Abs composite and method for producing the same

Abstract

The application discloses an ABS composite material and a preparation method thereof, and belongs to the technical field of high polymer materials.The ABS composite material comprises the following components in parts by weight: SAN resin 60-85 parts, glass fiber 10-15 parts and compatilizer 15-40 parts.The product can effectively overcome the lamp wick effect of the glass fiber, delay the horizontal burning rate, has high toughness and processing size stability, and is high in practicability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to an ABS composite material and a preparation method and application thereof. BACKGROUND

[0002] ABS (acrylonitrile-butadiene-styrene copolymer) material has good processing performance and stability, and at present, a certain amount of glass fiber is added as a filler in most ABS materials, which can improve the insulation, high temperature resistance and fatigue resistance of the product, so that the product is more widely applicable. However, the ABS composite material filled with glass fiber will have a much higher burning rate than the conventional ABS material due to the wick effect of the glass fiber, which cannot meet the normal fireproofing requirements. Therefore, people try to add additional flame retardants, especially halogen flame retardants, to the product for compounding, but such a method not only has poor environmental protection, but also significantly reduces the toughness of the product due to the large amount of flame retardant added, which cannot take into account the use performance. SUMMARY

[0003] Based on the defects of the prior art, the purpose of the present application is to provide an ABS composite material, which is prepared by compounding a compatible agent component in a high glass transition temperature SAN resin matrix to form a glass fiber reinforced system. The product not only effectively overcomes the wick effect of glass fiber and delays the horizontal burning rate, but also has high toughness and processing size stability, and high practicality.

[0004] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0005] An ABS composite material, comprising the following components by weight:

[0006] 60-85 parts of SAN resin matrix, 10-15 parts of glass fiber, and 15-40 parts of compatible agent;

[0007] The glass transition temperature of the SAN resin matrix is > 105℃;

[0008] The compatible agent is a core-shell material comprising a core and a shell, the core is a silicone-acrylic composite rubber, and the shell comprises at least one of MMA resin and SAN resin;

[0009] The compatible agent comprises a first compatible agent and a second compatible agent;

[0010] The average particle size of the first compatible agent is ≥ 500 nm, and the average particle size of the second compatible agent is ≤ 300 nm;

[0011] The mass ratio of the first compatible agent to the second compatible agent is (2-5) : 1.

[0012] Further preferably, the mass ratio of the first compatibilizer to the second compatibilizer is one of 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1 or a range value of any two thereof.

[0013] The glass fiber reinforced ABS composite material can have both processing stability and use toughness, but due to the wick effect of the glass fiber, the horizontal burning rate of such product is extremely large when it is heated and burns, so that the product cannot meet the HB40 requirement of the UL94 flame retardant standard and cannot be applied to the preparation of some products such as air conditioner fan blades which have requirements for fireproof performance. Therefore, in the prior art, a large amount of flame retardant powder is added to the ABS resin matrix to inhibit the burning of the resin matrix, so that the product meets the fireproof requirement. However, the introduction of the flame retardant not only reduces the use toughness of the product, but also causes the dispersion of the components of the product to decrease, which ultimately affects the processing dimensional stability of the product, and the fireproof performance and use and processing performance of the product cannot be balanced. Therefore, in the technical solution of the present application, the inventors use a SAN resin with a high glass transition temperature as the matrix, and then introduce two organic silicon rubbers with a core-shell structure as compatibilizers for compounding. The matrix SAN resin with a high glass transition temperature itself has strong dimensional stability due to cross-linking, and after compounding with glass fiber, good toughness performance can be achieved. In addition to further improving the toughness of the product, the two organic silicon rubbers with hierarchical sizes can also act as dimensional stabilizers, compatibilizers and flame retardants with hierarchical steric hindrance effect, which on the one hand inhibits the shrinkage of the product caused by resin crystallization during processing, and on the other hand improves the compatibility of the matrix SAN resin with the glass fiber and the flame retardancy of the overall product, inhibits the wick effect and reduces the horizontal burning rate of the overall product.

[0014] However, the ratio of the two compatibilizers with different sizes needs to be controlled, otherwise the steric hindrance function and the compatibility function cannot be achieved, and the performance of the product is poor. In addition, the amount of the compatibilizer cannot be excessive, otherwise due to its water absorption characteristics, the local organic resin and the inorganic glass fiber will be more closely attached, which will further aggravate the wick effect and cannot achieve the effect of improving the fireproof performance.

[0015] Preferably, the weight fraction of the matrix SAN resin is 60-85 parts, and specifically can be one of 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 78 parts, 80 parts, 82 parts, 85 parts or a range value of any two thereof.

[0016] Preferably, the weight fraction of the compatilizer is 15-40 parts, and specifically can be one of 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts or a range value of any two thereof.

[0017] More preferably, the weight fraction of the base SAN resin is 68-75 parts, and the weight fraction of the compatilizer is 20-30 parts.

[0018] Through the mutual matching of the two key organic resins and glass fibers, the product can achieve better toughness, processing dimensional stability and fireproof performance.

[0019] Preferably, in the ABS composite material, the mass percentage content of the base SAN resin is ≥50%.

[0020] Preferably, the density of the base SAN resin is 1-1.1 g / cm 3 .

[0021] Preferably, the glass transition temperature of the base SAN resin is 106-112℃, and more preferably 107-110℃.

[0022] The glass transition temperature of the base SAN resin according to the application is the glass transition temperature Tg.

[0023] More preferably, the glass transition temperature of the base SAN resin is confirmed according to the DSC method in ISO 11357-2-1999 Plastic Differential Scanning Calorimetry (DSC) Part 2, with a heating rate of 10℃ / min, a nitrogen atmosphere, an atmosphere flow rate of 50 mL / min, a room temperature-150℃, and an instrument model of DSC300A.

[0024] Preferably, the shell of the compatilizer is a MMA resin.

[0025] The MMA (methyl methacrylate) resin and the SAN resin as the shell layer of the compatilizer have high compatibility with the base SAN resin according to the application, and can be well dispersed in the base resin, so that the product can achieve better mechanical toughness and dimensional stability.

[0026] More preferably, the silicon content of the compatilizer is 10-40 wt%.

[0027] More preferably, the silicon content of the compatilizer is 20-38 wt%.

[0028] More preferably, the average particle size of the first compatilizer in the compatilizer is 550-700 nm.

[0029] Further preferably, the average particle size of the first compatibilizer is one of 550 nm, 580 nm, 600 nm, 620 nm, 650 nm, 680 nm, 700 nm or a range value of any two of them.

[0030] Further preferably, the average shell thickness of the first compatibilizer is 50-200 nm.

[0031] More preferably, the average particle size of the second compatibilizer in the compatibilizer is 50-280 nm.

[0032] Further preferably, the average particle size of the second compatibilizer in the compatibilizer is one of 50 nm, 80 nm, 100 nm, 120 nm, 150 nm, 180 nm, 200 nm, 220 nm, 250 nm, 280 nm or a range value of any two of them.

[0033] Further preferably, the average shell thickness of the second compatibilizer is 10-100 nm.

[0034] The silicon content, the average particle size and the average shell thickness of the compatibilizer according to the present application are determined by the following method: the compatibilizer is observed under 100 kV of JEM-1011 transmission electron microscope, and then the silicon element content of the compatibilizer is determined by EDS element analysis method; the specific method is as follows: the compatibilizer is cut and broken into powder after being frozen in liquid nitrogen, then loaded on a sample-loaded copper net, tabletted, steam dyed, the first compatibilizer and the second compatibilizer are distinguished by mapping software, then 30 particles of the first compatibilizer and 30 particles of the second compatibilizer are respectively screened for particle size test, the average value is calculated to obtain the average particle size of the first compatibilizer and the second compatibilizer; then the magnification is adjusted, the shell thickness of the above screened particles is determined by mapping software, the average value is calculated to obtain the average shell thickness of the first compatibilizer and the second compatibilizer.

[0035] Preferably, the average length of the glass fiber is 2-4 mm, and the average diameter is 10-15 μm.

[0036] Further preferably, the glass fiber can be HMG436S-10-4.0 produced by Taishan Glass, ECS13-4.5-508A, ECS13-03-534A, ECS13-4.5-560A produced by Jushi Glass and the like commercially available types, or other existing products, which are not particularly limited.

[0037] Preferably, the ABS composite material further comprises 0.8-3 parts of a functional aid.

[0038] Further preferably, the functional auxiliary agent includes, but is not limited to, at least one of antistatic agent, lubricant, hydrolysis resistance agent, antioxidant, ultraviolet light resistance agent, colorant, and various functional auxiliary agents can be added by those skilled in the art according to actual needs without affecting the expected performance of the ABS composite material, for example, in order to make the ABS composite material have oxidation resistance when applied, those skilled in the art can add an antioxidant in the product; in order to make the ABS composite material more easily demoulded when processing, those skilled in the art can add a lubricant in the product.

[0039] More preferably, the ABS composite material further comprises 0.5-2 parts of lubricant and / or 0.3-1 part of antioxidant.

[0040] More preferably, the antioxidant is at least one of hindered phenol antioxidant, hindered amine antioxidant, and phosphite antioxidant.

[0041] More preferably, the lubricant is at least one of amide lubricant and polyethylene wax lubricant.

[0042] Another object of the present application is to provide a preparation method of the ABS composite material, comprising the following steps:

[0043] Each component is added to a screw extruder for melt extrusion granulation, and the ABS composite material is obtained.

[0044] Preferably, the temperature zones of the screw extruder are set as zone 1 200-210℃, zone 2 200-210℃, zone 3 210-220℃, zone 4 210-220℃, zone 5 210-220℃, zone 6 220-230℃, zone 7 220-230℃, zone 8 230-240℃, zone 9 230-240℃, zone 10 230-240℃, the screw rotation speed is 450-550 rpm, and the screw length-diameter ratio is (40-60):1.

[0045] Another object of the present application is to provide the application of the ABS composite material in preparing air conditioner parts.

[0046] Preferably, the air conditioner parts include air conditioner axial fan blades and air conditioner axial flow fan blades.

[0047] The ABS composite material of the present application can achieve a low horizontal burning rate under a glass system based on the special selection of two organic resins, has good fireproof performance, high toughness and high processing dimensional stability, and is very suitable for application scenarios such as air conditioner parts which require high fireproof performance and use mechanics and use stability.

[0048] Another object of the present application is to provide an air conditioner part comprising the ABS composite material of the present application.

[0049] The ABS composite material provided by the application has the advantages that the ABS composite material is prepared by compounding a compatible agent component in a high-glass-transition-temperature base SAN resin to form a glass fiber reinforced system, the product can effectively overcome the wick effect of the glass fiber and delay the horizontal burning rate, the ABS composite material has high toughness and processing dimensional stability, and is highly practical. DETAILED DESCRIPTION

[0050] In order to better illustrate the purposes, technical solutions and advantages of the application, the application will be further described below in combination with specific examples and comparative examples, and the purpose is to understand the content of the application in detail, rather than to limit the application. All other examples obtained by those of ordinary skill in the art without creative labor fall within the protection scope of the application. Unless otherwise specified, the experimental reagents and instruments involved in the implementation of the application are common ordinary reagents and instruments.

[0051] Examples 1 to 15

[0052] An embodiment of the ABS composite material and the preparation method and application thereof provided by the application, the composition of the ABS composite material is shown in Table 1.

[0053] The preparation method of the ABS composite material comprises the following steps:

[0054] The components are uniformly mixed, and then granulated by melt extrusion in a double-screw extruder, to obtain the ABS composite material.

[0055] When the components are melt extruded, the temperature zones of the double-screw extruder are set as 200 DEG C for the first zone, 210 DEG C for the second zone, 210 DEG C for the third zone, 210 DEG C for the fourth zone, 220 DEG C for the fifth zone, 220 DEG C for the sixth zone, 230 DEG C for the seventh zone, 230 DEG C for the eighth zone, 240 DEG C for the ninth zone, and 240 DEG C for the tenth zone, the screw rotation speed is 500 rpm, and the screw length-diameter ratio is 48:1.

[0056] Comparative Examples 1 to 7

[0057] The difference between each comparative example and each example is only that the types and proportions of the components are different, as shown in Table 2.

[0058] In the components of each example and comparative example,

[0059] The base SAN resin 1 is DXG05 produced by Zhejiang Suiqi New Material Co., Ltd., and the glass transition temperature is 110 DEG C;

[0060] The base SAN resin 2 is DXG04 produced by Zhejiang Suiqi New Material Co., Ltd., and the glass transition temperature is 107 DEG C;

[0061] The base SAN resin 3 is KFA-130 produced by Liaoning Jinfa, with a glass transition temperature of 105℃;

[0062] The compatibilizer 1 is S-2100 produced by Mitsubishi, Japan, which comprises a core and a shell from inside to outside, the shell is MMA resin, the core is silicone-acrylic composite rubber, the average particle size is 600nm, the average thickness of the shell is 180nm, and the silicon content is 26wt%;

[0063] The compatibilizer 2 is S-2130 produced by Mitsubishi, Japan, which comprises a core and a shell from inside to outside, the shell is MMA resin, the core is silicone-acrylic composite rubber, the average particle size is 600nm, the average thickness of the shell is 200nm, and the silicon content is 30wt%;

[0064] The compatibilizer 3 is S-2030 produced by Mitsubishi, Japan, which comprises a core and a shell from inside to outside, the shell is MMA resin, the core is silicone-acrylic composite rubber, the average particle size is 200nm, the average thickness of the shell is 50nm, and the silicon content is 30wt%;

[0065] The compatibilizer 4 is SX-005 produced by Mitsubishi, Japan, which comprises a core and a shell from inside to outside, the shell is MMA resin, the core is silicone-acrylic composite rubber, the average particle size is 200nm, the average thickness of the shell is 60nm, and the silicon content is 35wt%;

[0066] The compatibilizer 5 is SRK-200A produced by Mitsubishi, Japan, which comprises a core and a shell from inside to outside, the shell is SAN resin, the core is silicone-acrylic composite rubber, the average particle size is 200nm, the average thickness of the shell is 50nm, and the silicon content is 30wt%;

[0067] The compatibilizer 6 is S-2001 produced by Mitsubishi, Japan, which comprises a core and a shell from inside to outside, the shell is MMA resin, the core is silicone-acrylic composite rubber, the average particle size is 200nm, the average thickness of the shell is 55nm, and the silicon content is 18wt%;

[0068] The compatibilizer 7 is SX-006 produced by Mitsubishi, Japan, which comprises a core and a shell from inside to outside, the shell is SAN resin, the core is silicone-acrylic composite rubber, the average particle size is 60nm, the average thickness of the shell is 20nm, and the silicon content is 18wt%;

[0069] The acrylic rubber is W450A produced by Mitsubishi, Japan, which comprises a core and a shell from inside to outside, the shell is SAN resin, the core is acrylic rubber, the average particle size is 500nm, and the average thickness of the shell is 200nm;

[0070] The glass fiber is HMG436S-10-4.0 produced by Taishan Glass, with an average length of 4 mm and an average diameter of 10 μm;

[0071] The lubricant is EBS B50 produced in Indonesia, which is an amide lubricant, ethylene bis-stearamide;

[0072] The antioxidant is Y-001 produced by BASF, which is a hindered phenolic antioxidant, tetra[β(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester.

[0073] The component raw materials used in each embodiment and comparative example of the present application are commercially available raw materials unless otherwise specified, and the component raw materials used in each parallel experiment are the same.

[0074] Table 1

[0075]

[0076] Table 2

[0077]

[0078] In order to verify the performance of the ABS composite material described in the present application, the products prepared in each embodiment and comparative example are subjected to the following performance tests, and the specific steps are as follows:

[0079] (1) Notched Izod impact strength test: tested according to ISO 180-2023, A-type notch, pendulum energy 2.75 J.

[0080] (2) Horizontal burning rate test: HB40 test according to UL94-2020, sample thickness 3.0 mm;

[0081] (3) Processing dimensional stability test: tested according to GB / T 15585-1995, cross shrinkage test method, test index along the direction parallel to the flow direction.

[0082] The test results are shown in Tables 3 and 4.

[0083] Table 3

[0084]

[0085] Table 4

[0086]

[0087] As can be seen from Tables 3 and 4, the ABS composite material described in the present application has ideal comprehensive performance, and the notched Izod impact strength of the product of each embodiment can reach 8 KJ / m 2and above, the horizontal burning rate meets the requirement of HB40, that is, the horizontal burning rate is not higher than 40 mm / min, and meanwhile the processing dimensional stability is high, and the cross shrinkage is less than 3‰. As can be seen from Examples 1-4, the performance of the product varies with the different proportions of the two different compatilizers, and in the range of (2-5):1, the product can have good impact strength, fireproof performance and dimensional stability. In comparison, the proportions of the two in Comparative Examples 2 and 3 do not meet the limitation of the scheme of the present application, and the impact strength of the product decreases, and the horizontal burning rate does not meet the requirement of HB40. As can be seen from Example 2, Example 5 and Comparative Examples 4 and 5, in the product, the addition proportion of the SAN resin and the compatilizer not only has a significant influence on the impact strength of the product, but also has an influence on the fireproof performance and the dimensional stability. When the content of the SAN resin is too low, the fireproof performance and the dimensional stability of the product are poor. With the increase of the proportion of the component, the horizontal burning rate of the product decreases, and the dimensional stability improves. However, when the proportion of the component is too large, not only the impact strength of the product is low, but also the probability of occurrence of the "wick effect" increases, and the fireproof performance becomes poor.

[0088] In the product of Comparative Example 1, the SAN resin used is not of high glass transition temperature, and in addition to the possible failure to guarantee the mechanical properties, the fireproof performance of the product also cannot achieve the same effect as the product of the example, and the main reason is that the conventional SAN resin cannot achieve ideal crosslinking effect and compatibility, and the degree of occurrence of the "wick effect" of the glass fiber is very serious. In the product of Comparative Example 6, the compound resin used is not a hierarchical composite silicone rubber, but a compound of acrylic rubber and silicone rubber with similar structure. As can be seen, although the product has good dimensional stability when used as a compatilizer, the fireproof performance cannot meet the standard, and the impact strength is low, and it cannot meet the use standard. As can be seen from Example 2, Example 9 and Examples 10-15, when the compatilizer particles of hierarchical size are used for matching, the product can achieve good comprehensive performance. When the shell of the compatilizer is selected to be MMA resin and the silicon content is more than 20wt%, the comprehensive performance of the product prepared is better.

[0089] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application, and are not intended to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. An ABS composite material, characterized in that, Includes the following components in parts by weight: The matrix consists of 60-85 parts SAN resin, 10-15 parts glass fiber, and 15-40 parts compatibilizer. The glass transition temperature of the matrix SAN resin is >105℃; The compatibilizer is a core-shell material comprising a core and a shell, wherein the core is an organosilicon-acrylic composite rubber and the shell comprises at least one of MMA resin and SAN resin; The compatibilizer includes a first compatibilizer and a second compatibilizer; The average particle size of the first compatibilizer is ≥500nm, and the average particle size of the second compatibilizer is ≤300nm; The mass ratio of the first compatibilizer to the second compatibilizer is (2~5):

1.

2. The ABS composite material as described in claim 1, characterized in that, The glass transition temperature of the matrix SAN resin is 106~112℃.

3. The ABS composite material as described in claim 1, characterized in that, The average particle size of the first compatibilizer in the compatibilizer is 550~700nm; the average particle size of the second compatibilizer in the compatibilizer is 50~280nm.

4. The ABS composite material as described in claim 1, characterized in that, The average thickness of the shell of the first compatibilizer is 50~200nm; the average thickness of the shell of the second compatibilizer is 10~100nm.

5. The ABS composite material as described in claim 1, characterized in that, The compatibilizer has a silicon content of 10-40 wt%.

6. The ABS composite material as described in claim 1, characterized in that, The ABS composite material also includes 0.8 to 3 parts of functional additives.

7. The ABS composite material as described in claim 6, characterized in that, The ABS composite material also includes 0.5 to 2 parts of lubricant and / or 0.3 to 1 part of antioxidant.

8. The method for preparing the ABS composite material according to any one of claims 1 to 7, characterized in that, Includes the following steps: The components are added to a screw extruder for melt extrusion and granulation to obtain the ABS composite material.

9. The use of the ABS composite material as described in any one of claims 1 to 7 in the manufacture of air conditioning components.

10. The application as described in claim 9, characterized in that, The air conditioning components include axial flow fan blades and jet flow fan blades.

11. An air conditioning component, characterized in that, Includes the ABS composite material described in any one of claims 1 to 7.

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