CN108543908B - Curing agent for 3D sand mold printing furan resin and preparation method thereof - Google Patents
Curing agent for 3D sand mold printing furan resin and preparation method thereof Download PDFInfo
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- CN108543908B CN108543908B CN201810359652.2A CN201810359652A CN108543908B CN 108543908 B CN108543908 B CN 108543908B CN 201810359652 A CN201810359652 A CN 201810359652A CN 108543908 B CN108543908 B CN 108543908B
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- acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/224—Furan polymers
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Mold Materials And Core Materials (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to a curing agent for 3D sand mold printing furan resin and a preparation method thereof, the curing agent is prepared from concentrated sulfuric acid, benzene series, organic acid, ethanol and a wetting agent, and has the excellent performances of low viscosity, low moisture and free acid and capability of realizing rapid curing: at 25 ℃, the viscosity is less than or equal to 10mPa.s, the water content is less than or equal to 15 percent, and the free acid is less than or equal to 10 percent. The rapid hardening can be realized, and the use requirement of sand mold ink-jet printing is met.
Description
Technical Field
The invention belongs to the technical field of organic chemistry, particularly relates to the technical field of casting binders, and particularly relates to an alkali phenolic resin for 3D sand mold printing and a preparation method thereof, in particular to a phenolic resin with the characteristics of rapid curing, low viscosity, high strength and high temperature resistance and a preparation method thereof.
Background
With the integration of the internet plus, the upgrade of the traditional manufacturing industry, and the digital green casting are the trend of future development. The 3D sand mold printing technology can quickly realize printing of precision casting sand molds with various sizes, complex structures and high requirements on precision and performance, quickens the research and development speed of new casting products, reduces the cost and risk of process research, and can meet the market of small single-piece batches.
The sand casting raw and auxiliary materials mainly comprise raw sand, a curing agent and an adhesive. The raw sand, the adhesive and other additives used in the traditional core making process are completely made in China, the performance and the quality almost reach the international product level of the same type, and the price is lower. The raw sand used for 3D printing has high requirements on granularity and uniformity, and the processing technology is complex. Some equipment manufacturers, especially import equipment manufacturers, accept adhesives and curing agents that are imported products because the quality of the adhesives or curing agents that fail to meet the requirements of the printing process has a significant impact on the printing quality and the service life of the components of the equipment. Therefore, there is some prospective interest in studying resin binder systems that can be used for 3D printing.
At present, a few enterprises and colleges in China have issued patents on 3D sand mold printing binders, the patents are at the front of China, but reports specially aiming at 3D sand mold printing curing agents are rarely seen, and the index level requirements of common curing agents for binders are not high, so that when the curing agents are applied to the field of 3D sand mold printing, the excessively high viscosity and the slow curing speed of the curing agents cannot meet the use requirements of ink-jet printers. In addition, the effect of the curing agent on the life of the equipment is also a significant problem which cannot be ignored. Therefore, it is necessary to improve the curing agent for different 3D printing binder systems. According to the invention, through technical innovation, the curing agent for the furan resin for 3D sand mold printing, which is low in viscosity, moisture and free acid, can realize rapid curing and has stable performance, is developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a curing agent for furan resin for 3D sand mold printing and a preparation method thereof, so that the curing agent for furan resin for 3D sand mold printing, which has low viscosity, low moisture and low free acid and can be rapidly cured, is obtained.
In order to solve the technical problem, the curing agent for furan resin for 3D sand mold printing is prepared by mixing the following components in parts by weight: 20-50 parts of concentrated sulfuric acid, 5-20 parts of benzene series, 5-20 parts of organic acid, 15-60 parts of ethanol and 1-5 parts of impregnating compound.
Preferably, the curing agent for furan resin for 3D sand mold printing is prepared by mixing the following components in parts by weight: 30-45 parts of concentrated sulfuric acid, 10-15 parts of benzene series, 5-15 parts of organic acid, 30-45 parts of ethanol and 3-5 parts of impregnating compound.
In a preferred technical scheme of the invention, the benzene series is one or a mixture of toluene, ethylbenzene and xylene, and toluene is preferred.
In a preferred embodiment of the present invention, the organic acid is one or more selected from salicylic acid, citric acid, oxalic acid, tannic acid and formic acid, preferably tannic acid.
In a preferred technical scheme of the invention, the impregnating compound is one or a mixture of more of liquid paraffin, epoxy emulsion, aliphatic polyoxy ethyl ether, stearic acid, hydroxyethyl methacrylate and vinyl acetate.
The invention provides a preparation method of a curing agent for furan resin for 3D sand mold printing, which comprises the following steps:
(1) adding a metered benzene series;
(2) dropwise adding metered concentrated sulfuric acid, and controlling the reaction temperature to be not more than 60 ℃;
(3) heating to 110-120 ℃, and preserving heat for 2-8 h;
(4) cooling to below 50 ℃, dropwise adding metered ethanol, and controlling the reaction temperature to be not more than 50 ℃;
(5) and adding metered organic acid and impregnating compound after the dropwise addition is finished, stirring and discharging.
In a preferred technical scheme of the invention, the benzene series is one or a mixture of toluene, ethylbenzene and xylene, and toluene is preferred.
In a preferred embodiment of the present invention, the organic acid is one or more selected from salicylic acid, citric acid, oxalic acid, tannic acid and formic acid, preferably tannic acid.
In a preferred technical scheme of the invention, the impregnating compound is one or a mixture of more of liquid paraffin, epoxy emulsion, aliphatic polyoxy ethyl ether, stearic acid, hydroxyethyl methacrylate and vinyl acetate.
The technical scheme of the invention greatly improves the prior art and formula, and has the following advantages: (1) the strength of the solidification of p-toluenesulfonic acid and xylene sulfonic acid is high;
(2) the organic acid is used for partially replacing concentrated sulfuric acid, so that the content of free sulfuric acid is reduced under the condition of not influencing the solidification speed, and the technical defects of pores, cracks, sulfurization and poor surface spheroidization of ductile iron castings are overcome;
(3) the curing speed depends on the hardness and permeability of the resin sand to a great extent, the furan resin can generate water in the curing process, and the water is volatilized in time and can seriously affect the curing speed and the final strength; therefore, the volatile absolute ethyl alcohol is introduced into the system, so that the moisture in the system is reduced, and the moisture generated in the reaction of a small amount of curing agent and adhesive can be removed through volatilization, the reaction speed is accelerated, and the final strength is improved;
(4) the addition of a small amount of impregnating compound solves the problems that the printing nozzle in the prior art can not smoothly spray stable liquid drops and the atomization is uneven.
The curing agent for furan resin for 3D sand mold printing obtained in the above way has the viscosity of less than or equal to 10mPa.s at 25 ℃, the water content of less than or equal to 15% and the free acid of less than or equal to 10%; when the addition amount of the curing agent is 40-60% (accounting for the mass ratio of the furan resin), the normal furan resin XY86-A (the furfuryl alcohol content is about 85%) is used, and the normal-temperature compressive strength of the standard sand test block with phi of 50mm by 50mm reaches more than 5.0 MPa. The rapid hardening can be realized, and the use requirement of sand mold ink-jet printing is met.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments.
Example 1
(1) 100g of toluene and 50g of ethylbenzene are added into a reaction kettle;
(2) dropwise adding 350g of concentrated sulfuric acid, controlling the reaction temperature not to exceed 60 ℃, and keeping the dropwise adding time for about 2 hours;
(3) heating to 110 ℃, and preserving heat for 3 hours in a reflux state;
(4) cooling to below 50 ℃, dropwise adding 400g of ethanol, and controlling the reaction temperature to be not more than 50 ℃;
(5) after the dropwise addition, 50g of tannic acid, 20g of oxalic acid and 30g of epoxy emulsion are added, stirred and discharged.
Example 2
(1) 75g of dimethylbenzene and 75g of ethylbenzene are added into a reaction kettle;
(2) dropwise adding 300g of concentrated sulfuric acid, controlling the reaction temperature not to exceed 60 ℃, and keeping the dropwise adding time for about 2 hours;
(3) heating to 115 ℃, and preserving heat for 2 hours in a reflux state;
(4) cooling to below 50 ℃, dropwise adding 380g of ethanol, and controlling the reaction temperature to be not more than 50 ℃;
(5) after the dropwise addition, 40g of tannic acid, 80g of salicylic acid, 30g of hydroxyethyl methacrylate and 20g of aliphatic polyoxyethylether are added, and the mixture is stirred and discharged.
Example 3
(1) 100g of toluene and 40g of xylene are added into a reaction kettle;
(2) dripping 450g of concentrated sulfuric acid, controlling the reaction temperature not to exceed 60 ℃, and keeping the dripping time about 2.5 h;
(3) heating to 110 ℃, and preserving heat for 4 hours in a reflux state;
(4) cooling to below 50 ℃, dropwise adding 300g of ethanol, and controlling the reaction temperature to be not more than 50 ℃;
(5) after the dropwise addition, 60g of formic acid, 30g of stearic acid and 20g of vinyl acetate were added, stirred and discharged.
Example 4
(1) 100g of toluene is put into a reaction kettle;
(2) dropwise adding 300g of concentrated sulfuric acid, controlling the reaction temperature not to exceed 60 ℃, and keeping the dropwise adding time about 1.5 h;
(3) heating to 120 ℃, and preserving heat for 2 hours in a reflux state;
(4) cooling to below 50 ℃, dropwise adding 400g of ethanol, and controlling the reaction temperature to be not more than 50 ℃;
(5) after the dropwise addition, 50g of tannic acid, 100g of formic acid, 30g of vinyl acetate and 20g of liquid paraffin were added, and the mixture was stirred and discharged.
The curing agent for 3D sand mold printing furan resin prepared in the above examples 1-4 was tested for viscosity, moisture, total acid content and free acid content according to a conventional method, and then tested according to the method required in JB/T7526-2008 "self-hardening furan resin for casting" with the conventional furan resin XY86-A (furfuryl alcohol content is about 85%) manufactured by my company. The other components and conditions used in the method are the same, and the main technical indexes obtained are shown in table 1.
TABLE 13D technical indexes of curing agent for furan resin for sand mold printing
Table 2 shows the technical indexes of common furan resin curing agents which are commercially available and contain low free acid, wherein the high-acid curing agents are mostly alcohol-based curing agents and are used in cold seasons in severe winter, such as 08 and 09 curing agents, the water content is low, the curing speed is high, the speed requirement of 3D furan resin sand mold printing can be met, but the viscosity is high, the general viscosity is more than 60mpa.s and far exceeds the viscosity use requirement (less than or equal to 10mpa.s) of 3D printing equipment, and the application is difficult; the low-acid curing agent is mostly a water-based curing agent, and is generally used in spring, summer and autumn, such as 03, 04 and 05 curing agents, the water content is high, the curing speed is slow, the viscosity is relatively low, and is mostly 10-30 mpa.s, although the viscosity of the part of curing agent can meet the use requirement, the defect of slow curing speed cannot be changed. The curing agent prepared by the invention has the excellent performances of low viscosity, low moisture and low free acid, can realize quick curing, and can meet the use requirements of sand mold ink-jet printing.
TABLE 2 technical indices of common Furan resin curing agent
The above examples are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (1)
- The curing agent for the furan resin for 3D sand mold printing is prepared from the following components:(1)350g of concentrated sulfuric acid, 100g of toluene, 50g of ethylbenzene, 400g of ethanol, 50g of tannic acid, 20g of oxalic acid and 30g of epoxy emulsion;(2)300g of concentrated sulfuric acid, 75g of xylene, 75g of ethylbenzene, 380g of ethanol, 40g of tannic acid, 80g of salicylic acid, 30g of hydroxyethyl methacrylate and 20g of aliphatic polyoxyethylether;(3)450g of concentrated sulfuric acid, 100g of toluene, 40g of xylene, 60g of formic acid, 30g of stearic acid and 20g of vinyl acetate;(4)300g of concentrated sulfuric acid, 100g of toluene, 400g of ethanol, 50g of tannic acid, 100g of formic acid, 30g of vinyl acetate and 20g of liquid paraffin.
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| CN110560628B (en) * | 2019-08-30 | 2021-08-31 | 宁夏共享化工有限公司 | Preparation method of curing agent for self-hardening furan resin |
| CN110842133B (en) * | 2019-10-31 | 2021-10-08 | 宁夏共享化工有限公司 | Curing agent for self-hardening furan resin sand automatic control instrument and preparation method thereof |
| CN111375726B (en) * | 2020-04-08 | 2021-04-13 | 四川东树新材料有限公司 | Low free acid sulfonic acid curing agent and production method thereof |
| CN111496178A (en) * | 2020-05-28 | 2020-08-07 | 苏州兴业材料科技股份有限公司 | Sulfonic acid curing agent for furan resin prepared from waste polystyrene and method thereof |
| CN114918364B (en) * | 2022-05-23 | 2024-03-26 | 广东中立鼎智能科技有限公司 | Resin composition for 3D printing, 3D printing product, and preparation method and application thereof |
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| CN101199982B (en) * | 2007-11-28 | 2012-07-25 | 济南圣泉集团股份有限公司 | Low sulfur curing agent for furan resin casting |
| CN102516132A (en) * | 2011-12-09 | 2012-06-27 | 宁夏共享集团有限责任公司 | Production method for sulfonic acid curing agent used for casting |
| CN102513500B (en) * | 2011-12-30 | 2014-01-15 | 济南圣泉集团股份有限公司 | Curing agent for Furane self-hardening resin, preparation method thereof and Furane self-hardening resin sand |
| CN106493286B (en) * | 2016-12-20 | 2019-08-02 | 苏州兴业材料科技股份有限公司 | A kind of low sulfur curing agent for furan resin casting |
| CN106825387B (en) * | 2017-02-15 | 2019-08-02 | 苏州兴业材料科技股份有限公司 | A kind of 3 D-printing increasing material moulding material |
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