl) dichlorosilane were added to toluene, stirring was started, and after a uniform reaction liquid was formed, the temperature was gradually increased to 65℃. After 1h of stirring, 0.2g of triethylamine was added, and after the addition, the temperature was continued to be kept and stirring was continued for 4h. The solvent was evaporated, the temperature was lowered to discharge, and the functional additive was prepared by post-treatment process. The whole process was carried out under nitrogen protection.
[0019] Figure 1 It is an infrared analysis test graph of the functional additive, in which the absorption peak appearing at 3282cm -1 -1 is the characteristic absorption peak of the hydroxyl group in the hindered phenol structure, and the absorption peak appearing at 3029cm -1The absorption peak appearing at 1093 cm -1 The absorption peak appearing at 1093 cm Embodiment
[0020] A polyethylene color master batch is prepared by using the following components in parts by weight: 32 parts of high-density polyethylene, 40 parts of low-density polyethylene, 0.5 parts of functional additive, 10 parts of titanium dioxide powder, 3 parts of polyethylene wax, and 0.1 parts of benzoyl peroxide. The preparation method of the polyethylene color master batch comprises the following steps: Firstly, each raw material is weighed according to the weight fraction, and then placed in a mixer, the stirring speed is controlled at 1200 r / min, and mechanically stirred and mixed for 20 min to form a mixture; Secondly, the mixture is fed into a double-screw extruder, and the temperature of each zone of the extruder is controlled in sequence as follows: 160℃ for the first zone, 170℃ for the second zone, 170℃ for the third zone, 180℃ for the fourth zone, 190℃ for the fifth zone, 180℃ for the sixth zone, and 170℃ for the seventh zone. After melting extrusion, granulation is performed, and the polyethylene color master batch is obtained.
[0021] The preparation method of the functional additive is shown in Preparation Example 1, and the following is the same. Embodiment
[0022] A polyethylene color master batch is prepared by using the following components in parts by weight: 32 parts of high-density polyethylene, 40 parts of low-density polyethylene, 0.5 parts of functional additive, 10 parts of titanium dioxide powder, 3 parts of polyethylene wax, and 0.1 parts of benzoyl peroxide. The preparation method of the polyethylene color master batch comprises the following steps: Firstly, each raw material is weighed according to the weight fraction, and then placed in a mixer, the stirring speed is controlled at 1200 r / min, and mechanically stirred and mixed for 20 min to form a mixture; Secondly, the mixture is fed into a double-screw extruder, and the temperature of each zone of the extruder is controlled in sequence as follows: 160℃ for the first zone, 170℃ for the second zone, 170℃ for the third zone, 180℃ for the fourth zone, 190℃ for the fifth zone, 180℃ for the sixth zone, and 170℃ for the seventh zone. After melting extrusion, granulation is performed, and the polyethylene color master batch is obtained. Embodiment
[0023] A polyethylene color master batch is prepared by using the following components in parts by weight: 32 parts of high-density polyethylene, 40 parts of low-density polyethylene, 0.5 parts of functional additive, 10 parts of titanium dioxide powder, 3 parts of polyethylene wax, and 0.1 parts of benzoyl peroxide. The preparation method of the polyethylene color master batch comprises the following steps: First step, each raw material is weighed according to the weight fraction, then placed in a mixer, the stirring speed is controlled at 1200 r / min, mechanically stirred and mixed for 20 min to form a mixture; Second step, the mixture is fed into a twin-screw extruder, the temperature of each zone of the extruder is controlled in turn as follows: zone one 160℃, zone two 170℃, zone three 170℃, zone four 180℃, zone five 190℃, zone six 180℃, zone seven 170℃, after melt extrusion, granulation, the polyethylene color masterbatch can be prepared.
[0024] Comparative Example 1 A polyethylene color masterbatch is prepared using the following components by weight fraction: 34 parts of high-density polyethylene, 41 parts of low-density polyethylene, 0.6 parts of antioxidant GM, 12 parts of titanium white powder, 3.5 parts of stearic acid, and 0.3 parts of dibenzoyl peroxide; The preparation method of the polyethylene color masterbatch comprises the following steps: First step, each raw material is weighed according to the weight fraction, then placed in a mixer, the stirring speed is controlled at 1200 r / min, mechanically stirred and mixed for 30 min to form a mixture; Second step, the mixture is fed into a twin-screw extruder, the temperature of each zone of the extruder is controlled in turn as follows: zone one 160℃, zone two 170℃, zone three 170℃, zone four 180℃, zone five 190℃, zone six 180℃, zone seven 170℃, after melt extrusion, granulation, the polyethylene color masterbatch can be prepared.
[0025] Test Example The polyethylene color masterbatch in the inventive example and the comparative example is subjected to performance testing, and the results are recorded in the following table: Note: The tensile strength test method refers to the standard GB / T 1040-1992, after the test is completed, the same specification test sample is placed at room temperature for 2 months, then treated at a temperature of 120℃ for 24h, taken out, and subjected to tensile strength test to evaluate the antioxidant performance of the sample; the impact strength test refers to the standard GB / T 1843-2008.
[0026] From the test results, it can be analyzed that the color masterbatch prepared by using the functional additive prepared in preparation example 1 as one of the raw materials has excellent mechanical properties and thermal oxidative aging resistance, while replacing the functional additive with a conventional hindered phenolic small molecule antioxidant, due to the volatilization and migration phenomenon during storage, the thermal oxidative aging resistance of the prepared color masterbatch is poor, and due to the inability to form a crosslinked structure with the matrix, the mechanical properties of the color masterbatch are also poor.
[0027] According to the ideal embodiments of the present application, through the above description, relevant personnel can make various changes and modifications without deviating from the technical idea of the present application. The technical scope of the present application is not limited to the content of the specification, and must be determined according to the scope of claims.
Claims
1. A method for preparing polyethylene masterbatch, characterized in that, The polyethylene masterbatch is made from the following components in parts by weight: 32-35 parts high-density polyethylene, 40-42 parts low-density polyethylene, 0.5-1.2 parts functional additives, 10-15 parts color powder, 3-4 parts processing aids, and 0.1-0.4 parts initiator. The preparation method includes the following steps: Step 1: Weigh each raw material according to the weight proportions, then place them in a mixer, control the stirring speed to 1000-1200 r / min, and mechanically mix for 20-40 minutes to form a mixture. The second step is to feed the mixture into a twin-screw extruder and control the temperature of each zone of the extruder as follows: Zone 1 160±5℃, Zone 2 170±5℃, Zone 3 170±5℃, Zone 4 180±5℃, Zone 5 190±5℃, Zone 6 180±5℃, and Zone 7 170±5℃. After melt extrusion, the mixture is granulated to obtain polyethylene masterbatch.
2. The method for preparing polyethylene masterbatch according to claim 1, characterized in that, The preparation method of the functional additive is as follows: 3,5-Di-tert-butyl-4-hydroxybenzyl alcohol and di(7-octenyl)dichlorosilane were added to toluene and stirred until a homogeneous reaction solution was formed. The temperature was gradually increased to 60-70°C and maintained under stirring for 1-2 hours. Then, an acid-containing agent was added. After the addition was complete, the mixture was kept warm and stirred for 3-6 hours. The solvent was evaporated and removed, and the mixture was cooled and discharged. The functional additive was obtained through post-processing. The entire process was carried out under nitrogen protection.
3. The method for preparing polyethylene masterbatch according to claim 1, characterized in that, The molar ratio of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol to di(7-octenyl)dichlorosilane is 1-2:
1.
4. A method for preparing polyethylene masterbatch according to claim 1, characterized in that, The furic acid agent is triethylamine, and the amount of triethylamine added is 10-15% of the total mass of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and di(7-octenyl)dichlorosilane.
5. The method for preparing polyethylene masterbatch according to claim 1, characterized in that, The pigment is at least one of titanium dioxide, azo compounds, naphthyl ketone compounds, phthalocyanine compounds, or anthrone compounds.
6. The method for preparing polyethylene masterbatch according to claim 1, characterized in that, The processing aid is at least one of polyethylene wax, zinc stearate, stearic acid, or calcium stearate.
7. The method for preparing polyethylene masterbatch according to claim 1, characterized in that, The initiator is any one of benzoyl peroxide, dicumyl peroxide, or dibenzoyl peroxide.
8. A polyethylene masterbatch as described in claim 1, characterized in that, It was prepared by the method described in claim 1.