CN102010503A - Production method of abietic maleic anhydride resin - Google Patents
Production method of abietic maleic anhydride resin Download PDFInfo
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- CN102010503A CN102010503A CN 201010507547 CN201010507547A CN102010503A CN 102010503 A CN102010503 A CN 102010503A CN 201010507547 CN201010507547 CN 201010507547 CN 201010507547 A CN201010507547 A CN 201010507547A CN 102010503 A CN102010503 A CN 102010503A
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Abstract
The invention relates to a production method of abietic maleic anhydride resin, comprising the following two reaction steps of: 1, carrying out addition reaction on abietyl and maleic anhydride to generate an abietic maleic anhydride addition product; and 2, carrying out esterification reaction on the abietic maleic anhydride addition product and pentaerythritol to generate the abietic maleic anhydride resin. The production method is easy and convenient to operate, has the advantages of large temperature control range, high operability, small investment and stable product quality and is a method suitable for industrialized production; in the production method, appropriate process conditions including raw material proportion, reaction temperature, reaction time, catalysts, and the like, are adopted, thereby the acid value and the molecular weight range of a resin product can be effectively controlled; in addition, the resin product obtained with the production method has higher acid value of 150-170 mg KOH/g, reasonable softening point at 140-155 DEG C and good water solubility and is suitable for producing water-based ink, and a formed coating film has toughness and better after-tackiness resistance, water resistance and alkali resistance.
Description
Technical field
The present invention relates to a kind of production method of rosin maleic resin
Background technology
Characteristics such as the rosin maleic resin is mainly used in industry such as coating, paper glazing, printing ink, and the paint film printing ink that makes has fast drying, and hardness gloss is excellent, and water resisting property is good.Now, along with the environmental protection concept popular feeling that deepens continuously, one green agitation starts in the whole world.The every profession and trade product more pays attention to incorporating the exploitation of green technology when implementing upgrading, for example the printing ink industry also develops to water-based ink from original oil soluble printing ink.In order to produce water color ink, press for a kind of water-soluble rosin resin as raw material, adopt the water-soluble rosin maleic resin as the raw material of producing water color ink usually.This water-soluble rosin maleic resin all has production at home and abroad, and their production method is also basic identical, all is to be main raw material with rosin, MALEIC ANHYDRIDE and tetramethylolmethane, makes by the reaction of two steps.The first step is that the addition reaction of rosin and MALEIC ANHYDRIDE generates affixture, and second step was that the esterification of affixture and tetramethylolmethane generates product rosin maleic resin.But in the at present external production method, its final resin can not be controlled its molecular weight ranges effectively when keeping high acid value, and softening temperature is higher, and promptly molecular weight is bigger, the product poorly water-soluble.In the production method at home, its final resin but can't keep high acid value when having controlled softening point range, water-soluble also poor, can't meet customer need.For this reason, the applicant carries out process modification to the production method of above-mentioned rosin maleic resin, overcomes the shortcoming of prior art, improves the quality of product, makes product have good aqueous solubility, to satisfy client's demand.
Summary of the invention
The invention provides a kind of production method of rosin maleic resin, it is a kind of method that is suitable for suitability for industrialized production.The present invention has selected reasonable raw material proportioning, optimum process condition, and the resin of making can effectively be controlled softening point range, can keep high acid value again, has good aqueous solubility, is applicable to the production water color ink, and it is tough and tensile to film, and is water-fast, alkaline resistance properties is excellent.
The production method of rosin maleic resin of the present invention also is to be main raw material with rosin, MALEIC ANHYDRIDE, tetramethylolmethane, comprise the reaction of two steps: the first step is that rosin and MALEIC ANHYDRIDE are carried out addition reaction, generate the rosin maleic anhydride addition compound, second step was that affixture and tetramethylolmethane carry out esterification, generated product rosin maleic resin.Two step reaction equations are as follows:
(1) rosin and MALEIC ANHYDRIDE addition reaction
(2) esterification of affixture and tetramethylolmethane
N=3-4 wherein
The step of rosin maleic resin production method of the present invention comprises:
1, the addition reaction of rosin and MALEIC ANHYDRIDE
Suck the rosin through pre-hot melt, add MALEIC ANHYDRIDE down for 150 ℃ at temperature of reaction kettle, heat temperature raising carried out addition reaction 1.0-2.0 hour 200-220 ℃ of temperature.The mole ratio of rosin and MALEIC ANHYDRIDE is 1: 0.40-1.0.
Two two keys that react in the rosin structure are not in same alicyclic ring, can not carry out addition reaction with MALEIC ANHYDRIDE at normal temperatures, but under high temperature 200-220 ℃, can be converted into sinistral corean pine perfume (or spice), be formed on same fat intra-annular conjugated double bond and MALEIC ANHYDRIDE and carry out 1,4 addition reaction.
2, the esterification of rosin maleic anhydride addition compound and tetramethylolmethane
After addition reaction finishes, add tetramethylolmethane and catalyst oxidation zinc, stir down at 220-230 ℃, solid materials is fully dissolved, be warming up to 250-265 ℃ then, affixture and tetramethylolmethane carried out esterification 5.5-6.5 hour.Control chemical examination in the sampling, acid number be at 150-170mg KOH/g, and softening temperature is 140-155 ℃ scope, and outward appearance is a transparent solid, color and luster (number)≤10 be qualified product rosin maleic resin.If middle control laboratory values is defective, then continue to keep reaction, till laboratory values is qualified.The mole ratio of rosin and tetramethylolmethane is 1: 0.1-0.5, every mol rosin add 0.1-0.6 kilogram catalyst oxidation zinc.
The rosin products that the inventive method is produced, through the Shanghai coating pigment quality supervision centralization figureofmerit of checking the quality, quality product reaches the product standard that enterprise is drafted.Tabulate 1 as follows.
Table 1
| Project | The enterprise-quality standard | The product measured data |
| Outward appearance | Transparent solid | Transparent solid |
| Color and luster (number) | ≤10 | 9 |
| Acid number (mgKOH/g) | 150-170 | 161.3 |
| Softening temperature (℃) | 140-155 | 148 |
The advantage of production method of the present invention
Production method of the present invention is that the technology of domestic and international prior art rosin maleic resin production method is improved, groping through testing repeatedly, work out the advanced operational path of a cover, selected reasonable raw material proportioning, optimal reaction temperature and reaction times.The add-on of MALEIC ANHYDRIDE is up to 29% of rosin amount in the 1st step addition reaction, and the consumption of domestic manufacturer's MALEIC ANHYDRIDE generally all is no more than 8%, owing to add the MALEIC ANHYDRIDE of excess, rosin products has higher acid number.The 2nd step esterification is selected Zinc oxide catalytic for use, esterification can be carried out in equilibrium, and effectively control molecular weight ranges, keeps certain carboxylic group on the molecular structure, and resin polarity is big and water-compatible is good, has strengthened the solvability of rosin products in water.Production method of the present invention is easy and simple to handle, and temperature controlling range is big, and is workable, less investment, constant product quality.The rosin products of production method of the present invention has higher acid value 150-170mgKOH/g, reasonably softening temperature 140-155 ℃, has good aqueous solubility.It is applicable to the production water color ink, and filming of formation is tough and tensile, and anti-preferably after tackiness, water resisting property and alkali resistance are arranged.The release of toxic solvents when using in the oil-based ink industry has been exempted in the manufacturing development of water color ink, ensures operator's physical and mental health, and product has the feature of environmental protection and security.Therefore, production method of the present invention has overcome the shortcoming of prior art, has improved the quality of product, has satisfied client's demand, and it is a kind of method that is suitable for suitability for industrialized production.
Embodiment
Embodiment 1
Suck 3500 kilograms of molten rosin in six tons of reactors, add 540 kilograms of MALEIC ANHYDRIDE at 144 ℃, heat temperature raising carried out addition reaction 1 hour at temperature 200-210 ℃.After addition reaction finishes, add 240 kilograms of tetramethylolmethanes, 3 kilograms in zinc oxide 220-225 ℃ of stirring, fully dissolves solid materials.Reheat heats up, and affixture and tetramethylolmethane carried out esterification 5.5 hours at 255-260 ℃.The control chemical examination is acid number 161.3mg KOH/g in the sampling, 148 ℃ of softening temperatures (seeing Table 1), and product meets the enterprise-quality standard.Be cooled to 255 ℃, by the 60-100 order filtering net of installing in the discharge plate, filter and remove impurity, filtrate is put into reaction tray be cooled to the transparent solid shape, No. 9, color and luster promptly gets the product maleic resin, and overall yield is 95.1%.
Embodiment 2
Suck 3500 kilograms of molten rosin in six tons of reactors, add 880 kilograms of MALEIC ANHYDRIDE at 147 ℃, heat temperature raising carried out addition reaction 1.5 hours at temperature 205-212 ℃.After addition reaction finishes, add 360 kilograms of tetramethylolmethanes, 4.5 kilograms in zinc oxide 220-228 ℃ of stirring, fully dissolves solid materials.Reheat heats up, and affixture and tetramethylolmethane carried out esterification 6 hours at 252-262 ℃.Control chemical examination in the sampling is acid number 175.3mg KOH/g, and 135 ℃ of softening temperatures continue 252-262 ℃ of esterification 1 hour, once more in the control chemical examination, be acid number 157mg KOH/g, 152 ℃ of softening temperatures, product meets the enterprise-quality standard.Be cooled to 255 ℃, by the 60-100 order filtering net of installing in the discharge plate, filter and remove impurity, filtrate is put into reaction tray be cooled to the transparent solid shape, No. 9, color and luster promptly gets the product maleic resin, and overall yield is 95.8%.
Embodiment 3
Suck 3500 kilograms of molten rosin in six tons of reactors, add 990 kilograms of MALEIC ANHYDRIDE at 148 ℃, heat temperature raising carried out addition reaction 2 hours at temperature 210-218 ℃.After addition reaction finishes, add 480 kilograms of tetramethylolmethanes, 5.5 kilograms in zinc oxide 222-230 ℃ of stirring, fully dissolves solid materials.Reheat heats up, and affixture and tetramethylolmethane carried out esterification 6.5 hours at 255-265 ℃.The control chemical examination is acid number 167mg KOH/g in the sampling, 154 ℃ of softening temperatures, and product meets the enterprise-quality standard.Be cooled to 255 ℃, by the 60-100 order filtering net of installing in the discharge plate, filter and remove impurity, filtrate is put into reaction tray be cooled to the transparent solid shape, No. 9, color and luster promptly gets the product maleic resin, and overall yield is 96.1%.
Claims (1)
1. the production method of a rosin maleic resin, comprise the reaction of two steps, the 1st step was that rosin and MALEIC ANHYDRIDE are carried out addition reaction, generate the rosin maleic anhydride addition compound, the 2nd step was that affixture and tetramethylolmethane carry out esterification, generate the rosin maleic resin, it is characterized in that:
The 1st step addition reaction: rosin and MALEIC ANHYDRIDE were carried out addition reaction 1-2 hour at temperature 200-220 ℃, and the mole ratio of rosin and MALEIC ANHYDRIDE is 1: 0.40-1.0;
The 2nd step esterification: after addition reaction finishes, add tetramethylolmethane and catalyst oxidation zinc, the mole ratio of rosin and tetramethylolmethane is 1: 0.1-0.5, every mol rosin adds 0.1-0.6 kilogram catalyst oxidation zinc, 220-230 ℃ of following stirring and dissolving, be warming up to 250-265 ℃ then, affixture and tetramethylolmethane carried out esterification 5.5-6.5 hour, control chemical examination in the sampling, and acid number is at 150-170mg KOH/g, softening temperature is 140-155 ℃ scope, outward appearance is a transparent solid, color and luster (number)≤10 be qualified product rosin maleic resin, if middle control laboratory values is defective, then continue to keep reaction, till laboratory values is qualified.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408525A (en) * | 2011-09-22 | 2012-04-11 | 中国林业科学研究院林产化学工业研究所 | Acrylate modified maleopimaric acid aqueous polyurethane emulsion and preparation method thereof |
| CN102993426A (en) * | 2012-12-06 | 2013-03-27 | 韦谷林 | Method for preparing rosin modified glass fiber reinforced plastic resin |
| CN103030793A (en) * | 2012-12-06 | 2013-04-10 | 韦谷林 | Preparation method of maleic rosin pentaerythritol ester resin |
| CN103555050A (en) * | 2013-11-01 | 2014-02-05 | 南华大学 | Water-based printing ink resin and preparation method thereof |
| CN103601876A (en) * | 2013-11-18 | 2014-02-26 | 广东科茂林产化工股份有限公司 | High molecular weight modified rosin resin for water-based ink and preparation method thereof |
| CN103820029A (en) * | 2014-03-05 | 2014-05-28 | 张雅静 | Preparation method for maleic anhydride rosin samarium resin |
| CN103992466A (en) * | 2014-03-20 | 2014-08-20 | 杭华油墨化学有限公司 | Rosin polyester resin for lithography printing ink and synthetic method thereof |
| CN104152048A (en) * | 2014-08-29 | 2014-11-19 | 南华松香厂 | Novel rosin resin for oil paints |
| CN105802458A (en) * | 2014-12-30 | 2016-07-27 | 天津天女化工集团股份有限公司 | Highlight offset printing gloss oil |
| CN105802331A (en) * | 2014-12-31 | 2016-07-27 | 天津天女化工集团股份有限公司 | Novel offset printing highlight quick-drying anti-skinning printing ink |
| CN106590472A (en) * | 2016-12-08 | 2017-04-26 | 桂林森泰林化技术有限公司 | Preparation method of hydrogenated rosin imitated resin type novel hot melt adhesive |
| CN107109092A (en) * | 2015-01-29 | 2017-08-29 | 哈利玛化成株式会社 | Hectographic printing black liquid resin |
| CN112011275A (en) * | 2020-09-15 | 2020-12-01 | 中国林业科学研究院林产化学工业研究所 | Edible-grade water-based rosin resin, and preparation method and application thereof |
| WO2021048879A1 (en) * | 2019-09-14 | 2021-03-18 | Asian Paints Ltd. | Polyester based wood coating composition |
| CN115028842A (en) * | 2022-06-20 | 2022-09-09 | 桂林理工大学 | Full-pinosyl epoxy glass high polymer material and preparation method and application thereof |
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| CN102408525B (en) * | 2011-09-22 | 2013-06-19 | 中国林业科学研究院林产化学工业研究所 | Acrylate modified maleopimaric acid aqueous polyurethane emulsion and preparation method thereof |
| CN102408525A (en) * | 2011-09-22 | 2012-04-11 | 中国林业科学研究院林产化学工业研究所 | Acrylate modified maleopimaric acid aqueous polyurethane emulsion and preparation method thereof |
| CN102993426A (en) * | 2012-12-06 | 2013-03-27 | 韦谷林 | Method for preparing rosin modified glass fiber reinforced plastic resin |
| CN103030793A (en) * | 2012-12-06 | 2013-04-10 | 韦谷林 | Preparation method of maleic rosin pentaerythritol ester resin |
| CN103030793B (en) * | 2012-12-06 | 2015-04-22 | 韦谷林 | Preparation method of maleic rosin pentaerythritol ester resin |
| CN103555050A (en) * | 2013-11-01 | 2014-02-05 | 南华大学 | Water-based printing ink resin and preparation method thereof |
| CN103601876A (en) * | 2013-11-18 | 2014-02-26 | 广东科茂林产化工股份有限公司 | High molecular weight modified rosin resin for water-based ink and preparation method thereof |
| CN103820029A (en) * | 2014-03-05 | 2014-05-28 | 张雅静 | Preparation method for maleic anhydride rosin samarium resin |
| CN103820029B (en) * | 2014-03-05 | 2015-06-24 | 张雅静 | Preparation method for maleic anhydride rosin samarium resin |
| CN103992466B (en) * | 2014-03-20 | 2016-04-20 | 杭华油墨股份有限公司 | A kind of planographic ink rosen polyester resin and synthetic method thereof |
| CN103992466A (en) * | 2014-03-20 | 2014-08-20 | 杭华油墨化学有限公司 | Rosin polyester resin for lithography printing ink and synthetic method thereof |
| CN104152048B (en) * | 2014-08-29 | 2016-07-13 | 南华松香厂 | A kind of new rosin resin for painting |
| CN104152048A (en) * | 2014-08-29 | 2014-11-19 | 南华松香厂 | Novel rosin resin for oil paints |
| CN105802458A (en) * | 2014-12-30 | 2016-07-27 | 天津天女化工集团股份有限公司 | Highlight offset printing gloss oil |
| CN105802458B (en) * | 2014-12-30 | 2018-05-04 | 天津天女化工集团股份有限公司 | A kind of bloom offset printing gloss oil |
| CN105802331A (en) * | 2014-12-31 | 2016-07-27 | 天津天女化工集团股份有限公司 | Novel offset printing highlight quick-drying anti-skinning printing ink |
| CN107109092B (en) * | 2015-01-29 | 2020-09-18 | 哈利玛化成株式会社 | Resin for offset printing ink |
| CN107109092A (en) * | 2015-01-29 | 2017-08-29 | 哈利玛化成株式会社 | Hectographic printing black liquid resin |
| CN106590472B (en) * | 2016-12-08 | 2018-06-29 | 桂林森泰林化技术有限公司 | A kind of preparation method of imitative hydrogenated rosin resin hot melt adhesive |
| CN106590472A (en) * | 2016-12-08 | 2017-04-26 | 桂林森泰林化技术有限公司 | Preparation method of hydrogenated rosin imitated resin type novel hot melt adhesive |
| WO2021048879A1 (en) * | 2019-09-14 | 2021-03-18 | Asian Paints Ltd. | Polyester based wood coating composition |
| CN112011275A (en) * | 2020-09-15 | 2020-12-01 | 中国林业科学研究院林产化学工业研究所 | Edible-grade water-based rosin resin, and preparation method and application thereof |
| CN112011275B (en) * | 2020-09-15 | 2022-04-15 | 中国林业科学研究院林产化学工业研究所 | Edible-grade water-based rosin resin, and preparation method and application thereof |
| CN115028842A (en) * | 2022-06-20 | 2022-09-09 | 桂林理工大学 | Full-pinosyl epoxy glass high polymer material and preparation method and application thereof |
| CN115028842B (en) * | 2022-06-20 | 2023-08-22 | 桂林理工大学 | Full rosin-based epoxy glass polymer material and preparation method and application thereof |
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Application publication date: 20110413 |