CN105622890A - Method for preparing tall oil water-based polyurethane - Google Patents
Method for preparing tall oil water-based polyurethane Download PDFInfo
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- CN105622890A CN105622890A CN201610114057.3A CN201610114057A CN105622890A CN 105622890 A CN105622890 A CN 105622890A CN 201610114057 A CN201610114057 A CN 201610114057A CN 105622890 A CN105622890 A CN 105622890A
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- Prior art keywords
- tall oil
- yatall
- aqueous polyurethane
- polyvalent alcohol
- oil modified
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 46
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 46
- 239000003784 tall oil Substances 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000839 emulsion Substances 0.000 claims abstract description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 150000002009 diols Chemical class 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000004945 emulsification Methods 0.000 claims description 7
- 238000005304 joining Methods 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229960004418 trolamine Drugs 0.000 claims description 7
- 239000004970 Chain extender Substances 0.000 claims description 6
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 5
- 235000005513 chalcones Nutrition 0.000 claims description 5
- 229960002725 isoflurane Drugs 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- -1 polyoxyethylene Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229940043237 diethanolamine Drugs 0.000 abstract 3
- 239000002699 waste material Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003265 pulping liquor Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
- C08G18/678—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups containing nitrogen
-
- 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a method for preparing tall oil water-based polyurethane. The method includes the steps that firstly, tall oil is weighed, placed into a reaction bottle, protected by inert gases and heated to 140-160 DEG C, then diethanol amine is added in the proportion that the molar ratio of the diethanol amine or triethanolamine to tall oil is 1:1-1:2 so that diethanol amine can react with tall oil, reduced pressure distillation is conducted to remove water generated in the reaction, tall oil diol is obtained, then the obtained tall oil diol is used for synthesis of waterborne polyurethane, and a series of water-based polyurethane emulsion modified by tall oil are prepared. By means of the method, the tall oil extracted from papermaking waste liquor is effectively utilized, and the application field of the tall oil is further broadened.
Description
Technical field
The invention belongs to water-base polyurethane material manufacture field, it is specifically related to the preparation method of a kind of Yatall MA aqueous polyurethane.
Background technology
Along with the enhancing of environmental consciousness and countries in the world are to the raising day by day of environmental requirement, take water as the concern that the aqueous polyurethane of dispersion medium also enjoys people, water-base polyurethane material have pollution-free, safe and reliable, mechanical property is excellent, consistency and good film-forming property, be easy to the advantages such as modification; Application Areas contains leather, papermaking, weaving, coating etc.
Yatall MA obtains from dark solution remaining during alkali method (being mainly sulphate process) wood pulp processed. By spent pulping liquor stratification, lower floor's black liquor, mainly containing xylogen, floats over the mainly thick Tuo Er soap (also claiming crude sulfate soap) on upper strata, is soaped by thick appropriate that and washs, and acidifying and essence put layering, and upper strata is thick Yatall MA.
Summary of the invention
In view of this, the main purpose of the present invention is to provide the preparation method of a kind of Yatall MA aqueous polyurethane.
For achieving the above object, the technical scheme of the present invention is achieved in that
The embodiment of the present invention provides the preparation method of a kind of tall oil modified aqueous polyurethane, and the method comprises the following steps:
Step one, take Yatall MA in reaction flask, protection of inert gas, it is heated to 140 ~ 160 DEG C, then in the ratio of diethanolamine and Yatall MA mol ratio 1:1 ~ 1:2, adding diethanolamine makes itself and Yatall MA react, product underpressure distillation, except the water generated in dereaction, obtains Yatall MA glycol;
Step 2, joining in reaction flask by polyvalent alcohol, vulcabond and described obtained Yatall MA glycol, wherein the mol ratio of polyvalent alcohol and vulcabond is 1:(1 ~ 4); The add-on of Yatall MA glycol is the 5% ~ 30% of polyvalent alcohol total mass; Adding taking the quality of vulcabond and polyvalent alcohol with as 0.003% ~ 0.006% catalyzer of benchmark, stirring reaction 3 ~ 6h at 50 ~ 90 DEG C, is then cooled to 40 ~ 70 DEG C again; Adding hydrophilic chain extender again, its add-on is the 2.0% ~ 6.0% of polyvalent alcohol and vulcabond total mass, and the reaction times is 1 ~ 4h, is cooled to discharging after room temperature, namely obtains aqueous polyurethane performed polymer;
Step 3, by the performed polymer neutralizing agent that obtains in described step 2 and after; Adding distil water carries out emulsify at a high speed, and after emulsification, decompression removes in reaction process a small amount of acetone added, and obtains tall oil modified aqueous polyurethane emulsion.
In such scheme, in described step one, synthesis Yatall MA glycol adopts Yatall MA and diethanolamine or trolamine.
In such scheme, in described step 2, vulcabond is isoflurane chalcone diisocyanate, diphenylmethanediisocyanate, tolylene diisocyanate or hexamethylene diisocyanate.
In such scheme, in described step 2, described polyvalent alcohol is polyoxyethylene glycol, polypropylene glycol or polytetrahydrofuran diol.
In such scheme, in described step 2, described catalyzer is dibutyl tin laurate.
In such scheme, in described step 2, described neutralizing agent is triethylamine, potassium hydroxide or sodium hydroxide.
In such scheme, in described step 2, after needing before reaction that Yatall MA glycol is become liquid state with the polyvalent alcohol heating and melting of interpolation, then carry out follow-up reaction.
In such scheme, in described step 2, described hydrophilic chain extender is dimethylol propionic acid or dimethylolpropionic acid.
In such scheme, in described step 2, described in the aqueous polyurethane performed polymer that obtains, if viscosity more namely reaction material be starchiness or stir when not moving, add the acetone of total mass 5% ~ 30%.
Compared with prior art, the useful effect of the present invention:
Yatall MA is carried out modification by the present invention, is then incorporated in the synthesis of aqueous polyurethane by the Yatall MA alcohol obtained, and then prepares a series of tall oil modified aqueous polyurethane emulsion. Adding of Yatall MA alcohol, it is possible not only to substitute part polyvalent alcohol and isocyanate reaction, increases its degree of crosslinking, and the mechanical property of aqueous polyurethane can be improved, it is to increase value-added content of product. The present invention utilizes Yatall MA renewable resources, alleviates environmental stress.
Accompanying drawing explanation
Fig. 1 provides the schema of the preparation method of a kind of amination Yatall MA for the embodiment of the present invention;
Fig. 2 provides the schema of the preparation method of a kind of tall oil modified aqueous polyurethane for the embodiment of the present invention.
Embodiment
In order to make the object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated. It is to be understood that specific embodiment described herein is only in order to explain the present invention, it is not intended to limit the present invention.
The embodiment of the present invention provides the preparation method of a kind of tall oil modified aqueous polyurethane, and the method comprises the following steps:
Step one, take Yatall MA in reaction flask, protection of inert gas, it is heated to 140 ~ 160 DEG C, then in the ratio of diethanolamine and Yatall MA mol ratio 1:1 ~ 1:2, adding diethanolamine makes itself and Yatall MA react, product underpressure distillation, except the water generated in dereaction, obtains Yatall MA glycol;
Specifically, synthesize Yatall MA glycol and adopt Yatall MA and diethanolamine, trolamine.
Step 2, joining in reaction flask by polyvalent alcohol, vulcabond and described obtained Yatall MA glycol, wherein the mol ratio of polyvalent alcohol and vulcabond is 1:(1 ~ 4); The add-on of Yatall MA glycol is the 5% ~ 30% of polyvalent alcohol total mass; Adding taking the quality of vulcabond and polyvalent alcohol with as 0.003% ~ 0.006% catalyzer of benchmark, stirring reaction 3 ~ 6h at 50 ~ 90 DEG C, is then cooled to 40 ~ 70 DEG C again; Adding hydrophilic chain extender again, its add-on is the 2.0% ~ 6.0% of polyvalent alcohol and vulcabond total mass, and the reaction times is 1 ~ 4h, is cooled to discharging after room temperature, namely obtains aqueous polyurethane performed polymer;
Specifically, described vulcabond is isoflurane chalcone diisocyanate, diphenylmethanediisocyanate, tolylene diisocyanate or hexamethylene diisocyanate.
Described polyvalent alcohol is polyoxyethylene glycol, polypropylene glycol or polytetrahydrofuran diol.
Described catalyzer is dibutyl tin laurate.
Described neutralizing agent is triethylamine, potassium hydroxide or sodium hydroxide.
After needing before reaction that Yatall MA glycol is become liquid state with the polyvalent alcohol heating and melting of interpolation, then carry out follow-up reaction.
Described hydrophilic chain extender is dimethylol propionic acid or dimethylolpropionic acid.
If the aqueous polyurethane performed polymer viscosity obtained described is relatively big, adds proper amount of acetone.
Step 3, by the performed polymer neutralizing agent that obtains in described step 2 and after; Adding distil water carries out emulsify at a high speed, and after emulsification, decompression removes in reaction process the acetone added, and obtains tall oil modified aqueous polyurethane emulsion;
Embodiment one
The embodiment of the present invention provides the preparation method of a kind of tall oil modified aqueous polyurethane, and as shown in Figure 1, 2, the method comprises the steps:
Step one, take Yatall MA in reaction flask, protection of inert gas, it is heated to 140 DEG C, then in the ratio of diethanolamine and Yatall MA mol ratio 1:1, adding diethanolamine makes itself and Yatall MA react, and product underpressure distillation, except the water generated in dereaction, obtains Yatall MA glycol;
Step 2, joining in reaction flask by polyoxyethylene glycol, tolylene diisocyanate and Yatall MA glycol, wherein the mol ratio of polyvalent alcohol and vulcabond is 1:1.5; The add-on of Yatall MA glycol is the 15% of polyvalent alcohol total amount; Adding the catalyzer that quality is the 0.005% of vulcabond and polyvalent alcohol total mass again, stirring reaction 3h at 50 DEG C, is then cooled to 40 DEG C; Adding dimethylol propionic acid again, its add-on is the 2.0% of polyvalent alcohol and vulcabond total mass, and the reaction times is 2h, is cooled to discharging after room temperature, obtains aqueous polyurethane performed polymer, if performed polymer viscosity is relatively big, can add proper amount of acetone;
Step 3, by the performed polymer triethylamine that obtains in step 2 and after; Adding distil water carries out emulsify at a high speed, and after emulsification, decompression removes in reaction process a small amount of acetone added, and obtains tall oil modified aqueous polyurethane emulsion.
Embodiment two
The embodiment of the present invention provides the preparation method of a kind of tall oil modified aqueous polyurethane, and the method comprises the steps:
Step one, take Yatall MA in reaction flask, protection of inert gas, it is heated to 140 DEG C, then in the ratio of trolamine and Yatall MA mol ratio 1:1 ~ 1:2, adding trolamine makes itself and Yatall MA react, and product underpressure distillation, except the water generated in dereaction, obtains Yatall MA glycol;
Step 2, joining in reaction flask by polypropylene glycol, hexamethylene diisocyanate and Yatall MA glycol, wherein the mol ratio of polyvalent alcohol and vulcabond is 1:1.5; The add-on of Yatall MA glycol is the 10% of polyvalent alcohol total amount; Adding the catalyzer that quality is the 0.006% of vulcabond and polyvalent alcohol total mass again, stirring reaction 4h at 60 DEG C, is then cooled to 40 DEG C; Adding dimethylol propionic acid again, its add-on is the 6.0% of polyvalent alcohol and vulcabond total mass, and the reaction times is 4h, is cooled to discharging after room temperature, obtains aqueous polyurethane performed polymer, if performed polymer viscosity is relatively big, can add proper amount of acetone;
Step 3, by after the performed polymer ammonia neutralization that obtains in step 2; Adding distil water carries out emulsify at a high speed, and after emulsification, decompression removes in reaction process a small amount of acetone added, and obtains tall oil modified aqueous polyurethane emulsion.
Embodiment three
The embodiment of the present invention provides the preparation method of a kind of tall oil modified aqueous polyurethane, and the method comprises the steps:
Step one, take Yatall MA in reaction flask, protection of inert gas, it is heated to 160 DEG C, then in the ratio of diethanolamine and Yatall MA mol ratio 1:1.5, adding diethanolamine makes itself and Yatall MA react, and product underpressure distillation, except the water generated in dereaction, obtains Yatall MA glycol;
Step 2, joining in reaction flask by polytetrahydrofuran diol, isoflurane chalcone diisocyanate and Yatall MA glycol, wherein the mol ratio of polyvalent alcohol and vulcabond is 1:2; The add-on of Yatall MA glycol is the 20% of polyvalent alcohol total amount; Adding the catalyzer that quality is the 0.005% of vulcabond and polyvalent alcohol total mass again, stirring reaction 6h at 50 DEG C, is then cooled to 40 DEG C; Adding dimethylol propionic acid again, its add-on is the 2.0% of polyvalent alcohol and vulcabond total mass, and the reaction times is 4h, is cooled to discharging after room temperature, obtains aqueous polyurethane performed polymer, if performed polymer viscosity is relatively big, can add proper amount of acetone;
Step 3, by the performed polymer triethylamine that obtains in step 2 and after; Adding distil water carries out emulsify at a high speed, and after emulsification, decompression removes in reaction process a small amount of acetone added, and obtains tall oil modified aqueous polyurethane emulsion.
Embodiment four
The embodiment of the present invention provides the preparation method of a kind of tall oil modified aqueous polyurethane, and the method comprises the steps:
Step one, take Yatall MA in reaction flask, protection of inert gas, it is heated to 160 DEG C, then in the ratio of trolamine and Yatall MA mol ratio 1:2, adding trolamine makes itself and Yatall MA react, and product underpressure distillation, except the water generated in dereaction, obtains Yatall MA glycol;
Step 2, joining in reaction flask by polytetrahydrofuran diol, isoflurane chalcone diisocyanate and Yatall MA glycol, wherein the mol ratio of polyvalent alcohol and vulcabond is 1:2; The add-on of Yatall MA glycol is the 30% of polyvalent alcohol total amount; Adding the catalyzer that quality is the 0.004% of vulcabond and polyvalent alcohol total mass again, stirring reaction 6h at 90 DEG C, is then cooled to 70 DEG C; Adding dimethylol propionic acid again, its add-on is the 6.0% of polyvalent alcohol and vulcabond total mass, and the reaction times is 1h, is cooled to discharging after room temperature, obtains aqueous polyurethane performed polymer, if performed polymer viscosity is relatively big, can add proper amount of acetone;
Step 3, by the performed polymer neutralizing agent that obtains in step 2 and after; Adding distil water carries out emulsify at a high speed, and after emulsification, decompression removes in reaction process a small amount of acetone added, and obtains tall oil modified aqueous polyurethane emulsion.
The above, be only the better embodiment of the present invention, be not intended to limit protection scope of the present invention.
Claims (9)
1. the preparation method of a tall oil modified aqueous polyurethane, it is characterised in that, the method comprises the following steps:
Step one, take Yatall MA in reaction flask, protection of inert gas, it is heated to 140 ~ 160 DEG C, then in the ratio of diethanolamine and Yatall MA mol ratio 1:1 ~ 1:2, adding diethanolamine makes itself and Yatall MA react, product underpressure distillation, except the water generated in dereaction, obtains Yatall MA glycol;
Step 2, joining in reaction flask by polyvalent alcohol, vulcabond and described obtained Yatall MA glycol, wherein the mol ratio of polyvalent alcohol and vulcabond is 1:(1 ~ 4); The add-on of Yatall MA glycol is the 5% ~ 30% of polyvalent alcohol total mass; Adding taking the quality of vulcabond and polyvalent alcohol with as 0.003% ~ 0.006% catalyzer of benchmark, stirring reaction 3 ~ 6h at 50 ~ 90 DEG C, is then cooled to 40 ~ 70 DEG C again; Adding hydrophilic chain extender again, its add-on is the 2.0% ~ 6.0% of polyvalent alcohol and vulcabond total mass, and the reaction times is 1 ~ 4h, is cooled to discharging after room temperature, namely obtains aqueous polyurethane performed polymer;
Step 3, by the performed polymer neutralizing agent that obtains in described step 2 and after; Adding distil water carries out emulsify at a high speed, and after emulsification, decompression removes in reaction process a small amount of acetone added, and obtains tall oil modified aqueous polyurethane emulsion.
2. the preparation method of tall oil modified aqueous polyurethane according to claim 1, it is characterised in that: in described step one, synthesis Yatall MA glycol adopts Yatall MA and diethanolamine or trolamine.
3. the preparation method of tall oil modified aqueous polyurethane according to claim 1, it is characterized in that: in described step 2, vulcabond is isoflurane chalcone diisocyanate, diphenylmethanediisocyanate, tolylene diisocyanate or hexamethylene diisocyanate.
4. the preparation method of tall oil modified aqueous polyurethane according to claim 1, it is characterised in that: in described step 2, described polyvalent alcohol is polyoxyethylene glycol, polypropylene glycol or polytetrahydrofuran diol.
5. the preparation method of tall oil modified aqueous polyurethane according to claim 1, it is characterised in that: in described step 2, described catalyzer is dibutyl tin laurate.
6. the preparation method of tall oil modified aqueous polyurethane according to claim 1, it is characterised in that: in described step 2, described neutralizing agent is triethylamine, potassium hydroxide or sodium hydroxide.
7. the preparation method of tall oil modified aqueous polyurethane according to claim 1, it is characterised in that: in described step 2, after needing before reaction that Yatall MA glycol is become liquid state with the polyvalent alcohol heating and melting of interpolation, then carry out follow-up reaction.
8. the preparation method of tall oil modified aqueous polyurethane according to claim 1, it is characterised in that: in described step 2, described hydrophilic chain extender is dimethylol propionic acid or dimethylolpropionic acid.
9. the preparation method of tall oil modified aqueous polyurethane according to claim 1, it is characterized in that: in described step 2, the described aqueous polyurethane performed polymer obtained, if viscosity more namely reaction material be starchiness or stir when not moving, add the acetone of total mass 5% ~ 30%.
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| CN113527623A (en) * | 2021-07-30 | 2021-10-22 | 浙江华峰合成树脂有限公司 | Solvent-free polyurethane resin and preparation method and application thereof |
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| CN102796228A (en) * | 2012-09-12 | 2012-11-28 | 湖南大学 | Preparation method of acrylic-modified water-based tall oil alkyd resin emulsion |
| CN103881049A (en) * | 2014-04-04 | 2014-06-25 | 中南林业科技大学 | Preparation method of eleostearic acid monoglyceride modified waterborne polyurethane emulsion |
| CN104761699A (en) * | 2015-04-16 | 2015-07-08 | 陕西科技大学 | Method for preparing carboxyl-containing castor oil modified waterborne polyurethane |
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| CN102796228A (en) * | 2012-09-12 | 2012-11-28 | 湖南大学 | Preparation method of acrylic-modified water-based tall oil alkyd resin emulsion |
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| CN113527623A (en) * | 2021-07-30 | 2021-10-22 | 浙江华峰合成树脂有限公司 | Solvent-free polyurethane resin and preparation method and application thereof |
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