An abs composition, its preparation and use

Abstract

The present application relates to an ABS composition and its preparation method and application, belong to the composition technical field of high molecular compound, the ABS composition of the present application includes the following weight parts of components: ABS resin 53~73 parts, PETG copolyester 15~30 parts, bromine flame retardant 11~13 parts, antimony flame retardant 1~3 parts, the weight percentage of butadiene in the ABS resin is greater than or equal to 20%, the weight percentage of 1,4-cyclohexane dimethanol in the PETG copolyester is 10%~30%, and the melt mass flow rate of the PETG copolyester under the condition of 220 DEG C, 10 kg is greater than or equal to 18 g / 10 min according to ISO 1133-1:2011 standard, the ABS composition not only has good flame retardant performance, but also has excellent marking effect and mechanical properties.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer compound compositions, and in particular to an ABS composition, a preparation method thereof, and applications thereof. Background Art

[0002] ABS resin is an amorphous polymer composed of three monomers: acrylonitrile, butadiene, and styrene. Acrylonitrile provides ABS resin with resistance to chemical solvents and heat, butadiene imparts good toughness and impact resistance, and styrene imparts excellent rigidity and processability. These excellent properties make ABS resin a preferred choice for structural component applications. However, ABS resin itself is flammable, making it difficult to meet the application requirements of industries with strict safety regulations. Therefore, ABS resin needs to be modified to enhance its flame retardancy.

[0003] Currently, flame retardant modification of ABS resin is primarily achieved by adding flame retardants. Bromine-based flame retardants, formed by combining halogen-antimony composite flame retardants (bromine-based flame retardants with antimony oxides) with ABS resin, have superior overall performance and are widely used in household appliance or electronic and electrical housings (e.g., relay housings, capacitor housings, low-voltage electrical appliances, plug connectors, etc.). Such housings typically require laser engraving for marking (i.e., laser marking). In actual industrial production, infrared laser engraving with a wavelength of 1064nm is often used. This method utilizes the thermal effect of the laser to rapidly carbonize, foam, or discolor the surface of an object, resulting in a marking that is different from the base color.

[0004] In actual applications, it has been found that during laser marking, shell products made of brominated flame-retardant ABS are prone to serious burnt yellowing and blurred fonts on the shell product surface, seriously affecting the marking effect. The existing technology generally improves the marking effect of brominated flame-retardant ABS products by adding laser marking agents or modified flame retardants. For example, patent CN118048011A discloses an ABS composite material and its application. By adding a large amount of inorganic components (silicates and flame retardant synergists) to replace conventional antimony white, the ABS composite material has better flame retardancy and laser marking effect. However, this also leads to a decrease in the toughness of the ABS composite material, that is, it is difficult to achieve good flame retardancy, laser marking effect, and mechanical properties at the same time. Summary of the Invention

[0005] The purpose of the present invention is to overcome the deficiencies of the prior art and provide an ABS composition and a preparation method and application thereof.

[0006] To achieve the above object, the technical solution adopted by the present invention is:

[0007] In a first aspect, the present invention provides an ABS composition comprising the following components in parts by weight:

[0008] 53-73 parts of ABS resin, 15-30 parts of PETG copolyester, 11-13 parts of brominated flame retardant, 1-3 parts of antimony flame retardant;

[0009] The weight percentage of butadiene in the ABS resin is ≥20%, and the weight percentage of 1,4-cyclohexanedimethanol in the PETG copolyester is 10% to 30%;

[0010] The PETG copolyester adopts ISO 1133-1:2011 standard, and has a melt mass flow rate of ≥18 g / 10 min at 220° C. and 10 kg.

[0011] The present invention regulates the butadiene content in ABS resin and combines it with a specific PETG copolyester. A bromine-based flame retardant and an antimony-based flame retardant are also added. The invention utilizes the penetrating effect of the PETG copolyester on marking light waves (reducing the absorption of laser waves by the ABS composition) and its role in promoting carbonization during the ABS absorption of laser energy. This allows the PETG copolyester and the ABS resin to interact during the laser marking process, thereby effectively alleviating the yellowing problem of the bromine-based flame-retardant ABS during laser marking and greatly improving the mechanical properties of the ABS composition.

[0012] Optionally, the weight proportion of the ABS resin in the ABS composition may be 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, or 72 parts; the weight proportion of the PETG copolyester may be 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, or 28 parts; the weight proportion of the brominated flame retardant may be 11.5 parts, 12 parts, or 12.5 parts; and the weight proportion of the antimony flame retardant may be 1.5 parts, 2 parts, or 2.5 parts.

[0013] The weight percentage of ABS resin in the ABS composition of the present invention is greater than or equal to 50%. The weight percentage of butadiene in the ABS resin is preferably 20% to 35%, specifically 21%, 22%, 23%, 24%, 24%, 25%, 26%, 27%, 28%, 29%, or 30%. The weight percentage of butadiene in the ABS resin can be determined by nuclear magnetic resonance. For details, please refer to the Chinese document "Nuclear Magnetic Resonance Study of ABS Resin and Effect of Monomer Content on Macroscopic Properties".

[0014] PETG copolyester is polyethylene terephthalate-1,4-cyclohexanedimethanol ester. The weight percentage of 1,4-cyclohexanedimethanol in the PETG copolyester can be 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, or 28%. The weight percentage of 1,4-cyclohexanedimethanol in the PETG copolyester can be determined by infrared absorption spectroscopy (IR) combined with nuclear magnetic resonance (NMR). For details, reference can be made to Chinese patent CN104569022B (a method for analyzing the content of 1,4-cyclohexanedimethanol units in a copolyester molecular chain).

[0015] Optionally, the melt mass flow rate of PETG copolyester can be specifically 22 g / 10 min, 24 g / 10 min, 26 g / 10 min, 28 g / 10 min, 30 g / 10 min, 32 g / 10 min, 34 g / 10 min, 36 g / 10 min, or 38 g / 10 min.

[0016] As a preferred embodiment of the ABS composition of the present invention, among the components of the ABS composition, the weight proportion of ABS resin is 57 to 65 parts, and the weight proportion of PETG copolyester is 20 to 25 parts.

[0017] As a preferred embodiment of the ABS composition of the present invention, the weight percentage of butadiene in the ABS resin is 22% to 29%.

[0018] As a preferred embodiment of the ABS composition of the present invention, the melt mass flow rate of the PETG copolyester is 20 to 40 g / 10 min.

[0019] As a preferred embodiment of the ABS composition of the present invention, the components of the ABS composition further include 0.5 to 1 parts by weight of a processing aid.

[0020] Optionally, the processing aid includes at least one of an anti-dripping agent, an antioxidant, and a lubricant; specifically, the anti-dripping agent can be at least one of SAN-coated polytetrafluoroethylene micropowder, acrylate-coated polytetrafluoroethylene micropowder, and silicone-coated polytetrafluoroethylene micropowder; the antioxidant can be at least one of a hindered phenol antioxidant and a phosphite antioxidant; the lubricant can be at least one of amides, stearates, esters, and silicones.

[0021] In a preferred embodiment of the ABS composition of the present invention, the brominated flame retardant includes at least one of bromotriazine and brominated epoxy; and / or the antimony flame retardant includes at least one of antimony oxide and antimonate. Specifically, the antimony oxide is antimony trioxide, and the antimonate is sodium antimonate.

[0022] In a second aspect, the present invention provides a method for preparing the above-mentioned ABS composition, comprising the following steps: uniformly mixing the components and then melt-extruding to obtain the ABS composition.

[0023] Specifically, in the above preparation method, a twin-screw extruder can be used for melt extrusion. The melt extrusion temperature is 160-210° C., and the screw speed of the twin-screw extruder is 400-600 rpm.

[0024] In a third aspect, the present invention provides the use of the above-mentioned ABS composition in preparing plastic housings for household appliances or electronic and electrical products. Specifically, the electronic and electrical products may be relays, capacitors, low-voltage electrical appliances, plug connectors, and the like.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] The present invention regulates the butadiene content in ABS resin, combines it with a specific PETG copolyester, and simultaneously adds a bromine-based flame retardant and an antimony-based flame retardant. Utilizing the transmittance effect of PETG copolyester on marking light waves and its role in promoting carbonization during ABS absorption of laser energy, the present invention enables the PETG copolyester and ABS resin to interact with each other during the laser marking process, thereby effectively alleviating the yellowing problem of bromine-based flame-retardant ABS during laser marking and greatly improving the mechanical properties of the ABS composition. DETAILED DESCRIPTION

[0027] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0028] Unless otherwise specified, other materials, reagents, etc. used in the Examples and Comparative Examples can be obtained from commercial sources.

[0029] 1. Raw materials and reagents

[0030] ABS resin 1: The weight percentage of butadiene in ABS resin is 29%, the brand is ABS PA-747S, and the manufacturer is Chi Mei, Taiwan, China;

[0031] ABS resin 2: The weight percentage of butadiene in the ABS resin is 25%, the brand is ABSDG-MG29, and the manufacturer is Trinseo;

[0032] ABS resin 3: The weight percentage of butadiene in ABS resin is 22%, the brand is ABSD-120A, and the manufacturer is Guoqiao, Taiwan, China;

[0033] ABS resin 4: The weight percentage of butadiene in the ABS resin is 16%, the brand is ABS GP-22, and the manufacturer is INEOS Styrolution;

[0034] PETG resin 1: The weight percentage of CHDM in the PETG resin is 20%, the melt mass flow rate is 22 g / 10 min, the brand is PETG K2012, and the manufacturer is SK Chemical;

[0035] PETG resin 2: The weight percentage of CHDM in the PETG resin is 30%, the melt mass flow rate is 40 g / 10 min, the brand is PETG PN300, and the manufacturer is SK Chemical;

[0036] PETG resin 3: The weight percentage of CHDM in the PETG resin is 10%, the melt mass flow rate is 20 g / 10 min, the brand is PETG WS-501, and the manufacturer is Huahong Chemical Fiber;

[0037] PETG resin 4: The weight percentage of CHDM in the PETG resin is 20%, the melt mass flow rate is 12 g / 10 min, the brand is PETG 5083, and the manufacturer is China Resources Chemical;

[0038] PETG resin 5: The weight percentage of CHDM in the PETG resin is 0%, the melt mass flow rate is 28 g / 10 min, the brand is PETG 5511, and the manufacturer is China Resources Chemical;

[0039] PETG resin 6: The weight percentage of CHDM in the PETG resin is 40%, the melt mass flow rate is 25 g / 10 min, the brand is JN200, and the manufacturer is SK Chemical;

[0040] Bromotriazine: brand FR-245, manufactured by Dead Sea Bromine, Israel;

[0041] Brominated epoxy: brand CXB-714C, manufactured by Yujin, South Korea;

[0042] Antimony trioxide and sodium antimonate were purchased from Xikuangshan Shanxing Antimony Industry Co., Ltd.

[0043] The processing aid is obtained by compounding an anti-dripping agent, a lubricant and an antioxidant in a mass ratio of 2:1:1. The anti-dripping agent is POLY TS 30A and the manufacturer is PIC of South Korea; the lubricant is pentaerythritol stearate, and the antioxidant is obtained by compounding a primary antioxidant (THANOX 1010) and a secondary antioxidant (THANOX 168) in a mass ratio of 3:2. Pentaerythritol stearate, THANOX 1010 and THANOX 168 are all commercially available.

[0044] 2. Preparation method of the ABS composition of the present invention

[0045] According to the formula, the components are mixed evenly and then added into a twin-screw extruder for melt extrusion to obtain an ABS composition; wherein the melt extrusion temperature is 160-210° C. and the screw speed of the twin-screw extruder is 400-600 rpm.

[0046] Table 1 Weight parts of each component of the ABS composition in Examples 1 to 12

[0047]

[0048] Table 2 Weight parts of each component of the ABS composition in Comparative Examples 1 to 6

[0049]

[0050]

[0051] 3. Performance testing

[0052] The ABS compositions of Examples 1-12 and Comparative Examples 1-6 were placed in a forced air oven and dried at 80°C for 4 hours. The compositions were then injection molded into standard test bars using a plastic injection molding machine at a temperature of 200-220°C. The molded standard test bars were then conditioned at a relative humidity of 50% and a temperature of 23°C for at least 24 hours before being subjected to various performance tests. The test results are shown in Table 3.

[0053] The specific test methods are as follows:

[0054] (1) Marking effect: A 30 × 30 mm square area was laser marked on the sample (the laser marking was performed using the TFL-M20 semiconductor-pumped fiber laser marking system produced by Ted Laser, with a laser wavelength of 1064 nm, a laser power of 20 W, a frequency of 40 kHz, and a speed of 1000 mm / s). A colorimeter (UltraScan XE, produced by Hunter Lab, USA) was then used to test the color change of the square marked area. The difference in b values ​​(Δb) before and after laser marking was recorded to characterize the yellowness of the laser mark. The smaller the value, the less yellowing the mark and the better the marking effect.

[0055] (2) Notched impact strength: tested according to ISO 180-2023, specimen thickness 4 mm, Izod notched impact, notch type A.

[0056] (3) Flame retardant performance: The flame retardant grade of 1.6 mm standard specimens was tested according to UL94 standard.

[0057] Table 3 Properties of ABS compositions in various examples and comparative examples

[0058]

[0059]

[0060] From the data in Table 3, it can be seen that the ABS compositions in Examples 1 to 12 have flame retardancy reaching V-1 level, marking yellowness Δb less than or equal to 1.2, and notched impact strength greater than or equal to 25 kJ / m 2 , indicating that the ABS composition of the present invention not only has good flame retardancy, but also exhibits excellent marking performance and toughness. Furthermore, Comparative Example 1 and Examples 1-3 show that the weight percentage of butadiene in the ABS resin significantly influences both the laser marking performance and toughness of the ABS composition. When the weight percentage of butadiene in the ABS resin is too low, it is difficult to effectively improve the marking performance and toughness of the ABS composition.

[0061] In addition, according to Examples 1, 4, 5, and Comparative Examples 2 to 4, it can be found that the melt mass flow rate of the PETG resin and the weight percentage of CHDM therein jointly affect the marking effect and toughness of the ABS composition. When the weight percentage of CHDM in the PETG copolyester is too large or too small, or when the melt mass flow rate of the PETG copolyester is too small, it is difficult to effectively improve the marking effect and toughness of the ABS composition. According to Comparative Examples 5 and 6, it can be further found that in addition to affecting the marking effect and toughness of the ABS composition, the PETG copolyester has a significant promoting effect on improving the flame retardant properties of the ABS composition. When the PETG copolyester is not added, the marking effect, toughness, and flame retardant properties of the ABS composition are reduced. When the amount of PETG copolyester added is too much, although good marking effect and flame retardant properties can be maintained, the toughness is greatly reduced.

[0062] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. An ABS composition, characterized in that: Calculated by weight, it includes the following components: 53-73 parts of ABS resin, 15-30 parts of PETG copolyester, 11-13 parts of brominated flame retardant, 1-3 parts of antimony flame retardant; The weight percentage of butadiene in the ABS resin is ≥20%, and the weight percentage of 1,4-cyclohexanedimethanol in the PETG copolyester is 10% to 30%; The PETG copolyester adopts ISO 1133-1:2011 standard, and has a melt mass flow rate of ≥18 g / 10 min at 220° C. and 10 kg.

2. The ABS composition according to claim 1, wherein Among the components of the ABS composition, the weight proportion of ABS resin is 57 to 65 parts, and the weight proportion of PETG copolyester is 20 to 25 parts.

3. The ABS composition according to claim 1, wherein The weight percentage of butadiene in the ABS resin is 22% to 29%.

4. The ABS composition according to claim 1, wherein The melt mass flow rate of the PETG copolyester is 20 to 40 g / 10 min.

5. The ABS composition according to claim 1, wherein The components of the ABS composition also include 0.5 to 1 parts by weight of a processing aid.

6. The ABS composition according to claim 5, wherein The processing aid includes at least one of an anti-dripping agent, an antioxidant, and a lubricant.

7. The ABS composition according to any one of claims 1 to 6, characterized in that: The brominated flame retardant includes at least one of brominated triazine and brominated epoxy; And / or, the antimony-based flame retardant includes at least one of antimony oxide and antimonate.

8. The ABS composition according to claim 7, wherein The antimony oxide is antimony trioxide, and the antimonate is sodium antimonate.

9. The method for preparing the ABS composition according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: uniformly mixing the components and then melt-extruding the components to obtain an ABS composition.

10. Use of the ABS composition according to any one of claims 1 to 8 in preparing plastic housings of household appliances or electronic and electrical products.

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