CN105524289B - The preparation method of shape memory polyurethane film covering solution - Google Patents
The preparation method of shape memory polyurethane film covering solution Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/42—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
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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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/57—Polyureas; Polyurethanes
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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
- C08G2280/00—Compositions for creating shape memory
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The preparation method and applications of shape memory polyurethane film covering solution, the invention belongs to field of material surface modification, it is also easy to produce the problem of fold weares and teares in use in order to solve existing paper products.The preparation of film covering solution：First, dry DMF and MDI is added to the PCL after dehydration, reaction obtains prepolymer at 70~80 DEG C；2nd, Isosorbide-5-Nitrae-BDO and DMF is added in prepolymer, chain extending reaction is carried out at a temperature of 70~80 DEG C, linear SMPU solution is obtained；3rd, the coating of SMPU solution on a glass, is dried processing, obtains shape memory polyurethane；4th, add DMF and be configured to solution.Application process is that paper products are immersed in shape memory polyurethane solution, and overlay film is completed after drying.The present invention is when the paper products for being coated with film produce fold, and when being heated to more than the glass transition temperature of polymer, paper products can recover smooth state.
Description
Technical field
The invention belongs to field of material surface modification, and in particular to a kind of preparation method and application side of polyurethane overlay film
Method.
Background technology
Shape-memory polymer, refers to the product with original shape, changes its primary condition under certain conditions simultaneously
After fixation, by the stimulation of external condition (such as heat, electricity, light, chemical co-ordination), the macromolecule material of its original shape can be recovered again
Material.From the point of view of high molecular Microphase Structure, polymer is " stationary phase " and " reversible to must just be included with shape memory
The phase structure of phase " two, its " stationary phase " can make polymer maintain solid shape (original shape), and " can anti-phase " be then with external condition (such as temperature
Degree) and polymer is occurred the reversible change of softening and hardening.Usually, shape-memory polymer passes through one or many shapings
Afterwards, the shape of article shaped fixes (remember) by chemistry or physics mode, and then less than one-shot forming temperature, higher than glass
Glass temperature TgWhen, then second shape, be now in glassy state can the strength of anti-phase be higher than the elastic restoring force of stationary phase,
Then this shape " freezing " is got off；When the condition that polymer turns to rubbery state by glassy state is realized, reversible phase resists solid
The strength that elasticity is recovered fixed mutually is reduced to a certain degree, and above-mentioned secondary forming frozen state dissolving, its shape returns to one again
The shape of secondary shaping.
Thermoplasticity shape-memory polymer is substantially that macromolecular chain forms stationary phase and reversible in the way of being physical crosslinking
Phase.When temperature is increased to glass transition temperature (Tg) more than when, the micro-Brownian movement aggravation of reversible phase molecule chain and is fixed
Still in solid state, now shape-memory polymer is deformed with certain external force, and keep external force to be allowed to cool down, can
The new shape i.e. deformation states that anti-phase solidification is stablized.When temperature is increased to T againg, can anti-phase softening, stationary phase holding during the above
Solidification, reversible phase molecule chain movement is brought back to life, and thermodynamic equilibrium state is progressively reached under the recovery stress effect of stationary phase, i.e., grand
Sight shows as restoring to the original state.Intelligent temperature-sensitive shape-memory polymer is exactly one kind of shape memory polymer material, the Type of Collective
Tetramune can automatically revert to original shape after deformation and fixation under specific external condition-thermostimulation.
Shape memory polyurethane has raw materials for production wide, and formula adjustability is big, and the advantages of shape memory temperature scope is wide is fitted
A variety of application needs should can be met in moulding process such as extruding, injection moulding, coating, castings, its good penetrability, heat are swollen
Swollen property, shock resistance and light refraction performance and temperature are closely related.
The content of the invention
The invention aims to solve existing paper products to be also easy to produce the problem of fold weares and teares in use, and carry
For a kind of method and its application of shape memory polyurethane overlay film.
The preparation method of shape memory polyurethane film covering solution of the present invention follows these steps to realize：
First, DMF (N,N-dimethylformamide) is usedMolecular sieve drying processing, obtains dry DMF, and liquid PCL is (poly-
Caprolactone) it is placed in reaction vessel and vacuumizes dehydration, then add dry DMF and MDI (hexichol under conditions of argon gas protection
Methane diisocyanate), 1.5~2.5h of stirring reaction, obtains prepolymer at 70~80 DEG C；
2nd, Isosorbide-5-Nitrae-BDO (BDO) and the DMF dried are added in the prepolymer obtained to step one, 70~80
Chain extending reaction is carried out at a temperature of DEG C, is obtained containing linear SMPU solution (the linear shape memory that solid content is 13%~18%
Polyurethane)；
3rd, by linear SMPU solution even application on a glass, it is positioned in 70~100 DEG C of baking ovens and fully dry
12~15h, then places 22~26h, obtains shape memory polyurethane at room temperature；
4th, the shape memory polyurethane for obtaining step 3 is added in reaction bulb with the DMF dried, prepares shape memory
Polyurethane mass content is 5%~10% solution, and magnetic agitation is completely dissolved up to polyurethane, obtains shape memory polyurethane
Film covering solution；
The mol ratio of liquid PCL and MDI wherein described in step one are 1：(2~4).
Follow these steps to realize using the method for shape memory polyurethane film covering solution overlay film：
First, shape memory polyurethane solution is poured into glass dish, paper products are immersed in shape memory polyurethane solution,
Take out paper products to be clipped between two pieces of polyfluortetraethylene plates, obtaining clamping has the polyfluortetraethylene plate of paper products；
2nd, the polyfluortetraethylene plate that clamping there are paper products is placed in drying box, it is molten to heat removing with 55~65 DEG C
Agent, the paper products that surface is covered with shape memory polyurethane film must be arrived after cooling down at room temperature by taking out.
The present invention can automatically revert to original shape under characteristic-thermostimulation using intelligent temperature-sensitive shape-memory polymer,
Shape memory polyurethane material is plated on paper products in the form of a film, will when the paper products for being coated with film produce fold
When paper products are heated to more than the glass transition temperature Tg of polymeric material, paper products can just recover smooth state.
The present invention is the economic loss brought for the breakage reduced by paper products, it is proposed that by the poly- ammonia of shape memory
Ester material overlay film paper products make its wrinkle resistant method.This prevents the method for paper curl to have using shape memory polyurethane solution
Advantages below：
1st, the raw material selected does not have no in oxide generation, preparation process add in itself without genotoxic potential during being made
Enter catalyst, therefore resulting polyurethane material does not have toxicity, it is fool proof as application material.
2nd, shape memory polyurethane formula adjustability is big, and shape memory temperature scope is wide, and is adapted to extruding, is injected into
The moulding process such as type, coating, casting.
3rd, the shape recovery of covering material can be more excellent, while overlay film is relatively thin, transparency is good, does not influence made of paper
The use of product.
Brief description of the drawings
Fig. 1 is the SEM electron microscopes for the paper products (bank note) that surface is covered with shape memory polyurethane film；
Fig. 2 is the SEM electron microscopes for the paper products (bank note) that surface is not covered with shape memory polyurethane film；
Fig. 3 is form photo figure when surface is covered with paper products (bank note) initial state of shape memory polyurethane film；
Fig. 4 is form when surface is covered with paper products (bank note) deformation states (generation fold) of shape memory polyurethane film
Photo figure；
Fig. 5 is form when surface is covered with paper products (bank note) reply state (the fold disappearance) of shape memory polyurethane film
Photo figure.
Embodiment
Embodiment one：The preparation method of present embodiment shape memory polyurethane film covering solution follows these steps reality
Apply：
First, DMF (N,N-dimethylformamide) is usedMolecular sieve drying processing, obtains dry DMF, liquid PCL
(polycaprolactone), which is placed in reaction vessel, vacuumizes dehydration, then adds dry DMF and MDI under conditions of argon gas protection
('-diphenylmethane diisocyanate), 1.5~2.5h of stirring reaction, obtains prepolymer at 70~80 DEG C；
2nd, Isosorbide-5-Nitrae-BDO (BDO) and the DMF dried are added in the prepolymer obtained to step one, 70~80
Chain extending reaction is carried out at a temperature of DEG C, is obtained containing linear SMPU solution (the linear shape memory that solid content is 13%~18%
Polyurethane)；
3rd, by linear SMPU solution even application on a glass, it is positioned in 70~100 DEG C of baking ovens and fully dry
12~15h, then places 22~26h, obtains shape memory polyurethane at room temperature；
4th, the shape memory polyurethane for obtaining step 3 is added in reaction bulb with the DMF dried, prepares shape memory
Polyurethane mass content is 5%~10% solution, and magnetic agitation is completely dissolved up to polyurethane, obtains shape memory polyurethane
Film covering solution；
The mol ratio of liquid PCL and MDI wherein described in step one are 1：(2~4).
The synthetic method of present embodiment shape memory polyurethane solution is mainly anti-including vacuumizing dehydration, pre-polymerization and chain extension
Answer the stage, building-up process can be carried out in fume hood.Test the number-average molecular weight M of obtained shape memory polyurethanenScope
For 52000~55000.
The principle of present embodiment synthesis shape memory polyurethane is shown below：
Need strictly to control moisture in the Preparatory work of experiment and experimentation of synthesis of polyurethane, one is because performed polymer often can
Moisture is absorbed, and the presence of moisture can cause unfavorable result：With in performed polymer-NCO group reacts, generation urea groups is simultaneously
Increase the viscosity of performed polymer, can also further be reacted in turn by branch point of urea groups with-NCO group, form biuret branch
Chain or crosslinking and make performed polymer bin stability reduce even gel；Two be in order to avoid occurring bubble in building-up process,
When synthesizing performed polymer, the generation of bubble is totally unfavorable, and substantial amounts of bubble can make temperature of reaction system fluctuation very big in liquid, enter
And reaction is difficult to control to, it should try one's best and reduce the generation of bubble, be that performed polymer deaeration can smoothly complete offer conveniently.This embodiment party
The shape memory polyurethane that formula synthesis is obtained, through surveying its glass transition temperature at 37 DEG C or so.
Embodiment two：Present embodiment and the liquid PCL described in step one unlike embodiment one
Solid-state PCL is placed in into heating melting in drying box to obtain.Other steps and parameter are identical with embodiment one.
Embodiment three：Present embodiment is (poly- from step one liquid PCL unlike embodiment one or two
Caprolactone) it is placed in reaction vessel under conditions of 120 DEG C of water-bath and vacuumizes dehydration 1h.Other steps and parameter and specific implementation
Mode one or two is identical.
Embodiment four：Unlike one of present embodiment and embodiment one to three described in step one
Liquid PCL and MDI mol ratio be 1：3.Other steps and parameter are identical with one of embodiment one to three.
The content of present embodiment hard section can influence the formation of shape memory polyurethane.When hard segment content increase, TgRise
Height, reaches required temperature range, and the compatibility increase in soft segment area and hard section area, so that the shape recovery ratio of material increases
Greatly.Simultaneously under this ratio, obtained polyurethane has more excellent tensile strength, the mechanical property such as hardness.
Embodiment five：Step one is at 75 DEG C unlike one of present embodiment and embodiment one to four
Lower stirring reaction 2h.Other steps and parameter are identical with one of embodiment one to four.
Embodiment six：Step 2 1,4 unlike one of present embodiment and embodiment one to five-
BDO addition is to make the mol ratio of NCO group in prepolymer and the OH groups in 1,4-BDO be 1：1.Other steps and
Parameter is identical with one of embodiment one to five.
Embodiment seven：Step 4 unlike one of present embodiment and embodiment one to six with
200r/min rotating speed carries out magnetic agitation.Other steps and parameter are identical with one of embodiment one to six.
Embodiment eight：The method of present embodiment application shape memory polyurethane film covering solution overlay film presses following step
It is rapid to implement：
First, shape memory polyurethane solution is poured into glass dish, paper products are immersed in shape memory polyurethane solution,
Take out paper products to be clipped between two pieces of polyfluortetraethylene plates, obtaining clamping has the polyfluortetraethylene plate of paper products；
2nd, the polyfluortetraethylene plate that clamping there are paper products is placed in drying box, it is molten to heat removing with 55~65 DEG C
Agent, the paper products that surface is covered with shape memory polyurethane film must be arrived after cooling down at room temperature by taking out.
Spin coater overlay film on the surface of the paper products can also be used in present embodiment.
Embodiment nine：Present embodiment is immersed in shape from step one paper products unlike embodiment eight
Time in shape memory polyurethane solution is 5~8 minutes.Other steps and parameter are identical with embodiment eight.
Embodiment ten：Present embodiment is used with de- from step one unlike embodiment eight or nine
The glass plate of mould cloth replaces polyfluortetraethylene plate.Other steps and parameter are identical with embodiment eight or nine.
Embodiment 11：It is described made of paper unlike one of present embodiment and embodiment eight to ten
Product are certificate made of paper, file books and periodicals, newspaper, poster, the certificate diploma, paper-cut or bill.Other steps and parameter and specific implementation
One of mode eight to ten is identical.
Embodiment one：The preparation method of the present embodiment shape memory polyurethane film covering solution follows these steps to implement：
First, DMF (N,N-dimethylformamide) is usedMolecular sieve drying handles 24h, obtains dry DMF, solid-state
PCL, which is placed in drying box, to be heated melting and obtains liquid PCL, 10g liquid PCL (molecular weight of polycaprolactone be 2000) and be placed in carry
Dehydration 1h is vacuumized under conditions of 120 DEG C of water-bath in mechanical agitation, argon gas protection, the four-hole boiling flask of condenser pipe and thermometer,
Then dry 60g DMF and 3.75g MDI ('-diphenylmethane diisocyanate) is added under conditions of argon gas protection, at 75 DEG C
Lower stirring reaction 2h, obtains prepolymer, takes out a small amount of prepolymer progress-NCO titration；
2nd, 0.9g Isosorbide-5-Nitraes-BDO (BDO) and 38g DMF is added in the prepolymer obtained to step one, 75
Chain extending reaction 2h is carried out at a temperature of DEG C, is obtained containing linear SMPU solution (the poly- ammonia of linear shape memory that solid content is 15%
Ester)；
3rd, by linear SMPU solution even application on a glass, it is positioned in 90 DEG C of baking ovens and carries out fully drying 12h,
Then 24h is placed at room temperature, obtains shape memory polyurethane；
4th, the shape memory polyurethane and DMF obtained step 3 is added in reaction bulb, prepares shape memory polyurethane
Mass content is 10% solution, with 200r/min rotating speed magnetic agitation 5 hours untill polyurethane is completely dissolved in DMF,
Obtain shape memory polyurethane film covering solution.
Application Example：The method of the present embodiment application shape memory polyurethane film covering solution overlay film follows these steps reality
It is existing：
First, shape memory polyurethane solution is poured into glass dish, 1 yuan (bank note) is immersed in the poly- ammonia of shape memory
5 minutes in ester solution, take out bank note and be clipped between two pieces of polyfluortetraethylene plates (size is 250mm × 200mm × 5mm), obtain
Clamping has the polyfluortetraethylene plate of bank note；
2nd, the polyfluortetraethylene plate that clamping has bank note is placed in drying box, it is molten to heat removing in 5 hours with 60 DEG C
Agent, takes out the bank note for obtaining showing to be covered with shape memory polyurethane film after cooling 10min at room temperature.
The smooth bank note for being covered with shape memory polyurethane film is heated to 40 DEG C or so doublings by the present embodiment, fixes it
Shape is simultaneously cooled to room temperature, when being again heated to 60 DEG C or so, by 3min or so time, it can be found that the bank note of doubling by
Gradually deploy, until folding line disappears, recover smooth state, return fully to initial form, reached this wrinkle resistant effect,
The transparency of overlay film is good simultaneously, and specific recovery process is as in Figure 3-5.
Embodiment two：The present embodiment and step one unlike embodiment one are by the 5g liquid PCL (molecular weight of polycaprolactone
4000) to be placed in the condition in mechanical agitation, argon gas protection, the four-hole boiling flask of condenser pipe and thermometer in 120 DEG C of water-bath
Under vacuumize dehydration 1h, then argon gas protection under conditions of add dry 60g DMF and 3.75g MDI (diphenyl-methanes two
Isocyanates), stirring reaction 2h, obtains prepolymer at 75 DEG C.
The glass transition temperature for the linear shape memory polyurethane that the present embodiment is obtained is at 45 DEG C or so.Smooth is covered
The bank note for having shape memory polyurethane film is heated to 50 DEG C or so doublings, fixes its shape and is cooled to room temperature, heats again
During to 60 DEG C or so, by 2min or so time, it is found that the bank note of doubling is gradually spread out, until folding line disappears, recover smooth
State, reached wrinkle resistant effect.And the time for the state that restores to the original state is shorter.
Claims (6)
1. the preparation method of shape memory polyurethane film covering solution, it is characterised in that be to follow these steps to realize：
First, DMF is usedMolecular sieve drying processing, obtains dry DMF, liquid PCL, which is placed in reaction vessel, vacuumizes dehydration,
Then dry DMF and MDI is added under conditions of argon gas protection, 1.5~2.5h of stirring reaction at 70~80 DEG C obtains pre-
Polymers；
2nd, Isosorbide-5-Nitrae-BDO and the DMF dried are added in the prepolymer obtained to step one, is expanded at a temperature of 70~80 DEG C
Chain reaction, is obtained containing the linear SMPU solution that solid content is 13%~18%；
3rd, by linear SMPU solution even application on a glass, be positioned in 70~100 DEG C of baking ovens and fully dry 12~
15h, then places 22~26h, obtains shape memory polyurethane at room temperature；
4th, the shape memory polyurethane for obtaining step 3 is added in reaction bulb with the DMF dried, prepares the poly- ammonia of shape memory
Ester mass content is 5%~10% solution, and magnetic agitation is completely dissolved up to polyurethane, obtains shape memory polyurethane overlay film
Solution；
The mol ratio of liquid PCL and MDI wherein described in step one are 1：(2~4).
2. the preparation method of shape memory polyurethane film covering solution according to claim 1, it is characterised in that step one institute
Solid-state PCL is placed in heating melting in drying box and obtained by the liquid PCL stated.
3. the preparation method of shape memory polyurethane film covering solution according to claim 1, it is characterised in that in step one
Described liquid PCL and MDI mol ratio is 1：3.
4. the preparation method of shape memory polyurethane film covering solution according to claim 1, it is characterised in that step one exists
Stirring reaction 2h at 75 DEG C.
5. the preparation method of shape memory polyurethane film covering solution according to claim 1, it is characterised in that step 21,
4-BDO addition is to make the mol ratio of NCO group in prepolymer and the OH groups in 1,4-BDO be 1：1.
6. the preparation method of shape memory polyurethane film covering solution according to claim 1, it is characterised in that step 4 with
200r/min rotating speed carries out magnetic agitation.
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| CN106854267B (en) * | 2017-01-11 | 2019-06-28 | 济南大学 | A method of polymer elasticity microballoon is prepared by precipitation polymerization |
| CN106987112A (en) * | 2017-04-11 | 2017-07-28 | 上海交通大学 | Electric drive resin base shape memory composite and preparation method thereof |
| CN108144557B (en) * | 2017-12-28 | 2020-03-31 | 哈尔滨工业大学 | Preparation method and driving method of shape memory polyurethane micro-nano capsule |
| 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 |
| CN112358595A (en) * | 2019-10-25 | 2021-02-12 | 四川大学华西医院 | Operation suture line with antibacterial and shape memory functions and preparation method thereof |
| CN112876816A (en) * | 2021-02-25 | 2021-06-01 | 刘龙汇 | Resin-based foam composite board and preparation method thereof |
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| CN101265317A (en) * | 2007-03-15 | 2008-09-17 | 张红 | High-strength shape memory polyurethane material and preparation method thereof |
| CN102786648A (en) * | 2011-05-20 | 2012-11-21 | 中国科学院化学研究所 | Cross-linking type shape memory polyurethane |
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