CN111496178A - Sulfonic acid curing agent for furan resin prepared from waste polystyrene and method thereof - Google Patents
Sulfonic acid curing agent for furan resin prepared from waste polystyrene and method thereof Download PDFInfo
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- CN111496178A CN111496178A CN202010467428.2A CN202010467428A CN111496178A CN 111496178 A CN111496178 A CN 111496178A CN 202010467428 A CN202010467428 A CN 202010467428A CN 111496178 A CN111496178 A CN 111496178A
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- curing agent
- sulfonic acid
- waste polystyrene
- polystyrene
- furan resin
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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
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a sulfonic acid curing agent for furan resin prepared from waste polystyrene, which comprises the following components: concentrated sulfuric acid, waste polystyrene, a solvent, ethanol or methanol, a regulator and water; the solvent is selected from one or more of ethyl acetate, trichloromethane, dichloroethane, acetone, tetrahydrofuran and N, N-dimethylformamide; the modifier is selected from one or more of oxalic acid, citric acid, lactic acid, phthalic anhydride, acetic anhydride and propionic anhydride. The polystyrene sulfonic acid curing agent prepared by the invention can meet the requirements of the field use speed and strength of the resin sand, effectively reduce the discharge of benzene series, and simultaneously can recycle and utilize waste polystyrene.
Description
Technical Field
The invention belongs to the technical field of organic chemistry, particularly relates to the field of waste material recovery, also relates to the field of preparation of casting auxiliary materials, and particularly relates to a method for preparing a sulfonic acid curing agent for furan resin from waste polystyrene.
Background
Polystyrene foams and plastics are widely used in people's daily life. Among them, the packing material of various household appliances and other vulnerable articles uses polystyrene foam, resulting in the production of a large amount of waste foam every year; polystyrene foam packaging boxes used daily for snack products are largely abandoned in every corner, forming the well-known "white stain"; the polystyrene foam plastic film used in agriculture stays and disperses in soil, is not easy to degrade, and seriously affects the quality of the soil. Because the waste polystyrene materials are difficult to recycle, the waste polystyrene is only put into a burning furnace for burning so as to solve the problem of waste residue of the waste polystyrene, but the burning of the waste polystyrene not only causes a certain degree of pollution to the environment, but also does not effectively recycle the styrene materials. The used waste polystyrene plastics are difficult to treat, seriously pollute the environment and become social public hazard. How to solve the recycling of waste plastics is one of the important issues for maintaining sustainable development in the world today.
The self-hardening furan resin sand process has a history of more than 100 years in casting production, and furan resin is the resin which is used in the largest amount and has the widest modeling in casting production so far. At present, the main components used for curing furan resin are sulfonic acid curing agents, including benzenesulfonic acid, toluenesulfonic acid, xylene sulfonic acid and the like, so that the prepared product cannot avoid residual toxic and harmful substances such as benzene, toluene, xylene and the like, and the residual substances are released in a large amount in the molding and casting processes, thereby seriously harming the physical and mental health of workers. Therefore, the selection of proper curing agent to reduce harmful substances in the product is a problem to be solved by the technical personnel in the field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing a sulfonic acid curing agent for furan resin by using waste polystyrene, so that the waste polystyrene is recycled, and the newly prepared sulfonic acid curing agent does not use harmful raw materials such as benzene, toluene, xylene and the like, can reduce the emission of free benzene series and improve the environmental protection performance of products.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention relates to a sulfonic acid curing agent for furan resin, which is characterized by comprising the following components: concentrated sulfuric acid, waste polystyrene, an organic solvent, ethanol or methanol, a regulator and water; the weight percentage of each component is as follows: 20-50% of concentrated sulfuric acid, 5-20% of waste polystyrene, 5-20% of solvent, 10-30% of ethanol or methanol, 5-20% of regulator and 0-50% of water.
The solvent is selected from one or more of ethyl acetate, chloroform, dichloroethane, acetone, tetrahydrofuran and N, N-dimethylformamide, and is preferably cyclohexane or tetrahydrofuran.
The modifier is selected from one or more of oxalic acid, citric acid, lactic acid, phthalic anhydride, acetic anhydride and propionic anhydride, preferably oxalic acid and phthalic anhydride.
The waste polystyrene is Expandable Polystyrene (EPS), and the weight average molecular weight of the waste polystyrene is less than 250000.
A sulfonic acid curing agent for furan resin comprises the following components: concentrated sulfuric acid, waste polystyrene, an organic solvent, ethanol or methanol, a regulator and water; the weight percentage of each component is as follows: 20-37% of concentrated sulfuric acid, 10-20% of waste polystyrene, 5-20% of a solvent, 10-30% of ethanol or methanol, 5-20% of a regulator and 0-50% of water.
Meanwhile, the invention provides a method for preparing a sulfonic acid curing agent for furan resin from waste polystyrene, which is characterized by comprising the following reaction steps:
(1) pretreatment of waste polystyrene: cleaning and purifying the foam or plastic of the waste polystyrene, and crushing the foam or plastic into small particles;
(2) putting the pretreated waste polystyrene and a solvent into a reaction kettle, and stirring;
(3) dropwise adding metered concentrated sulfuric acid, and controlling the reaction temperature not to exceed 45 ℃;
(4) heating to 75-95 ℃, and carrying out sulfonation reaction for 2-8 h;
(5) after the reaction is finished, dehydrating to 60-70 ℃ under negative pressure;
(6) cooling to below 50 ℃, dropwise adding metered methanol or ethanol, and controlling the reaction temperature to be not more than 60 ℃;
(7) and after the dropwise addition, adding a metered regulator and water, stirring and discharging.
Further, in the step (5), after negative pressure dehydration, the distilled solution is recycled for standby.
The technical scheme of the invention has the following advantages:
(1) the waste polystyrene is recycled and utilized, so that the pollution to the environment is reduced, waste is turned into wealth, the resource utilization rate is improved, and the production and social costs are saved;
(2) the main composition of the newly prepared polystyrene sulfonic acid curing agent is similar to that of a common sulfonic acid curing agent, and macromolecular chains of polystyrene are also reserved, so that an interpenetrating polymer network high polymer structure can be formed when the polystyrene sulfonic acid curing agent participates in a curing reaction, the rapid curing can be ensured, and the curing strength can be improved;
(3) the newly prepared sulfonic acid curing agent contains no harmful substances such as benzene, toluene, xylene and the like as raw materials, can reduce the emission of free harmful benzene series, protects the health of field operators in the production and use of the curing agent, and is environment-friendly.
The invention provides a method for preparing a sulfonic acid curing agent for furan resin by using waste polystyrene, so that the waste polystyrene is recycled, and the newly prepared sulfonic acid curing agent does not contain harmful substances such as benzene, toluene, xylene and the like, so that the waste can be utilized, the product performance can be improved, and two purposes are achieved at one stroke.
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
A sulfonic acid curing agent for furan resin comprises the following components in percentage by weight: 35% of concentrated sulfuric acid, 20% of waste polystyrene, 15% of ethyl acetate, 10% of ethanol or methanol, 5% of citric acid and 15% of water.
A preparation method of a sulfonic acid curing agent for furan resin comprises the following steps:
(1) putting 20kg of pretreated waste polystyrene and 15kg of ethyl acetate into a reaction kettle, and stirring;
(2) dripping 35kg of concentrated sulfuric acid, and controlling the reaction temperature not to exceed 45 ℃;
(3) heating to 80-82 ℃, and carrying out sulfonation reaction for 6 hours;
(4) after the reaction is finished, dehydrating to 70 ℃ under negative pressure, and recycling the distilled solution for later use;
(5) cooling to below 50 ℃, dropwise adding 10kg of metered methanol, and controlling the reaction temperature to be not more than 60 ℃;
(6) after the dropwise addition, 5kg of citric acid and 15kg of water are added, and the mixture is stirred and discharged.
Example 2
A sulfonic acid curing agent for furan resin comprises the following components in percentage by weight: 30% of concentrated sulfuric acid, 15% of waste polystyrene, 15% of trichloromethane, 10% of ethanol or methanol, 15% of oxalic acid and 15% of water.
A preparation method of a sulfonic acid curing agent for furan resin comprises the following steps:
(1) putting 15kg of pretreated waste polystyrene and 15kg of trichloromethane into a reaction kettle, and stirring;
(2) dropwise adding 30kg of concentrated sulfuric acid, and controlling the reaction temperature not to exceed 45 ℃;
(3) heating to 75-90 ℃, and carrying out sulfonation reaction for 8 hours;
(4) after the reaction is finished, dehydrating to 60 ℃ under negative pressure, and recycling the distilled solution for later use;
(5) cooling to below 50 ℃, dropwise adding 10kg of metered ethanol, and controlling the reaction temperature to be not more than 60 ℃;
(6) after the dropwise addition, 15kg of oxalic acid and 15kg of water are added, and the mixture is stirred and discharged.
Example 3
A sulfonic acid curing agent for furan resin comprises the following components in percentage by weight: 20% of concentrated sulfuric acid, 18% of waste polystyrene, 12% of tetrahydrofuran, 20% of ethanol or methanol, 15% of phthalic anhydride and 15% of water.
A preparation method of a sulfonic acid curing agent for furan resin comprises the following steps:
(1) putting 18kg of pretreated waste polystyrene and 12kg of tetrahydrofuran into a reaction kettle, and stirring;
(2) dripping 20kg of concentrated sulfuric acid, and controlling the reaction temperature not to exceed 45 ℃;
(3) heating to 75 ℃, and carrying out sulfonation reaction for 7 h;
(4) after the reaction is finished, dehydrating to 65 ℃ under negative pressure, and recycling the distilled solution for later use;
(5) cooling to below 50 ℃, dropwise adding 20kg of metered methanol, and controlling the reaction temperature to be not more than 60 ℃;
(6) after the dropwise addition, 15kg of phthalic anhydride and 15kg of water are added, and the mixture is stirred and discharged.
Example 4
A sulfonic acid curing agent for furan resin comprises the following components in percentage by weight: 36% of concentrated sulfuric acid, 17% of waste polystyrene, 18% of cyclohexane, 18% of ethanol or methanol, 5% of acetic anhydride and 6% of water.
A preparation method of a sulfonic acid curing agent for furan resin comprises the following steps:
(1) putting 17kg of pretreated waste polystyrene and 8kg of cyclohexane into a reaction kettle, and stirring;
(2) dripping 36kg of concentrated sulfuric acid, and controlling the reaction temperature not to exceed 45 ℃;
(3) heating to 86-90 ℃, and carrying out sulfonation reaction for 5 hours;
(4) after the reaction is finished, dehydrating to 70 ℃ under negative pressure, and recycling the distilled solution for later use;
(5) cooling to below 50 ℃, dropwise adding 18kg of metered ethanol, and controlling the reaction temperature to be not more than 60 ℃;
(6) after the dropwise addition, 5kg of acetic anhydride, 5kg of lactic acid and 6kg of water are added, and the mixture is stirred and discharged.
The curing agents prepared in the above examples are respectively tested for conventional indexes, the method is carried out according to national standard GB/T21872-2008 sulfonic acid curing agent for casting self-hardening furan resin, because the detection of the free sulfuric acid in the national standard GB/T21872-2008 adopts the titration method of ethylene diamine tetraacetic acid disodium standard titration solution and chrome black T indicator, the organic acid seriously interferes with the color development of the indicator, and the titration endpoint cannot be judged, so the detection is not carried out here, and the results are shown in Table 1.
TABLE 1 technical indices of curing agent
The performance of the curing agent is implemented according to the method for measuring the normal-temperature compressive strength of the resin sand in appendix D in the intensity standard JB/T7526-2008 self-hardening furan resin for casting of the sand mold, and is compared with the conventional B type curing agent (XY-) with similar total acidity (Table 2), and the result shows that: compared with the conventional curing agent of the corresponding type, the difference between the stripping speed and the final strength is not large, and the use requirements of sand casting can be completely met.
TABLE 2 conventional compressive Strength comparison data
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 (8)
1. The sulfonic acid curing agent for furan resin prepared from waste polystyrene is characterized by comprising the following components: concentrated sulfuric acid, waste polystyrene, an organic solvent, ethanol or methanol, a regulator and water; the weight percentage of each component is as follows: 20-50% of concentrated sulfuric acid, 5-20% of waste polystyrene, 5-20% of solvent, 10-30% of ethanol or methanol, 5-20% of regulator and 0-50% of water.
2. The sulfonic acid curing agent for furan resin according to claim 1, wherein the organic solvent is selected from one or more of ethyl acetate, chloroform, dichloroethane, acetone, tetrahydrofuran, and N, N-dimethylformamide.
3. The sulfonic acid curing agent for furan resin of claim 1, wherein said modifier is selected from the group consisting of one or more of oxalic acid, citric acid, lactic acid, phthalic anhydride, acetic anhydride, and propionic anhydride.
4. The sulfonic acid curing agent for furan resin according to claim 1, wherein the organic solvent is cyclohexane or tetrahydrofuran.
5. The sulfonic acid curing agent for furan resins of claim 1, wherein said modifier is selected from oxalic acid or phthalic anhydride or a combination thereof.
6. The sulfonic acid curing agent for furan resins of claim 1, wherein the waste polystyrene is Expandable Polystyrene (EPS) having a weight average molecular weight of < 250000.
7. A process for preparing a sulfonic acid curing agent for furan resins according to any of claims 1-6, characterized by comprising the reaction steps of:
(1) pretreatment of waste polystyrene: cleaning and purifying the foam or plastic of the waste polystyrene, and crushing the foam or plastic into small particles;
(2) putting the pretreated waste polystyrene and a solvent into a reaction kettle, and stirring;
(3) dropwise adding metered concentrated sulfuric acid, and controlling the reaction temperature not to exceed 45 ℃;
(4) heating to 75-95 ℃, and carrying out sulfonation reaction for 2-8 h;
(5) after the reaction is finished, dehydrating to 60-70 ℃ under negative pressure;
(6) cooling to below 50 ℃, dropwise adding metered methanol or ethanol, and controlling the reaction temperature to be not more than 60 ℃;
(7) and after the dropwise addition, adding a metered regulator and water, stirring and discharging.
8. The method as claimed in claim 7, wherein in the step (5), after the negative pressure dehydration, the distilled solution is recycled for standby.
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