CN113861371A - Preparation method of self-extinction waterborne polyurethane - Google Patents
Preparation method of self-extinction waterborne polyurethane Download PDFInfo
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- CN113861371A CN113861371A CN202111166433.0A CN202111166433A CN113861371A CN 113861371 A CN113861371 A CN 113861371A CN 202111166433 A CN202111166433 A CN 202111166433A CN 113861371 A CN113861371 A CN 113861371A
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- polyurethane
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
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- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
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- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 1
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 1
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- NKZQKINFDLZVRY-UHFFFAOYSA-N n-butylbutan-1-amine;toluene Chemical compound CC1=CC=CC=C1.CCCCNCCCC NKZQKINFDLZVRY-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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Images
Classifications
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
-
- 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
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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
- 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
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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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
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- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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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- 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
- C08G18/83—Chemically modified polymers
- C08G18/837—Chemically modified polymers by silicon containing compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a preparation method of self-extinction polyurethane, which comprises the following steps: dehydrating, preparing prepolymer, diluting, emulsifying and obtaining finished products. The prepared waterborne polyurethane has the advantages of large particle size, low glossiness, excellent performance, rough microscopic surface, good mechanical property, mechanical property and high temperature resistance.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a preparation method of self-extinction waterborne polyurethane.
Background
Waterborne Polyurethane (WPU) is an aqueous solution, a dispersoid or a water emulsion formed by dispersing polyurethane resin in water, and is widely applied to the fields of light textiles, leather, buildings, automobiles and the like due to the advantages of no toxicity, no combustion, green environmental protection and the like. The aqueous polyurethane can be divided into high gloss and low gloss according to the appearance gloss, and along with the change of aesthetic concepts of people, the extinction aqueous polyurethane is widely used in the surface finishing process of leather, fabric and paper due to natural appearance, good visual effect and excellent hand feeling.
At present, two common methods for matting waterborne polyurethane are adopted, one method is to add a certain amount of matting agent into resin, but the addition of the matting agent reduces the stability of a finishing agent system and reduces the bending resistance, scratch resistance and wear resistance of a coating, and the addition of the matting agent increases extra cost. The other method is to adopt self-extinction resin, not add flatting agent, but increase the grain diameter of polyurethane in the synthesis process, increase the surface roughness after the polyurethane film forming, and make the incident light perform random diffuse reflection, thereby reducing the surface glossiness.
CN111154391A A high temperature resistant self-extinction polyurethane surface treating agent, a preparation method and an application thereof, the high temperature resistant self-extinction polyurethane surface treating agent with multiple molecular structure branched chains and large micelle particle volume is synthesized by using HDI, IPDI and TDI tripolymer. However, the trimer used belongs to polyfunctional isocyanate, and in the synthesis process, because the winding structure between molecules is complex, the reaction viscosity is increased, and the gelation phenomenon is likely to occur, and the process is not easy to control in the actual production.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above and/or other problems occurring in the prior art polyurethane products.
Therefore, one of the purposes of the present invention is to overcome the defects of the existing polyurethane products and provide a preparation method of self-extinction polyurethane.
To solve the above technical problem, according to an aspect of the present invention, the present invention provides the following technical solutions: a preparation method of self-extinction polyurethane comprises the following steps:
and (3) dehydrating: heating and vacuumizing polyether polyol, and drying for a period of time;
preparing a prepolymer: and (3) after the dried polyol is cooled, adding diisocyanate, heating, controlling the-NCO content to reach a set value, cooling, adding a chain extender, a hydrophilic chain extender and a catalyst, uniformly stirring, heating to carry out chain extension reaction, and obtaining the water-based polyurethane prepolymer after the-NCO content reaches the set value again.
Diluting and emulsifying: adding a neutralizer and water, and uniformly stirring;
preparing a finished product: adding a rear chain extender, a silane coupling agent and a defoaming agent, uniformly stirring, heating, carrying out heat preservation reaction, cooling, and finally filtering to obtain the self-extinction type solvent-free waterborne polyurethane.
In the preparation method of the self-extinction polyurethane, the polyether polyol comprises one or two of polytetrahydrofuran glycol, polypropylene glycol and polyethylene glycol monomethyl alcohol in dehydration.
The preparation method of the self-extinction type polyurethane comprises the steps of adding diisocyanate into a prepolymer, and controlling the content of-NCO to be 4.0-5.0%.
The preparation method of the self-extinction type polyurethane comprises the steps of adding a chain extender, a hydrophilic chain extender and a catalyst into a prepolymer, wherein the-NCO content is 3.0-3.5%.
The preparation method of the self-extinction polyurethane is characterized in that the water content of the dried polyether polyol in the dehydration process is less than or equal to 0.05 percent.
As the preparation method of the self-extinction polyurethane, the diisocyanate is isophorone diisocyanate.
The preparation method of the self-extinction polyurethane is characterized in that the heating temperature in dehydration is 100-130 ℃.
The preparation method of the self-extinction polyurethane comprises the steps of adding diisocyanate into a prepolymer, and heating to control the temperature to be 70-100 ℃.
The preparation method of the self-extinction type polyurethane comprises the steps of adding a chain extender, a hydrophilic chain extender and a catalyst into a prepolymer, and heating to control the temperature to be 70-100 ℃.
The preparation method of the self-extinction polyurethane is characterized in that in the prepared finished product, the temperature is kept at 50-80 ℃ through heat preservation treatment.
The invention provides a preparation method of self-extinction polyurethane, which has the following beneficial effects:
1) the invention adopts a prepolymer synthesis method, and controls the molecular weight and viscosity of the prepolymer by controlling the r value of the prepolymer (the r value is the ratio of the amount of all-NCO group substances in isocyanate to the amount of all-OH substances in polyol, chain extender and hydrophilic chain extender). When the r value is in a proper range, the proportion of hard segments of the polyurethane is increased, and the degree of post chain extension is higher, so that the ionic strength of the emulsion is enhanced, the particle size is increased, and finally the solvent-free waterborne polyurethane with large particle size, low glossiness and excellent performance is obtained.
2) In the invention, hydrazine hydrate is used as a post-chain extender, and when the reaction is carried out, the hydrazine hydrate reacts with isocyanate groups (-NCO) in latex particles and also reacts with-NCO in surrounding latex particles, so that 2 latex particles are fused with each other to increase the particle size. And hydrazine hydrate is used for chain extension, the distance between the two hard sections is short, deformation is difficult to occur, the size of latex particles can be fixed, regular microspheres are formed, and a micro rough surface is generated.
3) The silane coupling agent is successfully connected into the waterborne polyurethane system in a chemical bond mode for modification, so that the defects of poor mechanical property and high temperature resistance of the original polyurethane are overcome;
4) the prepared self-extinction solvent-free waterborne polyurethane emulsion has low viscosity, excellent storage stability, low glossiness after film forming, excellent mechanical property and good high temperature resistance. Tests show that the emulsion can be stably stored for more than 6 months, the 60-degree gloss after film forming is reduced to below 2.0, the tensile strength can reach above 50MPa, and the film is baked at 120 ℃ for 7 days without obvious yellowing and stickiness;
5) the preparation method of the self-extinction waterborne polyurethane has the advantages of simple process, easily controlled conditions and easy realization of large-scale production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a diagram of a polyurethane film prepared from the finished polyurethane of example 2 after baking at 120 ℃ for 7 d;
FIG. 2 is a schematic representation of resin H-203NB after baking at 120 ℃ for 7 d.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. The following examples are set forth to enable those skilled in the art to practice the invention.
The names, source manufacturers, specifications and types of the raw materials adopted in the embodiment of the invention are shown in table 1:
TABLE 1 raw materials, sources, specifications and models
| Name of raw materials | Source manufacturer | Specification of | Model number |
| Polytetrahydrofuran ether glycol | Jining HuaKai resin Co Ltd | Industrial grade | PTMG2000 |
| Polypropylene glycol (Mn 3000) | SINOPHARM CHEMICAL REAGENT Co.,Ltd. | Analytical purity | PPG3000 |
| Isophorone diisocyanate | SINOPHARM CHEMICAL REAGENT Co.,Ltd. | Analytical purity | IPDI |
| Hexamethylene diisocyanate | SINOPHARM CHEMICAL REAGENT Co.,Ltd. | Analytical purity | HDI |
| Stannous octoate | Aladdin | Analytical purity | T～9 |
| Trimethylolpropane | Shanghai and melt chemical Co., Ltd | Industrial grade | TMP |
| 1, 4-butanediol | Aladdin | Analytical purity | BDO |
| Polyethylene glycol monomethyl ether | Boston (r) solution | Industrial grade | Ymer～N120 |
| Dimethylolpropionic acid | SINOPHARM CHEMICAL REAGENT Co.,Ltd. | Analytical purity | DMPA |
| Dimethylolbutanoic acid | SINOPHARM CHEMICAL REAGENT Co.,Ltd. | Analytical purity | DMBA |
| Triethylamine | SINOPHARM CHEMICAL REAGENT Co.,Ltd. | Analytical purity | TEA |
| Dimethylethanolamine | SINOPHARM CHEMICAL REAGENT Co.,Ltd. | Analytical purity | DMEA |
| Hydrazine hydrate | SINOPHARM CHEMICAL REAGENT Co.,Ltd. | Analytical purity | H2N2·H2O |
| Defoaming agent | Tegagbacke technologies, Inc | Industrial grade | TG-F156 |
| Deionized water | Self-made | / | / |
| Gamma-aminopropyltriethoxysilane | Needy New Material technology Co Ltd | Industrial grade | KH-550 |
| 3-aminopropyltrimethoxysilane | Needy New Material technology Co Ltd | Industrial grade | KH-540 |
The method for determining the-NCO content used in the examples of the present invention is as follows: the sample in the reaction was selected and weighed to 0.001 g. The sample was placed in a clean 250mL Erlenmeyer flask. Then, 40mL of a 0.1mol/L di-n-butylamine-toluene solution was accurately transferred by a pipette and added to the sample, and the mixture was shaken to be mixed uniformly and allowed to stand at room temperature for 40 min. After the reaction was completed, 50ml of isopropyl alcohol was added, and the bottle mouth was washed to terminate the reaction. 3 drops of bromocresol green ethanol solution (mass fraction is 0.1%) are added dropwise as an indicator, and the system is blue. Then titrating with 0.1mol/L hydrochloric acid standard solution until the blue color disappears, gradually changing from green to cyan and finally changing to yellow, keeping for 1min, and recording the volume of the consumed hydrochloric acid standard solution as V at the end point of titration2(ii) a According to the steps, a blank control test is carried out on an weighed sample, and the volume of the consumed hydrochloric acid standard solution is V1(ii) a Then substituting the mass fraction into the following formula for calculation to obtain the mass fraction of the-NCO in the mixture at the moment.
NCO％＝(V1～V2)C*0.042/M×100％
In the formula, V1The number of milliliters of hydrochloric acid standard solution used for the blank test;
V2the number of milliliters of hydrochloric acid standard solution used for the titration test;
c is the molar concentration of the standard hydrochloric acid solution, mol/L;
m is the mass gram number of the sample, g;
example 1
Weighing 100-300 g of polyether polyol in a closed container, raising the temperature to 100-130 ℃, adjusting the pressure to be less than or equal to-0.08 MPa, and drying for 0.5-2 h under constant pressure until the water content of the polyol is less than 0.05%.
Reducing the temperature of the polyol to be below 80 ℃, then adding 30-80 g of diisocyanate into the polyol by using a constant pressure funnel, uniformly stirring, gradually increasing the temperature to 70-100 ℃, and reacting for 1-3 h at constant temperature until the-NCO content in the mixture reaches 2.00-5.00%. And then cooling to below 80 ℃, adding 0-4 g of dried chain extender, 5-10 g of dried hydrophilic chain extender and 0.65-5 g of catalyst, uniformly stirring, gradually heating to 70-100 ℃, and carrying out chain extension reaction for 2-5 hours under the constant temperature condition until the-NCO content in the mixture reaches the design value again, thus obtaining the solvent-free waterborne polyurethane prepolymer. The used chain extender and the water-based chain extender are dried until the water content is less than 0.05 percent,
transferring the waterborne polyurethane prepolymer into an emulsifying kettle, opening a stirring device, adding 3-8 g of neutralizing agent, stirring for 5-30 min for neutralization, then adjusting the rotating speed to high-speed stirring, quickly adding 400-700 g of deionized water, and stirring for 10-30 min until the mixture is completely and uniformly dispersed.
The method comprises the following steps of carrying out chain growth reaction on a polyurethane prepolymer and a rear chain extender in a water solution, proposing that the molecular weight of polyurethane is not increased and the particle size is increased, slowly adding 10-70 g of a rear chain extender hydrazine hydrate solution with the mass fraction of 10-30% for reaction for 10-30 min, then slowly dropwise adding 2-10 g of a silane coupling agent and 3-8 g of a defoaming agent, uniformly stirring, slowly heating to 50-80 ℃, carrying out heat preservation reaction for 1-1.5 h, stopping the reaction, then cooling until the temperature reaches the room temperature, and finally filtering to obtain the self-extinction type solvent-free waterborne polyurethane.
Example 2
Adding 168g of polytetrahydrofuran glycol (PTMG2000) into a closed container, stirring at the rotating speed of 270rpm, heating and vacuumizing, heating when the temperature of the used polyether polyol reaches 105 ℃ and the vacuum pressure is less than or equal to-0.08 MPa, and carrying out vacuum dehydration for 2h under the conditions that the temperature is kept between 105 ℃ and 110 ℃ and the pressure is kept less than or equal to-0.08 MPa.
When the water content in the polyol is less than 0.05, closing the vacuum pump, performing cooling treatment, when the temperature is reduced to be below 75 ℃, slowly adding 52g of isophorone diisocyanate through a constant-pressure funnel, then stirring and heating at the rotating speed of 350r/min, and when the temperature is increased to be 90 ℃, performing constant-temperature reaction for 1 h. And (2) measuring the content of-NCO in the mixture by using a titration method, when the content is 4.0-5.0%, cooling to 75 ℃, adding 3g of dried 1, 4-butanediol, 9g of dried dimethylolpropionic acid and 8 drops (about 0.7g) of stannous octoate, stirring at the rotating speed of 350r/min, heating to 85 ℃, and then keeping the temperature for carrying out constant-temperature chain extension reaction for 3 hours until the content of-NCO in the mixture reaches the design value again, thus obtaining the solvent-free waterborne polyurethane prepolymer.
And (3) immediately transferring 218g of the obtained prepolymer into another container, adding 5g of dimethylethanolamine into the obtained solvent-free waterborne polyurethane, stirring for 5min at the rotating speed of 500rpm, increasing the rotating speed to 2000rpm after the prepolymer is completely neutralized, adding 500g of deionized water, and stirring for 10 min.
And slowly adding 21g of deionized water into the stirred emulsion to dilute the emulsion into a hydrazine hydrate solution with the mass fraction of 10%, stirring the mixture at a high speed of 2000rpm for 10min, slowly dropwise adding 5g of gamma-aminopropyltriethoxysilane (KH-550), continuously stirring the mixture for 10min, dropwise adding 0.2g of defoaming agent, reducing the stirring speed to 800r/min, and stirring and defoaming the mixture for 5 min. And then transferring the mixture into a container with temperature measurement and stirring functions, stirring and heating at the rotating speed of 400r/min, keeping the temperature at the constant temperature for reaction for 1h when the temperature rises to 60 ℃, turning off an oil bath pan to start cooling, and filtering the emulsion when the temperature drops to room temperature to obtain the silane coupling agent modified solvent-free waterborne polyurethane.
Example 3
Adding 200g of polypropylene glycol (PPG3000) and 15g of polyethylene glycol monomethyl ether (YMR-N120) into a closed container, stirring at the rotating speed of 200-300 rpm, heating and vacuumizing, timing when the temperature of the used polyether glycol reaches 105 ℃ and the vacuum pressure is less than or equal to-0.08 MPa, keeping the temperature between 105 ℃ and 110 ℃, and carrying out vacuum dehydration for 2 hours under the condition that the pressure is less than or equal to-0.08 MPa.
When the water content in the polyol is less than 0.05, the vacuum pump is closed, the temperature is reduced, when the temperature is reduced to be below 75 ℃, 52g of isophorone diisocyanate is slowly added through a constant-pressure funnel, then stirring and heating are carried out, and when the temperature is increased to be 90 ℃, the constant-temperature reaction is carried out for 1 hour. And (2) measuring the content of-NCO in the mixture by using a titration method, when the content is 4.0-5.0%, cooling to 75 ℃, then adding 1.04g of dried trimethylolpropane, 6.83g of dried dimethylolbutyric acid and 10 drops (about 0.8g) of stannous octoate, stirring uniformly, gradually heating to 85 ℃, and then carrying out constant-temperature chain extension reaction for 3 hours at the temperature until the content of-NCO in the mixture reaches the design value again, thus obtaining the solvent-free waterborne polyurethane prepolymer.
218.63g of the obtained prepolymer is immediately transferred to another container, 4.12g of triethylamine is added into the obtained solvent-free waterborne polyurethane, the mixture is stirred for 5min at the rotating speed of 500rpm, after the prepolymer is completely neutralized, the rotating speed is increased to 2000rpm, 418g of deionized water is added, and the mixture is stirred for 10 min.
And slowly adding 13g of deionized water into the stirred emulsion to dilute the solution to a hydrazine hydrate solution with the mass fraction of 10%, stirring the solution at a high speed of 2000rpm for 10min, slowly dropwise adding 3.43g of 3-aminopropyltrimethoxysilane (KH-540), continuously stirring the solution for 10min, dropwise adding 0.2g of a defoaming agent, reducing the stirring speed to 800r/min, and stirring and defoaming the solution for 5 min. And then transferring the mixture into a container with temperature measurement and stirring functions, heating while stirring, keeping the temperature at the constant temperature for reaction for 1h when the temperature rises to 60 ℃, turning off an oil bath pot, starting to cool, and filtering the emulsion when the temperature drops to room temperature to obtain the silane coupling agent modified solvent-free waterborne polyurethane.
Example 4
The silane coupling agent-modified solvent-free aqueous polyurethanes prepared in examples 2 and 3 were subjected to measurement of gloss, temperature resistance, organic solvent content and breaking strength, and the measured data were recorded in table 1 by the following methods:
gloss: testing the gloss at 60 ℃ by using a gloss tester of GB 9754;
temperature resistance: the prepared polyurethane material is made into a polyurethane film and is placed at 120 ℃ for 7 days, and the appearance change of the film is observed and compared;
breaking strength: a polyurethane mechanical property measuring method in GB/1040-;
content of organic solvent: refer to the assay method in GB/24409-.
TABLE 1 gloss, temperature resistance, organic solvent content, elongation at break, and breaking strength data for the aqueous polyurethanes prepared in examples 2 and 3 and for the control H-203NB
From table 1, the waterborne polyurethane obtained in the invention has a remarkable low-gloss effect, and meanwhile, the temperature resistance, the organic solvent content, the fracture growth rate and the fracture strength are remarkably improved compared with conventional products represented by H-203 NB.
From FIGS. 1 and 2, it can be seen that the polyurethanes produced in my invention produced further finished polyurethane films with a significantly lower gloss effect.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of self-extinction polyurethane is characterized by comprising the following steps: the method comprises the following steps:
and (3) dehydrating: heating and vacuumizing polyether polyol, and drying for a period of time;
preparing a prepolymer: and (3) after the dried polyol is cooled, adding diisocyanate, heating, controlling the-NCO content to reach a set value, cooling, adding a chain extender, a hydrophilic chain extender and a catalyst, uniformly stirring, heating to carry out chain extension reaction, and obtaining the water-based polyurethane prepolymer after the-NCO content reaches the set value again.
Diluting and emulsifying: adding a neutralizer and water, and uniformly stirring;
preparing a finished product: adding a rear chain extender, a silane coupling agent and a defoaming agent, uniformly stirring, heating, carrying out heat preservation reaction, cooling, and finally filtering to obtain the self-extinction type solvent-free waterborne polyurethane.
2. A process for preparing a self-matting polyurethane according to claim 1, characterized in that: in the dehydration, the polyether polyol comprises one or two of polytetrahydrofuran glycol, polypropylene glycol and polyethylene glycol monomethyl alcohol.
3. A process for preparing a self-matting polyurethane according to claim 1, characterized in that: in the preparation of the prepolymer, after diisocyanate is added, the content of-NCO is controlled to be 4.0-5.0%.
4. A process for preparing a self-matting polyurethane according to claim 1, characterized in that: and after a chain extender, a hydrophilic chain extender and a catalyst are added into the prepared prepolymer, the-NCO content is 3.0-3.5%.
5. A process for preparing a self-matting polyurethane according to claim 1, characterized in that: and in the dehydration, the water content of the dried polyether polyol is less than or equal to-0.08 MPa.
6. A process for preparing a self-matting polyurethane according to claim 1, characterized in that: the diisocyanate is isophorone diisocyanate.
7. A process for preparing a self-matting polyurethane according to claim 1, characterized in that: and in the dehydration, the heating temperature is 100-130 ℃.
8. A process for preparing a self-matting polyurethane according to claim 1, characterized in that: in the preparation of the prepolymer, diisocyanate is added and heated to control the temperature to be 70-100 ℃.
9. A process for preparing a self-matting polyurethane according to claim 1, characterized in that: in the preparation of the prepolymer, the chain extender, the hydrophilic chain extender and the catalyst are added and then heated to control the temperature to be 70-100 ℃.
10. A process for preparing a self-matting polyurethane according to claim 1, characterized in that: in the finished product, the heat preservation treatment is to keep the temperature at 50-80 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024099927A1 (en) * | 2022-11-09 | 2024-05-16 | Covestro Deutschland Ag | Aqueous polyurethane-polyurea dispersion |
| WO2024099926A1 (en) * | 2022-11-09 | 2024-05-16 | Covestro Deutschland Ag | A composition, a preparation method and use thereof |
| CN119307171A (en) * | 2024-10-15 | 2025-01-14 | 中山市盈丰泰水性涂料有限公司 | Environmentally friendly water-based skin-feel covering slurry with release paper-free effect, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019077A (en) * | 2019-12-27 | 2020-04-17 | 红宝丽集团股份有限公司 | Solvent-free polyurethane dispersion with controllable particle size and aqueous polyurethane coating liquid |
| CN111087568A (en) * | 2019-12-13 | 2020-05-01 | 北京高盟新材料股份有限公司 | Solvent-resistant self-extinction waterborne polyurethane resin and preparation method thereof |
| CN111333808A (en) * | 2020-02-18 | 2020-06-26 | 明新孟诺卡(辽宁)新材料有限公司 | Preparation method of solvent-free waterborne polyurethane |
| CN111944111A (en) * | 2019-04-30 | 2020-11-17 | 万华化学集团股份有限公司 | Aqueous self-extinction polyurethane dispersion, preparation method and composition thereof |
| CN112694591A (en) * | 2020-12-25 | 2021-04-23 | 明新孟诺卡(江苏)新材料有限公司 | Preparation method of silane coupling agent modified solvent-free waterborne polyurethane |
-
2021
- 2021-09-30 CN CN202111166433.0A patent/CN113861371A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111944111A (en) * | 2019-04-30 | 2020-11-17 | 万华化学集团股份有限公司 | Aqueous self-extinction polyurethane dispersion, preparation method and composition thereof |
| CN111087568A (en) * | 2019-12-13 | 2020-05-01 | 北京高盟新材料股份有限公司 | Solvent-resistant self-extinction waterborne polyurethane resin and preparation method thereof |
| CN111019077A (en) * | 2019-12-27 | 2020-04-17 | 红宝丽集团股份有限公司 | Solvent-free polyurethane dispersion with controllable particle size and aqueous polyurethane coating liquid |
| CN111333808A (en) * | 2020-02-18 | 2020-06-26 | 明新孟诺卡(辽宁)新材料有限公司 | Preparation method of solvent-free waterborne polyurethane |
| CN112694591A (en) * | 2020-12-25 | 2021-04-23 | 明新孟诺卡(江苏)新材料有限公司 | Preparation method of silane coupling agent modified solvent-free waterborne polyurethane |
Non-Patent Citations (3)
| Title |
|---|
| 丁琳 等: "氨基硅氧烷改性水性聚氨酯自消光树脂的制备及性能", 《高分子材料科学与工程》 * |
| 曹仙丽: "本体消光型水性聚氨酯的制备、性质及有机硅改性研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 董永兵 等: "水合肼对水性聚氨酯自消光树脂性能的影响", 《中国皮革》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024099927A1 (en) * | 2022-11-09 | 2024-05-16 | Covestro Deutschland Ag | Aqueous polyurethane-polyurea dispersion |
| WO2024099926A1 (en) * | 2022-11-09 | 2024-05-16 | Covestro Deutschland Ag | A composition, a preparation method and use thereof |
| CN119307171A (en) * | 2024-10-15 | 2025-01-14 | 中山市盈丰泰水性涂料有限公司 | Environmentally friendly water-based skin-feel covering slurry with release paper-free effect, preparation method and application thereof |
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