CN105461872A - Light-colored cardanol resin and preparation method thereof - Google Patents
Light-colored cardanol resin and preparation method thereof Download PDFInfo
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- CN105461872A CN105461872A CN201510895873.8A CN201510895873A CN105461872A CN 105461872 A CN105461872 A CN 105461872A CN 201510895873 A CN201510895873 A CN 201510895873A CN 105461872 A CN105461872 A CN 105461872A
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- cardanol
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- colored resin
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/34—Chemically modified polycondensates by natural resins or resin acids, e.g. rosin
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Abstract
The invention provides light-colored cardanol resin and a preparation method thereof. The light-colored cardanol resin is prepared from raw materials in parts by weight as follows: 13%-20% of cardanol, 4%-8% of an aldehyde compound, 0.25%-3% of a base catalyst, 6%-16% of vegetable oil, 8%-10% of rosin, 1.5%-3% of binary anhydride, 0.8%-1.3% of a drier and 49.70%-56.45% of solvent oil, and the weight sum of the raw materials is 100%. During preparation, cardanol-aldehyde resin as a component A is prepared firstly, then resin as a component B is prepared, and the two components are mixed into a finished resin product. Light-colored resin capable of reacting with a cardanol polymer is added to shallow a film color, and the original excellent performance of the cardanol resin is kept for the product, accordingly, the application field of a natural cashew nut shell liquid is expanded, and the cashew nut shell liquid can be applied to anti-corrosion engineering.
Description
Technical field
The invention belongs to field of polymer technology, relate to cardanol light-colored resin, be specifically related to a kind of cardanol light-colored resin and preparation method thereof.
Background technology
Cardanol refines through modern technique to form from natural cashew nut shell oil, and its similar is in the main component laccol of raw lacquer.The cashew pnenolic aldehyde fluoropolymer resin obtained by cardanol and formaldehyde has the excellent physicochemical property close to raw lacquer, and cheap, obtains practical application.Foreign scholar Krishnan and Schalkwyk utilizes cashew shell liquid and cis-butenedioic anhydride to react to prepare rubberizing and tackiness agent and so on material to do some and studies, but does not see the research report making Light-color Cashew phenol resins.Domestic scholars Hu Ping Huan cis-butenedioic anhydride and Light-color Cashew shell liquid react, and close the hydroxyl of cardanol, prepare Light-color Cashew phenol resins.Although a lot of about the synthesis report preparing cashew nut phenol resin, have two problems not avoid, one is that cashew pnenolic aldehyde polymer molecule contains phenolic hydroxyl group, make its film easily oxidized and alkali-resistivity is not good, should not use as protective system; Two is that most products film color is deeply dark, is unsuitable for the colored paint preparing light color, limits its use range.
Summary of the invention
For the deficiency that prior art exists, in order to improve the problem of cashew nut phenol resin color depth, reduce the pollution to environment, overcome the good solubility-resistence of resin, increase the over-all propertieies such as the hardness of plant oil resin, water tolerance simultaneously, the object of the invention is to, a kind of cardanol light-colored resin and preparation method thereof is provided, main with Light-color Cashew phenol resins and plant oil resin compound, make a kind of Light-color Cashew phenol compound resin, to adapt to many-sided needs.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme to be achieved:
A kind of cardanol light-colored resin, comprises cardanol, aldehyde compound, alkaline catalysts and solvent oil, also comprises vegetables oil, rosin, dibasic acid anhydride and siccative.
The present invention also has and distinguishes technical characteristic as follows:
Concrete, with weight parts, be prepared from by following raw material: cardanol is 13% ~ 20%, aldehyde compound is 4% ~ 8%, and alkaline catalysts is 0.25% ~ 3%, vegetables oil is 6% ~ 16%, rosin is 8% ~ 10%, and dibasic acid anhydride is 1.5% ~ 3%, and siccative is 0.8% ~ 1.3%, solvent oil is 49.70% ~ 56.45%, and the weight summation of raw material is 100%.
Described cardanol is separation and Extraction from cashew nut shell oil, and through deodorizing, decolouring, color is more shallow.
Described aldehyde compound is formaldehyde, furfural or trioxymethylene.
Described alkaline catalysts is pure ammonia, ammonium chloride or sodium hydroxide.
Described vegetables oil is more than one combinations in tung oil, oleum lini or Chinese catalpa oil.
Described rosin is that color is more shallow, quality superfine or one-level preferably.
Described dibasic acid anhydride is MALEIC ANHYDRIDE or succinyl oxide.
Described siccative is naphthenate.
Described siccative is more than one combinations in cobalt naphthenate, manganese naphthenate and zinc naphthenate.
Described solvent is No. 200 solvent oils, methylcarbonate or dimethylbenzene.
A preparation method for cardanol light-colored resin as above, the method specifically comprises the following steps:
Step one, preparation component A cardanol-aldehyde resin:
Step 1.1 first by cashew shell liquid sorbent material bleaching clay process, filtration, then is the vitriolization of 5% ~ 10% by mass concentration, carries out underpressure distillation, collect the fraction of 145 ± 5 DEG C/2000Pa, be Light-color Cashew phenol liquid after being separated, washing;
Step 1.2, drops into reactor by step 1 gained Light-color Cashew phenol liquid, aldehyde compound, alkaline catalysts, and logical nitrogen in reactor also begins to warm to 80 DEG C ~ 90 DEG C, is incubated 2 ~ 3 hours;
Step 1.3, adds a part of solvent oil to system, and heat up dehydration, separates reaction water, at 120 DEG C ~ 170 DEG C, keeps reaction 2 ~ 4 hours;
Step 1.4, reacted after 2 ~ 4 hours, stopped heating, was cooled to less than 90 DEG C, obtains component A cardanol-aldehyde resin to system;
Step 2, preparation B component resin:
Step 2.1, adds vegetables oil in reactor, heats up, and keeps temperature 80 DEG C ~ 100 DEG C;
Step 2.2, adds rosin and dibasic acid anhydride in system, melts, heats up at 180 DEG C ~ 220 DEG C mixing 2 ~ 4h;
Step 2.3, reduces system temperature below 80 DEG C, adds remaining solvent oil and siccative, obtain B` component resin;
Step 3, mixing:
Component A cardanol-aldehyde resin is mixed with B` component resin, reacts at 40 DEG C ~ 70 DEG C and meet GB/1723-1979 to viscosity namely cardanol light-colored resin finished product is obtained to the requirement of viscosity.
Preferably, the solvent oil added in the solvent oil added in described step one and step 2 is equal in weight.
The present invention compared with prior art, has following technique effect:
The present invention adopts that add can with the light-colored resin of cardanol polymer reaction to make film lighter, and product maintains the original premium properties of cardanol resinoid.Thus expand the Application Areas of natural cashew shell liquid, and can be applied in antiseptic project.
Raw material cashew shell liquid light is polymerized by the present invention again, adds again light color simultaneously and refines resin and its compound, make the features such as product colour is more shallow, sticking power good, time of drying is fast, solvent resistance is good, fully can meet user's demand in many ways.
Below in conjunction with embodiment, explanation is further explained in detail to particular content of the present invention.
Embodiment
Below provide specific embodiments of the invention, it should be noted that the present invention is not limited to following specific embodiment, all equivalents done on technical scheme basis all fall into protection scope of the present invention.
Embodiment 1:
The present embodiment provides a kind of cardanol light-colored resin, with weight parts, be prepared from by following polymerizable raw material: cardanol is 13%, aldehyde compound is 4%, and alkaline catalysts is 0.25%, and vegetables oil is 16%, rosin is 8%, dibasic acid anhydride is 1.5%, and siccative is 0.8%, and solvent oil is 56.45%.
Aldehyde compound is formaldehyde; Alkaline catalysts is sodium hydroxide; Vegetables oil is tung oil, and Chinese catalpa oil also can be adopted to replace; Dibasic acid anhydride is MALEIC ANHYDRIDE; Siccative is cobalt naphthenate, and zinc naphthenate also can be adopted to substitute; Solvent is No. 200 solvent oils.
The present embodiment Light-color Cashew phenol resins, according to above-mentioned raw materials formula batching, is synthesized into by following reactions steps:
Step one, preparation component A cardanol-aldehyde resin:
Step 1.1 first by cashew shell liquid sorbent material bleaching clay process, filtration, then is the vitriolization of 10% by mass concentration, carries out underpressure distillation, collect the fraction of 145 ± 5 DEG C/2000Pa, be Light-color Cashew phenol liquid after being separated, washing;
Step 1.2, drops into reactor by step 1 gained Light-color Cashew phenol liquid, aldehyde compound, alkaline catalysts, and logical nitrogen in reactor also begins to warm to 80 DEG C, is incubated 2 hours;
Step 1.3, adds a part of solvent oil to system, preferably the solvent oil of general weight part, and heat up dehydration gradually, separates reaction water, at 170 DEG C, keeps reaction 3 hours;
Step 1.4, reacted after 3 hours, stopped heating, was cooled to less than 90 DEG C, obtains component A cardanol-aldehyde resin to system;
Step 2, preparation B component resin:
Step 2.1, adds vegetables oil, heats up gradually in reactor, keeps temperature 100 DEG C;
Step 2.2, slowly adds rosin and dibasic acid anhydride in system, makes it slowly melt, slowly heats up, at 220 DEG C of mixing 2h;
Step 2.3, reduces system temperature below 80 DEG C, adds remaining solvent oil (preferably the solvent oil of residue half weight part) and siccative, obtains B` component resin;
Step 3, mixing:
Component A cardanol-aldehyde resin is mixed with B` component resin, reacts at 50 DEG C and meet GB/1723-1979 to viscosity namely cardanol light-colored resin finished product is obtained to the requirement of viscosity.
Embodiment 2:
The present embodiment provides a kind of cardanol light-colored resin, with weight parts, is prepared from by following polymerizable raw material: cardanol is 20%, and aldehyde compound is 8%, alkaline catalysts is 3%, and vegetables oil is 6%, and rosin is 8%, dibasic acid anhydride is 3%, and siccative is 1.3%, and solvent oil is 50.7%.
Aldehyde compound is furfural; Alkaline catalysts is ammoniacal liquor (being converted to pure ammonia meter); Vegetables oil is oleum lini, and tung oil, oleum lini and Chinese catalpa oil also can be adopted to replace according to the mixed vegetable oil that mass ratio is 8:1:1 composition; Dibasic acid anhydride is succinyl oxide; Siccative is manganese naphthenate, and the mixed drier that cobalt naphthenate, manganese naphthenate and zinc naphthenate also can be adopted to form according to mass ratio 3:0.5:0.5 is replaced; Solvent is methylcarbonate.
The present embodiment Light-color Cashew phenol resins, according to above-mentioned raw materials formula batching, is synthesized into by following reactions steps:
Step one, preparation component A cardanol-aldehyde resin:
Step 1.1 first by cashew shell liquid sorbent material bleaching clay process, filtration, then is the vitriolization of 8% by mass concentration, carries out underpressure distillation, collect the fraction of 145 ± 5 DEG C/2000Pa, be Light-color Cashew phenol liquid after being separated, washing;
Step 1.2, drops into reactor by step 1 gained Light-color Cashew phenol liquid, aldehyde compound, alkaline catalysts, and logical nitrogen in reactor also begins to warm to 90 DEG C, is incubated 3 hours;
Step 1.3, adds a part of solvent oil to system, preferably the solvent oil of general weight part, and heat up dehydration gradually, separates reaction water, at 120 DEG C, keeps reaction 4 hours;
Step 1.4, reacted after 3 hours, stopped heating, was cooled to less than 90 DEG C, obtains component A cardanol-aldehyde resin to system;
Step 2, preparation B component resin:
Step 2.1, adds vegetables oil, heats up gradually in reactor, keeps temperature 90 DEG C;
Step 2.2, slowly adds rosin and dibasic acid anhydride in system, makes it slowly melt, slowly heats up, at 200 DEG C of mixing 3h;
Step 2.3, reduces system temperature below 80 DEG C, adds remaining solvent oil (preferably the solvent oil of residue half weight part) and siccative, obtains B` component resin;
Step 3, mixing:
Component A cardanol-aldehyde resin is mixed with B` component resin, reacts at 40 DEG C and meet GB/1723-1979 to viscosity namely cardanol light-colored resin finished product is obtained to the requirement of viscosity.
Embodiment 3:
The present embodiment provides a kind of cardanol light-colored resin, with weight parts, be prepared from by following polymerizable raw material: cardanol is 15%, aldehyde compound is 5%, and alkaline catalysts is 0.5%, and vegetables oil is 16%, rosin is 10%, dibasic acid anhydride is 3%, and siccative is 0.8%, and solvent oil is 49.7%.
Aldehyde compound is trioxymethylene; Alkaline catalysts is ammonium chloride; Vegetables oil is tung oil and oleum lini is the mixed vegetable oil that 8:2 forms according to mass ratio, and tung oil and Chinese catalpa oil also can be adopted to be that the mixed vegetable oil that 8:2 forms is replaced according to mass ratio; Dibasic acid anhydride is MALEIC ANHYDRIDE; Siccative is cobalt naphthenate and manganese naphthenate is the mixed drier of 3:1 composition according to mass ratio, and cobalt naphthenate and zinc naphthenate also can be adopted to replace according to the mixed drier that mass ratio is 3:1 composition; Solvent is dimethylbenzene.
The present embodiment Light-color Cashew phenol resins, according to above-mentioned raw materials formula batching, is synthesized into by following reactions steps:
Step one, preparation component A cardanol-aldehyde resin:
Step 1.1 first by cashew shell liquid sorbent material bleaching clay process, filtration, then is the vitriolization of 5% by mass concentration, carries out underpressure distillation, collect the fraction of 145 ± 5 DEG C/2000Pa, be Light-color Cashew phenol liquid after being separated, washing;
Step 1.2, drops into reactor by step 1 gained Light-color Cashew phenol liquid, aldehyde compound, alkaline catalysts, and logical nitrogen in reactor also begins to warm to 80 DEG C, is incubated 2 hours;
Step 1.3, adds a part of solvent oil to system, preferably the solvent oil of general weight part, and heat up dehydration gradually, separates reaction water, at 150 DEG C, keeps reaction 2 hours;
Step 1.4, reacted after 3 hours, stopped heating, was cooled to less than 90 DEG C, obtains component A cardanol-aldehyde resin to system;
Step 2, preparation B component resin:
Step 2.1, adds vegetables oil, heats up gradually in reactor, keeps temperature 80 DEG C;
Step 2.2, slowly adds rosin and dibasic acid anhydride in system, makes it slowly melt, slowly heats up, at 180 DEG C of mixing 4h;
Step 2.3, reduces system temperature below 80 DEG C, adds remaining solvent oil (preferably the solvent oil of residue half weight part) and siccative, obtains B` component resin;
Step 3, mixing:
Component A cardanol-aldehyde resin is mixed with B` component resin, reacts at 70 DEG C and meet GB/1723-1979 to viscosity namely cardanol light-colored resin finished product is obtained to the requirement of viscosity.
The performance index of the Light-color Cashew phenol resins of above-described embodiment synthesis are as shown in table 1.
Table 1 Light-color Cashew phenol compound resin performance index
Claims (10)
1. a cardanol light-colored resin, comprises cardanol, aldehyde compound, alkaline catalysts and solvent oil, it is characterized in that: also comprise vegetables oil, rosin, dibasic acid anhydride and siccative.
2. cardanol light-colored resin as claimed in claim 1, it is characterized in that: with weight parts, be prepared from by following raw material: cardanol is 13% ~ 20%, aldehyde compound is 4% ~ 8%, and alkaline catalysts is 0.25% ~ 3%, vegetables oil is 6% ~ 16%, rosin is 8% ~ 10%, and dibasic acid anhydride is 1.5% ~ 3%, and siccative is 0.8% ~ 1.3%, solvent oil is 49.70% ~ 56.45%, and the weight summation of raw material is 100%.
3. cardanol light-colored resin as claimed in claim 1, is characterized in that: described aldehyde compound is formaldehyde, furfural or trioxymethylene.
4. cardanol light-colored resin as claimed in claim 1, is characterized in that: described alkaline catalysts is pure ammonia, ammonium chloride or sodium hydroxide.
5. cardanol light-colored resin as claimed in claim 1, is characterized in that: described vegetables oil is more than one combinations in tung oil, oleum lini or Chinese catalpa oil.
6. cardanol light-colored resin as claimed in claim 1, is characterized in that: described dibasic acid anhydride is MALEIC ANHYDRIDE or succinyl oxide.
7. cardanol light-colored resin as claimed in claim 1, is characterized in that: described siccative is naphthenate.
8. cardanol light-colored resin as claimed in claim 7, is characterized in that: described siccative is more than one combinations in cobalt naphthenate, manganese naphthenate and zinc naphthenate.
9. cardanol light-colored resin as claimed in claim 1, is characterized in that: described solvent is No. 200 solvent oils, methylcarbonate or dimethylbenzene.
10. a preparation method for the cardanol light-colored resin as described in claim as arbitrary in claim 1 to 9, is characterized in that: the method specifically comprises the following steps:
Step one, preparation component A cardanol-aldehyde resin:
Step 1.1 first by cashew shell liquid sorbent material bleaching clay process, filtration, then is the vitriolization of 5% ~ 10% by mass concentration, carries out underpressure distillation, collect the fraction of 145 ± 5 DEG C/2000Pa, be Light-color Cashew phenol liquid after being separated, washing;
Step 1.2, drops into reactor by step 1 gained Light-color Cashew phenol liquid, aldehyde compound, alkaline catalysts, and logical nitrogen in reactor also begins to warm to 80 DEG C ~ 90 DEG C, is incubated 2 ~ 3 hours;
Step 1.3, adds a part of solvent oil to system, and heat up dehydration, separates reaction water, at 120 DEG C ~ 170 DEG C, keeps reaction 2 ~ 4 hours;
Step 1.4, reacted after 2 ~ 4 hours, stopped heating, was cooled to less than 90 DEG C, obtains component A cardanol-aldehyde resin to system;
Step 2, preparation B component resin:
Step 2.1, adds vegetables oil in reactor, heats up, and keeps temperature 80 DEG C ~ 100 DEG C;
Step 2.2, adds rosin and dibasic acid anhydride in system, melts, heats up at 180 DEG C ~ 220 DEG C mixing 2 ~ 4h;
Step 2.3, reduces system temperature below 80 DEG C, adds remaining solvent oil and siccative, obtain B` component resin;
Step 3, mixing:
Component A cardanol-aldehyde resin is mixed with B` component resin, reacts at 40 DEG C ~ 70 DEG C and meet GB/1723-1979 to viscosity namely cardanol light-colored resin finished product is obtained to the requirement of viscosity.
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| CN201510895873.8A CN105461872B (en) | 2015-12-07 | 2015-12-07 | A kind of anacardol light-colored resin and preparation method thereof |
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| CN201510895873.8A CN105461872B (en) | 2015-12-07 | 2015-12-07 | A kind of anacardol light-colored resin and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109251288A (en) * | 2018-08-20 | 2019-01-22 | 贵阳学院 | A kind of preparation method of lamination type friction braking material biology base phenolic resin |
| CN111284088A (en) * | 2020-02-18 | 2020-06-16 | 江阴市明康绝缘玻纤有限公司 | Preparation method of heat-resistant modified phenolic paper-based copper-clad laminate |
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2015
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| JP2000080248A (en) * | 1998-09-07 | 2000-03-21 | Hitachi Chem Co Ltd | Phenolic resin composition, phenolic resin laminate and metal foil-laminated phenolic resin laminate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109251288A (en) * | 2018-08-20 | 2019-01-22 | 贵阳学院 | A kind of preparation method of lamination type friction braking material biology base phenolic resin |
| CN109251288B (en) * | 2018-08-20 | 2021-03-19 | 贵阳学院 | Preparation method of bio-based phenolic resin for laminated friction brake material |
| CN111284088A (en) * | 2020-02-18 | 2020-06-16 | 江阴市明康绝缘玻纤有限公司 | Preparation method of heat-resistant modified phenolic paper-based copper-clad laminate |
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