CN103059505A - CO2 cured alkaline phenolic resin and preparation method thereof - Google Patents
CO2 cured alkaline phenolic resin and preparation method thereof Download PDFInfo
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- CN103059505A CN103059505A CN2012104836704A CN201210483670A CN103059505A CN 103059505 A CN103059505 A CN 103059505A CN 2012104836704 A CN2012104836704 A CN 2012104836704A CN 201210483670 A CN201210483670 A CN 201210483670A CN 103059505 A CN103059505 A CN 103059505A
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Abstract
The invention aims to provide a CO2 cured alkaline phenolic resin and a preparation method thereof. The CO2 cured alkaline phenolic resin is characterized by being prepared from the following components in parts by weight: 150-200 parts of phenol compounds, 250-300 parts of aldehyde compounds, 30-50 parts of a modifier, 300-400 parts of 50% aqueous alkali, 50-70 parts of a hardening accelerating agent and 3-5 parts of a silane coupling agent. Compared with viscosity of 150mPa.s at the temperature of more than 25 DEG C of the CO2 cured alkaline phenolic resin in the prior art, the viscosity of the CO2 cured alkaline phenolic resin provided by the invention is reduced below 100mPa.s at the temperature of 25 DEG C. In addition, the CO2 cured alkaline phenolic resin can ensure that the strength of resin-bonded sand is high and the use performance is improved and can greatly facilitate the operation of sanding mixing during modeling and core making.
Description
Technical field
The present invention relates to the binding agent that uses in a kind of Foundry Production moulding, the coremaking process, this binding agent uses CO
2Gas hardening.The invention still further relates to the preparation method of this binding agent, particularly reduce the method for this binding agent normal temperature viscosity.
Background technology
CO
2Cured alkaline phenol resin is a kind of novel binders that begins to be applied to domestic Foundry Production the nineties in 20th century.CO
2Cured alkaline phenol resin is nonnitrogenous, sulphur, phosphoric, and is less to the detrimentally affect of foundry goods; The solidifying agent that adopts is CO
2Gas, toxic and harmful is few, environmental pollution is little, and moulding, coremaking place do not need expensive treating plant, and environmental-protecting performance is with the obvious advantage.In addition, CO
2The cured alkaline phenol resin curing process is simple, and is easy to operate, blows CO
2The over-blowing problem is lacked, do not existed to gas hardening, gassing time, higher than ester sclerosis production efficiency, both had been suitable for common sand mill mulling, core shooting machine coremaking, streamline production, also is suitable for hand moulding, coremaking.Therefore, CO
2Cured alkaline phenol resin has the feature of environmental protection and manufacturability double dominant, and the development trend that meet the Foundry Production greenization, cleans is called as one of air hardening cold-box material geared to the 21st century, is paid close attention to widely.
At present, the CO that uses on the domestic market
2The viscosity that the general deficiency that cured alkaline phenol resin exists is resin is larger, much all surpasses 150mPas(25 ℃), resin and silica sand are not easy to mix during molding and core making, and use properties is not good; Some CO
2The viscosity of cured alkaline phenol resin is lower, but its cohesive strength is also lower, occurs easily the situations such as crush during molding, affects production efficiency.
Summary of the invention
The object of the present invention is to provide a kind of CO
2Cured alkaline phenol resin and preparation method thereof, the method can be with CO
2The reduced viscosity of cured alkaline phenol resin is to 100mPas(25 ℃) below, guarantee that simultaneously resin sand has higher intensity, improves the use properties of resin sand.
The present invention specifically provides a kind of CO
2Cured alkaline phenol resin is characterized in that, described CO
2Cured alkaline phenol resin by following compositions by weight ratio form:
CO of the present invention
2Cured alkaline phenol resin is characterized in that, described phenolic compound is selected from one or both or the two or more mixtures in phenol, cresols, xylenol, meta-cresol, dihydroxyphenyl propane, the Resorcinol.
CO of the present invention
2Cured alkaline phenol resin is characterized in that, described aldehyde compound be selected from formaldehyde (37% ~ 40% aqueous solution), Paraformaldehyde 96, acetaldehyde, oxalic dialdehyde, one or both or two or more mixtures in the furfural.
CO of the present invention
2Cured alkaline phenol resin, it is characterized in that, described properties-correcting agent is selected from one or both or the two or more mixtures in furfuryl alcohol, triglycol, phenylcarbinol, phenylpropyl alcohol, 3-enanthol, ethylene glycol, sorbyl alcohol, Xylitol, the N.F,USP MANNITOL, and properties-correcting agent and alkali must participate in reaction simultaneously.
CO of the present invention
2Cured alkaline phenol resin is characterized in that, described alkali is selected from one or both or the two or more mixtures in potassium hydroxide, sodium hydroxide, the lithium hydroxide.
CO of the present invention
2Cured alkaline phenol resin is characterized in that, described accelerator for hardening is selected from one or both the mixture in borax or the calcium hydroxide.
CO of the present invention
2Cured alkaline phenol resin, it is characterized in that, described silane coupling agent is selected from one or both the mixture in γ-aminopropyl triethoxysilane, γ-(2,3) epoxy (propoxy-) propyl trimethoxy silicane, gamma-methyl allyl acyloxypropyl trimethoxysilane, N-(the β aminoethyl)-γ-aminopropyl methyl dimethoxysilane.
The present invention also provides a kind of CO
2The preparation method of cured alkaline phenol resin is characterized in that, this preparation method may further comprise the steps:
1) phenolic compound, aldehyde compound and 50% alkali aqueous solution that accounts for total mass 5% ~ 10% are added in the reactor, be warming up to 65 ℃ with the speed less than 1 ℃/min, be incubated 30 ~ 60 minutes;
2) add properties-correcting agent and 50% alkali aqueous solution that accounts for total mass 20% ~ 25%, be warming up to 100 ℃, be incubated 45 to 90 minutes;
3) be decompressed to-0.06MPa ~-distill under the pressure of 0.08MPa;
4) add remaining 50% alkali aqueous solution;
5) be cooled to below 60 ℃, add accelerator for hardening, stir;
6) be cooled to below 40 ℃, add silane coupling agent, stir discharging.
CO of the present invention
2The preparation method of cured alkaline phenol resin is characterized in that: described content of phenolic compounds is more than 99.0%, and the content of aldehyde compound is 37% ~ 40%.
Traditional CO
2The cured alkaline phenol resin binding agent in use mixes silica sand and resin glue first, passes into CO again
2Gas solidifies molding sand.In order to improve the cohesive strength of molding sand, usually in the building-up process of resin, improve temperature of reaction, prolong the reaction times, improve the molecular weight of resin, thereby reach the purpose that improves resin-bonded intensity.The molecular resin amount causes that also viscosity increases considerably after improving, and in the process of moulding, coremaking, silica sand and binding agent are difficult for mixing, and the molding sand use properties is not good.The present invention adopts the method for pure and mild alkali co-catalysis of polycondensation stage to reduce the viscosity of resin, and the while is not reduced the cohesive strength of resin, greatly strengthens the use properties of molding sand.
Compared with prior art, technical characterstic of the present invention is: in the resinifying polycondensation stage, add simultaneously pure and mild alkali, under the co-catalysis effect of pure and mild alkali, improve the molecular weight of resin, reduce the viscosity of resin, can be with the viscosity of resin by 150mPas(25 ℃) more than be reduced to 100mPas(25 ℃) below, keep simultaneously resin to have higher cohesive strength, be very easy to the mulling operation in moulding, the coremaking process.
Embodiment
Embodiment 1
Phenol, 300kg formalin (37%) that 195kg is dissolved add in the reactor, add sodium hydroxide solution (50% concentration) 20kg, are warming up to 65 ℃ with the speed less than 1 ℃/min, insulation 30min.Add 50kg triglycol, 80kg potassium hydroxide solution (50%), be warming up to 100 ℃, insulation 60min.Be cooled to 85 ℃ ,-0.06MPa ~-0.08MPa pressure under underpressure distillation dehydration 50kg.Add potassium hydroxide solution (50%) 300kg.Be cooled to 60 ℃, add the 60kg borax, stir.Be cooled to 40 ℃, add γ-(2,3) epoxy (propoxy-) propyl trimethoxy silicane 3kg, stir discharging.
Embodiment 2
Phenol and 30kg dihydroxyphenyl propane, 250kg formalin (37%) and 20kg Paraformaldehyde 96 that 150kg is dissolved add in the reactor, add sodium hydroxide solution (50%) 20kg, are warming up to 65 ℃ with the speed less than 1 ℃/min, insulation 60min.Add 50kg furfuryl alcohol, 80kg potassium hydroxide solution (50%), be warming up to 100 ℃, insulation 45min.Be cooled to 85 ℃ ,-0.06MPa ~-0.08MPa pressure under underpressure distillation dehydration 30kg.Add potassium hydroxide solution (50%) 300kg.Be cooled to 60 ℃, add the 60kg borax, stir.Be cooled to 40 ℃, add γ-(2,3) epoxy (propoxy-) propyl trimethoxy silicane 3kg, stir discharging.
Embodiment 3
Phenol and 15kg Resorcinol, 270kg formalin (37%) and 20kg oxalic dialdehyde that 165kg is dissolved add in the reactor, add sodium hydroxide solution (50%) 35kg, are warming up to 65 ℃ with the speed less than 1 ℃/min, insulation 60min.Add 35kg furfuryl alcohol and 15kg ethylene glycol, 80kg potassium hydroxide solution (50%), be warming up to 100 ℃, insulation 90min.Be cooled to 85 ℃ ,-0.06MPa～-0.08MPa pressure under underpressure distillation dehydration 40kg.Add potassium hydroxide solution (50%) 250kg.Be cooled to 60 ℃, add 55kg borax and 5kg calcium hydroxide, stir.Be cooled to 40 ℃, add γ-aminopropyl triethoxysilane 5kg, stir discharging.
Embodiment 4
Phenol, 270kg formalin (37%) and 20kg Paraformaldehyde 96 that 190kg is dissolved add in the reactor, add sodium hydroxide solution (50%) 25kg, are warming up to 65 ℃ with the speed less than 1 ℃/min, insulation 45min.Add 30kg phenylcarbinol and 20kg sorbyl alcohol, 75kg potassium hydroxide solution (50%), be warming up to 100 ℃, insulation 60min.Be cooled to 85 ℃ ,-0.06MPa ~-0.08MPa pressure under underpressure distillation dehydration 40kg.Add potassium hydroxide solution (50%) 270kg.Be cooled to 60 ℃, add 55kg borax and 5kg calcium hydroxide, stir.Be cooled to 40 ℃, add N-(β aminoethyl)-γ-aminopropyl methyl dimethoxysilane 5kg, stir discharging.
Comparative Examples 1
Phenol, 300kg formalin (37%) that 195kg is dissolved add in the reactor, add sodium hydroxide solution (50%) 20kg, are warming up to 65 ℃ with the speed less than 1 ℃/min, insulation 30min.Add 80kg potassium hydroxide solution (50%), be warming up to 100 ℃, insulation 60min.Be cooled to 85 ℃ ,-0.06MPa ~-0.08MPa pressure under underpressure distillation dehydration 50kg.Add potassium hydroxide solution (50%) 300kg.Be cooled to 60 ℃, add the 60kg borax, stir.Be cooled to 40 ℃, add γ-(2,3) epoxy (propoxy-) propyl trimethoxy silicane 3kg, stir discharging.
Performance Detection
Get the 1000g roughing sand, add 25g alkalescent phenol resin cakingagent, shake out behind the mixed 60s processed.The molding sand that will mix again after the system impacts 3 times at SAC paddle type mill sampling machine, makes the compressive sample of Φ 50mm * 50mm, then in test specimen tube with 0.7 ~ 0.8m
3The flow of/h is blown into CO
2Gas 120s hardens, and makes sand test specimen, places 24 hours, surveys its ultimate compression strength.
Table 1 the performance test results
Obviously, above-described embodiment only is for example clearly is described, and is not the restriction to embodiment, for those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give all embodiments exhaustive.And the apparent variation of being amplified out thus or change still are among the protection domain of the invention.
Claims (9)
1. CO
2Cured alkaline phenol resin is characterized in that, described CO
2Cured alkaline phenol resin by following compositions by weight ratio form:
2. CO according to claim 1
2Cured alkaline phenol resin is characterized in that, described phenolic compound is selected from one or both or the two or more mixtures in phenol, cresols, xylenol, meta-cresol, dihydroxyphenyl propane, the Resorcinol.
3. CO according to claim 1
2Cured alkaline phenol resin is characterized in that, described aldehyde compound be selected from formaldehyde, Paraformaldehyde 96, acetaldehyde, oxalic dialdehyde, one or both or two or more mixtures in the furfural, wherein formaldehyde is that concentration is 37% ~ 40% the aqueous solution.
4. CO according to claim 1
2Cured alkaline phenol resin, it is characterized in that, described properties-correcting agent is selected from one or both or the two or more mixtures in furfuryl alcohol, triglycol, phenylcarbinol, phenylpropyl alcohol, 3-enanthol, ethylene glycol, sorbyl alcohol, Xylitol, the N.F,USP MANNITOL, and properties-correcting agent and alkali must participate in reaction simultaneously.
5. CO according to claim 1
2Cured alkaline phenol resin is characterized in that, described alkali is selected from one or both or the two or more mixtures in potassium hydroxide, sodium hydroxide, the lithium hydroxide.
6. CO according to claim 1
2Cured alkaline phenol resin is characterized in that, described accelerator for hardening is selected from one or both the mixture in borax or the calcium hydroxide.
7. CO according to claim 1
2Cured alkaline phenol resin, it is characterized in that, described silane coupling agent is selected from one or both the mixture in γ-aminopropyl triethoxysilane, γ-(2,3) epoxy (propoxy-) propyl trimethoxy silicane, gamma-methyl allyl acyloxypropyl trimethoxysilane, N-(the β aminoethyl)-γ-aminopropyl methyl dimethoxysilane.
8. CO as claimed in claim 1
2The preparation method of cured alkaline phenol resin is characterized in that, this preparation method may further comprise the steps:
1) phenolic compound, aldehyde compound and 50% alkali aqueous solution that accounts for total mass 5% ~ 10% are added in the reactor, be warming up to 65 ℃ with the speed less than 1 ℃/min, be incubated 30 ~ 60 minutes;
2) add properties-correcting agent and 50% alkali aqueous solution that accounts for total mass 20% ~ 25%, be warming up to 100 ℃, be incubated 45 to 90 minutes;
3) be decompressed to-0.06MPa ~-distill under the pressure of 0.08MPa;
4) add remaining 50% alkali aqueous solution;
5) be cooled to below 60 ℃, add accelerator for hardening, stir;
6) be cooled to below 40 ℃, add silane coupling agent, stir discharging.
9. according to the described CO of claim 8
2The preparation method of cured alkaline phenol resin is characterized in that: described content of phenolic compounds is more than 99.0%, and the content of aldehyde compound is 37% ~ 40%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210483670.4A CN103059505B (en) | 2012-11-23 | 2012-11-23 | CO2 cured alkaline phenolic resin and preparation method thereof |
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|---|---|---|---|
| CN201210483670.4A CN103059505B (en) | 2012-11-23 | 2012-11-23 | CO2 cured alkaline phenolic resin and preparation method thereof |
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| CN103059505A true CN103059505A (en) | 2013-04-24 |
| CN103059505B CN103059505B (en) | 2015-06-10 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817665A (en) * | 2015-03-04 | 2015-08-05 | 宁夏共享化工有限公司 | Alkaline phenol formaldehyde resin for 3D printing, and preparation method thereof |
| CN105949418A (en) * | 2016-07-06 | 2016-09-21 | 宁夏共享化工有限公司 | 3D (three-dimensional) printing resin for aluminum castings and production method thereof |
| WO2017215117A1 (en) * | 2016-06-17 | 2017-12-21 | 宁夏共享化工有限公司 | Cold-curing phenolic resin for 3d moulding sand printing and preparation method therefor |
| CN108889898A (en) * | 2018-06-06 | 2018-11-27 | 山东怡泰恒环保材料有限公司 | A kind of cast aluminium binder |
| CN110918868A (en) * | 2020-01-02 | 2020-03-27 | 四川东树新材料有限公司 | Ester-cured phenolic resin for large-scale casting and molding and preparation method thereof |
| CN115921768A (en) * | 2022-12-08 | 2023-04-07 | 江苏华岗材料科技发展有限公司 | Cold core box resin for casting and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410466A (en) * | 2001-09-29 | 2003-04-16 | 济南圣泉集团股份有限公司 | Organic ester hardening alkaline phenolic resin and its preparation method |
| CN101274350A (en) * | 2007-03-29 | 2008-10-01 | 沈阳工业大学 | Hardening accelerating admixture of carbon dioxide cured phenol resin sand |
| CN101348549A (en) * | 2008-08-22 | 2009-01-21 | 辽宁福鞍铸业集团有限公司 | Hydroxyl-terminated alkaline phenolic resin and preparation thereof |
-
2012
- 2012-11-23 CN CN201210483670.4A patent/CN103059505B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410466A (en) * | 2001-09-29 | 2003-04-16 | 济南圣泉集团股份有限公司 | Organic ester hardening alkaline phenolic resin and its preparation method |
| CN101274350A (en) * | 2007-03-29 | 2008-10-01 | 沈阳工业大学 | Hardening accelerating admixture of carbon dioxide cured phenol resin sand |
| CN101348549A (en) * | 2008-08-22 | 2009-01-21 | 辽宁福鞍铸业集团有限公司 | Hydroxyl-terminated alkaline phenolic resin and preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张颖杰: "CO2硬化碱性酚醛树脂材料及工艺的研究", 《中国优秀硕士学位论文全文数据库-工程科技I辑》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817665A (en) * | 2015-03-04 | 2015-08-05 | 宁夏共享化工有限公司 | Alkaline phenol formaldehyde resin for 3D printing, and preparation method thereof |
| CN104817665B (en) * | 2015-03-04 | 2017-07-07 | 宁夏共享化工有限公司 | A kind of 3D printing alkalescent phenol resin and preparation method thereof |
| WO2017215117A1 (en) * | 2016-06-17 | 2017-12-21 | 宁夏共享化工有限公司 | Cold-curing phenolic resin for 3d moulding sand printing and preparation method therefor |
| CN105949418A (en) * | 2016-07-06 | 2016-09-21 | 宁夏共享化工有限公司 | 3D (three-dimensional) printing resin for aluminum castings and production method thereof |
| CN108889898A (en) * | 2018-06-06 | 2018-11-27 | 山东怡泰恒环保材料有限公司 | A kind of cast aluminium binder |
| CN108889898B (en) * | 2018-06-06 | 2019-12-31 | 孙梓宁 | Adhesive for cast aluminum |
| CN110918868A (en) * | 2020-01-02 | 2020-03-27 | 四川东树新材料有限公司 | Ester-cured phenolic resin for large-scale casting and molding and preparation method thereof |
| CN110918868B (en) * | 2020-01-02 | 2020-11-06 | 四川东树新材料有限公司 | Ester-cured phenolic resin for large-scale casting and molding and preparation method thereof |
| CN115921768A (en) * | 2022-12-08 | 2023-04-07 | 江苏华岗材料科技发展有限公司 | Cold core box resin for casting and preparation method thereof |
| CN115921768B (en) * | 2022-12-08 | 2023-10-24 | 江苏华岗材料科技发展有限公司 | Cold box resin for casting and preparation method thereof |
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