CN101722272B - Curing agent of self-hardening furan resin sand and preparation method thereof - Google Patents
Curing agent of self-hardening furan resin sand and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a curing agent of self-hardening furan resin sand, which comprises the following components in portions by weight: 1-300 portions of toluenesulfonic acid, 10-300 portions of xylene monosulfonic acid, 1-170 portions of sulfuric acid, 200-800 portions of phosphoric acid, 1-200 portions of methyl sulfate, 1-50 portions of ethanol, 1-50 portions of methanol, 40-900 portions of water and 0.05-1.0 portion of assistant. The preparation method comprises the following steps: (1) prefabricating the toluenesulfonic acid, the xylene monosulfonic acid and the methyl sulfate; (2) preparing all the raw materials according to the proportion of the curing agent; and (3) synthesizing the curing agent by the following steps: (a) mixing the toluenesulfonic acid, the xylene monosulfonic acid, the methyl sulfate and the sulfuric acid to react for 1.0 hour; (b) cooling to 55 DEG C, adding the mixture of methanol and ethanol to react at 50-70 DEG C for 1.0 hour; (c) adding the phosphoric acid to react at 55-70 DEG C for 1.0 hour; and (d) cooling to 50 DEG C, and adding water and assistant; and discharging after evenly mixing. The curing agent can adapt to the long (super long) use time in the molding process of large castings at high air temperature (above 28 DEG C) and high sand temperature (30-50 DEG C), and solves the problem that the large (super long and large) castings are difficult to produce since the temperature of the reclaimed sand can not drop to the designed value due to various reasons in the foundry corporations.
Description
Technical field
The present invention relates to curing agent, relate in particular to employed curing agent in a kind of self-hardening furan resin sand moulding (core) technology, belong to the industrial chemicals field.
Background technology
The curing agent that uses in self-hardening furan resin sand moulding (core) technology, be generally HG/T2345-92 class sulfonic acid curing agent or its curing agent of deriving, the molding sand up time was generally 2～10 minutes, suitable maximum temperature is lower than 30 ℃, be difficult to satisfy the heavy castings moulding and produce (casting weight 20-150 ton of longer up time of needs, be generally 8～30 minutes) demand, especially when summer temperature surpasses 28 ℃ or sand temperature and reaches more than 30 ℃, above-mentioned curing agent is not competent especially, can not satisfy moulding and produce the required up time, can not guarantee that molding sand has the required tension of production, compression strength value, and this moment, there were denseer peculiar smell such as formaldehyde the operating area.
Summary of the invention
The objective of the invention is: provide a kind of curing agent that makes the self-hardening furan resin molding sand can adapt to higher sand temperature (30～50 ℃) and have the longer up time at the problems referred to above; Further, provide the serial model No. of this curing agent, thereby can make self-hardening furan resin molding sand (10～50 ℃) in the sand temperature scope of broadness can both have the long up time; Further, what this curing agent was provided mixes mutually occupation mode, can avoid and solve all kinds of problems that do not match and brought because of curing agent model and sand temperature.
Technical solution of the present invention is:
A kind of self-hardening furan resin sand curing agent contains following components in part by weight:
Toluenesulfonic acid 1～300; Xylene monosulfonic acid 10～300; Sulfuric acid 1～170;
Phosphoric acid 200～800; Sulfuric acid formicester 1～200; Ethanol 1～50;
Methyl alcohol 1～50; Water 40～900; Auxiliary agent 0.05～1.0.
Described curing agent comprises the series of products of following Different Weight proportioning:
Above-mentioned serial curing agent contains the component of following weight proportion:
The preparation method of described curing agent comprises step:
(1), raw material is prefabricated
● toluenesulfonic acid raw material prefabricated:
The sulfuric acid of determining weight ratio is added in the toluene solution, 105～120 ℃ of reactions of temperature 2.0 hours; Discharging is standby after being cooled to 50 ℃ then;
● xylene monosulfonic acid raw material prefabricated:
The sulfuric acid of determining weight ratio is added in the xylene solution, 105～120 ℃ of reactions of temperature 2.0 hours; Discharging is standby after being cooled to 50 ℃ then;
● Methylsulfate raw material prefabricated:
The sulfuric acid of determining weight ratio is added in the methanol solution, 55～70 ℃ of reactions of temperature 1.0 hours; Discharging is standby after being cooled to 50 ℃ then;
(2), get all the raw material ready according to the proportioning of target model curing agent;
(3), above-mentioned raw materials is synthetic as follows:
1., be 55～70 ℃ of hybrid reactions 1.0 hours with toluenesulfonic acid, xylene monosulfonic acid, Methylsulfate and sulfuric acid in temperature;
2., be cooled to 55 ℃ after, add methyl alcohol, ethanol, be 50～70 ℃ of reactions 1.0 hours in temperature;
3., be between 55～70 ℃ in temperature, added phosphatase reaction 1.0 hours;
4., be cooled to 50 ℃ after, add entry, auxiliary agent, mix the back discharging.
Also can adopt the method for being prepared as follows, comprise step:
1., get the raw materials ready, when getting the raw materials ready, calculate the amount of required toluene, dimethylbenzene, methyl alcohol and sulfuric acid respectively according to the proportion relation of prefabricated toluenesulfonic acid, xylene monosulfonic acid, Methylsulfate according to the proportioning of target product;
2., will toluene, dimethylbenzene mixes the back and adds sulfuric acid, is 105～120 ℃ of reactions 2.0 hours in temperature;
3., be cooled to 55 ℃ after, add methyl alcohol, ethanol, be 50～70 ℃ of reactions 1.0 hours in temperature;
4., be between 55～70 ℃ in temperature, added phosphatase reaction 1.0 hours;
5., be cooled to 50 ℃ after, add entry, auxiliary agent; Mix the back discharging.
The product that above-mentioned two kinds of methods make is equivalence fully.
Technique effect of the present invention:
Through experiment test, the technical characteristic of this self-hardening furan resin sand curing agent such as following table 1:
Table 1
| The curing agent model | Optimum sand temperature (℃) | Addition (accounting for the % of amount of resin) | Up time (minute) |
| 0 | -5～5 | 35～70 | 2～50 |
| 1 | 0～15 | 35～70 | 2～50 |
| 2 | 5～20 | 35～70 | 2～50 |
| 3 | 10～25 | 35～70 | 2～50 |
| 4 | 15～30 | 35～70 | 2～50 |
| 5 | 20～35 | 35～70 | 2～50 |
| 6 | 25～40 | 30～45 | 2～45 |
| 7 | 35～50 | 30～65 | 2～40 |
At first, successfully solved too short problem of self-hardening furan resin sand up time, having satisfied heavy castings (reaching 20～150 tons as casting weight) moulding production must have the requirement of longer up time because of long needs molding sand of operating time; This curing agent has the kind that adapts to high temperature (above 28 ℃), high sand temperature (30～50 ℃), be model 5,6,7, solved foundry enterprise and can not reduce to design load (the general requirement is below 25 ℃) and cause producing and be difficult to a difficult problem of carrying out because of all kinds of reasons cause reclaimed sand sand temperature (being generally more than 35 ℃).
Secondly, compare with HG/T2345-92 class sulfonic acid curing agent, use this curing agent also can improve tension (or resistance to compression) intensity 20～30% of molding sand, for example under the R%=1.5% condition, cooperate the sand bond δ 24h 〉=2.2Mpa of commercially available self-hardening furan resin (better) preparation simultaneously with this curing agent as the DXF-super2000 self-hardening furan resin effect of producing with east steam turbine Co., Ltd, and the sand bond δ 24h ≈ 1.8Mpa for preparing with HG/T2345-92 class sulfonic acid curing agent.
In addition, also can slow down the speed that formaldehyde discharges in the resin curing process, reduce the airborne concentration of formaldehyde in operating area greatly, improve operating environment, favourable workers ' health with this curing agent.
The specific embodiment
Two step synthetic methods:
Prepare toluenesulfonic acid, xylene monosulfonic acid, Methylsulfate earlier, concrete grammar is:
● toluenesulfonic acid raw material prefabricated:
According to the toluene consumption of required toluenesulfonic acid, determine the proportioning of toluene and sulfuric acid, then sulfuric acid is added in the toluene solution, 105～120 ℃ of reactions of temperature 2.0 hours; Discharging is standby after being cooled to 50 ℃;
● xylene monosulfonic acid raw material prefabricated:
According to the dimethylbenzene consumption of required xylene monosulfonic acid, determine the proportioning of dimethylbenzene and sulfuric acid, then sulfuric acid is added in the xylene solution, 105～120 ℃ of reactions of temperature 2.0 hours; Discharging is standby after being cooled to 50 ℃;
● Methylsulfate raw material prefabricated:
According to the methanol usage of required Methylsulfate, determine the proportioning of methyl alcohol and sulfuric acid, then sulfuric acid is added in the methanol solution, 55～70 ℃ of reactions of temperature 1.0 hours; Discharging is standby after being cooled to 50 ℃.
When prefabricated above-mentioned three kinds of raw materials,, two a kind of excessive addings of participating in the reactive components can be deviate from the excessive part of excessive component again after the reaction for making reaction thoroughly.
Prepare after toluenesulfonic acid, xylene monosulfonic acid, the Methylsulfate, prepare curing agent again, according to the form below 2 proportionings are got all raw materials ready:
Table 2
Above-mentioned raw materials is synthetic as follows: is 55～70 ℃ of hybrid reactions 1.0 hours with p-methyl benzenesulfonic acid, xylene monosulfonic acid, Methylsulfate and sulfuric acid in temperature; After being cooled to 55 ℃, add methyl alcohol, alcohol mixture, temperature is 50～70 ℃ of reactions 1.0 hours; In temperature is between 55～70 ℃, adds phosphatase reaction 1.0 hours; After being cooled to 50 ℃, add entry, auxiliary agent; Mix the back discharging, promptly get product.
P-methyl benzenesulfonic acid also can be used replacements such as o-toluene sulfonic acid, m-toluene sulfonic acid.
One-step synthesis:
1., get the raw materials ready, when getting the raw materials ready, calculate the amount of required toluene, dimethylbenzene, methyl alcohol and sulfuric acid respectively according to the proportion relation of prefabricated toluenesulfonic acid, xylene monosulfonic acid, Methylsulfate according to the proportioning of target product in the table 2;
2., will toluene, dimethylbenzene mixes the back and adds sulfuric acid, is 105～120 ℃ of reactions 2.0 hours in temperature;
3., be cooled to 55 ℃ after, add methyl alcohol, ethanol, be 50～70 ℃ of reactions 1.0 hours in temperature;
4., be between 55～70 ℃ in temperature, added phosphatase reaction 1.0 hours;
5., be cooled to 50 ℃ after, add entry, auxiliary agent; Mix the back discharging.
Need to specify that the raw material components content among the present invention in the various prescriptions all calculates with pure product (being concentration 100%), therefore, in the real work, should convert for the raw material components of non-pure product.
This curing agent has 8 models, is applicable to all kinds of sand temperature (10～50 ℃) situation, each model curing agent corresponding respectively between certain optimum sand warm area.If can between its suitable sand warm area, cooperate self-hardening furan resin (as the DXF-super2000 of east steam turbine Co., Ltd production) to use, not only can make molding sand have casting mold and produce required up time and demould time, and the sand bond height, addition is less expensive also, and is as shown in table 3 below:
Table 3
| The curing agent model | Optimum sand temperature (℃) | Addition (accounting for the % of amount of resin) | Up time (minute) | Demould time (minute) | Favorable season | Remarks |
| 0 | -5～5 | 35～70 | 2～50 | 15～150 | Severe winter | Be equivalent to GC08 |
| 1 | 0～15 | 35～70 | 2～50 | 10～120 | Severe winter | Be equivalent to GC09 |
| 2 | 5～20 | 35～70 | 2～50 | 10～120 | The Winter-Spring | Be equivalent to GS03 |
| 3 | 10～25 | 35～70 | 2～50 | 10～120 | Spring, autumn | Be equivalent to GS02 |
| 4 | 15～30 | 35～70 | 2～50 | 10～120 | Spring, autumn, summer | Be equivalent to GS04 |
| 5 | 20～35 | 35～70 | 2～50 | 10～120 | Summer | / |
| 6 | 25～40 | 30～65 | 2～45 | 10～100 | Hot summer | / |
| 7 | 35～50 | 30～65 | 2～40 | 10～100 | Midsummer, hot sand | / |
Mixing mutually of curing agent used:
(1), model 0 is mixed with the mutual of model 7
Under equal addition condition, use curing agent model 0, the setting rate of resin sand is the fastest, uses curing agent model 7, and the setting rate of resin sand is the slowest; Mix mutually by model 0 and 7 two curing agent of model, can obtain the product with model 1～6 curing agent performance equivalence, mix the system curing agent and reduce, the increase of model 7 consumptions with sand temperature rising model 0 consumption.
(2), mix the use of curing agent mutually
The ratio of mixing mutually is as shown in table 4 below:
Table 4
| The sand temperature (℃) | Model 0: model 7 | Remarks |
| -5～5 | 100∶0 | Model 0 |
| 0～15 | 85∶15 | Be equivalent to model 1 |
| 5～20 | 75∶25 | Be equivalent to model 2 |
| 10～25 | 65∶35 | Be equivalent to model 3 |
| 15～30 | 60∶40 | Be equivalent to model 4 |
| 20～35 | 35∶65 | Be equivalent to model 5 |
| 25～40 | 20∶80 | Be equivalent to model 6 |
| 35～50 | 0∶100 | Model 7 |
This result of use of mixing mutually curing agent is suitable with curing agent model X of the present invention (X=0～7) series, and the addition of curing agent can be in more economic, more stable scope, promptly curing agent account for the resin addition 40～50%, sand temperature scope is for-10～50 ℃ the time, not only can make the setting rate of self-hardening furan resin sand stable, and the up time that can guarantee self-hardening furan resin sand reach 2～50 minutes, satisfy the demand that all kinds of foundry goods casting molds are produced.Change the harmful effect that is caused thereby thoroughly solved sand temperature (or temperature), this operational version has also solved the supply and the collocation problem of curing agent when changing according to the season simultaneously.
Claims (5)
1. self-hardening furan resin sand curing agent contains following components in part by weight:
Toluenesulfonic acid 1～300; Xylene monosulfonic acid 10～300; Sulfuric acid 1～170;
Phosphoric acid 200～800; Sulfuric acid formicester 1～200; Ethanol 1～50;
Methyl alcohol 1～50; Water 40～900; Auxiliary agent 0.05～1.0.
2. curing agent according to claim 1 is characterized in that, described curing agent comprises the series of products of following Different Weight proportioning:
3. curing agent according to claim 1 is characterized in that, described curing agent contains the component of following weight proportion:
4. the preparation method of claim 1 or 2 or 3 described curing agent comprises step:
(1), raw material is prefabricated
● toluenesulfonic acid raw material prefabricated:
The sulfuric acid of determining weight ratio is added in the toluene solution, 105～120 ℃ of reactions of temperature 2.0 hours; Discharging is standby after being cooled to 50 ℃ then;
● xylene monosulfonic acid raw material prefabricated:
The sulfuric acid of determining weight ratio is added in the xylene solution, 105～120 ℃ of reactions of temperature 2.0 hours; Discharging is standby after being cooled to 50 ℃ then;
● Methylsulfate raw material prefabricated:
The sulfuric acid of determining weight ratio is added in the methanol solution, 55～70 ℃ of reactions of temperature 1.0 hours; Discharging is standby after being cooled to 50 ℃ then;
(2), get all the raw material ready according to the proportioning of target model curing agent;
(3), above-mentioned raw materials is synthetic as follows:
1., be 55～70 ℃ of hybrid reactions 1.0 hours with toluenesulfonic acid, xylene monosulfonic acid, Methylsulfate and sulfuric acid in temperature;
2., be cooled to 55 ℃ after, add methyl alcohol, ethanol, be 50～70 ℃ of reactions 1.0 hours in temperature;
3., be between 55～70 ℃ in temperature, added phosphatase reaction 1.0 hours;
4. after being cooled to 50 ℃, add entry, auxiliary agent, mix the back discharging.
5. the preparation method of claim 1 or 2 or 3 described curing agent comprises step:
1., get the raw materials ready, when getting the raw materials ready, calculate the amount of required toluene, dimethylbenzene, methyl alcohol and sulfuric acid respectively according to the proportion relation of prefabricated toluenesulfonic acid, xylene monosulfonic acid, Methylsulfate according to the proportioning of target product;
2., will toluene, dimethylbenzene mixes the back and adds sulfuric acid, is 105～120 ℃ of reactions 2.0 hours in temperature;
3., be cooled to 55 ℃ after, add methyl alcohol, ethanol, be 50～70 ℃ of reactions 1.0 hours in temperature;
4., be between 55～70 ℃ in temperature, added phosphatase reaction 1.0 hours;
5., be cooled to 50 ℃ after, add entry, auxiliary agent; Mix the back discharging.
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927316A (en) * | 2010-09-03 | 2010-12-29 | 吴江市液铸液压件铸造有限公司 | Furan resin self curing sand |
| 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 |
| CN102861866B (en) * | 2012-09-27 | 2015-02-25 | 珠海市斗门福联造型材料实业有限公司 | Curing agent for furan resin self-hardening sand for casting and preparation method thereof |
| 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 |
| CN109108213A (en) * | 2017-06-23 | 2019-01-01 | 宁夏共享化工有限公司 | Curing agent is used in a kind of casting |
| CN107282870B (en) * | 2017-07-11 | 2019-01-11 | 马鞍山市兴隆铸造有限公司 | A kind of preparation method of high intensity furan resin-sand |
| CN108515139A (en) * | 2018-05-11 | 2018-09-11 | 佛山市高明利钢精密铸造有限公司 | A kind of preparation method for the hot investment casting molding sand that gas permeability is good |
| CN108515140A (en) * | 2018-05-11 | 2018-09-11 | 佛山市高明利钢精密铸造有限公司 | A kind of preparation method casting special molding sand for precision stainless steel |
| CN108568493A (en) * | 2018-05-11 | 2018-09-25 | 佛山市高明利钢精密铸造有限公司 | A kind of preparation method of moulding sand for casting |
| CN108568492A (en) * | 2018-05-11 | 2018-09-25 | 佛山市高明利钢精密铸造有限公司 | A kind of preparation method of the special molding sand of hot investment casting |
| CN109175221B (en) * | 2018-10-16 | 2020-07-10 | 阜新力达钢铁铸造有限公司 | Curing agent for casting 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 |
| 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 |
| CN114393175B (en) * | 2021-12-30 | 2023-12-22 | 广东省铸力铸材科技有限公司 | Curing agent and preparation method thereof |
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Effective date of registration: 20170315 Address after: Mount Lu road 618000 Deyang city Sichuan province Jingyang District No. 36 three Patentee after: Sichuan East tree new material Co., Ltd. Address before: 618000 Jiangxi hi tech Industrial Park, Sichuan, Jinsha Road, No. 666, No. Patentee before: Dongfang Turbine Co., Ltd., Dongfang Electric Group |