CN113336664A - Bio-based waterborne polyurethane resin and preparation method and application thereof - Google Patents
Bio-based waterborne polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN113336664A CN113336664A CN202110495182.4A CN202110495182A CN113336664A CN 113336664 A CN113336664 A CN 113336664A CN 202110495182 A CN202110495182 A CN 202110495182A CN 113336664 A CN113336664 A CN 113336664A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/24—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid
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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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7862—Nitrogen containing cyano groups or aldimine or ketimine groups
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Abstract
The invention relates to a bio-based waterborne polyurethane resin, a preparation method and application thereof, and the bio-based waterborne polyurethane resin can fundamentally solve the problem of poor hydrolysis resistance of waterborne polyurethane products. In addition, the bio-based waterborne polyurethane with the structure has higher bio-based content, higher environmental protection effect, and is aliphatic waterborne polyurethane resin, has excellent weather resistance and aging resistance, and can be used outdoors or in occasions with higher requirements on weather resistance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a bio-based waterborne polyurethane resin and a preparation method and application thereof.
Background
With the improvement of the quality of life of human beings, the emission of Volatile Organic Compounds (VOC) and the content of harmful solvents need to be more strictly limited, so that the production of waterborne polyurethane by adopting biomass raw materials with higher environmental protection effect becomes the mainstream of the development of times.
In recent years, the main raw materials for preparing the traditional waterborne polyurethane, such as isocyanate, diol and polyester diol, are petroleum, and the usage amount of the raw materials needs to be controlled in the face of the severe reality that petroleum resources are gradually exhausted. At present, the bio-based waterborne polyurethane mainly adopts vegetable oil polyalcohol based on natural renewable resources to replace or partially replace polyester diol, or modifies the waterborne polyurethane, so that the performance of the product is improved, the energy crisis caused by petroleum resources can be relieved, and the current sustainable development requirement is met. Therefore, the continuous improvement of the bio-based ratio of the raw materials of the aqueous polyurethane resin, the further reduction of the long-term harm of the over-exploitation of petroleum to the environment, and the improvement of the stability, hydrolysis resistance, weather resistance and other properties of polyurethane gradually become important research and development directions and urgent problems to be solved in the field.
Disclosure of Invention
Based on the above, there is a need to provide a bio-based waterborne polyurethane resin with a high environmental protection effect, and a preparation method and an application thereof.
A bio-based secondary amine hydrophilic chain extender has a structure shown in formula (I):
wherein R is1And R2Each independently of the others is an isocyanate non-reactive organic group, preferably C1-4An alkyl group;
R3and R4Each independently hydrogen or an isocyanate non-reactive organic group.
A preparation method of a bio-based secondary amine hydrophilic chain extender comprises the following steps:
carrying out Michael addition reaction on a first reagent and a second reagent, and carrying out deesterification on the obtained product to obtain the bio-based secondary amine hydrophilic chain extender;
wherein the first reagent is lysine ester; the second agent is a maleate or fumarate.
In some of these embodiments, the lysine ester is lysine C1-4Alkyl esters or lysine benzyl esters;
the second reagent has the following structure:
R1OOC-CR3＝CR4-COOR2
wherein R is1And R2Each independently of the others is an isocyanate non-reactive organic group, preferably C1-4An alkyl group; r3And R4Each independently hydrogen or an isocyanate non-reactive organic group.
In some of these embodiments, the molar ratio of the first reagent to the second reagent is 1 (2.3-2.5).
In some of these embodiments, the first reagent is lysine benzyl ester, and the preparation method comprises the following steps:
mixing lysine benzyl ester, alkali and a solvent, dropwise adding the solution of the second reagent in the inert gas atmosphere at the temperature of 40-50 ℃, reacting completely at the temperature of 60-65 ℃ after dropwise adding, and performing post-treatment to obtain a crude product;
and carrying out debenzylation reaction on the crude product to prepare the hydrophilic chain extender of the secondary biology base amine.
The application of the bio-based secondary amine hydrophilic chain extender or the bio-based secondary amine hydrophilic chain extender prepared by the preparation method in preparing the bio-based aqueous polyurethane resin.
A preparation method of bio-based waterborne polyurethane resin comprises the following steps:
mixing the raw materials for polymerization reaction to prepare the bio-based waterborne polyurethane resin;
wherein the raw materials comprise the following components in parts by weight:
the biological secondary amine hydrophilic chain extender is the biological secondary amine hydrophilic chain extender or the biological secondary amine hydrophilic chain extender prepared by the preparation method.
In some of these embodiments, the step of preparing the bio-based aqueous polyurethane resin comprises the steps of:
reacting the dehydrated polyol, the bio-based diisocyanate, the bio-based polycarbodiimide, and the catalyst at 70 ℃ to 90 ℃ for a predetermined time;
cooling to 50-65 ℃, adding the small molecular alcohol chain extender and the organic solvent, and reacting for a preset time at the temperature of 70-90 ℃;
cooling to below 30 ℃, adding the bio-based secondary amine hydrophilic chain extender and an organic solvent, and reacting for a preset time at the temperature of 15-30 ℃;
adding a neutralizing agent and water, uniformly dispersing, adding the aqueous solution of the bio-based diamine chain extender, stirring, and distilling to remove the organic solvent to obtain the bio-based waterborne polyurethane resin;
wherein the organic solvent is an organic solvent which can be mutually dissolved with water.
In some of these embodiments, the bio-based diisocyanate is 1, 5-pentamethylene diisocyanate; and/or
The bio-based polycarbodiimide is a micromolecular oligomer which takes 1, 5-pentamethylene diisocyanate as a reaction monomer, and the polymerization degree of the oligomer is less than or equal to 6;
the polyol is polyester diol, polycarbonate diol and polyether diol with the number average molecular weight of 500-5000, and preferably the polyester diol, the polycarbonate diol and the polyether diol with the number average molecular weight of 1000-3000;
the catalyst is an organic tin catalyst or an organic zinc catalyst;
the neutralizing agent is triethylamine or triethanolamine;
the micromolecular alcohol chain extender is bio-based 1, 3-propylene glycol;
the bio-based diamine chain extender is at least one of 1, 5-pentamethylene diamine and lysine.
A bio-based aqueous polyurethane resin comprises the following structural units:
wherein: r is ethyl and hydroxyethyl;
R1and R2Each independently of the others is an isocyanate non-reactive organic group, preferably C1-4An alkyl group;
R3and R4Each independently hydrogen or an isocyanate non-reactive organic group; n is an integer of 6 or less, preferably 4, 5, 6;
r' is C5H10Or
The bio-based waterborne polyurethane resin prepared by the preparation method or the application of the bio-based waterborne polyurethane resin in preparing paint or adhesive.
The invention has the following beneficial effects:
the invention can effectively and continuously improve the bio-based proportion of the raw material of the aqueous polyurethane dispersion by adopting the bio-based hydrophilic secondary amine chain extender, improve the stability of the aqueous polyurethane emulsion, add the bio-based polycarbodiimide to react with other components, introduce the bio-based polycarbodiimide into the main chain structure of the polyurethane, and can fundamentally solve the problem of poor hydrolysis resistance of the aqueous polyurethane product. Most of the components belong to bio-based materials, so that the content of bio-based materials in the waterborne polyurethane can be effectively improved, the raw materials are wide in source, the dependence on non-renewable resources such as petroleum can be effectively reduced, and the environment-friendly effect is high.
The bio-based waterborne polyurethane disclosed by the invention is aliphatic waterborne polyurethane resin, has excellent weather resistance and aging resistance, can be used outdoors or in occasions with higher requirements on weather resistance, and has the advantages of mild preparation process conditions, low energy consumption, good product stability, excellent performance and easiness in scale-up production.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The invention provides a bio-based secondary amine hydrophilic chain extender, which has a structure shown in a formula (I):
wherein R is1And R2Each independently an isocyanate non-reactive organic group;
R3and R4Each independently hydrogen or an isocyanate non-reactive organic group.
The invention adopts the bio-based secondary amine hydrophilic chain extender with the structure shown in the formula (I) and the asymmetric structure as the bio-based reagent, and has the advantages that:
1) compared with primary amine with higher reaction activity, the conversion rate of the polyurethane resin prepared by using the method as a raw material can be greatly improved (the conversion rate of secondary amine can reach 100 percent basically). And the secondary amine group of the biological secondary amine hydrophilic chain extender can form a urea bond with isocyanic acid radical, so that the mechanical property of the polyurethane can be obviously improved.
2) The bio-based secondary amine hydrophilic chain extender can be obtained by only adopting lysine ester and maleic acid ester or fumaric acid ester to carry out Michael addition reaction, has wide raw material source, mild reaction and low energy consumption, overcomes the problems of large reaction activity, difficult control of reaction process, easy occurrence of gel phenomenon and the like of the common primary amine hydrophilic chain extender, and can also overcome the problems of higher reaction temperature and large energy consumption of the traditional hydroxyl carboxylic acid hydrophilic chain extender.
3) The bio-based secondary amine hydrophilic chain extender is a bio-based renewable resource, can improve the bio-based proportion of the raw material of the aqueous polyurethane dispersion, can be used by being compounded with other bio-based reagents (such as bio-based diisocyanate), has a large proportion of the bio-based source of the final product, and meets the requirements of modern environmental protection and sustainable development.
It is understood that the "isocyanate non-reactive organic group" in the present invention means an organic group that is not reactive with isocyanate, and the specific kind is not particularly limited, and is understood to be within the scope of the present invention.
In some embodiments, R1And R2Each independently is C1-4An alkyl group; further, R1And R2Each independently being methyl, ethyl or n-butyl.
In some embodiments, R3、R4Is hydrogen.
The second aspect of the invention provides a preparation method of a bio-based secondary amine hydrophilic chain extender, which comprises the following steps:
s100: carrying out Michael addition reaction on the first reagent and the second reagent, and carrying out deesterification on the obtained product to obtain a bio-based secondary amine hydrophilic chain extender; wherein the first reagent is lysine ester; the second agent is a maleate or fumarate.
The inventor discovers in research that the bio-based secondary amine hydrophilic chain extender with asymmetric secondary amine and carboxyl can be obtained by using asymmetric lysine ester as a raw material and performing de-esterification reaction on lysine ester, the stability of the polyurethane emulsion can be improved, the conversion rate of the bio-based secondary amine hydrophilic chain extender is high, and the conversion rate of the secondary amine can reach 100%. On the other hand, if lysine is used as a reactant without ester group protection, the yield is affected because lysine is prone to self-polymerization. Protecting carboxyl by adopting an ester group, wherein a second reagent can be slightly excessive in the reaction process, the reaction is stopped after the reaction degree is detected to reach 100% by adopting an iodometry method, and then the esterification protection is carried out, so that the bio-based secondary amine hydrophilic chain extender is obtained, the operation is simple, and the yield is high; meanwhile, the secondary amine group can form a urea bond with the isocyanic acid radical, so that the mechanical property of the product can be improved.
It is understood that the "hydrophilic chain extender of secondary biobased amine" of the present invention may be isolated from the reaction system or may not be isolated, i.e., may be used in the form of a pure substance or may be used in the form of a mixture, and should be understood to fall within the scope of the present invention.
It is understood that in step S100, the ester group removed by the de-esterification reaction can be selected according to the need, and preferably forms the structure shown in formula (I).
In some embodiments, the lysine ester is a lysine alkyl ester and/or a lysine aryl ester; further, lysine ester is lysine C1-4Alkyl esters and/or lysine benzyl esters; further, lysine ester is one or more of lysine benzyl ester, lysine methyl ester and lysine tert-butyl ester; preferably lysine benzyl ester; further, lysine dibenzyl ester p-toluenesulfonate is preferable; it is easy to hydrogenate and remove benzyl in the synthesis process, thereby improving the yield of the product.
In some embodiments, the second agent has the following structure:
R1OOC-CR3＝CR4-COOR2
wherein R is1And R2Each independently an isocyanate non-reactive organic group;
R3and R4Each independently hydrogen or an isocyanate non-reactive organic group.
Further, R1And R2Each independently is C1-4An alkyl group; further, R1And R2Each independently being methyl, ethyl or n-butyl.
In some embodiments, R3、R4Is hydrogen.
In some embodiments, the second agent is dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, or dibutyl fumarate.
In some embodiments, the molar ratio of the first reagent to the second reagent is 1:2.3 to 2.5. On the basis of ensuring the yield and the purity by controlling the raw material ratio in the range, the residue of unreacted raw materials and byproducts is reduced as much as possible, and the difficulty of post-treatment is reduced.
Further, the preparation method of the bio-based secondary amine hydrophilic chain extender comprises the following steps:
s101: carrying out Michael addition reaction on the first reagent and the second reagent to prepare a crude product;
the relevant features of the first and second reagents are as described above and will not be described in further detail herein.
In some embodiments, the first reagent is lysine benzyl ester, which may be present in the form of a salt, such as lysine dibenzyl ester p-toluenesulfonate.
In some embodiments, step S101 includes the steps of: mixing lysine dibenzyl ester, p-toluenesulfonate, alkali and a solvent, dropwise adding a solution of a second reagent in the inert gas atmosphere at the temperature of 40-50 ℃, and reacting at the temperature of 60-65 ℃ after dropwise adding.
In some embodiments, in step S101, the base used in the michael addition is sodium ethoxide and the solvent is Dimethylformamide (DMF).
In some embodiments, step S101 further includes a post-processing step, and the post-processing method includes: the reaction solution was washed with water, extracted, and the solvent was distilled off.
S102: and performing debenzylation reaction on the crude product to prepare the bio-based secondary amine hydrophilic chain extender.
The step S102 may be performed by a conventional debenzylation method, which is not particularly limited and is understood to be within the scope of the present invention.
The third aspect of the invention provides an application of the hydrophilic chain extender of secondary biology base amine of the first aspect or the hydrophilic chain extender of secondary biology base amine prepared by the preparation method of the second aspect in preparing the waterborne polyurethane resin of biology base.
The invention provides a bio-based polycarbodiimide, which is a small molecular oligomer using 1, 5-pentamethylene diisocyanate as a reaction monomer, and further is a small molecular polymer prepared by MPPO (3-methyl-1-phenyl-2-phosphole-1-oxide) catalyzed reaction of 1, 5-Pentamethylene Diisocyanate (PDI), specifically:
wherein R is pentamethylene; n is an integer greater than or equal to 1;
in some embodiments, n ≦ 6; further, n is 4, 5 or 6. Wherein the polymerization degree can be obtained by titration of NCO% by the di-n-butylamine method (HG-T4144) -2010.
Controlling the polymerization degree (n) in the range ensures the proper number of imino groups to improve the water resistance of the resin, can also ensure that the emulsion has better stability, and avoids the influence of a large amount of water added to the emulsion when the viscosity is too high on the solid content of the product and even the influence of the viscosity on the stability of the product.
The fifth aspect of the present invention provides the method for preparing bio-based polycarbodiimide according to the fourth aspect, comprising the steps of:
1, 5-Pentamethylene Diisocyanate (PDI) and a catalyst (such as MPPO) are placed in an inert gas atmosphere to react at 160-220 ℃, and after reaction for preset time, post-treatment is carried out to obtain the bio-based polycarbodiimide.
In some embodiments, the reaction temperature is from 170 ℃ to 190 ℃; in some embodiments, the MPPO is added in an amount of 0.2 wt.% to 0.5 wt.% of the mass of the bio-based diisocyanate.
In some embodiments, the post-treatment is conducted by distilling off the catalyst and unreacted biobased diisocyanate under reduced pressure.
The sixth aspect of the invention provides a preparation method of bio-based waterborne polyurethane resin, which comprises the following steps:
s200: mixing the raw materials for polymerization reaction to prepare bio-based waterborne polyurethane resin;
the hydrophilic chain extender of the secondary biology base amine is the hydrophilic chain extender of the secondary biology base amine in the first aspect of the invention or the hydrophilic chain extender of the secondary biology base amine prepared by the preparation method in the second aspect of the invention.
The bio-based secondary amine hydrophilic chain extender can effectively improve the stability of the aqueous polyurethane emulsion, and the bio-based polycarbodiimide is added into the components to react with other components, so that the bio-based polycarbodiimide is introduced into the main chain structure of the polyurethane, thereby not only fundamentally solving the problem of poor hydrolysis resistance of the existing aqueous polyurethane product, but also ensuring that the bio-based aqueous polyurethane resin has better mechanical properties. Most of the components belong to bio-based materials, so that the content of bio-based materials in the waterborne polyurethane can be effectively improved, the raw materials are wide in source, the dependence on non-renewable resources such as petroleum can be effectively reduced, and the environment-friendly effect is high.
In some embodiments, the bio-based polycarbodiimide and the preparation method thereof are as described in the fourth and fifth aspects of the present invention, and will not be described herein.
In some embodiments, the biobased diisocyanate is 1, 5-pentamethylene diisocyanate;
in some embodiments, the polyol is one or more of a polyester diol, a polycarbonate diol, and a polyether diol. In some embodiments, the polyol is a combination of a polyester diol and a polyether diol; further, the mass ratio of the polyester diol to the polyether diol is 1: 0.05-0.2.
In some embodiments, the polyester diol has a number average molecular weight of 500 to 5000; preferably 1000 to 3000; further, the polyester diol is poly-1, 4-butylene adipate diol (PBA).
In some embodiments, the polyether glycol has a number average molecular weight of 500 to 5000; preferably 1000 to 3000; further, the polyether glycol is one or more of 1, 3-propylene glycol polyether glycol and castor oil glycol.
In some embodiments, the catalyst is one or more of an organotin-based catalyst and an organozinc-based catalyst, preferably an organotin-based catalyst; further, the catalyst was dibutyltin laurate.
In some embodiments, the neutralizing agent is one or more of triethylamine, diethanolamine, and triethanolamine.
In some embodiments, the small molecule alcohol chain extender is one or more of 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol. 1, 3-propanediol is preferably employed to increase the biobased content.
In some embodiments, the bio-based diamine chain extender is one or more of 1, 5-pentamethylene diamine and lysine.
Further, step S200 includes the steps of:
s201: reacting the polyol, the bio-based diisocyanate, the bio-based polycarbodiimide and the catalyst subjected to vacuum dehydration at the temperature of 70-90 ℃ for a preset time;
s202: cooling to 50-65 ℃, adding a small molecular alcohol chain extender and an organic solvent, and reacting for a preset time at the temperature of 70-90 ℃;
s203: cooling to below 30 ℃, adding a bio-based secondary amine hydrophilic chain extender and an organic solvent, and reacting for a preset time at the temperature of 15-30 ℃;
s204: adding a neutralizer and water, uniformly dispersing, adding a water solution of a bio-based diamine chain extender, stirring, and distilling to remove an organic solvent to obtain a bio-based waterborne polyurethane resin;
wherein the organic solvent is an organic solvent which can be mutually dissolved with water.
The reagents in steps S201-S204 are as described above and will not be described herein.
In some embodiments, step S201 is preceded by the step of pretreating the polyol to reduce the water content of the polyol to less than 0.05 wt%; further, step S201 is preceded by the steps of: and (3) placing the polyhydric alcohol under the vacuum degree of-0.09 MPa and the temperature of 115-120 ℃, and drying for more than 2 hours until the moisture content is below 0.05 wt%.
In some embodiments, the reaction time in step S201 is 1-3 h; in some embodiments, in step S202, the reaction time is 0.5h to 1.5 h; in some embodiments, in step S203, the reaction time is 20min to 40 min;
in some embodiments, step S204 includes the steps of: adding a neutralizing agent and an organic solvent, stirring for 20min-40min, then adding water, dispersing at a high speed (preferably 1500rpm-3000rpm) for 15-20min, distilling to remove the organic solvent, and filtering the remaining aqueous solution to obtain the required waterborne polyurethane resin.
In some embodiments, the organic solvent is acetone.
The preparation method of the bio-based waterborne polyurethane resin is simple to operate, wide in source of production raw materials, mild in condition, low in energy consumption, good in product stability and excellent in water resistance.
The seventh aspect of the invention provides a bio-based waterborne polyurethane resin, which comprises the following structural units:
wherein: r is ethyl and hydroxyethyl; r1And R2Each independently an isocyanate non-reactive organic group; r3And R4Each independently hydrogen or an isocyanate non-reactive organic group; n is an integer of 6 or less, preferably 4, 5, 6; r' is C5H10Or
In some embodiments, R1And R2Each independently is C1-4An alkyl group; further, R1And R2Each independently being methyl, ethyl or n-butyl. In some embodiments, R3、R4Is hydrogen.
The bio-based waterborne polyurethane resin can fundamentally solve the problem of poor hydrolysis resistance of waterborne polyurethane products. In addition, the bio-based waterborne polyurethane with the structure has higher bio-based content, higher environmental protection effect, and is aliphatic waterborne polyurethane resin, has excellent weather resistance and aging resistance, and can be used outdoors or in occasions with higher requirements on weather resistance.
The present invention will be described below by way of specific examples, which are intended to be illustrative only and should not be construed as limiting the invention.
Example 1
(1) Synthesis of biological polycarbodiimide
Introducing nitrogen into a reactor provided with an electric stirring device, a temperature control device, a reflux condensation device and a nitrogen protection device, slowly adding 1, 5-pentamethylene diisocyanate, heating to 180 ℃, adding an organophosphorus catalyst MPPO (3-methyl-1-phenyl-2-phosphole-1-oxide), controlling the catalyst dosage to be 0.2-0.5 wt% of the reactant 1, 5-pentamethylene diisocyanate by monitoring and determining the value (HG-T4144-2010) of-NCO content reduction of the solution in real time to obtain bio-based polycarbodiimide with the average polymerization degree not greater than 6, removing the catalyst and unreacted PDI by reduced pressure distillation, and carrying out sealed preservation at low temperature after rapid cooling to obtain the bio-based polycarbodiimide for later use;
(2) synthesis of bio-based secondary amine hydrophilic chain extender
Adding a certain amount of L-lysine benzyl ester p-toluenesulfonic acid disalt (cas: 16259-78-2) into a reactor equipped with a stirring, temperature control and nitrogen protection device at room temperature, starting stirring, introducing nitrogen, heating to 40-50 ℃ under an alkaline condition, and slowly dropwise adding diethyl maleate (wherein the mass ratio of diethyl maleate to L-lysine is 2.3-2.5: 1); after the dropwise addition is finished, heating to 60-65 ℃, continuously reacting for 20-24 h, measuring the unsaturation degree of the system according to an iodometry method, and stopping the reaction when the conversion rate of reactants reaches 100% to obtain a reaction solution; and then washing, extracting and distilling the reaction solution to obtain a crude product, and then carrying out hydrogenation and debenzylation reaction under the action of a catalyst Pd/C to obtain a bio-based secondary amine hydrophilic chain extender product for later use.
(3) Synthesis of bio-based waterborne polyurethane
Adding 600g of PBA (Mn ═ 2000) into a reaction device with stirring, temperature control and reflux condensation, vacuum-drying at 115-120 ℃ for more than 2h under the vacuum degree of-0.09 MPa, and replacing vacuum with nitrogen when the moisture content is less than 0.05 wt%; cooling to 60 ℃, sequentially adding 300g of PDI, 15g of the biological polycarbodiimide obtained in the step (1) and 0.8g of dibutyltin laurate (T12), heating to 80 ℃, and reacting for 2 h; cooling to 60 ℃, adding 50g of 1, 3-propylene glycol and 50g of acetone, heating to 80 ℃, and continuing to react for 1 h; cooling to 25 ℃, adding 60g of the hydrophilic chain extender (3-6%) of the secondary biology base amine obtained in the step (2) and 100g of acetone, and keeping the temperature at 25 ℃ to continue reacting for 0.5 h; adding 100g of acetone and 13g of triethylamine, reacting for 30min, and adding 1700g of distilled water; transferring all materials in the reactor into a high-speed dispersing agent, dispersing at a high speed of 2000rpm, slowly dropwise adding 36g of lysine water solution, and stirring at a high speed for 15-20 min; finally, acetone is removed through reduced pressure distillation, and the mixture is filtered by a 100-mesh nylon net and discharged to obtain the bio-based waterborne polyurethane resin product in the embodiment 1.
Example 2 to example 4
Examples 2-4 the process was substantially similar to example 1, except for the type and amount of starting materials, as shown in Table 1.
Comparative example 1
The preparation process of comparative example 1 is substantially similar to that of example 1, except for the kinds and amounts of the raw materials, as shown in Table 1. It should be noted that comparative example 1 requires a low temperature reaction (below 5 ℃) when adding the hydrophilic chain extender, otherwise, the local reaction speed is too fast due to high reactivity, and the gel reaction is easy to occur due to improper control.
Performance testing
The biobased aqueous polyurethane resin products of examples 1 to 4 and comparative example 1 were subjected to performance tests, and the test methods of the indexes are as follows, and the test results are shown in table 1.
The solid content is tested according to GB 1725-2007;
testing the tensile strength of the cured film according to GB/T1040.3-2006;
the tensile strength after hydrolysis is the tensile property test of the product after the product is placed in water for 3 days;
tensile strength retention is the percentage of the tensile strength value after hydrolysis divided by the tensile strength before hydrolysis.
TABLE 1
Note 1: lysine is primary amine, the reaction activity is high, when the lysine is used as a hydrophilic chain extender, the reaction time, the dropping speed and the reaction temperature need to be strictly controlled, the experiment is completed in a manner of dropping for 30 minutes at 5 ℃ and reducing the dosage, and the step is not easy to control during amplification production.
The experimental results are as follows:
as can be seen from the above Table 1, the bio-based waterborne polyurethane of examples 1 to 4 has very excellent mechanical strength and hydrolysis resistance, and compared with comparative example 1, the performances are obviously improved. The biological-based waterborne polyurethane resin can fundamentally solve the problem of poor hydrolysis resistance of waterborne polyurethane products and has better mechanical properties. In addition, the bio-based proportion of the raw material of the aqueous polyurethane dispersion is high, the long-term harm of excessive exploitation of petroleum to the environment can be further reduced, and the aqueous polyurethane dispersion has a high environment-friendly effect.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. A bio-based secondary amine hydrophilic chain extender is characterized by having a structure shown in a formula (I):
wherein R is1And R2Each independently of the others is an isocyanate non-reactive organic group, preferably C1-4An alkyl group;
R3and R4Each independently hydrogen or an isocyanate non-reactive organic group.
2. A preparation method of a bio-based secondary amine hydrophilic chain extender is characterized by comprising the following steps:
carrying out Michael addition reaction on a first reagent and a second reagent, and carrying out deesterification on the obtained product to obtain the bio-based secondary amine hydrophilic chain extender;
wherein the first reagent is lysine ester; the second agent is a maleate or fumarate.
3. The process according to claim 2, wherein the lysine ester is lysine C1-4Alkyl esters or lysine benzyl esters;
the second reagent has the following structure:
R1OOC-CR3＝CR4-COOR2
wherein R is1And R2Each independently of the others is an isocyanate non-reactive organic group, preferably C1-4An alkyl group; r3And R4Each independently hydrogen or an isocyanate non-reactive organic group.
4. The method according to any one of claims 2 to 3, wherein the molar ratio of the first reagent to the second reagent is 1 (2.3 to 2.5).
5. The preparation method according to any one of claims 2 to 3, wherein the first reagent is lysine benzyl ester, and the preparation method comprises the following steps:
mixing lysine benzyl ester, alkali and a solvent, dropwise adding the solution of the second reagent in the inert gas atmosphere at the temperature of 40-50 ℃, reacting completely at the temperature of 60-65 ℃ after dropwise adding, and performing post-treatment to obtain a crude product;
and carrying out debenzylation reaction on the crude product to prepare the hydrophilic chain extender of the secondary biology base amine.
6. Use of the secondary biobased amine hydrophilic chain extender of claim 1 or the secondary biobased amine hydrophilic chain extender prepared by the preparation method of any one of claims 2 to 5 in preparation of a waterborne polyurethane resin.
7. A preparation method of bio-based waterborne polyurethane resin is characterized by comprising the following steps:
carrying out polymerization reaction on the raw materials to prepare the bio-based waterborne polyurethane resin;
wherein the raw materials comprise the following components in parts by weight:
the secondary biobased amine hydrophilic chain extender is the secondary biobased amine hydrophilic chain extender in claim 1 or the secondary biobased amine hydrophilic chain extender prepared by the preparation method in any one of claims 2 to 6.
8. The method for preparing the bio-based aqueous polyurethane resin according to claim 7, wherein the step of preparing the bio-based aqueous polyurethane resin comprises the steps of:
reacting the dehydrated polyol, the bio-based diisocyanate, the bio-based polycarbodiimide, and the catalyst at 70 ℃ to 90 ℃ for a predetermined time;
cooling to 50-65 ℃, adding the small molecular alcohol chain extender and the organic solvent, and reacting for a preset time at the temperature of 70-90 ℃;
cooling to below 30 ℃, adding the bio-based secondary amine hydrophilic chain extender and an organic solvent, and reacting for a preset time at the temperature of 15-30 ℃;
adding a neutralizing agent and water, uniformly dispersing, adding the aqueous solution of the bio-based diamine chain extender, stirring, and distilling to remove the organic solvent to obtain the bio-based waterborne polyurethane resin;
wherein the organic solvent is an organic solvent which can be mutually dissolved with water.
9. The method according to claim 7 or 8, wherein the bio-based diisocyanate is 1, 5-pentamethylene diisocyanate;
the bio-based polycarbodiimide is a micromolecular oligomer which takes 1, 5-pentamethylene diisocyanate as a reaction monomer, and the polymerization degree of the oligomer is less than or equal to 6;
the polyol is polyester diol, polycarbonate diol and polyether diol with the number average molecular weight of 500-5000, and preferably the polyester diol, the polycarbonate diol and the polyether diol with the number average molecular weight of 1000-3000;
the catalyst is an organic tin catalyst or an organic zinc catalyst;
the neutralizing agent is triethylamine or triethanolamine;
the micromolecular alcohol chain extender is bio-based 1, 3-propylene glycol;
the bio-based diamine chain extender is at least one of 1, 5-pentamethylene diamine and lysine.
10. A bio-based aqueous polyurethane resin is characterized by comprising the following structural units:
wherein: r is ethyl and hydroxyethyl;
R1and R2Each independently of the others is an isocyanate non-reactive organic group, preferably C1-4An alkyl group;
R3and R4Each independently hydrogen or an isocyanate non-reactive organic group;
n is an integer of 6 or less, preferably 4, 5, 6;
r' is C5H10Or
11. Use of the bio-based aqueous polyurethane resin prepared by the preparation method according to any one of claims 7 to 9 or the bio-based aqueous polyurethane resin according to claim 10 in preparing a coating or an adhesive.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105164219A (en) * | 2013-03-19 | 2015-12-16 | 温科莱斯法国公司 | Allophanate composition |
| CN109749053A (en) * | 2018-12-29 | 2019-05-14 | 华南理工大学 | A kind of dispersions of polyurethanes and preparation method thereof containing polycarbodiimide |
| CN110818873A (en) * | 2019-11-20 | 2020-02-21 | 万华化学集团股份有限公司 | Waterborne polyurethane resin and preparation method and application thereof |
| CN112225871A (en) * | 2020-10-20 | 2021-01-15 | 上海华峰新材料研发科技有限公司 | Organic silicon modified bio-based waterborne polyurethane resin composition and preparation method thereof |
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| CN105164219A (en) * | 2013-03-19 | 2015-12-16 | 温科莱斯法国公司 | Allophanate composition |
| CN109749053A (en) * | 2018-12-29 | 2019-05-14 | 华南理工大学 | A kind of dispersions of polyurethanes and preparation method thereof containing polycarbodiimide |
| CN110818873A (en) * | 2019-11-20 | 2020-02-21 | 万华化学集团股份有限公司 | Waterborne polyurethane resin and preparation method and application thereof |
| CN112225871A (en) * | 2020-10-20 | 2021-01-15 | 上海华峰新材料研发科技有限公司 | Organic silicon modified bio-based waterborne polyurethane resin composition and preparation method thereof |
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