CN102977300B - Preparation method of maleated rosin glycerin ester phenol formaldehyde resin - Google Patents
Preparation method of maleated rosin glycerin ester phenol formaldehyde resin Download PDFInfo
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- CN102977300B CN102977300B CN201210512729.8A CN201210512729A CN102977300B CN 102977300 B CN102977300 B CN 102977300B CN 201210512729 A CN201210512729 A CN 201210512729A CN 102977300 B CN102977300 B CN 102977300B
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Abstract
The invention relates to a preparation method of a maleated rosin glycerin ester phenol formaldehyde resin, which comprises the following steps: heating 100 parts of rosin to 150-160 DEG C until the rosin is molten; adding 10-15 parts of bisphenol A, stirring for 0.3-0.5 hour, and cooling to 90-100 DEG C; adding 12-30 parts of formaldehyde and accelerator hexamethylenetetramine, and stirring for 2-2.5 hours at 90-100 DEG C; adding 5-15 parts of cis-ethylene dicarboxylic anhydride, and performing addition reaction at 180-200 DEG C for 1.5-2 hours; adding at least 80 parts of glycerol and 2-2.2 parts of catalyst magnesium oxide, heating to 180-200 DEG C, and reacting while stirring for 2-2.5 hours; and heating to 270-280 DEG C, and vacuumizing for 1 hour to obtain the product. The preparation method provided by the invention has the advantages that the reaction temperature is low, the process is easy to control, the reaction speed is accelerated by 3-5 times or above and the product is low in production cost and good in quality.
Description
Technical field
The invention belongs to a kind of rosin deep processing method.
Background technology
Rosin is the renewable resources of China's abundant, and annual production reaches more than 60 ten thousand tons, ranks first in the world.It is made up of a series of resinous acid, and have unique chemical structure and mulitiple chiral centers, the carboxyl in structure and phenanthrene ring frame can carry out a series of chemical modification, are a kind of natural chiral source materials.Rosin can obtain a series of deep processed product through chemical modification, is widely used in the every field in daily life, plays very important effect in the national economic development.The value ratio raw material rosin of these deep processed products mentions 2-10 doubly, and even decades of times, current China mainly earns foreign exchange to export gum resin.China is the maximum country of gum resin export volume, and account for about 60% of volume of world trade, many developed countries are from China's imported raw material rosin, and after a series of deep processing, product exports go back to again China back, to the conservation of resources of China and Economic development very unfavorable.China is 35% to rosin deep processing and utilization rate, and by contrast, the developed countries such as America and Europe close to 100%, also exist very large gap to the deep processing and utilization rate of rosin.Therefore, carry out Abietyl modified research, develop meet China market demand deep processing rosin product not only to country and the development of local economy, and to the reasonable development of China's forest resourceies and utilization and at present industrial energy saving consumption reduction be all of great significance.Resinous acid as rosin main component is that one has two chemical reactivity centers---the chemically reactive substance of carboxylic acid and double bond, atom or group at quarter just can be introduced by these two chain carriers, thus imparting rosin has desired character, reach the object of modification, thus change the rational performance of rosin, greatly expand the Application Areas of rosin, defined miscellaneous rosin derivative product, be widely used in pressure sensitive adhesive, tackiness agent industry.Manufacture multiple film glue, decorating glue, trademark adhesive, adhesive tape glue, hot melt adhesive, sanitary towel glue, non-setting adhesive, EVA hot-melt adhesive, polyamide hot, seal gum, varnish paint vehicle, bookbinding glue, pipeline glue etc.In recent decades, rosin deep processing aspect, its product category, preparation method are all without large progress; , there is the deficiencies such as sluggish length consuming time in prior art products preparation method.
Retrieve through Chinese publication, find Invention patent 416, utility model patent 64, do not find the scheme identical with present patent application.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, propose a kind of Lewisol 28 preparation method of phenolic resin.
Lewisol 28 preparation method of phenolic resin of the present invention, is characterized in that: by weight, rosin 100 parts, heat 150-160 DEG C of meltings, add dihydroxyphenyl propane, 10-15 parts, stir 0.3-0.5 hour, be cooled to 90-100 DEG C, add 12-30 parts, formaldehyde, promotor hexamethylenetetramine, 90-100 DEG C are stirred 2-2.5 hours, add MALEIC ANHYDRIDE 5-15 parts, at 180-200 DEG C, carry out addition reaction 1.5-2 hours; Add glycerine and be no less than 80 parts, 2-2.2 parts, catalyst oxidation magnesium heats up 180-200 DEG C, and stirring reaction 2-2.5 hours, is warming up to 270-280 DEG C and vacuumizes 1 hour; Both Lewisol 28 resol product was obtained.
Lewisol 28 preparation method of phenolic resin of the present invention, reaction principle:
1. the synthesis of resole: add alkylphenol in the rosin of melting, paraformaldehyde exists with particulate state in system, resolves into monomer formaldehyde subsequently, with alkylphenol generation polycondensation.
2. the formation of methyne quinone: heat up dehydration, and in the process heated up, the activity of the methylol in system increases rapidly, there occurs the intramolecular dehydration of methylol, and the intermolecular condensation etherification reaction of methylol, defines the phenolic condensation compound of various different polymerization degree.
3. the addition of rosin and methyne quinone and maleic anhydride: add maleic anhydride 180 DEG C time, utilize the double bond addition in the unsaturated double-bond of maleic anhydride and sylvic acid, methyne quinone and sylvic acid also carry out Diels-Alder addition reaction simultaneously, generate maleation coumaran compound.
4. the esterification of polyvalent alcohol: the existence of a large amount of carboxyl in system, can destroy the balance of system, cause the instability of resin.So we add polyvalent alcohol, utilize the esterification of carboxyl in the hydroxyl of polyvalent alcohol and system, reduce the acid value of system.Meanwhile, by the esterification of polyvalent alcohol, define the superpolymer being applicable to flexographic ink and needing.
The present invention's beneficial effect compared with prior art: pass through larger catalyst, make it speed of response and accelerate more than 3-5 times, by rich polyxol method, can react under lesser temps, reaction become steadily, relaxes, be easy to control, thus the production cycle is shortened greatly, production and plant efficiency greatly improve, and production cost reduces; And obtain that look shallow is, colory product.
Embodiment
Lewisol 28 preparation method of phenolic resin of the present invention, pass through larger catalyst, make it speed of response and accelerate more than 3-5 times, by rich polyxol method, can react under lesser temps, reaction be become steadily, relaxes, be easy to control, thus the production cycle is shortened greatly, production and plant efficiency greatly improve, and production cost reduces; And obtain that look shallow is, colory product
Lewisol 28 preparation method of phenolic resin of the present invention, is characterized in that: by weight, rosin 100 parts, heat 150-160 DEG C of meltings, add dihydroxyphenyl propane, 10-15 parts, stir 0.3-0.5 hour, be cooled to 90-100 DEG C, add 12-30 parts, formaldehyde, promotor hexamethylenetetramine, 90-100 DEG C are stirred 2-2.5 hours, add MALEIC ANHYDRIDE 5-15 parts, at 180-200 DEG C, carry out addition reaction 1.5-2 hours; Add glycerine and be no less than 80 parts, 2-2.2 parts, catalyst oxidation magnesium heats up 180-200 DEG C, and stirring reaction 2-2.5 hours, is warming up to 270-280 DEG C and vacuumizes 1 hour; Both Lewisol 28 resol product was obtained.
Products obtained therefrom quality index reaches following index:
Claims (1)
1. a Lewisol 28 preparation method of phenolic resin, it is characterized in that: pass through larger catalyst, make it speed of response and accelerate more than 3-5 times, by rich polyxol method, can react under lesser temps, reaction be become steadily, relaxes, be easy to control, thus the production cycle is shortened greatly, production and plant efficiency greatly improve, and production cost reduces; And obtain that look shallow is, colory product, its by weight, rosin 100 parts, heat 150-160 DEG C of meltings, add dihydroxyphenyl propane, 10-15 parts, stir 0.3-0.5 hour, be cooled to 90-100 DEG C, add 12-30 parts, formaldehyde, promotor hexamethylenetetramine, 90-100 DEG C are stirred 2-2.5 hours, add MALEIC ANHYDRIDE 5-15 parts, at 180-200 DEG C, carry out addition reaction 1.5-2 hours; Add glycerine and be no less than 80 parts, 2-2.2 parts, catalyst oxidation magnesium heats up 180-200 DEG C, and stirring reaction 2-2.5 hours, is warming up to 270-280 DEG C and vacuumizes 1 hour; Obtain Lewisol 28 resol product, its softening temperature is 135-155 DEG C of scopes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210512729.8A CN102977300B (en) | 2012-12-04 | 2012-12-04 | Preparation method of maleated rosin glycerin ester phenol formaldehyde resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201210512729.8A CN102977300B (en) | 2012-12-04 | 2012-12-04 | Preparation method of maleated rosin glycerin ester phenol formaldehyde resin |
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| CN102977300A CN102977300A (en) | 2013-03-20 |
| CN102977300B true CN102977300B (en) | 2015-04-22 |
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| CN201210512729.8A Active CN102977300B (en) | 2012-12-04 | 2012-12-04 | Preparation method of maleated rosin glycerin ester phenol formaldehyde resin |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103421430B (en) * | 2013-08-20 | 2015-01-28 | 广西梧州龙鱼漆业有限公司 | Modified abietate for water-based alkyd resin and method for manufacturing modified abietate |
| CN103820033B (en) * | 2014-03-05 | 2015-06-24 | 张健 | Preparation method for gadolinium trioxide rosin glyceride resin |
| CN104140540A (en) * | 2014-07-25 | 2014-11-12 | 广西众昌树脂有限公司 | Preparation method of rosin tackifying resin emulsion |
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- 2012-12-04 CN CN201210512729.8A patent/CN102977300B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 2116#松香改性酚醛树脂生产新工艺;程珍发等;《林产化工通讯》;20020228;第36卷(第1期);第16-18页 * |
| 马来松香生产工艺的改进;王丘艳;《林产化工通讯》;20011230;第35卷(第6期);第38-40页 * |
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Address after: 542800 the Guangxi Zhuang Autonomous Region Hezhou City eight step Xiyuan No. 40 Lane eight new materials research and Development Institute Patentee after: Zhang Yajing Address before: 542800 the Guangxi Zhuang Autonomous Region Hezhou Fuchuan County eight step new material research and Development Institute Patentee before: Zhang Yajing |
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Effective date of registration: 20190816 Address after: 526600 Huilong Town Industrial Development Zone, Deqing County, Zhaoqing City, Guangdong Province Patentee after: Deqing Jiyuan Synthetic Resin Co., Ltd. Address before: 542800 the Guangxi Zhuang Autonomous Region Hezhou City eight step Xiyuan No. 40 Lane eight new materials research and Development Institute Patentee before: Zhang Yajing |