CN106632961A - Method for preparing shape memory polyurethane by utilizing 4,4'-diphenol chain extension - Google Patents

Method for preparing shape memory polyurethane by utilizing 4,4'-diphenol chain extension Download PDF

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Publication number
CN106632961A
CN106632961A CN201610925825.3A CN201610925825A CN106632961A CN 106632961 A CN106632961 A CN 106632961A CN 201610925825 A CN201610925825 A CN 201610925825A CN 106632961 A CN106632961 A CN 106632961A
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China
Prior art keywords
shape memory
chain extension
memory polyurethane
diphenol
utilizing
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CN201610925825.3A
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CN106632961B (en
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李裕琪
徐旭
陆绍荣
韦春
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Guilin University of Technology
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Guilin University of Technology
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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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 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
    • 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
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G2280/00—Compositions for creating shape memory

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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 method for preparing shape memory polyurethane by utilizing 4,4'-diphenol chain extension. The method comprises the following steps: putting 2.0g of polycaprolactone diol with the weight-average molecular weight of 1000 into a round bottomed flask and heating under a nitrogen atmosphere to 80 DEG C; magnetically stirring until the polycaprolactone diol is melted; then adding 20ml of N,N-dimethylformamide and 0.1ml of dibutyltin dilaurate; heating a mixture to 105 DEG C and keeping the heat for 15min to remove water; cooling to 80 DEG C; adding 0.67ml of hexamethylene diisocyanate and reacting at 80 DEG C for 3h-5h, so as to prepare a mixed solution containing a terminal isocyanate polyurethane prepolymer; adding 0.38g of 4,4'-diphenol and stirring and reacting in the nitrogen atmosphere and at 80 DEG C for 12h; pouring the materials into a mold pre-heated at 50 DEG C-80 DEG C; and heating and curing at 70 DEG C-90 DEG C for 6h-8h, so as to prepare the shape memory polyurethane by utilizing the 4,4'-diphenol chain extension. The method disclosed by the invention is simple to operate; and a prepared shape memory polyurethane material has excellent mechanical and thermal properties and shape memory property.

Description

The method for preparing shape memory polyurethane using 4,4 '-'-biphenyl diphenol chain extension
Technical field
The invention belongs to intelligent macromolecule material technical field, more particularly to one kind utilize 4,4 '-'-biphenyl diphenol chain extension system The method of standby shape memory polyurethane.
Background technology
Shape-memory material has important using value in bio-medical field, structural member field, field of textiles, is near Nian Lai academias and the study hotspot and emphasis of industrial quarters.Especially shape memory high molecule（Shape Memory Polymer, Abbreviation SMP）Material has the advantages that easy processing, easy-formation, light weight, with very huge potential using value, from the eighties Start, the researcher of countries in the world increases the input to SMP and research so that the research of SMP has obtained quick development, Become when the important functional material of former.
Be used to research and develop one of material of SMP, shape memory polyurethane as early start（Shape Memory Polyurethane, abbreviation SMPU）From the eighties by having obtained extensive concern after Mitsubishi heavy industry commercial development success.It is poly- Urethane is as chain extender by polyisocyanates and PPG or PEPA and small molecule polyol, polyamine etc. Deng a kind of polymer prepared by raw material.In the polymer, the chain rigidity of NCO and chain extender shows as hard section, between hard section Hydrogen bond and other chain windings effect can play a part of physical crosslinking in SMP, and polyester or polyether Glycols are soft Section, then can play a part of molecular switch.So, the structure design and proportion adjustment of soft and hard segments prepare high-performance SMPU Key point.
Polycaprolactone（Polycaprolactone, abbreviation PCL）It is that the hypocrystalline obtained by 6-caprolactone ring-opening polymerisation gathers Ester macromolecule, is usually used in the preparation of SMPU.Because PCL has end group reactable, can pass through to select different initiator systems The standby PCL for obtaining the different structure such as starlike, dendritic, so as to the SMPU of different structure is obtained, this causes PCL to study in SMP material In occupy an important seat.But the mechanical performance of PCL is poor, the application of SMP is limited.
4,4 '-'-biphenyl diphenol（4,4 '-Biphenol, abbreviation BP）It is synthetic high polymer because its heat resistance is splendid Important intermediate raw material, is used for example as the modified monomer of polyester, polyurethane, Merlon, polysulfones and epoxy resin, to manufacture Excellent engineering plastics and composite.
The present invention carries out chain extension by MOLECULE DESIGN using BP, is prepared by cross-linking modified mechanism with reference to PCL comprehensive The good SMPU of energy.This thinking has no at present document report.
The content of the invention
It is an object of the invention to provide a kind of method for utilizing 4,4 '-'-biphenyl diphenol chain extension to prepare shape memory polyurethane.
Concretely comprise the following steps：
(1) polycaprolactone diols that 2.0g weight average molecular weight is 1000 is put in round-bottomed flask, is heated under nitrogen atmosphere 80 DEG C and magnetic agitation are subsequently adding 20ml DMFs until melt（DMF）With the fourth of 0.1 ml tin dilaurates two Ji Xi（DBTDL）, 105 DEG C of insulation 15min eliminating waters are heated the mixture to, then 80 DEG C are cooled to, addition 0.67ml hexa-methylenes Diisocyanate（HDI）, 3 ~ 5h is reacted at 80 DEG C, the mixed liquor containing isocyanate terminated base polyurethane prepolymer for use as is obtained.
(2) 0.38g 4,4 '-'-biphenyl diphenol is added to into step (1) obtained containing isocyanate terminated base polyurethane prepolymer for use as Mixed liquor in, in blanket of nitrogen at 80 DEG C stirring reaction 12h, then pour into together in mould preheated at 50 ~ 80 DEG C, Be heating and curing 6 ~ 8h at 70 ~ 90 DEG C, that is, be obtained and utilize 4, the shape memory polyurethane of 4 '-'-biphenyl diphenol chain extension.
The inventive method is simple to operate, and obtained shape memory polyurethane material have excellent mechanics, calorifics and Shape-memory properties.Its main performance index is as follows：Elongation at break reaches nearly 600%；Tensile strength reaches 35MPa or so；3% Thermal weight loss temperature >=275 DEG C；Secondary cycle shape fixed rate is 80% ~ 100%；Secondary cycle shape recovery rate be 90% ~ 100%。
Specific embodiment
Embodiment：
(1) polycaprolactone diols that 2.0g weight average molecular weight is 1000 is put in round-bottomed flask, is heated under nitrogen atmosphere 80 DEG C and magnetic agitation are subsequently adding 20ml DMFs until melt（DMF）With the fourth of 0.1 ml tin dilaurates two Ji Xi（DBTDL）, 105 DEG C of insulation 15min eliminating waters are heated the mixture to, then 80 DEG C are cooled to, addition 0.67ml hexa-methylenes Diisocyanate（HDI）, 4h is reacted at 80 DEG C, the mixed liquor containing isocyanate terminated base polyurethane prepolymer for use as is obtained.
(2) 0.38g 4,4 '-'-biphenyl diphenol is added to into step (1) obtained containing isocyanate terminated base polyurethane prepolymer for use as Mixed liquor in, in blanket of nitrogen at 80 DEG C stirring reaction 12h, then pour into together in mould preheated at 60 DEG C, Be heating and curing 7h at 80 DEG C, that is, be obtained and utilize 4, the shape memory polyurethane of 4 '-'-biphenyl diphenol chain extension.
Shape memory polyurethane obtained in the present embodiment is tested, its elongation at break is 599.5%, tensile strength For 34.67MPa；Secondary cycle shape fixed rate is 83.24%, and secondary cycle shape recovery rate is 93.78%；3% thermal weight loss temperature For 277 DEG C, maximum decomposition temperature is 336 DEG C, and 550 DEG C of Residual carbon is 4.438%, and combination property is more excellent.

Claims (1)

1. one kind utilizes 4, the method that 4 '-'-biphenyl diphenol chain extension prepares shape memory polyurethane, it is characterised in that concretely comprise the following steps：
(1) polycaprolactone diols that 2.0g weight average molecular weight is 1000 is put in round-bottomed flask, is heated under nitrogen atmosphere 80 DEG C and magnetic agitation are subsequently adding 20ml DMFs and 0.1 ml dibutyl tin laurates until melt, 105 DEG C of insulation 15min eliminating waters are heated the mixture to, then is cooled to 80 DEG C, add 0.67ml hexamethylene diisocyanates, in 3 ~ 5h is reacted at 80 DEG C, the mixed liquor containing isocyanate terminated base polyurethane prepolymer for use as is obtained；
(2) 0.38g 4,4 '-'-biphenyl diphenol is added to into step (1) obtained mixed containing isocyanate terminated base polyurethane prepolymer for use as Close liquid in, in blanket of nitrogen at 80 DEG C stirring reaction 12h, then pour into together in mould preheated at 50 ~ 80 DEG C, 70 Be heating and curing 6 ~ 8h at ~ 90 DEG C, that is, be obtained and utilize 4, the shape memory polyurethane of 4 '-'-biphenyl diphenol chain extension.
CN201610925825.3A 2016-10-31 2016-10-31 The method for preparing shape memory polyurethane using 4,4 '-'-biphenyl diphenol chain extensions Active CN106632961B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109880054A (en) * 2019-03-29 2019-06-14 中国科学院宁波材料技术与工程研究所 Polyurethane and preparation method thereof with shape memory function
CN109912773A (en) * 2019-03-29 2019-06-21 中国科学院宁波材料技术与工程研究所 A kind of shape memory polyurethane and preparation method thereof
CN110437402A (en) * 2019-08-09 2019-11-12 中国科学院兰州化学物理研究所 A kind of preparation method of the interpenetrating net polymer with shape-memory properties
CN112094397A (en) * 2020-09-23 2020-12-18 广东石油化工学院 Preparation method of sisal hemp based shape memory polyurethane foam

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* Cited by examiner, † Cited by third party
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US20090093606A1 (en) * 2007-10-09 2009-04-09 The Hong Kong Polytechnic University Shape memory fibers prepared via wet, reaction, dry, melt, and electro spinning
CN105622888A (en) * 2016-03-28 2016-06-01 桂林理工大学 Method for preparing shape memory polymer material with high strength and low response temperature

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US20090093606A1 (en) * 2007-10-09 2009-04-09 The Hong Kong Polytechnic University Shape memory fibers prepared via wet, reaction, dry, melt, and electro spinning
CN105622888A (en) * 2016-03-28 2016-06-01 桂林理工大学 Method for preparing shape memory polymer material with high strength and low response temperature

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109880054A (en) * 2019-03-29 2019-06-14 中国科学院宁波材料技术与工程研究所 Polyurethane and preparation method thereof with shape memory function
CN109912773A (en) * 2019-03-29 2019-06-21 中国科学院宁波材料技术与工程研究所 A kind of shape memory polyurethane and preparation method thereof
CN109912773B (en) * 2019-03-29 2021-10-26 中国科学院宁波材料技术与工程研究所 Shape memory polyurethane and preparation method thereof
CN110437402A (en) * 2019-08-09 2019-11-12 中国科学院兰州化学物理研究所 A kind of preparation method of the interpenetrating net polymer with shape-memory properties
CN112094397A (en) * 2020-09-23 2020-12-18 广东石油化工学院 Preparation method of sisal hemp based shape memory polyurethane foam

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Application publication date: 20170510

Assignee: Guangxi Yunzhi Jiuwo Experimental Instrument Co.,Ltd.

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Denomination of invention: Method of preparing shape memory polyurethane by chain extension of 4,4 - dihydroxybenzene

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Record date: 20221215

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