CN101880362B - Preparation method of aqueous polyamide resin emulsion - Google Patents
Preparation method of aqueous polyamide resin emulsion Download PDFInfo
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- CN101880362B CN101880362B CN2010102201740A CN201010220174A CN101880362B CN 101880362 B CN101880362 B CN 101880362B CN 2010102201740 A CN2010102201740 A CN 2010102201740A CN 201010220174 A CN201010220174 A CN 201010220174A CN 101880362 B CN101880362 B CN 101880362B
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Abstract
The invention discloses a preparation method of aqueous polyamide resin emulsion, which comprises the following steps of: performing the amidation reaction between dimeric dibasic acid and ethylenediamine in the atmosphere of nitrogen to obtain terminal carboxyl group polyamide resin; performing the ring-opening addition reaction between epoxy compound and acrylicresin monomer in inert organic solvent to obtain epoxy acrylate monoester, under the condition of the catalytic agents such as polymerization inhibitor, tertiary amine or quaternary ammonium salt and the like; performing the ring-opening addition reaction between the terminal carboxyl group polyamide resin and the epoxy acrylate monoester in the inert organic solvent to obtain end double bonds polyamide resin, under the catalysis conditions such as the tertiary amine or the quaternary ammonium salt and the like; and performing chemical reaction between the end double bonds polyamide resin and unsaturated monomer as well as the unsaturated monomer or unsaturated monomer acid in the inert organic solvent to obtain high-acid value polyamide resin under the action of free radical initiator; distilling the inert organic solvent by means of pressure reduction; neutralizing; and emulsifying by adding deionized water to obtain the aqueous polyamide resin emulsion. The preparation method takes the water as the dissolvent, has low cost, is free of pollution, is environment-friendly, and has simple preparation technology.
Description
Technical field
The invention belongs to the polyamide resin field, be specifically related to a kind of preparation method of aqueous polyamide resin emulsion.
Background technology
Polyamide resin can be divided into solvent-borne type polymeric amide and non-solvent polymeric amide by solvability, and the polyamide resin that uses is the solvent-borne type polymeric amide at present, and (VOC) is more for organic volatile, and the solution smell is big, contaminate environment, harm workers ' health.Reducing volatile organic compounds (VOC) and air noxious pollutant (HAP) has become the research direction of brand-new material.The aqueous polyamide emulsion has the environmental protection advantage such as does not fire, nontoxic, pollution-free, particularly in recent years, surging and the environmental administration of organic solvent price uses organic solvent and the strictness of waste discharge limits, and makes aqueous polyamide replace the important directions that the organic solvent type polymeric amide becomes current this field development.
Summary of the invention
In order to solve the shortcoming of the present high VOC of polyamide resin lipoprotein solution, the invention provides a kind of preparation method of aqueous polyamide resin emulsion, cost of material is cheap, low VOC, preparation technology are simple.
Technical scheme of the present invention is: a kind of preparation method of aqueous polyamide resin emulsion is made by following steps:
The first step: hold the synthetic of carboxyl polyamides
Second step: propylene oxide acid monoester synthetic
The 3rd step: terminal double link polymeric amide synthetic
The 4th step: aqueous polyamide resin emulsion synthetic
Used catalyzer is tertiary amine or quaternary ammonium salt catalyst in second step and the 3rd step, and the acid number of described high acid value polymeric amide is 50～100mg/g.
Used dimeracid is any one or any several mixture of oleic acid dimer acid, tung oil dimeracid, rosin and oleic acid synthetic dimeracid in the first step.
Used epoxy compounds is that oxirane value is 0.42～0.51 bisphenol A diglycidyl ether, any one or several mixture arbitrarily in the ethylene glycol diglycidylether in second step.
Used tertiary amine or quaternary ammonium salt catalyst are any one in triethylamine, xylidine, the etamon chloride in second step, the 3rd step.
Used acrylic monomer is a kind of in vinylformic acid, the methacrylic acid in second step.
Unsaturated monomer or unsaturated monomer acid used in the 4th step are a kind of or any several mixture of vinylformic acid, methyl acrylate, vinylbenzene, butyl acrylate, 2-acrylamido-2-methyl propane sulfonic acid.
Used radical initiator is a kind of of azo diisobutyl amidine hydrochloride, benzoyl peroxide, Potassium Persulphate in the 4th step.
Temperature of reaction in the first step is 190～240 ℃, and the temperature of reaction in second step and the 3rd step is 90～140 ℃, and the temperature of reaction in the 4th step is 60～100 ℃.
The reaction in second step, the 3rd step and the 4th step is to carry out in inert organic solvents, and described inert organic solvents is any one or any several mixture among tetrahydrofuran (THF), toluene, dimethylbenzene, the DMF.
Be dimeracid in molar ratio in the first step: quadrol is that 1～1.4: 1 ratio feeds intake, in second step epoxy compounds and acrylic monomer by etc. mol ratio feed intake, the 3rd step middle-end carboxyl polyamides resin and propylene oxide acid monoester are that 1: 2 ratio feeds intake in molar ratio, and the ratio in every 10g terminal double link polyamide resin and 5g～40g unsaturated monomer or unsaturated monomer acid-respons in the 4th step feeds intake.
Beneficial effect:
1. use the aqueous polyamide resin emulsion that method of the present invention makes, have the carboxyl or the sulfonic group of strongly hydrophilic in its molecular structure, contain hydrophobic aliphatic group again, can solve the contradiction between wetting ability and the water tolerance.
2. preparation method's technology of the present invention is simple, and the reaction conditions gentleness has been saved the energy, has reduced consumption of petroleum resources.
3. no small-molecule substance discharging in the preparation process, operational path has environment friendly.
Description of drawings
Fig. 1 is the infrared spectra spectrogram of aqueous polyamide resin emulsion.
Fig. 2 is the size distribution figure of aqueous polyamide resin emulsion.
Embodiment
The present invention adopts following technological line to prepare the aqueous polyamide resin.
The first step: hold the synthetic of carboxyl polyamides
Second step: propylene oxide acid monoester synthetic
The 3rd step: terminal double link polymeric amide synthetic
The 4th step: aqueous polyamide resin emulsion synthetic
Used catalyzer is tertiary amine or quaternary ammonium salt catalyst in second step and the 3rd step,, the acid number of described high acid value polymeric amide is 50～100mg/g.
Step is more specifically:
The first step, in nitrogen atmosphere, 190 ℃～240 ℃, after 1～1.4mol dimeracid and 1mol quadrol carried out amidate action 2～3h, when amine value during less than 3mg/g, termination reaction promptly got and holds the carboxyl polyamides resin.
Second step, 90 ℃～140 ℃, epoxy compounds and acrylic monomer by etc. mol ratio feed intake, in the presence of hydroquinone of polymerization retarder and tertiary amine or quaternary ammonium salt catalyst, after in inert organic solvents, carrying out opening 1.5～3h, when acid number during, promptly get the propylene oxide acid monoester less than 5mg/g.Wherein stopper and catalyst consumption are conventional amount used, can be as stopper for accounting for 0.05%～0.15% of epoxy compounds and acrylic monomer total mass, and catalyst levels can be epoxy compounds and acrylic monomer total mass 0.5%～1%,
The 3rd step, 90 ℃～140 ℃, in the presence of tertiary amine or quaternary ammonium salt catalyst, end carboxyl polyamides resin and propylene oxide acid monoester are 1: 2 ratio in molar ratio, after in inert organic solvents, carrying out opening 1.5～3h, acid number promptly gets the terminal double link polyamide resin during less than 5mg/g, and what catalyst levels was still the same is that 0.5～1% of reactant total mass gets final product.
The 4th step, 60 ℃～100 ℃, under action of free radical initiator, every 10g terminal double link polyamide resin and 5g～40g unsaturated monomer or unsaturated monomer acid are reacted 2～5h in inert organic solvents after, getting acid number is the high acid value polyamide resin of 50～100mg/g, decompression steams inert organic solvents then, is neutralized to pH 8.5～9.5 again, adds deionized water emulsification and promptly gets aqueous polyamide resin emulsion.The amount of radical initiator can be for accounting for 0.5%～3% of unsaturated monomer or unsaturated monomer acid total mass, and the pressure during decompression can be for-0.1～-0.09MPa, can adopt alkaline matter to be neutralized to pH 8.5～9.5.
Used dimeracid is any one or a few of oleic acid dimer acid, tung oil dimeracid, rosin and oleic acid synthetic dimeracid in the first step.
Used epoxy compounds is bisphenol A diglycidyl ether (oxirane value is respectively 0.51,0.44,0.42) in second step, any one or a few in the ethylene glycol diglycidylether (epoxy 669).Acrylic monomer is a kind of in vinylformic acid, the methacrylic acid.
Used tertiary amine or quaternary ammonium salt catalyst are a kind of in triethylamine, xylidine, etamon chloride, the benzyltriethylammoinium chloride etc. in second and third step.
One or more that used unsaturated monomer or unsaturated monomer acid are vinylformic acid, methyl acrylate, vinylbenzene, butyl acrylate, 2-acrylamido-2-methyl propane sulfonic acid (AMPS) etc. in the 4th step.Radical initiator is any one in azo diisobutyl amidine hydrochloride (V-550 initiator), benzoyl peroxide (BPO), the Potassium Persulphate.
The used alkaline matter of the 4th step neutralization is sodium hydroxide, potassium hydroxide, triethylamine, ammoniacal liquor, quaternary ammonium hydroxide etc.
Second the step, the 3rd the step and four-step reaction in inert organic solvents, carry out, the inert organic solvents that uses as among tetrahydrofuran (THF), toluene, dimethylbenzene, the DMF one or more.
(1) preparation of end carboxyl polyamides resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1.3mol tung oil dimeracid and 1mol quadrol, feed nitrogen then, be warming up to 200 ℃, behind the reaction 2h, the amine value must be held the carboxyl polyamides resin less than 3mg/g.
(2) preparation of propylene oxide acid monoester
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1mol bisphenol A diglycidyl ether (E-51, oxirane value is 0.44), 1mol vinylformic acid and account for epoxy compounds and the Resorcinol of vinylformic acid total mass 0.06% is a stopper, the xylidine of total mass 0.5% is a catalyzer, is solvent with the tetrahydrofuran (THF), behind 100 ℃ of following reaction 2h, acid number gets the propylene oxide acid monoester less than 5mg/g.
(3) preparation of terminal double link polyamide resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, with the tetrahydrofuran (THF) is solvent, the benzyltriethylammoinium chloride that adds end carboxyl polyamides resin and the propylene oxide acid monoester in the 2mol step (two) in the 1mol step () and account for total mass 1% is made catalyzer, with the tetrahydrofuran (THF) is solvent, after reacting 2.5h under 110 ℃, acid number gets the terminal double link polyamide resin less than 5mg/g.
(4) preparation of aqueous polyamide resin emulsion
Heating jacket is being housed, whipping appts, in the 500ml there-necked flask of thermometer, with the tetrahydrofuran (THF) is solvent, add 10g step (three) gained terminal double link polyamide resin and 5g vinylformic acid, 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and account for vinylformic acid, the benzoyl peroxide (BPO) of 2-acrylamido-2-methyl propane sulfonic acid (AMPS) total mass 1% is an initiator, 80 ℃ of reaction 2h, reduce pressure-0.1 then～-0.09MPa, steam solvents tetrahydrofurane, slowly add sodium hydroxide again and be neutralized to pH 8.5～9.5, add deionized water emulsification and promptly get aqueous polyamide resin emulsion.
The aqueous polyamide resin emulsion of present embodiment preparation, its infrared spectrogram is shown in 1: 3461cm (a)
-1Be the hydroxyl absorption peak that epoxy addition produces, 1634cm
-1Be the charateristic avsorption band of C=C, 1727cm
-1The charateristic avsorption band that ester carbonyl group occurred, addition reaction has taken place to illustrate that epoxy group(ing) is opened.(b) in 1250 and 830cm
-1The charateristic avsorption band of place's epoxy group(ing) disappears, and 3289cm
-1Near the hydroxyl absorption peak obvious, simultaneously 1637 and 1458cm
-1Near the charateristic avsorption band of C=C, 1726cm have appearred
-1Near the charateristic avsorption band of ester carbonyl group has appearred, prove that end carboxyl polyamides and propylene oxide acid monoester react.(c) in 1637 and 1458cm
-1The charateristic avsorption band of C=C near disappears, and proves that polyreaction has taken place for terminal double link polymeric amide and unsaturated monomer.The intermediate of following examples preparation and product have with the infrared spectra of embodiment 1 similar, no longer specifically describe.
(1) preparation of end carboxyl polyamides resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1.2mol oleic acid dimer acid and 1mol quadrol, feed nitrogen then, be warming up to 190 ℃, behind the reaction 3h, the amine value must be held the carboxyl polyamides resin less than 3.
(2) preparation of propylene oxide acid monoester
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1mol bisphenol A diglycidyl ether (E-42, oxirane value is 0.42), 1mol methacrylic acid and account for epoxy and the Resorcinol of methacrylic acid total mass 0.1% is a stopper, the benzyltriethylammoinium chloride of total mass 0.7% is a catalyzer, is solvent with toluene, behind 140 ℃ of following reaction 1.5h, acid number gets the propylene oxide acid monoester less than 5mg/g.
(3) preparation of terminal double link polyamide resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, with toluene is solvent, the etamon chloride that adds end carboxyl polyamides resin and the propylene oxide acid monoester in the 2mol step (two) in the 1mol step () and account for total mass 0.5% is made catalyzer, with toluene is solvent, after reacting 2h under 120 ℃, acid number gets the terminal double link polyamide resin less than 5mg/g.
(4) preparation of aqueous polyamide resin emulsion
Heating jacket is being housed, whipping appts, in the 500ml there-necked flask of thermometer, with toluene is solvent, add 10g step (three) gained terminal double link polyamide resin and 10g methyl acrylate, 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and account for methyl acrylate, the Potassium Persulphate of 2-acrylamido-2-methyl propane sulfonic acid (AMPS) total mass 1.5% is an initiator, 60 ℃ of reaction 3h, reduce pressure-0.1 then～-0.09MPa, steam solvent toluene, slowly add ammoniacal liquor again and be neutralized to pH 8.5～9.5, add deionized water emulsification and promptly get aqueous polyamide resin emulsion.
Embodiment 3
(1) preparation of end carboxyl polyamides resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1.1mol rosin and oleic acid polymeric dimeracid and 1mol quadrol, feed nitrogen then, be warming up to 220 ℃, behind the reaction 2.5h, the amine value must be held the carboxyl polyamides resin less than 3mg/g.
(2) preparation of propylene oxide acid monoester
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1mol bisphenol A diglycidyl ether (E-44, oxirane value is 0.44), 1mol methacrylic acid and account for epoxy and the Resorcinol of methacrylic acid total mass 0.1% is a stopper, the etamon chloride of total mass 0.7% is a catalyzer, is solvent with DMF, behind 90 ℃ of following reaction 2h, acid number gets the propylene oxide acid monoester less than 5mg/g.
(3) preparation of terminal double link polyamide resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, with DMF is solvent, the triethylamine that adds end carboxyl polyamides resin and the propylene oxide acid monoester in the 2mol step (two) in the 1mol step () and account for total mass 1% is made catalyzer, with DMF is solvent, after reacting 2.5h under 140 ℃, acid number gets the terminal double link polyamide resin less than 5mg/g.
(4) preparation of aqueous polyamide resin emulsion
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, with DMF is solvent, the Potassium Persulphate that adds 10g step (three) gained terminal double link polyamide resin and 20g vinylbenzene, 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and account for vinylbenzene, 2-acrylamido-2-methyl propane sulfonic acid (AMPS) total mass 3% is an initiator, 80 ℃ of reaction 4h, reduce pressure-0.1 then～-0.09MPa, steam solvent DMF, slowly add triethylamine again and be neutralized to pH 8.5～9.5, add deionized water emulsification and promptly get aqueous polyamide resin emulsion.
(1) preparation of end carboxyl polyamides resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1.4mol oleic acid dimer acid and 1mol quadrol, feed nitrogen then, be warming up to 210 ℃, behind the reaction 2h, the amine value must be held the carboxyl polyamides resin less than 3mg/g.
(2) preparation of propylene oxide acid monoester
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1mol bisphenol A diglycidyl ether (E-51, oxirane value is 0.51), 1mol vinylformic acid and account for epoxy and the Resorcinol of vinylformic acid total mass 0.05% is a stopper, the triethylamine of total mass 0.9% is a catalyzer, is solvent with dimethylbenzene, behind 100 ℃ of following reaction 2.5h, acid number gets the propylene oxide acid monoester less than 5mg/g.
(3) preparation of terminal double link polyamide resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, with dimethylbenzene is solvent, the benzyltriethylammoinium chloride that adds end carboxyl polyamides resin and the propylene oxide acid monoester in the 2mol step (two) in the 1mol step () and account for total mass 0.6% is made catalyzer, with dimethylbenzene is solvent, after reacting 3h under 90 ℃, acid number gets the terminal double link polyamide resin less than 5mg/g.
(4) preparation of aqueous polyamide resin emulsion
Heating jacket is housed, whipping appts, in the 500ml there-necked flask of thermometer, with dimethylbenzene is solvent, the azo diisobutyl amidine hydrochloride (V-550 initiator) that adds 10g step (three) gained terminal double link polyamide resin and 30g 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and account for 2-acrylamido-2-methyl propane sulfonic acid (AMPS) total mass 2% is an initiator, 90 ℃ of reaction 3h, reduce pressure-0.1 then～-0.09MPa, steam solvent xylene, slowly add potassium hydroxide again and be neutralized to pH 8.5～9.5, add deionized water emulsification and promptly get aqueous polyamide resin emulsion.
During institute synthetic aqueous polyamide resin emulsion solid content 20%, viscosity 14.3mPas/25 ℃, water-intake rate 60.9%, surface tension 43.6MN/m, particle diameter 0.215 μ m, good mechanical stability.The size distribution of aqueous polyamide resin emulsion as shown in Figure 2.The product of all embodiment preparations has emulsion particle diameter substantially the same manner as Example 4 and distributes as figure, no longer specifically describes.
Embodiment 5
(1) preparation of end carboxyl polyamides resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1.2mol rosin and oleic acid polymeric dimeracid and 1mol quadrol, feed nitrogen then, be warming up to 230 ℃, behind the reaction 3h, the amine value must be held the carboxyl polyamides resin less than 3mg/g.
(2) preparation of propylene oxide acid monoester
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1mol ethylene glycol diglycidylether (epoxy 669), 1mol vinylformic acid and account for epoxy and the Resorcinol of vinylformic acid total mass 0.06% is a stopper, the etamon chloride of total mass 1% is a catalyzer, with toluene is solvent, behind the reaction 2h, acid number gets the propylene oxide acid monoester less than 5mg/g under 130 ℃.
(3) preparation of terminal double link polyamide resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, with toluene is solvent, the benzyltriethylammoinium chloride that adds end carboxyl polyamides resin and the propylene oxide acid monoester in the 2mol step (two) in the 1mol step () and account for total mass 0.8% is made catalyzer, with toluene is solvent, after reacting 2.5h under 110 ℃, acid number gets the terminal double link polyamide resin less than 5mg/g.
(4) preparation of aqueous polyamide resin emulsion
Heating jacket is housed, whipping appts, in the 500ml there-necked flask of thermometer, with toluene is solvent, add 10g step (three) gained terminal double link polyamide resin and 20g butyl acrylate, 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and account for butyl acrylate, the azo diisobutyl amidine hydrochloride (V-550 initiator) of 2-acrylamido-2-methyl propane sulfonic acid (AMPS) total mass 3% is an initiator, 100 ℃ of reaction 5h, reduce pressure-0.1 then～-0.09MPa, steam solvent toluene, slowly add ammoniacal liquor again and be neutralized to pH 8.5～9.5, add deionized water emulsification and promptly get aqueous polyamide resin emulsion.
(1) preparation of end carboxyl polyamides resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1.3mol rosin and oleic acid polymeric dimeracid and 1mol quadrol, feed nitrogen then, be warming up to 200 ℃, behind the reaction 3h, the amine value must be held the carboxyl polyamides resin less than 3mg/g.
(2) preparation of propylene oxide acid monoester
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1mol bisphenol A diglycidyl ether (E-44, oxirane value is 0.44), 1mol vinylformic acid and account for epoxy and the Resorcinol of vinylformic acid total mass 0.1% is a stopper, the xylidene(s) of total mass 1% is a catalyzer, is solvent with toluene, behind 110 ℃ of following reaction 2h, acid number gets the propylene oxide acid monoester less than 5mg/g.
(3) preparation of terminal double link polyamide resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, with toluene is solvent, the benzyltriethylammoinium chloride that adds end carboxyl polyamides resin and the propylene oxide acid monoester in the 2mol step (two) in the 1mol step () and account for total mass 0.7% is made catalyzer, with toluene is solvent, after reacting 2.5h under 140 ℃, acid number gets the terminal double link polyamide resin less than 5mg/g.
(4) preparation of aqueous polyamide resin emulsion
Heating jacket is housed, whipping appts, in the 500ml there-necked flask of thermometer, with toluene is solvent, the azo diisobutyl amidine hydrochloride (V-550 initiator) that adds 10g step (three) gained terminal double link polyamide resin and 25g2-acrylamido-2-methyl propane sulfonic acid (AMPS) total mass and account for 2-acrylamido-2-methyl propane sulfonic acid (AMPS) total mass 3% is an initiator, 100 ℃ of reaction 2h, reduce pressure-0.1 then～-0.09MPa, steam solvent toluene, slowly add ammoniacal liquor again and be neutralized to pH 8.5～9.5, add deionized water emulsification and promptly get aqueous polyamide resin emulsion.
Embodiment 7
(1) preparation of end carboxyl polyamides resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1.2mol tung oil dimeracid and 1mol quadrol, feed nitrogen then, be warming up to 190 ℃, behind the reaction 3h, the amine value must be held the carboxyl polyamides resin less than 3mg/g.
(2) preparation of propylene oxide acid monoester
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1mol ethylene glycol diglycidylether (epoxy 669), 1mol methacrylic acid and account for epoxy and the Resorcinol of vinylformic acid total mass 0.15% is a stopper, the triethylamine of total mass 0.6% is a catalyzer, with the tetrahydrofuran (THF) is solvent, behind the reaction 3h, acid number gets the propylene oxide acid monoester less than 5mg/g under 120 ℃.
(3) preparation of terminal double link polyamide resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, with the tetrahydrofuran (THF) is solvent, the benzyltriethylammoinium chloride that adds end carboxyl polyamides resin and the propylene oxide acid monoester in the 2mol step (two) in the 1mol step () and account for total mass 0.5% is made catalyzer, with the tetrahydrofuran (THF) is solvent, after reacting 2.5h under 90 ℃, acid number gets the terminal double link polyamide resin less than 5mg/g.
(4) preparation of aqueous polyamide resin emulsion
Be equipped with in the 500ml there-necked flask of heating jacket, whipping appts, thermometer, with the tetrahydrofuran (THF) is solvent, the Potassium Persulphate that adds 10g step (three) gained terminal double link polyamide resin and 40g vinylformic acid, methyl acrylate, vinylbenzene and account for vinylformic acid, methyl acrylate, vinylbenzene total mass 1.5% is an initiator, 70 ℃ of reaction 5h, reduce pressure-0.1 then～-0.09MPa, steam solvents tetrahydrofurane, slowly add triethylamine again and be neutralized to pH 8.5～9.5, add deionized water emulsification and promptly get aqueous polyamide resin emulsion.
(1) preparation of end carboxyl polyamides resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1.4mol oleic acid dimer acid and 1mol quadrol, feed nitrogen then, be warming up to 230 ℃, behind the reaction 2.5h, the amine value must be held the carboxyl polyamides resin less than 3mg/g.
(2) preparation of propylene oxide acid monoester
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1mol bisphenol A diglycidyl ether (E-51, oxirane value is 0.51), 1mol vinylformic acid and account for epoxy and the Resorcinol of vinylformic acid total mass 0.08% is a stopper, the benzyltriethylammoinium chloride of total mass 0.7% is a catalyzer, is solvent with DMF, behind 140 ℃ of following reaction 1.5h, acid number gets the propylene oxide acid monoester less than 5mg/g.
(3) preparation of terminal double link polyamide resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, with DMF is solvent, the triethylamine that adds end carboxyl polyamides resin and the propylene oxide acid monoester in the 2mol step (two) in the 1mol step () and account for total mass 0.6% is made catalyzer, with DMF is solvent, after reacting 3h under 120 ℃, acid number gets the terminal double link polyamide resin less than 5mg/g.
(4) preparation of aqueous polyamide resin emulsion
Be equipped with in the 500ml there-necked flask of heating jacket, whipping appts, thermometer, with DMF is solvent, the benzoyl peroxide (BPO) that adds 10g step (three) gained terminal double link polyamide resin and 25g vinylformic acid, 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and account for vinylformic acid, 2-acrylamido-2-methyl propane sulfonic acid (AMPS) total mass 2% is an initiator, 60 ℃ of reaction 4h, reduce pressure-0.1 then～-0.09MPa, steam solvent DMF, slowly add ammoniacal liquor again and be neutralized to pH 8.5～9.5, add deionized water emulsification and promptly get aqueous polyamide resin emulsion.
Embodiment 9
(1) preparation of end carboxyl polyamides resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1.1mol rosin and oleic acid polymeric dimeracid and 1mol quadrol, feed nitrogen then, be warming up to 220 ℃, behind the reaction 3h, the amine value must be held the carboxyl polyamides resin less than 3mg/g.
(2) preparation of propylene oxide acid monoester
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1mol bisphenol A diglycidyl ether (E-42, oxirane value is 0.42), 1mol methacrylic acid and account for epoxy and the Resorcinol of methacrylic acid total mass 0.15% is a stopper, the etamon chloride of total mass 0.5% is a catalyzer, is solvent with dimethylbenzene, behind 90 ℃ of following reaction 3h, acid number gets the propylene oxide acid monoester less than 5mg/g.
(3) preparation of terminal double link polyamide resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, with dimethylbenzene is solvent, the triethylamine that adds end carboxyl polyamides resin and the propylene oxide acid monoester in the 2mol step (two) in the 1mol step () and account for total mass 0.9% is made catalyzer, with dimethylbenzene is solvent, after reacting 2h under 100 ℃, acid number gets the terminal double link polyamide resin less than 5mg/g.
(4) preparation of aqueous polyamide resin emulsion
Heating jacket is housed, whipping appts, in the 500ml there-necked flask of thermometer, with dimethylbenzene is solvent, add 10g step (three) gained terminal double link polyamide resin and 15g vinylbenzene, 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and account for vinylbenzene, the benzoyl peroxide (BPO) of 2-acrylamido-2-methyl propane sulfonic acid (AMPS) total mass 2% is an initiator, 100 ℃ of reaction 2h, reduce pressure-0.1 then～-0.09MPa, steam solvent xylene, slowly add quaternary ammonium hydroxide again and be neutralized to pH 8.5～9.5, add deionized water emulsification and promptly get aqueous polyamide resin emulsion.
(1) preparation of end carboxyl polyamides resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1.2mol oleic acid dimer acid and 1mol quadrol, feed nitrogen then, be warming up to 220 ℃, behind the reaction 3h, the amine value must be held the carboxyl polyamides resin less than 3mg/g.
(2) preparation of propylene oxide acid monoester
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, add 1mol bisphenol A diglycidyl ether (E-51, oxirane value is 0.51), 1mol methacrylic acid and account for epoxy and the Resorcinol of methacrylic acid total mass 0.1% is a stopper, the benzyltriethylammoinium chloride of total mass 1% is a catalyzer, is solvent with DMF, behind 110 ℃ of following reaction 3h, acid number gets the propylene oxide acid monoester less than 5mg/g.
(3) preparation of terminal double link polyamide resin
In the 500ml there-necked flask of heating jacket, whipping appts, thermometer is housed, with DMF is solvent, the benzyltriethylammoinium chloride that adds end carboxyl polyamides resin and the propylene oxide acid monoester in the 2mol step (two) in the 1mol step () and account for total mass 0.9% is made catalyzer, with DMF is solvent, after reacting 3h under 110 ℃, acid number gets the terminal double link polyamide resin less than 5mg/g.
(4) preparation of aqueous polyamide resin emulsion
Be equipped with in the 500ml there-necked flask of heating jacket, whipping appts, thermometer, with DMF is solvent, the benzoyl peroxide (BPO) that adds 10g step (three) gained terminal double link polyamide resin and 20g 2-acrylamido-2-methyl propane sulfonic acid (AMPS) and account for 2-acrylamido-2-methyl propane sulfonic acid (AMPS) total mass 1.5% is an initiator, 100 ℃ of reaction 2h, reduce pressure-0.1 then～-0.09MPa, steam solvent DMF, slowly add ammoniacal liquor again and be neutralized to pH 8.5～9.5, add deionized water emulsification and promptly get aqueous polyamide resin emulsion.
Claims (7)
1. the preparation method of an aqueous polyamide resin emulsion is characterized in that, is made by following steps:
The first step: hold the synthetic of carboxyl polyamides
Second step: propylene oxide acid monoester synthetic
The 3rd step: terminal double link polymeric amide synthetic
The 4th step: aqueous polyamide resin emulsion synthetic
Used catalyzer is tertiary amine or quaternary ammonium salt catalyst in second step and the 3rd step, and the acid number of described high acid value polymeric amide is 50～100mg/g;
Used dimeracid is any one or any several mixture of oleic acid dimer acid, tung oil dimeracid, rosin and oleic acid synthetic dimeracid in the first step;
Used epoxy compounds is that oxirane value is 0.42～0.51 bisphenol A diglycidyl ether, any one or several mixture arbitrarily in the ethylene glycol diglycidylether in second step;
Used unsaturated monomer is a kind of or any several mixture of vinylformic acid, methyl acrylate, vinylbenzene, butyl acrylate, 2-acrylamido-2-methyl propane sulfonic acid in the 4th step.
2. the preparation method of aqueous polyamide resin emulsion as claimed in claim 1 is characterized in that, used tertiary amine or quaternary ammonium salt catalyst are any one in triethylamine, xylidine, the etamon chloride in second step, the 3rd step.
3. the preparation method of aqueous polyamide resin emulsion as claimed in claim 1 is characterized in that, used acrylic monomer is a kind of in vinylformic acid, the methacrylic acid in second step.
4. the preparation method of aqueous polyamide resin emulsion as claimed in claim 1 is characterized in that, used radical initiator is a kind of of azo diisobutyl amidine hydrochloride, benzoyl peroxide, Potassium Persulphate in the 4th step.
5. the preparation method of aqueous polyamide resin emulsion as claimed in claim 1 is characterized in that, the temperature of reaction in the first step is 190～240 ℃, and the temperature of reaction in second step and the 3rd step is 90～140 ℃, and the temperature of reaction in the 4th step is 60～100 ℃.
6. the preparation method of aqueous polyamide resin emulsion as claimed in claim 1, it is characterized in that, the reaction in second step, the 3rd step and the 4th step all is to carry out in inert organic solvents, and described inert organic solvents is any one or any several mixture among tetrahydrofuran (THF), toluene, dimethylbenzene, the DMF.
7. the preparation method of aqueous polyamide resin emulsion as claimed in claim 1, it is characterized in that, be dimeracid in molar ratio in the first step: quadrol is that 1～1.4: 1 ratio feeds intake, in second step epoxy compounds and acrylic monomer by etc. mol ratio feed intake, the 3rd step middle-end carboxyl polyamides resin and propylene oxide acid monoester are that 1: 2 ratio feeds intake in molar ratio, and the ratio in every 10g terminal double link polyamide resin and 5g～40g unsaturated monomer reaction in the 4th step feeds intake.
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| CN103739839B (en) * | 2013-12-31 | 2015-10-21 | 四川大学 | Half aromatics polyarylether amide and preparation method thereof |
| CN105017750B (en) * | 2014-04-28 | 2017-10-24 | 乐凯胶片股份有限公司 | A kind of aqueous aromatic polyamides emulsion, preparation method and applications |
| EP3115400A1 (en) * | 2015-07-09 | 2017-01-11 | Basf Se | Preparation of surface functionalised polyamides |
| CN107082706A (en) * | 2017-05-27 | 2017-08-22 | 金正大生态工程集团股份有限公司 | A kind of interpenetrating net polymer coated fertilizer and preparation method thereof |
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| CN109021666B (en) * | 2018-08-01 | 2021-05-25 | 佛山市高明绿色德化工有限公司 | Water-based self-drying glass printing ink and preparation method thereof |
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| US4992500A (en) * | 1988-02-05 | 1991-02-12 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous dispersions of polyamides emulsified with rosin derivatives |
| CN101613472A (en) * | 2009-06-30 | 2009-12-30 | 中国林业科学研究院林产化学工业研究所 | The preparation method of polyamide resin used for water color ink |
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| US4992500A (en) * | 1988-02-05 | 1991-02-12 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous dispersions of polyamides emulsified with rosin derivatives |
| CN101613472A (en) * | 2009-06-30 | 2009-12-30 | 中国林业科学研究院林产化学工业研究所 | The preparation method of polyamide resin used for water color ink |
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