CN107501498A - Carboxylate/sulfonate double-hydrophilic hydrophilic chain extender and its preparation method and application - Google Patents
Carboxylate/sulfonate double-hydrophilic hydrophilic chain extender and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/12—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing esterified hydroxy groups bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/49—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
Abstract
The invention belongs to organic synthesis field, discloses a kind of carboxylate/sulfonate double-hydrophilic hydrophilic chain extender and its preparation method and application.The chain extender is prepared by following four step；(1) synthesis of polyunsaturated vegetable oil acid；(2) synthesis of polyunsaturated vegetable oil acid D A reaction products；(3) synthesis of polyunsaturated vegetable oil base hydrophilic chain extender；(4) synthesis of carboxylate/sulfonate double-hydrophilic hydrophilic chain extender.Renewable plant resources polyunsaturated vegetable oil is used for the raw material for preparing hydrophilic chain extender by the present invention, not only alleviates the pressure of petroleum chemical industry, the also source for hydrophilic chain extender opens new approach.And the more traditional small molecule chain extender molecular weight of hydrophilic chain extender prepared by the present invention increases many times, avoids the use of small molecule chain extender to negative effect caused by WPU emulsion properties.
Description
Technical field
The invention belongs to organic synthesis field, more particularly to a kind of carboxylate/sulfonate double-hydrophilic hydrophilic chain extender and
Its preparation method and application.
Background technology
During aqueous polyurethane is synthesized, it is necessary to which, using hydrophilic chain extender, hydrophilic chain extender is different in opposite end
Cyanic acid ester-based polyurethane performed polymer introduced while chain extension the material of hydrophilic radical.It is different according to hydrophilic radical type,
Aqueous polyurethane (WPU) is divided into cationic, anionic and the class of nonionic 3, and the introducing of hydrophilic radical is that synthesis is water-based poly-
The key of urethane, anionic hydrophilic radical are always the emphasis of the area research, mainly there is sulfonic acid type and the class of carboxylic acid type two.Mesh
Before, WPU hydrophilic radical is mainly introduced by chain extender in hard section, and experimental procedure is cumbersome, soft without hydrophilic radical in product soft segment
Section accounting in PU strands is maximum, and uneven distribution of the hydrophilic radical on strand easily causes the decline of WPU stability of emulsion,
Soft and hard segments microphase-separated in PU strands is also easily caused simultaneously, influences properties of product.With carboxyl into salt in carboxylic acid type WPU, by
Belong to weak acid in carboxylic acid, hydrophily is poor, and WPU emulsion viscosities prepared by introducing carboxyl are big, and solid content is not easy to improve.Sulfonic acid base stage
Property is strong, and hydrophily is good, is easier to prepare high solids content WPU emulsions, but in simple sulfonate type WPU building-up process in order to
Improve molecular weight, it is necessary to first using small molecule chain extenders such as 1,4- butanediols, then carry out sulfonic group hydrophilic grafts.By carboxylate and
Sulfonate introduces polyurethane segment simultaneously, prepares carboxylate/sulfonate double-hydrophilic hydrophilic chain extender, so as to avoid 1,4- fourths
The use of the small molecule hydrophilic chain extender such as glycol, the stabilization and solid content for being very beneficial to emulsion improve.On PU molecule segments simultaneously
Carboxyl, sulfonic group are introduced, the mutual supplement with each other's advantages of two kinds of hydrophilic radicals can be achieved, to prepare high solids content, high-performance WPU adhesive carries
For a kind of effective thinking.
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 be to provide a kind of carboxylate/
Sulfonate double-hydrophilic hydrophilic chain extender.
Another object of the present invention is the preparation method for providing above-mentioned carboxylate/sulfonate double-hydrophilic hydrophilic chain extender.
Still a further object of the present invention is to provide above-mentioned carboxylate/sulfonate double-hydrophilic hydrophilic chain extender in aqueous polyurethane
Synthesis etc. application.
The purpose of the present invention is realized by following proposal：
A kind of carboxylate/sulfonate double-hydrophilic hydrophilic chain extender, its structural formula can be any one in formula 1：
Wherein, p=7, n=0 or 1,0<m+s<4, t=2,4,5.
The structural formula of described carboxylate/sulfonate double-hydrophilic hydrophilic chain extender is by binary amido sulfonate or two
First hydroxy sulfonate grafts on the molecular structure obtained by any one hydroxyl in following formula 2.
Wherein, p=7, n=0 or 1,0<m+s<4, t=2,4,5.
Described binary amido sulfonate can be ethylenediamine base esilate, 2,4- sodium p-phenylenediamines, 1,2- diamines
At least one of base-β-propane sulfonic acid salt, the amido-β of 1,3- bis--propane sulfonic acid salt；Described dihydroxylic sulfonate can be second two
Isethionate.
A kind of preparation method of carboxylate/sulfonate double-hydrophilic hydrophilic chain extender, it 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, reaction add acid after terminating and neutralized, the liquid 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 add
Vegetable oil acid made from step (1), catalyst is added after well mixed, is stirred；Reacted under conditions of UV light irradiations, instead
Products therefrom is isolated and purified after should terminating and obtains the D-A reaction products；
(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 existence condition, the heating and melting at 80~120 DEG C, then adds catalyst and carries out esterification by ring opening, that is, is planted
Thing oil base carboxylic acid type hydrophilic chain extender；
(4) synthesis of carboxylate/sulfonate double-hydrophilic hydrophilic chain extender：By the vegetable oil yl carboxylic acid obtained by step (3)
Salt form hydrophilic chain extender occurs normal temperature neutralization reaction with neutralization type small molecule sulfonate hydrophilic molecules and obtains carboxylate/sulfonate pair
Hydrophilic group hydrophilic chain extender；Or by the vegetable oil yl carboxylic acid salt form hydrophilic chain extender obtained by step (3) and esterification type small molecule
Under catalyst action in 80~120 DEG C esterification occurs for sulfonate hydrophilic molecules, obtains carboxylate/sulfonate double-hydrophilic
Hydrophilic chain extender.
Polyunsaturated vegetable oil described in step (1) is tung oil, peanut oil, sesame oil, soybean oil, cashew nut shell oil, linseed oil,
At least one of castor oil, rapeseed oil；Alkali in described alkaline solution is sodium hydroxide or potassium hydroxide；Described acid is
At least one of sulfuric acid, phosphoric acid, pyrovinic acid, p-methyl benzenesulfonic acid, formic acid and acetic acid.
The quality of alkali in step (1) in alkali lye used for polyunsaturated vegetable oil quality 0.5~3%, preferably 1~
2%；Described refers to polyunsaturated vegetable oil being heated to 50~80 DEG C by polyunsaturated vegetable oil heating；Described condensing reflux is anti-
30~90min of reaction should be referred to.
Isolating and purifying described in step (1) refers to stand the liquid after neutralization, is layered, and separates lower floor's glycerin layer, then
After the liquid on upper strata is washed with water, except the water layer of sub-cloud, it is evaporated under reduced pressure and removes Organic Alcohol and most of water etc., Ran Hougan
It is dry, then isolated and purified with Silver nitrate silica gel column chromatograph method and produce vegetable oil acid；
Described drying preferably refers to addition drier and is dried, and drier is preferably anhydrous calcium chloride, anhydrous sodium sulfate
At least one of with phosphorus pentoxide；
Organic solvent described in step (2) is acetone, absolute ether, benzene,toluene,xylene, tetrahydrofuran, chloroform and
At least one of dichloromethane；Described catalyst is solid catalyst, preferably cationic photoinitiator.
Cationic photoinitiator described in step (2) is preferably diazol, diaryl group iodized salt, triaryl sulphur
At least one of salt, alkyl sulfosalt, iron arene salt, sulfonyloxy ketone and triaryl silica ether.
The reaction under conditions of UV light irradiations described in step (2) refers to reaction raw materials being placed under UV photo solidification machines
Irradiation 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 excellent
Elect 5~20s/r as, the UV photochemically reactive times are preferably 5~30min.
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 used is the 1~10% of maleic anhydride and vegetable oil acid gross mass；
Isolating and purifying described in step (2) refers to that adding organic solvent extracts product and raw material, makes itself and catalyst point
From then rotary distillation, then the polyunsaturated vegetable oil acid D-A that the liquid column chromatography after rotary distillation is produced after purification react production
Thing；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 shown in following formula 3
Structure：
In formula 3, p=7, n=0 or 1,0<m+s<4, t=2,4,5.
Dihydric alcohol described in step (3) is ethylene glycol, one kind in propane diols, BDO, described dihydric alcohol
Dosage mol ratio with D-A reaction products is 1:1~1.1:1.
Solvent described in step (3) is one in acetone, absolute ether, benzene, tetrahydrofuran, toluene, dimethylbenzene, acetonitrile
Kind；Catalyst described in step (3) be preferably in sulfuric acid, phosphoric acid, pyrovinic acid, p-methyl benzenesulfonic acid, formic acid and acetic acid extremely
Few one kind, the amount of catalyst used is catalytic amount.
The time of esterification by ring opening described in step (3) is 2~4h.
The structural formula of vegetable oil yl carboxylic acid salt form hydrophilic chain extender described in step (3) is foregoing formula 3, by diamine
Base sulfonate or dihydroxylic sulfonate graft on the molecular structure as present invention obtained by any one hydroxyl in following formula 3
Carboxylate/sulfonate double-hydrophilic hydrophilic chain extender structure.
Neutralization type small molecule sulfonate hydrophilic molecules described in step (4) are ethylenediamine base esilate, 2,4- diamines
At least one of base benzene sulfonic acid sodium salt, 1,2- bis- amido-β-propane sulfonic acid salt, the amido-β of 1,3- bis--propane sulfonic acid salt；Described normal temperature
Neutralization reaction refers to react 2~4h under normal temperature；Vegetable oil yl carboxylic acid salt form hydrophilic chain extender and neutralization type described in step (4)
The mol ratio of small molecule sulfonate hydrophilic molecules is 1:1~1.1:1.
Esterification type small molecule sulfonate hydrophilic molecules described in step (4) are second dihydroxy esilate；Described urges
Agent is at least one of sulfuric acid, phosphoric acid, pyrovinic acid, p-methyl benzenesulfonic acid, formic acid and acetic acid；Described esterification refers to
React 2~4h；Vegetable oil yl carboxylic acid salt form hydrophilic chain extender and hydrophilic point of esterification type small molecule sulfonate described in step (4)
The mol ratio of son is 1:1~1.1:1.
Application of the above-mentioned carboxylate/sulfonate double-hydrophilic hydrophilic chain extender in the synthesis of aqueous polyurethane etc..
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.
(3) two kinds of hydrophilic radicals of carboxyl and sulfonic group are contained simultaneously in hydrophilic chain extender of the invention, can be in PU molecules
Carboxyl, sulfonic group are introduced simultaneously on segment, the mutual supplement with each other's advantages of two kinds of hydrophilic radicals can be achieved, to prepare high solids content, high-performance
WPU adhesive provides a kind of effective thinking.
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 1mol 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.
(4) synthesis of carboxylate/sulfonate double-hydrophilic hydrophilic chain extender：By the plant oil base obtained by 1mol steps (3)
With 1mol ethylenediamine bases esilate normal temperature neutralization reaction occurs for carboxylic acid type hydrophilic chain extender, and it is double to obtain carboxylate/sulfonate
Hydrophilic group 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：1.1mol propane diols and the D-A obtained by 1mol steps (2) is anti-
Product is answered in solvent absolute ether is added, the heating and melting at 80 DEG C, catalyst phosphoric acid is added and carries out esterification by ring opening, that is, obtain
Vegetable oil yl carboxylic acid salt form hydrophilic chain extender.
(4) synthesis of carboxylate/sulfonate double-hydrophilic hydrophilic chain extender：By the plant obtained by (3) the step of 1.1mol
Oil base carboxylic acid type hydrophilic chain extender and 1mol 2,4- sodium p-phenylenediamines occur normal temperature neutralization reaction, obtain carboxylate/
Sulfonate double-hydrophilic 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 1mol 1,4- 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.
(4) synthesis of carboxylate/sulfonate double-hydrophilic hydrophilic chain extender：By the plant oil base obtained by 1mol steps (3)
Normal temperature neutralization reaction occurs for carboxylic acid type hydrophilic chain extender and the 1mol amido-β of 1,2- bis--propane sulfonic acid salt, obtains carboxylate/sulphur
Hydrochlorate double-hydrophilic hydrophilic chain extender.1H NMR、13Compound obtained by CNMR and MS results show is target product.
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：By the D-A obtained by 1.1mol ethylene glycol and 1mol steps (2)
Reaction product is in solvent toluene is added, the heating and melting at 110 DEG C, adds catalyst p-methyl benzenesulfonic acid and carries out esterification by ring opening,
Obtain vegetable oil yl carboxylic acid salt form hydrophilic chain extender.
(4) synthesis of carboxylate/sulfonate double-hydrophilic hydrophilic chain extender：By the vegetable oil obtained by 1.1mol steps (3)
Normal temperature neutralization reaction occurs for yl carboxylic acid salt form hydrophilic chain extender and 1mol amido-β of 1,3- bis--propane sulfonic acid salt, obtain carboxylate/
Sulfonate double-hydrophilic 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：D-A obtained by 1mol ethylene glycol and 1mol steps (2) is reacted
Product is in solvent xylene is added, the heating and melting at 80 DEG C, adds catalyst formic acid and carries out esterification by ring opening, that is, obtains plant
Oil base carboxylic acid type hydrophilic chain extender.
(4) synthesis of carboxylate/sulfonate double-hydrophilic hydrophilic chain extender：By the plant oil base obtained by 1mol steps (3)
It is anti-that under catalyst sulfuric acid effect in 120 DEG C esterification occurs for carboxylic acid type hydrophilic chain extender and 1mol second dihydroxy esilate
Should, obtain carboxylate/sulfonate double-hydrophilic hydrophilic chain extender.1HNMR、13CNMR and MS results show resulting chemical combination
Thing 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 1mol 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.
(4) synthesis of carboxylate/sulfonate double-hydrophilic hydrophilic chain extender：By the vegetable oil obtained by 1.1mol steps (3)
Yl carboxylic acid salt form hydrophilic chain extender and 1mol second dihydroxy esilate are esterified under the effect of catalyst formic acid in 80 DEG C
Reaction, obtains carboxylate/sulfonate double-hydrophilic hydrophilic chain extender.1HNMR、13CNMR and MS results show resulting change
Compound is target product.
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 (10)
1. a kind of carboxylate/sulfonate double-hydrophilic hydrophilic chain extender, it is characterised in that structural formula is any one in following formula：
Wherein, p=7, n=0 or 1,0<m+s<4, t=2,4,5.
2. a kind of preparation method of carboxylate according to claim 1/sulfonate double-hydrophilic hydrophilic chain extender, its feature
It is to 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, reaction add acid after terminating and neutralized, the liquid 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
Products therefrom is isolated and purified after beam and obtains 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
In solvent existence condition, the heating and melting at 80~120 DEG C, then add catalyst and carry out esterification by ring opening, that is, obtain vegetable oil
Yl carboxylic acid salt form hydrophilic chain extender；
(4) synthesis of carboxylate/sulfonate double-hydrophilic hydrophilic chain extender：By the vegetable oil yl carboxylic acid salt form obtained by step (3)
Hydrophilic chain extender occurs normal temperature neutralization reaction with neutralization type small molecule sulfonate hydrophilic molecules and obtains carboxylate/sulfonate parents' water
Base hydrophilic chain extender；Or by the vegetable oil yl carboxylic acid salt form hydrophilic chain extender obtained by step (3) and esterification type small molecule sulfonic acid
Under catalyst action in 80~120 DEG C esterification occurs for salt hydrophilic molecules, and it is hydrophilic to obtain carboxylate/sulfonate double-hydrophilic
Chain extender.
3. the preparation method of carboxylate according to claim 2/sulfonate double-hydrophilic hydrophilic chain extender, its feature exist
In：
Polyunsaturated vegetable oil described in step (1) is tung oil, peanut oil, sesame oil, soybean oil, cashew nut shell oil, linseed oil, castor-oil plant
At least one of 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 quality of alkali in step (1) in alkali lye used is the 0.5~3% of polyunsaturated vegetable oil quality；It is described by insatiable hunger
Refer to polyunsaturated vegetable oil being heated to 50~80 DEG C with vegetable oil heating；Described condensing reflux reaction refer to reaction 30~
90min；
Isolating and purifying described in step (1) refers to stand the liquid after neutralization, is layered, and separates lower floor's glycerin layer, then will be upper
After the liquid of layer is washed with water, except the water layer of sub-cloud, it is evaporated under reduced pressure and removes Organic Alcohol and most of water, then dry, then use
Silver nitrate silica gel column chromatograph method, which isolates and purifies, produces vegetable oil acid.
4. the preparation method of carboxylate according to claim 3/sulfonate double-hydrophilic hydrophilic chain extender, its feature exist
In：
Drying described in step (1) refers to addition drier and is dried, and drier is anhydrous calcium chloride, anhydrous sodium sulfate and five
Aoxidize at least one of two phosphorus.
5. the preparation method of carboxylate according to claim 2/sulfonate double-hydrophilic hydrophilic chain extender, its feature exist
In：
Organic solvent described in step (2) is acetone, absolute ether, benzene,toluene,xylene, tetrahydrofuran, chloroform and dichloro
At least one of methane；Described catalyst is cationic photoinitiator；
Being reacted under conditions of UV light irradiations described in step (2), which refers to reaction raw materials being placed under UV photo solidification machines, irradiates
Reaction, 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 time are 5~30min；
The mol ratio of maleic anhydride and vegetable oil acid described in step (2) is 1:1~2:1；The amount of catalyst used is horse
Come the 1~10% of acid anhydrides and vegetable oil acid gross mass；
Isolating and purifying described in step (2) refers to that adding organic solvent extracts product and raw material, makes it be separated with catalyst, so
Rotary distillation afterwards, then the liquid column chromatography after rotary distillation is produced into D-A reaction products after purification；Wherein described is organic molten
Agent is at least one of hexamethylene, petroleum ether and ethyl acetate.
6. the preparation method of carboxylate according to claim 5/sulfonate double-hydrophilic hydrophilic chain extender, its feature exist
In：
Cationic photoinitiator described in step (2) is diazol, diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfide
At least one of salt, iron arene salt, sulfonyloxy ketone and triaryl silica ether.
7. the preparation method of carboxylate according to claim 2/sulfonate double-hydrophilic hydrophilic chain extender, its feature exist
In：
Dihydric alcohol described in step (3) is ethylene glycol, one kind in propane diols, BDO, described dihydric alcohol and D-A
The dosage mol ratio of reaction product is 1:1~1.1:1；
Solvent described in step (3) is acetone, one kind in absolute ether, benzene, tetrahydrofuran, toluene, dimethylbenzene, acetonitrile；
Catalyst described in step (3) is at least one of sulfuric acid, phosphoric acid, pyrovinic acid, p-methyl benzenesulfonic acid, formic acid and acetic acid,
The amount of catalyst used is catalytic amount；The time of esterification by ring opening described in step (3) is 2~4h.
8. the preparation method of carboxylate according to claim 2/sulfonate double-hydrophilic hydrophilic chain extender, its feature exist
In：
Neutralization type small molecule sulfonate hydrophilic molecules described in step (4) are ethylenediamine base esilate, the amido benzene of 2,4- bis-
At least one of sodium sulfonate, 1,2- bis- amido-β-propane sulfonic acid salt, the amido-β of 1,3- bis--propane sulfonic acid salt；Described normal temperature neutralizes
Reaction refers to react 2~4h under normal temperature；Vegetable oil yl carboxylic acid salt form hydrophilic chain extender and small point of neutralization type described in step (4)
The mol ratio of sub- sulfonate hydrophilic molecules is 1:1~1.1:1.
9. the preparation method of carboxylate according to claim 2/sulfonate double-hydrophilic hydrophilic chain extender, its feature exist
In：
Esterification type small molecule sulfonate hydrophilic molecules described in step (4) are second dihydroxy esilate；Described catalyst
For at least one of sulfuric acid, phosphoric acid, pyrovinic acid, p-methyl benzenesulfonic acid, formic acid and acetic acid；Described esterification refers to react
2~4h；Vegetable oil yl carboxylic acid salt form hydrophilic chain extender and esterification type small molecule sulfonate hydrophilic molecules described in step (4)
Mol ratio is 1:1~1.1:1.
10. carboxylate according to claim 1/sulfonate double-hydrophilic hydrophilic chain extender is in the synthesis side of aqueous polyurethane
The application in face.
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| CN114805783B (en) * | 2021-01-18 | 2023-05-26 | 万华化学集团股份有限公司 | Preparation method of hydrophilic chain extender and application of chain extender in waterborne polyurethane |
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