CN108299753B - 3D printing polystyrene resin and preparation method thereof - Google Patents
3D printing polystyrene resin 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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a 3D printing polystyrene resin and a preparation method thereof, wherein the styrene resin is polymerized by a bulk method, styrene, acrylic ester, a chain transfer agent and a solvent are added, and the styrene resin and the acrylic ester are polymerized by the bulk method at a certain temperature through an initiator to obtain a product, wherein raw material monomers comprise 50-95 parts of styrene, 5-50 parts of acrylic ester and 5-15 parts of solvent; 0.1-1 part of initiator; and the chain transfer agent is 0.1-3 parts. The 3D printing polystyrene resin disclosed by the invention is prepared by polymerizing through a bulk method, has the characteristics of simple post-treatment, pure product, adjustable molecular weight, simplicity in operation and wide application prospect, and cannot block a spray head of a 3D printer.
Description
The technical field is as follows:
the invention belongs to the field of high polymer materials, and particularly relates to 3D printing polystyrene resin prepared by a bulk method.
Technical background:
3D printing has experienced recent 30 years of development since the first 3D printer in the eighties of the last century became available, and has gradually become one of the most viable advanced manufacturing technologies. 3D printing is also known as additive manufacturing technology, and the general principle is a manufacturing technology that produces a three-dimensional solid from bondable materials such as powdered metals and polymeric materials by layer-by-layer printing based on digital models. At present, the 3D printing technology is widely applied to the fields of bioengineering, medicine, aerospace, construction, automobile, mold manufacturing, art manufacturing and the like.
Different 3D printing technologies have different requirements on forming materials, but the forming materials are all favorable for quick and accurate forming of printing, and the performance of the forming materials determines whether the quick printing technology is successful or not. The polymer material for 3D printing is heated to a temperature higher than the melting temperature in the printing process in an electric heating mode, and the molten material is coated on the workbench under the control of a computer and stacked layer by layer to form a three-dimensional workpiece. The polymer 3D printing material should have the basic conditions of high mechanical strength, low shrinkage rate, proper melting temperature and the like. The high polymer material used for 3D printing in the market at present needs to maintain a high printing temperature, which is usually higher than 200 ℃ in the processing process, so that the universality of material use is limited, and ash in the high polymer material can volatilize at high temperature to influence the health of people.
If the material can realize realizing 3D processing under the lower temperature, will increase the material and print the in-process fail safe nature at 3D to can realize that the material uses on more 3D printers, change the popularization of popularization material. If the selected product is pure, no toxic auxiliary agent volatilizes in the printing process, the damage and pollution to human bodies and the environment are reduced, and the printing ink is more suitable for being popularized and used in office and family environments.
The invention content is as follows:
in order to solve the defects of the existing materials, the invention aims to provide a novel 3D printing polystyrene resin material and a preparation method thereof, the 3D printing polystyrene material adopts bulk polymerization, the novel 3D printing polystyrene resin product produced by the method is pure, has good mechanical property and high adhesion, and when the novel 3D printing polystyrene resin is used for 3D printing, no toxic substances volatilize in the printing process, and the printed product has high precision, high adhesion strength and good mechanical property. The specific technical scheme is as follows:
50-95 parts of styrene; 5-50 parts of acrylate, 5-15 parts of solvent, 0.1-1 part of initiator and 0.1-3 parts of chain transfer agent.
The acrylate is at least one of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate or isooctyl acrylate.
The initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide and peroxydicarbonate.
The chain transfer agent is at least one of n-dodecyl mercaptan or isooctyl 3-mercaptopropionate.
The solvent is at least one of toluene or ethylbenzene.
The preparation method comprises the following steps:
uniformly mixing and stirring styrene, acrylate, an initiator, a chain transfer agent and a solvent in proportion, adding 20-40% of raw material liquid into a four-neck flask, adding the rest 60-80% of raw material liquid into a dropping funnel, vacuumizing, continuously introducing nitrogen, starting stirring at the stirring speed of 200 plus 400r/min, keeping the oil bath temperature at 80 ℃, dropwise adding the rest raw material liquid after reacting for 30 minutes, and completing dropwise adding within 2-6 hours. And (3) reacting for 1-4 hours after the dropwise adding is finished, stopping the reaction, cooling to room temperature, adding N-N' dimethylformamide for dissolving, pouring into a methanol or ethanol aqueous solution with the ratio of 1:1 to separate out a product, and performing suction filtration and vacuum drying on the product to obtain the 3D printing material.
The invention adopts bulk polymerization, adjusts the glass transition temperature of the resin by changing the proportion of styrene and acrylate, and adjusts the molecular weight and the distribution of the resin by the proportion of an initiator and a chain transfer agent.
The invention has the beneficial effects that:
according to the 3D printing polystyrene resin material and the preparation method thereof, the bulk polymerization is adopted, the glass transition temperature of the resin is adjusted by changing the ratio of styrene to acrylate, products with different molecular weights and molecular weight distributions can be obtained by adjusting the ratio of the initiator to the chain transfer agent, and the industrial production of the products can be realized by selecting a reaction type polymerization device.
The 3D printing polystyrene resin product prepared by the invention is pure, has good mechanical property and high bonding strength, is used for 3D printing, has no volatilization of toxic and harmful substances in the printing process, and has high precision, high bonding strength and good mechanical property.
The thermoplastic polystyrene resin product prepared by the invention can be subjected to 3D printing and forming by a selective laser sintering method after being prepared into powder.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
Weighing 62 parts of styrene, 38 parts of methyl acrylate, 0.25 part of benzoyl peroxide, 0.5 part of isooctyl 3-mercaptopropionate and 10 parts of toluene, uniformly stirring and mixing, adding 30% of raw material liquid into a four-neck flask, adding the rest 70% of raw material liquid into a dropping funnel, continuously introducing nitrogen after vacuumizing, starting stirring, keeping the oil bath temperature at 80 ℃ at the stirring speed of 300 revolutions per minute, dropwise adding the rest raw material liquid after reacting for 30 minutes, and completing dropwise adding within 4 hours. And reacting for 4 hours after the dropwise addition is finished, stopping the reaction, cooling to room temperature, adding N-N' dimethylformamide for dissolving, pouring into a methanol aqueous solution with the ratio of 1:1 to separate out a product, performing suction filtration, and performing vacuum drying to obtain the product.
The obtained product was characterized as shown in Table 1
| Tensile strength/MPa | 38.1 |
| Elongation at break/% | 6.22 |
| Impact Strength/kJ/m2 | 5.32 |
| Mn | 314055 |
| Mw/Mn | 1.494 |
| Glass transition temperature/. degree.C | 58.8 |
Example 2
Weighing 75 parts of styrene, 25 parts of ethyl acrylate, 0.25 part of benzoyl peroxide, 0.5 part of isooctyl 3-mercaptopropionate and 10 parts of toluene, uniformly stirring and mixing, adding 30% of raw material liquid into a four-neck flask, adding the rest 70% of raw material liquid into a dropping funnel, continuously introducing nitrogen after vacuumizing, starting stirring, keeping the oil bath temperature at 80 ℃ at the stirring speed of 300 revolutions per minute, reacting for 30 minutes, dropwise adding the rest raw material liquid, and completing dropwise adding within 4 hours. And reacting for 4 hours after the dropwise addition is finished, stopping the reaction, cooling to room temperature, adding N-N' dimethylformamide for dissolving, pouring into a methanol aqueous solution with the ratio of 1:1 to separate out a product, performing suction filtration, and performing vacuum drying to obtain the product.
The obtained product was characterized as shown in Table 2
| Tensile strength/MPa | 40.2 |
| Elongation at break/% | 6.35 |
| Impact Strength/kJ/m2 | 4.99 |
| Mn | 373460 |
| Mw/Mn | 1.532 |
| Glass transition temperature/. degree.C | 57.8 |
Example 3
Weighing 83.3 parts of styrene, 16.7 parts of n-butyl acrylate, 0.3 part of dicumyl peroxide, 0.6 part of isooctyl 3-mercaptopropionate and 7 parts of ethylbenzene, uniformly stirring and mixing, adding 30% of raw material liquid into a four-neck flask, adding the rest 70% of raw material liquid into a dropping funnel, continuously introducing nitrogen after vacuumizing, starting stirring, keeping the stirring speed at 300 revolutions per minute, keeping the oil bath temperature at 80 ℃, dropwise adding the rest raw material liquid after reacting for 30 minutes, and completing dropwise adding within 4 hours. And reacting for 4 hours after the dropwise addition is finished, stopping the reaction, cooling to room temperature, adding N-N' dimethylformamide for dissolving, pouring into a methanol aqueous solution with the ratio of 1:1 to separate out a product, performing suction filtration, and performing vacuum drying to obtain the product.
The obtained product was characterized as shown in Table 3
| Tensile strength/MPa | 42.1 |
| Elongation at break/% | 6.12 |
| Impact Strength/kJ/m2 | 5.45 |
| Mn | 332316 |
| Mw/Mn | 1.44 |
| Glass transition temperature/. degree.C | 58.5 |
Example 4
Weighing 85.5 parts of styrene, 14.5 parts of isooctyl acrylate, 0.3 part of azodiisobutyronitrile, 0.6 part of isooctyl 3-mercaptopropionate and 7 parts of ethylbenzene, uniformly stirring and mixing, adding 30% of raw material liquid into a four-neck flask, adding the rest 70% of raw material liquid into a dropping funnel, continuously introducing nitrogen after vacuumizing, starting stirring, keeping the oil bath temperature at 80 ℃, dropwise adding the rest raw material liquid after reacting for 30 minutes, and completing dropwise adding within 4 hours. And reacting for 4 hours after the dropwise addition is finished, stopping the reaction, cooling to room temperature, adding N-N' dimethylformamide for dissolving, pouring into a methanol aqueous solution with the ratio of 1:1 to separate out a product, performing suction filtration, and performing vacuum drying to obtain the product.
The obtained product was characterized as shown in Table 4
| Tensile strength/MPa | 40.41 |
| Elongation at break/% | 7.41 |
| Impact Strength/kJ/m2 | 5.22 |
| Mn | 345683 |
| Mw/Mn | 1.522 |
| Glass transition temperature/. degree.C | 57.7 |
Example 5
Weighing 73 parts of styrene, 27 parts of n-octyl acrylate, 0.3 part of azodiisobutyronitrile, 0.6 part of isooctyl 3-mercaptopropionate and 7 parts of ethylbenzene, uniformly stirring and mixing, adding 30% of raw material liquid into a four-neck flask, adding the rest 70% of raw material liquid into a dropping funnel, continuously introducing nitrogen after vacuumizing, starting stirring, keeping the oil bath temperature at 80 ℃ at the stirring speed of 300 revolutions per minute, dropwise adding the rest raw material liquid after reacting for 30 minutes, and completing dropwise adding within 4 hours. And reacting for 4 hours after the dropwise addition is finished, stopping the reaction, cooling to room temperature, adding N-N' dimethylformamide for dissolving, pouring into a methanol aqueous solution with the ratio of 1:1 to separate out a product, performing suction filtration, and performing vacuum drying to obtain the product.
The obtained product was characterized as shown in Table 5
| Tensile strength/MPa | 40.11 |
| Elongation at break/% | 7.01 |
| Impact Strength/kJ/m2 | 5.19 |
| Mn | 362328 |
| Mw/Mn | 1.632 |
| Glass transition temperature/. degree.C | 59.9 |
Comparative example 1
Weighing 82.4 parts of styrene, 17.6 parts of methyl acrylate, 0.5 part of benzoyl peroxide, 0.5 part of isooctyl 3-mercaptopropionate and 10 parts of toluene, uniformly stirring and mixing, adding 30% of raw material liquid into a four-neck flask, adding the rest 70% of raw material liquid into a dropping funnel, continuously introducing nitrogen after vacuumizing, starting stirring, keeping the oil bath temperature at 80 ℃, dropwise adding the rest raw material liquid after reacting for 30 minutes, and completing dropwise adding within 2 hours. And reacting for 2 hours after the dropwise addition is finished, stopping the reaction, cooling to room temperature, adding N-N' dimethylformamide for dissolution, pouring into a methanol aqueous solution with the ratio of 1:1 to separate out a product, performing suction filtration, and performing vacuum drying to obtain the product.
The obtained product was characterized as shown in Table 6
Comparative example 2
Weighing 88.3 parts of styrene, 11.7 parts of ethyl acrylate, 0.5 part of benzoyl peroxide, 0.5 part of isooctyl 3-mercaptopropionate and 10 parts of toluene, uniformly stirring and mixing, adding 30% of raw material liquid into a four-neck flask, adding the rest 70% of raw material liquid into a dropping funnel, continuously introducing nitrogen after vacuumizing, starting stirring, keeping the oil bath temperature at 80 ℃, dropwise adding the rest raw material liquid after reacting for 30 minutes, and completing dropwise adding within 2 hours. And reacting for 2 hours after the dropwise addition is finished, stopping the reaction, cooling to room temperature, adding N-N' dimethylformamide for dissolution, pouring into a methanol aqueous solution with the ratio of 1:1 to separate out a product, performing suction filtration, and performing vacuum drying to obtain the product.
The obtained product was characterized as shown in Table 7
| Tensile strength/MPa | 33.23 |
| Elongation at break/% | 6.53 |
| Impact Strength/kJ/m2 | 4.31 |
| Mn | 253255 |
| Mw/Mn | 1.602 |
| Glass transition temperature/. degree.C | 77.8 |
Comparative example 3
Weighing 92.1 parts of styrene, 7.9 parts of n-butyl acrylate, 0.5 part of dicumyl peroxide, 0.6 part of 3-isooctyl mercaptopropionate and 7 parts of ethylbenzene, uniformly stirring and mixing, adding 30% of raw material liquid into a four-neck flask, adding the rest 70% of raw material liquid into a dropping funnel, continuously introducing nitrogen after vacuumizing, starting stirring, keeping the stirring speed at 400 revolutions per minute, keeping the oil bath temperature at 80 ℃, dropwise adding the rest raw material liquid after reacting for 30 minutes, and completing dropwise adding within 2 hours. And reacting for 2 hours after the dropwise addition is finished, stopping the reaction, cooling to room temperature, adding N-N' dimethylformamide for dissolution, pouring into a methanol aqueous solution with the ratio of 1:1 to separate out a product, performing suction filtration, and performing vacuum drying to obtain the product.
The obtained product was characterized as shown in Table 8
| Tensile strength/MPa | 37.99 |
| Elongation at break/% | 5.55 |
| Impact Strength/kJ/m2 | 5.67 |
| Mn | 245218 |
| Mw/Mn | 1.492 |
| Glass transition temperature/. degree.C | 79.2 |
Comparative example 4
Weighing 93.2 parts of styrene, 6.8 parts of isooctyl acrylate, 0.5 part of azodiisobutyronitrile, 1 part of isooctyl 3-mercaptopropionate and 10 parts of ethylbenzene, uniformly stirring and mixing, adding 30% of raw material liquid into a four-neck flask, adding the rest 70% of raw material liquid into a dropping funnel, continuously introducing nitrogen after vacuumizing, starting stirring, keeping the oil bath temperature at 80 ℃, dropwise adding the rest raw material liquid after reacting for 30 minutes, and completing dropwise adding within 2 hours. And reacting for 2 hours after the dropwise addition is finished, stopping the reaction, cooling to room temperature, adding N-N' dimethylformamide for dissolution, pouring into a methanol aqueous solution with the ratio of 1:1 to separate out a product, performing suction filtration, and performing vacuum drying to obtain the product.
The obtained product was characterized as shown in Table 9
Comparative example 5
Weighing 87.3 parts of styrene, 12.7 parts of n-octyl acrylate, 0.5 part of azodiisobutyronitrile, 0.6 part of isooctyl 3-mercaptopropionate and 10 parts of ethylbenzene, uniformly stirring and mixing, adding 30% of raw material liquid into a four-neck flask, adding the rest 70% of raw material liquid into a dropping funnel, continuously introducing nitrogen after vacuumizing, starting stirring, keeping the stirring speed at 300 revolutions per minute, keeping the oil bath temperature at 80 ℃, dropwise adding the rest raw material liquid after reacting for 30 minutes, and completing dropwise adding within 2 hours. And reacting for 2 hours after the dropwise addition is finished, stopping the reaction, cooling to room temperature, adding N-N' dimethylformamide for dissolution, pouring into a methanol aqueous solution with the ratio of 1:1 to separate out a product, performing suction filtration, and performing vacuum drying to obtain the product.
The obtained product was characterized as shown in Table 10
| Tensile strength/MPa | 32.1 |
| Elongation at break/% | 6.55 |
| Impact Strength/kJ/m2 | 4.85 |
| Mn | 313298 |
| Mw/Mn | 1.544 |
| Glass transition temperature/. degree.C | 78.7 |
Claims (2)
1. A3D printing polystyrene resin material is characterized in that the 3D printing polystyrene resin material is prepared by the following method: weighing 83.3 parts of styrene, 16.7 parts of N-butyl acrylate, 0.3 part of dicumyl peroxide, 0.6 part of isooctyl 3-mercaptopropionate and 7 parts of ethylbenzene, uniformly stirring and mixing to obtain a raw material solution, adding 30% of the raw material solution into a four-neck flask, adding the rest 70% of the raw material solution into a dropping funnel, vacuumizing, continuously introducing nitrogen, starting stirring at a stirring speed of 300 revolutions per minute, keeping the oil bath temperature at 80 ℃, dropwise adding the rest raw material solution after reacting for 30 minutes, completing dropwise adding after 4 hours, reacting for 4 hours, stopping the reaction, cooling to room temperature, adding N, N' -dimethylformamide for dissolving, pouring into a methanol aqueous solution with a ratio of 1:1 to separate out a product, performing suction filtration, and performing vacuum drying to obtain the 3D printing polystyrene resin material.
2. The preparation method of the 3D printing polystyrene resin according to claim 1, which is characterized by comprising the following steps: weighing 83.3 parts of styrene, 16.7 parts of N-butyl acrylate, 0.3 part of dicumyl peroxide, 0.6 part of isooctyl 3-mercaptopropionate and 7 parts of ethylbenzene, uniformly stirring and mixing to obtain a raw material solution, adding 30% of the raw material solution into a four-neck flask, adding the rest 70% of the raw material solution into a dropping funnel, vacuumizing, continuously introducing nitrogen, starting stirring at a stirring speed of 300 revolutions per minute, keeping the oil bath temperature at 80 ℃, dropwise adding the rest raw material solution after reacting for 30 minutes, completing dropwise adding after 4 hours, reacting for 4 hours, stopping the reaction, cooling to room temperature, adding N, N' -dimethylformamide for dissolving, pouring into a methanol aqueous solution with a ratio of 1:1 to separate out a product, performing suction filtration, and performing vacuum drying to obtain the 3D printing polystyrene resin material.
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| WO2003095499A1 (en) * | 2002-05-10 | 2003-11-20 | Ps Japan Corporation | Styrene polymer resin and composition thereof |
| US10246540B2 (en) * | 2015-09-29 | 2019-04-02 | Ada Foundation | Rapid azeotropic photo-copolymerization of styrene and methacrylate derivatives and uses thereof |
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