CN107573245A - One vegetable oil yl carboxylic acid salt form hydrophilic chain extender and its preparation method and application - Google Patents
One vegetable oil yl carboxylic acid salt form hydrophilic chain extender and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to organic synthesis field, discloses vegetable oil yl carboxylic acid salt form hydrophilic chain extender and its preparation method and application.The structural formula of vegetable oil yl carboxylic acid salt form hydrophilic chain extender is as follows：
Description
Technical field
The invention belongs to organic synthesis field, more particularly to a vegetable oil yl carboxylic acid salt form hydrophilic chain extender and its preparation
Methods and applications.
Background technology
For polyurethane (PU) as a kind of synthetic resin of function admirable, application is quite varied, particularly in adhesive area,
It is widely used in the fields such as carpenter, shoemaking, papermaking, civil engineering, the product of different properties can be developed by adjusting synthesizing formula.Will
PU is dispersed in water, and is existed in the form of an emulsion, and environmental-protecting performance is excellent, and PU does not possess hydrophily in itself, to make it stable in water
Disperse it is necessary to by introducing hydrophilic radical in its molecule segment, make strand possess completely or partly possess hydrophily.It is hydrophilic
The introducing of group is to synthesize the key of aqueous polyurethane (WPU), and hydrophilic chain extender is pre- in opposite end isocyanate based polyurethane
Aggressiveness introduced while chain extension the material of hydrophilic radical, common hydrophilic radical such as carboxyl, sulfonic acid group or secondary amino group
Deng when in its pendant to polyurethane molecular chain, allowing in polyurethane segment with the functional groups that can be ionized.It is conventional
Hydrophilic chain extender mainly have dihydromethyl propionic acid, dimethylolpropionic acid, second diaminourea ethyl sulfonic acid sodium, polyethylene glycol, divinyl
Triamine etc..At present, the existing wide research of nonionic, cation and anionic hydrophilic chain extender in domestic and international WPU, but mesh
Preceding hydrophilic chain extender used is all based on fossil resources, without reference to the hydrophilic chain extender of natural reproducible plant resources.
Polyunsaturated vegetable oil is the triglycerides of unrighted acid, and polyunsaturated vegetable oil acid can be obtained after being hydrolyzed, and will not
Contain in molecular structure after the product plant oil base maleic anhydride hydrolysis that saturated fatty acid reacts to obtain with maleic anhydride by D-A
There are three carboxyls, the architecture basics for possessing structure vegetable oil yl carboxylic acid salt form hydrophilic chain extender.
The content of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide vegetable oil yl carboxylic acid
Salt form hydrophilic chain extender.
Another object of the present invention is the preparation method for providing above-mentioned vegetable oil yl carboxylic acid salt form hydrophilic chain extender.
Still a further object of the present invention is to provide conjunction of the above-mentioned vegetable oil yl carboxylic acid salt form hydrophilic chain extender in aqueous polyurethane
Into etc. application.
The purpose of the present invention is realized by following proposal：
One vegetable oil yl carboxylic acid salt form hydrophilic chain extender, its structural formula are as shown in Equation 1：
Formula 1
Wherein, p=7, n=0 or 1,0<m+s<4, t=2,4,5.
A kind of preparation method of above-mentioned vegetable oil yl carboxylic acid salt form hydrophilic chain extender, is mainly included the following steps that：
(1) synthesis of polyunsaturated vegetable oil acid：Alkaline solution is added after polyunsaturated vegetable oil is heated, in the condition of stirring
Lower condensing reflux reaction, then add acid and neutralize, the reaction solution after neutralization is isolated and purified and obtains vegetable oil acid；
(2) synthesis of polyunsaturated vegetable oil acid D-A reaction products：Maleic anhydride is taken, is first dissolved with organic solvent；Then plus
Enter vegetable oil acid made from step (1), add catalyst after well mixed, stir；Reacted under conditions of UV light irradiations,
Gained reaction product is isolated and purified and produces the D-A reaction products by reaction after terminating；
(3) synthesis of polyunsaturated vegetable oil base hydrophilic chain extender：D-A obtained by dihydric alcohol and step (2) is reacted and produced
Thing is in solvent is added, the heating and melting at 80~120 DEG C, adds catalyst and carries out esterification by ring opening, that is, obtains vegetable oil base carboxylic
Hydrochlorate type hydrophilic chain extender.
Polyunsaturated vegetable oil described in step (1) be preferably tung oil, peanut oil, sesame oil, soybean oil, cashew nut shell oil,
At least one of linseed oil, castor oil, rapeseed oil；Alkali in described alkaline solution is preferably sodium hydroxide or hydroxide
Potassium；Described acid is preferably at least one of sulfuric acid, phosphoric acid, pyrovinic acid, p-methyl benzenesulfonic acid, formic acid and acetic acid.
The alkali in alkaline solution described in step (1) is preferably the 0.5~3% of polyunsaturated vegetable oil quality, more preferably
For 1~2%；The polyunsaturated vegetable oil, which heats, to be referred to be heated to 50~80 DEG C, and the condensing reflux reaction time is 30~90min.
Isolating and purifying described in step (1) refers to stand the reaction solution after neutralization, is layered, and separates lower floor's glycerin layer；
The liquid on upper strata is washed with water again, except the aqueous phase of sub-cloud, is evaporated under reduced pressure and removes Organic Alcohol and most of water, then dry,
Vegetable oil acid after purification is produced using silver nitrate silica gel chromatography chromatography to dried product.
Preferably, the drying described in step (1) is preferably and adds drier to be dried, and described drier is anhydrous
At least one of calcium chloride, anhydrous sodium sulfate and phosphorus pentoxide.
Catalyst described in step (2) is solid catalyst, preferably cationic photoinitiator；Described is organic molten
Agent is preferably at least one of acetone, absolute ether, benzene,toluene,xylene, tetrahydrofuran, chloroform and dichloromethane.
Preferably, described cationic photoinitiator be preferably diazol, diaryl group iodized salt, triaryl sulfonium salts,
At least one of alkyl sulfosalt, iron arene salt, sulfonyloxy ketone and triaryl silica ether.
The mol ratio of maleic anhydride and vegetable oil acid described in step (2) is preferably 1:1~2:1, more preferably 1.3:
1；The amount of catalyst is preferably the 1~10% of maleic anhydride and vegetable oil acid gross mass；
Reaction, which refers to reaction raw materials being placed under UV photo solidification machines, under the conditions of UV light irradiations described in step (2) irradiates
Reaction, the power of described UV photo solidification machines is preferably 2.5~10KW, and the speed of described UV photo solidification machine conveyer belts is preferably
5~20s/r, the UV photochemically reactive time are preferably 5~30min.
Isolating and purifying gained reaction product described in step (2) is directed to add organic solvent extraction in reaction product
Product and raw material, make it be separated with catalyst；Then rotary distillation, then carry out column chromatographic isolation and purification and produce D-A after purification
Reaction product；Wherein described organic solvent is preferably at least one of hexamethylene, petroleum ether and ethyl acetate.
Described in step (2) based on UV photocatalysis polyunsaturated vegetable oil D-A reaction products, it has with shown in following formula 2
Structure：
Formula 2
In formula 2, p=7, n=0 or 1,0<m+s<4, t=2,4,5.
Dihydric alcohol described in step (3) is at least one of ethylene glycol, propane diols, 1,4- butanediols；Described is molten
Agent is one kind in acetone, absolute ether, benzene, tetrahydrofuran, toluene, dimethylbenzene, acetonitrile；Described catalyst is sulfuric acid, phosphorus
At least one of acid, pyrovinic acid, p-methyl benzenesulfonic acid, formic acid and acetic acid.
The dosage mol ratio of dihydric alcohol and D-A reaction products described in step (3) is 2:1~2.1:1；Described catalysis
The amount of agent is catalytic amount.
The time of esterification by ring opening described in step (3) is 2~4h.
The present invention is had the following advantages and beneficial effect relative to prior art：
(1) renewable plant resources polyunsaturated vegetable oil is used to prepare hydrophilic chain extender by the present invention, alleviates oil
The pressure of industrial and commercial bank's industry, new approach is opened for the source of hydrophilic chain extender.
(2) the more traditional small molecule chain extender molecular weight of hydrophilic chain extender prepared by the present invention increases many times, from
And the use of small molecule chain extender is avoided to negative effect caused by WPU emulsion properties.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Agents useful for same can routinely be bought from market unless otherwise specified in embodiment.
Embodiment 1
(1) synthesis of linolenic acid and isolate and purify：87.2g linseed oil is added in 250mL three-necked flasks
(0.10mol), condensation reflux unit is installed, after thermostat water bath is heated to 60 DEG C, adds the KOH solution prepared, wherein KOH
For the 2% of flax oil quality；Magnetic agitation is opened, after reacting about 80min, stops reaction；Appropriate phosphoric acid is added to neutralize, while hot will be anti-
Answer liquid to be transferred to separatory funnel, stand, separate glycerin layer (lower floor)；The liquid on upper strata is washed 3~4 times with hot distilled water, removed
The aqueous phase of sub-cloud, it is evaporated under reduced pressure and removes most of water etc., use anhydrous sodium sulfate drying；Obtain linolenic acid.Linolenic acid
Isolate and purify using Silver nitrate silica gel column chromatograph method.
(2) synthesis of linolenic acid D-A reaction products：26mmol maleic anhydride is taken, 20mmol linolenic acid, is used
10mL acetone solution, then adds 5% cation light initiator (triaryl silica ether) of total quality of material, and mixing is equal
It is even.UV photo solidification machines are opened, regulation conveyer belt rotating speed is 15s/r, and UV lamp power is 5KW, irradiates 15min under w light.Solvent
After acetone volatilization is evaporated, a certain amount of hexamethylene is added, when having the solid to occur, filtering at once is (to remove catalyst and not anti-
The maleic anhydride answered).The cyclohexane solution of reaction mixture is transferred in separatory funnel and stood, AUTOMATIC ZONING, collects lower floor
Yellow liquid (upper strata is the light yellow cyclohexane solution of unreacted linolenic acid, and hexamethylene and linolenic acid can be separately recovered)
Lower floor's yellow liquid rotary distillation is removed into residual solvent, obtains the limpid product of buff.It is evaporated under reduced pressure and removes solvent and moisture,
Then purified using column chromatography：Using petroleum ether：Ethyl acetate (volume ratio)=1:0、7:1、4:1、2:1 carries out gradient successively washes
It is de-, separating obtained sample, analyzed.
(3) synthesis of flax oil base hydrophilic chain extender：D-A obtained by 2mol ethylene glycol and 1mol steps (2) is reacted
Product is in solvent acetone is added, the heating and melting at 120 DEG C, adds catalyst sulfuric acid and carries out esterification by ring opening, that is, obtains plant
Oil base carboxylic acid type hydrophilic chain extender.1H NMR、13Compound obtained by CNMR and MS results show is target product.
Embodiment 2
(1) synthesis of soybean oleic acid and isolate and purify：87.8g soybean oils are added in 250mL three-necked flasks
(0.10mol), condensation reflux unit is installed, after thermostat water bath is heated to 80 DEG C, adds the KOH prepared, wherein KOH is big
The 2% of soya-bean oil quality；Magnetic agitation is opened, after reacting about 50min, stops reaction；Appropriate phosphoric acid is added to neutralize, while hot by reaction solution
Separatory funnel is transferred to, stands, separates glycerin layer (lower floor)；The liquid on upper strata is washed 3~4 times, under removing with hot distilled water
The aqueous phase of layer, it is evaporated under reduced pressure and removes most of water etc., dried with anhydrous calcium chloride；Obtain soybean oil acid.Point of soybean oleic acid
Silver nitrate silica gel column chromatograph method is used from purifying.
(2) synthesis of soybean oleic acid D-A reaction products：26mmol maleic anhydride is taken, 20mmol soybean oleic acid, is used
10mL acetone solution, then adds 5% cation light initiator (triaryl silica ether) of total quality of material, and mixing is equal
It is even.UV photo solidification machines are opened, regulation conveyer belt rotating speed is 15s/r, and UV lamp power is 5KW, irradiates 15min under w light.Solvent
After acetone volatilization is evaporated, a certain amount of hexamethylene is added, when having the solid to occur, filtering at once is (to remove catalyst and not anti-
The maleic anhydride answered).The cyclohexane solution of reaction mixture is transferred in separatory funnel and stood, AUTOMATIC ZONING, collects lower floor
Yellow liquid (upper strata is the light yellow cyclohexane solution of unreacted soybean oleic acid, and hexamethylene and soybean oleic acid can be separately recovered)
Lower floor's yellow liquid rotary distillation is removed into residual solvent, obtains the limpid product of buff.It is evaporated under reduced pressure and removes solvent and moisture,
Then purified using column chromatography：Using petroleum ether：Ethyl acetate (volume ratio)=1:0、7:1、4:1、2:1 carries out gradient successively washes
It is de-, separating obtained sample, analyzed.
(3) synthesis of soybean oil base hydrophilic chain extender：D-A obtained by 2mol propane diols and 1mol steps (2) is reacted
Product is in solvent absolute ether is added, the heating and melting at 80 DEG C, adds catalyst phosphoric acid and carries out esterification by ring opening, that is, is planted
Thing oil base carboxylic acid type hydrophilic chain extender.1H NMR、13Compound obtained by CNMR and MS results show is target product.
Embodiment 3
(1) synthesis of eleostearic acid and isolate and purify：87.2g tung oil (0.10mol), peace are added in 250mL three-necked flasks
Condensation reflux unit is filled, after thermostat water bath is heated to 70 DEG C, adds the KOH prepared, wherein KOH is the 2% of tung oil quality；
Magnetic agitation is opened, after reacting about 80min, stops reaction；Add appropriate phosphoric acid to neutralize, reaction solution is transferred to liquid separation leakage while hot
Bucket, stand, separate glycerin layer (lower floor)；The liquid on upper strata is washed 3~4 times with hot distilled water, except the aqueous phase of sub-cloud, decompression
Ethanol and most of water etc. is distilled off, uses anhydrous sodium sulfate drying；Obtain eleostearic acid.Eleostearic acid is isolated and purified using nitre
The silver-colored silica gel column chromatography of acid.
(2) synthesis of eleostearic acid D-A reaction products：Take 26mmol maleic anhydride, 20mmol eleostearic acid, with 5mL's
Acetone solution, 10% cationic photoinitiator (diaryl group iodized salt) of total quality of material is then added, be well mixed.Open
UV photo solidification machines, regulation conveyer belt rotating speed is 10s/r, UV lamp power 10KW, irradiates 10min under w light.Treat that solvent acetone is waved
After hair is evaporated, a certain amount of hexamethylene is added, when having the solid to occur, filtering is (to remove catalyst and unreacted horse at once
Carry out acid anhydrides).The cyclohexane solution of reaction mixture is transferred in separatory funnel and stood, AUTOMATIC ZONING, collects lower floor's yellow liquid
Body (upper strata is the light yellow cyclohexane solution of unreacted eleostearic acid, and hexamethylene and eleostearic acid can be separately recovered) is by lower floor's yellow
Residual solvent is distilled off in liquid in rotation, obtains the limpid product of buff.It is evaporated under reduced pressure and removes solvent and moisture, then using post
Chromatographic purification：Using petroleum ether：Ethyl acetate (volume ratio)=1:0、7:1、4:1、2:1 carries out gradient elution successively, separates institute
Sample is obtained, is analyzed.
(3) synthesis of tung oil base hydrophilic chain extender：By the D-A obtained by 2.1mol1,4- butanediols and 1mol steps (2)
Reaction product is in solvent benzol is added, the heating and melting at 100 DEG C, adds catalyst pyrovinic acid and carries out esterification by ring opening, produces
To vegetable oil yl carboxylic acid salt form hydrophilic chain extender.1H NMR、13Compound obtained by CNMR and MS results show is produced for target
Thing.
Embodiment 4
(1) synthesis of cashew nut shell oleic acid and isolate and purify：87.2g cashew nut shell oils are added in 250mL three-necked flasks
(0.10mol), condensation reflux unit is installed, after thermostat water bath is heated to 60 DEG C, adds the KOH prepared, wherein KOH is waist
The 2% of shell oil quality；Magnetic agitation is opened, after reacting about 50min, stops reaction；Appropriate phosphoric acid is added to neutralize, while hot will reaction
Liquid is transferred to separatory funnel, stands, separates glycerin layer (lower floor)；The liquid on upper strata is washed 3~4 times with hot distilled water, removed
The aqueous phase of lower floor, it is evaporated under reduced pressure and removes ethanol and most of water etc., use anhydrous sodium sulfate drying；Obtain cashew nut shell oil acid.Waist
Shell oleic acid is isolated and purified using Silver nitrate silica gel column chromatograph method.
(2) synthesis of cashew nut shell oleic acid D-A reaction products：Take 26mmol maleic anhydride, 20mmol cashew nut shell oleic acid,
With 5mL acetone solution, 10% cationic photoinitiator (sulfonyloxy ketone) of total quality of material is then added, mixing is
It is even.UV photo solidification machines are opened, regulation conveyer belt rotating speed is 20s/r, UV lamp power 2.5KW, irradiates 20min under w light.Treat molten
After the volatilization of agent acetone is evaporated, a certain amount of hexamethylene is added, when having the solid to occur, filtering at once is (to remove catalyst and not
The maleic anhydride of reaction).The cyclohexane solution of reaction mixture is transferred in separatory funnel and stood, AUTOMATIC ZONING, under collection
(upper strata is the light yellow cyclohexane solution of unreacted cashew nut shell oleic acid to layer yellow liquid, and hexamethylene and cashew nut can be separately recovered
Shell oleic acid) lower floor yellow liquid rotary distillation removed into residual solvent, obtain the limpid product of buff.It is evaporated under reduced pressure and removes solvent
And moisture, then purified using column chromatography：Using petroleum ether：Ethyl acetate (volume ratio)=1:0、7:1、4:1、2:1 enters successively
Row gradient elution, separating obtained sample, is analyzed.
(3) synthesis of cashew nut shell oil base hydrophilic chain extender：2mol ethylene glycol and the D-A obtained by 1mol steps (2) is anti-
Product is answered in solvent toluene is added, the heating and melting at 110 DEG C, catalyst p-methyl benzenesulfonic acid is added and carries out esterification by ring opening, i.e.,
Obtain vegetable oil yl carboxylic acid salt form hydrophilic chain extender.1H NMR、13Compound obtained by CNMR and MS results show is target
Product.
Embodiment 5
(1) synthesis of arachic acid and isolate and purify：87.2g peanut oil (0.1mol) is added in 250mL three-necked flasks,
Condensation reflux unit is installed, after thermostat water bath is heated to 80 DEG C, adds the KOH prepared, wherein KOH is Quality of Peanut Oil
2%；Magnetic agitation is opened, after reacting about 50min, stops reaction；Add appropriate phosphoric acid to neutralize, reaction solution is transferred to liquid separation while hot
Funnel, stand, separate glycerin layer (lower floor)；The liquid on upper strata is washed 3~4 times with hot distilled water, except the aqueous phase of sub-cloud, subtracted
Ethanol and most of water etc. is distilled off in pressure, uses anhydrous sodium sulfate drying；Obtain arachic acid.Arachic acid isolates and purifies
Using Silver nitrate silica gel column chromatograph method.
(2) synthesis of arachic acid D-A reaction products：26mmol maleic anhydride is taken, 20mmol arachic acid, is used
5mL acetone solution, 10% cationic photoinitiator (sulfonyloxy ketone) of total quality of material is then added, be well mixed.
UV photo solidification machines are opened, regulation conveyer belt rotating speed is 20s/r, UV lamp power 2.5KW, irradiates 20min under w light.Treat solvent third
After ketone volatilization is evaporated, a certain amount of hexamethylene is added, when having the solid to occur, filtering is (to remove catalyst and unreacted at once
Maleic anhydride).The cyclohexane solution of reaction mixture is transferred in separatory funnel and stood, AUTOMATIC ZONING, it is yellow to collect lower floor
Color liquid (upper strata is the light yellow cyclohexane solution of unreacted arachic acid, and hexamethylene and arachic acid can be separately recovered) will
Lower floor's yellow liquid rotary distillation removes residual solvent, obtains the limpid product of buff.It is evaporated under reduced pressure and removes solvent and moisture, so
Purified afterwards using column chromatography：Using petroleum ether：Ethyl acetate (volume ratio)=1:0、7:1、4:1、2:1 carries out gradient successively washes
It is de-, separating obtained sample, analyzed.
(3) synthesis of peanut oil base hydrophilic chain extender：2.1mol ethylene glycol and the D-A obtained by 1mol steps (2) is anti-
Product is answered in solvent xylene is added, the heating and melting at 80 DEG C, catalyst formic acid is added and carries out esterification by ring opening, that is, planted
Thing oil base carboxylic acid type hydrophilic chain extender.1H NMR、13Compound obtained by CNMR and MS results show is target product.
Embodiment 6
(1) synthesis of castor oil acid and isolate and purify：87.2g castor oil is added in 250mL three-necked flasks
(0.10mol), condensation reflux unit is installed, after thermostat water bath is heated to 60 DEG C, adds the KOH solution prepared, wherein KOH
For the 2% of castor-oil plant oil quality；Magnetic agitation is opened, after reacting about 80min, stops reaction；Appropriate phosphoric acid is added to neutralize, while hot will be anti-
Answer liquid to be transferred to separatory funnel, stand, separate glycerin layer (lower floor)；The liquid on upper strata is washed 3~4 times with hot distilled water, removed
The aqueous phase of sub-cloud, it is evaporated under reduced pressure and removes most of water etc., use anhydrous sodium sulfate drying；Obtain castor oil acid.Castor oil acid
Isolate and purify using Silver nitrate silica gel column chromatograph method.
(2) synthesis of castor oil acid D-A reaction products：26mmol maleic anhydride is taken, 20mmol castor oil acid, is used
5mL acetone solution, 5% cationic photoinitiator (triaryl silica ether) of total quality of material is then added, be well mixed.
UV photo solidification machines are opened, regulation conveyer belt rotating speed is 15s/r, UV lamp power 5KW, irradiates 30min under w light.Treat solvent acetone
After volatilization is evaporated, a certain amount of hexamethylene is added, when having the solid to occur, filtering at once is (to remove catalyst and unreacted
Maleic anhydride).The cyclohexane solution of reaction mixture is transferred in separatory funnel and stood, AUTOMATIC ZONING, collects lower floor's yellow
Liquid (upper strata is the light yellow cyclohexane solution of unreacted castor oil acid, and hexamethylene and castor oil acid can be separately recovered) is by under
Layer yellow liquid rotary distillation removes residual solvent, obtains the limpid product of buff.It is evaporated under reduced pressure and removes solvent and moisture, then
Purified using column chromatography：Using petroleum ether：Ethyl acetate (volume ratio)=1:0、7:1、4:1、2:1 carries out gradient elution successively,
Separating obtained sample, is analyzed.
(3) synthesis of castor oil-base hydrophilic chain extender：D-A obtained by 2mol propane diols and 1mol steps (2) is reacted
Product is in solvents tetrahydrofurane is added, the heating and melting at 100 DEG C, adds catalyst acetic acid and carries out esterification by ring opening, that is, obtains
Vegetable oil yl carboxylic acid salt form hydrophilic chain extender.1H NMR、13Compound obtained by CNMR and MS results show is produced for target
Thing.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
- A 1. vegetable oil yl carboxylic acid salt form hydrophilic chain extender, it is characterised in that there is the structure being shown below：Wherein, p=7, n=0 or 1,0<m+s<4, t=2,4,5.
- A kind of 2. preparation method of vegetable oil yl carboxylic acid salt form hydrophilic chain extender according to claim 1, it is characterised in that Comprise the following steps：(1) synthesis of polyunsaturated vegetable oil acid：Alkaline solution is added after polyunsaturated vegetable oil is heated, it is cold under conditions of stirring Solidifying back flow reaction, then add acid and neutralize, the reaction solution after neutralization is isolated and purified and obtains vegetable oil acid；(2) synthesis of polyunsaturated vegetable oil acid D-A reaction products：Maleic anhydride is taken, is dissolved with organic solvent；Then step is added (1) vegetable oil acid made from, catalyst is added after well mixed, is stirred；Reacted under conditions of UV light irradiations, reaction knot Gained reaction product is isolated and purified after beam and produces the D-A reaction products；(3) synthesis of polyunsaturated vegetable oil base hydrophilic chain extender：D-A reaction products obtained by dihydric alcohol and step (2) are existed Add in solvent, the heating and melting at 80~120 DEG C, add catalyst and carry out esterification by ring opening, that is, obtain vegetable oil yl carboxylic acid salt Type hydrophilic chain extender.
- 3. the preparation method of vegetable oil yl carboxylic acid salt form hydrophilic chain extender according to claim 2, it is characterised in that：Polyunsaturated vegetable oil described in step (1) is tung oil, peanut oil, sesame oil, soybean oil, cashew nut shell oil, linseed oil, castor At least one of sesame oil, rapeseed oil；Alkali in described alkaline solution is sodium hydroxide or potassium hydroxide；Described acid is sulphur At least one of acid, phosphoric acid, pyrovinic acid, p-methyl benzenesulfonic acid, formic acid and acetic acid；The alkali in alkaline solution described in step (1) is the 0.5~3% of polyunsaturated vegetable oil quality；The unsaturated plant Oil, which heats, to be referred to be heated to 50~80 DEG C, and the condensing reflux reaction time is 30~90min；Isolating and purifying described in step (1) refers to stand the reaction solution after neutralization, is layered, and separates lower floor's glycerin layer；Again will The liquid on upper strata is washed with water, and except the aqueous phase of sub-cloud, is evaporated under reduced pressure and removes Organic Alcohol and most of water, then dry, to dry Product after dry produces vegetable oil acid after purification using silver nitrate silica gel chromatography chromatography.
- 4. the preparation method of vegetable oil yl carboxylic acid salt form hydrophilic chain extender according to claim 3, it is characterised in that：Drying described in step (1) refers to addition drier and is dried, and described drier is anhydrous calcium chloride, anhydrous slufuric acid At least one of sodium and phosphorus pentoxide.
- 5. the preparation method of vegetable oil yl carboxylic acid salt form hydrophilic chain extender according to claim 2, it is characterised in that：Catalyst described in step (2) is cationic photoinitiator, described organic solvent be acetone, absolute ether, benzene, At least one of toluene, dimethylbenzene, tetrahydrofuran, chloroform and dichloromethane；The mol ratio of maleic anhydride and vegetable oil acid described in step (2) is 1:1~2:1；The amount of catalyst is maleic anhydride With the 1~10% of vegetable oil acid gross mass；Reaction refers to reaction raw materials being placed under UV photo solidification machines and irradiated instead under the conditions of UV light irradiations described in step (2) Should, the power of described UV photo solidification machines is 2.5~10KW, and the speed of described UV photo solidification machine conveyer belts is 5~20s/r, The UV photochemically reactive times are 5~30min；Isolating and purifying gained reaction product described in step (2) is directed to add organic solvent extraction product in reaction product And raw material, it is separated with catalyst；Then rotary distillation, then carry out column chromatographic isolation and purification；Organic solvent therein is ring At least one of hexane, petroleum ether and ethyl acetate.
- 6. the preparation method of vegetable oil yl carboxylic acid salt form hydrophilic chain extender according to claim 5, it is characterised in that：Described cationic photoinitiator is diazol, diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt, iron virtue At least one of hydrocarbon salt, sulfonyloxy ketone and triaryl silica ether.
- 7. the preparation method of vegetable oil yl carboxylic acid salt form hydrophilic chain extender according to claim 2, it is characterised in that：Dihydric alcohol described in step (3) is ethylene glycol, at least one of propane diols, BDO, described dihydric alcohol Dosage mol ratio with D-A reaction products is 2:1~2.1:1；Solvent described in step (3) is acetone, one kind in absolute ether, benzene, tetrahydrofuran, toluene, dimethylbenzene, acetonitrile； Described catalyst is at least one of sulfuric acid, phosphoric acid, pyrovinic acid, p-methyl benzenesulfonic acid, formic acid and acetic acid；The time of esterification by ring opening described in step (3) is 2~4h.
- 8. vegetable oil yl carboxylic acid salt form hydrophilic chain extender according to claim 1 answering in terms of the synthesis of aqueous polyurethane With.
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| CN113637146A (en) * | 2021-07-30 | 2021-11-12 | 华南农业大学 | Tung oil acid maleic anhydride modified vinyl ester resin and preparation method and application thereof |
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| CN106565651A (en) * | 2016-10-14 | 2017-04-19 | 华南农业大学 | Preparation method and application of UV (Ultraviolet) photocatalysis-based unsaturated vegetable oil D-A (Diels-Alder) reaction product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113637146A (en) * | 2021-07-30 | 2021-11-12 | 华南农业大学 | Tung oil acid maleic anhydride modified vinyl ester resin and preparation method and application thereof |
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