CN110511349B - A kind of preparation method of hyperbranched temperature-sensitive water-based polyurethane - Google Patents
A kind of preparation method of hyperbranched temperature-sensitive water-based polyurethane Download PDFInfo
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 62
- 239000004814 polyurethane Substances 0.000 title claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002009 diols Chemical class 0.000 claims abstract description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 10
- 238000006845 Michael addition reaction Methods 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 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 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 2
- UABRYPURASNHRO-UHFFFAOYSA-N trimethyltin;hydrate Chemical compound O.C[Sn](C)C UABRYPURASNHRO-UHFFFAOYSA-N 0.000 claims description 2
- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000006903 response to temperature Effects 0.000 abstract 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 10
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical group CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 10
- 229920000570 polyether Polymers 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 3
- -1 isocyanic acid radical Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000007342 radical addition reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- GMCXXHRAQIUECM-UHFFFAOYSA-N C(CCCCCCCCCCC)[S].C(CCCCCCCCCCC)[S].C(CCC)[Sn]CCCC Chemical compound C(CCCCCCCCCCC)[S].C(CCCCCCCCCCC)[S].C(CCC)[Sn]CCCC GMCXXHRAQIUECM-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011557 critical solution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- OJZNYUDKNVNEMV-UHFFFAOYSA-M trimethylstannanylium;hydroxide Chemical compound C[Sn](C)(C)O OJZNYUDKNVNEMV-UHFFFAOYSA-M 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- 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
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino 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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
- C08G18/833—Chemically modified polymers by nitrogen containing compounds
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Abstract
提供一种超支化型温敏型水性聚氨酯的制备方法，步骤：1合成线性水性聚氨酯，将线性二元醇和二羟甲基丙酸混合，在溶剂、惰性气体和搅拌下，保持温度为70‑85℃，加入异佛尔酮二异氰酸酯和催化剂，反应得到线性水性聚氨酯；2超支化，室温下在产物中加入聚醚胺，聚醚胺和步骤1产物摩尔比为1:1，搅拌反应；3N‑乙烯吡咯烷酮接枝，2产物中加入聚醚胺等摩尔量的N‑乙烯吡咯烷酮搅拌，至溶液深黄色，与二羟甲基丙酸等摩尔量的三乙胺以及去离子水，搅拌；4，去除溶剂，得到超支化型温敏型水性聚氨酯。优点在于，改性在常温下进行，N‑乙烯吡咯烷酮载入量更高。产品热稳定性和力学性能好，对温度变化有敏锐的智能响应，温敏性能长时间保持，且毒性小。
A preparation method of hyperbranched temperature-sensitive water-based polyurethane is provided. The steps are: 1. synthesizing linear water-based polyurethane, mixing linear diol and dimethylol propionic acid, and maintaining a temperature of 70- 85°C, adding isophorone diisocyanate and catalyst, and reacting to obtain linear water-based polyurethane; 2. Hyperbranching, adding polyetheramine to the product at room temperature, the molar ratio of polyetheramine and the product of step 1 is 1:1, and stirring the reaction; 3 N-vinyl pyrrolidone grafting, 2 products, adding N-vinyl pyrrolidone of equimolar amount of polyetheramine and stirring, to solution dark yellow, and equimolar triethylamine and deionized water with dimethylolpropionic acid, stir; 4. The solvent is removed to obtain a hyperbranched temperature-sensitive waterborne polyurethane. The advantage is that the modification is carried out at room temperature and the N-vinylpyrrolidone loading is higher. The product has good thermal stability and mechanical properties, has a sensitive and intelligent response to temperature changes, maintains temperature-sensitive properties for a long time, and has low toxicity.
Description
Technical Field
The invention relates to a preparation method of novel hyperbranched temperature-sensitive waterborne polyurethane, belonging to the technical field of temperature-sensitive materials.
Background
The environmental stimulus response type material is more and more interesting to people at present, wherein the temperature-sensitive type material is particularly hot, and the temperature-sensitive type waterborne polyurethane can combine the excellent mechanical property of polyurethane with the temperature sensitivity of a temperature-sensitive substance, has the advantages of good water solubility, small environmental pollution, good viscosity, higher strength, higher wear resistance and the like, has the characteristics of intelligent temperature stimulus responsiveness, shape memory effect and the like, and is widely applied to the aspects of coatings, biological materials and the like in recent years.
A temperature-sensitive monomer commonly used for preparing temperature-sensitive waterborne polyurethane at the present stage is N-isopropylacrylamide (NIPAM), wherein the lowest critical solution temperature (LCST,32 ℃) of a polymer (PNIPAM) in water exists, and when the temperature is lower than the LCST, a large amount of hydrogen bonds exist between hydrophilic groups and water molecules, so that the polymer is dissolved in water; when the temperature is higher than LCST, hydrogen bonds are greatly destroyed, and the polymer begins to separate out of aqueous solution, so that the polymer has wide application in the aspect of human bodies. However, the compound is very easy to hydrolyze, loses the temperature sensitivity, generates toxic amide groups and causes harm to human bodies.
In terms of synthesis methods, two methods exist for synthesizing the temperature-sensitive waterborne polyurethane at the present stage, one method is physical blending, and the synthesized waterborne polyurethane is mixed with poly-N-isopropyl acrylamide; the second method is chemical grafting, which is the free radical addition reaction of double bond terminated polyurethane with N-isopropyl acrylamide. Both of them mainly act by NIPAM, and avoid the disadvantage that they are easy to hydrolyze and produce toxic substances. The compatibility problem of the former is difficult to solve, and the temperature sensitivity and the durability of the former are poor; the latter free radical addition reaction has the disadvantages of harsher reaction condition, higher reaction temperature, long time and easy self-polymerization of NIPAM.
N-vinyl pyrrolidone (NVP) is generally used together with NIPAM mainly in the aspect of temperature sensitivity, and is used less singly. In the aspect of temperature-sensitive waterborne polyurethane, NVP is less explored.
Based on the background, the invention adopts N-vinyl pyrrolidone as a temperature-sensitive monomer, and a polymer (PNVP) thereof has temperature sensitivity at 30-40 ℃. Compared with N-isopropyl acrylamide, the N-isopropyl acrylamide has better water solubility and biocompatibility, can be hydrolyzed under the condition of strong acid, generates carboxyl, has lower toxicity, and has more advantages than PNIPAM in the field of biological medicine.
Disclosure of Invention
In order to solve the problems in the prior art, the invention adopts triamine monomers to carry out hyperbranched treatment on the waterborne polyurethane, and then the N-vinyl pyrrolidone is accessed through Michael addition reaction.
In order to achieve the above technical object, the present invention adopts the following technical solutions.
The invention provides a preparation method of novel hyperbranched temperature-sensitive waterborne polyurethane, which comprises the following steps:
s1 synthesizing linear water-based polyurethane.
S2 triamine monomer hyperbranched treatment is carried out on the linear waterborne polyurethane synthesized by S1.
S3 grafts N-vinylpyrrolidone to S2 product by the Michael addition reaction.
The preparation method of the novel hyperbranched temperature-sensitive waterborne polyurethane comprises the following steps:
s1 synthesizing linear water-based polyurethane.
Mixing the dried linear dihydric alcohol with dimethylolpropionic acid, adding a solvent, keeping the temperature at 70-85 ℃ under the protection of inert gas and stirring, adding isophorone diisocyanate, adding a catalyst, and reacting for 2-3h to obtain the linear waterborne polyurethane.
Specifically, the molar ratio of-NCO to-OH in the system is kept to be 1.5-3: 1;
the linear diol is preferably polytetrahydrofuran diol having a molecular weight of 1000-4000, preferably 2000;
the solvent is acetone, toluene, xylene, one of N, N-dimethylformamide and N-methylpyrrolidone, and preferably the solvent is a mixture of acetone and N-methylpyrrolidone; specifically, the volume ratio of acetone to N-methylpyrrolidone is 10: 1.
The catalyst is an organic tin catalyst, specifically, one of dibutyltin bis (dodecyl sulfur), tetra-n-butyltin, hydroxyl trimethyltin and dibutyltin dilaurate, and preferably dibutyltin dilaurate.
The adding amount of the catalyst is 3-8% of the mass of the reactant.
S2 triamine monomer hyperbranched treatment is carried out on the linear waterborne polyurethane synthesized by S1.
And (3) at room temperature, adding polyether amine into the product S1, keeping the molar ratio of the polyether amine to the polyurethane prepolymer obtained from S1 to be 1:1, and stirring at room temperature to react for 2-3h to complete the hyperbranched reaction.
Wherein the polyether amine is trifunctional polyether amine.
S3 was grafted onto the S2 product by the Michael addition reaction N-vinylpyrrolidone.
After the hyperbranched reaction of S2 is completed, adding N-vinyl pyrrolidone with the same molar amount as that of polyether amine, continuously stirring and reacting at room temperature until the solution becomes dark yellow, moving to the room temperature, adding triethylamine with the same molar amount as that of dimethylolpropionic acid and deionized water, and fully stirring for 2-3 h.
S4 solvent removal.
And (3) carrying out rotary evaporation on the product of S3 at the vacuum degree of-0.08 to-0.095 MPa and at normal temperature to remove the solvent, thus obtaining the novel hyperbranched temperature-sensitive waterborne polyurethane.
The preparation method of the novel hyperbranched temperature-sensitive waterborne polyurethane comprises the following steps:
s1 synthesizing linear water-based polyurethane.
Taking 0.00125mol of dried polytetrahydrofuran diol, adding 0.00225mol of dimethylolpropionic acid under the protection of inert gas and stirring, adding 5-10mL of acetone and N-methyl pyrrolidone serving as a solvent, wherein the volume ratio of the acetone to the N-methyl pyrrolidone is 10:1, heating to 75 ℃, adding 0.00525mol of isophorone diisocyanate and 0.3g of catalyst dibutyltin dilaurate, and reacting for 2-3h at the temperature.
S2 triamine monomer hyperbranched treatment is carried out on the linear waterborne polyurethane synthesized by S1.
And (3) at room temperature, adding 0.00175mol of polyetheramine into the product S1, wherein the molar ratio of the polyetheramine to the polyurethane prepolymer obtained in S1 is 1:1, and stirring for reaction for 2-3h to complete the hyperbranched reaction.
S3 grafts N-vinylpyrrolidone to S2 product by the Michael addition reaction.
After the hyperbranched reaction of S2 is completed, 0.00175mol N-vinyl pyrrolidone is added and continuously stirred to react at room temperature until the solution turns to dark yellow, and then the solution is shifted to the room temperature, triethylamine with the same molar quantity as dimethylolpropionic acid and 20-30ml deionized water are added and fully stirred for 2 hours.
S4 solvent removal.
And (3) carrying out rotary evaporation on the product of S3 at the vacuum degree of-0.095 MPa and at normal temperature to remove acetone, thus obtaining the novel hyperbranched temperature-sensitive waterborne polyurethane.
According to the preparation method of the novel hyperbranched temperature-sensitive waterborne polyurethane, the chemical reaction formula is as follows:
by adopting the technical scheme, the invention achieves the following technical effects.
1. The novel hyperbranched temperature-sensitive waterborne polyurethane synthesized by the invention integrates two advantages of hyperbranched property and temperature-sensitive property: the hyperbranched polymer reduces the viscosity of the emulsion, improves the forming and processing capacity of the emulsion, and improves the thermal stability and mechanical property of the emulsion by introducing urea bonds; the temperature sensitivity enables the temperature-sensitive intelligent response characteristic to be acute to the temperature change; and both are connected through chemical bonds, so that the performance is stable.
2. According to the preparation method of the novel hyperbranched temperature-sensitive waterborne polyurethane disclosed by the invention, two modifications can be carried out at normal temperature: the amino and the isocyanic acid radical can quickly react at normal temperature, and the Michael addition reaction of the double bond and the amino belongs to electrolytic chemistry and can be easily carried out at normal temperature. And because no initiator is used, the N-vinyl pyrrolidone cannot be self-polymerized, and the loading amount is higher.
3. The novel hyperbranched temperature-sensitive waterborne polyurethane disclosed by the invention is safe and stable in performance: compared with NIPAM, N-vinylpyrrolidone has better water solubility and biocompatibility, is hydrolyzed under the condition of strong acid, keeps the temperature-sensitive performance for a long time, generates carboxyl and has lower toxicity.
Drawings
FIG. 1 is an infrared spectrum of the novel hyperbranched temperature-sensitive waterborne polyurethane obtained in example 1;
FIG. 2 is a graph showing the change of particle size of the novel hyperbranched temperature-sensitive aqueous polyurethane obtained in example 1 with temperature.
Detailed Description
The following describes the technical solutions of the present invention in detail with reference to the detailed description and the accompanying drawings, so that those skilled in the art can better understand the present invention and can implement the present invention.
The preparation method of the novel hyperbranched temperature-sensitive waterborne polyurethane comprises the following steps:
s1 synthesizing linear water-based polyurethane.
Mixing the dried linear dihydric alcohol with dimethylolpropionic acid, adding a solvent, keeping the temperature at 70-85 ℃ under the protection of inert gas and stirring, adding isophorone diisocyanate, adding a catalyst, and reacting for 2-3h to obtain the linear waterborne polyurethane.
S2 triamine monomer hyperbranched treatment is carried out on the linear waterborne polyurethane synthesized by S1.
And (3) at room temperature, adding polyether amine into the product S1, keeping the molar ratio of the polyether amine to the polyurethane prepolymer obtained from S1 to be 1:1, and stirring at room temperature to react for 2-3h to complete the hyperbranched reaction.
Wherein the polyether amine is trifunctional polyether amine.
S3 was grafted onto the S2 product by the Michael addition reaction N-vinylpyrrolidone.
After the hyperbranched reaction of S2 is completed, adding N-vinyl pyrrolidone with the same molar amount as that of polyether amine, continuously stirring and reacting at room temperature until the solution becomes dark yellow, moving to the room temperature, adding triethylamine with the same molar amount as that of dimethylolpropionic acid and deionized water, and fully stirring for 2-3 h.
S4 solvent removal.
And (3) carrying out rotary evaporation on the product of S3 at the vacuum degree of-0.08 to-0.095 MPa and at normal temperature to remove the solvent, thus obtaining the novel hyperbranched temperature-sensitive waterborne polyurethane.
In some preferred embodiments, in step S1, the molar ratio of-NCO to-OH in the system is maintained at 1.5 to 3: 1;
in some preferred embodiments, in step S1, the linear diol is preferably polytetrahydrofuran diol, which has a molecular weight of 1000-4000; more preferably 2000.
In some preferred embodiments, in step S1, the solvent is acetone, toluene, xylene, a mixture of N, N-dimethylformamide and N-methylpyrrolidone, and more preferably, the solvent is a mixture of acetone and N-methylpyrrolidone. Specifically, the volume ratio of acetone to N-methylpyrrolidone is 10: 1.
In some preferred embodiments, in step S1, the catalyst is an organotin catalyst, specifically, one of dibutyltin bis (dodecylthio), tetra-n-butyltin, hydroxytrimethyltin, dibutyltin dilaurate, and more preferably, dibutyltin dilaurate.
The adding amount of the catalyst is 3-8% of the mass of the reactant.
In some preferred embodiments, the vacuum level is-0.095 MPa in step S4.
The above method is described by the following specific examples, and it should be noted that, although the following examples are prepared according to the corresponding parameter conditions, the other parameters in the above method are selected for preparation, and the corresponding novel hyperbranched temperature-sensitive waterborne polyurethane can also be prepared.
Example 1
A preparation method of novel hyperbranched temperature-sensitive waterborne polyurethane comprises the following steps:
s1 synthesizing linear water-based polyurethane.
Weighing 0.00125mol of dried polytetrahydrofuran diol into a 250ml four-neck flask, and filling the flask with a condensation reflux device, a mechanical stirrer and N2And introducing into the device, adding 0.00225mol of dimethylolpropionic acid, adding 5-10mL of a mixture of acetone and N-methylpyrrolidone as a solvent (the volume ratio of the acetone to the N-methylpyrrolidone is 10:1), heating and stirring until the temperature reaches 75 ℃, adding 0.00525mol of isophorone diisocyanate and 0.3g of catalyst dibutyltin dilaurate, and reacting for 3 hours at the temperature.
S2 triamine monomer hyperbranched treatment is carried out on the linear waterborne polyurethane synthesized by S1.
And (3) moving the four-mouth bottle to room temperature, adding 0.00175mol of polyetheramine, wherein the molar ratio of the polyetheramine to the polyurethane prepolymer obtained from S1 is 1:1, and stirring for reaction for 2 hours to complete the hyperbranched reaction.
S3 grafts N-vinylpyrrolidone to S2 product by the Michael addition reaction.
After the hyperbranched reaction is finished, 0.00175mol of N-vinyl pyrrolidone is added, the reaction is continued at room temperature until the solution becomes dark yellow, the solution is moved to the room temperature, triethylamine with the same molar weight as dimethylolpropionic acid is added, and the mixture and 20ml of deionized water are fully stirred for 2 hours.
S4 solvent removal.
And (3) carrying out rotary evaporation on the product of S3 at the vacuum degree of-0.095 MPa and at normal temperature to remove acetone, thus obtaining the novel hyperbranched temperature-sensitive waterborne polyurethane.
Experimental example:
see fig. 1-2. Fig. 1 is an infrared spectrum of the novel hyperbranched temperature-sensitive waterborne polyurethane obtained in example 1, and fig. 2 is a graph of a change in particle size of the novel hyperbranched temperature-sensitive waterborne polyurethane obtained in example 1 with temperature.
See FIG. 1, 3543.69cm-1Is the NH stretching vibration peak in-NHCO-; 2944.32cm-1And 2863.81cm-1is-CH3and-CH2-a stretching vibration peak; 1708.22cm-1C ═ O for-NHCO-and stretching vibrational peaks; 1306.03cm-1Is the stretching vibration peak of C-N in the quinary ring. These demonstrate the successful synthesis of novel hyperbranched temperature-sensitive waterborne polyurethanes.
Referring to fig. 2 and table 1, table 1 shows the rate of change of particle size with temperature of the novel hyperbranched temperature-sensitive aqueous polyurethane of example 1.
TABLE 1 Change rate of particle size of novel hyperbranched temperature-sensitive waterborne polyurethane with temperature
As can be seen from FIG. 1 and Table 1, the particle size change is more prominent at the temperatures of 35 deg.C, 37 deg.C and 40 deg.C, which indicates that the novel hyperbranched temperature-sensitive waterborne polyurethane prepared has better temperature-sensitive performance. Meanwhile, the mutation interval is suitable for the temperature interval of the human body, and the characteristics of low toxicity and low harm make the mutant have great prospect in the field of biomedicine.
The technical solution provided by the present invention is not limited by the above embodiments, and all technical solutions formed by utilizing the structure and the mode of the present invention through conversion and substitution are within the protection scope of the present invention.
Claims (4)
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