CN112266444A - Polyacrylate modified waterborne polyurethane composite emulsion and preparation method thereof - Google Patents
Polyacrylate modified waterborne polyurethane composite emulsion and preparation method thereof Download PDFInfo
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- CN112266444A CN112266444A CN202011218034.XA CN202011218034A CN112266444A CN 112266444 A CN112266444 A CN 112266444A CN 202011218034 A CN202011218034 A CN 202011218034A CN 112266444 A CN112266444 A CN 112266444A
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- waterborne polyurethane
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 45
- 239000000839 emulsion Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 34
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000004945 emulsification Methods 0.000 title description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- 239000013638 trimer Substances 0.000 claims description 7
- 150000002009 diols Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 3
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000005303 weighing Methods 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000957678 Mus musculus Cytochrome P450 7B1 Proteins 0.000 description 1
- 101000957679 Rattus norvegicus 25-hydroxycholesterol 7-alpha-hydroxylase Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BQYIXOPJPLGCRZ-REZTVBANSA-N chembl103111 Chemical compound CC1=NC=C(CO)C(\C=N\NC(=O)C=2C=CN=CC=2)=C1O BQYIXOPJPLGCRZ-REZTVBANSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
Abstract
The invention belongs to the technical field of composite emulsion, and particularly relates to polyacrylate modified waterborne polyurethane composite emulsion and a preparation method thereof.
Description
Technical Field
The invention belongs to the technical field of composite emulsion, and particularly relates to polyacrylate modified waterborne polyurethane composite emulsion and a preparation method thereof.
Background
The waterborne polyurethane material is widely applied to the fields of coatings, printing inks, adhesives and the like at present due to the excellent performance and the environmental protection characteristic of the waterborne polyurethane material, but the application of the waterborne polyurethane material is limited to a great extent due to the high price of the used raw material isocyanate. The acrylic emulsion has good aging resistance and color and gloss retention, and low cost, and well makes up for the defects of polyurethane materials. Therefore, the waterborne polyurethane and the waterborne polyacrylate are combined to prepare the waterborne polyurethane-polyacrylate composite emulsion, and a product with high cost performance can be obtained. In recent years, aqueous polyurethane-polyacrylate composite emulsion (hereinafter referred to as PUA composite emulsion) has been rapidly developed. The existing methods for preparing the PUA composite emulsion mainly comprise two methods: firstly, the water-based polyurethane and the water-based polyacrylate resin are prepared by cold splicing; secondly, dripping an acrylate monomer for polymerization on the basis of the aqueous polyurethane emulsion to prepare the core-shell composite emulsion. The PUA composite emulsion prepared by the two methods is still a physical mixture of polyurethane and polyacrylate in essence, but the composite emulsion prepared by physical blending has the compatibility problem and cannot exert the advantages of the two components to the maximum extent. The focus of current research is how to combine polyurethane and polyacrylate components by means of chemical bonds. Although various methods have been disclosed, the properties and cost of the obtained PUA composite emulsion are difficult to be compatible, especially, the electrolyte resistance and storage stability of the PUA composite emulsion are insufficient, and the water resistance and mechanical properties of the emulsion after film formation cannot meet the application requirements. On the other hand, the side chain of the PUA composite emulsion resin is functionally modified, so that the prepared product can obtain certain specific properties, and further certain specific requirements of the product in practical application are met, but a reliable preparation method cannot be provided at present, and the emulsion with good stability is obtained.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polyacrylate modified waterborne polyurethane composite emulsion and a preparation method thereof, and the polyacrylate modified waterborne polyurethane composite emulsion has good thermal stability.
The invention relates to polyacrylate modified waterborne polyurethane composite emulsion which comprises, by weight, 5-8 parts of polyester diol, 5-7 parts of diisocyanate, 4-6 parts of dimethylolbutyric acid, 4-6 parts of trimethylolpropane, 15-25 parts of methyl methacrylate, 20-25 parts of butyl acrylate, 3-5 parts of hydroxyethyl methacrylate, 25-35 parts of triethylamine, 20-25 parts of deionized water and 1-2 parts of hexamethylene diisocyanate trimer.
Preferably, the polyurethane adhesive comprises the following components, by weight, 7 parts of polyester diol, 6.2 parts of diisocyanate, 5.3 parts of dimethylolbutyric acid, 5 parts of trimethylolpropane, 20 parts of methyl methacrylate, 21 parts of butyl acrylate, 4 parts of hydroxyethyl methacrylate, 30 parts of triethylamine, 22 parts of deionized water and 1.2 parts of hexamethylene diisocyanate trimer.
Preferably, the polyacrylate modified waterborne polyurethane composite emulsion also comprises 2-3 parts of sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 1-2 mol/L.
The invention also provides a preparation method of the polyacrylate modified waterborne polyurethane composite emulsion, which comprises the steps of mixing polyester diol, diisocyanate, dimethylolbutyric acid, trimethylolpropane, methyl methacrylate and butyl acrylate, stirring and reacting at 70-80 ℃ to obtain a PU prepolymer, adding hydroxyethyl methacrylate into the PU prepolymer to end-cap the PU prepolymer, reacting for a period of time, adding triethylamine to neutralize the dimethylolbutyric acid, stirring and adding a sodium hydroxide solution after reacting for a period of time, dropwise adding a hexamethylene diisocyanate trimer after reacting for a period of time, stirring, and obtaining the polyacrylate modified waterborne polyurethane composite emulsion after the reaction is finished.
Stirring and reacting at 70-80 ℃ for 2-3 h. And adding hydroxyethyl methacrylate into the PU prepolymer to carry out end capping on the PU prepolymer, and reacting for 20-30 min. Adding triethylamine to neutralize dimethylolbutyric acid, and reacting for 15-20 min. Adding deionized water dropwise for reaction for 110-120 min. Dropwise adding hexamethylene diisocyanate tripolymer, stirring, and reacting for 120-150 min.
The polyacrylate modified waterborne polyurethane composite emulsion has the beneficial effects that the polyacrylate modified waterborne polyurethane composite emulsion has better thermal stability and still has better performance at high temperature.
Detailed Description
Example 1
Weighing a proper amount of dried PCL1000 (polyester dihydric alcohol), IPDI (diisocyanate), DMBA (dimethylolbutyric acid), TMP (trimethylolpropane) and MMA (methyl methacrylate) and BA (butyl acrylate) mixed solution serving as a solvent, adding the mixed solution into a reaction kettle, stirring and reacting at the temperature of 70-80 ℃ for 120-160min, and then adding a proper amount of HEMA (hydroxyethyl methacrylate) to terminate the PU prepolymer; after reacting for 20-30min, adding TEA (triethylamine) to neutralize DMBA (dimethylolbutanoic acid), and reacting for about 15-20 min; adding a certain amount of NaOH solution (the concentration is 1mol/L) under high-speed stirring, and then dropwise adding a plurality of amounts of deionized water to initiate the free radical polymerization of the vinyl monomer in the system. After the reaction time is 110-.
Formulation (unit kg): the weight ratio of PCL1000, IPDI, DMBA, TMP, MMA, BA, HEMA, TEA, NaOH solution, TEA, deionized water and PIH was 7:6.2:5.3:5:20:21:4: 2.4:30:22: 1.2.
Comparative example 1
Adding 1g of polypropylene glycol, 20g of isophorone diisocyanate and 0.1g of 2, 2-dimethylolpropionic acid into a four-neck flask, and dissolving with 12g of acetone; heating to 100 ℃ to start reaction, reacting for 80 minutes, cooling to 30 ℃, adding 0.1g of triethylamine, and neutralizing for 30 minutes; adding 15g of distilled water, and dispersing for 30 minutes by high-speed stirring (the rotating speed is 120r/min) to obtain the waterborne polyurethane emulsion. And mixing the aqueous polyurethane emulsion and the polyacrylate emulsion according to the weight ratio of 1:2 to obtain the emulsion.
Experimental example 1
(l) The preparation of PUA adhesive film comprises weighing 40g of emulsion, pouring into a polytetrafluoroethylene mold, naturally drying at room temperature for 48h, drying in an oven at 50 deg.C for 4h, and drying at 80 deg.C for 4 h. PUA adhesive films having a thickness of about l mm were prepared and stored in a silica gel dryer for further use.
(2) And (3) TG analysis of the adhesive film, namely performing thermal weight loss analysis on the adhesive film by using an HCT-1 type thermobalance under the conditions that the Nz flow is 25mL/min and the heating rate is 10 ℃/min and the temperature is in a range of 25-800 ℃.
| Emulsion and method of making | Thermal stability |
| Example 1 | The weight loss rate is 10-13 wt% |
| Comparative example 1 | The weight loss rate is 22-27 wt% |
Through the analysis of the weight loss ratio, it can be found that the thermal stability of the present invention is significantly superior to that of comparative example 1.
Claims (9)
1. The polyacrylate modified waterborne polyurethane composite emulsion is characterized by comprising, by weight, 5-8 parts of polyester diol, 5-7 parts of diisocyanate, 4-6 parts of dimethylolbutyric acid, 4-6 parts of trimethylolpropane, 15-25 parts of methyl methacrylate, 20-25 parts of butyl acrylate, 3-5 parts of hydroxyethyl methacrylate, 25-35 parts of triethylamine, 20-25 parts of deionized water and 1-2 parts of hexamethylene diisocyanate trimer.
2. The polyacrylate modified waterborne polyurethane composite emulsion as claimed in claim 1, which comprises, by weight, 7 parts of polyester diol, 6.2 parts of diisocyanate, 5.3 parts of dimethylolbutyric acid, 5 parts of trimethylolpropane, 20 parts of methyl methacrylate, 21 parts of butyl acrylate, 4 parts of hydroxyethyl methacrylate, 30 parts of triethylamine, 22 parts of deionized water, and 1.2 parts of hexamethylene diisocyanate trimer.
3. The polyacrylate modified waterborne polyurethane composite emulsion of claim 1, further comprising 2 to 3 parts of sodium hydroxide solution.
4. A method for preparing the polyacrylate modified waterborne polyurethane composite emulsion as claimed in any one of claims 1 to 3, wherein the method comprises the steps of mixing polyester diol, diisocyanate, dimethylolbutyric acid, trimethylolpropane, methyl methacrylate and butyl acrylate, stirring and reacting at 70-80 ℃ to obtain a PU prepolymer, adding hydroxyethyl methacrylate into the PU prepolymer to end-cap the PU prepolymer, reacting for a period of time, adding triethylamine to neutralize the dimethylolbutyric acid, reacting for a period of time, stirring, adding a sodium hydroxide solution, adding deionized water, reacting for a period of time, adding hexamethylene diisocyanate trimer, stirring, and reacting to obtain the polyacrylate modified waterborne polyurethane composite emulsion.
5. The method for preparing the polyacrylate modified waterborne polyurethane composite emulsion as claimed in claim 4, wherein the reaction is carried out under stirring at 70-80 ℃ for 2-3 h.
6. The method for preparing the polyacrylate modified waterborne polyurethane composite emulsion as claimed in claim 4, wherein hydroxyethyl methacrylate is added into the PU prepolymer to cap the PU prepolymer for reaction for 20-30 min.
7. The method for preparing the polyacrylate modified waterborne polyurethane composite emulsion as claimed in claim 4, wherein triethylamine is added to neutralize dimethylolbutyric acid, and the reaction lasts for 15-20 min.
8. The method for preparing the polyacrylate modified waterborne polyurethane composite emulsion as claimed in claim 4, wherein the reaction is performed by dropping deionized water for 110-120 min.
9. The method for preparing the polyacrylate modified waterborne polyurethane composite emulsion as claimed in claim 4, wherein the hexamethylene diisocyanate trimer is added dropwise, stirred, and reacted for 120-150 min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011218034.XA CN112266444A (en) | 2020-11-04 | 2020-11-04 | Polyacrylate modified waterborne polyurethane composite emulsion and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011218034.XA CN112266444A (en) | 2020-11-04 | 2020-11-04 | Polyacrylate modified waterborne polyurethane composite emulsion and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977282A (en) * | 2012-12-06 | 2013-03-20 | 陕西科技大学 | Preparation method of anionic organic-solvent-free and emulsifier-free polyurethane microemulsion |
| CN107722236A (en) * | 2017-11-07 | 2018-02-23 | 陕西科技大学 | A kind of organic-silicon-modified preparation method and application from delustring aqueous polyurethane of use for synthetic leather |
-
2020
- 2020-11-04 CN CN202011218034.XA patent/CN112266444A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977282A (en) * | 2012-12-06 | 2013-03-20 | 陕西科技大学 | Preparation method of anionic organic-solvent-free and emulsifier-free polyurethane microemulsion |
| CN107722236A (en) * | 2017-11-07 | 2018-02-23 | 陕西科技大学 | A kind of organic-silicon-modified preparation method and application from delustring aqueous polyurethane of use for synthetic leather |
Non-Patent Citations (2)
| Title |
|---|
| GUIQIANG FEI等: "Micromorphology, phase behavior, and properties of environmental, multi-cross-linked polyurethane/polyacrylate microemulsions based on in situ surfactant-free polymerization", 《COLLOID POLYM SCI 》 * |
| RUI SHI等: "Synthesis of TDI-Polyurethane/Polyacrylate Composite Emulsion by Solvent-free Method and Performances of the Latex Film", 《JOURNAL OF MACROMOLECULAR SCIENCE, PART A: PURE AND APPLIED CHEMISTRY》 * |
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