CN108543908A - A kind of 3D sand molds printing furane resins curing agent and preparation method thereof - Google Patents
A kind of 3D sand molds printing furane resins curing agent and preparation method thereof Download PDFInfo
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- CN108543908A CN108543908A CN201810359652.2A CN201810359652A CN108543908A CN 108543908 A CN108543908 A CN 108543908A CN 201810359652 A CN201810359652 A CN 201810359652A CN 108543908 A CN108543908 A CN 108543908A
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- Prior art keywords
- acid
- curing agent
- parts
- mixing
- furane resins
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Classifications
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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
Abstract
The present invention relates to a kind of 3D sand molds to print furane resins curing agent and preparation method thereof, the curing agent is prepared by the concentrated sulfuric acid, benzene homologues, organic acid, ethyl alcohol, size, low with viscosity, moisture is low, and free acid is low and can realize quick-setting excellent properties：At 25 DEG C, viscosity≤10mPa.s, water content≤15%, free acid≤10%.It can realize quick-hardening, meet the requirement of sand mold inkjet printing.
Description
Technical field
The invention belongs to technical field of organic chemistry, more particularly to casting binder technical field, and in particular to a kind of 3D
Sand mold printing alkali phenolic resin and preparation method thereof, especially a kind of rapid curing, low viscosity, high intensity, heat safe phenol
Urea formaldehyde and preparation method thereof.
Background technology
With the fusion with " internet+", the upgrading of traditional manufacture, digitized Green foundry is becoming for future development
Gesture.3D sand molds printing technique can quickly realize all kinds of size dimensions, complicated, precision and the higher precision of performance requirement
The printing of casting sand mold accelerates the speed of casting new-product development, reduces the cost and risk of technical study, while again can
Meet the market of single and mini-batch production.
Sand casting supplementary material is mainly made of roughing sand, curing agent and bonding agent.Original used in traditional core manufacturing craft
Sand, bonding agent and other additives have fully achieved domestic, performance and the almost international similar-type products level of quality, and valence
Lattice are lower.Roughing sand used in 3D printing is more demanding in terms of granularity and uniformity, and processing technology is complicated.Equipment component factory
The bonding agent and curing agent that family, especially import equipment producer are approved all are imported products, because of bonding agent off quality
Or curing agent can generate significant impact to print quality and equipment component service life.Therefore, research can be used for the resin of 3D printing
Binder system has certain perspective meaning.
Existing a small number of enterprises domestic at present and colleges and universities have delivered the patent about 3D sand mold printing binders, walk in state
Interior forward position, the rarely seen report specifically for 3D sand mold printing curing agent, and the index level of common bond curing agent
It is required that not high, so as to cause when being applied to 3D sand molds and printing field, excessively high viscosity and slower curing rate without
Method meets the requirement of ink-jet printer.In addition, curing agent is also ignorable significant problem to the aging effects of equipment.
Therefore, it is necessary to make improvements, the mating curing agent for developing different 3D printing binder systems.The present invention is created by technology
Newly, a kind of low viscosity, low moisture, low free acid are developed, can realize the 3D sand molds printing furans that rapid curing, performance are stablized
Resin curing agent.
Invention content
It is an object of the invention to overcome the deficiency of the above-mentioned prior art, a kind of 3D sand molds printing furane resins use is provided
Curing agent and preparation method thereof has obtained a kind of low viscosity, low moisture, low free acid, can realize that rapid curing 3D sand molds are beaten
Print furane resins curing agent.
In order to solve the above technical problems, the 3D sand molds of the present invention print furane resins curing agent, by following parts by weight
Component be mixed with to obtain：20~50 parts of the concentrated sulfuric acid, 5~20 parts of benzene homologues, 5~20 parts of organic acid, 15~60 parts of ethyl alcohol, leaching
Moisten 1~5 part of agent.
Preferably, 3D sand molds of the invention print furane resins curing agent, and system is mixed by the component of following parts by weight
It is standby to obtain：30~45 parts of the concentrated sulfuric acid, 10~15 parts of benzene homologues, 5~15 parts of organic acid, 30~45 parts of ethyl alcohol, 3~5 parts of size.
In currently preferred technical solution, the benzene homologues are one or more in toluene, ethylbenzene and dimethylbenzene
Mixing, preferably toluene.
In currently preferred technical solution, the organic acid is in salicylic acid, citric acid, oxalic acid, tannic acid and formic acid
One or more mixing, preferably tannic acid.
In currently preferred technical solution, the size is selected from atoleine, epoxy emulsion, aliphatic polyoxy second
One or more mixing in ether, stearic acid, hydroxyethyl methacrylate and vinylacetate.
Second aspect of the present invention provides the preparation method of 3D sand molds printing furane resins curing agent comprising following step
Suddenly：
(1) benzene homologues of input metering；
(2) concentrated sulfuric acid of metering is added dropwise, controlling reaction temperature is no more than 60 DEG C；
(3) 110~120 DEG C are warming up to, 2~8h is kept the temperature；
(4) 50 DEG C are cooled to hereinafter, the ethyl alcohol of metering is added dropwise, controlling reaction temperature is no more than 50 DEG C；
(5) it is added dropwise, the organic acid and size of metering, stirring discharging is added.
In currently preferred technical solution, the benzene homologues are one or more in toluene, ethylbenzene and dimethylbenzene
Mixing, preferably toluene.
In currently preferred technical solution, the organic acid is in salicylic acid, citric acid, oxalic acid, tannic acid and formic acid
One or more mixing, preferably tannic acid.
In currently preferred technical solution, the size is selected from atoleine, epoxy emulsion, aliphatic polyoxy second
One or more mixing in ether, stearic acid, hydroxyethyl methacrylate and vinylacetate.
Technical solutions according to the invention have larger promotion to prior art and formula, have the following advantages that：(1) have
There is the cured intensity of p-methyl benzenesulfonic acid, xylene monosulfonic acid；
(2) use organic acid portion to substitute the concentrated sulfuric acid reduces free sulfuric acid and contains under conditions of not influencing curing rate
Amount improves the technological deficiency of the stomata of casting, crackle, sulfurizing and G. Iron Castings surface abnormal nodularizing；
(3) curing rate is heavily dependent on the thorough hardening of resin sand, can be along in furane resins solidification process
The generation of moisture, this part water volatilize not in time, can seriously affect curing rate and whole intensity；Therefore it is introduced into system volatile
Absolute ethyl alcohol, when not only having reduced the moisture carried in system, but also a small amount of curing agent and binder can be taken away by volatilization reacted
The moisture of generation, accelerates reaction speed, improves whole intensity；
(4) addition of a small amount of size, solving printing head in the prior art can not smooth jetting stability drop and mist
Change uneven phenomenon.
The 3D sand molds printing furane resins curing agent obtained through the above way, viscosity≤10mPa.s at 25 DEG C are aqueous
Amount≤15%, free acid≤10%；When curing agent addition is 40%~60% (mass ratio for accounting for furane resins), routine is used
The normal sand test block room temperature compression strength of furane resins XY86-A (furfuryl alcohol content is 85% or so), Φ 50mm*50mm reach
More than 5.0MPa.It can realize quick-hardening, meet the requirement of sand mold inkjet printing.
Specific implementation mode
Said program is described further below in conjunction with specific embodiment.It should be understood that these embodiments are for illustrating
The present invention and be not limited to limit the scope of the invention.The implementation condition used in embodiment can be done according to the condition of specific producer
Further adjustment, the implementation condition being not specified is usually the condition in routine experiment.
Embodiment 1
(1) toluene of 100g is thrown, 50g ethylbenzene is in reaction kettle；
(2) concentrated sulfuric acid of 350g is added dropwise, controlling reaction temperature is no more than 60 DEG C, time for adding about 2h；
(3) 110 DEG C are warming up to, 3h is kept the temperature under reflux state；
(4) 50 DEG C are cooled to hereinafter, 400g ethyl alcohol is added dropwise, controlling reaction temperature is no more than 50 DEG C；
(5) it is added dropwise, 50g tannic acids, 20g oxalic acid and 30g epoxy emulsions, stirring discharging is added.
Embodiment 2
(1) dimethylbenzene of 75g is thrown, 75g ethylbenzene is in reaction kettle；
(2) concentrated sulfuric acid of 300g is added dropwise, controlling reaction temperature is no more than 60 DEG C, time for adding about 2h；
(3) 115 DEG C are warming up to, 2h is kept the temperature under reflux state；
(4) 50 DEG C are cooled to hereinafter, 380g ethyl alcohol is added dropwise, controlling reaction temperature is no more than 50 DEG C；
(5) it is added dropwise, 40g tannic acids, 80g salicylic acids, 30g hydroxyethyl methacrylates and 20g aliphatic polyoxies is added
Ether, stirring discharging.
Embodiment 3
(1) toluene of 100g is thrown, 40g dimethylbenzene is in reaction kettle；
(2) concentrated sulfuric acid of 450g is added dropwise, controlling reaction temperature is no more than 60 DEG C, time for adding about 2.5h；
(3) 110 DEG C are warming up to, 4h is kept the temperature under reflux state；
(4) 50 DEG C are cooled to hereinafter, 300g ethyl alcohol is added dropwise, controlling reaction temperature is no more than 50 DEG C；
(5) it is added dropwise, 60g formic acid, 30g stearic acid and 20g vinylacetates, stirring discharging is added.
Embodiment 4
(1) toluene of 100g is thrown in reaction kettle；
(2) concentrated sulfuric acid of 300g is added dropwise, controlling reaction temperature is no more than 60 DEG C, time for adding about 1.5h；
(3) 120 DEG C are warming up to, 2h is kept the temperature under reflux state；
(4) 50 DEG C are cooled to hereinafter, 400g ethyl alcohol is added dropwise, controlling reaction temperature is no more than 50 DEG C；
(5) it is added dropwise, 50g tannic acids, 100g formic acid, 30g vinylacetates and 20g atoleines, stirring discharging is added.
3D sand molds printing furane resins are prepared in above-described embodiment 1-4 conventionally to be detected respectively with curing agent
Viscosity, moisture, total acid content and free acid content, then (furfuryl alcohol content exists with my the conventional furane resins XY86-A of company's production
85% or so) JB/T7526-2008 is pressed《Casting self-hardening furan resin》In require method to test.Other groups used in method
Divide and condition is all identical, obtained the key technical indexes such as table 1.
1 3D sand molds of table print furane resins curing agent technology index
Table 2 is the commercially available lower common furan resin hardener technical indicator containing free acid, wherein high acid as curing agent is mostly
Alcohol radical curing agent is used in cold season in severe winter, such as 08 and 09 curing agent, and moisture content is relatively low, and curing rate is fast, can meet 3D furans
The rate request of furane resins sand mold printing, but its viscosity is larger, and usual viscosity is more than 60mpa.s, is set far beyond 3D printing
Standby viscosity requirement (≤10mpa.s), it is difficult to apply；Low acid as curing agent is mostly water-based curing dose, generally in spring, summer, autumn
Season uses, and such as 03,04 and 05 curing agent, moisture content are high, and curing rate is slow, and viscosity is relatively low, mostly in 10~30mpa.s,
Although this partially cured dose viscosity can reach requirement, the slower defect of curing rate can not be changed.Pass through this
The curing agent prepared is invented, not only has viscosity low, moisture is low, the low excellent properties of free acid, while can also realize quickly
Solidification, disclosure satisfy that the requirement of sand mold inkjet printing.
2 common furan resin hardener technical indicator of table
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow person skilled in the art's energy
Solution present disclosure much of that is simultaneously implemented according to this, and it is not intended to limit the scope of the present invention.It is all according to spirit of that invention
The equivalent transformation or modification that essence is done, should be covered by the protection scope of the present invention.
Claims (9)
1.3D sand molds print furane resins curing agent, are mixed with to obtain by the component of following parts by weight：The concentrated sulfuric acid 20~
50 parts, 5~20 parts of benzene homologues, 5~20 parts of organic acid, 15~60 parts of ethyl alcohol, 1~5 part of size.
2. curing agent according to claim 1, which is characterized in that 3D sand molds print furane resins curing agent, by such as
The component of lower parts by weight is mixed with to obtain：30~45 parts of the concentrated sulfuric acid, 10~15 parts of benzene homologues, 5~15 parts of organic acid, ethyl alcohol 30
~45 parts, 3~5 parts of size.
3. curing agent according to claim 1, which is characterized in that the benzene homologues are in toluene, ethylbenzene and dimethylbenzene
One or more mixing.
4. curing agent according to claim 1, which is characterized in that the organic acid be selected from salicylic acid, citric acid, oxalic acid,
One or more mixing in tannic acid and formic acid.
5. curing agent according to claim 1, which is characterized in that the size is selected from atoleine, epoxy emulsion, fat
One or more mixing in fat adoption oxygen ether, stearic acid, hydroxyethyl methacrylate and vinylacetate.
6. the method for preparing 3D sand molds printing furane resins curing agent as described in any one in claim 1-5 comprising such as
Lower step：
(1) benzene homologues of input metering；
(2) concentrated sulfuric acid of metering is added dropwise, controlling reaction temperature is no more than 60 DEG C；
(3) 110~120 DEG C are warming up to, 2~8h is kept the temperature；
(4) 50 DEG C are cooled to hereinafter, the ethyl alcohol of metering is added dropwise, controlling reaction temperature is no more than 50 DEG C；
(5) it is added dropwise, the organic acid and size of metering, stirring discharging is added.
7. preparation method according to claim 6, which is characterized in that the benzene homologues are in toluene, ethylbenzene and dimethylbenzene
One or more mixing.
8. preparation method according to claim 6, which is characterized in that the organic acid is selected from salicylic acid, citric acid, grass
One or more mixing in acid, tannic acid and formic acid.
9. preparation method according to claim 6, which is characterized in that the size be selected from atoleine, epoxy emulsion,
One or more mixing in aliphatic polyoxy ether, stearic acid, hydroxyethyl methacrylate and vinylacetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810359652.2A CN108543908B (en) | 2018-04-20 | 2018-04-20 | Curing agent for 3D sand mold printing furan resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810359652.2A CN108543908B (en) | 2018-04-20 | 2018-04-20 | Curing agent for 3D sand mold printing furan resin and preparation method thereof |
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| Publication Number | Publication Date |
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| CN108543908A true CN108543908A (en) | 2018-09-18 |
| CN108543908B CN108543908B (en) | 2020-06-02 |
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| CN201810359652.2A Active CN108543908B (en) | 2018-04-20 | 2018-04-20 | Curing agent for 3D sand mold printing furan resin and preparation method thereof |
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Cited By (5)
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| CN110560628A (en) * | 2019-08-30 | 2019-12-13 | 宁夏共享化工有限公司 | Curing agent for self-hardening furan resin and preparation method thereof |
| CN110842133A (en) * | 2019-10-31 | 2020-02-28 | 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 |
| CN111375726A (en) * | 2020-04-08 | 2020-07-07 | 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 |
| CN114918364A (en) * | 2022-05-23 | 2022-08-19 | 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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| CN106825387A (en) * | 2017-02-15 | 2017-06-13 | 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560628A (en) * | 2019-08-30 | 2019-12-13 | 宁夏共享化工有限公司 | Curing agent for self-hardening furan resin and preparation method thereof |
| 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 |
| CN110842133A (en) * | 2019-10-31 | 2020-02-28 | 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 |
| 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 |
| CN111375726A (en) * | 2020-04-08 | 2020-07-07 | 四川东树新材料有限公司 | Low free acid sulfonic acid curing agent and production 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 |
| CN114918364A (en) * | 2022-05-23 | 2022-08-19 | 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 |
| 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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| CN108543908B (en) | 2020-06-02 |
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