CN104693405B - A kind of super branched polyurethane and preparation method thereof containing active amino - Google Patents
A kind of super branched polyurethane and preparation method thereof containing active amino Download PDFInfo
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- CN104693405B CN104693405B CN201510141212.6A CN201510141212A CN104693405B CN 104693405 B CN104693405 B CN 104693405B CN 201510141212 A CN201510141212 A CN 201510141212A CN 104693405 B CN104693405 B CN 104693405B
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 32
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title abstract description 8
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 13
- 229920000570 polyether Polymers 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 9
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 16
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 125000003277 amino group Chemical group 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229940113116 polyethylene glycol 1000 Drugs 0.000 claims description 2
- 229920006264 polyurethane film Polymers 0.000 abstract description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 abstract description 3
- 150000003384 small molecules Chemical group 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract 2
- 229920000642 polymer Polymers 0.000 abstract 2
- 125000003368 amide group Chemical group 0.000 abstract 1
- 229920005749 polyurethane resin Polymers 0.000 abstract 1
- 230000006872 improvement Effects 0.000 description 7
- 230000035699 permeability Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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
-
- 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
- C08G18/30—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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular 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
- C08G18/40—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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
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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 a kind of super branched polyurethane and preparation method thereof containing active amino, preparation method first mixes polyether polyol with diisocyanate, it is stirred to react, catalyst is added, using aprotic organic solvent as solvent, after reacting a period of time, small molecule chain extender is added, carries out chain extension, is eventually adding end-capping reagent, carry out partially end-blocked, obtained linear polyester performed polymer；Then Hyperbranched Polymer with Terminal Amido is mixed with linear polyester performed polymer, it is stirred to react, super branched polyurethane is made, super branched polyurethane resin synthesized by the present invention contains a large amount of active amino and imino group, the sanitation performance of polyurethane film not only can be improved, but also dyeability can be improved.
Description
Technical Field
The invention relates to the technical field of polyurethane material processing, in particular to hyperbranched polyurethane containing active amino and a preparation method thereof.
Background
Hyperbranched polymers have attracted attention because of their unique structures and physicochemical properties. Has been widely applied to the fields of coatings, modification aids and processing agents of resins, cross-linking agents, drugs and gene carriers, nanotechnology, supramolecular science and the like.
Polyurethane (PU) is a macromolecular compound containing repeated urethane groups in the backbone, has properties of high strength, wear resistance, low temperature resistance, chemical resistance, excellent resilience and the like, and has been widely used in PU synthetic leather, leather finishing agents and textile coatings. Although the solvent-based dry-process polyurethane film has excellent mechanical properties, the surface of the film is compact, water vapor is difficult to permeate, and the molecular chain segment has few hydrophilic groups, poor affinity to water and poor moisture absorption and air permeability, so that the use comfort of a finished product is poor.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide hyperbranched polyurethane containing amino groups and a preparation method thereof, and overcomes the defect of poor moisture absorption and air permeability of the existing polyurethane film.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of hyperbranched polyurethane containing active amino groups comprises the following steps:
1) dissolving polyether polyol in a dried aprotic organic solvent, dropwise adding diisocyanate and adding a catalyst under the protection of nitrogen, and stirring and reacting for 1-2 hours at 75-85 ℃; then adding a micromolecular chain extender, stirring and reacting for 2-3 h at 75-85 ℃, and carrying out chain extension; finally adding an end-capping reagent, stirring and reacting for 1-2 h at 70-80 ℃, and carrying out partial end capping to obtain a linear polyurethane prepolymer; wherein the mass ratio of the polyether polyol to the dried aprotic organic solvent is 1: 1.5-1: 2, and diisocyanate is dropwise added according to the mass ratio of-NCO to-OH being 2.5: 1-3: 1;
2) mixing the amino-terminated hyperbranched polymer and the linear polyurethane prepolymer for reaction at the temperature of 0-25 ℃ for 0.5-2.5 h to obtain viscous liquid; wherein the mass ratio of the amino-terminated hyperbranched polymer to the dried aprotic organic solvent is 1: 4-1: 5, and-NH (NH) in the amino-terminated hyperbranched polymer and the linear polyurethane prepolymer2The molar ratio of the compound to-NCO is 1: 1-1: 2.
3) And washing the viscous liquid with ethanol and acetone, and drying in vacuum to obtain the hyperbranched polyurethane.
As a further improvement of the invention, in the step 1), the polyether polyol is polytetrahydrofuran ether glycol, polyethylene glycol or polypropylene glycol, and the number average molecular weight is 1000.
As a further improvement of the present invention, in the step 1) and the step 2), the aprotic organic solvent is N, N-dimethylformamide, N-dimethylacetamide, N-methyl-pyrrolidone, or acetone, wherein the aprotic organic solvent used in the step 1) and the step 2) is the same or different.
As a further improvement of the invention, the diisocyanate is isophorone diisocyanate, toluene diisocyanate or diphenylmethane-4, 4' -diisocyanate.
As a further development of the invention, the catalyst is dibutyltin dilaurate; the addition amount of the catalyst was 0.007% of the total mass of the diisocyanate and polyether polyol.
As a further improvement of the invention, in the step 1), the small molecule chain extender is 1, 4-butanediol, 1, 6-hexanediol; and dripping a micromolecule chain extender according to the mass ratio of-NCO to-OH of 1: 1.1-1: 1.2.
As a further improvement of the invention, in the step 1), the end-capping reagent is methanol or ethanol; and dropwise adding an end-capping agent according to the mass ratio of-NCO to-OH being 1: 1-1: 1.1.
As a further improvement of the invention, the structural formula of the linear polyurethane prepolymer prepared in the step 1) is as follows:
a hyperbranched polyurethane containing active amino groups is prepared by the preparation method of the hyperbranched polyurethane containing the amino groups.
As a further improvement of the invention, the hyperbranched polyurethane containing reactive amino groups has the following structural formula:
wherein,
R1is composed of
Compared with the prior art, the invention has the following advantages:
according to the preparation method, the amino-terminated hyperbranched polymer with a branched structure is introduced into the linear polyurethane prepolymer, so that the prepared hyperbranched polyurethane contains a large amount of active amino and imino, dye binding points are increased, an anionic dye and amino with positive charges are bound by ionic bonds to enhance the dyeing effect, and the dyeing performance of a polyurethane film is improved; meanwhile, the number of active hydrophilic groups is increased, and the sanitary performance is improved. The method is simple, mild in reaction and easy to operate. The number of active hydrophilic groups is increased, and the moisture absorption and air permeability are strong.
The hyperbranched polyurethane prepared by the hyperbranched polyurethane containing amino contains a large amount of active amino and imino, has excellent mechanical property, loose membrane surface and high water vapor permeability, and has more hydrophilic groups in molecular chain segments, good affinity to water, high moisture absorption and air permeability and high use comfort of finished products.
Drawings
FIG. 1 is a schematic diagram of the synthesis reaction of a polyurethane prepolymer.
FIG. 2 is a schematic diagram of a synthesis reaction of a hyperbranched polyurethane.
FIGS. 1 and 2 are reaction schemes for the preparation of hyperbranched polyurethanes containing amino groups, exemplified by IPDI and PTMG 1000.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
as shown in fig. 1 and fig. 2, a method for preparing hyperbranched polyurethane containing amino groups comprises the following steps:
1) weighing 10.00g polytetrahydrofuran ether glycol 1000 (abbreviated as PTMG1000) and dissolving in 15ml of dried N, N-dimethylformamide (abbreviated as DMF);
2) under the protection of nitrogen, according to the mass ratio of-NCO to-OH being 2.5:1, 0.007% dibutyltin dilaurate (DBTDL for short) is used as a catalyst, 5.55g of isophorone diisocyanate (IPDI for short) is dripped to react with polyether polyol at 85 ℃ for 1.5h under stirring, then 0.81g of 1, 4-butanediol is added to react at 85 ℃ for 2.5h under stirring, and chain extension is carried out; finally, 0.37g of absolute ethyl alcohol is added, stirred and reacted for 2 hours at the temperature of 80 ℃, and partial end capping is carried out to prepare a linear polyurethane prepolymer;
3) according to the mol ratio of the amino-terminated hyperbranched polymer to the linear polyurethane prepolymer of 1:1.1, the reaction temperature is 5 ℃, and the reaction time is 1.5h, so as to obtain viscous liquid.
4) And (3) washing the viscous liquid prepared in the third step with ethanol and acetone, and drying in vacuum to obtain the hyperbranched polyurethane.
Example 2:
a preparation method of hyperbranched polyurethane containing amino groups is provided, the preparation process is as shown in figure 1 and figure 2, and the preparation method comprises the following steps:
1) weighing 10.00g of polyethylene glycol 1000 (PEG 1000 for short) and dissolving in 15ml of dried N, N-dimethylacetamide (DMAC for short);
2) under the protection of nitrogen, according to the mass ratio of-NCO to-OH being 2.5:1, 0.007% dibutyltin dilaurate (DBTDL for short) is used as a catalyst, 4.35g of toluene diisocyanate (TDI for short) is dropwise added to react with polyether polyol at 85 ℃ for 1.5 hours under stirring, then 0.81g of 1, 4-butanediol is added to react at 85 ℃ for 2.5 hours under stirring, and chain extension is carried out; finally, 0.37g of absolute ethyl alcohol is added, stirred and reacted for 2 hours at the temperature of 80 ℃, and partial end capping is carried out to prepare a linear polyurethane prepolymer;
3) according to the mol ratio of the amino-terminated hyperbranched polymer to the linear polyurethane prepolymer of 1:1.15, the reaction temperature is 10 ℃, and the reaction time is 1h, so as to obtain viscous liquid.
4) Washing the viscous liquid prepared in the third step with ethanol and acetone, and drying in vacuum to obtain the hyperbranched polyurethane
Example 3:
a preparation method of hyperbranched polyurethane containing amino groups is provided, the preparation process is as shown in figure 1 and figure 2, and the preparation method comprises the following steps:
1) weighing 10.00g of polypropylene glycol 1000 (PPG 1000 for short) and dissolving in 15ml of dried N, N-dimethylformamide (DMF for short);
2) under the protection of nitrogen, according to the mass ratio of-NCO to-OH being 3:1, 0.007% dibutyltin dilaurate (DBTDL for short) is used as a catalyst, 6.66g of isophorone diisocyanate (IPDI for short) is dropwise added to react with polyether polyol at 85 ℃ for 1.5h under stirring, then 1.08g of 1, 4-butanediol is added to react at 85 ℃ for 2.5h under stirring, and chain extension is carried out; finally, 0.46g of absolute ethyl alcohol is added, stirred and reacted for 2 hours at the temperature of 80 ℃, and partial end capping is carried out to prepare a linear polyurethane prepolymer;
3) according to the mol ratio of the amino-terminated hyperbranched polymer to the linear polyurethane prepolymer of 1:1.1, the reaction temperature is 5 ℃, and the reaction time is 1.5h, so as to obtain viscous liquid.
4) Washing the viscous liquid prepared in the step 3) with ethanol and acetone, and drying in vacuum to obtain the hyperbranched polyurethane
Example 4:
a preparation method of hyperbranched polyurethane containing amino groups is provided, the preparation process is as shown in figure 1 and figure 2, and the preparation method comprises the following steps:
1) weighing 10.00g polytetrahydrofuran ether glycol 1000 (abbreviated as PTMG1000) and dissolving in 10ml of dried N, N-dimethylformamide (abbreviated as DMF);
2) under the protection of nitrogen, according to the mass ratio of-NCO to-OH being 2.55:1, 0.007% dibutyltin dilaurate (DBTDL for short) is used as a catalyst, 4.437g of toluene diisocyanate (TDI for short) is dropwise added to react with polyether polyol at 85 ℃ for 1.5 hours under stirring, then 1.42g of 1, 6-hexanediol is added to react at 85 ℃ for 2.5 hours under stirring, and chain extension is carried out; finally, 0.32g of anhydrous methanol is added, stirred and reacted for 2 hours at the temperature of 80 ℃, and partial end capping is carried out to prepare a linear polyurethane prepolymer;
3) according to the mol ratio of the amino-terminated hyperbranched polymer to the linear polyurethane prepolymer of 1:1.2, the reaction temperature is 15 ℃, and the reaction time is 0.5h, so as to obtain viscous liquid.
4) And (3) washing the viscous liquid prepared in the third step with ethanol and acetone, and drying in vacuum to obtain the hyperbranched polyurethane.
The amino-terminated hyperbranched polymer in the embodiment can be specifically
Claims (2)
1. A preparation method of hyperbranched polyurethane containing active amino groups is characterized by comprising the following steps:
1) dissolving polyether polyol in a dried aprotic organic solvent, dropwise adding diisocyanate and adding a catalyst dibutyltin dilaurate accounting for 0.007% of the total mass of the diisocyanate and the polyether polyol under the protection of nitrogen, and stirring and reacting for 1-2 h at 75-85 ℃; then dropwise adding a micromolecule chain extender, stirring and reacting for 2-3 h at 75-85 ℃, and carrying out chain extension; finally, adding an end-capping reagent, stirring and reacting for 1-2 h at 70-80 ℃, and carrying out partial end capping to obtain a linear polyurethane prepolymer with-NCO at one end; wherein the mass ratio of the polyether polyol to the dried aprotic organic solvent is 1: 1.5-1: 2, and diisocyanate is dropwise added according to the mass ratio of-NCO to-OH being 2.5: 1-3: 1;
wherein the polyether polyol is polytetrahydrofuran ether glycol, polyethylene glycol or polypropylene glycol, and the number average molecular weight is 1000; the diisocyanate is isophorone diisocyanate, toluene diisocyanate or diphenylmethane-4, 4' -diisocyanate; the micromolecular chain extender is 1, 4-butanediol or 1, 6-hexanediol; the end capping agent is methanol or ethanol; dropwise adding a micromolecule chain extender and an end capping agent according to the following dosage:
10.00g of polytetrahydrofuran ether glycol 1000; according to the mass ratio of-NCO to-OH being 2.5:1, 5.55g of isophorone diisocyanate is dripped, then 0.81g of 1, 4-butanediol is added, and finally 0.37g of absolute ethyl alcohol is added; or,
10.00g of polyethylene glycol 1000; according to the mass ratio of-NCO to-OH being 2.5:1, 4.35g of toluene diisocyanate is added dropwise, then 0.81g of 1, 4-butanediol is added, and finally 0.37g of absolute ethyl alcohol is added; or,
10.00g of polypropylene glycol 1000; according to the mass ratio of-NCO to-OH being 3:1, 6.66g of isophorone diisocyanate is dripped, and then 1.08g of 1, 4-butanediol is added; finally, 0.46g of absolute ethyl alcohol is added;
2) mixing the amino-terminated hyperbranched polymer and the linear polyurethane prepolymer for reaction at the temperature of 0-25 ℃ for 0.5-2.5 h to obtain viscous liquid; wherein the mass ratio of the amino-terminated hyperbranched polymer to the dried aprotic organic solvent is 1: 4-1: 5, and-NH (NH) in the amino-terminated hyperbranched polymer and the linear polyurethane prepolymer2The mol ratio of the compound to-NCO is 1: 1-1: 2;
3) washing the viscous liquid with ethanol and acetone, and drying in vacuum to obtain hyperbranched polyurethane;
in the step 1) and the step 2), the aprotic organic solvent is N, N-dimethylformamide, N-dimethylacetamide, N-methyl-pyrrolidone or acetone, wherein the aprotic organic solvents used in the step 1) and the step 2) are the same or different.
2. A hyperbranched polyurethane containing a reactive amino group, which is prepared by the preparation method according to claim 1.
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| CN115232542B (en) * | 2022-07-21 | 2024-01-02 | 宁波爱甬新材料科技有限公司 | Graphene anticorrosive paint and preparation method thereof |
| CN116947404B (en) * | 2023-05-10 | 2024-04-16 | 湖南中大设计院有限公司 | Concrete for mountain gas tunnel and preparation method thereof |
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