CN104371084A - Shape memory polyurethane with high-temperature restorability - Google Patents
Shape memory polyurethane with high-temperature restorability Download PDFInfo
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- 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
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- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- 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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- C08K2201/00—Specific properties of additives
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- C08K2201/004—Additives being defined by their length
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Abstract
The invention relates to a shape memory polyurethane material with high-temperature restorability, which is characterized in that irradiation-activated carbon fibers are added as a reinforcer to synthesize the polyurethane shape memory material with high-temperature restorability in situ. The synthesis method comprises the following steps: (1) activating treatment of carbon fibers: activating the carbon fibers to be activated at room temperature under the irradiation of radioactive Co rays; (2) synthesis and purification treatment of hexanediol polyadipate; and (3) in-situ synthesis of shape memory polyurethane: firstly synthesizing a polyurethane prepolymer, then adding the activated carbon fibers into the prepolymer to continue the reaction, and adding a chain extender for further polymerization, thereby forming the polyurethane with shape memory function. The method can overcome the operating restrictions caused by lower glass transition temperature in the common shape memory polyurethane material, well solves the problem of poor mechanical properties, enhances the tensile strength of the shape memory polyurethane material, and widens the application range of the material.
Description
Technical field
The invention belongs to polymeric material field.Be specifically related to a kind of shape memory polyurethane material with high temperature restorability.
Background technology
Shape memory polyurethane material is a kind of novel functional materials, has many excellent over-all propertieies.Shape-memory material refers to have original shape, after deformation is also fixing, can changes external conditions make it recover a class type material of original shape by methods such as heating.Since the ORKEM company of France develops first case shape-memory polymer (SMP) polynorbornene for 1984, the shape memory high molecule material be applied at present has polynorbornene, trans 1,4-polyisoprene, styrene butadiene, urethane etc., fluorine-containing polymer, polycaprolactone, polymeric amide etc. also have shape memory function in addition.Among many materials, shape memory polyurethane becomes the focus of SMP research with the performance of its excellence, and compared with other SMP, shape memory polyurethane (SMPU) has following advantages: (1) has thermoplasticity, handling ease; (2) proportioning raw materials change is many, and shape recovery temperature, at 30 ~ 80 DEG C, is easy to adjustment; (3) deformation rate is large, maximumly reaches 400%; (4) light weight, relative density is about 1.1 ~ 1.2; (5) cost is low, is less than 1/10 of shape memory alloy.Therefore, shape memory polyurethane (SMPU) becomes that use value is the highest, applied research Thermally stimulated shape memory polymer material the most widely.
Although there are so many advantages, traditional shape memory polyurethane material has larger defect, is first that its second-order transition temperature is lower, and generally below 50 DEG C, 40 DEG C time, some polyurethane materials just start to soften; Secondly, traditional polyurethane material non-refractory, just loses shape-recovery capabilities more than 80 DEG C, and therefore developing a kind of shape memory polyurethane material with high temperature restorability has important using value.
The present invention, by adding the carbon fiber of irradiation activation as reinforcement, has prepared a kind of polyurethane shape memory material with high temperature restorability, and this material can overcome the lower use restriction caused of common SMPU second-order transition temperature.Adopt activated carbon fibre to be that filler solves the poor problem of common SMPU mechanical property to a great extent in addition, substantially increase the tensile strength of SMPU material.
Summary of the invention
The object of the invention is to develop a kind of shape memory polyurethane material with high temperature restorability, this material is obtained by following steps:
The activation treatment of 1 carbon fiber
At room temperature the carbon fiber of required activation is activated under radioactive rays Co radiation exposure;
The synthesis of 2 poly-hexanodioic acid hexylene glycol esters and purification process
Agitator is being housed, water-and-oil separator, in the four-hole bottle of nitrogen tube, add hexylene glycol, succinic acid, hexanodioic acid, the amount of substance of acid and alcohol is equal, and tin protochloride is catalyzer, perhydronaphthalene is solvent, and oil bath is heated, control temperature, after reacting completely, product is transferred in beaker, adds trichloromethane and dissolve, cross and filter impurity, then with methyl alcohol process filtrate, produce precipitation, to precipitate vacuum-drying, and obtain white solid, this material is poly-hexanodioic acid hexylene glycol ester.The poly-hexanodioic acid hexylene glycol ester synthesized is put in heating and melting in four footpath bottles, and being evacuated under high temperature does not have bubble to produce, and is all removed by moisture content.
The fabricated in situ of 3 shape memory polyurethanes
Agitator is being housed, prolong, add the poly-hexanodioic acid hexylene glycol ester that purification process is crossed in four footpath bottles of thermometer, add the Toluene-2,4-diisocyanate measured, 4-vulcabond (TDI), obtains performed polymer after rapid reaction.By proportioning activated carbon fibre added in performed polymer and react, and carry out emulsification.Measure-NCO% in performed polymer, then according to measured-NCO%, calculate chainextender (1,4-butyleneglycol) amount, be put in after adding chainextender in mould, aggregated into the urethane with shape memory function in an oven further, just can have been remembered by the shape of mould shape, after this urethane is rubbed distortion by high temperature, under low temperature, this urethane returns to again the shape of original mould sizing.
Wherein in step 1, the irradiation intensity of Co ray is 1.25kGy/h, and the radiation treatment time is 80 hours.
Wherein in step 2, reaction vessel is 250mL four-hole bottle, adds 0.20 mol hexylene glycol, and the ratio of succinic acid and hexanodioic acid amount of substance is 1:9, the amount of substance of acid and alcohol is equal, tin protochloride is 0.02mmol, and perhydronaphthalene is 100 mL, and temperature of reaction controls as follows: first 150 ~ 160 DEG C of reactions 2 hours, again 190 ~ 200 DEG C of reactions 12 hours, trichloromethane is 150 mL, and precipitation agent methanol is 500mL, is deposited in 60 DEG C of vacuum-dryings 24 hours.Purifying dehydration temperaturre is at 105 DEG C, and vacuum tightness is 0.09MPa.
Wherein in step 3, Toluene-2,4-diisocyanate, the add-on of 4-vulcabond (TDI) is 1.04 times of poly-hexanodioic acid hexylene glycol ester amount of substance, the temperature that TDI adds controls at 60 DEG C, and at 80 DEG C, rapid stirring solution reaction obtained performed polymer after 2 hours, now added activated carbon fibre, the incorporation of carbon fiber is 1% of poly-hexanodioic acid hexylene glycol ester and TDI quality sum, the length of activated carbon fibre is 2mm, and at 80 DEG C, performed polymer and carbon fiber continue reaction 1 hour, carry out emulsification simultaneously.After adding chainextender, performed polymer temperature of reaction is in an oven 120 DEG C, and the reaction times is 30 minutes.
the advantage with the shape memory polyurethane of high temperature restorability of the present invention is as follows:
1, the present invention is by adding the carbon fiber of irradiation activation as reinforcement at urethane situ, substantially increase polyurethane material shape memory recovery temperature, test shows, irradiation activation carbon fiber reinforced urethane is transferred postpone at 170 DEG C and is still had the ability recovering deformation, and this extends the scope of application and the field of polyurethane shape memory material greatly.
2, the phase transition temperature of polyurethane material of the present invention is at 100 DEG C, can overcome the use restriction that common shape memory polyurethane second-order transition temperature lower (40-50 DEG C) causes.
3, adopt irradiation activation carbon fiber to be that filler solves the poor problem of common shape memory polyurethane mechanical property to a great extent, improve the tensile strength of SMPU material, hardness and rigidity are also significantly improved.
Embodiment
Below in conjunction with example, the present invention is described in further detail:
The preparation of the required reagent of reaction:
Be the concentrated hydrochloric acid of 36.6% with massfraction, the dilute hydrochloric acid of preparation 1mol/L.With the sodium hydroxide solution titration concentration of hydrochloric acid demarcated.
The preparation of 2mol/L Di-n-Butyl Amine-toluene solution: get 130g Di-n-Butyl Amine solution, in the volumetric flask of 500ml by dilution with toluene to scale, shake up, put into solvent bottle for subsequent use.
The activation treatment of carbon fiber: under the condition of room temperature by the carbon fiber of required activation under radioactive rays Co ray, radiation treatment.
The synthesis of poly-hexanodioic acid hexylene glycol ester: in four-necked bottle, add hexylene glycol, succinic acid and hexanodioic acid in proportion successively, catalyzer tin protochloride, solvent perhydronaphthalene, oil bath is heated, first 150 ~ 160 DEG C of reactions 2 hours, then 190 ~ 200 DEG C of reactions 12 hours, reaction stopped, after trichloromethane dissolves, use methanol extraction again, drying precipitated, obtain white solid product and be obtained intermediate product.
The purification process of raw material: poly-hexanodioic acid hexylene glycol ester is put in heating and melting in four-necked bottle, is evacuated to bubble-free and produces.
The fabricated in situ of fibre reinforced shape memory polyurethane: by processed poly-hexanodioic acid hexylene glycol ester in four-necked bottle, add than the TDI of calculated value little over amount, performed polymer is obtained after rapid stirring reacts for some time, activated carbon fibre is treated as chopped carbon fiber simultaneously, then activated carbon fibre is added total middle continuation of prepolymer reaction system to react, carry out emulsification simultaneously, after reaction for some time, after adding chainextender, then this performed polymer is placed in mould, namely reaction for some time obtains the urethane with shape memory function in an oven.
example 1
(1) preparation of the required reagent of reaction: the concentrated hydrochloric acid that 50g massfraction is 36.6% is got in the preparation of 1mol/L hydrochloric acid soln, in the volumetric flask of 500ml with distilled water diluting to scale, mixing.Get 20g sodium hydroxide distilled water to dissolve, in the volumetric flask then pouring 500ml into and with distilled water diluting to scale, mixing.Get a certain amount of Potassium Hydrogen Phthalate to be placed on respectively in Erlenmeyer flask, dissolve with distilled water, add several phenolphthalein indicator, with the sodium hydroxide solution titration prepared, when solution from colourless become redness time be terminal, survey and calculate the concentration that its mean value obtains sodium hydroxide solution for three times.With the sodium hydroxide solution titration hydrochloric acid demarcated, make indicator by tropeolin-D, solution is terminal when redness becomes yellow.Survey and calculate the actual concentrations that its mean value is hydrochloric acid for three times.
(2) 130g Di-n-Butyl Amine solution is got in the preparation of 2mol/L Di-n-Butyl Amine-toluene solution, in the volumetric flask of 500ml by dilution with toluene to scale, shake up, put into that to hold agent bottle for subsequent use.
(3) activation treatment of carbon fiber: under the condition of room temperature by the carbon fiber of required activation under the irradiation intensity of radioactive rays Co ray 1.25kGy/h, radiation treatment 80 hours.
(4) synthesis of poly-hexanodioic acid hexylene glycol ester: mechanical stirrer is being housed, water trap, in the four-hole bottle of thermometer, add 0.20 mol hexylene glycol, 0.02mol succinic acid and 0.18mol hexanodioic acid, make the amount of substance of acid and alcohol equal, 0.02mmol tin protochloride, 100 mL perhydronaphthalenes, oil bath is heated, first 150 ~ 160 DEG C of reactions 2 hours, again 190 ~ 200 DEG C of reactions 12 hours, stopped reaction, cooling, after adding 150 mL trichloromethanes dissolvings, with 500mL methyl alcohol, the poly-hexanodioic acid hexylene glycol ester in solution is precipitated out again, at 60 DEG C, this sample of vacuum-drying 24 hours, obtain white solid product both for obtained intermediate product gathers hexanodioic acid hexylene glycol ester.
(5) react the purification process of desired raw material: the poly-hexanodioic acid hexylene glycol ester of 34.20g is put in heating and melting in four footpath bottles, and maintains the temperature between 100-110 DEG C, vacuum tightness is be evacuated to bubble-free under the condition of 0.09MPa to produce.
(6) synthesis of shape memory polyurethane: processed poly-hexanodioic acid hexylene glycol ester is being equipped with agitator, prolong, in four footpath bottles of thermometer, at about the 60 DEG C TDI(isocyanos adding 6.02g in theory excessive 4%), at 80 DEG C, rapid stirring obtains performed polymer after reacting 2 hours.
(7) the adding of activated carbon fibre: 0.4000g activated carbon fibre proportioning being accounted for total mass 1% is treated as the chopped strand of 2mm, add at 80 DEG C in performed polymer and participate in reaction, the reaction times is 1 hour, and carries out emulsification.
(8) isocyanic acid root is the massfraction (%) of isocyano group (-NCO) contained by the performed polymer that synthesizes in pre-polymerization method, and this value is the foundation of next step chain extending reaction, and the mensuration of isocyanic acid root adopts Di-n-Butyl Amine method.
Get performed polymer 1.1583g and performed polymer 1.4181g respectively in Erlenmeyer flask, get an Erlenmeyer flask again as white test, adding 20ml toluene respectively makes it dissolve, then 10ml Di-n-Butyl Amine-toluene solution (2mol/L) is added, leave standstill 20-30min, add 40-50ml Virahol, several tetrabromo-mcresolsulfonphthalein indicator, solution becomes blueness, drops to yellow be terminal with hydrochloric acid soln.Same method makes blank assay.Calculate the content of isocyano in performed polymer:
Measure-NCO% in performed polymer, record-NCO% content 6.65%, then according to measured, calculate the amount of required chainextender BDO, in chainextender, the molar weight of hydroxyl must be identical with the molar weight of isocyano.Be positioned over after adding chainextender in the mould of 80 DEG C of preheating in advance in baking oven.Performed polymer temperature of reaction is in an oven 120 DEG C, and the reaction times is 30 minutes.
the shape memory polyurethane the performance test results with high temperature restorability is as follows:
1, shape-memory properties test
Sample is cut into the rectangular of wide 20mm, at rectangular mid labels 30mm, and in the water bath with thermostatic control of 70 DEG C after preheat stretch, formalizes in tap water, survey the length L after the stretching of its marker field
1(mm), put into this water bath with thermostatic control heating retraction after test, sample is placed on room temperature and makes its cooling and shaping, again measure its length L2 (mm), with its deformation-recovery rate of formulae discovery.Data are listed in table 1-1.Data as can be seen from table, the shape memory effect that four kinds of products draw is all fine.
Deformation-recovery rate=(L1-L2)/(L1-30) × 100%
Table 1 each sample shape memory and recovery situation
| Numbering | Former length, cm | Memory span, cm | Length after recovering, cm | Deformation-recovery rate, % |
| 1 | 3 | 6 | 3.1 | 98.3 |
| 2 | 3 | 6 | 3.0 | 100 |
| 3 | 3 | 6 | 3.2 | 96.7 |
| 4 | 3 | 13 | 3.3 | 97.7 |
2, the mensuration of maximum operation (service) temperature
Get a block length 80mm, the irradiation carbon fiber reinforced urethane resin of wide 30mm, the baking oven putting into 70 DEG C heats half an hour, and taking-up sample is also curling by it, formalizes, put it into baking oven again and recover shape by it after setting in tap water.Recover to be increased to by oven temperature after shape 80 DEG C of heating half an hour completely until it, again qualitative test its whether have shape memory function.Each intensification 10 DEG C, tests its shape memory function, oven temperature is risen to 170 DEG C always, and this polyurethane material still possesses shape-recovery capabilities, to material modification when 180 DEG C, chaps.This illustrates that the urethane of irradiation activation carbon fiber reinforced at high temperature also has shape memory function.
3, the test of mechanical property
Obtained sheet finished product is cut into dumbbell shaped according to the standard of GB/T1040-92: total length (minimum) L=115mm, spacing jig is from L
2=80mm, intermediate parallel fillet partial-length L
1=33mm, gauge length (distance in the middle of the parallel gauge length that central parallel part draws, for surveying tensile elongation) L
0=25mm, end portion width W=25mm, narrow portion width W
0=6mm, sample thickness D=2mm.
Tensile strength: according to GB/T 1040-92 standard operation;
Elongation: according to GB/T528-98 standard operation.
Experimental installation: WDW1400 type universal tensile testing machine.
Experiment condition: draw speed 200mm/min, room temperature 20 DEG C.
Test result: urethane tensile strength of the present invention is 6.86MPa.
Claims (4)
1. the present invention relates to a kind of shape memory polyurethane material with high temperature restorability, it is characterized in that carbon fiber by adding irradiation activation is as reinforcement, a kind of polyurethane shape memory material with high temperature restorability of fabricated in situ, comprises the following steps:
(1) activation treatment of carbon fiber: at room temperature the carbon fiber of required activation is activated under radioactive rays Co radiation exposure;
(2) gather synthesis and the purification process of hexanodioic acid hexylene glycol ester: hexylene glycol, succinic acid, hexanodioic acid are reaction raw materials, and tin protochloride is catalyzer, perhydronaphthalene is solvent, oil bath is heated, and adds trichloromethane and dissolves, filter after having reacted, use methanol extraction again, vacuum-drying, obtains product, is put in heating and melting in four footpath bottles, being evacuated under high temperature does not have bubble to produce, and is all removed by moisture content;
(3) fabricated in situ of shape memory polyurethane: poly-hexanodioic acid hexylene glycol ester purification process crossed, add Toluene-2,4-diisocyanate, 4-vulcabond (TDI), obtains performed polymer after rapid reaction.
2. by proportioning, activated carbon fibre is added continuation reaction in performed polymer, and carry out emulsification, be placed on after adding chainextender in mould, aggregate into the urethane with shape memory function in an oven further, according to carbon fiber activating treatment process according to claim 1, it is characterized in that: the irradiation intensity of the Co ray described in step (1) is 1.25kGy/h, and the radiation treatment time is 80 hours.
3. according to synthesis and the purification treating method of poly-hexanodioic acid hexylene glycol ester according to claim 1, it is characterized in that: when the reaction vessel described in step (2) is 250mL four-hole bottle, add hexylene glycol 0.20 mol, the ratio of succinic acid and hexanodioic acid amount of substance is 1:9, the amount of substance of acid and alcohol is equal, tin protochloride is 0.02mmol, perhydronaphthalene is 100 mL, temperature of reaction controls as follows: first 150 ~ 160 DEG C of reactions 2 hours, again 190 ~ 200 DEG C of reactions 12 hours, thick product was 60 DEG C of vacuum-dryings 24 hours, purifying dehydration temperaturre controls at 105 DEG C, vacuum tightness is 0.09MPa.
4. according to the in-situ synthetic method of shape memory polyurethane according to claim 1, it is characterized in that: the poly-hexanodioic acid hexylene glycol ester described in step (3) is 1:1.04 with the ratio of the amount of substance of TDI, the temperature that TDI adds controls at 60 DEG C, at 80 DEG C, rapid stirring solution reaction obtained performed polymer after 2 hours, now add activated carbon fibre, the incorporation of carbon fiber is 1% of poly-hexanodioic acid hexylene glycol ester and TDI quality sum, the length of activated carbon fibre is 2mm, at 80 DEG C, performed polymer and carbon fiber continue reaction 1 hour, carry out emulsification simultaneously, after adding chainextender, performed polymer temperature of reaction is in an oven 120 DEG C, reaction times is 30 minutes.
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| 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 |
| CN106832879A (en) * | 2017-01-13 | 2017-06-13 | 广东工业大学 | A kind of TEMP conductive polymer composite based on bidirectional shape memory |
| CN108070071A (en) * | 2017-12-06 | 2018-05-25 | 东莞市雄林新材料科技股份有限公司 | A kind of mattress polyurethane memory foamed material and preparation method thereof |
| CN113320231A (en) * | 2021-07-05 | 2021-08-31 | 江苏环宇汽车零部件有限公司 | Ultra-light high-resilience sound-absorbing cotton for automobile shock absorption and sound absorption and preparation method thereof |
| CN113320231B (en) * | 2021-07-05 | 2022-12-02 | 江苏环宇汽车零部件有限公司 | Ultra-light high-resilience sound-absorbing cotton for automobile shock absorption and sound absorption and preparation method thereof |
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