CN103449979A - Bisphenol epoxy resin and preparation method thereof - Google Patents
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- CN103449979A CN103449979A CN2013103606682A CN201310360668A CN103449979A CN 103449979 A CN103449979 A CN 103449979A CN 2013103606682 A CN2013103606682 A CN 2013103606682A CN 201310360668 A CN201310360668 A CN 201310360668A CN 103449979 A CN103449979 A CN 103449979A
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Abstract
The invention relates to bisphenol epoxy resin. The structural formula of the bisphenol epoxy resin is shown in a drawing, wherein n is 0-200. The invention further provides a preparation method of the bisphenol epoxy resin. The invention further provides a bisphenol structural formula of an intermediate compound for preparing the bisphenol epoxy resin and a preparation method thereof. According to the method, flexible epoxy resin is prepared from a cardanol-phenol adduct serving as a raw material. The resin disclosed by the invention can solidify independently, can be used for improving the toughness of the traditional rigid epoxy resin, and has broad application prospects and values.
Description
Technical field
The present invention relates to chemical field, relate in particular to a kind of epoxy resin, is a kind of bisphenol epoxy and preparation method thereof specifically.
Background technology
In prior art, epoxy resin is mainly bisphenol A type epoxy resin, and due to the constructional feature of dihydroxyphenyl propane itself, that it is had advantages of is very many, but it also has that thermotolerance and toughness are not high, humidity resistance and the poor problem of weathering resistance.The main source of raw material dihydroxyphenyl propane is that petroleum products extracts and synthesizes, complex process, and process is cumbersome, and cost is higher, and oil is a kind of strategic resource, and non-renewable.
Cardanol (Cardanol) is a kind ofly from natural cashew nut shell oil, through modern technique, to refine and to form, and containing benzene ring structure, has resistance to elevated temperatures; 2. the hydroxyl of polarity can provide wetting and active to contact surface of system; 3. a position, containing carbon 15 straight chains of unsaturated double-bond, can provide system good toughness, excellent hydrophobic nature and low-permeability and from dryness.
The good innate advantage of cardanol has been used to introduce or has manufactured epoxy resin in order to improve the performance of epoxy resin.Similar invention is as follows.
The CN201110147347.5 patent of grinding scientific and technological Industrial Co., Ltd in Xuzhou discloses a kind of synthetic technology of epoxy resin, cardanol epoxy resin wherein is mainly cardanol and dihydroxyphenyl propane is raw material, add epoxy chloropropane and sodium hydroxide, in this technology, directly in the manufacturing processed of bisphenol A epoxide resin, add cardanol.But, if the cardanol epoxy resin of its formation can not solidify as an independent component, similarly be more a kind of active additive, and the addition of active additive is limited.
The CN2012103344448.8 patent that Southern Yangtze University is separately arranged, a kind of preparation method of novel monohydroxy type bio-based epoxy resin is disclosed, it adopts cardanol glycidyl ether and cardanol or unsaturated fatty acids acid-respons to generate the unsaturated bio-based resin A of monohydroxy type, then the unsaturated double-bond on the A chain is carried out to epoxidation makes monohydroxy type epoxy resin.Because it adopts the epoxidation step of two keys, this step is very dangerous owing to using superoxide.
Summary of the invention
The object of the present invention is to provide a kind of bisphenol epoxy, described this bisphenol epoxy will solve bisphenol A type epoxy resin thermotolerance of the prior art and toughness is not high, humidity resistance and the poor technical problem of weathering resistance.
The invention provides a kind of bis-phenol, its structural formula is:
Or
Or
Or
Or
Or
Or
Or
Or
Or
Or
The present invention also provides a kind of method for preparing above-mentioned bis-phenol; the method comprises: according to cardanol: the mol ratio=1:1 of phenol～10 take each material; catalyzer adds in reactor according to 0.02～10% amount of cardanol quality; being heated to 70～160 ℃ under nitrogen protection stirs 1～10 hour; then discharging, use organic solvent diluting, with hot wash at least twice; remove unnecessary phenol, vacuum boils off the organic phase solvent and obtains the yellowish brown viscous liquid and be cardanol-phenol adducts.
Further, the temperature of described hot water is between 60～90 ℃.
Further, described catalyzer is that acid includes but not limited to sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, acetic acid, perchloric acid, Periodic acid, Hydrogen bromide or hydroiodic acid HI.
Further, described organic solvent is dimethylbenzene, toluene or methyl alcohol.
Further, described phenol can be also other phenol that can be combined with cardanol, includes but not limited to bis-phenol base propane, nonyl phenol, faces tert-butyl phenol, p-tert-butylphenol, p-phenyl phenol or orthoxenol.
The invention provides a kind of bisphenol epoxy, its structural formula is as follows:
N=0-200 wherein, w wherein, m, x, y, a, b, f, p represents numeral, w+x=15 wherein, m+y=32-2b (b=0-2), a+f=15, b+p=31-2c (c=0-2), w, a is in 7,10,13 one, w, a can be identical, also can be different; M, b is in 14,18,22 one, m, b, can be identical, also can be different.
The present invention also provides a kind of method for preparing above-mentioned bisphenol epoxy, according to bis-phenol: epoxy chloropropane: the quality of the mol ratio=1:1.5 of highly basic～10:1.5～10 takes each material, then bis-phenol is added in reaction vessel, stir, pass into the nitrogen exhausted air, add again epoxy chloropropane after 1～5 minute, continue to stir, control temperature at 40～50 degrees centigrade, add highly basic, be warming up to 70～100 degrees centigrade after dropwising, be incubated 2～9 hours, use organic solvent dissolution, hot wash at least twice, the red-brown thick liquid that underpressure distillation obtains is bisphenol epoxy.
Further, described highly basic is sodium hydroxide or potassium hydroxide.
Further, the mass percent concentration of described highly basic is 30-50%.
Further, the temperature of described hot water is between 60～90 ℃.
Further, described organic solvent is dimethylbenzene, toluene or methyl alcohol.
The chemical equation of bis-phenol of the present invention is as follows:
The chemical equation of epoxy resin of the present invention is as follows:
The present invention and prior art are compared, and its effect is actively with obvious.Currently available technology raw material dihydroxyphenyl propane main source is that petroleum products extracts and synthesizes, complex process, and process is cumbersome, cost is higher, and raw material of the present invention is mainly cardanol, the process of refinement that its main source is cashew shell liquid, derive from plant, environmental protection, with low cost, renewable, there is cost low, pure plant, renewable, the advantages such as environmental protection.At first the present invention has prepared cardanol-phenol adducts, then adopt bis-phenol to prepare a kind of epoxy resin of flexibility as raw material, resin of the present invention not only can independently solidify but also can be used for improving the toughness of conventional rigid epoxy resin, was with a wide range of applications and was worth.In the present invention, bisphenol synthesis epoxy resin can independently solidify.Addition can be determined as required, and the adjusting degree of freedom of filling a prescription is increased greatly.The bis-phenol that the present invention uses cardanol-phenol to form, as raw material, has been avoided the epoxidation step of two keys, makes that reactions steps reduces, technique is simpler, safe, controlled, is easy to suitability for industrialized production.The bisphenol epoxy that the present invention is synthetic, owing to having long alkyl chain C15H31-2n, thereby have good toughness and humidity resistance.The synthetic bisphenol epoxy of the present invention can be separately solidifies with common epoxy curing agent also can be mixed with other epoxy resin to improve the toughness of other epoxy resin, humidity resistance.Due to the chemical structure characteristics of cardanol itself, be the general characteristic that bisphenol epoxy had both had epoxy resin, there are again some special propertys, such as high tenacity, from dryness, hydrophobic nature and humidity resistance.
The accompanying drawing explanation
Fig. 1 is the preparation flow figure of epoxy resin of the present invention.
Fig. 2 is the TLC analysis chart of the bis-phenol in the present invention, SM-phenol, cardanol mixture; 1 is the column chromatography component; 2 is the column chromatography component.
Embodiment
The invention provides a kind of preparation method of epoxy resin raw material bis-phenol; according to cardanol: the mol ratio=1:1 of phenol～10; catalyzer adds in four-hole boiling flask according to 0.02～10% amount of cardanol amount; be heated to 70-160 ℃ under nitrogen protection and stir 1-10 hour, then discharging, dilute with dimethylbenzene; with (80 ℃ of hot water; 500mL*5～10) washing, remove unnecessary phenol, and vacuum boils off the dimethylbenzene phase solvent and obtains the yellowish brown viscous liquid and be cardanol-phenol adducts.Viscosity is 8000-150000mPa.S, and this column chromatography for compound (silica gel 100-200 order, eluent adopts benzene) is isolated two groups of structures (component one and component two), then with nuclear-magnetism, identifies respectively:
Generated new material by reaction as seen from Figure 2, due to complicated components, column chromatography can not separate fully, so be divided into two groups, performs an analysis.
Component one nuclear magnetic data is as follows
1hNMR (CDCl3), 0.85 (d, 3H ,-CH3), 1.20-1.61 (m, 24H ,-(CH
2)
12-), 2.52 (t, 2H ,-CH
2-) 2.59-2.87 (m, 1H ,-CH-), 4.67-6.75 (brs, 2H, 2X-OH, the heavy water exchange disappears), 6.65-7.24(m, 8H, Ar-H), m/z (M+H)
+, 393.2,395.2,397.2.
Component two nuclear magnetic datas are as follows
1hNMR (CDCl3), 0.84 (d, 3H ,-CH3), 1.19-1.54 (m, 24H ,-(CH
2)
12-), 2.50 (m, 3H ,-CH
2-and1H ,-CH-), 4.80 (brs, 2H, 2X-OH, the heavy water exchange disappears), 6.50-7.20(m, 8H, Ar-H), m/z (M+H)
+, 393.2,395.2,397.2.
11 molecules are because structural similitude has been divided into two groups, and then the nuclear magnetic data of each group as mentioned above.Top data are not single molecule, but mixture, because column chromatography is inseparable, so can only be divided into two groups, is done nuclear-magnetism.We notice that the number of phenolic hydroxyl group in two components is all two.
Wherein catalyzer is that acid includes but not limited to sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, acetic acid, perchloric acid, Periodic acid, Hydrogen bromide, hydroiodic acid HI etc.
As shown in Figure 2, can find out that from this TLC plate raw material disappears, and has generated new point.Also illustrate that the bis-phenol building-up reactions successfully carries out.
By nuclear-magnetism, MS and TLC, can be found out.We successfully synthesize this bis-phenol structure.Synthetic bis-phenol is mixture, but no matter addition at 8, or 11, or 14 synthetic bis-phenols may be used to bisphenol synthesis epoxy resin.
As shown in Figure 1, the invention provides a kind of preparation method of bisphenol epoxy, according to bis-phenol: epoxy chloropropane: the quality of the mol ratio=1:1.5 of sodium hydroxide～10:1.5～10 takes each material, then bis-phenol is added in reaction vessel, stir, pass into the nitrogen exhausted air, add again epoxy chloropropane after 1～5 minute, continue to stir, control temperature at 40～50 degrees centigrade, add sodium hydroxide, the mass percent concentration of described sodium hydroxide is 30-50%, be warming up to 70～100 degrees centigrade after dropwising, be incubated 2～9 hours, use xylene soluble, after hot wash repeatedly, underpressure distillation obtains firstling red-brown thick liquid and is prepared product.The bis-phenol that the present embodiment adopts is the bisphenol mixture that embodiment 1 obtains.
The epoxy resin obtained has been done to basic detection, and oxirane value is 0.23eq/100g, and viscosity is: 25200mPa.S, solid content: 97%.
| Project | Data |
| Oxirane value (eq/100g) | 0.23 |
| Viscosity (mPa.s) | 25200 |
| Gu containing (%) | 97 |
The cure test of embodiment 3 bisphenol epoxies and MD650 solidifying agent.
The general preparation method of paint film is according to GB GB1727-79, pencil hardness test method GB/T6739-1996, paint film adhesion assay method GB1720-79, paint film flexibility assay method (bending) GB1731-1993, paint film shock-resistance assay method GB1732-93, plastics shore hardness test method GB-T2411-2008.
| Project | Data |
| Supporting proportioning | Bisphenol epoxies/MD650=100/28 |
| Paint film appearance | Smooth smooth Gao Guang |
| Dry film | 25-31um |
| Impact | 50cm |
| Crooked | |
| Sticking power | |
| 1 grade | |
| Surface hardness | 2B |
| Shore hardness | 21° |
Embodiment 4
Though in view of bisphenol epoxy and the MD650 solidifying agent curable, after solidifying, shore hardness is on the low side, thus mixed and curing with the MD650 epoxy hardener according to the 1:1 mass ratio with the E51 resin with bisphenol epoxy, and provided concrete performance data.
The general preparation method of paint film is according to GB GB1727-79, pencil hardness test method GB/T6739-1996, paint film adhesion assay method GB1720-79, paint film flexibility assay method (bending) GB1731-1993, paint film shock-resistance assay method GB1732-93, plastics shore hardness test method GB-T2411-2008.
A, fundamental property:
| Project | Data |
| Oxirane value (eq/100g) | 0.37 |
| Viscosity (mPa.s) | 18000 |
| Gu containing (%) | 99% |
B, cure test:
| Project | Data |
| Supporting proportioning | E51/MD650=100/80 |
| Paint film appearance | Smooth smooth Gao Guang |
| Gel time (25 ℃) | 1h30min |
| Surface hardness | H |
| Shore hardness | 80-85 ° (25 ℃/7 days) |
| Dry film | 25-44um |
| Impact | 30-40cm |
| Crooked | |
| Sticking power | |
| 1 grade |
Performance data after embodiment 5E51 resin and MD650 solidifying agent solidify
The general preparation method of paint film is according to GB GB1727-79, pencil hardness test method GB/T6739-1996, paint film adhesion assay method GB1720-79, paint film flexibility assay method (bending) GB1731-1993, paint film shock-resistance assay method GB1732-93, plastics shore hardness test method GB-T2411-2008.
A, fundamental property:
| Project | Data |
| Oxirane value (eq/100g) | 0.51 |
| Viscosity (mPa.s) | 12000 |
| Gu containing (%) | 99% |
B, cure test:
| Project | Data |
| Supporting proportioning | E51/MD650=100/80 |
| Paint film appearance | Smooth smooth Gao Guang |
| Gel time (25 ℃) | 1h30min |
| Surface hardness | H |
| Shore hardness | 80-85 ° (25 ℃/7 days) |
| Dry film | 25-44um |
| Impact | 30-40cm |
| Crooked | |
| Sticking power | |
| 1 grade |
MD650: be the solidifying agent model that Mei Dong biological company limited in Shanghai produces, viscosity 20000-50000mPa.S, amine value: 270～300mgKOH/g, gel time: 40-70(min, 50g, 25 ℃)
E51:E51 epoxy resin, oxirane value is 0.48-0.54.
Bisphenol epoxies: for the preparation the bisphenol epoxies model in a kind of.
Conclusion: top form, for the curing properties of the epoxy resin of preparation, can be found out from this form, even if add in the situation of 50% bisphenol epoxy, follows and uses E51 resin-phase ratio fully, and shore hardness, surface hardness descend and be not obvious, and sticking power is identical.Impact property and bending property improve obviously, have shown the utility value of this bisphenol epoxy as the toughness strongthener.
Claims (11)
1. a bis-phenol, its structural formula is:
Or
Or
Or
Or
Or
or
Or
2. a method for preparing bis-phenol claimed in claim 1; it is characterized in that: according to cardanol: the mol ratio=1:1 of phenol～10 take each material; catalyzer adds in reactor according to 0.02～10% amount of cardanol quality; being heated to 70～160 ℃ under nitrogen protection stirs 1～10 hour; then discharging; use organic solvent diluting, with hot wash at least twice, vacuum boils off the organic phase solvent and obtains the yellowish brown viscous liquid and be cardanol-phenol adducts.
3. the preparation method of bis-phenol as claimed in claim 2, it is characterized in that: the temperature of described hot water is between 60～90 ℃.
4. the preparation method of bis-phenol as claimed in claim 2 is characterized in that: described catalyzer, for acid, comprises sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, acetic acid, perchloric acid, Periodic acid, Hydrogen bromide or hydroiodic acid HI.
5. the preparation method of bis-phenol as claimed in claim 2, it is characterized in that: described organic solvent is dimethylbenzene, toluene or methyl alcohol.
6. the preparation method of bis-phenol as claimed in claim 2, it is characterized in that: described phenol can be other phenol that can be combined with cardanol, comprises bis-phenol base propane, nonyl phenol, faces tert-butyl phenol, p-tert-butylphenol, p-phenyl phenol or orthoxenol.
7. a bisphenol epoxy, it is characterized in that: its structural formula is as follows:
N=0-200 wherein, w wherein, m, x, y, a, b, f, p represents numeral, w+x=15 wherein, m+y=32-2b (b=0-2), a+f=15, b+p=31-2c (c=0-2), w, a is in 7,10,13 one, w, a can be identical, also can be different; M, b is in 14,18,22 one, m, b, can be identical, also can be different.
8. a method for preparing bisphenol epoxy claimed in claim 7, it is characterized in that: according to bis-phenol: epoxy chloropropane: the quality of the mol ratio=1:1.5 of highly basic～10:1.5～10 takes each material, then bis-phenol is added in reaction vessel, stir, pass into the nitrogen exhausted air, add again epoxy chloropropane after 1～5 minute, continue to stir, control temperature at 40～50 degrees centigrade, add highly basic, be warming up to 70～100 degrees centigrade after dropwising, be incubated 2～9 hours, use organic solvent dissolution, hot wash at least twice, the red-brown thick liquid that underpressure distillation obtains is bisphenol epoxy.
9. the preparation method of bisphenol epoxy as claimed in claim 7, it is characterized in that: described highly basic is sodium hydroxide or potassium hydroxide.
10. the preparation method of bisphenol epoxy as claimed in claim 7, it is characterized in that: the temperature of described hot water is between 60-90 ℃.
11. the preparation method of bisphenol epoxy as claimed in claim 7 is characterized in that: described organic solvent is dimethylbenzene, toluene or methyl alcohol.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881305A (en) * | 2014-03-04 | 2014-06-25 | 天津虹炎科技有限公司 | Epoxy resin composition |
| CN104014152A (en) * | 2014-06-25 | 2014-09-03 | 泸州北方化学工业有限公司 | Debenzolization technology for plastic stabilizer |
| CN108864409A (en) * | 2018-07-09 | 2018-11-23 | 安徽善孚新材料科技股份有限公司 | A kind of weather-proof epoxide resin material and preparation method thereof |
| CN113402698A (en) * | 2021-04-15 | 2021-09-17 | 常熟耐素生物材料科技有限公司 | Plant-based multifunctional toughening epoxy resin and preparation method thereof |
| CN114478200A (en) * | 2020-10-28 | 2022-05-13 | 中国石油化工股份有限公司 | Phenol derivative and preparation method and application thereof |
| CN115975694A (en) * | 2021-10-15 | 2023-04-18 | 中国石油化工股份有限公司 | Hydraulic oil composition and preparation method thereof |
| CN115975706A (en) * | 2021-10-15 | 2023-04-18 | 中国石油化工股份有限公司 | Industrial lubricating oil composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881305A (en) * | 2014-03-04 | 2014-06-25 | 天津虹炎科技有限公司 | Epoxy resin composition |
| CN103881305B (en) * | 2014-03-04 | 2016-03-02 | 天津虹炎科技有限公司 | Composition epoxy resin |
| CN104014152A (en) * | 2014-06-25 | 2014-09-03 | 泸州北方化学工业有限公司 | Debenzolization technology for plastic stabilizer |
| CN104014152B (en) * | 2014-06-25 | 2016-02-10 | 泸州北方化学工业有限公司 | The de-benzene process of stabilizer for plastics |
| CN108864409A (en) * | 2018-07-09 | 2018-11-23 | 安徽善孚新材料科技股份有限公司 | A kind of weather-proof epoxide resin material and preparation method thereof |
| CN108864409B (en) * | 2018-07-09 | 2020-08-18 | 安徽善孚新材料科技股份有限公司 | Weather-resistant epoxy resin material and preparation method thereof |
| CN114478200A (en) * | 2020-10-28 | 2022-05-13 | 中国石油化工股份有限公司 | Phenol derivative and preparation method and application thereof |
| CN113402698A (en) * | 2021-04-15 | 2021-09-17 | 常熟耐素生物材料科技有限公司 | Plant-based multifunctional toughening epoxy resin and preparation method thereof |
| CN115975694A (en) * | 2021-10-15 | 2023-04-18 | 中国石油化工股份有限公司 | Hydraulic oil composition and preparation method thereof |
| CN115975706A (en) * | 2021-10-15 | 2023-04-18 | 中国石油化工股份有限公司 | Industrial lubricating oil composition and preparation method thereof |
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Application publication date: 20131218 |