CN103484023A - Method for preparing polyol ester resin of terpene and rosin diene addition product from rosin - Google Patents
Method for preparing polyol ester resin of terpene and rosin diene addition product from rosin Download PDFInfo
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Abstract
The invention discloses a method for preparing polyol ester resin of terpene and rosin diene addition compound from rosin. The preparation method comprises the following steps: (1) mixing turpentine and turpentine, heating, stirring, dissolving, filtering, washing with water, removing impurities, clarifying, removing water, distilling at normal pressure, distilling residual water and part of turpentine in turpentine by using oil-water azeotropic principle to obtain pure turpentine liquid, analyzing the content of turpentine and rosin in the turpentine liquid, and preparing into a certain proportion; (2) preparing a reaction raw material A by metering pure turpentine liquid and turpentine, and reacting the reaction raw material A with a dienophile addition agent under catalysis to generate a diene addition product of the turpentine and rosin; (3) esterification reaction of polyhydric alcohol and diene addition compound of turpentine and rosin; (4) distilling under vacuum reduced pressure to remove water, unreacted alcohol and low molecular weight substances generated by side reaction during esterification reaction to obtain the polyol ester resin of terpene and rosin diene addition product. The invention has simple process flow, and the preparation method is energy-saving and environment-friendly.
Description
Technical field
What the present invention relates to is rosin, rosin, turps deep processing method, is specifically related to a kind of method for preparing the polyol ester resin of terpenes and rosin Diene-addition thing from rosin.
Background technology
Rosin be a kind of from the Pinus pine tree through tapping the natural resin of collection.The pine tree kind that China mainly taps has Pinus massoniana Lamb, slash pine, pinus khasys etc.Rosin is a kind of renewable resources, and nearly 1,000,000 tons of the output in China every year, account for more than 70% of the average annual output of world's rosin.The rosin converted products is widely used in all conglomeraties such as sizing agent, synthetic rubber, papermaking, printing ink, electronics, food.
Main component in rosin is rosin and turps.Rosin is a kind of di-terpene resinous acid of solid, and its molecule contains the luxuriant and rich with fragrance skeleton structure of three rings, a carboxyl, a conjugated double bond.Utilize carboxyl and two key in rosin can carry out esterification and addition reaction, make the Gum Rosin of different physicochemical properties, apply as tackifier or membrane-forming agent in sizing agent, coating, paint, printing ink.Turps is comprised of the monoterpene firpene, take α firpene, beta pinene, kautschin as main, can carry out the reactions such as isomery, polymerization, addition, oxidation, at present mainly for the manufacture of products such as terpine resin, camphor, borneol, Terpineol 350s, terpine resin is as the tackifier of tackiness agent, printing ink industry, and camphor, borneol, Terpineol 350 are used for the raw material of medicine and perfume industry.The research and the application that prepare terpenes and rosin Diene-addition thing polyol ester resin with rosin there is not yet relevant report.
It is existing that to prepare the resinoid technology retrieval of rosin, turps deep processing with rosin as follows:
Chinese patent CN93105520.2, by the method for rosin manufacture rosin modified phenolic resin.A kind of method of directly with rosin, manufacturing rosin modified phenolic resin of this disclosure of the invention, after being about to rosin melting filtration, magnesium oxide and the alkali metal lithium compound of significant quantity of take is catalyzer, directly and phenol and formaldehyde consolute generation condensation, addition reaction, the mole ratio of phenol and formaldehyde is 1: 1.2～2.0, and the dehydration that heats up afterwards, fractionate out byproduct turps, use again glycerine esterification, can obtain rosin products of light color, that softening temperature is high, oil soluble is good.
Chinese patent ZL94108045.5, take the method for rosin as the raw material production nilox resin.This has been invented with rosin after the hydroterpin dissolving is made into finite concentration, the method for the nilox resin of directly making under palladium/carbon catalyst.
Chinese patent CN200910114381.5, take the method for rosin as the raw material production refined light-color rosin.This disclosure of the invention take the method that rosin is the raw material production refined light-color rosin, the rosin made has lighter color, acid number is high, unsaponifiable matter content is low characteristics, reaches or higher than the performance index of vacuum distilling technique gained refined light-color rosin.
Chinese patent CN102344751A, the rosin of take prepares the method for terpenes Gum Rosin and polymerized rosin as raw material simultaneously.This disclosure of the invention a kind ofly take rosin as raw material, carry out polyreaction with sulfuric acid-Glacial acetic acid catalysis under solvent system, obtain through washing, distillation, vacuum distilling the terpenes Gum Rosin that molecular weight is 438, prepare polymerized rosin simultaneously.
Chinese patent CN102875738A, the preparation method of a kind of rosin type mixed alcohols 191 resins.This disclosure of the invention a kind ofly take rosin and substitute phthalic anhydride as raw material and MALEIC ANHYDRIDE addition reaction obtain affixture, then add diprotic acid, dibasic alcohol to carry out polycondensation, polycondensation product becomes a kind of similar 191 unsaturated polyesters after the vinylbenzene dilution.
Chinese patent CN201010578625.8, a kind of manufacture method of colourless hydrogenated wood rosin glycerol ester resin.Invented a kind of manufacture method of colourless hydrogenated wood rosin glycerol ester resin, take through the rosin of distilation, the rosin ester obtained through esterification again is raw material, shortening under the effect of solvent and effective catalyst, then through the fractionation by distillation solvent, obtain colourless hydrogenated wood rosin glycerol ester resin.
Chinese patent CN201210149937.6, a kind of low temperature resistant rosin tackifying resin, Preparation Method And The Use.The preparation method of a kind of low temperature resistant rosin tackifying resin of this disclosure of the invention; said method comprising the steps of: under protection of inert gas; by after the rosin fusing, under catalyst action, with polyol reaction, react 4-24 hour under 200-290 ℃; discharging; obtain polyalcohol modified rosin ester, then, under protection of inert gas, described polyalcohol modified rosin ester is reacted under 200-290 ℃ with higher fatty acid; react discharging after 4-24 hour, obtain the rosin tackifying resin.
In sum, people do a lot of work to research and the application of rosin, rosin, but do not see the research report of the polyol ester resin about prepare terpenes and rosin Diene-addition thing with rosin.
Summary of the invention
For the deficiency existed on prior art, the present invention seeks to be to provide a kind of method for preparing the polyol ester resin of terpenes and rosin Diene-addition thing from rosin.
To achieve these goals, the present invention realizes by the following technical solutions:
Prepare the method for the polyol ester resin of terpenes and rosin Diene-addition thing from rosin, it is characterized in that, its processing step is:
(1) take rosin and turps joins reaction kettle of the esterification as the reaction raw materials A that starting material preparations is comprised of turps and rosin, and wherein the weight ratio of turps and rosin is (0.33-1): 1;
(2) add Diene-addition catalysts and close Diene-addition agent in esterifying kettle, the weight ratio of Diene-addition catalysts and reaction raw materials A is (0.005-0.01): 1, the weight ratio of described close Diene-addition agent and reaction raw materials A is (0.25-0.44): 1, reflux stirring reaction liquid, make temperature of reaction to 120 ℃, and be raised to gradually 190-210 ℃ of lower back flow reaction 2 hours, be warmed up to again or keep 210 ℃ to react 1 hour, normal pressure steams the turps that can not react, the Diene-addition reaction that this step is acid catalysis turps, rosin;
(3) add the catalyst for esterification reaction of rosin weight 0.04%-0.08% in reaction raw materials A, after temperature of reaction is heated to 220～230 ℃, the polyvalent alcohol of dropwise reaction raw material A weight 31.2%-65.6% carries out esterification, control esterification reaction temperature and be raised to gradually 245～260 ℃, reaction 3-5 hour, the esterification of the Diene-addition thing that this step is polyvalent alcohol and turps, rosin;
(4) after the acid value of sampling and measuring reactant is less than 40mgKOH/g, vacuum decompression, material temperature is controlled under 250 ℃ and steams low boiler cut, and the product in still is the polyol ester resin of terpenes and rosin Diene-addition thing.
Further, the preparation process of described (1) step reaction raw material A is: starting material turps and rosin are mixed, remove impurity through methods such as heated and stirred dissolving, filtration, washings, clarification divides the rear air distillation of anhydrating, utilize the profit azeotropic principles to distill out moisture content and part turps remaining in rosin, obtain pure rosin liquid, analyze the wherein content of turps and rosin, until the weight ratio of final turps and rosin is 2:8; Then choose a certain amount of pure rosin liquid, then the weight ratio of components that adds turps to be mixed with turps and rosin is (0.33-1): 1 reaction raw materials A.
Further, in the preparation process of described (1) step reaction raw material A, the mixed heating of starting material turps and rosin specifically refers in the water-bath of 80-85 ℃ heats.
Further, in the preparation process of described (1) step reaction raw material A, described washing specifically refers to that filtrate is with the water washing of 70-80 ℃ 3 times.
Further, one or more mixtures that described close Diene-addition agent is maleic anhydride, toxilic acid, fumaric acid.
Further, described Diene-addition catalysts is phosphoric acid.
Further, described catalyst for esterification reaction is a kind of or its mixture of zinc oxide, magnesium oxide, calcium oxide.
Further again, the polyvalent alcohol of described esterification is a kind of or its mixture of glycerine, glycol ether, triglycol, ethylene glycol.
Beneficial effect of the present invention:
(1) the present invention prepares the method for the polyol ester resin of terpenes and rosin Diene-addition thing from rosin, and technical process is simple, it is easy to operate to produce, preparation method's energy-saving and environmental protection, economy.
(2) the resin that the inventive method obtains has the performance of terpenes and rosin ester concurrently simultaneously.
(3) the inventive method, by adjusting turps, the ratio of rosin and the kind of polyvalent alcohol in rosin, can obtain different softening temperatures and the rosin products of thickening property.
(4) the product that the inventive method obtains can be applicable to the fields such as sizing agent, printing ink, paint, coating.
The accompanying drawing explanation
Describe the present invention in detail below in conjunction with the drawings and specific embodiments;
Fig. 1 is that pure rosin liquid of the present invention is prepared schema;
Fig. 2 is process flow diagram of the present invention.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with embodiment, further set forth the present invention.
This embodiment adopts the preparation process shown in accompanying drawing 1-2 to prepare the polyol ester resin (the following stated umber all refers to parts by weight) of terpenes and rosin Diene-addition thing from rosin.
The preparation of pure rosin liquid:
Get 1000 parts, raw material rosin, add 1000 parts of commodity turps, heating stirring and dissolving in the water-bath of 80-85 ℃, solids removed by filtration impurity, the water washing that filtrate use is 70-80 ℃ 3 times, divide and remove most of water static clarification rosin liquid, divide again remaining moisture content, air distillation steams part turps, take the remaining moisture content remained in rosin liquid out of by the principle of profit azeotropic, until the turpentine fluid flowed out is limpid, accurately take clean rosin liquid, the content mass ratio of analyzing its turps and rosin reaches 2:8 standby for reaction.The turps that distillation obtains can be used for preparing the reaction raw material of different ratios after saltouing.
Embodiment 1
In the four-hole boiling flask of the 500ml with stirring, backflow, water distilling apparatus function, 100 parts of the clean rosin liquids that the mass ratio that takes turps and rosin is 2:8,60 parts, turps, the reaction raw materials A that the weight ratio that is mixed with turps and rosin is 50:50.Add 55 parts of maleic anhydrides, phosphatase 11 .6 part, the stirring heating back flow reaction, control temperature of reaction, from 120 ℃, increases the temperature to gradually 190 ℃.After refluxing appears in reaction, clock reaction is 2 hours, then normal pressure steams unreacted turps, again temperature of reaction is brought up to 210 ℃ and continued reaction 1 hour, add 0.032 part of zinc oxide, drip 50 parts of glycerine, temperature of reaction is brought up to 220-230 ℃, and be controlled under 245-250 ℃ reaction 3 hours, acid value is surveyed in sampling, (acid value is less than 40mgKOH/g) vacuum (20mmHg) decompression after qualified, the reaction flask material temperature is controlled under 250 ℃ and steams lower boiling component, and in bottle, resin is the glyceryl ester resin of terpenes and rosin Diene-addition thing.The glyceryl ester resin of the prepared terpenes of the present embodiment and rosin Diene-addition thing, softening temperature: 97.2 ℃, acid value: 35.6mgKOH/g, color and luster (iron cobalt colorimetric): No. 8.
Embodiment 2
Take 120 parts of clean rosin liquids in the four-hole boiling flask of the 500ml with stirring, backflow, water distilling apparatus function, 40 parts, turps, the reaction raw materials A that the weight ratio that is mixed with turps and rosin is 64:96.Add 60 parts of toxilic acids, phosphatase 11 .2 part, the stirring heating back flow reaction, control temperature of reaction, from 120 ℃ of degree, increases the temperature to gradually 200 ℃.After backflow occurring, clock reaction is 2 hours, then normal pressure steams unreacted turps, again temperature of reaction is brought up to 210 ℃ and continued reaction 1 hour, add 0.04 part of zinc oxide, drip 50 parts of glycerine, temperature of reaction is brought up to 220-230 ℃, and be controlled under 250-260 ℃ reaction 4 hours, acid value is surveyed in sampling, (acid value is less than 40mgKOH/g) vacuum (20mmHg) decompression after qualified, the reaction flask material temperature is controlled under 250 ℃ and steams lower boiling component, and in bottle, resin is the glyceryl ester resin of terpenes and rosin Diene-addition thing.The glyceryl ester resin of the prepared terpenes of the present embodiment and rosin Diene-addition thing, softening temperature: 113.8 ℃, acid value: 30.7mgKOH/g, color and luster (iron cobalt colorimetric): No. 7.
Embodiment 3
Take 150 parts of clean rosin liquids in the four-hole boiling flask of the 500ml with stirring, backflow, water distilling apparatus function, 10 parts, turps, the reaction raw materials A that the weight ratio that is mixed with turps and rosin is 40:120.Add 40 parts of maleic anhydrides, 0.8 part of phosphoric acid, the stirring heating back flow reaction, control temperature of reaction, from 120 ℃ of degree, increases the temperature to gradually 210 ℃.After backflow occurring, clock reaction is 2 hours, then normal pressure steams unreacted turps, continue again reaction 1 hour under 210 ℃, add 0.048 part of zinc oxide, drip 60 parts of glycerine, temperature of reaction is brought up to 220-230 ℃, and be controlled under 245-250 ℃ reaction 3 hours, acid value is surveyed in sampling, (acid value is less than 40mgKOH/g) vacuum (20mmHg) decompression after qualified, the reaction flask material temperature is controlled under 250 ℃ and steams lower boiling component, and in bottle, resin is the glyceryl ester resin of terpenes and rosin Diene-addition thing.The glyceryl ester resin of the prepared terpenes of the present embodiment and rosin Diene-addition thing, softening temperature: 125.8 ℃, acid value: 28.3mgKOH/g, color and luster (iron cobalt colorimetric): No. 7.
Embodiment 4
Take 100 parts of clean rosin liquids in the four-hole boiling flask of the 500ml with stirring, backflow, water distilling apparatus function, 60 parts, turps, the reaction raw materials A that the weight ratio that is mixed with turps and rosin is 50:50.Add 60 parts of toxilic acids, phosphatase 11 .6 part, the stirring heating back flow reaction, control temperature of reaction, from 120 ℃ of degree, increases the temperature to gradually 190 ℃.After refluxing appears in turps, clock reaction is 2 hours, then normal pressure steams unreacted turps, again temperature of reaction is brought up to 210 ℃ and continued reaction 1 hour, add 0.050 part of magnesium oxide, drip 74 portions of glycol ethers, temperature of reaction is brought up to 220-230 ℃, and be controlled under 250-260 ℃ reaction 5 hours, acid value is surveyed in sampling, (acid value is less than 40mgKOH/g) vacuum (20mmHg) decompression after qualified, the reaction flask material temperature is controlled under 250 ℃ and steams lower boiling component, and in bottle, resin is the glycol ether ester resin of terpenes and rosin Diene-addition thing.The glycol ether ester resin of the prepared terpenes of the present embodiment and rosin Diene-addition thing, softening temperature: 59.6 ℃, acid value: 29.0mgKOH/g, color and luster (iron cobalt colorimetric): No. 7.
Embodiment 5
Take 120 parts of clean rosin liquids in the four-hole boiling flask of the 500ml with stirring, backflow, water distilling apparatus function, 40 parts, turps, the reaction raw materials A that the weight ratio that is mixed with turps and rosin is 64:96.Add 55 parts of maleic anhydrides, phosphatase 11 .0 part, the stirring heating back flow reaction, control temperature of reaction, from 120 ℃, increases the temperature to gradually 190 ℃.After refluxing appears in turps, clock reaction is 2 hours, then normal pressure steams unreacted turps, again temperature of reaction is brought up to 210 ℃ and continued reaction 1 hour, add 0.077 part of magnesium oxide, drip 78 portions of glycol ethers, temperature of reaction is brought up to 220-230 ℃, and be controlled under 245-250 ℃ reaction 4 hours, acid value is surveyed in sampling, (acid value is less than 40mgKOH/g) vacuum (20mmHg) decompression after qualified, the reaction flask material temperature is controlled under 250 ℃ and steams lower boiling component, and in bottle, resin is the glycol ether ester resin of terpenes and rosin Diene-addition thing.The glycol ether ester resin of the prepared terpenes of the present embodiment and rosin Diene-addition thing, softening temperature: 65.4 ℃, acid value: 31.7mgKOH/g, color and luster (iron cobalt colorimetric): No. 7.
Embodiment 6
Take 150 parts of clean rosin liquids in the four-hole boiling flask of the 500ml with stirring, backflow, water distilling apparatus function, 10 parts, turps, the reaction raw materials A that the weight ratio that is mixed with turps and rosin is 40:120.Add 70 parts of fumaric acid, 0.8 part of phosphoric acid, the stirring heating back flow reaction, control temperature of reaction, from 120 ℃ of degree, increases the temperature to gradually 210 ℃.After backflow occurring, clock reaction is 2 hours, then normal pressure steams unreacted turps, continue again reaction 1 hour under 210 ℃, add 0.096 part of magnesium oxide, drip 82 portions of glycol ethers, temperature of reaction is brought up to 220-230 ℃, and be controlled under 245-250 ℃ reaction 5 hours, acid value is surveyed in sampling, (acid value is less than 40mgKOH/g) vacuum (20mmHg) decompression after qualified, the reaction flask material temperature is controlled under 250 ℃ and steams lower boiling component, and in bottle, resin is the glycol ether ester resin of terpenes and rosin Diene-addition thing.The glycol ether ester resin of the prepared terpenes of the present embodiment and rosin Diene-addition thing, softening temperature: 76.8 ℃, acid value: 30.1mgKOH/g, color and luster (iron cobalt colorimetric): No. 7.
Embodiment 7
Take 100 parts of clean rosin liquids in the four-hole boiling flask of the 500ml with stirring, backflow, water distilling apparatus function, 60 parts, turps, the reaction raw materials A that the weight ratio that is mixed with turps and rosin is 50:50.Add 55 parts of maleic anhydrides, phosphatase 11 .6 part, the stirring heating back flow reaction, control temperature of reaction, from 120 ℃ of degree, increases the temperature to gradually 190 ℃.After refluxing appears in turps, clock reaction is 2 hours, then normal pressure steams unreacted turps, again temperature of reaction is brought up to 210 ℃ and continued reaction 1 hour, add 0.03 part of zinc oxide and 0.03 part of magnesium oxide, drip the 105g triglycol, temperature of reaction is brought up to 220-230 ℃, and be controlled under 245-250 ℃ reaction 4 hours, acid value is surveyed in sampling, (acid value is less than 40mgKOH/g) vacuum (20mmHg) decompression after qualified, the reaction flask material temperature is controlled under 250 ℃ and steams lower boiling component, the triethyleneglycol ester resin that in bottle, resin is terpenes and rosin Diene-addition thing, under room temperature (25 ℃) be slightly can be mobile the thickness resin.The triethyleneglycol ester resin of the prepared terpenes of the present embodiment and rosin Diene-addition thing, acid value: 29.5mgKOH/g, color and luster (iron cobalt colorimetric): No. 8.
Embodiment 8
Take 100 parts of clean rosin liquids in the four-hole boiling flask of the 500ml with stirring, backflow, water distilling apparatus function, 60 parts, turps, the reaction raw materials A that the weight ratio that is mixed with turps and rosin is 50:50.Add 55 parts of maleic anhydrides, phosphatase 11 .6 part, the stirring heating back flow reaction, control temperature of reaction, from 120 ℃ of degree, increases the temperature to gradually 190 ℃.After turps refluxes, clock reaction is 2 hours, then normal pressure steams unreacted turps, temperature of reaction is brought up to 210 ℃ and continue reaction 1 hour, add 0.06 part of calcium oxide, first drip 40 parts of ethylene glycol under 210 ℃, drip 12g glycerine after again temperature of reaction being raised to 220-230 ℃, and be controlled under 245-250 ℃ reaction 4 hours, acid value is surveyed in sampling, (acid value is less than 40mgKOH/g) vacuum (20mmHg) decompression after qualified, the reaction flask material temperature is controlled under 250 ℃ and steams lower boiling component, the glycol glycerin ester resin that in bottle, resin is terpenes and rosin Diene-addition thing.The glycol glycerin ester resin of the prepared terpenes of the present embodiment and rosin Diene-addition thing, softening temperature: 83.3 ℃, acid value: 32.6mgKOH/g, color and luster (iron cobalt colorimetric): No. 8.
In above embodiment, the close Diene-addition agent of the Diene-addition reaction that maleic anhydride and toxilic acid are acid catalysis turps, rosin, in other embodiment, this parent's Diene-addition agent can be one or more mixtures of maleic anhydride, toxilic acid, fumaric acid; The catalyst for esterification reaction of the Diene-addition thing that zinc oxide, magnesium oxide, calcium oxide are polyvalent alcohol and turps, rosin, in other embodiment, this catalyst for esterification reaction can be a kind of or its mixture of zinc oxide, magnesium oxide, calcium oxide; Glycerine, glycol ether, triglycol, ethylene glycol are the polyvalent alcohols for esterification, and in other embodiment, polyvalent alcohol can be a kind of or its mixture of glycerine, glycol ether, triglycol, ethylene glycol.
Above demonstration and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (8)
1. prepare the method for the polyol ester resin of terpenes and rosin Diene-addition thing from rosin, it is characterized in that, its processing step is:
(1) take rosin and turps joins reaction kettle of the esterification as the reaction raw materials A that starting material preparations is comprised of turps and rosin, and wherein the weight ratio of turps and rosin is (0.33-1): 1;
(2) add Diene-addition catalysts and close Diene-addition agent in esterifying kettle, the weight ratio of Diene-addition catalysts and reaction raw materials A is (0.005-0.010): 1, the weight ratio of described close Diene-addition agent and reaction raw materials A is (0.25-0.44): 1, reflux stirring reaction liquid, make temperature of reaction to 120 ℃, and be raised to gradually 190-210 ℃ of lower back flow reaction 2 hours, then be warmed up to or keep 210 ℃ of reactions 1 hour, normal pressure steams the turps that can not react;
(3) add the catalyst for esterification reaction of rosin weight 0.04%-0.08% in reaction raw materials A, after temperature of reaction is heated to 220～230 ℃, the polyvalent alcohol of dropwise reaction raw material A weight 31.2%-65.6% carries out esterification, control esterification reaction temperature and be raised to gradually 245～260 ℃, reaction 3-5 hour;
(4) after the acid value of sampling and measuring reactant is less than 40mgKOH/g, vacuum decompression, material temperature is controlled under 250 ℃ and steams low boiler cut, and the product in still is the polyol ester resin of terpenes and rosin Diene-addition thing.
2. the method for preparing the polyol ester resin of terpenes and rosin Diene-addition thing from rosin according to claim 1, it is characterized in that, the preparation process of described (1) step reaction raw material A is: starting material turps and rosin are mixed, remove impurity through methods such as heated and stirred dissolving, filtration, washings, clarification divides the rear air distillation of anhydrating, utilize the profit azeotropic principles to distill out moisture content and part turps remaining in rosin, obtain pure rosin liquid, analyze the wherein content of turps and rosin, until the weight ratio of final turps and rosin is 2:8; Then choose a certain amount of pure rosin liquid, then the weight ratio of components that adds turps to be mixed with turps and rosin is (0.33-1): 1 reaction raw materials A.
3. the method for preparing the polyol ester resin of terpenes and rosin Diene-addition thing from rosin according to claim 2, it is characterized in that, in the preparation process of described (1) step reaction raw material A, the mixed heating of starting material turps and rosin specifically refers in the water-bath of 80-85 ℃ heats.
4. the method for preparing the polyol ester resin of terpenes and rosin Diene-addition thing from rosin according to claim 2, it is characterized in that, in the preparation process of described (1) step reaction raw material A, described washing specifically refers to that filtrate is with the water washing of 70-80 ℃ 3 times.
5. the method for preparing the polyol ester resin of terpenes and rosin Diene-addition thing from rosin according to claim 1, is characterized in that, described close Diene-addition agent is one or more mixtures of maleic anhydride, toxilic acid, fumaric acid.
6. the method for preparing the polyol ester resin of terpenes and rosin Diene-addition thing from rosin according to claim 1, is characterized in that, described Diene-addition catalysts is phosphoric acid.
7. the method for preparing the polyol ester resin of terpenes and rosin Diene-addition thing from rosin according to claim 1, is characterized in that, described catalyst for esterification reaction is a kind of or its mixture of zinc oxide, magnesium oxide, calcium oxide.
8. the method for preparing the polyol ester resin of terpenes and rosin Diene-addition thing from rosin according to claim 1, is characterized in that, the polyvalent alcohol of described esterification is a kind of or its mixture of glycerine, glycol ether, triglycol, ethylene glycol.
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| CN104211597A (en) * | 2014-08-14 | 2014-12-17 | 广西众昌树脂有限公司 | Preparation method of rosin acid |
| CN106916535A (en) * | 2017-04-28 | 2017-07-04 | 南宁市青秀区嘉利林化有限公司 | A kind of method that rosin vacuum distillation fractionates out middle oil |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211596A (en) * | 2014-08-14 | 2014-12-17 | 广西众昌树脂有限公司 | Preparation method of rosin acid |
| CN104211597A (en) * | 2014-08-14 | 2014-12-17 | 广西众昌树脂有限公司 | Preparation method of rosin acid |
| CN104211596B (en) * | 2014-08-14 | 2016-03-09 | 广西众昌树脂有限公司 | The preparation method of rosin acid |
| CN104211597B (en) * | 2014-08-14 | 2016-03-09 | 广西众昌树脂有限公司 | The preparation method of rosin acid |
| CN106916535A (en) * | 2017-04-28 | 2017-07-04 | 南宁市青秀区嘉利林化有限公司 | A kind of method that rosin vacuum distillation fractionates out middle oil |
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| CN103484023B (en) | 2015-06-17 |
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