CN110627967A - Preparation method of novel comb-shaped temperature-sensitive waterborne polyurethane - Google Patents

Preparation method of novel comb-shaped temperature-sensitive waterborne polyurethane Download PDF

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Publication number
CN110627967A
CN110627967A CN201910833638.6A CN201910833638A CN110627967A CN 110627967 A CN110627967 A CN 110627967A CN 201910833638 A CN201910833638 A CN 201910833638A CN 110627967 A CN110627967 A CN 110627967A
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Prior art keywords
preparation
sensitive
waterborne polyurethane
temperature
steps
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CN201910833638.6A
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Chinese (zh)
Inventor
易昌凤
陈奇
严正
陈俊
朱梦雨
徐祖顺
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Hubei University
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Hubei University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—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
    • C08G18/65—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
    • C08G18/28—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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  • 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 preparation method of novel comb-shaped temperature-sensitive waterborne polyurethane, which is characterized in that N-vinyl pyrrolidone (NVP) is used for preparing temperature-sensitive waterborne polyurethane, the synthesis method is greatly different from the temperature-sensitive monomer introduction method in the prior art, monoglyceride with double bonds on side chains is selected as a dihydric alcohol raw material, NVP is grafted on the side chains in the polyurethane synthesis process, and comb-shaped waterborne polyurethane with temperature sensitivity is synthesized. The invention has the advantages of simple process and low cost.

Description

Preparation method of novel comb-shaped temperature-sensitive waterborne polyurethane
Technical Field
The invention relates to the technical field of polyurethane production, in particular to a preparation method of novel comb-shaped temperature-sensitive waterborne polyurethane.
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.
The temperature-sensitive waterborne polyurethane synthesized at the present stage is mainly prepared by introducing NIPAM, and generally comprises two methods: one is physical blending, and directly mixing the synthesized waterborne polyurethane with a PNIPAM solution; the second method is chemical grafting, which is a free radical addition reaction of a double bond terminated polyurethane with NIPAM. Both of them are mainly acted by NIPAM, and the disadvantage that they are easy to hydrolyze to produce toxic substances is avoided. The two preparation methods have the defects of complicated synthesis steps, slow reaction speed, high production cost and no contribution to the actual production in the use process, which is the defect of the prior art. Based on the reasons, the invention provides a preparation method of novel comb-shaped temperature-sensitive waterborne polyurethane to solve the defects.
Disclosure of Invention
The invention provides a preparation method of novel comb-shaped temperature-sensitive waterborne polyurethane, which aims to overcome the defects of complex synthesis and high cost in the prior art. The preparation method of the novel comb-shaped temperature-sensitive waterborne polyurethane has the characteristics of simple process, low cost and the like.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of novel comb-shaped temperature-sensitive waterborne polyurethane comprises the steps of synthesizing the temperature-sensitive waterborne polyurethane (TWPU), firstly synthesizing linear waterborne polyurethane with double bonds on side chains, and then grafting N-vinyl pyrrolidone (NVP) to the side chains through a free radical polymerization method so as to synthesize the linear temperature-sensitive waterborne polyurethane.
Preferably, 0.00125mol (2.5g) of polytetrahydrofuran diol (PTMG2000) is weighed into a 250ml four-necked flask and water is removed under vacuum at 130 ℃ under a vacuum of-0.095 MPa for 2 h.
Preferably, a reflux condenser, a mechanical stirrer and an N2 flow-through device were installed, 0.00175mol (0.2342g) dimethylolpropionic acid (DMPA) and 0.0015mol (0.5318g) monoglyceride were added, 40ml acetone and 5ml N-methylpyrrolidone (NMP) were added as a solvent, and the mixture was heated with stirring until the temperature reached 75 ℃ and 0.005mol (1.1115g) isophorone diisocyanate (IPDI) and 0.3g dibutyltin dilaurate (DBTDL) as a catalyst were added and reacted at this temperature for 3 hours.
Preferably, 0.0015mol of 1, 4-Butanediol (BDO) is then added and the chain extension reaction is continued at 75 ℃ for 3 h.
Preferably, 0.0015mol of NVP and 0.04g of Azobisisobutyronitrile (AIBN) are added and reacted at 75 ℃ for 4 h.
Preferably, the mixture is transferred to normal temperature, triethylamine (with the same molar amount as DMPA) and 20ml of deionized water are added, and the mixture is fully stirred for 2 hours.
Preferably, then the acetone is removed by rotary evaporation at normal temperature under the vacuum degree of-0.095 MPa, and the comb-shaped temperature-sensitive waterborne polyurethane is obtained.
Compared with the prior art, the invention has the beneficial effects that: the invention uses N-vinyl pyrrolidone (NVP) to prepare temperature-sensitive waterborne polyurethane, and the synthetic method is different from the temperature-sensitive monomer introduction method in the prior art, monoglyceride with double bonds on the side chain is selected as a dihydric alcohol raw material, NVP is grafted on the side chain in the polyurethane synthesis process, and comb-shaped waterborne polyurethane with temperature sensitivity is synthesized.
Drawings
FIG. 1 is a schematic synthesis route of a TWPU of the present invention;
FIG. 2 is an infrared spectrum of a TWPU of the present invention;
FIG. 3 is a graph of TWPU particle size versus temperature for the inventive TWPU;
FIG. 4 is a table showing the variation of particle size with temperature for TWPU of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-4, the present invention provides a technical solution: firstly synthesizing linear waterborne polyurethane with double bonds on side chains, then grafting N-vinyl pyrrolidone (NVP) on the side chains by a free radical polymerization method to synthesize linear temperature-sensitive waterborne polyurethane, weighing 0.00125mol (2.5g) of polytetrahydrofuran diol (PTMG2000) in a 250ml four-neck flask, removing water for 2h under vacuum at 130 ℃ under the vacuum degree of-0.095 MPa, filling a condensation reflux device, a mechanical stirrer and an N2 filling device, adding 0.00175mol (0.2342g) of dimethylolpropionic acid (DMPA) and 0.0015mol (0.5318g) of monoglyceride, adding 40ml of acetone and 5ml of N-methyl pyrrolidone (NMP) as solvents, heating and stirring to 75 ℃, adding 0.005mol (1.1115g) of isophorone diisocyanate (IPDI) and 0.3g of dibutyltin dilaurate (DBTDL) as a catalyst, reacting for 3h at the temperature, then adding 0.0015mol of 1, 4-Butanediol (BDO), continuously carrying out chain extension reaction for 3h at 75 ℃, adding 0.0015mol of NVP and 0.04g of Azobisisobutyronitrile (AIBN), carrying out reaction for 4h at 75 ℃, moving to normal temperature, adding triethylamine (with the same molar weight as DMPA) and 20ml of deionized water, fully stirring for 2h, and then carrying out rotary evaporation at normal temperature under the vacuum degree of-0.095 MPa to remove acetone, thus obtaining the comb-shaped temperature-sensitive waterborne polyurethane.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (7)

1. A preparation method of novel comb-shaped temperature-sensitive waterborne polyurethane is characterized by comprising the following steps: synthesizing the temperature-sensitive waterborne polyurethane (TWPU), firstly synthesizing linear waterborne polyurethane with double bonds on the side chain, and then grafting N-vinyl pyrrolidone (NVP) on the side chain by a free radical polymerization method so as to synthesize the linear temperature-sensitive waterborne polyurethane.
2. The preparation method of the novel comb-shaped temperature-sensitive waterborne polyurethane as claimed in claim 1, wherein the preparation method comprises the following steps: 0.00125mol (2.5g) of polytetrahydrofuran diol (PTMG2000) was weighed into a 250ml four-necked flask and water was removed under vacuum at 130 ℃ under a vacuum of-0.095 MPa for 2 hours.
3. The preparation method of the novel comb-shaped temperature-sensitive waterborne polyurethane as claimed in claim 2, wherein the preparation method comprises the following steps: a reflux condenser, a mechanical stirrer and an N2 flow-through device were placed, 0.00175mol (0.2342g) dimethylolpropionic acid (DMPA) and 0.0015mol (0.5318g) monoglyceride were added, 40ml acetone and 5ml N-methylpyrrolidone (NMP) were added as solvents, the mixture was heated with stirring to a temperature of 75 ℃ and 0.005mol (1.1115g) isophorone diisocyanate (IPDI) and 0.3g dibutyltin dilaurate (DBTDL) as a catalyst were added and reacted at this temperature for 3 hours.
4. The preparation method of the novel comb-shaped temperature-sensitive waterborne polyurethane as claimed in claim 3, wherein the preparation method comprises the following steps: then 0.0015mol of 1, 4-Butanediol (BDO) is added, and the chain extension reaction is continued for 3 hours at 75 ℃.
5. The preparation method of the novel comb-shaped temperature-sensitive waterborne polyurethane as claimed in claim 4, wherein the preparation method comprises the following steps: 0.0015mol of NVP and 0.04g of Azobisisobutyronitrile (AIBN) were added and reacted at 75 ℃ for 4 hours.
6. The preparation method of the novel comb-shaped temperature-sensitive waterborne polyurethane as claimed in claim 5, wherein the preparation method comprises the following steps: after the mixture was cooled to room temperature, triethylamine (equimolar to DMPA) and 20ml of deionized water were added and the mixture was stirred well for 2 hours.
7. The preparation method of the novel comb-shaped temperature-sensitive waterborne polyurethane as claimed in claim 6, wherein the preparation method comprises the following steps: and then, rotationally evaporating at normal temperature under the vacuum degree of-0.095 MPa to remove acetone to obtain the comb-shaped temperature-sensitive waterborne polyurethane.
CN201910833638.6A 2019-09-04 2019-09-04 Preparation method of novel comb-shaped temperature-sensitive waterborne polyurethane Pending CN110627967A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115449051A (en) * 2022-10-09 2022-12-09 安徽圣达生物药业有限公司 Temperature-sensitive waterborne polyurethane and preparation method thereof

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JPS6431814A (en) * 1987-07-28 1989-02-02 Fujikura Kasei Kk Unsaturated group-containing polyurethane resin
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CN101519479A (en) * 2009-01-22 2009-09-02 广东天银化工实业有限公司 Method for preparing self-cross linking type water-based fluorine-contained acrylic resin and polyurethane hybrid
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CN101175783A (en) * 2005-02-24 2008-05-07 巴斯福股份公司 Radiation-curable aqueous polyurethane dispersions
CN101522740A (en) * 2006-10-09 2009-09-02 巴斯夫欧洲公司 Radiation-curable compounds
CN101519479A (en) * 2009-01-22 2009-09-02 广东天银化工实业有限公司 Method for preparing self-cross linking type water-based fluorine-contained acrylic resin and polyurethane hybrid
CN107001570A (en) * 2014-12-17 2017-08-01 巴斯夫欧洲公司 The coating composition of radiation-hardenable based on chain growth and the polyurethane being crosslinked
CN105418853A (en) * 2015-11-27 2016-03-23 武汉仕全兴聚氨酯科技股份有限公司 Hydroxyl type water-borne cationic polyurethane-acrylic acid resin and preparation method thereof
CN109485827A (en) * 2018-10-26 2019-03-19 湖北大学 A kind of preparation method of aqueous polyurethane

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115449051A (en) * 2022-10-09 2022-12-09 安徽圣达生物药业有限公司 Temperature-sensitive waterborne polyurethane and preparation method thereof
CN115449051B (en) * 2022-10-09 2023-09-26 安徽圣达生物药业有限公司 Temperature-sensitive aqueous polyurethane and preparation method thereof

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