CN112538227A - ASA/PC3D printing wire with low VOC (volatile organic compound) release and preparation method thereof - Google Patents
ASA/PC3D printing wire with low VOC (volatile organic compound) release and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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Abstract
The invention discloses an ASA/PC3D printing wire with low VOC (volatile organic compound) release, which takes ASA/PC resin as a raw material and is added with modified porous calcium silicate, an accelerator, a heat stabilizer, an antioxidant and a lubricant. In addition, the invention also discloses a preparation method of the 3D printing wire rod, the prepared ASA/PC3D printing wire rod has less VOC release amount in the 3D printing and forming process, the smell in the forming process is good, and the greenization of the 3D printing and forming process is effectively realized.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an ASA/PC3D printing wire with low VOC (volatile organic compound) release and a preparation method thereof.
Background
3D printing is a novel manufacturing technology integrating multiple disciplines of machinery, software and materials. The method is based on the principle of material accumulation and molding and is widely applied to the fields of engineering, education, medical treatment and the like. Fused deposition modeling has attracted attention as one of the mainstream techniques for 3D printing due to its low cost, safe operation, and simple post-processing.
ASA resins are ternary block copolymers consisting of acrylonitrile, styrene and acrylates. The material has excellent processing performance, mechanical performance and chemical corrosion resistance, and also has good weather resistance. The PC resin has good mechanical property, heat resistance and stability, is an ideal thermoplastic engineering plastic, and is widely applied to the fields of automobiles, electronic instruments and the like.
However, in the fused deposition modeling process, the ASA/PC material is melted and stacked mainly by continuous high-temperature heating of a nozzle, which causes degradation behavior of the ASA/PC material, and the degradation behavior releases a large amount of organic volatile compounds (VOCs), generates pungent odor, and seriously affects the working environment and physical and psychological health of operators. Therefore, it becomes important to solve the problem of greenness in the 3D printing and forming process of the ASA/PC material.
In addition, the application of the ASA/PC material in 3D printing and forming is not reported, and the report of the VOC (volatile organic Compounds) release amount in the forming process is not involved.
Disclosure of Invention
In view of the above, the invention aims to provide an ASA/PC3D printing wire with low VOC emission and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the ASA/PC3D printing wire with low VOC release comprises, by weight, 50-70% of ASA resin, 20-30% of PC resin, 5-15% of modified porous calcium silicate, 0.2-2% of accelerator, 0.2-2% of heat stabilizer, 0.2-1% of antioxidant and 0.2-2% of lubricant. The sum of all the components is 100 percent.
Further, the preparation method of the modified porous calcium silicate comprises the following steps: firstly, 20-50 g of porous calcium silicate is placed into 1L of deionized water for ultrasonic dispersion for 0.5-2 h, 5-20 ml of acetic acid is added under stirring, then 1-10 g of chitosan is added, reaction is carried out for 2-6 h under the condition of stirring at room temperature, and then filtration, washing and drying are carried out to obtain the modified porous calcium silicate.
Further, the modified porous calcium silicate contains hydroxyl groups and amino groups.
Further, the heat stabilizer includes at least one of calcium stearate, zinc stearate, and magnesium stearate.
Further, the promoter comprises at least one of monobutyl tin oxide, dibutyl tin oxide, tributyl tin chloride and butyl tin trichloride.
Further, the antioxidant comprises at least one of antioxidant DNP, antioxidant 1010 and antioxidant CA.
Further, the lubricant includes at least one of silicone oil, stearic acid, and paraffin wax.
After the technical scheme is adopted, the ASA/PC3D printing wire with low VOC release has the following beneficial effects:
(1) according to the invention, the modified porous calcium silicate, the accelerator and the heat stabilizer are added to promote the modified porous calcium silicate to act with ASA/PC molecular chains or act between ASA and PC molecular chains, so that the thermal stability of the ASA/PC molecular chains is improved, the thermal degradation behavior of the material is inhibited, and the VOC release source is reduced. Through experimental tests, the wire forming process of the invention has low VOC (VOC value is lower than 32 mu g/m)3Basically maintained at 22-32 μ g/m3)；
(2) The irritant gas is effectively reacted or adsorbed by the modified porous calcium silicate, and volatilization is reduced, so that the problem of irritant odor generated in the 3D printing and forming process is solved. Through experimental tests, the 3D printing wire rod has good smell in the forming process. The modified ASA/PC material has high thermal stability, and the release amount of synchronously generated irritant gas is reduced;
(3) through experimental tests, the 3D printing wire rod disclosed by the invention has good forming performance and mechanical property. The modified ASA/PC material has proper melt flow rate and lower thermal expansion coefficient, i.e. the material has smooth printing performance and dimensional stability. In addition, after the modified porous calcium silicate and the accelerant are added, the mechanical property of the material is effectively improved due to the reinforcing effect of the modified porous calcium silicate and the promoting effect of the accelerant on ester exchange.
Furthermore, the modified porous calcium silicate is rich in active sites such as hydroxyl, amino and the like, has excellent adsorption performance, and can efficiently react or adsorb generated VOC under the catalysis of the accelerator, so that the VOC is fixed to reduce escape, and the release amount of the VOC in the forming process is reduced.
A preparation method of an ASA/PC3D printing wire with low VOC (volatile organic compound) release comprises the following steps:
step 1: preparation of modified porous calcium silicate: putting 20-50 g of porous calcium silicate into 1L of deionized water, performing ultrasonic dispersion for 0.5-2 h, adding 5-20 ml of acetic acid under stirring, then adding 1-10 g of chitosan, reacting for 2-6 h under the condition of stirring at room temperature, filtering, washing to be neutral, and drying to obtain modified porous calcium silicate;
step 2: respectively vacuum-drying ASA resin, PC resin, modified porous calcium silicate, an accelerant, a heat stabilizer and an antioxidant, and weighing the dried components in percentage by weight as follows: 50-70% of ASA resin, 20-30% of PC resin, 5-15% of modified porous calcium silicate, 0.2-2% of accelerator, 0.2-2% of heat stabilizer, 0.2-1% of antioxidant and 0.2-2% of lubricant, then uniformly mixing the weighed components to obtain a mixture, and carrying out melt extrusion and molding on the mixture through a double-screw extruder to obtain blended particles, wherein the temperature of a charging barrel is 180-240 ℃, and the rotating speed of a screw is 80-200 rpm;
and step 3: and (3) extruding and shaping the blended particles prepared in the step (2) through a wire machine, drawing and rolling to obtain the 3D printing wire, wherein the temperature of a charging barrel is 180-240 ℃, and the rotating speed of a screw is 20-100 rpm.
Further, the heat stabilizer includes at least one of calcium stearate, zinc stearate, and magnesium stearate.
Further, the promoter comprises at least one of monobutyl tin oxide, dibutyl tin oxide, tributyl tin chloride and butyl tin trichloride.
After the technical scheme is adopted, the preparation method of the ASA/PC3D printing wire with low VOC release, disclosed by the invention, has the following beneficial effects:
(1) according to the invention, the modified porous calcium silicate, the accelerator and the heat stabilizer are added to promote the modified porous calcium silicate to act with ASA/PC molecular chains or act between ASA and PC molecular chains, so that the thermal stability of the ASA/PC molecular chains is improved, the thermal degradation behavior of the material is inhibited, and the VOC release source is reduced. Through experimental tests, the wire forming process of the invention has low VOC (VOC value is lower than 32 mu g/m)3Basically maintained at 22-32 μ g/m3)；
(2) The modified porous calcium silicate is rich in active sites such as hydroxyl, amino and the like, has excellent adsorption performance, and can efficiently react or adsorb generated VOC (volatile organic compounds) under the catalysis of the accelerator, so that the VOC is fixed and escaped outwards, and the release amount of the VOC in the forming process is reduced.
(3) The irritant gas is effectively reacted or adsorbed by the modified porous calcium silicate, and volatilization is reduced, so that the problem of irritant odor generated in the 3D printing and forming process is solved. Through experimental tests, the 3D printing wire rod has good smell in the forming process. The modified ASA/PC material has high thermal stability, and the release amount of synchronously generated irritant gas is reduced;
(4) through experimental tests, the 3D printing wire rod disclosed by the invention has good forming performance and mechanical property. The modified ASA/PC material has proper melt flow rate and lower thermal expansion coefficient, i.e. the material has smooth printing performance and dimensional stability. In addition, after the modified porous calcium silicate and the accelerant are added, the mechanical property of the material is effectively improved due to the reinforcing effect of the modified porous calcium silicate and the promoting effect of the accelerant on ester exchange.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
The ASA/PC3D printing wire with low VOC release comprises the following components in percentage by weight: 50% of ASA, 30% of PC, 15% of modified porous calcium silicate, 0.5% of monobutyl tin oxide, 2% of zinc stearate, 0.5% of antioxidant 1010{ tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester } and 2% of paraffin.
A preparation method of an ASA/PC3D printing wire with low VOC (volatile organic compound) release comprises the following steps:
(1) the preparation method of the modified porous calcium silicate comprises the following steps:
A. putting 25g of porous calcium silicate into 1L of deionized water, performing ultrasonic dispersion for 1h, and adding 8ml of acetic acid under stirring;
B. then 2g of chitosan is added, the reaction is carried out for 2h under the condition of stirring at room temperature, and then the mixture is filtered, washed to be neutral and dried to obtain the modified porous calcium silicate.
(2) Respectively vacuum-drying ASA, PC, modified porous calcium silicate, monobutyl tin oxide, zinc stearate and an antioxidant 1010, accurately weighing the dried components and paraffin according to the weight percentage, then uniformly mixing the weighed components in a high-speed mixer to obtain a mixture, and melting and extruding the mixture by a double-screw extruder to obtain blended particles, wherein the charging barrel temperature is 180, 195, 220, 235, 240 and 235 ℃, and the screw rotation speed is 100 rpm.
(3) And (3) carrying out extrusion molding, traction and winding on the blended particles prepared in the step (2) through a wire machine to obtain a 3D printing wire, wherein the temperature of a charging barrel is 180, 198, 220, 236, 240 and 236 ℃, and the rotating speed of a screw is 40 rpm.
Further, 3D printing molding is carried out on the 3D printing wire rod obtained in the step (3), the VOC release amount (DB 35/1784-.
Compared with the prior art, the invention has the beneficial effects that:
(1) the molding process has low VOC emission. On one hand, the modified porous calcium silicate, the accelerator and the heat stabilizer are added to promote the modified porous calcium silicate to act with ASA/PC molecular chains or act between ASA and PC molecular chains, so that the heat stability of the ASA/PC molecular chains is improved, the thermal degradation behavior of the material is inhibited, and the VOC release source is reduced; on the other hand, the modified porous calcium silicate is rich in active sites such as hydroxyl, amino and the like, has excellent adsorption performance, and can efficiently react or adsorb generated VOC (volatile organic compounds) under the catalysis of the accelerator, so that the generated VOC can be fixed to reduce escape, and the release amount of the VOC in the forming process is reduced.
(2) The smell is good in the molding process. The modified ASA/PC material has high thermal stability, and the release amount of synchronously generated irritant gas is reduced; meanwhile, the irritant gas is effectively reacted or adsorbed by the modified porous calcium silicate, and volatilization is reduced, so that the problem of irritant odor generated in the 3D printing and forming process is solved.
(3) Good forming performance and mechanical property. The modified ASA/PC material has proper melt flow rate and lower thermal expansion coefficient, i.e. the material has smooth printing performance and dimensional stability. In addition, after the modified porous calcium silicate and the accelerant are added, the mechanical property of the material is effectively improved due to the reinforcing effect of the modified porous calcium silicate and the promoting effect of the accelerant on ester exchange.
Example 2
The ASA/PC3D printing wire with low VOC release comprises the following components in percentage by weight: ASA 53%, PC 28%, modified porous calcium silicate 14%, tributyltin chloride 0.3%, calcium stearate 2%, antioxidant CA [1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane ] 0.7% and silicone oil 2%.
A preparation method of an ASA/PC3D printing wire with low VOC (volatile organic compound) release comprises the following steps:
(1) the preparation method of the modified porous calcium silicate comprises the following steps:
A. putting 35g of porous calcium silicate into 1L of deionized water, performing ultrasonic dispersion for 0.5h, and adding 10ml of acetic acid under stirring;
B. then 5g of chitosan was added, reacted for 3 hours at room temperature with stirring, and then filtered, washed to neutrality and dried to obtain modified porous calcium silicate.
(2) Respectively vacuum-drying ASA, PC, modified porous calcium silicate, tributyltin chloride, calcium stearate and an antioxidant CA, accurately weighing the dried components and silicone oil according to the weight percentage ratio, then uniformly mixing the weighed components in a high-speed mixer to obtain a mixture, and melting and extruding the mixture by a double-screw extruder to obtain blended particles, wherein the charging barrel temperature is 182, 195, 218, 235, 240 and 237 ℃, and the screw rotation speed is 120 rpm.
(3) And (3) carrying out extrusion molding and traction winding on the blended particles prepared in the step (2) through a wire machine to obtain a 3D printing wire, wherein the temperature of a charging barrel is 180 ℃, 200 ℃, 218 ℃, 238 ℃, 240 ℃ and 235 ℃, and the rotating speed of a screw is 65 rpm.
Further, 3D printing molding is carried out on the 3D printing wire rod obtained in the step (3), the VOC release amount (DB 35/1784-.
Example 3
The ASA/PC3D printing wire with low VOC release comprises the following components in percentage by weight: ASA 63%, PC 21%, modified porous calcium silicate 12%, butyltin trichloride 0.6%, magnesium stearate 1.3%, antioxidant DNP [ N, N' -di (beta-naphthyl) p-phenylenediamine) ] 0.6% and stearic acid 1.5%.
A preparation method of an ASA/PC3D printing wire with low VOC (volatile organic compound) release comprises the following steps:
(1) the preparation method of the modified porous calcium silicate comprises the following steps:
A. putting 20g of porous calcium silicate into 1L of deionized water, performing ultrasonic dispersion for 2 hours, and adding 5ml of acetic acid under stirring;
B. then 1.5g of chitosan was added, reacted for 2 hours at room temperature with stirring, and then filtered, washed to neutrality and dried to obtain modified porous calcium silicate.
(2) Respectively vacuum-drying ASA, PC, modified porous calcium silicate, butyltin trichloride, magnesium stearate and antioxidant DNP, accurately weighing the dried components and stearic acid according to the weight percentage, then uniformly mixing the weighed components in a high-speed mixer to obtain a mixture, and melting and extruding the mixture by a double-screw extruder to obtain blended particles, wherein the charging barrel temperature is 180, 195, 219, 234, 240 and 236 ℃, and the screw rotation speed is 80 rpm.
(3) And (3) carrying out extrusion molding and traction winding on the blended particles prepared in the step (2) through a wire machine to obtain a 3D printing wire, wherein the temperature of a charging barrel is 180, 200, 215, 235, 240 and 235 ℃, and the rotating speed of a screw is 65 rpm.
Further, 3D printing molding is carried out on the 3D printing wire rod obtained in the step (3), the VOC release amount (DB 35/1784-.
Example 4
The ASA/PC3D printing wire with low VOC release comprises the following components in percentage by weight: ASA 65%, PC 20%, modified porous calcium silicate 11%, monobutyl tin oxide 0.5%, magnesium stearate 1.8%, antioxidant 10100.3% and stearic acid 1.4%.
A preparation method of an ASA/PC3D printing wire with low VOC (volatile organic compound) release comprises the following steps:
(1) the preparation method of the modified porous calcium silicate comprises the following steps:
A. 50g of porous calcium silicate is put into 1L of deionized water for ultrasonic dispersion for 2 hours, and 15ml of acetic acid is added under stirring;
B. then 10g of chitosan was added, reacted for 6 hours at room temperature with stirring, and then filtered, washed to neutrality and dried to obtain modified porous calcium silicate.
(2) Respectively vacuum-drying ASA, PC, modified porous calcium silicate, monobutyl tin oxide, magnesium stearate and an antioxidant 1010, accurately weighing the dried components and stearic acid according to the weight percentage, then uniformly mixing the weighed components in a high-speed mixer to obtain a mixture, and carrying out melt extrusion and material manufacturing on the mixture through a double-screw extruder to obtain blended particles, wherein the charging barrel temperature is 180, 195, 220, 235, 240 and 235 ℃, and the screw rotation speed is 150 rpm.
(3) And (3) carrying out extrusion molding, traction and winding on the blended particles prepared in the step (2) through a wire machine to obtain a 3D printing wire, wherein the temperature of a charging barrel is 180, 198, 216, 238, 240 and 236 ℃, and the rotating speed of a screw is 80 rpm.
Further, 3D printing molding is carried out on the 3D printing wire rod obtained in the step (3), the VOC release amount (DB 35/1784-.
Example 5
The ASA/PC3D printing wire with low VOC release comprises the following components in percentage by weight: 70% of ASA, 20% of PC, 7% of modified porous calcium silicate, 0.2% of dibutyltin oxide, 1.5% of zinc stearate, 0.3% of antioxidant CA and 1% of silicone oil.
A preparation method of an ASA/PC3D printing wire with low VOC (volatile organic compound) release comprises the following steps:
(1) the preparation method of the modified porous calcium silicate comprises the following steps:
A. 30g of porous calcium silicate is put into 1L of deionized water for ultrasonic dispersion for 1.5h, and 10ml of acetic acid is added under stirring;
B. then 8g of chitosan was added, reacted for 4 hours at room temperature with stirring, and then filtered, washed to neutrality and dried to obtain modified porous calcium silicate.
(2) Respectively vacuum-drying ASA, PC, modified porous calcium silicate, dibutyltin oxide, zinc stearate and an antioxidant CA, accurately weighing the dried components and silicone oil according to the weight percentage, then uniformly mixing the weighed components in a high-speed mixer to obtain a mixture, and melting and extruding the mixture by a double-screw extruder to obtain blended particles, wherein the charging barrel temperature is 180, 196, 220, 235, 240 and 235 ℃, and the screw rotation speed is 90 rpm.
(3) And (3) carrying out extrusion molding and traction winding on the blended particles prepared in the step (2) through a wire machine to obtain a 3D printing wire, wherein the temperature of a charging barrel is 180, 200, 215, 236, 240 and 235 ℃, and the rotating speed of a screw is 35 rpm.
Further, 3D printing molding is carried out on the 3D printing wire rod obtained in the step (3), the VOC release amount (DB 35/1784-.
Comparative example 1
According to the formula composition of the embodiment 1, the modified porous calcium silicate is not added, a 3D printing wire is prepared through melt extrusion and shaping traction, the wire is subjected to 3D printing molding, the VOC release amount (DB 35/1784-.
Comparative example 2
According to the formula composition of the embodiment 1, modified porous calcium silicate is replaced with porous calcium silicate in equal amount (before modification of the invention), a 3D printing wire is prepared through melt extrusion and shaping traction, the wire is subjected to 3D printing and molding, the VOC release amount (DB 35/1784-.
Comparative example 3
According to the formula composition of the embodiment 1, monobutyl tin oxide is not added, a 3D printing wire rod is prepared through melt extrusion and shaping traction, the wire rod is subjected to 3D printing molding, the VOC release amount (DB 35/1784-.
TABLE 1 test results of Material Properties
Remarking: the odor grade is divided into three grades of stimulation, partial stimulation and no stimulation.
From the above table, it can be seen that: after the modified porous calcium silicate is added, the VOC release value of the material is obviously reduced, and the odor grade in the material forming process is obviously improved. Meanwhile, the thermal expansion coefficient of the material is obviously reduced, and the thermal stability and the dimensional stability of the material are effectively improved. In addition, the tensile strength and impact strength of the material are improved and the melt flow rate is maintained at a suitable level.
The above examples are not intended to limit the composition and preparation of the present invention, and any suitable changes or modifications made by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (10)
1. The utility model provides a low VOC releases's ASA/PC3D prints wire rod which characterized in that: the heat stabilizer comprises, by weight, 50-70% of ASA resin, 20-30% of PC resin, 5-15% of modified porous calcium silicate, 0.2-2% of an accelerator, 0.2-2% of a heat stabilizer, 0.2-1% of an antioxidant and 0.2-2% of a lubricant.
2. The low VOC emitting ASA/PC3D printing wire of claim 1, wherein the modified porous calcium silicate is prepared by the following method: firstly, 20-50 g of porous calcium silicate is placed into 1L of deionized water for ultrasonic dispersion for 0.5-2 h, 5-20 ml of acetic acid is added under stirring, then 1-10 g of chitosan is added, reaction is carried out for 2-6 h under the condition of stirring at room temperature, and then filtration, washing and drying are carried out to obtain the modified porous calcium silicate.
3. A low VOC emission ASA/PC3D printing wire as claimed in claim 1 or 2 wherein: the modified porous calcium silicate contains hydroxyl and amino groups.
4. The low VOC emission ASA/PC3D printing wire of claim 1, wherein: the heat stabilizer comprises at least one of calcium stearate, zinc stearate and magnesium stearate.
5. The low VOC emission ASA/PC3D printing wire of claim 1, wherein: the accelerant comprises at least one of monobutyl tin oxide, dibutyl tin oxide, tributyl tin chloride and butyl tin trichloride.
6. The low VOC emission ASA/PC3D printing wire of claim 1, wherein: the antioxidant comprises at least one of antioxidant DNP, antioxidant 1010 and antioxidant CA.
7. The low VOC emission ASA/PC3D printing wire of claim 1, wherein: the lubricant includes at least one of silicone oil, stearic acid, and paraffin wax.
8. A preparation method of an ASA/PC3D printing wire with low VOC release is characterized by comprising the following steps:
step 1: preparation of modified porous calcium silicate: putting 20-50 g of porous calcium silicate into 1L of deionized water, performing ultrasonic dispersion for 0.5-2 h, adding 5-20 ml of acetic acid under stirring, then adding 1-10 g of chitosan, reacting for 2-6 h under the condition of stirring at room temperature, filtering, washing to be neutral, and drying to obtain modified porous calcium silicate;
step 2: respectively vacuum-drying ASA resin, PC resin, modified porous calcium silicate, an accelerant, a heat stabilizer and an antioxidant, and weighing the dried components in percentage by weight as follows: 50-70% of ASA resin, 20-30% of PC resin, 5-15% of modified porous calcium silicate, 0.2-2% of accelerator, 0.2-2% of heat stabilizer, 0.2-1% of antioxidant and 0.2-2% of lubricant, then uniformly mixing the weighed components to obtain a mixture, and carrying out melt extrusion and molding on the mixture through a double-screw extruder to obtain blended particles, wherein the temperature of a charging barrel is 180-240 ℃, and the rotating speed of a screw is 80-200 rpm;
and step 3: and (3) extruding and shaping the blended particles prepared in the step (2) through a wire machine, drawing and rolling to obtain the 3D printing wire, wherein the temperature of a charging barrel is 180-240 ℃, and the rotating speed of a screw is 20-100 rpm.
9. The method of claim 8, wherein the ASA/PC3D printing wire with low VOC emission comprises: the heat stabilizer comprises at least one of calcium stearate, zinc stearate and magnesium stearate.
10. The method of claim 8, wherein the ASA/PC3D printing wire with low VOC emission comprises: the accelerant comprises at least one of monobutyl tin oxide, dibutyl tin oxide, tributyl tin chloride and butyl tin trichloride.
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