CN103214643B - Method for performing two-step catalyzed synthesis on basic resin by using natural melanin - Google Patents
Method for performing two-step catalyzed synthesis on basic resin by using natural melanin Download PDFInfo
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- CN103214643B CN103214643B CN201310156246.3A CN201310156246A CN103214643B CN 103214643 B CN103214643 B CN 103214643B CN 201310156246 A CN201310156246 A CN 201310156246A CN 103214643 B CN103214643 B CN 103214643B
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Abstract
The invention discloses a method for performing two-step catalyzed synthesis on a basic resin by using natural melanin. According to the method, the natural melanin serves as a basic raw material, the aldehyde material serves as a cross-linking agent, the natural melanin basic resin is synthesized through a two-step catalyzed synthesis method for performing base catalysis and acid catalysis sequentially. In the method, the aldehyde substances which can serve as the cross-linking agents comprise formaldehyde, paraformaldehyde, glyoxal, glutaraldehyde, furfural and the like, and the simple phenolic substances which can be added comprise phenol, resorcinol, m-cresol, xylenol and the like. The basic resin gel synthesized by the method has the advantages of environmental friendliness, energy conservation, simplicity in operation, easy industrial production and the like.
Description
Technical field
The invention belongs to bio-based base resin synthesis technical field, specifically relate to a kind of method with the synthetic base resin of acid catalysis after the first base catalysis of natural black pigment.
Background technology
Base resin is one of important synthesis material of matrix material.Resol is the important base resin of a class wherein, there is the premium propertiess such as acid and alkali-resistance, cold-resistant, fire-retardant, electric insulation, dimensional stabilizing, have a wide range of applications in fields such as packaging, building materials, electromechanics, environmental protection, traffic, become the indispensable material of industrial production.Traditional resol is crosslinked synthetic by phenol, Resorcinol, meta-cresol etc. and aldehyde material, and these aldehydes matters are petroleum-based products, all belong to Nonrenewable resources.
Melanochrome (Melanin) is the general name that a class is extensively present in the various polymer pigment of the complex structure being formed by phenols or Benzazole compounds oxypolymerization in organic sphere.This class pigment is generally black or brown, due to composition structure difference, also has minority redness, yellow, purple, blueness and green melanochrome.Such material can be organism structural strength or the biological injury of avoiding the environment-stress such as ultraviolet ray, ionizing rays, heavy metal, low temperature and high temperature of protection is provided.They are not only a class bright protective agent, antiradiation agent, sequestrant, antioxidant and immunopotentiating agent, but also are class bio-semiconductor materials.At present, melanochrome both can carry out chemosynthesis by the oxidation of tyrosine or derivatives thereof, also can in driven vegetable material, extract, and can also utilize microbe fermentation method synthetic.Natural black pigment wide material sources, aboundresources, in hair, eyes, skin and the internal organ of some animals, content is higher in the pericarp of some plants, seed coat, leaf and in the sporophore of some fungies or conidial cell wall.Tealeaves melanochrome and squid ink can batch production be produced, and also from the biomass such as the meat of fragrans seed, horse-chestnut, chestnut shell, civil official fruit seed coat, almond peel, Semen Sesami Nigrum seed coat, Pericarpium Musae, squid ink sac, Gallus Domesticus and bone, animal hair, black fungus, extract and have obtained melanochrome at present.Because natural black pigment comes from organism, there is recyclability, be therefore bio-based materials as the synthetic material of raw material, the product of production belongs to bio-based product, has good application prospect.
Up to now, in prior art, there is not yet the method with the synthetic base resin of natural black pigment.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of method of utilizing the synthetic base resin of natural black pigment is provided, in the situation that using no or little simple aldehydes matter, the synthetic base resin of acid catalysis after first base catalysis, use pollution on the environment thereby effectively reduce simple phenols raw material, and the dependency of production of resins to oil.
Object of the present invention is achieved by the following technical programs.
Except as otherwise noted, percentage ratio of the present invention is mass percent; Umber is mass fraction.
By a method for the synthetic base resin of natural black pigment, comprise the following steps:
(1) natural black pigment aqueous solution preparation: 100 parts of natural black pigments are put into reactor, add the deionized water of 1000～5000 parts, regulate pH value to 10～14, pigment is fully dissolved and make the natural black pigment aqueous solution that concentration is 20～100g/L;
(2) in the natural black pigment aqueous solution making, add 140～600 parts of linking agents and 0～500 part of simple aldehydes matter, regulate pH value to 7～12, be warming up to 60～100 DEG C, base catalyzed reactions 3～24 hours;
(3) complete the material obtaining after base catalyzed reactions and first regulate pH value to 1～3, then acid catalyzed reaction 0.5～6 hour under 60～100 DEG C of conditions, then through centrifugal or filter after obtain natural black pigment base resin.
Described linking agent be formaldehyde, paraformaldehyde, oxalic dialdehyde, one or more arbitrary combination in glutaraldehyde or furfural; Described simple aldehydes matter is one or more the arbitrary combination in phenol, Resorcinol, meta-cresol or xylenol.
With respect to prior art, the present invention has the following advantages:
1, the method substitutes with the natural black pigment of bio-based or the simple aldehydes matter of part petroleum replacing base, taking aldehyde material as linking agent, by the synthetic base resin of two-step catalysis synthesis method, can effectively reduce the consumption of simple phenols raw material in traditional phenolic resin synthesis technique, reducing the pollution and the dependency of production of resins to oil that use simple aldehydes matter to bring environment, is a kind of environmental protection and energy saving and continuable base resin synthetic method.
2, the made natural black pigment base resin of the present invention is gel, can after convection drying, utilize, or as raw material synthetic composite material, be applicable to the fields such as packaging, building materials, electromechanics, environmental protection, traffic.
Brief description of the drawings
Fig. 1 does not add the process flow sheet that utilizes the synthetic base resin of natural black pigment two-step catalysis in simple aldehydes matter situation described in embodiment 1～5;
Fig. 2 adds the process flow sheet that utilizes the synthetic base resin of natural black pigment two-step catalysis in simple aldehydes matter situation described in embodiment 6～8.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.But drawings and Examples only, for understanding the present invention, are not limited to the technical solution.
Embodiment 1
As shown in Figure 1, get chestnut shell pigment 10g and put into the reactor that volume is 500mL, add 200mL deionized water, be adjusted to pH 10 with NaOH, pigment is fully dissolved, then adding 40mL concentration is 37% formaldehyde, regulates pH to 11 with NaOH, is warming up to 60 DEG C, react after 24 hours and regulate pH to 2 with HCl, at continuing 60 DEG C, react discharging after 6 hours, centrifugal 5 minutes of 5000g centrifugal acceleration after naturally cooling, abandoning supernatant obtains natural black pigment base base resin.
Embodiment 2
As shown in Figure 1, get black sesame melanin 10g and put into reactor, add 100mL deionized water, be adjusted to pH 11 with KOH, pigment is fully dissolved, then add 50% glutaraldehyde 60mL, regulate pH to 12 with KOH, be placed under 95 DEG C of constant temperature and react 3 hours, then use H
2sO
4regulate pH to 1, react discharging after 2 hours at continuing 95 DEG C, centrifugal 5 minutes of 5000g centrifugal acceleration after naturally cooling, abandoning supernatant obtains natural black pigment base base resin.
Embodiment 3
As shown in Figure 1, get Spermoderm of Xanthoceras sorbifolia Bunge melanochrome 10g and put into reactor, add 200mL deionized water, be adjusted to pH 12 with NaOH, pigment is fully dissolved, then add 99% furfural 60mL, with NaOH adjusting pH to 10, be placed under 90 DEG C of constant temperature and react 6 hours, then use H
3pO
4regulate pH to 3, react discharging after 1 hour at continuing 95 DEG C, centrifugal 5 minutes of 5000g centrifugal acceleration after naturally cooling, abandoning supernatant obtains natural black pigment base base resin.
Embodiment 4
As shown in Figure 1, get squid ink 10g and put into reactor, add 400mL deionized water, be adjusted to pH 14 with NaOH, pigment is fully dissolved, then add 15g paraformaldehyde, with NaOH and HCl adjusting pH to 12, be placed under 60 DEG C of constant temperature and react 24 hours, then regulate pH to 2 with Phenylsulfonic acid, at continuing 60 DEG C, react discharging after 6 hours, centrifugal 5 minutes of 5000g centrifugal acceleration after naturally cooling, abandoning supernatant obtains natural black pigment base base resin.
Embodiment 5
As shown in Figure 1, get auricularia auriculajudae melanochrome 10g and put into reactor, add 400mL deionized water, be adjusted to pH 11 with NaOH, pigment is fully dissolved, then add the glutaraldehyde that 20mL concentration is 37% formaldehyde, 5mL concentration is 99% furfural and 12mL concentration are 50%, with NaOH and HCl adjusting pH to 10, be warming up to 100 DEG C, base catalyzed reactions 3 hours, then uses careless acid for adjusting pH to 2, reacts discharging after 0.5 hour at continuing 100 DEG C, after naturally cooling, filter, filter residue is natural black pigment base base resin.
Embodiment 6
As shown in Figure 2, get chestnut shell pigment 10g and put into reactor, add 300mL deionized water, be adjusted to pH 11 with KOH, pigment is fully dissolved, then add Resorcinol 1g, meta-cresol 5g and 37% formaldehyde 50mL, regulate pH to 10 with KOH until completely dissolved, be placed under 60 DEG C of constant temperature and react 12 hours, then regulate pH to 2 with HCl, at continuing 60 DEG C, react discharging after 6 hours, centrifugal 5 minutes of 5000g centrifugal acceleration after naturally cooling, abandoning supernatant obtains natural black pigment base base resin.
Embodiment 7
As shown in Figure 2, get squid ink 10g and put into reactor, add 300mL deionized water, be adjusted to pH 14 with KOH, pigment is fully dissolved, then add phenol 2g and 37% formaldehyde 60mL, regulate until completely dissolved pH to 10, be placed under 60 DEG C of constant temperature and react 12 hours, then regulate pH to 2 with HCl, at continuing 60 DEG C, react discharging after 6 hours, centrifugal 5 minutes of 5000g centrifugal acceleration after naturally cooling, abandoning supernatant obtains natural black pigment base base resin.
Embodiment 8
As shown in Figure 2, get auricularia auriculajudae melanochrome 10g and put into 1000mL reactor, add 500mL deionized water, be adjusted to pH 11 with KOH, pigment is fully dissolved, then add phenol 20g, Resorcinol 30g, 40% oxalic dialdehyde 51mL and 99% furfural 40mL, use until completely dissolved NaCO
3regulate pH to 7, be placed under 90 DEG C of constant temperature and react 6 hours, then regulate pH to 1 with HCl, then react discharging after 2 hours at 90 DEG C, after naturally cooling, filter, filter residue is natural black pigment base base resin.
Claims (2)
1. by a method for the synthetic base resin of natural black pigment, comprise the following steps:
(1) natural black pigment aqueous solution preparation: 100 parts of natural black pigments are put into reactor, add the deionized water of 1000～5000 parts, regulate pH value to 10～14, pigment is fully dissolved and make the natural black pigment aqueous solution that concentration is 20～100g/L;
(2) in the natural black pigment aqueous solution making, add 140～600 parts of linking agents and 0～500 part of simple aldehydes matter, regulate pH value to 7～12, be warming up to 60～100 DEG C, base catalyzed reactions 3～24 hours; Described linking agent be formaldehyde, paraformaldehyde, oxalic dialdehyde, one or more arbitrary combination in glutaraldehyde or furfural;
(3) complete the material obtaining after base catalyzed reactions and first regulate pH value to 1～3, then acid catalyzed reaction 0.5～6 hour under 60～100 DEG C of conditions, then through centrifugal or filter after obtain natural black pigment base resin.
2. the method with the synthetic base resin of natural black pigment according to claim 1, is characterized in that: described simple aldehydes matter is one or more the arbitrary combination in phenol, Resorcinol, meta-cresol or xylenol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310156246.3A CN103214643B (en) | 2013-04-28 | 2013-04-28 | Method for performing two-step catalyzed synthesis on basic resin by using natural melanin |
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| CN201310156246.3A CN103214643B (en) | 2013-04-28 | 2013-04-28 | Method for performing two-step catalyzed synthesis on basic resin by using natural melanin |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104672430B (en) * | 2015-02-05 | 2017-01-04 | 西南林业大学 | Preparation method of natural melanin-based epoxy resin |
| CN106140107B (en) * | 2015-03-27 | 2019-06-21 | 西南林业大学 | A kind of method that ammonia catalysis-heat cure prepares natural black pigment base resin |
| CN106146773B (en) * | 2015-03-29 | 2018-05-04 | 西南林业大学 | A kind of method of the directly natural melanin synthesized base resin of acid catalysis |
| CN106146770A (en) * | 2015-03-30 | 2016-11-23 | 西南林业大学 | A kind of method of radical polymerization natural melanin synthesized base resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012340A (en) * | 2007-02-02 | 2007-08-08 | 西北农林科技大学 | Method of extracting and purifying melanin from almond peel |
| CN102757663A (en) * | 2011-04-26 | 2012-10-31 | 中国科学院沈阳应用生态研究所 | Chestnut shell pigment grading method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012340A (en) * | 2007-02-02 | 2007-08-08 | 西北农林科技大学 | Method of extracting and purifying melanin from almond peel |
| CN102757663A (en) * | 2011-04-26 | 2012-10-31 | 中国科学院沈阳应用生态研究所 | Chestnut shell pigment grading method |
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