CN112480593A - Heat-resistant low-odor bulk ABS composite material and preparation method thereof - Google Patents

Abstract

The invention provides a heat-resistant low-odor ABS composite material and a preparation method thereof, and the ABS composite material comprises the following components in percentage by mass: the balance of the ABS, 5-20 percent of heat-resistant agent, 0.5-2 percent of lubricant, 0.1-1 percent of antioxidant and 0.5-2 percent of stripping agent. After the reaction of the bulk ABS is finished and before extrusion granulation, the heat-resistant agent is melted by a plasticizing machine and then sent into an extruder capable of being stripped together with the bulk ABS, and then the product is obtained through melt extrusion and granulation. The scale of the plasticizing machine is 0.05-0.2 times of that of the extruder. The odor grade of the ABS resin product prepared by the method reaches below grade 3, the COD value reaches within 50ppm, and the heat-resistant temperature reaches 106-120 ℃. The heat-resistant low-odor ABS resin prepared by the method has low production cost, high heat resistance and low odor, and can be applied to automotive upholsteries.

Description

Heat-resistant low-odor bulk ABS composite material and preparation method thereof

Technical Field

The invention belongs to the field of ABS composite materials, and particularly relates to a heat-resistant low-odor bulk ABS composite material and a preparation method thereof.

Background

The continuous body process belongs to a clean production process, accords with the strategy of sustainable development, and is an ABS production process encouraged by the nation. At present, manufacturers for producing ABS in China have: in 2006, high-bridge petrochemical companies introduced DOW chemical technology, and built 20 million tons per year of bulk ABS devices, which were put into production in 2007. In 2008, the DOW chemical body ABS technology was introduced by the Liaoning Huajin chemical industry (group) Limited liability company of the Chinese weapon industry group, 14 million tons/year devices were built, and the production was carried out in 11 months in 2010. In 2007, the company qimei (zhenjiang) bought the technology of the new international material company of the Zhonghua group, constructed 10 ten thousand tons of devices every year, and put into production in 11 months in 2009. Shanghai Huayi polymer Co., Ltd adopts a technology of multiple series-connected full mixed polymerization reactors (CSTR), a 3.8 ten thousand ton/year device is built in 2011, and the production is stopped at present. Because the ABS in China is incomplete in variety, low in quality, high in cost and serious in homogenization, only the Qimei (Zhenjiang) company produces the low-odor high-temperature-resistant body ABSPA-1730 in China, and the ABS can be used for closed space products such as automotive interiors, household articles and the like.

Only a few international companies, such as oslo, produce low odor low VOC bulk ABS resins and have achieved industrialization. The European Shengxi ao low-odor ABS resin not only keeps the characteristics of good fluidity, impact property and the like of the original resin, but also meets the requirement of food contact safety because of the unique preparation process, the monomer residual quantity is controlled below 50ppm, the odor grade reaches below 3 grades, and the ABS resin is widely applied to any parts which can be contacted with food and beverage, and has different brands for market selection.

At present, composite material manufacturers blend the ABS body with PC, PA, PBT and the like to produce matte, low-odor and heat-resistant composite materials, and open a door for the application of the ABS body. However, the modification mode of composite material manufacturers causes the ABS to be subjected to secondary processing, the product is aged and degraded, and the phenomenon of color change occurs, so that the use effect of the product is influenced.

There are various methods for reducing odor and VOC, such as adding essence odor masking agent, adding chemical odor removing agent, adding physical adsorbent, adopting devolatilization drying method, adopting gas extraction method, adopting extraction devolatilization process, etc., wherein the most basic method is physical adsorption method and chemical reaction method, but both methods have certain defects and poor effect; the air stripping method is a new process for preparing low-emission plastics developed in recent years, and the process is characterized in that inert gases such as nitrogen, carbon dioxide and water (gasified after injection) are introduced into a screw rod in the extrusion modification of the plastics, and the gases are used as carriers (so-called stripping agents) to carry out and discharge harmful volatile matters escaping from high-viscosity fluids in a carrying manner, so that the effect is very good.

Disclosure of Invention

The invention aims to provide a heat-resistant low-odor bulk ABS composite material and a preparation method thereof, and the following technical scheme is adopted to achieve the aim of the invention.

A heat-resistant low-odor bulk ABS material comprises the following raw materials in percentage by weight:

the heat-resistant agent is a styrene-N-phenylmaleimide-anhydrous maleic anhydride copolymer. Preferably, the ABS heat resistance modifier XIRAN IZ1018M, POLYSCOPE, DENKA IP MS-NB, the Netherlands, the electrochemical industry

The lubricant is ethylene bis stearamide EBS, pentaerythritol stearate PETS, German Kening.

The antioxidant is 1010, 1076 and the like.

The stripping agent is water or carbon dioxide.

The invention also provides a preparation method of the heat-resistant low-odor bulk ABS material, which comprises the following steps:

(1) weighing the heat-resistant agent, the lubricant and the antioxidant according to the weight percentage and uniformly mixing according to the yield of the ABS;

(2) and (2) putting the uniformly mixed raw materials in the step (1) into a main machine barrel of a plasticizing machine, controlling the temperature of the barrel in a segmented mode, controlling the temperature from a feed inlet to a machine head outlet at 220 ℃, 230 ℃, 235 ℃, 225 ℃ and 225 ℃ at a main machine rotating speed of 300 r/min, fusing, then merging the fused raw materials into a feed inlet in a first area of the body ABS extruder through an extrusion die port through a pipeline, simultaneously opening a stripping agent feed pump, adjusting the using amount of the stripping agent, adding the stripping agent into an opening in a third area of the body ABS extruder, controlling the vacuum degree to be-0.099 MPa, and obtaining the product after melt extrusion, water tank cooling and grain cutting.

The invention has the advantages of

The invention adopts the prior body ABS device to directly produce the high-performance composite material, thereby improving the market consumption proportion of the body ABS. The ABS body does not need secondary processing, and the high-performance composite material can be produced directly on the ABS body production device. The odor grade of the product reaches below grade 3, and the COD value reaches within 50 ppm.

After the reaction of the ABS body is finished and before extrusion granulation, the heat-resistant agent is melted by a plasticizing machine and then is sent into an extruder capable of being stripped together with the ABS body, and then the product is obtained through melt extrusion and granulation. The scale of the plasticizing machine is 0.05-0.2 times of that of the extruder. The ABS resin product prepared by the method has the heat-resistant temperature of 106-120 ℃.

The heat-resistant low-odor ABS resin prepared by the method has the advantages of low production cost, high heat resistance and low odor, and can be applied to automotive upholsteries.

Detailed Description

The present invention will be described in detail with reference to the following specific examples, but the present invention is not limited to the following examples and should not be construed as being limited thereto.

The embodiment of the invention is implemented on a body ABS pilot test device: the yield of the northern China brocade body ABS device is 6 t/h.

Heat-resistant agent: heat resistant modifier XIRAN IZ1018M, POLYSCOPE or DENKA IP MS-NB in the Netherlands, the electrochemical industry

Lubricant: ethylene bis stearamide EBS, pentaerythritol stearate PETS, German Kenin

Antioxidant: antioxidant 1010, antioxidant 1076

Stripping agent: desalted water

Example 1

(1) The yield of the ABS device body is 6t/h, 300kg/h of heat-resistant agent, 30kg/h of lubricant EBS and 107612 kg/h of antioxidant are respectively weighed and uniformly mixed;

(2) and (2) putting the uniformly mixed raw materials into a main machine barrel of a plasticizing machine, controlling the temperature of the barrel in a sectional manner, controlling the temperature from a feed inlet to a machine head outlet at 220 ℃, 230 ℃, 235 ℃, 225 ℃ and 225 ℃ at a main machine rotating speed of 300 r/min, fusing, then adding the fused raw materials into a feed inlet of a first area of a main ABS stripping extruder from an extrusion die port through a pipeline, controlling the dosage of a stripping agent desalted water to be 30kg/h, controlling the vacuum degree to be-0.099 MPa, and carrying out processes of melt extrusion, water tank cooling, grain cutting and the like to obtain the product.

Example 2

(1) The yield of the ABS device body is 6t/h, 480kg/h of heat-resistant agent, 60kg/h of lubricant EBS and 107612 kg/h of antioxidant are respectively weighed and uniformly mixed;

(2) and (2) putting the uniformly mixed raw materials into a main machine barrel of a plasticizing machine, controlling the temperature of the barrel in a sectional manner, controlling the temperature from a feed inlet to a machine head outlet at 220 ℃, 230 ℃, 235 ℃, 225 ℃ and 225 ℃ at a main machine rotating speed of 300 r/min, fusing, then adding the fused raw materials into a feed inlet of a first area of the main ABS extruder from an extrusion die port through a pipeline, controlling the dosage of desalted water of an air stripping agent to be 48kg/h, controlling the vacuum degree to be-0.099 MPa, and carrying out procedures of melt extrusion, water tank cooling, grain cutting and the like to obtain the product.

Example 3

(1) The yield of the ABS device body is 6t/h, 600kg/h of heat-resistant agent, 90kg/h of lubricant EBS90kg and 107630 kg/h of antioxidant are respectively weighed and uniformly mixed;

(2) and (2) putting the uniformly mixed raw materials into a main machine barrel of a plasticizing machine, controlling the temperature of the barrel in a sectional manner, controlling the temperature from a feed inlet to a machine head outlet at 220 ℃, 230 ℃, 235 ℃, 225 ℃ and 225 ℃ at a main machine rotating speed of 300 r/min, fusing, then adding the fused raw materials into a feed inlet of a first area of the main ABS extruder from an extrusion die port through a pipeline, controlling the dosage of desalted water of a stripping agent to be 60kg/h, controlling the vacuum degree to be-0.099 MPa, and carrying out procedures of melt extrusion, water tank cooling, grain cutting and the like to obtain the product.

Example 4

(1) The yield of the ABS device body is 6t/h, 720kg/h of heat-resistant agent, 90kg/h of lubricant PETS and 107630 kg/h of antioxidant are respectively weighed and uniformly mixed;

(2) and (2) putting the uniformly mixed raw materials into a main machine barrel of a plasticizing machine, controlling the temperature of the barrel in a sectional manner, controlling the temperature from a feed inlet to a machine head outlet at 220 ℃, 230 ℃, 235 ℃, 225 ℃ and 225 ℃ at a main machine rotating speed of 300 r/min, fusing, then adding the fused raw materials into a feed inlet of a first area of the main ABS extruder from an extrusion die port through a pipeline, controlling the dosage of desalted water of a stripping agent to be 72kg/h, controlling the vacuum degree to be-0.099 MPa, and carrying out procedures of melt extrusion, water tank cooling, grain cutting and the like to obtain the product.

Example 5

(1) The yield of the ABS device body is 6t/h, 840kg/h of heat-resistant agent, 60kg/h of lubricant PETS60kg and 107630 kg/h of antioxidant are respectively weighed and mixed uniformly;

(2) and (2) putting the uniformly mixed raw materials into a main machine barrel of a plasticizing machine, controlling the temperature of the barrel in a sectional manner, controlling the temperature from a feed inlet to a machine head outlet at 220 ℃, 230 ℃, 235 ℃, 225 ℃ and 225 ℃ at a main machine rotating speed of 300 r/min, fusing, then adding the fused raw materials into a feed inlet of a first area of the main ABS extruder from an extrusion die port through a pipeline, controlling the dosage of desalted water of a stripping agent to be 90kg/h, controlling the vacuum degree to be-0.099 MPa, and carrying out procedures such as melt extrusion, water tank cooling, granulation and the like to obtain the product.

Example 6

(1) The yield of the ABS device body is 6t/h, 960kg/h of heat-resistant agent, 90kg 90kg/h of lubricant PETS and 107648 kg/h of antioxidant are respectively weighed and uniformly mixed;

(2) and (2) putting the uniformly mixed raw materials into a main machine barrel of a plasticizing machine, controlling the temperature of the barrel in a sectional manner, controlling the temperature from a feed inlet to a machine head outlet at 220 ℃, 230 ℃, 235 ℃, 225 ℃ and 225 ℃ at a main machine rotating speed of 300 r/min, fusing, then adding the fused raw materials into a feed inlet of a first area of the main ABS extruder from an extrusion die port through a pipeline, controlling the dosage of desalted water of a stripping agent to be 108kg/h, controlling the vacuum degree to be-0.099 MPa, and carrying out procedures of melt extrusion, water tank cooling, grain cutting and the like to obtain the product.

The composites of the above examples were tested for performance. The tensile strength, impact strength, Vicat softening point, total TVOC content and odor grade of the products obtained in examples 1-6 and the modified ABS product were tested according to the national Standard GB/T12672-2009 ABS resin test Standard, and the results are shown in the following table.

As can be seen from the table above, the heat resistance of the product is obviously improved along with the increase of the heat-resistant dosage, and the effect is best when the VOC content of the ABS resin product is reduced to below 50ppm, the odor grade reaches 3 levels and the dosage of the desalted water of the stripping agent is 1.2 percent of the ABS yield through the stripping extrusion system. The heat-resistant low-odor material provided by the invention can be well applied to automotive upholsteries, and the riding safety is improved. The process technology can also be applied to the production of low-odor products of ABS/PC alloy, ABS/PA alloy and ABS/PBT alloy.

Claims (6)

1. A heat-resistant low-odor bulk ABS composite material is characterized in that: the material composition comprises the following raw materials by weight percent:

2. the heat resistant low odor body ABS composite of claim 1 wherein: the heat-resistant agent is a styrene-N-phenylmaleimide-anhydrous maleic anhydride copolymer.

3. The heat resistant low odor body ABS composite of claim 1 wherein: the lubricant is ethylene bis stearamide EBS, pentaerythritol stearate PETS, or German Kenin.

4. The heat resistant low odor body ABS composite of claim 1 wherein: the antioxidant is antioxidant 1010 or antioxidant 1076.

5. The heat resistant low odor body ABS composite of claim 1 wherein: the stripping agent is water or carbon dioxide.

6. The method of preparing a heat resistant low odor bulk ABS composite of claim 1 wherein: the method comprises the following steps:

(1) weighing the heat-resistant agent, the lubricant and the antioxidant according to the weight percentage of the ABS, and uniformly mixing;

(2) and (2) putting the uniformly mixed raw materials in the step (1) into a main machine barrel of a plasticizing machine, controlling the temperature of the barrel in a segmented mode, controlling the temperature from a feed inlet to a machine head outlet at 220 ℃, 230 ℃, 235 ℃, 225 ℃ and 225 ℃ at a main machine rotating speed of 300 r/min, fusing, then merging the fused raw materials into a feed inlet in a first area of the body ABS extruder through an extrusion die port through a pipeline, simultaneously opening a stripping agent feed pump, adjusting the using amount of the stripping agent, adding the stripping agent into an opening in a third area of the body ABS extruder, controlling the vacuum degree to be-0.099 MPa, and obtaining the product after melt extrusion, water tank cooling and grain cutting.