CN102942726A - A kind of preparation method of sulfur-fixed ash replacing CaCO3 filled polyolefin resin - Google Patents

Abstract

The invention relates to a method for preparing sulfur-fixed ash instead of _CaCO3 filled polyolefin resin. Provide a new way for the recovery and reuse of sulfur-fixed ash. Firstly, the diluted modifier whose active content is 0.5-6% of the total sulfur-fixed ash is mixed with the sulfur-fixed ash at high speed to prepare modified sulfur-fixed ash; secondly, the plasticizer, antioxidant and polyolefin resin Melt, then add toughening agent, lubricant and modified sulfur-fixed ash to continue melt blending; finally, use compression molding to prepare a composite material in which modified sulfur-fixed ash replaces CaCO ₃ filled polyolefin. The modified sulfur-fixing ash treated by organic modification has good compatibility with the polymer matrix. Using it to replace _CaCO3 to fill polyolefin resin fully meets the technical requirements of plastic industry fillers. It not only has a large filling amount and good effect, but also The preparation method is simple and the production cost is low.

Description

A kind of preparation method of sulfur-fixed ash replacing CaCO3 filled polyolefin resin

technical field

The invention relates to a method for replacing _CaCO3 filled polyolefin resin with modified sulfur-fixing ash, which belongs to the field of inorganic-organic composite materials.

Background technique

Circulating fluidized bed coal ash is solid waste produced by burning sulfur-fixing agents such as sulfur-containing coal and limestone at a temperature of 850°C to 900°C in a circulating fluidized-bed boiler, including sulfur-fixed ash collected from the flue and Sulfur-fixing slag discharged from the bottom of the furnace. With the enlargement of circulating fluidized bed boilers and the rapid development of power generation technology, the discharge of circulating fluidized bed ash has increased significantly, and the annual discharge of sulfur-fixed ash has reached about 150 million tons (of which sulfur-fixed ash emissions are significantly greater than that of sulfur-fixed ash). At present, the use of sulfur-fixed ash is seldom, and a large amount of sulfur-fixed ash is simply piled up and discharged randomly, which not only occupies a large amount of land resources, but also pollutes the ecological environment, and even endangers human health. To popularize circulating fluidized bed combustion technology in China on a large scale, the comprehensive utilization of sulfur-fixed ash must be solved first.

Many scholars generally pay attention to the research of sulfur-fixed ash as a building material resource. The main application methods include cement mixture, concrete admixture and expansion agent, such as Chinese patents CN101863678A, CN101367635A, CN101913786A, CN101544015A and CN101913790A. However, these studies also have limitations. The utilization rate of sulfur-fixed ash is far from satisfying the increasing accumulation of sulfur-fixed ash. In order to avoid secondary pollution caused by sulfur-fixed ash, it is urgent to explore the application of sulfur-fixed ash in other systems. .

Sulfur-fixing ash and fly ash belong to mineral waste residues with similar chemical components; a large number of studies have shown that modified fly ash as a polymer filler has a better filling effect than unmodified fly ash, and can Improve the processing performance of polymers; CaCO ₃ as a common polymer filler can reduce the cost of polymer products, and play a role in strengthening and toughening; use sulfur-fixed ash, especially modified sulfur-fixed ash to replace CaCO ₃ filled polymer Olefin, which has certain economic benefits, also provides a new way for the application of sulfur-fixed ash.

Contents of the invention

1. Modification of sulfur-fixed ash:

Mix and stir the dry sulfur-fixed ash with a maximum particle size of ≤25 μm at high speed, use it to preheat to 40-60°C by self-friction, and sprinkle in batches the dilute stearin with an active content of 0.5-6% of the total amount of sulfur-fixed ash acid, titanate coupling agent or silane coupling agent, and then continue high-speed stirring at 60-120° C. for 2-8 minutes, and dry to obtain modified sulfur-fixing ash.

2. Application of modified sulfur-fixing ash filler in polyolefin:

The ratio of plasticizer, antioxidant, toughening agent, lubricant, modified sulfur-fixed ash and polyolefin resin is calculated in parts by mass:

Polyolefin resin 100.0 parts

Plasticizer 10.0～30.0 parts

Antioxidant 1.0～3.0 parts

Toughener 10.0～30.0 parts

Lubricant 2.0～6.0 parts

Modified sulfur-fixing ash 5.0～40.0 parts

Melt and mix plasticizer, antioxidant and polyolefin resin, then add toughener, lubricant and modified sulfur-fixed ash to continue melt blending; the melt blending temperature is 165-220°C, and the mixing time is 10-30 minutes; molding samples are obtained by compression molding; the temperature of the compression molding is 165-200° C., the pressure is 8-12 MPa, and the holding time is 6-10 minutes.

Detailed ways

Embodiment one

Application of stearic acid modified sulfur-fixing ash instead of CaCO ₃ in polypropylene/high-density polyethylene/ethylene-vinyl acetate (PP/HDPE/EVA).

1. Stearic acid modified sulfur-fixing ash:

The dry sulfur-fixed ash with a maximum particle size of 8 μm is mixed and stirred at high speed, and after being preheated to 40°C by self-friction, the diluted stearic acid with an active content of 3% of the total amount of the sulfur-fixed ash is sprinkled in batches. Continue high-speed stirring at 70°C for 5 minutes, and dry to obtain stearic acid-modified sulfur-fixed ash (S-modified sulfur-fixed ash).

2. Application of S-modified sulfur-fixed ash in polyolefin:

The ratio of PP, HDPE, EVA, antioxidant 1010 and S-modified sulfur-fixed ash to PP is:

PP 100.0 parts

HDPE 10.0 parts

Antioxidant 1010 1.0 parts

EVA 20.0 parts

Liquid paraffin 2.0 parts

S modified sulfur-fixed ash 15.0/20.0/30.0 parts

Melt and mix HDPE, antioxidant 1010 and PP, then add EVA, liquid paraffin and S-modified sulfur-fixed ash to continue melt blending; the melt blending temperature is 190°C; the mixing time is 20 minutes; molding is adopted , to prepare a standard sample; the molding temperature is 180°C, the pressure is 10MPa, and the holding time is 8min; the sample is made according to the national standard GB/T1040-1992 and GB/T9341-2000, and its mechanical properties See Table 1.

Embodiment two

Application of silane coupling agent modified sulfur-fixing ash instead of CaCO ₃ in polypropylene/high-density polyethylene/ethylene-vinyl acetate (PP/HDPE/EVA).

1. Silane coupling agent modified sulfur-fixing ash:

Mix and stir the dry sulfur-fixed ash with a median particle size of 8 μm at high speed, use it to preheat to 30°C by self-friction, and sprinkle in batches diluted vinyl triethoxylate with an active content of 1% of the total amount of sulfur-fixed ash base silane (A151), and then continue high-speed stirring at 70 ° C for 8 minutes, and dry to obtain 1% A151 modified sulfur-fixed ash (A-1 modified sulfur-fixed ash).

2. Application of A-1 modified sulfur-fixing ash in polyolefin:

The ratio of PP, HDPE, EVA, antioxidant 1010 and A-1 modified sulfur-fixing ash to PP is:

PP 100.0 parts

HDPE 10.0 parts

Antioxidant 1010 1.0 parts

EVA 20.0 copies

Liquid paraffin 2.0 parts

A-1 modified sulfur-fixing ash 30.0 parts

Melt and mix HDPE, antioxidant 1010 and PP, then add EVA, liquid paraffin and A-1 modified sulfur-fixed ash to continue melt blending; the melt blending temperature is 180°C, and the mixing time is 20min; Compression molding to prepare standard samples; the temperature of the compression molding is 180°C, the pressure is 10MPa, and the holding time is 10min; the sample is made according to the national standard GB/T1040-1992 and GB/T9341-2000, and its See Table 1 for mechanical properties.

Embodiment three

Application of silane coupling agent modified sulfur-fixing ash instead of CaCO ₃ in polypropylene/high-density polyethylene/ethylene-vinyl acetate (PP/HDPE/EVA).

1. Silane coupling agent modified sulfur-fixing ash:

Mix and stir the dry sulfur-fixed ash with a median particle size of 8 μm at high speed, use it to preheat to 40°C by self-friction, and sprinkle in batches diluted vinyl triethoxylate with an active content of 1.5% of the total amount of sulfur-fixed ash base silane (A151), and then continue high-speed stirring at 70°C for 8 minutes, and dry to obtain 1.5% A151 modified sulfur-fixed ash (A-2 modified sulfur-fixed ash).

2.A-2 Application of modified sulfur-fixing ash in polyolefin:

The ratio of PP, HDPE, EVA, antioxidant 1010 and modified sulfur-fixed ash to PP is:

PP 100.0 parts

HDPE 10.0 parts

Antioxidant 1010 1.0 parts

EVA 20.0 copies

Liquid paraffin 2.0 parts

A-2 modified sulfur-fixing ash 30.0 parts

Melt and mix HDPE, antioxidant 1010 and PP, then add EVA, liquid paraffin and A-2 modified sulfur-fixed ash to continue melt blending; the melt blending temperature is 180°C, and the mixing time is 20 minutes; Compression molding to prepare standard samples; the temperature of the compression molding is 180°C, the pressure is 10MPa, and the holding time is 10min; the sample is made according to the national standard GB/T1040-1992 and GB/T9341-2000, and its See Table 1 for mechanical properties.

Embodiment four

Application of commercially available modified _CaCO3 in polypropylene/high-density polyethylene/ethylene-vinyl acetate (PP/HDPE/EVA).

The ratio of PP, HDPE, EVA, antioxidant 1010 and commercially available modified _CaCO3 to PP is:

PP 100.0 parts

HDPE 10.0 parts

Antioxidant 1010 1.0 parts

EVA 20.0 copies

Liquid paraffin 2.0 parts

Commercially available modified CaCO ₃ 15.0/20.0/30.0 parts

Melt and mix HDPE, antioxidant 1010 and PP, then add EVA, liquid paraffin and commercially available modified CaCO ₃ to continue melt blending; the melt blending temperature is 190°C, and the mixing time is 20 minutes; molded , to prepare a standard sample; the molding temperature is 180°C, the pressure is 10MPa, and the holding time is 8min; the sample is made according to the national standard GB/T1040-1992 and GB/T9341-2000, and its mechanical properties See Table 1.

Embodiment five

Application of Heavy CaCO ₃ in Polypropylene/High Density Polyethylene/Ethylene Vinyl Acetate (PP/HDPE/EVA).

The ratio of PP, HDPE, EVA, antioxidant 1010 and _CaCO3 to PP is:

PP 100.0 parts

HDPE 10.0 parts

Antioxidant 1010 1.0 parts

EVA 20.0 parts

Liquid paraffin 2.0 parts

Heavy CaCO ₃ 15.0/20.0 parts

Melt and mix HDPE, antioxidant 1010 and PP, and then add EVA, liquid paraffin and heavy CaCO ₃ to continue melt blending; the melt blending temperature is 190°C, and the mixing time is 20 minutes; molding is used to prepare Standard sample; the molding temperature is 180°C, the pressure is 10MPa, and the holding time is 8min; the sample is made according to national standards GB/T1040-1992 and GB/T9341-2000, and its mechanical properties are shown in the table 1.

Embodiment six

Application of sulfur-fixed ash with a median particle size of 8 μm in polypropylene/high-density polyethylene/ethylene-vinyl acetate (PP/HDPE/EVA).

The ratio of PP, HDPE, EVA, antioxidant 1010 and sulfur-fixed ash to PP is:

PP 100.0 parts

HDPE 10.0 parts

Antioxidant 1010 1.0 parts

EVA 20.0 copies

Liquid paraffin 2.0 parts

Sulfur-fixed ash 15.0/20.0 parts

Melt and mix HDPE, antioxidant 1010 and PP, then add EVA, liquid paraffin and sulfur ash to continue melt blending; the melt blending temperature is 190°C, and the mixing time is 20 minutes; molding is used to prepare the standard Sample; the molding temperature is 180°C, the pressure is 10MPa, and the holding time is 8min; the sample is made according to national standards GB/T1040-1992 and GB/T9341-2000, and its mechanical properties are shown in Table 1 .

Table 1 Mechanical properties of sulfur-fixed ash, modified sulfur-fixed ash, heavy CaCO ₃ and commercially available modified CaCO ₃ filled polypropylene/high-density polyethylene/ethylene-vinyl acetate (PP/HDPE/EVA) (where the mass of PP is M)

The above case illustrates:

1. The flexural strength, elongation at break and yield elongation of PP/HDPE/EVA filled with unmodified sulfur-fixing ash are far lower than those modified by stearic acid, titanate coupling agent and silane coupling agent, And the elastic modulus is much higher than that of stearic acid, titanate coupling agent and silane coupling agent modified sulfur-fixing ash, so it cannot replace CaCO ₃ filled PP/HDPE/EVA.

2. The mechanical properties of polyolefin filled with stearic acid, titanate coupling agent and silane coupling agent are equivalent to those of CaCO ₃ filled polyolefin plastics, and the filling amount of modified sulfur-fixed ash is 30%. , the modification effect is still particularly obvious, therefore, the modified sulfur-fixed ash can partially or completely replace the application of CaCO ₃ in polyolefin plastics.

Claims (3)

1. the solid sulphur ash of modification substitutes CaCO ₃The preparation method of filled polyolefin resin, it is characterized in that: the method is keeping on the constant basis of plastic processing, the solid sulphur ash of softening agent, toughner, lubricant, oxidation inhibitor and modification is directly added in the polyolefin resin, made by the solid sulphur ash of modification and substitute CaCO ₃Composite polyolefine material.

2. the solid sulphur ash of modification according to claim 1 substitutes CaCO ₃The preparation method of filled polyolefin resin, it is characterized in that: the solid sulphur ash of the drying of maximum particle diameter≤25 μ m high-speed mixing is stirred, utilize it after friction is preheated to 40-60 ℃, be spilled in batches that active quantities is stearic acid, titanate coupling agent or the silane coupling agent of solid sulphur ash total amount 0.5～6% after dilution, at 60～120 ℃ of lower high-speed stirring 2～8min that continue, obtain the solid sulphur ash of modification again.

3. the solid sulphur ash of modification according to claim 1 substitutes CaCO ₃The preparation method of filled polyolefin resin is characterized in that: the ratio of softening agent, oxidation inhibitor, toughner, lubricant, the solid sulphur ash of modification and polyolefin resin is calculated as with mass fraction:

With softening agent, oxidation inhibitor and polyolefin resin melting mixing, the more solid sulphur ash of toughner, lubricant and modification is added, continue melt blending; Described melt blending temperature is 165～220 ℃, and mixing time is 10～30min; Adopt compression molding, obtain the moulding sample; The temperature of described compression molding is 165～230 ℃, and pressure is 8～12MPa, and the dwell time is 6～10min.