CN102911330B - Vegetable oil modified rosin phenolic resin and preparation method thereof - Google Patents
Vegetable oil modified rosin phenolic resin and preparation method thereof Download PDFInfo
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- CN102911330B CN102911330B CN201210391826.6A CN201210391826A CN102911330B CN 102911330 B CN102911330 B CN 102911330B CN 201210391826 A CN201210391826 A CN 201210391826A CN 102911330 B CN102911330 B CN 102911330B
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- phenolic resin
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Abstract
The invention discloses vegetable oil modified rosin phenolic resin and a preparation method thereof. Alkyl phenol reacts with formaldehyde under an alkaline condition to obtain an alkyl phenol resin condensation compound; molten rosin and vegetable oil are firstly used to conduct a Diels-Alder addition reaction; then the alkyl phenol resin condensation compound is dripped into a reaction product of the molten rosin and the vegetable oil to conduct a Diels-Alder addition reaction; and finally, after a final reaction product is esterified, the vegetable oil modified rosin phenolic resin is prepared. The preparation method has the advantages that through the Diels-Alder reaction of the rosin and the vegetable oil, an aliphatic chain is led to a molecular structure, so that the solubility of the rosin phenolic resin in mineral oil is effectively improved, and a softening point of the resin is guaranteed at the same time; the n-heptane accommodation degree is larger than or equal to 20mL/2g and the acid value is smaller than or equal to 25mgKOH/g, so that the vegetable oil modified rosin phenolic resin can serve as matrix resin of heat-set ink and satisfies the requirements of fast drying, high gloss, demulsibility, and the like of the heat-set ink.
Description
Technical field
The present invention relates to a kind of phenolic resin for printing ink, especially relate to high heptane degree of the holding rosin phenolic resin that a kind of heat-set offset ink is used, and the preparation method of this resol.
Background technology
Resin used for offset ink is mainly rosin modified phenolic resin, the domestic two-step approach production technique that always uses is processed this resinoid for many years, first prepare resol with alkylphenol and formaldehyde, then this resin is jointly reacted and prepares rosin modified phenolic resin with rosin, polyvalent alcohol.The ink of producing with this resinoid have adhesion well, the feature such as body bone is good.
Along with the development of current printing industry, print speed improves constantly, and requires heat-set offset ink to possess the feature of high softening-point, high viscosity, high heptane degree of holding.But general rosin modified phenolic resin, along with softening temperature raises, dies down to the solvability of mineral oil, heptane degree of holding reduces, and is difficult to meet the requirement of heat-set offset ink resin quick-drying, high softening-point.In recent years, become the focus of research to meet performance requriements by introduced plant oil or polyol structure.
CN1341673A has reported a kind of preparation technology of rosen modified mixed alkyl phenolic resin, and the resinous luster degree of preparation is high, and resistance to emulsion is good, but normal heptane value is on the low side, poorly soluble.More than 140 vegetables oil is to Abietyl modified with iodine number for CN1950467B report, and further, by the above polyvalent alcohol esterification of ternary, the method has been abandoned the use of phenolic aldehyde in conventional resins, has reached environmental requirement.But exist as residual solvent owing to containing unreacted vegetables oil in resin, in follow-up ink preparation, resin dissolves is a kind of illusion, and actual heptane degree of holding is also little, and softening temperature is also difficult to reach the requirement of heat-set offset ink.Therefore, how, the aspect of performance such as balanced softening temperature, heptane degree of holding also exists continuation improvement, continuous perfect space to plant oil modified rosin phenolic resin.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned technology, a kind of plant oil modified rosin phenolic resin and preparation method thereof is provided, react with the Diels-Alder of vegetables oil by rosin, aliphatic chain is introduced in molecular structure, effectively improve the solvability of rosin phenolic resin in mineral oil, guarantee the softening temperature of resin simultaneously, improve the heptane degree of holding of resin.
Plant oil modified rosin phenolic resin of the present invention is under alkaline condition, to be reacted and obtain alkyl phenolic resin condenses with formaldehyde by alkylphenol, first carry out Diels-Alder addition reaction with rosin and the vegetables oil of melting, drip again alkyl phenolic resin condenses and carry out Diels-Alder addition reaction, finally to prepare after glycerine or tetramethylolmethane esterification.
Wherein, described vegetables oil is one or more the mixture in soya-bean oil, Chinese catalpa oil, tung oil, oleum lini, Viscotrol C.
In plant oil modified rosin phenolic resin of the present invention, described alkylphenol is one or more the arbitrary proportion mixture in p-tert-butylphenol, p-tert-octylphenol, p-nonylphenol, p-dodecyl phenol.
The preparation method of the plant oil modified rosin phenolic resin of the present invention comprises the following steps:
A, alkylphenol react under alkali metal hydroxide exists with formaldehyde, obtain alkyl phenolic resin condenses;
The rosin of b, melting with mix with vegetables oil, carry out Diels-Alder addition reaction;
C, alkyl phenolic resin condenses is added dropwise in step reaction product b), proceeds Diels-Alder addition reaction;
D, catalyzer exist under, with glycerine or tetramethylolmethane, step addition reaction product c) is carried out to esterification, to acid number≤25mgKOH/g, obtain plant oil modified rosin phenolic resin.
In above-mentioned preparation method, the ratio of quality and the number of copies of rosin and vegetables oil is 100:5～30, and the ratio of quality and the number of copies of the mixture of alkyl phenolic resin condenses and rosin and vegetables oil is 80～100:100.
Wherein, addition reaction b) and c) of described step is carried out at 180～210 ℃, 2～3 hours reaction times.
In above-mentioned preparation method, be to be that esterification is carried out in 1:1～1.2 by described addition reaction material and glycerine or tetramethylolmethane according to the mol ratio of-COOH:-OH, 230～270 ℃ of temperature of reaction.Described esterifying catalyst is MgO or ZnO.
The plant oil modified rosin phenolic resin that the present invention prepares is light yellow transparent solid, softening temperature (℃, ring and ball method), > 140; Mass ratio by it according to 1:2 is dissolved in oleum lini, measures its Main physical performance index: color (Fe-Co colorimetry) ,≤12; Rotary viscosity (mPas/25 ℃), 5000～15000; Normal heptane degree of holding (mL/2g), >=20; Acid number (mgKOH/g) ,≤25.
Plant oil modified rosin phenolic resin provided by the invention reacts with the Diels-Alder of vegetables oil by rosin, and aliphatic chain is introduced in molecular structure, has effectively improved the solvability of rosin phenolic resin in mineral oil, has guaranteed the softening temperature of resin simultaneously.The resin of making can be used as a kind of matrix resin of heat-set ink, meets the requirements such as its quick-drying, Gao Guang, resistance to emulsion.Advantage of the present invention is mainly reflected in the following aspects.
1, the present invention reacts by Diels-Alder, and the long carbon-chain structure of vegetables oil is introduced in rosin modified phenolic resin structure, has improved the solvability of rosin phenolic resin in aliphatic hydrocarbon.
2, rosin phenolic resin is mainly by the structures shape of aliphatic chain in molecular structure to the solvability of mineral oil, the present invention is by selecting different phenol, control condensation temp to prepare the higher degree of polycondensation, the controlled alkyl phenolic resin condenses of molecular weight, and when making product softening temperature higher, oil soluble reaches best.
3, the introducing of vegetables oil, can reduce the usage quantity of alkyl phenolic resin condenses in resin, increases the usage quantity of renewable resources rosin and vegetables oil, and environment protecting is remarkable.
Embodiment
Embodiment 1
Get p-special octyl phenol 185.4g, NaOH 14g and 100g toluene, add in the 1000mL four-hole reaction flask with condenser, heating and melting is to bright state, be cooled to 60 ℃, slowly drip 37% formaldehyde 153g, after adding 80 ℃ of insulation reaction 4 hours, be cooled to 50 ℃, be neutralized to pH=6 with 10% hydrochloric acid soln, stratification, twice of organic layer washing, abandon water layer, underpressure distillation obtains alkyl phenolic resin condenses (condensated liquid) 320g.
By rosin 302g, tung oil 30g joins in 1000mL four-hole reaction flask, is warming up to 185 ℃ after heating and melting, slowly drips condensated liquid 320g, within 2.5 hours, drip off, add 0.6gZnO, stir, slowly add glycerine 30g at 220 ℃, after adding, keep 2 hours at 230 ℃, be warming up to 250 ℃ and react to acid number and be less than 25mgKOH/g, obtain plant oil modified rosin phenolic resin 560g.152 ℃ of softening temperatures, viscosity 5500mPas, acid number 22mgKOH/g, normal heptane degree of holding 24mL/2g.
Embodiment 2
Get p-nonyl phenol 220g, NaOH 17g and 140g toluene, add in the 1000mL four-hole reaction flask with condenser, heating and melting is to bright state, be cooled to 60 ℃, slowly drip 37% formaldehyde 170g, after adding 75 ℃ of insulation reaction 5 hours, be cooled to 50 ℃, be neutralized to pH=6 with 10% hydrochloric acid soln, stratification, twice of organic layer washing, abandon water layer, underpressure distillation obtains alkyl phenolic resin condenses (condensated liquid) 400g.
By rosin 302g, oleum lini 70g joins in 1000mL four-hole reaction flask, is warming up to 190 ℃ after heating and melting, slowly drips condensated liquid 400g, within 3 hours, drip off, add 0.6gMgO, stir, slowly add tetramethylolmethane 37g at 220 ℃, after adding, keep 2 hours at 230 ℃, be warming up to 270 ℃ and react to acid number and be less than 25mgKOH/g, obtain plant oil modified rosin phenolic resin 560g.141 ℃ of softening temperatures, viscosity 12000mPas, acid number 21mgKOH/g, normal heptane degree of holding 26mL/2g.
Embodiment 3
Get p-tert-butyl phenol 48g, p-special octyl phenol 132g, NaOH 9g and 130g toluene, add in the 1000mL four-hole reaction flask with condenser, heating and melting, to bright state, is cooled to 60 ℃, slowly drip 37% formaldehyde 160g, after adding, 70 ℃ of insulation reaction 6 hours, be cooled to 50 ℃, be neutralized to pH=6 with 10% hydrochloric acid soln, stratification, organic layer washing twice, abandons water layer, and underpressure distillation obtains alkyl phenolic resin condenses (condensated liquid) 350g.
By rosin 302g, Viscotrol C 60g joins in 1000mL four-hole reaction flask, is warming up to 190 ℃ after heating and melting, slowly drips condensated liquid 350g, within 2.5 hours, drip off, add 0.6gZnO, stir, slowly add tetramethylolmethane 37g at 220 ℃, after adding, keep 2 hours at 230 ℃, be warming up to 270 ℃ and react to acid number and be less than 25mgKOH/g, obtain plant oil modified rosin phenolic resin 560g.142 ℃ of softening temperatures, viscosity 8000mPas, acid number 19mgKOH/g, normal heptane degree of holding 21mL/2g.
Embodiment 4
Get p-tert-butyl phenol 45g, p-nonyl phenol 132g, NaOH 10g and 130g toluene, add in the 1000mL four-hole reaction flask with condenser, heating and melting, to bright state, is cooled to 60 ℃, slowly drip 37% formaldehyde 153g, after adding, 74 ℃ of insulation reaction 4 hours, be cooled to 50 ℃, be neutralized to pH=6 with 10% hydrochloric acid soln, stratification, organic layer washing twice, abandons water layer, and underpressure distillation obtains alkyl phenolic resin condenses (condensated liquid) 350g.
By rosin 302g, Chinese catalpa oil 19g joins in 1000mL four-hole reaction flask, is warming up to 190 ℃ after heating and melting, slowly drips condensated liquid 350g, within 2.5 hours, drip off, add 0.6gMgO, stir, slowly add glycerine 30g at 220 ℃, after adding, keep 2 hours at 230 ℃, be warming up to 250 ℃ and react to acid number and be less than 25mgKOH/g, obtain plant oil modified rosin phenolic resin 540g.148 ℃ of softening temperatures, viscosity 6800mPas, acid number 21mgKOH/g, normal heptane degree of holding 23mL/2g.
Embodiment 5
Get p-4-dodecylphenol 210g, NaOH 19g and 120g toluene, add in the 1000mL four-hole reaction flask with condenser, heating and melting is to bright state, be cooled to 60 ℃, slowly drip 37% formaldehyde 136g, after adding 78 ℃ of insulation reaction 4.5 hours, be cooled to 50 ℃, be neutralized to pH=6 with 10% hydrochloric acid soln, stratification, twice of organic layer washing, abandon water layer, underpressure distillation obtains alkyl phenolic resin condenses (condensated liquid) 360g.
By rosin 302g, Viscotrol C 30g joins in 1000mL four-hole reaction flask, is warming up to 185 ℃ after heating and melting, slowly drips condensated liquid 360g, within 2.5 hours, drip off, add 0.6gZnO, stir, slowly add tetramethylolmethane 37g at 220 ℃, after adding, keep 2 hours at 230 ℃, be warming up to 270 ℃ and react to acid number and be less than 25mgKOH/g, obtain plant oil modified rosin phenolic resin 560g.145 ℃ of softening temperatures, viscosity 6000mPas, acid number 18mgKOH/g, normal heptane degree of holding 27mL/2g.
Embodiment 6
Get p-tert-butyl phenol 52.5g, p-4-dodecylphenol 170g, NaOH 21g and 130g toluene, add in the 1000mL four-hole reaction flask with condenser, heating and melting, to bright state, is cooled to 60 ℃, slowly drip 37% formaldehyde 170g, after adding, 65 ℃ of insulation reaction 4 hours, be cooled to 50 ℃, be neutralized to pH=6 with 10% hydrochloric acid soln, stratification, organic layer washing twice, abandons water layer, and underpressure distillation obtains alkyl phenolic resin condenses (condensated liquid) 400g.
By rosin 302g, soya-bean oil 24g joins in 1000mL four-hole reaction flask, is warming up to 185 ℃ after heating and melting, slowly drips condensated liquid 400g, within 3 hours, drip off, add 0.6gMgO, stir, slowly add glycerine 30g at 220 ℃, after adding, keep 2 hours at 230 ℃, be warming up to 250 ℃ and react to acid number and be less than 25mgKOH/g, obtain plant oil modified rosin phenolic resin 560g.150 ℃ of softening temperatures, viscosity 13000mPas, acid number 20mgKOH/g, normal heptane degree of holding 25mL/2g.
Claims (5)
1. plant oil modified rosin phenolic resin, under alkaline condition, to react and obtain alkyl phenolic resin condenses with formaldehyde by alkylphenol, first at 180～210 ℃, rosin take melting mixes as 100:5～30 according to ratio of quality and the number of copies with vegetables oil, carry out Diels-Alder addition reaction 2～3 hours, be that 80～100:100 drips alkyl phenolic resin condenses according to the ratio of quality and the number of copies of the mixture of alkyl phenolic resin condenses and rosin and vegetables oil again, at 180～210 ℃, carry out Diels-Alder addition reaction 2～3 hours, finally to prepare after glycerine or tetramethylolmethane esterification, wherein, described vegetables oil is soya-bean oil, Chinese catalpa oil, tung oil, oleum lini, the mixture of one or more in Viscotrol C.
2. plant oil modified rosin phenolic resin according to claim 1, is characterized in that described alkylphenol is one or more the arbitrary proportion mixture in p-tert-butylphenol, p-tert-octylphenol, p-nonylphenol, p-dodecyl phenol.
3. the preparation method of plant oil modified rosin phenolic resin, comprises the following steps:
A, alkylphenol react under alkali metal hydroxide exists with formaldehyde, obtain alkyl phenolic resin condenses;
It is characterized in that also comprising:
B, at 180～210 ℃, the rosin of melting is that mix 100:5～30 with vegetables oil according to ratio of quality and the number of copies, carries out Diels-Alder addition reaction 2～3 hours;
C, at 180～210 ℃, alkyl phenolic resin condenses is added dropwise in step reaction product b), proceed Diels-Alder addition reaction 2～3 hours; Wherein the ratio of quality and the number of copies of the mixture of alkyl phenolic resin condenses and rosin and vegetables oil is 80～100:100;
D, catalyzer exist under, with glycerine or tetramethylolmethane, step addition reaction product c) is carried out to esterification, to acid number≤25mgKOH/g, obtain plant oil modified rosin phenolic resin.
4. the preparation method of plant oil modified rosin phenolic resin according to claim 3, is characterized in that described esterifying catalyst is MgO or ZnO.
5. the preparation method of plant oil modified rosin phenolic resin according to claim 3, it is characterized in that be that esterification is carried out in 1:1～1.2 by described addition reaction material and glycerine or tetramethylolmethane according to the mol ratio of-COOH:-OH, 230～270 ℃ of temperature of reaction.
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| CN103665285B (en) * | 2013-12-16 | 2016-03-16 | 山东圣泉新材料股份有限公司 | A kind of modified phenolic resins, its preparation method and rubber for tire |
| CN103865019B (en) * | 2014-03-19 | 2016-08-17 | 中钞油墨有限公司 | Rosin modified phenolic resin and preparation method thereof |
| CN104356328B (en) * | 2014-10-28 | 2017-01-11 | 中山市康和化工有限公司 | Preparation method of soybean oil rosin combined chemical modified phenolic resin and modified phenolic resin |
| CN104356327B (en) * | 2014-10-28 | 2016-08-24 | 中山市康和化工有限公司 | The synthetic method of a kind of soya-bean ink soybean oil rosin modified phenolic resin and phenol-formaldehyde resin modified |
| CN104710591A (en) * | 2015-03-18 | 2015-06-17 | 桂林兴松林化有限责任公司 | Preparation method for rosin-modified phenolic resin |
| CN105061708A (en) * | 2015-08-03 | 2015-11-18 | 山西科诺奥合成材料有限公司 | Preparation method for rosin modified long-chain alkyl phenolic resin for thermsetting ink |
| CN105001388B (en) * | 2015-08-31 | 2017-03-01 | 桂林兴松林化有限责任公司 | The preparation method of plant oil modified rosin phenolic resin |
| CN108329446B (en) * | 2017-01-20 | 2019-07-05 | 中国科学院化学研究所 | Phenolic resin is esterified sulfonate and its synthetic method, printing hydrophilic version and application and galley |
| CN111363411B (en) * | 2020-05-11 | 2022-06-07 | 厦门德瑞雅喷码科技有限公司 | Rubber ink composition, preparation method and application method |
| CN111647303B (en) * | 2020-06-30 | 2022-10-14 | 湖南科茂林化有限公司 | Phenolic-free rosin ester resin for offset printing ink and preparation method thereof |
| CN113667076A (en) * | 2021-02-23 | 2021-11-19 | 广西藤县通轩立信化学有限公司 | Preparation method of phosphorus-modified rosin phenolic resin catalyzed by acid and then base |
| CN114989377B (en) * | 2022-07-25 | 2023-07-14 | 杭华油墨股份有限公司 | Rosin modified phenolic resin and preparation method and application thereof |
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| CN1341673A (en) * | 2001-08-30 | 2002-03-27 | 山西省应用化学研究所 | Preparation of rosen modified mixed alkyl phenolic resin |
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