WO2024011848A1 - Highly-weather-resistant black thermal insulation asa resin and preparation method therefor - Google Patents

Abstract

The present invention relates to a highly-weather-resistant black thermal insulation ASA resin and a preparation method therefor. The resin comprises a SAN resin, ASA high rubber powder, low-heat-absorption ASA black masterbatch, and an auxiliary agent, wherein the mass ratio of the SAN resin to the low-heat-absorption ASA black masterbatch is (50-80):(0.5-25). The resin comprises the following components in parts by weight: 50-80 parts of the SAN resin; 10-50 parts of the ASA high rubber powder; 0.5-25 parts of the low-heat-absorption ASA black masterbatch; 0.1-2 parts of a weathering agent; 0.1-2 parts of an antioxidant; and 0.1-2 parts of other auxiliary agents. The preparation method comprises the following steps: A-2, weighing the components in parts by weight; B-2, mixing the components in a high-speed mixer for 5-25 minutes to obtain a mixture; and C-2, feeding the mixture obtained in step B-2 from a main feed of a twin-screw extruder, and carrying out melt extrusion, cooling, drying, and pelletizing to obtain the highly-weather-resistant black thermal insulation ASA resin. Compared with the prior art, the present invention not only remarkably improves the heat absorption performance of materials, but also has excellent comprehensive physical properties.

Description

A highly weather-resistant black heat-insulating ASA resin and its preparation method Technical field

The invention relates to the field of polymer materials, and in particular to a highly weather-resistant black heat-insulating ASA resin and a preparation method thereof.

Background technique

At present, due to the excellent weather resistance of ASA materials, they are widely used in plastic parts casings of automobiles and outdoor equipment. Especially black ASA, which has better weather resistance, is widely used in automobile grilles, pillars, rear panels, etc. Sight mirrors and other parts, agricultural machine casings, doorbell casings and other outdoor products. As the application of black ASA becomes more and more widespread, the problem of high surface temperature of black ASA parts under sunlight or infrared light has attracted more and more attention of material selection engineers. Although the color of ASA is made into white, due to Titanium dioxide's strong covering and light-reflecting effects can significantly reduce the surface and back temperatures of the material. However, when black becomes the customer's color scheme, the problem of high surface and internal temperatures caused by the conventional black ASA scheme not only affects the customer experience, and even cause functional failure of the equipment. Therefore, black ASA materials with high weather resistance are in urgent need of development.

Although the existing technology has done a lot of research on the reflection and low absorption of infrared light by conventional resins, such as the use of indium tin oxide (ITO), antimony tin oxide (ATP), aluminum zinc oxide (AZO), etc. and strong reflective properties. However, these solutions often have factors such as high cost, complex preparation processes, shortage of raw material supply, and effects on the appearance and color of the material, which limit their wide application.

Contents of the invention

The purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a highly weather-resistant black heat-insulating ASA resin that not only significantly improves the heat absorption performance of the material but also has excellent comprehensive physical properties and a preparation method thereof.

The object of the present invention can be achieved through the following technical solutions:

The present invention aims at the shortcomings of the existing black ASA's strong absorption of infrared light. By preparing low-endothermic ASA black masterbatch, using common toner and metal oxide forms, by adjusting the ratio of toner and particle size, etc. Screening and optimization, at extremely low cost, have greatly improved the problem of high surface temperature of black ASA under light or infrared irradiation, and the weather resistance of the prepared black ASA is close to that of the weather-resistant carbon black system, which is better than that of ordinary black ASA. Better weather resistance, the specific solutions are as follows:

A highly weather-resistant black heat-insulating ASA resin. The resin includes: SAN resin, ASA high rubber powder, low heat-absorbing ASA black masterbatch and additives; among which, the mass ratio of SAN resin and low heat-absorbing ASA black masterbatch is ( 50-80):(0.5-25).

Further, the resin includes the following components by weight:

Further, the weight average molecular weight of the SAN resin is 80,000-180,000, the acrylonitrile content is 18-34wt%; the melt index (220°C×10kg) is 5-250g/10min; the ASA high rubber powder The rubber content is 40-70wt%, the weight average molecular weight is 100,000-400,000, the acrylonitrile content is 10-45wt%, and the average particle size of ASA high rubber powder is 100-500nm.

Further, the low endothermic ASA black masterbatch includes: ASA resin, mixed modulated toner (I), antioxidant, lubricant and dispersant; wherein, the quality of ASA resin and mixed modulated toner (I) The ratio is (40-80): (20-60), specifically including the following components by weight:

Further, the mixed modulated toner (I) includes: phthalocyanine blue, ultramarine blue, titanium dioxide, permanent yellow, zinc oxide and tin oxide, wherein the mass ratio of zinc oxide and tin oxide is (0.5-10) :(0.5-8), specifically including the following components by weight:

Further, the phthalocyanine blue is in β crystal form, and its molecular structural formula is as shown in the figure below:

The ultramarine is a blue powder containing special crystalline aluminosilicate of sodium polysulfide, with a refractive index of 1.5-1.54 and a relative density of 2.35-2.74; the titanium dioxide is a rutile white powder with a single alumina surface. layer or multiple layers of cladding. The particle size is 50-900nm; the permanent yellow has a molecular weight of 817.86, a red-yellow powder, and a relative density of 1.37; the zinc oxide is white hexagonal crystal or spherical particles, with a refractive index of 2.1, a relative density of 5.6, and The diameter is 10-300nm; the tin oxide has a molecular weight of 150.69, a tetragonal crystal, and a refractive index of 1.9968.

Further, the antioxidants include primary antioxidants and auxiliary antioxidants, wherein the primary antioxidants are aromatic amine tertiary amine type antioxidants, alkyl monophenols, alkyl polyphenols, thioesters or One or more bisphosphites, the auxiliary antioxidant is a phosphite antioxidant; the weathering agent is benzotriazole, resorcinol benzoic acid monoester, tert-octyl phenyl One or more of salicylates, oxalamides, benzophenones, hindered amines or cyanoacrylates;

The weight average molecular weight of the ASA resin is 50,000-200,000, the acrylonitrile content is 12-38wt%; the melt index (220℃×10kg) is 5-40g/10min, the glue content is 10-40wt%, and the ASA rubber powder is The average particle size is 100-500nm.

Further, the preparation method of the low endothermic ASA black masterbatch includes the following steps:

A-1. Weigh each component of the mixed prepared toner (I) in parts by weight and mix evenly;

B-1. Weigh the remaining components in parts by weight and mix them in a high-speed mixer for 5-25 minutes to obtain a mixture;

C-1. Enter the mixture obtained in step B-1 from the main feed of the twin-screw extruder, and undergo melt extrusion, cooling, drying, and pelletizing to obtain low endothermic ASA black masterbatch.

A method for preparing the highly weather-resistant black heat-insulating ASA resin as described above, including the following steps:

A-2. Weigh each component in parts by weight;

B-2. Mix in a high-speed mixer for 5-25 minutes to obtain a mixture;

C-2. Enter the mixture obtained in step B-2 from the main feed of the twin-screw extruder, and undergo melt extrusion, cooling, drying, and pelletizing to obtain highly weather-resistant black heat-insulating ASA resin.

Further, in the step C, the twin-screw extruder is a co-rotating twin-screw extruder, the length-to-diameter ratio of the screw is 25-40, and the screw barrel is equipped with a vacuum extraction device and a temperature control unit. control device; the feed section temperature of the twin-screw extruder is 180-210°C, the plasticizing section temperature is 210-240°C, the homogenizing section temperature is 220-250°C; the screw speed is 200-700rpm.

Compared with the existing technology, the present invention aims to improve the surface heat absorption performance of black ASA and uses a compound toner system. While ensuring the weather resistance of the material, the blackness of the material is close to that of conventional black ASA. The optimization of toner and inorganic fillers, including the type of toner and the particle size of the toner, not only significantly improves the heat absorption performance of the material, but also the prepared resin has excellent comprehensive physical properties.

Detailed ways

The following is a detailed description of the embodiments of the present invention. This embodiment is implemented based on the technical solution of the present invention and provides detailed implementation modes and specific operating processes. However, the protection scope of the present invention is not limited to the following implementations. example.

The raw materials used in the following examples and comparative examples are:

Styrene-acrylonitrile copolymer SAN was selected from Kumho Petrochemical Co., Ltd. in South Korea, with a weight average molecular weight of 130,000 and an acrylonitrile content of 28 wt%; ASA rubber powder was selected from Kumho Petrochemical Co., Ltd. in South Korea, with a gum content of 42%. The particle size is 370nm, and the AN content is 14.7%; the weathering agent is selected from Ciba’s Tinuvins UVP and 770DF; the main antioxidant is selected from ADK’s AO-50, and the auxiliary antioxidant is selected from Chemtura’s 619F; the lubricant is EBS lubricant ; ASA resin is selected from ASA XC811 of Shanghai Jinhu Rili; dispersant zinc stearate is selected from Hebei Yutian County Auxiliary Factory; ultramarine, the model used is Ultramarine No. 464, produced from Zhejiang Huangyan Chemical Factory No. 5; phthalocyanine blue It was selected from Tianjin Paint Factory; the titanium dioxide was selected from Xinli, Yunnan; and the permanent yellow was selected from Xinxiang Deke Effect Pigment Co., Ltd. Zinc oxide was selected from Shandong Jinyuan New Material Technology Co., Ltd.; tin oxide was selected from Hangzhou Hengge Nano Technology Co., Ltd. Ordinary carbon black was selected from Longxing Chemical Co., Ltd.

After drying at 80°C for 5 hours, the ASA resin prepared in Examples 1-6 and Comparative Examples 1-5 was injection molded into standard physical property strips and large high-gloss plates (140×90×3mm) under the same injection molding conditions according to ASTM standards. Each resin composition was tested for its physical properties and surface temperature under sunlight.

Table 1

Physical properties	Test Conditions	standard test
MFR(g/10min)	220℃,10kg	ASTM D1238-10
Izod notched impact strength (1/8) (J/m)	23℃	ASTM D256-10
Tensile strength(MPa)	50mm/min	ASTM D638-10
Bending strength(MPa)	3mm/min	ASTM D790-10
Flexural modulus (MPa)	3mm/min	ASTM D790-10
Vicat(℃)	5kg,50℃/h	ASTM D1525-09
Material surface temperature (℃)	5 hours of sunshine at noon in summer	—

Example 1

This embodiment provides a highly weather-resistant black heat-insulating ASA resin and a preparation method thereof. The specific steps are as follows:

(1) Weigh each component according to the weight ratio in Table 2 to prepare low endothermic ASA black masterbatch;

(2) Weigh the components of the low endothermic ASA black masterbatch prepared in (1) and mix them in a high-speed mixer for 5-25 minutes to obtain a mixture;

The above-mentioned mixed mixture is fed into the main feed of a twin-screw extruder, and a sample is obtained through melt extrusion, cooling, drying, and pelletizing; wherein, the twin-screw extruder is a co-rotating twin-screw extruder. After exiting the machine, the length-to-diameter ratio of the screw is 25-40, and the screw barrel is equipped with a vacuum evacuation device and a temperature control device; the feed section temperature of the twin-screw extruder is 180-210°C, and the plasticizing section temperature is 210-210°C. 240℃, the homogenizing section temperature is 220-250℃, and the screw speed is 200-700rpm.

Example 2

This embodiment provides a highly weather-resistant black heat-insulating ASA resin and its preparation method. The raw material weight ratio is shown in Table 2, and the preparation method is the same as in Example 1.

Example 3

This embodiment provides a highly weather-resistant black heat-insulating ASA resin and its preparation method. The raw material weight ratio is shown in Table 2, and the preparation method is the same as in Example 1.

Example 4

This embodiment provides a highly weather-resistant black heat-insulating ASA resin and its preparation method. The raw material weight ratio is shown in Table 2, and the preparation method is the same as in Example 1.

Example 5

This embodiment provides a highly weather-resistant black heat-insulating ASA resin and its preparation method. The raw material weight ratio is shown in Table 2, and the preparation method is the same as in Example 1.

Example 6

This embodiment provides a highly weather-resistant black heat-insulating ASA resin and its preparation method. The raw material weight ratio is shown in Table 2, and the preparation method is the same as in Example 1.

Comparative example 1

This comparative example provides an ASA resin and its preparation method. The weight ratio of raw materials is shown in Table 2. The preparation method is the same as in Example 1.

Comparative example 2

This comparative example provides an ASA resin and its preparation method. The weight ratio of raw materials is shown in Table 2. The preparation method is the same as in Example 1.

Comparative example 3

This comparative example provides an ASA resin and its preparation method. The weight ratio of raw materials is shown in Table 2. The preparation method is the same as in Example 1.

Comparative example 4

This comparative example provides an ASA resin and its preparation method. The weight ratio of raw materials is shown in Table 2. The preparation method is the same as in Example 1.

Comparative example 5

This comparative example provides an ASA resin and its preparation method. The weight ratio of raw materials is shown in Table 2. The preparation method is the same as in Example 1.

Table 2

table 3

Low endothermic ASA black masterbatch components	MB-1	MB-2	MB-3	MB-4
ASA resin	50	50	50	50
Phthalocyanine blue	​	4	4	​
ultramarine	​	36	36	​
Titanium dioxide	50	9	9	​
Forever yellow	​	1	1	​
Zinc oxide	​	​	2	​
tin oxide	​	​	1	​
carbon black	​	​	​	50
Auxiliary-1	2	2	2	2

Among them, additive-1 is a lubricant and dispersant with a mass ratio of 1:1.

The physical properties, surface temperature and weather resistance test results of the ASA resins of Examples 1-6 and Comparative Examples 1-5 are shown in Table 4 below.

Table 4

The test results of Examples 1-8 and Comparative Examples 1-4 in Table 4 show that through the preparation of toner and the introduction of low-endothermic ASA masterbatch, the surface temperature of black ASA is significantly reduced, and it is also improved to a certain extent. the mechanical properties of the material.

The addition of carbon black can easily achieve the effect of blackening the material, corresponding to a reduction in the L value of the material. However, carbon black dyeing causes the material to strongly absorb various bands of sunlight, resulting in a significant increase in the surface temperature of the material. Of course, if the material is not black, its absorption of sunlight will be relatively weak, and the surface temperature of the corresponding material will also decrease. Especially for white samples (higher L values), their reflection of sunlight is stronger. Therefore, the material surface temperature of the white sample is lower. Because different toners have significant differences in their absorption, reflection and transmission effects on different bands of sunlight, if you want to achieve a visual black effect while reducing the absorption of heat-generating bands of sunlight on the surface of the material, then This can be achieved by modulating the corresponding toner.

In the present invention, through Comparative Examples 1-3 and Example 3, it can be found that compared with MB-4, the modulated MB-3 black masterbatch not only achieves the effect of making the material black, but also achieves a significant temperature rise of the material after being irradiated by sunlight. The temperature rise is almost the same as that of white parts. Although MB-3 achieves a better cooling effect on black parts, the parts need to ensure certain impact performance in practical applications. From Comparative Example 4 and Example 3, it can be found that when the rubber powder in the system is too small, it is difficult to form enough Silver crazing and shear bands result in low impact performance and difficulty in practical application.

The above are only preferred embodiments of the present invention, and are not intended to limit the present invention in other forms. Any skilled person familiar with the art may make changes or modifications to equivalent changes using the technical contents disclosed above. Example. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (10)

1. A highly weather-resistant black heat-insulating ASA resin, characterized in that the resin includes: SAN resin, ASA high rubber powder, low heat-absorbing ASA black masterbatch and auxiliaries; wherein, SAN resin and low heat-absorbing ASA black masterbatch are The mass ratio is (50-80): (0.5-25).
2. A highly weather-resistant black heat-insulating ASA resin according to claim 1, characterized in that the resin includes the following components by weight:

   
3. A highly weather-resistant black heat-insulating ASA resin according to claim 1, characterized in that the weight average molecular weight of the SAN resin is 80,000-180,000, the acrylonitrile content is 18-34wt%; the melt index (220°C ×10kg) is 5-250g/10min; the gum content in the ASA high rubber powder is 40-70wt%, the weight average molecular weight is 100,000-400,000, the acrylonitrile content is 10-45wt%, and the ASA high rubber powder The average particle size is 100-500nm.
4. A highly weather-resistant black heat-insulating ASA resin according to claim 1, characterized in that the low heat-absorbing ASA black masterbatch includes: ASA resin, mixed modulated toner (I), antioxidant, lubricant and dispersant; wherein, the mass ratio of ASA resin and mixed prepared toner (I) is (40-80): (20-60), specifically including the following components by weight:

   
5. A highly weather-resistant black heat-insulating ASA resin according to claim 4, characterized in that the mixed modulated toner (I) includes: phthalocyanine blue, ultramarine blue, titanium dioxide, permanent yellow, zinc oxide and oxide Tin, wherein the mass ratio of zinc oxide and tin oxide is (0.5-10): (0.5-8), specifically including the following components by weight:

   

   
6. A highly weather-resistant black heat-insulating ASA resin according to claim 5, characterized in that the phthalocyanine blue is a β crystal form, and the molecular structural formula is as shown in the figure below:

   

   The ultramarine is a blue powder containing special crystalline aluminosilicate of sodium polysulfide, with a refractive index of 1.5-1.54 and a relative density of 2.35-2.74; the titanium dioxide is a rutile white powder with a single alumina surface. layer or multiple layers of cladding. The particle size is 50-900nm; the permanent yellow has a molecular weight of 817.86, a red-yellow powder, and a relative density of 1.37; the zinc oxide is white hexagonal crystal or spherical particles, with a refractive index of 2.1, a relative density of 5.6, and The diameter is 10-300nm; the tin oxide has a molecular weight of 150.69, a tetragonal crystal, and a refractive index of 1.9968.
7. A kind of highly weather-resistant black heat-insulating ASA resin according to claim 4, characterized in that the antioxidant includes a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is an aromatic amine tertiary amine type antioxidant. One or more of oxygenating agents, alkyl monophenols, alkyl polyphenols, thioesters or bisphosphites, the auxiliary antioxidant is a phosphite antioxidant; the weathering agent is benzo One or more of triazoles, resorcinol benzoic acid monoester, tert-octylphenyl salicylate, oxamide, benzophenone, hindered amine or cyanoacrylate;

   The weight average molecular weight of the ASA resin is 50,000-200,000, the acrylonitrile content is 12-38wt%; the melt index (220℃×10kg) is 5-40g/10min, the glue content is 10-40wt%, and the ASA rubber powder is The average particle size is 100-500nm.
8. A highly weather-resistant black heat-insulating ASA resin according to claim 4, characterized in that the preparation method of the low-endothermic ASA black masterbatch includes the following steps:

   A-1. Weigh each component of the mixed prepared toner (I) in parts by weight and mix evenly;

   B-1. Weigh the remaining components in parts by weight and mix them in a high-speed mixer for 5-25 minutes to obtain a mixture;

   C-1. Enter the mixture obtained in step B-1 from the main feed of the twin-screw extruder, and undergo melt extrusion, cooling, drying, and pelletizing to obtain low endothermic ASA black masterbatch.
9. A method for preparing highly weather-resistant black heat-insulating ASA resin according to any one of claims 1 to 8, characterized in that it includes the following steps:

   A-2. Weigh each component in parts by weight;

   B-2. Mix in a high-speed mixer for 5-25 minutes to obtain a mixture;

   C-2. Enter the mixture obtained in step B-2 from the main feed of the twin-screw extruder, and undergo melt extrusion, cooling, drying, and pelletizing to obtain highly weather-resistant black heat-insulating ASA resin.
10. The preparation method of a highly weather-resistant black heat-insulating ASA resin according to claim 9, characterized in that in the step C, the twin-screw extruder is a co-rotating twin-screw extruder, The aspect ratio of the screw is 25-40, and the screw barrel is equipped with a vacuum evacuation device and a temperature control device; the feed section temperature of the twin-screw extruder is 180-210°C, and the plasticizing section temperature is 210-210°C. 240℃, the homogenizing section temperature is 220-250℃; the screw speed is 200-700rpm.