CN112266460A - Thermosetting polyurethane and preparation method thereof - Google Patents
Thermosetting polyurethane and preparation method thereof Download PDFInfo
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- CN112266460A CN112266460A CN202011232315.0A CN202011232315A CN112266460A CN 112266460 A CN112266460 A CN 112266460A CN 202011232315 A CN202011232315 A CN 202011232315A CN 112266460 A CN112266460 A CN 112266460A
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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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/65—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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses thermosetting polyurethane, which is characterized in that: the thermosetting polyurethane comprises the following components of 50-100 parts of polyoxypropylene glycol, 10-30 parts of isophorone diisocyanate, 1-5 parts of dimethylolpropionic acid, 1-5 parts of 1-2 propylene glycol, 0.5 part of catalyst, 1-5 parts of triethylamine, 200-250 parts of deionized water and 5-20 parts of ketone hydrazine crosslinking monomer. The product for preparing the fabric has the advantages of high rigidity, high hardness, high temperature resistance, non-flammability, good product size stability and excellent water resistance.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to thermosetting polyurethane and a preparation method thereof.
Background
The molecular structure of the thermosetting resin is body type, which refers to a large class of synthetic resin which is subjected to chemical reaction under the action of heating, pressurizing or curing agent and ultraviolet light, and is crosslinked and cured into insoluble infusible substances. Such resins are generally solids or viscous liquids of low molecular weight prior to curing; can soften or flow in the forming process, has plasticity, can be made into a certain shape, and simultaneously has chemical reaction to crosslink and solidify; some by-products, such as water, are sometimes evolved. This reaction is irreversible, and once cured, it is not possible to soften or flow again by heating under pressure; if the temperature is too high, the decomposition or carbonization occurs. This is a fundamental difference from the thermoplastic resin.
Polyurethane is one of the most important polymeric materials, and has unique advantages, such as low density, low thermal conductivity, good moisture permeability, excellent mechanical properties, good chemical stability, and the like. The polyurethane industry has developed rapidly since 80 years ago when polyurethane was obtained by Bayer et al by polymerization of an isocyanate with a polyol component. The product family extends through thermoplastic materials and thermosetting materials, and the product family is widely applied to daily life, such as foams, elastomers, adhesives, coatings and the like.
In China, the thermosetting property of the aqueous polyurethane resin is mainly cross-linked by isocyanate groups, aziridine and carboxyl groups, hydrolytic polycondensation cross-linking of siloxane groups, and cross-linking based on Michael addition reaction. The crosslinking of isocyanate groups and aziridine is mainly carried out by two components, and the use of blocked isocyanates can cause the temperature required for crosslinking to be very high, which is not favorable for the general popularization of the resin. The hydrolytic polycondensation of siloxane groups has the disadvantage that the siloxane addition is not too high, otherwise the system is not stable.
Thermosetting polyurethane also has great industrial and commercial demands due to the excellent characteristics of thermosetting plastics, and as industrial production is continuously optimized, thermosetting polyurethane itself and its production process are optimally designed.
Disclosure of Invention
The invention aims to provide a preparation method of an ultrahigh-hardness acrylic resin, which is put into use and solves the problems in the background technology.
In order to achieve the above object, the present invention discloses a thermosetting polyurethane comprising the following components,
50-100 parts of polyoxypropylene glycol, 10-30 parts of isophorone diisocyanate, 1-5 parts of dimethylolpropionic acid, 1-5 parts of 1-2 propylene glycol, 0.5 part of catalyst, 1-5 parts of triethylamine, 200-250 parts of deionized water and 5-20 parts of ketone hydrazine crosslinking monomer.
Also discloses a preparation method of the thermosetting polyurethane, which is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
s1, preparing a ketohydrazine crosslinking monomer by using a substance containing at least one amino group and at least one hydroxyl group and DAAM through a Michael addition reaction, and then adding metered deionized water to prepare a ketohydrazine crosslinking monomer aqueous solution;
s2, weighing polyalcohol and isocyanate according to the ratio of 5:1, adding the polyalcohol and the isocyanate into a reaction kettle, and reacting for 2 hours under the condition of keeping the temperature at 85-100 ℃;
s3, adding a proper amount of acetone, DMPA (2, 2-dimethylolpropionic acid), a small molecular chain extender and/or an internal crosslinking agent, and reacting at 70-80 ℃ for 1 h;
s4, controlling the temperature of the reaction kettle at 40-45 ℃, adding sulfonate, continuing to react for 0.5h, and adding triethylamine for neutralization;
s5, starting an emulsifying mechanism of the reaction kettle again, and adding 120g of deionized water under the condition of high-speed stirring for dispersing and emulsifying for 10 min;
s6, finally, dropwise adding and metering the ketohydrazine cross-linking monomer aqueous solution prepared in the step S1, removing acetone, and adding ADH to obtain the ketohydrazine cross-linking monomer aqueous solution.
Preferably, the substance containing at least one amine group and at least one hydroxyl group in step S1 is DETA (diethylenetriamine).
Preferably, the small molecule chain extender and the internal crosslinking agent are one or more of TMP (trimethylolpropane), castor oil and N303.
Preferably, the polyol comprises at least one or more of polyoxypropylene glycol, polyethylene adipate, polycaprolactone, hydroxyl-terminated polybutadiene, polytetramethylene ether glycol, polyethylene glycol and propylene glycol.
Preferably, the method for removing acetone in the step S6 is reduced pressure cooking.
The invention has the technical effects and advantages that: the thermosetting polyurethane and the preparation method thereof,
1. after the thermosetting polyurethane is cured, a network structure is formed due to intermolecular crosslinking, so that the thermosetting polyurethane has the advantages of high rigidity, high hardness, high temperature resistance, nonflammability, good product dimensional stability and excellent water resistance.
2. The preparation method of the thermosetting polyurethane is also disclosed, excessive crosslinking reaction temperature is not needed, the applicability is stronger, the process optimization is relatively simple, and the preparation method is suitable for popularization and use.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention discloses thermosetting polyurethane, which comprises the following components,
50-100 parts of polyoxypropylene glycol, 10-30 parts of isophorone diisocyanate, 1-5 parts of dimethylolpropionic acid, 1-5 parts of 1-2 propylene glycol, 0.5 part of catalyst, 1-5 parts of triethylamine, 200-250 parts of deionized water and 5-20 parts of ketone hydrazine crosslinking monomer.
After the thermosetting polyurethane is cured, a network structure is formed due to intermolecular crosslinking, so that the thermosetting polyurethane has the advantages of high rigidity, high hardness, high temperature resistance, non-flammability and good product size stability.
Also discloses a preparation method of the thermosetting polyurethane, which comprises the following steps,
s1, preparing a ketohydrazine crosslinking monomer by using a substance containing at least one amino group and at least one hydroxyl group and DAAM through a Michael addition reaction, and then adding metered deionized water to prepare a ketohydrazine crosslinking monomer aqueous solution;
s2, weighing polyalcohol and isocyanate according to the ratio of 5:1, adding the polyalcohol and the isocyanate into a reaction kettle, and reacting for 2 hours under the condition of keeping the temperature at 85-100 ℃;
s3, adding a proper amount of acetone, DMPA (2, 2-dimethylolpropionic acid), a small molecular chain extender and/or an internal crosslinking agent, and reacting at 70-80 ℃ for 1 h;
s4, controlling the temperature of the reaction kettle at 40-45 ℃, adding sulfonate, continuing to react for 0.5h, and adding triethylamine for neutralization;
s5, starting an emulsifying mechanism of the reaction kettle again, and adding 120g of deionized water under the condition of high-speed stirring for dispersing and emulsifying for 10 min;
s6, finally, dropwise adding and metering the ketohydrazine cross-linking monomer aqueous solution prepared in the step S1, removing acetone, and adding ADH to obtain the ketohydrazine cross-linking monomer aqueous solution.
Adding 20g of DETA and 32g of DAAM into a three-neck flask, reacting for 5 hours at the temperature of 45 ℃, and adding metered deionized water to prepare a ketohydrazine cross-linking monomer aqueous solution;
adding 100g of polyoxypropylene glycol and 20g of isocyanate into a reaction kettle, and reacting for 2 hours at the temperature of 85-90 ℃;
then adding 2g of hydrophilic chain extender dimethylolpropionic acid and 0.6g of 1-2 propylene glycol, and reacting for 1 h;
then adding 0.3g of stannous octoate, keeping the temperature for 3.5 hours, adding 2g of sulfonate at 45 ℃, and continuing to react for 0.5 hour;
then adding 2g of triethylamine for neutralization, adding 120g of deionized water under the condition of high-speed stirring for dispersion and emulsification for 10min, dropwise adding a metered ketohydrazine cross-linking monomer aqueous solution, removing acetone under reduced pressure, and adding 2g of ADH to obtain the required emulsion
The substance containing at least one amine group and at least one hydroxyl group in the step S1 is DETA (diethylenetriamine).
The chain extender and the internal cross-linking agent are one or more of TMP (trimethylolpropane), castor oil and N303.
The polyalcohol comprises at least one or more of polypropylene oxide glycol, polyethylene glycol adipate, polycaprolactone, hydroxyl-terminated polybutadiene, polytetramethylene ether glycol, polyethylene glycol and propylene glycol.
The method for removing acetone in the step S6 is reduced pressure cooking.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (6)
1. A thermoset polyurethane characterized by: comprises the following components in percentage by weight,
50-100 parts of polyoxypropylene glycol, 10-30 parts of isophorone diisocyanate, 1-5 parts of dimethylolpropionic acid, 1-5 parts of 1-2 propylene glycol, 0.5 part of catalyst, 1-5 parts of triethylamine, 200-250 parts of deionized water and 5-20 parts of ketone hydrazine crosslinking monomer.
2. A method for preparing the thermosetting polyurethane as claimed in claim 1, wherein: comprises the following steps of (a) carrying out,
s1, preparing a ketohydrazine crosslinking monomer by using a substance containing at least one amino group and at least one hydroxyl group and DAAM through a Michael addition reaction, and then adding metered deionized water to prepare a ketohydrazine crosslinking monomer aqueous solution;
s2, weighing polyalcohol and isocyanate according to the ratio of 5:1, adding the polyalcohol and the isocyanate into a reaction kettle, and reacting for 2 hours under the condition of keeping the temperature at 85-100 ℃;
s3, adding a proper amount of acetone, DMPA (2, 2-dimethylolpropionic acid), a small molecular chain extender and/or an internal crosslinking agent, and reacting at 70-80 ℃ for 1 h;
s4, controlling the temperature of the reaction kettle at 40-45 ℃, adding sulfonate, continuing to react for 0.5h, and adding triethylamine for neutralization;
s5, starting an emulsifying mechanism of the reaction kettle again, and adding 120g of deionized water under the condition of high-speed stirring for dispersing and emulsifying for 10 min;
s6, finally, dropwise adding and metering the ketohydrazine cross-linking monomer aqueous solution prepared in the step S1, removing acetone, and adding ADH to obtain the ketohydrazine cross-linking monomer aqueous solution.
3. The method for producing a thermosetting polyurethane according to claim 2, wherein: the substance containing at least one amine group and at least one hydroxyl group in the step S1 is DETA (diethylenetriamine).
4. The method for producing a thermosetting polyurethane according to claim 2, wherein: the chain extender and the internal cross-linking agent are one or more of TMP (trimethylolpropane), castor oil and N303.
5. The method for producing a thermosetting polyurethane according to claim 2, wherein: the polyalcohol comprises at least one or more of polypropylene oxide glycol, polyethylene glycol adipate, polycaprolactone, hydroxyl-terminated polybutadiene, polytetramethylene ether glycol, polyethylene glycol and propylene glycol.
6. The method for producing a thermosetting polyurethane according to claim 2, wherein: the method for removing acetone in the step S6 is reduced pressure cooking.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011232315.0A CN112266460A (en) | 2020-11-06 | 2020-11-06 | Thermosetting polyurethane and preparation method thereof |
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| CN202011232315.0A CN112266460A (en) | 2020-11-06 | 2020-11-06 | Thermosetting polyurethane and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2157111A1 (en) * | 2008-08-20 | 2010-02-24 | E. I. du Pont de Nemours and Company | Process for the production of polyurethane urea resin dispersions |
| CN102757546A (en) * | 2012-07-30 | 2012-10-31 | 富思特新材料科技有限公司 | Preparation method of self-crosslinking aqueous polyurethane for terrace |
| CN103805122A (en) * | 2014-02-13 | 2014-05-21 | 温州市大宝树脂有限公司 | Waterborne polyurethane patch adhesive and preparation method thereof |
| CN103980792A (en) * | 2014-05-30 | 2014-08-13 | 陕西科技大学 | Room-temperature ketone-hydrazine-crosslinked VOC (Volatile Organic Compounds)-free water-based paint and preparation method thereof |
| CN109337034A (en) * | 2018-09-26 | 2019-02-15 | 上海维凯光电新材料有限公司 | A kind of polyaminoester emulsion and its synthetic method of composite multiple cross-linking system |
| CN110305287A (en) * | 2019-07-22 | 2019-10-08 | 安徽聚合辐化化工有限公司 | A kind of light aqueous polyurethane and preparation method thereof |
-
2020
- 2020-11-06 CN CN202011232315.0A patent/CN112266460A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2157111A1 (en) * | 2008-08-20 | 2010-02-24 | E. I. du Pont de Nemours and Company | Process for the production of polyurethane urea resin dispersions |
| CN102757546A (en) * | 2012-07-30 | 2012-10-31 | 富思特新材料科技有限公司 | Preparation method of self-crosslinking aqueous polyurethane for terrace |
| CN103805122A (en) * | 2014-02-13 | 2014-05-21 | 温州市大宝树脂有限公司 | Waterborne polyurethane patch adhesive and preparation method thereof |
| CN103980792A (en) * | 2014-05-30 | 2014-08-13 | 陕西科技大学 | Room-temperature ketone-hydrazine-crosslinked VOC (Volatile Organic Compounds)-free water-based paint and preparation method thereof |
| CN109337034A (en) * | 2018-09-26 | 2019-02-15 | 上海维凯光电新材料有限公司 | A kind of polyaminoester emulsion and its synthetic method of composite multiple cross-linking system |
| CN110305287A (en) * | 2019-07-22 | 2019-10-08 | 安徽聚合辐化化工有限公司 | A kind of light aqueous polyurethane and preparation method thereof |
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