CN108409941A - A kind of cleanly production technique of solid epoxy - Google Patents
A kind of cleanly production technique of solid epoxy Download PDFInfo
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- CN108409941A CN108409941A CN201810240701.0A CN201810240701A CN108409941A CN 108409941 A CN108409941 A CN 108409941A CN 201810240701 A CN201810240701 A CN 201810240701A CN 108409941 A CN108409941 A CN 108409941A
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- lignin
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- cardanol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention belongs to chemical technology fields, and in particular to a kind of cleanly production technique of solid epoxy.Step includes：Alcohol deposition method is carried from extracting lignose from papermaking black liquor using acid；It is modified as hydroxymethylated lignin with formalin again, it is further then modified as to modified by cardanol lignin with anacardol.Reaction kettle is added in modified by cardanol lignin, epoxychloropropane, phase transfer catalyst, lye is added while stirring and is reacted.Acquired solution is adjusted to neutrality with alkene hydrochloric acid, vacuum distillation is washed to neutrality after removing excessive epoxychloropropane, is dried in vacuo to get solid powdery epoxy resin.The present invention is using paper-making industry waste liquid, anacardol as raw material, non-toxic degradable, energy conservation and environmental protection, while improving the problem of epoxy resin toughness deficiency, and the yield of the epoxy resin prepared is up to 99% or more, and epoxide number also reaches ideal state.
Description
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of cleanly production technique of solid epoxy.
Background technology
Epoxy resin has excellent chemical performance：Shrinking percentage is low, adhesion strength is big, high mechanical strength, electrical isolation
Property it is good etc., be widely used in the every field of production and living.But its raw materials for production, it is most of all from petrochemical industry, it is right
Oil degree of dependence is very high, and the bisphenol A type epoxy resin that application range is most wide, and bisphenol-A is toxic, pollutes environment and has victimization
Body health.Therefore, it is focus on research direction now to prepare high performance epoxy resin using new material.
Lignin is unique non-oil resource that can provide renewable compound aromatic base in nature, is widely present in height
In equal plants, collectively constituted the primary structure of plant with cellulose, hemicellulose, quantity only this be the world in cellulose
The organic matter that upper content is number two.With the increasingly depleted of petroleum resources on the earth, people open reproducible lignin
Hair, which utilizes, more to be paid attention to.And containing a large amount of phenolic hydroxyl groups, alcoholic extract hydroxyl group, methoxyl group, carboxyl isoreactivity group in lignin, in asphalt mixtures modified by epoxy resin
It obviously can play a significant role in the synthesis of fat.
Meanwhile in the black liquor that generates of paper-making industry, there are a large amount of lignin, so-called black liquid, exactly being used in plant
After the cellulose extraction separation of papermaking, remaining alkalinity black liquor.In previous idea, it is considered that black liquor is waste liquid, directly
Burning disposal is carried out, big energy is wasted and secondary pollution is caused to environment.If this partial lignin is extracted and is used to close
At epoxy resin, will achieve many things at one stroke.
Currently with lignin synthesis epoxy resin, there are mainly two types of modes.One is directly utilize lignin synthesis ring
Oxygen resin, but the problems such as generally existing epoxide number is relatively low.Another kind is to carry out various modifications to lignin, and recycling changes
Property after lignin synthesis epoxy resin, but generally existing chemistry of lignin activity is relatively low, the epoxy resin toughness of synthesis is insufficient
The problems such as.Therefore, for using lignin as the method for Material synthesis epoxy resin, a kind of new technical solution of exploitation has important
Realistic meaning.
Invention content
The object of the present invention is to provide a kind of cleanly production techniques of solid epoxy.
For achieving the above object, the technical solution adopted in the present invention is：A kind of solid epoxy cleans
Production technology includes the following steps：
(1) it is 1 by volume by black liquid and absolute ethyl alcohol from extracting lignose from papermaking black liquor:1~1:1.5 mixed
It is even, first 1~3h of water-bath is carried out at 45~75 DEG C, stratification takes supernatant；After supernatant evaporative removal ethyl alcohol, slowly
Add the concentrated sulfuric acid or concentrated nitric acid pH=2, then by the solution at 45~75 DEG C 6~7h of heating water bath again, until in solution not
There are more precipitations to generate again, solution and precipitation are centrifuged, dry centrifugation obtained solid is to get lignin；
(2) modified by cardanol lignin, by lignin obtained by above-mentioned steps (1) and 35% formalin in mass ratio
It is 1:1 mixing, it is 12 to adjust pH using sodium hydroxide, is stirred to react 3h at 95 DEG C, obtains hydroxymethylated lignin；
Again plus anacardol that quality is above-mentioned lignin quality half, it is stirred to react at 95 DEG C, after the reaction was complete, with dilute salt
Acid-conditioning solution pH=2 precipitates to obtain modified by cardanol lignin；
(3) it is 1 in mass ratio by modified by cardanol lignin and epoxychloropropane:6~20 are added reaction kettle, stir and rise
The phase transfer catalyst that quality is modified by cardanol lignin quality 5% is added to 50~100 DEG C in temperature；Then one is stirred on one side
Lye is added in side, and 1g modified by cardanol lignin adds 1~10ml lye, keeps the temperature 1~5h, acquired solution is adjusted to dilute hydrochloric acid
Neutrality, vacuum distillation remove excessive epoxychloropropane, and distillation and concentration object is washed to neutrality, is dried in vacuo to get solid powder
Powdered epoxy.
Preferably, the black liquid described in step (1) and absolute ethyl alcohol volume ratio are 1:1, first and bath temperature again
It it is 75 DEG C, water bath time is 3h for the first time and again.
Preferably, the sodium hydroxide that step (3) described lye is 10%.
Preferably, the phase transfer catalyst described in step (3) be tetramethyl ammonium chloride, hexadecyltri-n-butylphosp,
One kind in benzyltrimethylammonium chloride.
Preferably, the phase transfer catalyst described in step (3) is hexadecyltri-n-butylphosp.
Preferably, the mass ratio of the modified by cardanol lignin described in step (3) and epoxychloropropane is 1:6 or 1:10.
Preferably, the mass ratio of the modified by cardanol lignin and epoxychloropropane is 1:When 6, the warming temperature is
95 DEG C, the lye additive amount is：1g modified by cardanol lignin adds 2ml lye, and the soaking time is 2h.
Preferably, the mass ratio of the modified by cardanol lignin and epoxychloropropane is 1:When 10, the warming temperature
It it is 70 DEG C, the lye additive amount is：1g modified by cardanol lignin adds 1ml lye, and the soaking time is 4h.
Correspondingly, a kind of novel solid epoxy resin, is prepared using the cleanly production technique.
The invention has the advantages that：
1, lignin is extracted from paper-making industry waste liquid as raw material, instead of the bisphenol-A in traditional handicraft, has been saved a large amount of
The energy, and nontoxic, biodegradable, environment-friendly and green.
2, the present invention is creatively modified lignin using anacardol, and anacardol is during production cashew nut
Cashew nut shell belongs to the utilization again of waste；Meanwhile effectively improving the problem of epoxy resin toughness deficiency.
3, the yield of solid epoxy production technology provided by the invention, epoxy resin is up to 99% or more, epoxide number
Also reach ideal state.
When 4, producing epoxy resin, more times of Use out of range epoxychloropropane are typically necessary, and exceed the epoxy chlorine of part
Propane often can not be collected all and be utilized again, cause largely to waste, it is also possible to pollute environment.In spy provided by the invention
Determine under technical solution, when the epoxychloropropane of relatively low amount can be used to achieve the effect that several times Use out of range epoxychloropropane.
Specific implementation mode
Operating procedure of the present invention is as follows：
1, acid carries alcohol deposition method, from extracting lignose from papermaking black liquor.
It is 1 by volume by black liquid purchased in market and absolute ethyl alcohol:1~1:1.5 mixings, 1~3h of water-bath at 45~75 DEG C,
Stratification takes supernatant.By supernatant evaporative removal ethyl alcohol (ethyl alcohol recycling), no alcoholic solution is obtained, into the solution
It is slowly added the concentrated sulfuric acid or concentrated nitric acid, is stirred in addition, until pH=2, the then water-bath again at 45~75 DEG C by the solution
6~7h is heated, is completed until lignin is basically separated precipitation.When being generated in the solution there is no more precipitations, by solution and precipitation
It is centrifuged, 10000r/min, obtained solid will be centrifuged and be dried to get the required lignin of the present invention.
2, modified by cardanol lignin.
(1) it is 1 in mass ratio by the formalin of the lignin of step 1 gained and 35%:1 mixing, uses hydroxide
It is 12 that sodium, which adjusts pH, is stirred to react 3h at 95 DEG C, obtains hydroxymethylated lignin.
(2) in the solution containing hydroxymethylated lignin obtained by step (1), then add a certain amount of anacardol, additive amount
For the half of the lignin quality of step (1) addition, 3h is stirred to react at 95 DEG C, and after the reaction was complete, solution is adjusted with dilute hydrochloric acid
PH=2 precipitates to obtain modified by cardanol lignin.
3, modified by cardanol lignin synthesis epoxy resin is utilized.
It is 1 in mass ratio by modified by cardanol lignin and epoxychloropropane:6~20 are added reaction kettle, stir and heat up
To 50~100 DEG C, phase transfer catalyst (tetramethyl ammonium chloride, hexadecyltri-n-butylphosp, benzyl trimethyl chlorination is added
Ammonium), 5% that quality is modified by cardanol lignin quality is added in catalyst.
It stirring evenly, and lye (10% sodium hydroxide) is added while stirring, 1g lignin adds 1~10ml lye,
1~5h is kept the temperature, acquired solution is adjusted to neutrality with 0.1mol/L hydrochloric acid, vacuum distillation removes excessive epoxychloropropane, will steam
It evaporates concentrate and is washed to neutrality, be dried in vacuo to get solid powdery epoxy resin.
Embodiment 1：Extract the parameter selection of lignin
(1) step 1 of aforesaid operations step is used to extract lignin, the other design parameter of each group is as shown in table 1.
1 each group design parameter table of table
(2) in above-mentioned each group, the average yield of lignin is 86%, wherein the yield highest of group 4, up to 97%.Cause
This, selects the parameter of group 4 to carry out in subsequent operation.
Embodiment 2：Utilize the parameter selection of modified by cardanol lignin synthesis epoxy resin
(1) method for using 1 group 4 of embodiment extracts lignin, using the step 2 of operating procedure, to the wooden of extraction
Element carries out modified by cardanol.
(2) step 3 of operating procedure is used, synthetic epoxy resin, the other design parameter of each group is as shown in table 2.
2 each group design parameter table of table
(3) interpretation of result
The other epoxy resin yield of each group and epoxy amount are as shown in table 3.
3 each group result of table
| Group | Epoxy resin yield | Epoxy amount (mol/100g) |
| 1 | 99.2% | 0.47 |
| 2 | 99.0% | 0.45 |
| 3 | 99.2% | 0.43 |
| 4 | 85.9% | 0.31 |
| 5 | 93.3% | 0.40 |
| 6 | 93.2% | 0.25 |
| 7 | 95.1% | 0.30 |
| 8 | 98.1% | 0.27 |
| 9 | 98.3% | 0.29 |
| 10 | 98.2% | 0.31 |
| 11 | 98.3% | 0.31 |
| 12 | 99.0% | 0.27 |
| 13 | 84.0% | 0.23 |
| 14 | 84.5% | 0.25 |
| 15 | 97.7% | 0.38 |
| 16 | 99.2% | 0.47 |
| 17 | 99.3% | 0.47 |
(1) as shown above, when 1~3 display epoxychloropropane additive amount of group is 10 times of modified by cardanol lignin, you can
The maximum yield for reaching epoxy resin, continues growing epoxychloropropane dosage, and yield will not continue to rise.Meanwhile ring at any time
The increase of oxygen chloropropane dosage, epoxide number have also appeared downward trend.
(2) 1,13~16 display of group, reaction are acted in 4h, and yield is then further added by the time close to the limit, and yield will not
It continues growing.
(3) in the case where organizing 1 parameter, yield and epoxide number best results.But applicant operates under technical scheme of the present invention
Shi Faxian, under the parameter of group 17, epoxychloropropane dosage is seldom, and soaking time is shorter, but can still reach and organize 1 class
Like the even slightly excellent effect with group 1.This may be the property of modified by cardanol lignin, it is also possible to the component of specific quantity
Between unknown role has occurred.
Claims (9)
1. a kind of cleanly production technique of solid epoxy, it is characterised in that：Include the following steps：
(1) it is 1 by volume by black liquid and absolute ethyl alcohol from extracting lignose from papermaking black liquor:1~1:1.5 mixings, 45
First 1~3h of water-bath is carried out at~75 DEG C, stratification takes supernatant；After supernatant evaporative removal ethyl alcohol, it is slowly added dense
Sulfuric acid or concentrated nitric acid pH=2, then by the solution at 45~75 DEG C 6~7h of heating water bath again, until there is no more in solution
More precipitations generate, and solution and precipitation are centrifuged, and dry centrifugation obtained solid is to get lignin；
(2) modified by cardanol lignin, the formalin by lignin obtained by above-mentioned steps (1) and 35% are 1 in mass ratio:
1 mixing, it is 12 to adjust pH using sodium hydroxide, is stirred to react 3h at 95 DEG C, obtains hydroxymethylated lignin；
Again plus anacardol that quality is above-mentioned lignin quality half, it is stirred to react at 95 DEG C, after the reaction was complete, with dilute hydrochloric acid tune
PH value of solution=2 are saved, modified by cardanol lignin is precipitated to obtain；
(3) it is 1 in mass ratio by modified by cardanol lignin and epoxychloropropane:6~20 are added reaction kettle, stir and are warming up to
50~100 DEG C, the phase transfer catalyst that quality is modified by cardanol lignin quality 5% is added；Then add while stirring
Enter lye, 1g modified by cardanol lignin adds 1~10ml lye, 1~5h is kept the temperature, during acquired solution is adjusted to dilute hydrochloric acid
Property, vacuum distillation removes excessive epoxychloropropane, distillation and concentration object is washed to neutrality, is dried in vacuo to get solid powder
Shape epoxy resin.
2. the cleanly production technique of solid epoxy according to claim 1, it is characterised in that：Step (1) is described
Black liquid and absolute ethyl alcohol volume ratio be 1:1, first and bath temperature is 75 DEG C again, first and water bath time again
It is 3h.
3. the cleanly production technique of solid epoxy according to claim 1, it is characterised in that：Step (3) is described
The sodium hydroxide that lye is 10%.
4. the cleanly production technique of solid epoxy according to claim 1, it is characterised in that：Step (3) is described
Phase transfer catalyst be tetramethyl ammonium chloride, hexadecyltri-n-butylphosp, one kind in benzyltrimethylammonium chloride.
5. the cleanly production technique of solid epoxy according to claim 1, it is characterised in that：Step (3) is described
Phase transfer catalyst be hexadecyltri-n-butylphosp.
6. the cleanly production technique of solid epoxy according to claim 5, it is characterised in that：Step (3) is described
Modified by cardanol lignin and epoxychloropropane mass ratio be 1:6 or 1:10.
7. the cleanly production technique of solid epoxy according to claim 5, it is characterised in that：The anacardol changes
Property lignin and epoxychloropropane mass ratio be 1:When 6, the warming temperature is 95 DEG C, and the lye additive amount is：1g waists
Fruit phenol modified lignin resin adds 2ml lye, and the soaking time is 2h.
8. the cleanly production technique of solid epoxy according to claim 5, it is characterised in that：The anacardol changes
Property lignin and epoxychloropropane mass ratio be 1:When 10, the warming temperature is 70 DEG C, and the lye additive amount is：1g waists
Fruit phenol modified lignin resin adds 1ml lye, and the soaking time is 4h.
9. a kind of novel solid epoxy resin, it is characterised in that：It is prepared into using cleanly production technique described in claim 1
It arrives.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810240701.0A CN108409941B (en) | 2018-03-22 | 2018-03-22 | Clean production process of solid epoxy resin |
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| CN201810240701.0A CN108409941B (en) | 2018-03-22 | 2018-03-22 | Clean production process of solid epoxy resin |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675592A (en) * | 2012-06-08 | 2012-09-19 | 吉林大学 | Synthesizing method of epoxy resin by autocatalysis of lignin |
| CN102775568A (en) * | 2012-07-27 | 2012-11-14 | 山东圣泉化工股份有限公司 | Preparation method of modified phenolic resin |
| CN103756060A (en) * | 2013-12-16 | 2014-04-30 | 华南理工大学 | Rubber composite material filled by cardanol modified lignin and preparation method thereof |
| CN106750067A (en) * | 2016-12-16 | 2017-05-31 | 沙县宏盛塑料有限公司 | A kind of preparation method of lignin Cardanol Modified PF Resin |
-
2018
- 2018-03-22 CN CN201810240701.0A patent/CN108409941B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675592A (en) * | 2012-06-08 | 2012-09-19 | 吉林大学 | Synthesizing method of epoxy resin by autocatalysis of lignin |
| CN102775568A (en) * | 2012-07-27 | 2012-11-14 | 山东圣泉化工股份有限公司 | Preparation method of modified phenolic resin |
| CN103756060A (en) * | 2013-12-16 | 2014-04-30 | 华南理工大学 | Rubber composite material filled by cardanol modified lignin and preparation method thereof |
| CN106750067A (en) * | 2016-12-16 | 2017-05-31 | 沙县宏盛塑料有限公司 | A kind of preparation method of lignin Cardanol Modified PF Resin |
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Address after: 245900 Changsheng Road, Yao Cun village, Yansi Town, Huizhou District, Huangshan City, Anhui, 9 Applicant after: Mount Huangshan Wuhuan Technology Co., Ltd. Address before: 245900 Changsheng Road, Circular Economy Park, Huizhou District, Huangshan City, Anhui 9 Applicant before: Huangshan City Huizhou Wuhuan Chemical Industry Co., Ltd. |
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