CN101050260A - High polymer with self-crosslinked functional radicle and preparation method - Google Patents
High polymer with self-crosslinked functional radicle and preparation method Download PDFInfo
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- CN101050260A CN101050260A CN 200710051902 CN200710051902A CN101050260A CN 101050260 A CN101050260 A CN 101050260A CN 200710051902 CN200710051902 CN 200710051902 CN 200710051902 A CN200710051902 A CN 200710051902A CN 101050260 A CN101050260 A CN 101050260A
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Abstract
This invention discloses a method for preparing a self-crosslinking functional polymer, poly (glycol propylene maleic rosin ester). The method comprises: esterifying maleic rosin and ethylene glycol in the presence of catalyst to obtain ethylene glycol maleic rosin ester, esterifying ethylene glycol maleic rosin ester and acrylic acid in the presence of catalyst to obtain glycol propylene maleic rosin ester, and performing free radical polymerization to obtain the product. The product has -COOH group, thus can be used for separation of organic compounds and as carrier of polymer complexes and immobilized enzymes.
Description
Technical field
The present invention relates to a kind of self-crosslinking high molecular polymer and preparation method thereof field.
Background technology
Self-crosslinking maleated rosin ethylene glycol propylene ester of the present invention is a kind of new crosslinking kinetic energy based high polymer, and up to the present this material and preparation method thereof is not reported.
Summary of the invention
The purpose of this invention is to provide a kind of brand-new kinetic energy based high polymer and preparation method thereof, this polymkeric substance has purposes widely, can be used for the separation of natural product, for example, is used to separate ginkgolic flavone glycoside, the little wall alkali of berberine etc.; And the carrier of being used for fixing enzyme, for example, the carrier of being used for fixing amylase, lipase, laccase.
The present invention has two contents:
1. summary of the invention 1:
(1) chemical name of high polymer with self-crosslinked functional radicle of the present invention is the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking;
(2) molecular weight: the monomer molecule amount is 535～614
Structural formula: the structural formula of monomer maleated rosin ethylene glycol propylene ester:
Self-crosslinking gathers maleated rosin ethylene glycol propylene ester structure formula:
(3) physico-chemical property: outward appearance, light yellow spherical particle; Acid number 60～120mgKOHg
-1, 180～300 ℃ of softening temperatures, degree of crosslinking 15～75% is not dissolved in organic solvents such as dehydrated alcohol, gasoline, hexanaphthene, toluene, acetone, acetate.
2. summary of the invention 2: the preparation method of the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking of the present invention is to be basic raw material with rosin, maleic anhydride or toxilic acid, ethylene glycol, vinylformic acid, is undertaken by following four steps:
(1), the preparation of maleated rosin
With the rosin porphyrize, place three-necked bottle, thermometer, water trap and reflux condensing tube are installed.Use the electric mantle heat fused, when temperature is raised to 140 ℃, start agitator, add and press excessive maleic anhydride of chemical equation or toxilic acid, thermostatically heating refluxed 8 hours when temperature was raised to 190 ℃.Reaction back product is poured out while hot, and product is cooled to below 100 ℃, and porphyrize with 80 ℃ of hot water washed product repeatedly, is eliminated unnecessary toxilic acid, approximates 7,60 ℃ of dryings up to pH value, obtains the thick product of maleated rosin.The gasoline of the thick product of maleated rosin with 100 ℃ is washed 3 times, remove impurity in the crude product, obtain meeting the maleated rosin raw material of requirement of the present invention, stand-by.
(2), the preparation of maleated rosin glycol ester
Get the maleated rosin that a certain amount of (1) prepares, porphyrize in 250 milliliters there-necked flask, is a solvent with 200# gasoline and toluene, adds 1～8% FeCl
3Or tosic acid or the mixture of the two be catalyzer, and press chemical equation and add excessive ethylene glycol, loads onto thermometer, water trap, agitator and reflux condensing tube.Agitator is started in heating, and temperature of reaction is controlled at 100～140 ℃, reacting by heating 2～5 hours, stop heating, while hot reaction solution is poured out, static, be cooled to room temperature, isolate the gasoline layer, with 80 ℃ deionized water repetitive scrubbing product, the ethylene glycol of removing catalyzer and not having to have reacted, product is put into oven drying, and it is 60～130mgKOHg that dry back product is surveyed its acid number
-1
(3), the preparation of maleated rosin ethylene glycol propylene ester
Get a certain amount of by the dry good maleated rosin glycol ester of (2) preparation in 250 milliliters there-necked flask, press the excessive vinylformic acid of chemical equation adding, add 1.5～5% FeCl
3Or tosic acid or phosphoric acid or three's mixture is catalyzer, and the stopper about 1.6%, is solvent with 200# gasoline, loads onto thermometer, water trap, agitator and reflux condensing tube.Heating, temperature of reaction is controlled at 100～140 ℃, reacting by heating 2～5 hours stops heating, and reaction solution is poured out, be cooled to room temperature, isolate the gasoline layer, with 80 ℃ deionized water repetitive scrubbing product, the vinylformic acid of removing catalyzer, stopper and not having to have reacted, separate water outlet, product is standby.
(4), the preparation of the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking
Get the maleated rosin ethylene glycol propylene ester a certain amount of (3) prepared in 250 milliliters there-necked flask, with 200# gasoline is solvent, the azo-bis-isobutyl cyanide (AIBN) of adding 1～10% or benzoyl peroxide (BPO) or Potassium Persulphate or three's mixture are initiator, load onto thermometer, agitator and reflux condensing tube, heating, start agitator, temperature of reaction is controlled at 70～100 ℃, and reacting by heating stopped heating after 0.5～3 hour, non-shock chilling is isolated the gasoline layer.Add a certain amount of gasoline again and reflux half an hour, isolate the gasoline layer more while hot, the gasoline cleaning product will be removed less than the maleated rosin ethylene glycol propylene ester that has reacted, and drying products gets self-crosslinking maleated rosin ethylene glycol propylene ester product of the present invention.
3. the purposes of the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking of the present invention.
The poly-maleated rosin ethylene glycol propylene ester of self-crosslinking of the present invention is a kind of brand-new functional group high molecular polymer, it is widely used in the separation of natural product, as separate ginkgolic flavone glycoside, separate the little wall alkali of berberine etc., and the carrier of being used for fixing enzyme, as the carrier of being used for fixing amylase, lipase, laccase.
The present invention has the following advantages:
1, maleated rosin monomer molecule skeleton is big, and chiral molecules is arranged in the rosin, can synthetic aperture bigger, as to have chiral radicals polymer;
2, rosin Nantural non-toxic, environmental friendliness, polymkeric substance can be used for the carrier of Separation of Natural Products and immobilized enzyme better.
Description of drawings
Fig. 1 is the infrared spectrogram of preparation method's of the present invention basic raw material maleated rosin.
Fig. 2 is the infrared spectrogram of preparation method's of the present invention intermediate product maleated rosin glycol ester.
Fig. 3 is the infrared spectrogram of preparation method's of the present invention polymer monomer maleated rosin ethylene glycol propylene ester.
Fig. 4 is the infrared spectrogram of the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking of the present invention.
Fig. 5 is the ultraviolet spectrogram of preparation method's of the present invention basic raw material maleated rosin.
Fig. 6 is the ultraviolet spectrogram of preparation method's of the present invention intermediate product maleated rosin glycol ester.
Fig. 7 is the ultraviolet spectrogram of preparation method's of the present invention polymer monomer maleated rosin ethylene glycol propylene ester.
Fig. 8 is the ultraviolet spectrogram of the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking of the present invention.
Embodiment
Crosslinking kinetic energy based high polymer is widely used in natural drug separation, immobilized enzyme and polymer catalyst aspect.Most widely used kinetic energy based high polymer is the polystyrene type polymer at present, and it is to be skeleton with the polystyrene, adopts method complex functionality based high-polymers such as copolymerization, grafting.Many scholars have synthesized the functional polymer of many special constructions according to different application requiring, compare with the polystyrene type polymer, and rosin has special construction: the one, and molecular skeleton is big, can the bigger polymer of synthetic aperture; The 2nd, contain conjugated double bond, be convenient to grafting, modification; The 3rd, chiral molecules is arranged in the rosin, help the synthesis of chiral superpolymer; The 4th, Nantural non-toxic, environmental friendliness.Therefore, with rosin is that raw material synthetic macroporous netlike kinetic energy based high polymer has novel texture and new function, the present invention carries out esterification with maleated rosin and ethylene glycol and prepares the maleated rosin glycol ester, maleated rosin glycol ester and vinylformic acid reaction obtain maleated rosin ethylene glycol propylene ester, be monomer with maleated rosin ethylene glycol propylene ester again, make the poly-maleated rosin ethylene glycol propylene ester polymer of self-crosslinking by free radical polymerization.This polymer has-COOH functional group.
Preparation method's of the present invention technical scheme is as follows:
1. the first step rosin and toxilic acid (or maleic anhydride) are the raw material synthesizing maleated rosin:
2. the second step maleated rosin and ethylene glycol are that raw material has synthesized the maleated rosin glycol ester by esterification
Reaction conditions is to the influence of the esterification of maleated rosin and ethylene glycol
2.1 temperature of reaction is to the influence of esterification
Along with the rising of temperature, the acid number of product descends gradually, but the acid number of product is not low more good more, and acid number is crossed the shared ratio decline of carboxyl in the low esterification products molecular structure, and the functional group-COOH content in the final resulting polymers is few; And acid number is when too high, and the vinylformic acid ratio that the secondary esterification connects is lower, is difficult to obtain the polymkeric substance of higher molecular weight, so the product acid number is controlled at 60～120mgKOHg
-1, temperature of reaction is controlled at 100～140 ℃.
2.2 the ratio of quality amount is to the influence of esterification between the reactant
Along with the raising of ethylene glycol, the acid number of esterification products descends gradually, and it is favourable to esterification therefore to press the suitably excessive ethylene glycol of chemical equation adding.
2.3 catalytic amount is to the influence of esterification.
Adopt FeCl
3Or tosic acid is made maleated rosin and ethylene glycol esterification catalyst for reaction.Along with catalyst levels increases, the acid number of product descends gradually, surpasses a certain amount of back acid number and changes not quite, and present method selecting catalyst amount is 1～8%.
2.4 the reaction times, along with the prolongation in reaction times, the product acid number descended gradually to the influence of esterification, present method selective reaction time is 2～5h
3. the 3rd step maleated rosin glycol ester and vinylformic acid reaction obtain maleated rosin ethylene glycol propylene ester
Because the solubleness of an esterification products maleated rosin glycol ester in gasoline is not fine, the way that adds excessive propene acid consumption is adopted in this experiment, has both guaranteed that reactant was dissolved preferably, selects 1.5～5% FeCl for use
3Or tosic acid is catalyzer, and esterification is carried out towards forward, and temperature of reaction is controlled at 100～140 ℃, reacting by heating time 2～5h.In addition, polymerization takes place in order to prevent vinylformic acid from high temperature reacting for a long time, the Resorcinol of adding about 1.6% is as stopper.
4. the 4th step was a monomer with maleated rosin ethylene glycol propylene ester, made the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking of the present invention by free radical polymerization.
4.1 polymeric reaction temperature is to the influence of polymer performance, along with polymeric reaction temperature improves, the polymkeric substance softening temperature raises, but the free radical that produces in the too high reaction process of temperature is many, and molecular weight and molecular weight consolidates method selective polymerization temperature of reaction and is controlled at 70～100 ℃.
4.2 initiator azo-bis-isobutyl cyanide or benzoyl peroxide or Potassium Persulphate or three's mixture amount is to the influence of polymer performance; along with initiator amount increases; the polymkeric substance softening temperature raises gradually; when increasing to when a certain amount of; the polymkeric substance softening temperature begins to descend, and it is 1～10% that the method that consolidates is selected amount of initiator.
4.3 polymerization reaction time is to the influence of polyreaction, along with the prolongation in reaction times, the productive rate of product increases gradually, surpasses certain reaction times, and the productive rate of product no longer changes, and it is 0.5～3h that preparation method of the present invention selects controlling reaction time.
4.4 the acid number of maleated rosin glycol ester is to the influence of polyreaction, reduction along with maleated rosin glycol ester acid number, the softening temperature of phase emergencing copolymer improves gradually, but acid number is low excessively, the functional group of polymkeric substance-COOH reduces, the performance of impact polymer is taken into account it greatly again and is had absorption property preferably so should guarantee polymericular weight again, and the acid number of the inventive method control maleated rosin glycol ester is 60～120mgKOHg
-1
Two, the affirmation of the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking of the present invention
The affirmation of product of the present invention mainly is acid number, softening temperature, degree of crosslinking and the solubility property in organic solvent of the product prepared by the inventive method of check, and with infrared spectrometer and ultraviolet-visible photometer the monomer and the product of the present invention of basic raw material, intermediate product, polymkeric substance is carried out monitoring analysis.
1. measure the acid number of product with chemical analysis method (acid base titration), acid number should be at 60～120mgKOHg
-1
2. utilize melting point detector to measure the softening temperature of product, softening temperature should be at 180～300 ℃.
3. measure the degree of crosslinking of product with the gel content method, degree of crosslinking should be 15～75%.
4. use infrared spectrometer and ultraviolet-visible photometer to basic raw material maleated rosin of the present invention, intermediate product maleated rosin glycol ester, the poly-maleated rosin ethylene glycol propylene ester of polymer monomer maleated rosin ethylene glycol propylene ester and final product self-crosslinking carries out assay determination, obtain their infrared spectrogram and ultraviolet spectrogram respectively, Fig. 1 is the infrared spectrogram of maleated rosin, Fig. 2 is the infrared spectrogram of maleated rosin glycol ester, Fig. 3 is the infrared spectrogram of maleated rosin ethylene glycol propylene ester, Fig. 4 is the infrared spectrogram of the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking of the present invention, Fig. 5 is the ultraviolet spectrogram of maleated rosin, Fig. 6 is the ultraviolet spectrogram of maleated rosin glycol ester, Fig. 7 is the ultraviolet spectrogram of maleated rosin ethylene glycol propylene ester, and Fig. 8 is the ultraviolet spectrogram of the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking of the present invention.The product that meets above condition is exactly the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking of the present invention; And serve as according to detecting the specification of quality whether monitoring starting material, intermediate product, monomer and invention product meet the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking of the present invention with these.
Preparation method of the present invention is with the starting material title specification place of production, and is as shown in table 1
| Sequence number | The starting material title | Specification | The place of |
| 1 | Rosin | One-level | The Guangxi Wuzhou Rosin Plant |
| 2 | Toxilic acid or maleic anhydride | Chemical pure | Shanghai chemical reagent factory of traditional |
| 3 | Ethylene glycol | Analytical pure | Chemical plant, Xinning, Guangdong |
| 4 | Vinylformic acid | Chemical pure | Shanghai chemical reagent factory of traditional |
| 5 | Toluene | Analytical pure | Shantou City's brilliance laboratory |
| 6 | 200# gasoline | Industry reagent | Maoming Petro-Chemical Corporation |
| 7 | Azo-bis-isobutyl cyanide | Analytical pure | Shanghai chemical reagent factory of traditional |
| 8 | Toxilic acid | Chemical pure | The same |
| 9 | Resorcinol | Analytical pure | Chemical plant, Shantou, Guangdong |
Preparation method of the present invention is as shown in table 2 with instrument, equipment, title, model, the place of production
| Sequence number | Instrument, equipment, title, model | The place of | |
| 1 | Nicolet Magna IR 550 (II) infrared spectrometer | The U.S. | |
| 2 | 916 ultraviolet- | Australia | |
| 3 | The X42 melting point detector | Tyke, Beijing Instr Ltd. | |
| 4 | The LCT21 differential thermal analyzer | Beijing Optical Instrument Factory |
Concrete experimental technique
Embodiment 1:
1), the preparation of maleated rosin
With 200 gram rosin porphyrizes, place three-necked bottle, thermometer, water trap and reflux condensing tube are installed.Use the electric mantle heat fused, when temperature is raised to 140 ℃, start agitator, press chemical equation and add excessive toxilic acid or maleic anhydride, thermostatically heating refluxed 8 hours when temperature was raised to 190 ℃.Reaction back product is poured out while hot, and product is cooled to below 100 ℃, and porphyrize with 80 ℃ of hot water washed product repeatedly, is removed unnecessary maleic anhydride or toxilic acid, approximates 7,60 ℃ of dryings up to pH value, obtains the thick product of maleated rosin.The gasoline of the thick product of maleated rosin with 100 ℃ is washed 3 times.Remove impurity in the thick product, obtain meeting the maleated rosin of requirement of the present invention.
2), the preparation of maleated rosin glycol ester
Getting 30 gram maleated rosins (porphyrize) in 250 milliliters there-necked flask, is solvent with 200# gasoline and toluene, adds 2 gram Catalyzed by p-Toluenesulfonic Acid agent, and 15 milliliters ethylene glycol is loaded onto thermometer, water trap, agitator and reflux condensing tube.Agitator is started in heating, and temperature of reaction is controlled at 100～125 ℃, reacting by heating 4 hours, stop heating, while hot reaction solution is poured out, static, be cooled to room temperature, isolate the gasoline layer, with 80 ℃ deionized water repetitive scrubbing product, the ethylene glycol of removing catalyzer and not having to have reacted, product is put into oven drying, and it is 65mgKOHg that acid number is surveyed in dry back
-1
3), the preparation of maleated rosin ethylene glycol propylene ester
Get the above-mentioned dry good maleated rosin glycol ester of 20 grams in 250 milliliters there-necked flask, the vinylformic acid that adds 18 milliliters adds 1 gram Catalyzed by p-Toluenesulfonic Acid agent, the stopper of 0.6 gram, with 200# gasoline is solvent, loads onto thermometer, water trap, agitator and reflux condensing tube.Heating, temperature of reaction is controlled at 100～140 ℃, and reacting by heating 3 hours stops heating, reaction solution is poured out, be cooled to room temperature, isolate the gasoline layer, with 80 ℃ deionized water repetitive scrubbing product, the vinylformic acid of removing catalyzer, stopper and not having to have reacted separates water outlet, and product is standby.
4), the preparation of self-crosslinking maleated rosin ethylene glycol propylene ester polymer
The maleated rosin ethylene glycol propylene ester of getting 15 grams is in 250 milliliters there-necked flask, with 200# gasoline is solvent, add azo-bis-isobutyl cyanide (AIBN) initiator of 0.4 gram, load onto thermometer, agitator and reflux condensing tube, heating, start agitator, temperature of reaction is controlled at 70～100 ℃, reacts after 3 hours, stops heating, non-shock chilling is isolated the gasoline layer.Add a certain amount of gasoline again and reflux half an hour, isolate the gasoline layer more while hot, the gasoline cleaning product is removed the maleated rosin ethylene glycol propylene ester of small molecular weight, dry 12 gram self-crosslinking maleated rosin ethylene glycol propylene ester polymer products, the acid number 60mgKOHg of getting
-1, 300 ℃ of softening temperatures, degree of crosslinking 75%.
Embodiment 2
1), the preparation of maleated rosin
With 200 gram rosin porphyrizes, place three-necked bottle, thermometer, water trap and reflux condensing tube are installed.Use the electric mantle heat fused, when temperature is raised to 140 ℃, start agitator, press chemical equation and add excessive maleic anhydride or toxilic acid, thermostatically heating refluxed 8 hours when temperature was raised to 190 ℃.Reaction back product is poured out while hot, and product is cooled to below 100 ℃, and porphyrize with 80 ℃ of hot water washed product repeatedly, is removed unnecessary maleic anhydride or toxilic acid, approximates 7,60 ℃ of dryings up to pH value, obtains the thick product of maleated rosin.The gasoline of the thick product of maleated rosin with 100 ℃ is washed 3 times.Remove impurity in the thick product, obtain meeting the maleated rosin of requirement of the present invention.
2), the preparation of maleated rosin glycol ester
Getting 200 gram maleated rosins (porphyrize) in there-necked flask, is solvent with 200# gasoline and a certain amount of toluene, adds 2.8 grams to FeCl
3Catalyzer, 68 milliliters ethylene glycol is loaded onto thermometer, water trap, agitator and reflux condensing tube.Agitator is started in heating, and temperature of reaction is controlled at 100～130 ℃, reacting by heating 5 hours, stop heating, while hot reaction solution is poured out, static, be cooled to room temperature, isolate the gasoline layer, with 80 ℃ deionized water repetitive scrubbing product, the ethylene glycol of removing catalyzer and not having to have reacted, product is put into oven drying, and it is 95mgKOHg that acid number is surveyed in dry back
-1
3), the preparation of maleated rosin ethylene glycol propylene ester
Get the above-mentioned dry good maleated rosin glycol ester of 150 grams in there-necked flask, add 55 milliliters vinylformic acid, add 6 gram Catalyzed by p-Toluenesulfonic Acid agent, the stopper of 4 grams is a solvent with 200# gasoline, loads onto thermometer, water trap, agitator and reflux condensing tube.Heating, temperature of reaction is controlled at 100～140 ℃, and reacting by heating 2 hours stops heating, reaction solution is poured out, be cooled to room temperature, isolate the gasoline layer, with 80 ℃ deionized water repetitive scrubbing product, the vinylformic acid of removing catalyzer, stopper and not having to have reacted separates water outlet, and product is standby.
4), the preparation of self-crosslinking maleated rosin ethylene glycol propylene ester polymer
The maleated rosin ethylene glycol propylene ester of getting 100 grams is in 250 milliliters there-necked flask, with 200# gasoline is solvent, add benzoyl peroxide (BPO) initiator of 8 grams, load onto thermometer, agitator and reflux condensing tube, heating, start agitator, temperature of reaction is controlled at 70～100 ℃, reacts after 2 hours, stops heating, non-shock chilling is isolated the gasoline layer.Adding a certain amount of gasoline again refluxes half an hour, isolate the gasoline layer more while hot, the gasoline cleaning product is removed the maleated rosin ethylene glycol propylene ester of small molecular weight, dry 90 gram self-crosslinking maleated rosin ethylene glycol propylene ester polymer products, the product acid number 85mgKOHg of getting
-1, 220 ℃ of softening temperatures, degree of crosslinking 60%.
1), the preparation of maleated rosin
With 200 gram rosin porphyrizes, place three-necked bottle, thermometer, water trap and reflux condensing tube are installed.Use the electric mantle heat fused, when temperature is raised to 140 ℃, start agitator, press chemical equation and add excessive maleic anhydride or toxilic acid, thermostatically heating refluxed 8 hours when temperature was raised to 190 ℃.Reaction back product is poured out while hot, and product is cooled to below 100 ℃, and porphyrize with 80 ℃ of hot water washed product repeatedly, is removed unnecessary maleic anhydride or toxilic acid, approximates 7,60 ℃ of dryings up to pH value, obtains the thick product of maleated rosin.The gasoline of the thick product of maleated rosin with 100 ℃ is washed 3 times.Remove impurity in the thick product, obtain meeting the maleated rosin of requirement of the present invention.
2), the preparation of maleated rosin glycol ester
Getting 300 gram maleated rosins (porphyrize) in 250 milliliters there-necked flask, is solvent with 200# gasoline and a certain amount of toluene, adds 33 gram Catalyzed by p-Toluenesulfonic Acid agent, and 95 milliliters ethylene glycol is loaded onto thermometer, water trap, agitator and reflux condensing tube.Agitator is started in heating, and temperature of reaction is controlled at 100～130 ℃, reacting by heating 5 hours, stop heating, while hot reaction solution is poured out, static, be cooled to room temperature, isolate the gasoline layer, with 80 ℃ deionized water repetitive scrubbing product, the ethylene glycol of removing catalyzer and not having to have reacted, product is put into oven drying, and it is 115mgKOHg that acid number is surveyed in dry back
-1
3), the preparation of maleated rosin ethylene glycol propylene ester
Get the above-mentioned dry good maleated rosin glycol ester of 250 grams in there-necked flask, add 55 milliliters vinylformic acid, add 6 gram Catalyzed by p-Toluenesulfonic Acid agent, 5 gram stoppers are solvent with 200# gasoline, load onto thermometer, water trap, agitator and reflux condensing tube.Heating, temperature of reaction is controlled at 100～140 ℃, and reacting by heating 5 hours stops heating, reaction solution is poured out, be cooled to room temperature, isolate the gasoline layer, with 80 ℃ deionized water repetitive scrubbing product, the vinylformic acid of removing catalyzer, stopper and not having to have reacted separates water outlet, and product is standby.
4), the preparation of self-crosslinking maleated rosin ethylene glycol propylene ester polymer
The maleated rosin ethylene glycol propylene ester of getting 200 grams is in 250 milliliters there-necked flask, with 200# gasoline is solvent, add 10 gram Potassium Persulphate initiators, load onto thermometer, agitator and reflux condensing tube, heating, start agitator, temperature of reaction is controlled at 70～100 ℃, reacts after 3 hours, stops heating, non-shock chilling is isolated the gasoline layer.Add a certain amount of gasoline again and reflux half an hour, isolate the gasoline layer more while hot, the gasoline cleaning product is removed the maleated rosin ethylene glycol propylene ester of small molecular weight, dry 180 gram self-crosslinking maleated rosin ethylene glycol propylene ester polymer products, the acid number 98mgKOHg of getting
-1, 200 ℃ of softening temperatures, degree of crosslinking 50%.
Embodiment 4
1), the preparation of maleated rosin
With 200 gram rosin porphyrizes, place three-necked bottle, thermometer, water trap and reflux condensing tube are installed.Use the electric mantle heat fused, when temperature is raised to 140 ℃, start agitator, press chemical equation and add excessive maleic anhydride or toxilic acid, thermostatically heating refluxed 8 hours when temperature was raised to 190 ℃.Reaction back product is poured out while hot, and product is cooled to below 100 ℃, and porphyrize with 80 ℃ of hot water washed product repeatedly, is removed unnecessary maleic anhydride or toxilic acid, approximates 7,60 ℃ of dryings up to pH value, obtains the thick product of maleated rosin.The gasoline of the thick product of maleated rosin with 100 ℃ is washed 3 times.Remove impurity in the thick product, obtain meeting the maleated rosin of requirement of the present invention.
2), the preparation of maleated rosin glycol ester
Get 418 gram maleated rosins, porphyrize in 250 milliliters there-necked flask, is a solvent with 200# gasoline and toluene, adds FeCl
3Mixture 29 grams with tosic acid add 86 milliliters of ethylene glycol, load onto thermometer, water trap, agitator and reflux condensing tube.Agitator is started in heating, and temperature of reaction is controlled at 100～140 ℃, reacting by heating 3 hours, stop heating, while hot reaction solution is poured out, static, be cooled to room temperature, isolate the gasoline layer, with 80 ℃ of deionized water repetitive scrubbing products, the ethylene glycol of removing catalyzer and not having to have reacted, product is put into oven drying, and it is 128mgKOHg that acid number is surveyed in dry back
-1
3), the preparation of maleated rosin ethylene glycol propylene ester
Get the above-mentioned dry good maleated rosin glycol ester of 250 grams in there-necked flask, add 55 milliliters vinylformic acid, add 13 gram FeCl
3Catalyzer adds 5 gram stoppers, and 200# gasoline is solvent, loads onto thermometer, water trap, agitator and reflux condensing tube.Heated 4 hours, and stopped heating, reaction solution is poured out, be cooled to room temperature, isolate the gasoline layer, with 80 ℃ deionized water repetitive scrubbing product, the vinylformic acid of removing catalyzer, stopper and not having to have reacted, separate water outlet, product is standby.
4), the preparation of self-crosslinking maleated rosin ethylene glycol propylene ester
The maleated rosin ethylene glycol propylene ester of getting 150 grams is in 250 milliliters there-necked flask, with 200# gasoline is solvent, add the mixture initiator of 15 gram azo-bis-isobutyl cyanide, vitriolate of tartar and benzoyl peroxides, load onto thermometer, agitator and reflux condensing tube, heating, start agitator, temperature of reaction is controlled at 70～100 ℃, reacts after 1.5 hours, stops heating, non-shock chilling is isolated the gasoline layer.Add gasoline again and reflux half an hour, isolate the gasoline layer more while hot, use the gasoline cleaning product, remove the maleated rosin ethylene glycol propylene ester of small molecular weight, dry that product gets the poly-maleated rosin ethylene glycol propylene ester of 135g self-crosslinking, acid number is 120mgKOHg
-1, 180 ℃ of softening temperatures, degree of crosslinking 15%.
Claims (2)
1. high polymer with self-crosslinked functional radicle is characterized in that:
(1) chemical name of this high polymer with self-crosslinked functional radicle is the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking;
(2) molecular weight, structural formula:
Monomer maleated rosin ethylene glycol propylene ester molecule amount is 535～614;
Structural formula:
Monomer maleated rosin ethylene glycol propylene ester structure formula:
Self-crosslinking gathers maleated rosin ethylene glycol propylene ester structure formula:
(3) physico-chemical property: the light yellow spherical particle of outward appearance, acid number 60～120mgKOHg
-1, 180～300 ℃ of softening temperatures, degree of crosslinking 15～75% is not dissolved in organic solvents such as dehydrated alcohol, gasoline, hexanaphthene, toluene, acetone, acetate.
2. the preparation method of the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking is characterized in that with rosin, maleic anhydride or toxilic acid, ethylene glycol, vinylformic acid be basic raw material, comprises following four steps:
(1), the preparation of maleated rosin
The rosin porphyrize is placed three-necked bottle, thermometer is installed, water trap and reflux condensing tube, use the electric mantle heat fused, when temperature is raised to 140 ℃, start agitator, press chemical equation and add excessive maleic anhydride or toxilic acid, thermostatically heating refluxed 8 hours when temperature was raised to 190 ℃, and reaction back product is poured out while hot, and product is cooled to below 100 ℃, porphyrize, with 80 ℃ of hot water washed product repeatedly, remove unnecessary toxilic acid, approximate 7 up to pH value, 60 ℃ of dryings, obtain the thick product of maleated rosin, the gasoline of thick product with 100 ℃ is washed 3 times, remove impurity in the crude product, obtain meeting the maleated rosin of requirement of the present invention, stand-by;
(2), the preparation of maleated rosin glycol ester
Get the maleated rosin that a certain amount of (1) prepares, porphyrize in the there-necked flask of 250ml, is a solvent with 200# gasoline and toluene, adds 1～8% FeCl
3Or tosic acid or the mixture of the two are catalyzer, and press chemical equation and add excessive ethylene glycol, load onto thermometer, water trap, agitator and reflux condensing tube, heating, start agitator, temperature of reaction is controlled at 100～140 ℃, reacting by heating 2～5 hours stops heating, while hot reaction solution is poured out, non-shock chilling is to room temperature, isolate the gasoline layer, with 80 ℃ deionized water repetitive scrubbing product, the ethylene glycol of removing catalyzer and not having to have reacted, product is put into oven drying, and it is 60～130mgKOHg that dry back product is surveyed its acid number
-1
(3), the preparation of maleated rosin ethylene glycol propylene ester
Get a certain amount of by the dry good maleated rosin glycol ester of (2) preparation in the there-necked flask of 250ml, press the excessive vinylformic acid of chemical equation adding, add 1.5～5% FeCl
3Or tosic acid or phosphoric acid or three's mixture is catalyzer, and the stopper about 1.6%, is solvent with 200# gasoline, load onto thermometer, water trap, agitator and reflux condensing tube, heating, temperature of reaction is controlled at 100～140 ℃, reacting by heating 2～5 hours stops heating, and reaction solution is poured out, be cooled to room temperature, isolate the gasoline layer, with 80 ℃ of deionized water repetitive scrubbing products, the vinylformic acid of removing catalyzer, stopper and not having to have reacted, separate water outlet, product is standby;
(4), the preparation of the poly-maleated rosin ethylene glycol propylene ester of self-crosslinking
Get the maleated rosin ethylene glycol propylene ester a certain amount of (3) prepared in the there-necked flask of 250ml, with 200# gasoline is solvent, the azo-bis-isobutyl cyanide (AIBN) of adding 2.5～10% or benzoyl peroxide (BP0) or Potassium Persulphate or three's mixture are initiator, load onto thermometer, agitator and reflux condensing tube, heating, start agitator, temperature of reaction is controlled at 70～100 ℃, react after 0.5～3 hour, stop heating, non-shock chilling is isolated the gasoline layer, adds gasoline backflow 0.5h again, isolate the gasoline layer while hot, gasoline is cleaning product repeatedly, will remove less than the maleated rosin ethylene glycol propylene ester that has reacted, and drying products gets self-crosslinking maleated rosin ethylene glycol propylene ester product of the present invention.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177498B (en) * | 2007-10-26 | 2011-02-16 | 广西民族大学 | Molecular engram polymer containing ternary phenanthrene ring frame and preparation method thereof |
| CN101338006B (en) * | 2008-08-11 | 2011-08-17 | 江门市制漆厂有限公司 | Acrylic resin with self-crosslinking characteristic and method for preparing same |
| CN102432722A (en) * | 2011-10-09 | 2012-05-02 | 中国林业科学研究院林产化学工业研究所 | Method for preparing rosin-based regular polymers |
| CN103232349A (en) * | 2013-03-28 | 2013-08-07 | 中国林业科学研究院林产化学工业研究所 | Rosin or rosin derivative long chain flexible monomer preparation method |
| CN106748855A (en) * | 2016-11-14 | 2017-05-31 | 南京林业大学 | A kind of fumaropimaric acid modified propylene amide compound, its preparation method and its prepared polymer |
| CN106905452A (en) * | 2017-01-07 | 2017-06-30 | 北京化工大学 | Alpha-olefin polymerization catalyst and preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177498B (en) * | 2007-10-26 | 2011-02-16 | 广西民族大学 | Molecular engram polymer containing ternary phenanthrene ring frame and preparation method thereof |
| CN101338006B (en) * | 2008-08-11 | 2011-08-17 | 江门市制漆厂有限公司 | Acrylic resin with self-crosslinking characteristic and method for preparing same |
| CN102432722A (en) * | 2011-10-09 | 2012-05-02 | 中国林业科学研究院林产化学工业研究所 | Method for preparing rosin-based regular polymers |
| CN103232349A (en) * | 2013-03-28 | 2013-08-07 | 中国林业科学研究院林产化学工业研究所 | Rosin or rosin derivative long chain flexible monomer preparation method |
| CN106748855A (en) * | 2016-11-14 | 2017-05-31 | 南京林业大学 | A kind of fumaropimaric acid modified propylene amide compound, its preparation method and its prepared polymer |
| CN106748855B (en) * | 2016-11-14 | 2018-07-17 | 南京林业大学 | A kind of fumaropimaric acid modified propylene amide compound, preparation method and its prepared polymer |
| CN106905452A (en) * | 2017-01-07 | 2017-06-30 | 北京化工大学 | Alpha-olefin polymerization catalyst and preparation method and application |
| CN106905452B (en) * | 2017-01-07 | 2019-12-24 | 北京化工大学 | Alpha-olefin polymerization catalyst, preparation method and application |
| CN113527925A (en) * | 2021-08-13 | 2021-10-22 | 台州格凌机械股份有限公司 | Wear-resistant gear and production process thereof |
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