Antistatic masterbatch and preparation method and application thereof

Abstract

The invention discloses an antistatic masterbatch, which comprises the following components by weight: 30-70 parts of carboxylic acid ionomer; 15-45 parts of PC resin; and 15-45 parts of antistatic agent. The antistatic masterbatch of the invention can be applied to PC resin to achieve uniform antistatic surface resistance and maintain good mechanical properties.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to an antistatic masterbatch and a preparation method and application thereof. Background Art

[0002] The antistatic technology of polycarbonate is mainly achieved by adding antistatic agents. However, on the one hand, the direct addition of antistatic agents has the defects of uneven dispersion and difficult processing. On the other hand, the antistatic agent needs to be enriched on the surface of the workpiece to form a sufficiently uniform and dense conductive network. Therefore, the antistatic agent is generally prepared into a masterbatch and then processed. However, in the prior art, the main formula of antistatic masterbatch for PC (polycarbonate) is antistatic agent / PC resin, which is extremely limited for the good dispersion of the antistatic agent in the PC resin matrix.

[0003] Chinese patent application 2013103243778 discloses a PC antistatic masterbatch, which solves the defect of insufficient dispersibility by using a plasticizer (di(2-ethylhexyl) phthalate or dibutyl phthalate) and a dispersant (ethylene bisstearamide). Chinese patent application 201510705392.6 discloses an antistatic masterbatch for PC, which improves the defect of insufficient dispersion of the antistatic agent by using an amphiphilic siloxane complex with a block structure as a dispersant. However, the above method cannot achieve uniform antistatic properties, that is, the antistatic agent is concentrated and evenly distributed on the surface of the product, and a uniform antistatic network can also be formed inside. Summary of the invention

[0004] The object of the present invention is to provide an antistatic masterbatch, which can be applied to PC composite materials to achieve uniform antistatic surface resistance and maintain good mechanical properties.

[0005] The present invention is achieved through the following technical solutions:

[0006] An antistatic masterbatch, comprising the following components by weight:

[0007] 30-70 parts of carboxylic acid ionomer;

[0008] 15-45 parts of PC resin;

[0009] Antistatic agent 15-45 parts.

[0010] Preferably, the following components are included by weight:

[0011] 40-60 parts of carboxylic acid ionomer;

[0012] 20-39 parts of PC resin;

[0013] Antistatic agent 25-40 parts.

[0014] The carboxylic acid-based ionomer is an ethylene / methacrylic acid copolymer, wherein 25 mol%-90 mol% of the carboxyl groups in the methacrylic acid units are neutralized by metal ions; preferably, 40 mol%-80 mol% of the carboxyl groups in the methacrylic acid units are neutralized by metal ions.

[0015] The amount of carboxyl groups neutralized by metal ions can be estimated based on the characteristic absorption peak area of ​​carboxylate after acid-base titration or Fourier transform infrared detector testing.

[0016] The metal ion is selected from at least one of sodium ion, zinc ion, magnesium ion and potassium ion. The melt index of the carboxylic acid-based ionomer is between 0.5-6 g / 10 min. The test conditions are 190° C. and 2.16 kg.

[0017] The weight average molecular weight of the antistatic masterbatch PC resin of the present invention may be in the range of 15000-30000, preferably 18000-25000.

[0018] The antistatic agent is selected from at least one of ethoxylated alkylamines, ethoxylated lauramide, glycerides, higher alcohol sulfates, polyethylene oxide (PEO), polyether ester amide (PEEA), and polyether ester imide (PEAI); preferably, the antistatic agent is selected from at least one of polyethylene oxide (PEO) and polyether ester amide (PEEA).

[0019] In order to improve the antistatic masterbatch and obtain other properties, a certain amount of auxiliary agent can be selectively added. By weight, 0-2 parts of auxiliary agent are also included; the auxiliary agent is selected from at least one of an antioxidant and a lubricant.

[0020] The preparation method of the antistatic masterbatch of the present invention comprises the following steps: according to the proportion, carboxylic acid-based ionomer, PC resin and antistatic agent are uniformly mixed and then extruded into granules by a twin-screw extruder, the screw temperature is 200-270°C, and the speed range is 180-500r / min.

[0021] The application of the antistatic masterbatch of the present invention is characterized in that it is used to prepare an antistatic PC composite material, and comprises the following components in parts by weight:

[0022] 60-80 parts of PC resin;

[0023] Antistatic masterbatch 10-40 parts.

[0024] The present invention has the following beneficial effects:

[0025] The present invention adds a certain amount of carboxylic acid ionomer to the traditional antistatic masterbatch formula. On the one hand, the ionic groups in the carboxylic acid ionomer are used to improve the dispersion of the antistatic agent in the ionomer, so that more antistatic agent is dispersed in the carboxylic acid ionomer, and a part of the antistatic agent is retained in the PC resin matrix. On the other hand, the carboxylic acid ionomer has a certain compatibility with the PC resin, but the carboxylic acid ionomer tends to be distributed on the surface of the PC resin. Therefore, after the masterbatch is applied to the PC composite material, the carboxylic acid ionomer carries most of the antistatic agent and is continuously dispersed on the surface of the PC composite material, thereby achieving the technical effects of high resistance density and uniform distribution. DETAILED DESCRIPTION

[0026] The present invention is described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several variations and improvements may be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0027] The sources of raw materials used in the present invention are as follows:

[0028] PC resin: brand name is PC S-2000F, weight average molecular weight is 22000-25000.

[0029] PC resin A: weight average molecular weight 19000, POLYCARBONATE RESIN TARFLON FN1900;

[0030] PC resin B: weight average molecular weight 23000, POLYCARBONATE RESIN TARFLON FN2200;

[0031] PC resin C: weight average molecular weight 15000, POLYCARBONATE RESIN TARFLON FN 1500;

[0032] PC resin D: weight average molecular weight 30000, PC 7030PJ;

[0033] PC resin E: weight average molecular weight 14000, brand PC H-4000;

[0034] PC resin F: weight average molecular weight 33000, brand name PC E-1000F.

[0035] Carboxylic acid ionomer A: The main chain is ethylene / methacrylic acid copolymer, the melt index is 3.5 g / 10 min, the test conditions are 190° C., 2.16 kg, and 78 mol% of the carboxyl groups of the methacrylic acid units are neutralized by sodium ions.

[0036] Carboxylic acid ionomer B: The main chain is ethylene / methacrylic acid copolymer, the melt index is 1.4 g / 10 min, the test conditions are 190° C., 2.16 kg, and 45 mol% of the carboxyl groups of the methacrylic acid units are neutralized by zinc ions.

[0037] Carboxylic acid ionomer C: The main chain is ethylene / methacrylic acid copolymer, the melt index is 5.9 g / 10 min, the test conditions are 190° C., 2.16 kg, and 26 mol% of the carboxyl groups of the methacrylic acid units are neutralized by zinc ions.

[0038] Carboxylic acid ionomer D: The main chain is ethylene / methacrylic acid copolymer, the melt index is 4.0 g / 10 min, the test conditions are 190° C., 2.16 kg, and 86 mol% of the carboxyl groups of the methacrylic acid units are neutralized by zinc ions.

[0039] Antistatic agent A: polyethylene oxide, manufacturer: Sanyo Chemical industries;

[0040] Antistatic agent B: polyetheresteramide, manufacturer IonPhasE;

[0041] Antistatic agent C: ethoxy lauramide, manufacturer Adeka;

[0042] Preparation method of A series and B series antistatic masterbatch: according to the ratio, carboxylic acid-based ionomer, PC resin and antistatic agent are uniformly mixed and then extruded into granules through a twin-screw extruder, the screw temperature is 200-270°C, and the speed range is 180-500r / min.

[0043] Preparation method of PC composite material of embodiment and comparative example: PC resin and antistatic masterbatch (or antistatic agent) are mixed evenly, and then extruded and granulated by a twin-screw extruder (screw speed is 150-450r / min, temperature range is 210-300°C) to obtain PC / ABS alloy.

[0044] Various test methods:

[0045] (1) Izod notched impact strength: tested in accordance with standard ISO 180, test temperature 23°C.

[0046] (2) Surface resistance: Tested in accordance with standard ASTM D257.

[0047] Table 1: Distribution ratio of each group of A1-A4 antistatic masterbatch (parts by weight)

[0048] A1 A2 A3 A4 Carboxylate Ionomer A 45 Carboxylic acid ionomer B 45 Carboxylic acid ionomer C 45 Carboxylic acid ionomer D 45 PC Resin A 28 28 28 28 Antistatic Agent A 27 27 27 27

[0049] Table 2: Distribution ratio of each group of A5-A9 antistatic masterbatch (parts by weight)

[0050] A5 A6 A7 A8 A9 Carboxylate Ionomer A 45 45 45 45 45 PC resin B 28 PC Resin C 28 PC resin D 28 PC Resin E 28 PC Resin F 28 Antistatic Agent A 27 27 27 27 27

[0051] Table 3: Distribution ratio of each group of A10-A15 antistatic masterbatch (parts by weight)

[0052] A10 A11 A12 A13 A14 A15 Carboxylate Ionomer A 45 45 30 40 60 70 PC Resin A 28 28 40 35 20 15 Antistatic Agent A 40 35 25 15 Antistatic Agent B 27 Antistatic Agent C 27

[0053] Table 4: Distribution ratio of each group of antistatic masterbatch B (parts by weight)

[0054] B1 B2 B3 B4 Carboxylate Ionomer A 50 10 80 PC Resin A 50 40 10 Antistatic Agent A 40 40 40 25

[0055] Table 5: Distribution ratios (parts by weight) and test results of each group of PC / ABS alloys in the examples and comparative examples

[0056] Example 1 Example 2 Example 3 Example 4 PC resin 70 70 70 70 Antistatic Masterbatch, Types A1 A2 A3 A4 Antistatic masterbatch, added amount 30 30 30 30 Antistatic Agents - - - - Surface resistance - front side Ω 10^10 10^9 10^9 10^9 Surface resistance - reverse side Ω 10^10 10^9 10^10 10^10 <![CDATA[Izod impact strength of cantilever beam kJ / m 2 > 62 52 41 48

[0057] Table 5 continued:

[0058] Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Embodiment 11 PC resin 70 70 70 70 70 70 70 Antistatic Masterbatch, Types A5 A6 A7 A8 A9 A10 A11 Antistatic masterbatch, added amount 30 30 30 30 30 30 30 Antistatic Agents - - - - - - - Surface resistance - front side Ω 10^9 10^8 10^8 10^7 10^8 10^9 10^9 Surface resistance - reverse side Ω 10^9 10^9 10^9 10^9 10^10 10^9 10^10 <![CDATA[Izod impact strength of cantilever beam kJ / m 2 > 56 47 38 32 41 59 44

[0059] As can be seen from Examples 1-4, the carboxyl groups in the carboxyl ionomers, preferably 40 mol % to 90 mol % of the methacrylic acid units, are neutralized by metal ions, which not only makes the front and back surface resistance values ​​more stable, but also improves the Izod notched impact strength.

[0060] It can be seen from Examples 1 / 5-10 that the preferred weight average molecular weight of the PC resin is 18,000-25,000.

[0061] It can be seen from Examples 1 / 10 / 11 that the antistatic agent is preferably polyethylene oxide or polyether ester amide.

[0062] Table 5 continued:

[0063] Example 12 Example 13 Embodiment 14 Embodiment 15 PC resin 70 70 70 70 Antistatic Masterbatch, Types A12 A13 A14 A15 Antistatic masterbatch, added amount 22.3 25.5 34 54 Antistatic Agents - - - - Surface resistance - front side Ω 10^8 10^9 10^9 10^9 Surface resistance - reverse side Ω 10^9 10^9 10^9 10^10 <![CDATA[Izod impact strength of cantilever beam kJ / m 2 > 46 56 58 53

[0064] It can be seen from Examples 1 / 12-15 that the preferred content is 40-60 parts of carboxylic acid-based ionomer, 20-39 parts of PC resin, and 25-40 parts of antistatic agent.

[0065] Table 5 continued:

[0066] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 PC resin 70 70 70 70 70 Antistatic Masterbatch, Types B1 B2 B3 B4 - Antistatic masterbatch, added amount 18.2 18.2 18.2 37.3 - Antistatic Agents - - - - 8.1 Surface resistance - front side Ω 10^6 10^7 10^6 10^7 10^8 Surface resistance - reverse side Ω 10^10 10^10 10^9 10^10 10^11 <![CDATA[Izod impact strength of cantilever beam kJ / m 2 > 57 46 42 39 44

[0067] It can be seen from Comparative Example 1 that the antistatic masterbatch without adding carboxylic acid-based ionomer has a large difference in resistance between the front and back surfaces.

[0068] It can be seen from Comparative Example 2 that the resistance values ​​of the front and back surfaces are quite different when no PC resin is added to the antistatic masterbatch.

[0069] It can be seen from Comparative Examples 3 / 4 that when the amount of carboxylic acid-based ionomer added is too low or too high, it is difficult to achieve uniform distribution of the antistatic agent (the resistance value is also low).

[0070] It can be seen from Comparative Example 5 that directly adding the antistatic agent will result in unstable resistance values ​​on the front and back surfaces.

Claims

1. An antistatic masterbatch, It is characterized in that By weight, it includes the following components: 30-70 parts of carboxylic acid ionomer; 15-45 parts of PC resin; Antistatic agent 15-45 parts; The carboxylic acid-based ionomer is an ethylene / methacrylic acid copolymer, wherein 25 mol%-90 mol% of the carboxyl groups in the methacrylic acid units are neutralized by metal ions, and the metal ions are selected from at least one of sodium ions, zinc ions, magnesium ions, and potassium ions.

2. The antistatic masterbatch according to claim 1, It is characterized in that By weight, it includes the following components: 40-60 parts of carboxylic acid ionomer; 20-39 parts of PC resin; Antistatic agent 25-40 parts.

3. The antistatic masterbatch according to claim 1, It is characterized in that 40 mol % to 80 mol % of the carboxyl groups in the methacrylic acid units are neutralized by metal ions.

4. The antistatic masterbatch according to claim 3, It is characterized in that The melt index of the carboxylic acid-based ionomer is between 0.5-6 g / 10 min, and the test conditions are 190° C. and 2.16 kg.

5. The antistatic masterbatch according to claim 1, It is characterized in that The weight average molecular weight of the PC resin is in the range of 15000-30000.

6. The antistatic masterbatch according to claim 5, It is characterized in that The weight average molecular weight of the PC resin is in the range of 18000-25000.

7. The antistatic masterbatch according to claim 1, It is characterized in that The antistatic agent is selected from at least one of ethoxylated alkylamines, ethoxylated lauramide, glyceric acid esters, higher alcohol sulfates, polyethylene oxide, polyether ester amides, and polyether ester imides.

8. The antistatic masterbatch according to claim 7, It is characterized in that The antistatic agent is selected from at least one of polyethylene oxide and polyether ester amide.

9. The antistatic masterbatch according to claim 1, It is characterized in that By weight, the invention also includes 0-2 parts of auxiliary agents; the auxiliary agents are selected from at least one of antioxidants and lubricants.

10. A method for preparing the antistatic masterbatch according to any one of claims 1 to 9, It is characterized in that The method comprises the following steps: according to the proportion, the carboxylic acid-based ionomer, PC resin and antistatic agent are uniformly mixed and then extruded into granules through a twin-screw extruder, the screw temperature is 200-270°C, and the speed range is 180-500r / min.

11. Application of the antistatic masterbatch according to any one of claims 1 to 9, It is characterized in that For preparing antistatic PC composite material, the following components are included by weight: 60-80 parts of PC resin; Antistatic masterbatch 10-40 parts.