CN113416290A - Hyperbranched polyurethane capable of being modified in multiple functionalization manner and preparation method thereof - Google Patents
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 23
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000007306 functionalization reaction Methods 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 4
- 238000005935 nucleophilic addition reaction Methods 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- -1 alkyl alkene Chemical group 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 239000012263 liquid product Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 150000003141 primary amines Chemical group 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000587 hyperbranched polymer Polymers 0.000 abstract description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- FSRIVDLBMYWIAO-UHFFFAOYSA-N 1-(2-aminoethylamino)butan-2-ol Chemical compound CCC(O)CNCCN FSRIVDLBMYWIAO-UHFFFAOYSA-N 0.000 description 7
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 6
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000007717 exclusion Effects 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- DKCXSDUGABSSJB-UHFFFAOYSA-N 1-(2-aminoethylamino)but-3-en-2-ol Chemical compound NCCNCC(O)C=C DKCXSDUGABSSJB-UHFFFAOYSA-N 0.000 description 2
- OBDADEXGEWOMQI-UHFFFAOYSA-N 5-aminopentane-1,2-diol Chemical compound NCCCC(O)CO OBDADEXGEWOMQI-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000010751 BS 2869 Class A2 Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000010586 diagram Methods 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000001228 spectrum 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
-
- 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
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses hyperbranched polyurethane capable of being modified by multiple functions and a preparation method thereof, wherein A is utilized2+B3The type monomer (A represents isocyanate group, B represents hydroxyl group) adopts nucleophilic addition reaction to synthesize the polyurethane hyperbranched polymer containing carbon-carbon double bond and hydroxyl group by controlling the feeding ratio. The preparation method has the advantages of simple steps, mild reaction conditions and easy control, and the prepared hyperbranched polyurethane contains various reaction groups capable of being functionally modified.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to hyperbranched polyurethane capable of being modified in multiple functionalization modes and a preparation method thereof.
Background
At present, the preparation methods of hyperbranched polymers are mainly four, namely polycondensation reaction, addition polymerization reaction, self-condensation vinyl polymerization (SCVP) and ring-opening polymerization. Among these, the most mature method is via AB2The self-polycondensation reaction of monomers of the type is used for preparing hyperbranched polymers, and the method has universality and practicability. But currently AB2The monomer type is not commercialized in large quantity, and only a few AB types are available on the market2Monomer is not sufficient to meet the demand, so use A2+B3The polymerization of monomers of type (I) to prepare hyperbranched polymers has attracted attention. But A is2+B3For the isocynatic polyfunctional reaction system, the reaction conditions must be strictly controlled, such as lower monomer concentration and strictly controlled dropping, in order to avoid gel formation during polymerizationAcceleration and monomer conversion, etc.
For tradition A2+B3The system is easy to gel in the polymerization process, and the Yande et al propose the method for preparing hyperbranched polymer by utilizing the group unequal activity reaction, and the reaction condition is controlled to enable A2+CB2The monomers first forming AB by selective reaction2Intermediate of type, and then polymerized into hyperbranched polymer (Macromolecules, 2000, 33, 7693-7699). Using a similar theory, Wudecheng et al reported diacrylate class A2Monomers and amines B' B such as N-ethylethylenediamine2The hyperbranched poly (ester-amine) polymer is synthesized by a one-step method through Michael addition reaction by using monomers as raw materialsMacromolecules, 2004, 37, 6763-6770). Limited by the method of synthesis and type of monomer, using AB2、A2+B3、A2+CB2、A2+B'B2Most of hyperbranched polymers prepared by the polymerization systems only have functional groups on the surface, so that the internal cavity of the hyperbranched polymer cannot be fully utilized.
Disclosure of Invention
In order to solve the technical problem, the invention uses the ring-opening reaction of an epoxy compound and ethylenediamine to synthesize RB' B based on the molecular design of a branched monomer2(B represents a primary amine, B' represents a secondary amine, R represents a hydroxyl or an alkyl alkene which does not participate in the polymerization) monomer, using A2Monomers of type (A represents an acrylate) and RB' B2The one-pot method of Michael addition reaction of the type monomer is used for synthesizing hyperbranched poly (ester-amine) with acrylate groups on the surface and reaction sites R (hydroxyl or alkyl alkene) in internal branching units. The method for synthesizing the hyperbranched poly (ester-amine) is simple, the operation is simple and easy to implement, no gel is generated in the reaction, and the surface and the interior of the prepared hyperbranched poly (ester-amine) both contain reactive groups, so that the selective functionalization modification can be further carried out.
The technical scheme adopted by the invention is as follows: hyperbranched polyurethane capable of being modified by multiple functionalization, which utilizes diisocyanate A2Monomers and B3Nucleophilic addition reaction of monomersA hyperbranched polyurethane containing carbon-carbon double bonds and hydroxyl groups is synthesized, and has the structure shown in the following formula:
a preparation method of hyperbranched polyurethane capable of being modified by multiple functionalization comprises the following steps:
step a, B3Preparation of monomers: adding 3-6 moles of allyl glycidyl ether, 1 mole of amine compound and methanol into a reactor at one time, and reacting for 6-24 hours at the temperature of 30-70 ℃; after the reaction is finished, removing the solvent and excessive reactants by using a rotary evaporator to obtain a product B3A monomer.
Step b, preparation of hyperbranched polyurethane: 1 mol of B3Adding a monomer and toluene into a reactor for azeotropic dehydration, and then adding a catalyst into the reactor; adding 0.8 to 0.9 mol of diisocyanate A2Dissolving the monomer in toluene, dropwise adding the monomer to a reaction system, and reacting at 40-80 ℃ for 24-48 h; and after the reaction is finished, removing the toluene by using a rotary evaporator, dissolving the crude product in tetrahydrofuran, and precipitating and purifying in diethyl ether to obtain a light yellow viscous liquid product, namely the hyperbranched polyurethane.
The amine compound in the step a is selected from one of N-ethyl ethylenediamine, ethylenediamine and ethanolamine.
Diisocyanates A in said step b2The monomer is one of isophorone diisocyanate, dicyclohexyl methane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
The invention has the beneficial effects that: the invention relates to a polyurethane hyperbranched polymer containing carbon-carbon double bonds and hydroxyl groups and a preparation method thereof. The method for synthesizing the hyperbranched polyurethane is simple, has mild reaction conditions, is easy to control, contains various reactive functional groups, can perform multiple functional modification, and can be applied to the technical fields of nano medicines, nano catalysis, functional membrane materials and the like.
Drawings
FIG. 1 shows the present invention B3A method for synthesizing a monomer;
FIG. 2 shows 1- ((2-aminoethyl) amino) -2-butanol B prepared in example 13Of monomers1H NMR spectrum;
FIG. 3 is a schematic diagram of the synthesis of a hyperbranched polyurethane capable of being modified by multiple functionalization;
FIG. 4 is a drawing of the preparation of hyperbranched poly (triethylene glycol diacrylate-1- ((2-aminoethyl) amino) -2-butanol) as prepared in example 71H NMR spectrum.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples. It is to be understood that the present invention is not limited to the following examples, which are deemed to be conventional unless otherwise specified, and that the materials may be commercially available from the open literature without further reference to the following examples.
Examples 1 to 3 are methods for preparing B3 monomer, and examples 4 to 9 are methods for preparing hyperbranched polyurethane capable of being modified by multiple functionalization.
Example 1:
a100 mL flask was charged with 6.840 g (60 mmol) of allyl glycidyl ether and 9 mL of methanol. 1.763 g (20 mmol) of N-ethyl ethylenediamine is added into the flask and reacts for 6 hours at 30 ℃ under the nitrogen atmosphere; after the reaction was completed, the reaction solution was subjected to rotary evaporation to remove methanol, followed by vacuum drying to obtain 1- ((2-aminoethyl) amino) -2-butanol (7.980 g, yield 92.66%) as a milky viscous liquid product.
Method for producing 1- ((2-aminoethyl) amino) -2-butanol obtained in example 11The H NMR chart is shown in the attached figure 2, and the proton signal a of a methylene group connected with an acrylate group and the proton signal b of the methylene group connected with the ester group appear in the chart, so that the synthesis success of the hyperbranched poly (triethylene glycol diacrylate-1- ((2-aminoethyl) amino) -2-butanol) is proved.
Example 2:
a100 mL flask was charged with 6.840 g (60 mmol) of allyl glycidyl ether and 8 mL of methanol. Then 1.202 g (20 mmol) of ethanolamine is added into the flask and reacted for 6 h under the conditions of nitrogen atmosphere and 30 ℃; after the reaction was completed, the reaction solution was subjected to rotary evaporation to remove methanol, followed by vacuum drying to obtain 1- ((2-aminoethyl) amino) -2-butanol (7.364 g, yield 91.57%) as a milky viscous liquid product.
Example 3:
a100 mL flask was charged with 6.840 g (60 mmol) of allyl glycidyl ether and 8 mL of methanol. Then adding 1.222 g (20 mmol) of N-ethyl ethylenediamine into the flask, and reacting for 6 hours at 30 ℃ under the nitrogen atmosphere; after the reaction was completed, the reaction solution was subjected to rotary evaporation to remove methanol, followed by vacuum drying to obtain 1- ((2-aminoethyl) amino) -2-butanol (7.507 g, yield 93.12%) as a milky viscous liquid product.
Example 4:
a250 mL flask was charged with 5.000 g (11.6 mmol) of diethylene glycol diacrylate and 70 mL of toluene to azeotropically remove water; after cooling to room temperature, 1.322 g (0.01 mol) of 1- ((2-aminoethyl) amino) -2-butanol synthesized in example 1 was added to the flask under nitrogen atmosphere at 60 ℃ and reacted for 24 hours with exclusion of light. After the reaction is finished, the reaction solution is precipitated in a mixed solvent of diethyl ether and petroleum ether (volume ratio = 1: 1), and after drying, the product hyperbranched poly (diethylene glycol diacrylate-1- ((2-aminoethyl) amino) -2-butanol) (4.214 g, 75.16% yield) is obtained as a yellow viscous liquid.
Example 5:
a125 mL flask was charged with 4.284 g (0.02 mol) of diethylene glycol diacrylate, 30 mL of DMSO; 1.342 g (0.01 mol) of 3- ((2-aminoethyl)) -1, 2-propanediol synthesized in example 2 was added to the flask under nitrogen atmosphere at 60 ℃ and reacted for 24 hours with exclusion of light. After the reaction is finished, the reaction solution is precipitated in a mixed solvent of diethyl ether and petroleum ether (the volume ratio = 1: 1), and after drying, the product hyperbranched poly (diethylene glycol diacrylate-3- ((2-aminoethyl)) -1, 2-propylene glycol) (4.051 g, the yield is 72.00%) is obtained as a yellow viscous liquid.
Example 6:
a125 mL flask was charged with 4.284 g (0.02 mol) of diethylene glycol diacrylate, 30 mL of DMSO; 1.302 g (0.01 mol) of 1- ((2-aminoethyl) amino) -2-hydroxy-3-butene synthesized in example 3 was added to the flask under nitrogen atmosphere at 60 ℃ and reacted for 24 hours with exclusion of light. After the reaction is finished, the reaction solution is precipitated in a mixed solvent of diethyl ether and petroleum ether (volume ratio = 1: 1), and after drying, the product hyperbranched poly (diethylene glycol diacrylate-1- ((2-aminoethyl) amino) -2-hydroxy-3-butene) which is a yellow viscous liquid is obtained (4.071 g, yield 72.86%).
Example 7:
a125 mL flask was charged with 5.000 g (0.02 mol) of triethylene glycol diacrylate, 30 mL of DMSO; 1.322 g (0.01 mol) of 1- ((2-aminoethyl) amino) -2-butanol synthesized in example 1 was added to the flask under nitrogen atmosphere at 60 ℃ and reacted for 24 hours with exclusion of light. After the reaction is finished, the reaction solution is precipitated in a mixed solvent of diethyl ether and petroleum ether (volume ratio = 1: 1), and after drying, the product hyperbranched poly (triethylene glycol diacrylate-1- ((2-aminoethyl) amino) -2-butanol) (4.804 g, yield 75.98%) is obtained as a yellow viscous liquid.
The nuclear magnetic hydrogen spectrum of the hyperbranched poly (triethylene glycol diacrylate-1- ((2-aminoethyl) amino) -2-butanol) obtained in example 7 is shown in FIG. 4, wherein a proton signal a of a methylene group connected to an acrylate group and a proton signal b of a methylene group connected to an ester group appear, and the successful synthesis of the hyperbranched poly (triethylene glycol diacrylate-1- ((2-aminoethyl) amino) -2-butanol) is proved.
Example 8:
a125 mL flask was charged with 5.000 g (0.02 mol) of triethylene glycol diacrylate, 30 mL of DMSO; 1.342 g (0.01 mol) of 3- ((2-aminoethyl)) -1, 2-propanediol synthesized in example 2 was added to the flask under nitrogen atmosphere at 60 ℃ and reacted for 24 hours with exclusion of light. After the reaction is finished, the reaction solution is precipitated in a mixed solvent of diethyl ether and petroleum ether (the volume ratio = 1: 1), and after drying, a yellow viscous liquid product, namely hyperbranched poly (triethylene glycol diacrylate-3- ((2-aminoethyl)) -1, 2-propylene glycol) (4.375 g, the yield is 68.98%) is obtained.
Example 9:
a125 mL flask was charged with 5.000 g (0.02 mol) of triethylene glycol diacrylate, 30 mL of DMSO; 1.302 g (0.01 mol) of 1- ((2-aminoethyl) amino) -2-hydroxy-3-butene synthesized in example 3 was added to the flask under nitrogen atmosphere at 60 ℃ and reacted for 24 hours with exclusion of light. After the reaction is finished, the reaction solution is precipitated in a mixed solvent of diethyl ether and petroleum ether (volume ratio = 1: 1), and after drying, the product hyperbranched poly (triethylene glycol diacrylate-1- ((2-aminoethyl) amino) -2-hydroxy-3-butene) which is a yellow viscous liquid is obtained (4.679 g, the yield is 74.25%).
The present invention is not limited to the above-described embodiments, but may be combined in many operations, and all cases that can be directly derived or suggested from the disclosure of the present invention by those skilled in the art should be considered as the protection scope of the present invention.
Claims (4)
1. A hyperbranched polyurethane capable of being modified by multiple functionalization is characterized in that: by using diisocyanates A2Monomers and B3Performing nucleophilic addition reaction on the monomer to synthesize hyperbranched polyurethane containing carbon-carbon double bonds and hydroxyl; the structure of the hyperbranched polyurethane is shown as follows:
hyperbranched poly (ester-amine) polymers with acrylate groups, internal branching units with reactive sites R, wherein B represents a primary amine, B' represents a secondary amine, and R represents a hydroxyl or alkyl alkene that does not participate in the polymerization reaction; the structure of the hyperbranched poly (ester-amine) is shown as follows:
2. the preparation method of hyperbranched polyurethane capable of being modified by multiple functionalization according to claim 1, wherein the preparation method comprises the following steps: the method comprises the following steps:
step a, B3Preparation of monomers: adding 3-6 moles of allyl glycidyl ether, 1 mole of amine compound and methanol into a reactor at one time, and reacting for 6-24 hours at the temperature of 30-70 ℃; after the reaction is finished, removing the solvent and excessive reactants by using a rotary evaporator to obtain a product B3A monomer;
step b, preparation of hyperbranched polyurethane: 1 mol of B3Adding monomer and toluene into a reactor for azeotropic dehydration, and adding a catalyst into the reactor for reactionA machine; adding 0.8 to 0.9 mol of diisocyanate A2Dissolving the monomer in toluene, dropwise adding the monomer to a reaction system, and reacting at 40-80 ℃ for 24-48 h; and after the reaction is finished, removing the toluene by using a rotary evaporator, dissolving the crude product in tetrahydrofuran, and precipitating and purifying in diethyl ether to obtain a light yellow viscous liquid product, namely the hyperbranched polyurethane.
3. The preparation method of hyperbranched polyurethane capable of being modified by multiple functionalization according to claim 2, wherein the preparation method comprises the following steps: the amine compound is one of N-ethyl ethylenediamine, ethylenediamine and ethanolamine.
4. The preparation method of hyperbranched polyurethane capable of being modified by multiple functionalization according to claim 2, wherein the preparation method comprises the following steps: diisocyanates A2The monomer is one of isophorone diisocyanate, dicyclohexyl methane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117624550A (en) * | 2023-12-18 | 2024-03-01 | 中国林业科学研究院木材工业研究所 | Aqueous hyperbranched polyurethane modifier emulsion, preparation method and application thereof in cracking prevention of plates |
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| CN102838718A (en) * | 2012-09-12 | 2012-12-26 | 西安交通大学 | Hyperbranched polyurethane containing isocyanate groups, as well as preparation method and application of hyperbranched polyurethane |
| CN106519158A (en) * | 2016-10-26 | 2017-03-22 | 江南大学 | Preparation method of hyperbranched poly (urethane-amine) with hydroxide radical serving as end group and internal branched units provided with vinyl |
| CN107652443A (en) * | 2017-10-31 | 2018-02-02 | 江南大学 | A kind of surface and the internal hyperbranched poly (ester amine) containing functional group and preparation method thereof |
| US20180194893A1 (en) * | 2016-05-12 | 2018-07-12 | Jiangnan University | Method of Preparing Hyperbranched Polyether Ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102838718A (en) * | 2012-09-12 | 2012-12-26 | 西安交通大学 | Hyperbranched polyurethane containing isocyanate groups, as well as preparation method and application of hyperbranched polyurethane |
| US20180194893A1 (en) * | 2016-05-12 | 2018-07-12 | Jiangnan University | Method of Preparing Hyperbranched Polyether Ester |
| CN106519158A (en) * | 2016-10-26 | 2017-03-22 | 江南大学 | Preparation method of hyperbranched poly (urethane-amine) with hydroxide radical serving as end group and internal branched units provided with vinyl |
| CN107652443A (en) * | 2017-10-31 | 2018-02-02 | 江南大学 | A kind of surface and the internal hyperbranched poly (ester amine) containing functional group and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117624550A (en) * | 2023-12-18 | 2024-03-01 | 中国林业科学研究院木材工业研究所 | Aqueous hyperbranched polyurethane modifier emulsion, preparation method and application thereof in cracking prevention of plates |
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