CN103113551A - Preparation method of rosin-based shape-memory polyurethane - Google Patents
Preparation method of rosin-based shape-memory polyurethane Download PDFInfo
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Abstract
The invention discloses a preparation method of rosin-based shape-memory polyurethane. According to the preparation method, the rosin-based shape-memory polyurethane is obtained in a manner that polylol, diisocyanate and a rosin-based chain extender are synthesized under the action of a catalyst by a one-step or two-step method; and the rosin-based chain extender is a compound with the structure of a formula I or II (shown in drawings). According to the preparation method of the rosin-based shape-memory polyurethane, disclosed by the invention, the preparation is simple, the implementation is easy, and the operability is strong, so that the large-scale industrial production is facilitated; and meanwhile, the prepared rosin-based shape-memory polyurethane has excellent resilience, is very suitable for serving as a shape memory material and expresses excellent shape-memory properties.
Description
Technical field
The present invention relates to the polyurethane shape memory high molecule material field, be specifically related to a kind of preparation method of rosinyl shape memory polyurethane.
Background technology
Shape-memory material is a class stimulating responsive intelligent material.So-called shape memory after referring to that material by original shape (playing primary state), deformation and fixing (deformation states) occurs under certain condition, can be returned to the characteristic of original shape again under external stimulus (as light, heat, electricity, magnetic, potential of hydrogen etc.).
The sixties in 20th century, people have found the shape memory function of Ni-Ti alloy at first, and shape-memory material has just caused world's extensive concern subsequently.The eighties in 20th century, the people such as Ota.SLl find that by the method for radiant crosslinked polyethylene resulting materials has extraordinary heat and replys shape memory effect, become first case shapememory polymer (SMP in the world, Shape Memory Polymer) material (Ota.S.The heat shrinkage properties of polyethylene[J] .Radiate Physics Chemistry, 1981, (18): 81).With shape memory alloy (SMA, Shape Memory Alloy) compare, SMP has that deflection is large, figuration easily, the advantage such as shape memory temperature wide ranges, light weight be inexpensive, can be widely used in the fields such as medicine equipment, sports, textile garment, packing, military affairs and aerospace, thereby since the eighties in last century, the research of SMP has caused academia and industry member broad interest.
SMP can be thermoplastic, can be also heat cured.The thermoplasticity shapememory polymer has the product that deformation quantity is large, working method simple, can be processed into various complicated shapes, but compares the non-constant of its rebound performance with heat cured.The elongation at break of thermoplasticity shapememory polymer can reach more than 1000%, but maximum resilience deformation only has 400% left and right at present.Therefore, studying the thermoplasticity shapememory polymer with high recoverability has very important significance.
At present the synthetic overwhelming majority of macromolecular material is all to adopt the chemical take oil as raw material synthetic, is that the disclosed epoxy resin-matrix shapememory polymer of Chinese patent of 200710031342.X, the disclosed polyurethane shape memory high molecule material of Chinese patent, application number that application number is 200610043121.X are 200810203251.4 the disclosed crust type liquid crystal polymer shape memory high polymer material of Chinese patent application etc. as application number.But the fossil resources such as oil are Nonrenewable resources, use simultaneously fossil resource to cause the environmental problems such as Greenhouse effect.For economize on resources, the consideration such as protection of the environment, be that raw material comes synthesising biological based high molecular material to become people's study hotspot with natural reproducible resources such as biomass resources.The double effects that the bio-based macromolecular material has protection of the environment and economizes on resources.The states such as the U.S., Japan, European Union have successively passed through the development that bill and standard promote bio-based materials.Therefore take the regeneration biological resource as raw material, the research and development high performance material is complied with era development trend, meets national strategy demand, and important using value and good development prospect are arranged.
But be up to the present, that raw material synthesizes the thermoplasticity shapememory polymer with high recoverability and yet there are no report with biomass resource.
Summary of the invention
The invention provides a kind of preparation method of rosinyl shape memory polyurethane, the method preparation is simple, easy to implement, workable, be easy to large-scale industrial production, simultaneously, the rosinyl shape memory polyurethane of preparation has excellent recovery, is suitable as very much shape-memory material.
A kind of preparation method of rosinyl shape memory polyurethane comprises the following steps:
Polyvalent alcohol, vulcabond and rosinyl chainextender are adopted single stage method or two step synthesis obtain the rosinyl shape memory polyurethane under catalyst action;
Described rosin chainextender is the compound of formula I structure or formula II structure;
Wherein, R
1Be selected from aromatic series segment or C
1～C
14The aliphatics segment; R
2Be selected from aromatic series segment or C
1～C
14The aliphatics segment; R
1With R
2Identical or different.Further preferred, R
1Be selected from phenyl ring segment or C
1～C
4The aliphatics segment; R
2Be selected from phenyl ring segment or C
1～C
4The aliphatics segment; R
1With R
2Identical or different.
As preferably, described single stage method comprises: polyvalent alcohol, vulcabond, rosin chainextender and catalyzer are being reacted 3h～5h under the protection of shielding gas together under 50 ℃～150 ℃, after reaction finishes, discharging obtains the rosinyl shape memory polyurethane.
Described two-step approach comprises: at first polyvalent alcohol, vulcabond and catalyzer are reacted 1h～3h under 50 ℃～100 ℃ under the shielding gas protection; obtain performed polymer; then add the rosinyl chainextender to carry out chain extending reaction 3h～5h, after reaction finishes, discharging obtains the rosinyl shape memory polyurethane.
As preferably, described polyvalent alcohol, vulcabond, rosinyl chainextender three's mol ratio is 1:1.1～5:0.1～4, is conducive to obtain the rosinyl shape memory polyurethane of high recovery.Further preferred, the mole dosage of described vulcabond equals the mole dosage sum of polyvalent alcohol and rosinyl chainextender, is conducive to obtain the urethane of high molecular.Further preferred, described polyvalent alcohol, vulcabond, rosinyl chainextender three's mol ratio is 1:3～5:2～4, can obtain the rosinyl shape memory polyurethane of high recovery.
The add-on of described catalyzer can adopt a small amount of that those skilled in the art know, and as preferably, the mol ratio of described catalyzer and polyvalent alcohol is 0.001～0.01:1, and assurance has good catalytic effect.
As preferably, described polyvalent alcohol is a kind of in polyester polyol, polyether glycol or two kinds.Wherein, the number-average molecular weight of polyester polyol, polyether glycol is 500～20000.Further preferred, the number-average molecular weight of polyester polyol, polyether glycol is 500～6000.Further preferred, described polyvalent alcohol is a kind of or two or more in PTMG, poly butylene succinate dibasic alcohol, polyoxyethylene glycol, polycaprolactone dibasic alcohol.
As preferably, described vulcabond is a kind of or two or more in aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate.Further preferred, described vulcabond is a kind of or two or more in diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), dicyclohexyl vulcabond (HMDI).
As preferably, described catalyzer is a kind of or two or more in organic tin urethane catalyst for synthesizing, titanate ester urethane catalyst for synthesizing, organo-bismuth class urethane catalyst for synthesizing.Further preferred, described catalyzer is stannous octoate, dibutyl tin laurate or tetrabutyl titanate.
As preferably, adopt in single stage method or two step synthesis, add the organic solvent adjusting viscosity, adjusting viscosity organic solvent used is the good solvent of urethane, as acetone, butanone, ethyl acetate, DMF, N, one or more in N-N,N-DIMETHYLACETAMIDE, toluene etc., be that described organic solvent is one or more in acetone, butanone, ethyl acetate, DMF, N,N-dimethylacetamide, toluene.As preferably, the add-on of described organic solvent is 20%～50% of polyvalent alcohol, vulcabond, rosinyl chainextender and catalyzer total mass.
Shielding gas can be selected nitrogen or rare gas element, and an inert reaction environment is provided.
The rosinyl shape memory polyurethane of described preparation method's preparation, polyvalent alcohol forms soft section, and the carbamate segment that vulcabond and the reaction of rosin chainextender form is hard section.
Rosinyl chainextender of the present invention with rosinyl as basic structure, in the formula I, by introducing R
1, R
2Chain extension in the formula II, is introduced R
2Chain extension, and the rosinyl chainextender of formula I and formula II structure is the rosinyl dibasic alcohol, is conducive to and other compound reactions, generates high performance macromolecular material.
The preparation method of described rosinyl chainextender, its preparation is simple, easy to implement, workable, is easy to suitability for industrialized production.
The preparation method of described rosinyl chainextender comprises the following steps:
Colophony diacid and dibasic alcohol HO-R with formula III or formula IV structure
2-OH reaction makes the rosinyl chainextender of formula I or formula II structure;
Wherein, the R in formula III
1With the R in formula I
1All has identical implication, dibasic alcohol HO-R
2R in-OH
2With R in formula I and formula II
2Has identical implication.
The colophony diacid of formula III structure can obtain by maleic anhydride modified rosin and the compound reaction that contains simultaneously amino and carboxyl, and concrete preparation process can be 201010225279.5 Chinese patent application with reference to application number.
The colophony diacid of formula IV structure can obtain by acrylic acid modified rosin, also claim acrylic acid modified rosin, concrete preparation process can be with reference to existing document (Preparation of Acrylic Modified Rosin Ind.Eng.Chem.Prod.Res.Dev., 1972,11 (2), pp200 – 202).Acrylic acid modified rosin can adopt the commercially available prod, the product that as green in domestic Guangdong Jiangmen Buddhist Li Co., Ltd, Guangzhou bright and beautiful resin company limited produces.。
Dibasic alcohol HO-R
2-OH, R
2Be selected from aromatic series segment or C
1～C
14The aliphatics segment, namely dibasic alcohol is one or more in aromatic diol, aliphatic diol; Can select the commercially available prod.
The colophony diacid of formula III or formula IV structure and dibasic alcohol HO-R
2-OH reaction specifically can be adopted esterification process, ester-interchange method or chloride-alcoholysis method.
Described esterification process comprises: under the protection of shielding gas, and colophony diacid and the dibasic alcohol HO-R of formula III or formula IV structure
2-OH is reacting 5h～10h under the esterifying catalyst effect under 100 ℃～200 ℃, purifying after reaction finishes obtains the rosinyl chainextender of formula I or formula II structure.
Dibasic alcohol HO-R
2-OH is excessive, can improve the transformation efficiency of the colophony diacid of formula III or formula IV structure, as preferably, and colophony diacid and the dibasic alcohol HO-R of described formula III or formula IV structure
2The mol ratio of-OH is 1:2～10, can make the formula that the is converted into I of colophony diacid of more multimodal III or formula IV structure or the rosinyl chainextender of formula II structure.
Described ester-interchange method comprises: first the colophony diacid of formula III or formula IV structure and methyl alcohol are reacted 3h～8h under 45 ℃～75 ℃ and obtain methyl abietate, methyl abietate again with dibasic alcohol HO-R
2-OH carries out transesterification reaction 3h～5h in 100 ℃～200 ℃ under the transesterification catalyst effect, purifying after reaction finishes obtains the rosinyl chainextender of formula I or formula II structure.
In order to improve transformation efficiency, methyl alcohol and dibasic alcohol HO-R
2-OH is all excessive, as preferably, and colophony diacid, methyl alcohol, the dibasic alcohol HO-R of described formula III or formula IV structure
2-OH three's mol ratio is 1:2～10:2～10, can improve the transformation efficiency of the colophony diacid of formula III or formula IV structure, can transform the rosinyl chainextender that obtains more formula I or formula II structure.
Described chloride-alcoholysis method comprises: first colophony diacid and the chloride reagent with formula III or formula IV structure carrying out acyl chloride reaction 3h～5h under the chloride catalyst action under-15 ℃～100 ℃, after reaction finishes, underpressure distillation (removing unnecessary chloride reagent) obtains the rosin diacid chloride, then the rosin diacid chloride under the acid binding agent effect with dibasic alcohol HO-R
2-OH after reaction finishes, processes the rosinyl chainextender that obtains formula I or formula II structure in 20 ℃～100 ℃ reaction 3h～5h.
In order to improve transformation efficiency, chloride reagent and dibasic alcohol HO-R
2-OH is all excessive, as preferably, and colophony diacid, chloride reagent, the dibasic alcohol HO-R of described formula III or formula IV structure
2-OH three's mol ratio is 1:10～40:2～10, can improve the transformation efficiency of the colophony diacid of formula III or formula IV structure, can transform the rosinyl chainextender that obtains more formula I or formula II structure.
Esterifying catalyst and transesterification catalyst can be a kind of or two or more in inorganic acids catalyzer such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, tosic acid etc., can be also the solid acid catalysts.The addition of esterifying catalyst and transesterification catalyst can be those skilled in the art know a small amount of.The addition of this catalyzer (referring to mole dosage) is 0.01%～0.4% of the mole dosage (being amount of substance) of the colophony diacid of formula III or formula IV structure.
Chloride reagent is thionyl chloride, phosphorus pentachloride, phosphorus trichloride or oxalyl chloride, the chloride catalyzer is N, one or more in dinethylformamide, imdazole derivatives, triethylamine, pyridine etc., the addition of chloride catalyzer (referring to mole dosage) is 0.01%～6% of the mole dosage (being amount of substance) of the colophony diacid of formula III or formula IV structure.Acid binding agent is the inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, hydrated barta, lithium hydroxide or is one or more in the organic weak base classes such as pyridine, triethylamine, be that described acid binding agent is one or more in sodium hydroxide, potassium hydroxide, sodium carbonate, hydrated barta, lithium hydroxide, pyridine, triethylamine, mole addition of acid binding agent is 2～3 times of mole dosage (being amount of substance) of the colophony diacid of formula III or formula IV structure.
Rosinyl chainextender of the present invention is the rosinyl dibasic alcohol, can react with other compounds, and the macromolecular material of synthesized high-performance, high performance macromolecular material such as rosinyl shape memory polyurethane, this rosinyl shape memory polyurethane has high recovery.
Compared with prior art, the present invention has the following advantages:
In the present invention, the starting material of synthetic rosinyl chainextender are rosin, and rosin is a kind of important natural reproducible resource of China, and China produces rosin 50～600,000 ton per year, are the countries of rosin output maximum in the world, have the power to make decision of world's rosin price.The rosin low price, the rosinyl shape memory polyurethane added value of product of preparation is high.Rosin is renewable resources, and the utilization of renewable resources is all significant to saving petroleum resources, protection of the environment.In addition, the preparation method of rosinyl chainextender of the present invention, its preparation is simple, easy to implement, workable, is easy to large-scale industrial production.
In the present invention, the preparation method of rosinyl shape memory polyurethane, preparation is simple, easy to implement, workable, be easy to large-scale industrial production, simultaneously, the rosinyl shape memory polyurethane of preparation has excellent recovery, is suitable as very much shape-memory material.In hard section of the rosinyl shape memory polyurethane, vulcabond and the reaction of rosinyl chainextender form amino-formate bond, very strong hydrogen bond action is arranged each other, and rosin has very large hydrogen phenanthrene ring structure, be difficult for occuring deformation, therefore served as stable physical crosslinking point effect in whole system.After deformation occured, the physical crosslinking point was difficult for destroyed, and recoverability is excellent.In the present invention, the T of soft section that polyvalent alcohol forms
gPerhaps T
mBe texturing temperature, according to actual needs, can regulate the transition temperature of gained shape memory polyurethane by the composition of regulating soft section.This urethane is shaped higher than texturing temperature the time, finalize the design when then cooling temperature is extremely lower than texturing temperature; When temperature during again higher than texturing temperature this polyurethane material can be returned to rapidly original shape again, show the performance of shape memory.
Description of drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of rosinyl chainextender of the formula I structure of embodiment 1 preparation;
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of rosinyl chainextender of the formula II structure of embodiment 2 preparation;
Fig. 3 is the infrared spectrum of rosinyl chainextender of the formula I structure of embodiment 1 preparation;
Fig. 4 is the infrared spectrum of the rosinyl shape memory polyurethane of embodiment 7 preparations.
Embodiment
For embodiment be for content of the present invention is described better, but be not that content of the present invention only limits to illustrated embodiment, those of ordinary skill in the art know in the situation that do not depart from spirit of the present invention or essential characteristic, can carry out suitable modification to the proportioning of raw material, material choice, operational condition, synthesis technique, material structure etc., therefore, the disclosed embodiment of embodiment is illustrative in all respects, rather than restrictive.
Embodiment is divided into two portions: first part, rosinyl chainextender synthetic; Second section, the preparation of rosinyl shape memory polyurethane.
Synthesizing of first part's rosinyl chainextender
Colophony diacid (formula III, R
1Be the phenyl ring segment) 51.926g, ethylene glycol (HO-R
2-OH, R
2Be C
2The aliphatics segment) 12.4g; sulfuric acid 0.04g; react 5h in 150 ℃ under nitrogen protection; after finishing, reaction uses 0.1mol NaOH solution washing; remove excessive ethylene glycol and may obtain crude product by unreacted colophony diacid; crude product is used methanol wash again, and vacuum-drying obtains the rosinyl chainextender (being colophony diacid glycol ester glycol) of formula I structure.
The nucleus magnetic hydrogen spectrum figure of the rosinyl chainextender of the formula I structure of embodiment 1 preparation as shown in Figure 1, solvent is deuterochloroform, in be designated as tetramethylsilane.δ=5.5ppm is the hydrogen on two keys on the rosin skeleton (on figure shown in a position), and its integral area is 1, can prove the existence of rosin skeleton.δ=3.8ppm, δ=3.9ppm, δ=4.2ppm, four groups of peaks at δ=4.5ppm place, its integral area is 2, the hydrogen atom on 4 methylene radical on each representative graph shown in b, c, d, e.δ=7.3ppm, two groups of peaks at δ=8.1ppm place, 4 hydrogen atoms on representative graph shown in h, i, f, g.Gained nucleus magnetic hydrogen spectrum figure and structure fit like a glove, and can prove the rosinyl chainextender of successful preparation formula I structure.
The infrared spectrum of the rosinyl chainextender of the formula I structure of embodiment 1 preparation as shown in Figure 3,1778cm
-1Be the stretching vibration absorption peak of C=O key on imide ring, 3456cm
-1Be the stretching vibration absorption peak of-OH, 1708cm
-1Be the stretching vibration absorption peak of C=O key on ester bond, the rosinyl chainextender that can further prove preparation is formula I structure.
Embodiment 2
Colophony diacid (formula IV) 37.4g, ethylene glycol (HO-R
2-OH, R
2Be C
2The aliphatics segment) 12.4g; tosic acid 0.04g; the lower 150 ℃ of reaction 5h of nitrogen protection; after finishing, reaction uses 0.1mol NaOH solution washing; remove excessive ethylene glycol and may obtain crude product by unreacted colophony diacid; crude product is used washing with alcohol again, and vacuum-drying obtains the rosinyl chainextender (being colophony diacid glycol ester glycol) of formula II structure.
Wherein, R
2For
The nucleus magnetic hydrogen spectrum figure of the rosinyl chainextender of the formula II structure of embodiment 2 preparation as shown in Figure 2, solvent is deuterochloroform, in be designated as tetramethylsilane.δ=5.5ppm is the hydrogen on two keys on the rosin skeleton (on figure shown in a position), and its integral area is 1, can prove the existence of rosin skeleton.δ=3.8ppm-3.9ppm, two groups of peaks at δ=4.2ppm-4.5ppm place, its integral area is 4, and totally 8 hydrogen atoms on 4 methylene radical on each representative graph shown in b, c, d, e can prove the rosinyl chainextender of successful preparation formula II structure in conjunction with infrared spectrum.
Colophony diacid (formula III, R
1Be methylene radical) 45.73g, methyl alcohol 6.4g, phosphoric acid 0.036g reacts 5h under 45 ℃, and underpressure distillation evaporates excessive methanol and obtains the colophony diacid dimethyl ester.Then add 36g1, ammediol (HO-R
2-OH, R
2Be C
3The aliphatics segment), reaction under 150 ℃, during steam methyl alcohol, the 5h afterreaction finishes.Reaction finishes after washing, and wash excessive 1,3-PD off and obtain thick product, methanol wash then, vacuum-drying obtains the rosinyl chainextender (being colophony diacid propylene glycol ester glycol) of formula I structure.Can prove that by nucleus magnetic hydrogen spectrum figure and infrared spectrum the rosinyl chainextender of preparation is formula I structure.
Embodiment 4
Colophony diacid (formula IV) 37.4g, methyl alcohol 9.6g, tosic acid 0.036g reacts 4h under 65 ℃, and underpressure distillation evaporates excessive methanol and obtains the colophony diacid dimethyl ester.Then add 36g1,4-butyleneglycol (HO-R
2-OH, R
2Be C
4The aliphatics segment), reaction under 120 ℃, during steam methyl alcohol, the 5h afterreaction finishes.Reaction finishes after washing, and wash excessive BDO off and obtain thick product, methanol wash then, vacuum-drying obtains the rosinyl chainextender (being colophony diacid glycol ester glycol) of formula II structure.Can prove that by nucleus magnetic hydrogen spectrum figure and infrared spectrum the rosinyl chainextender of preparation is formula II structure.
Wherein, R
2For
Colophony diacid (formula III, R
1Be a position phenyl) 51.926g, thionyl chloride 150mL, catalyst n, dinethylformamide 0.3g reacts 5h under 25 ℃, and after reaction finishes, underpressure distillation is removed unnecessary thionyl chloride and is obtained the colophony diacid diacid chloride.Then add ethylene glycol (HO-R
2-OH, R
2Be C
2The aliphatics segment) 24.8g, acid binding agent pyridine 16g, acetone 50mL in 35 ℃ of reaction 5h, evaporates solvent after reaction finishes, the by products such as pyridine hydrochloride that excessive ethylene glycol, pyridine and generation are removed in washing obtain thick product.Thick product is through washing with alcohol, and drying obtains the rosinyl chainextender of formula I structure.Can prove that by nucleus magnetic hydrogen spectrum figure and infrared spectrum the rosinyl chainextender of preparation is formula I structure.
Embodiment 6
Colophony diacid (IV) 37.4g, oxalyl chloride 150mL, catalyzer pyridine 0.5g reacts 3h under-15 ℃, and after reaction finishes, underpressure distillation is removed unnecessary oxalyl chloride and is obtained the colophony diacid diacid chloride.Then add ethylene glycol (HO-R
2-OH, R
2Be C
2The aliphatics segment) 24.8g, acid binding agent triethylamine 21g, toluene 50mL in 80 ℃ of reaction 5h, evaporates solvent after reaction finishes, the by products such as triethylamine salt that excessive ethylene glycol, triethylamine and generation are removed in washing obtain thick product.Thick product is through washing with alcohol, and drying obtains the rosinyl chainextender (being colophony diacid glycol ester glycol) of formula II structure.Can prove that by nucleus magnetic hydrogen spectrum figure and infrared spectrum the rosinyl chainextender of preparation is formula II structure.
Wherein, R
2For
The preparation of second section rosinyl shape memory polyurethane
Embodiment 7
After 1:3:2:0.005 mixes in molar ratio with the rosinyl chainextender of PTMG (number-average molecular weight 2000), diphenylmethanediisocyanate (MDI), embodiment 1 gained, stannous octoate, join in reactor, in 75 ℃ of reaction 3h, the centre adds anhydrous propanone (add-on be PTMG, diphenylmethanediisocyanate, rosinyl chainextender and stannous octoate total mass 30%) adjusting viscosity.After reaction finished, vacuum-drying was removed acetone and is obtained the rosinyl shape memory polyurethane.
The infrared spectrum of the rosinyl shape memory polyurethane of embodiment 7 preparation as shown in Figure 4,1772cm wherein
-1Be the C=O stretching vibration absorption peak on imide group on the rosinyl chainextender, prove that the rosinyl chainextender successfully is incorporated on polyurethane backbone; 3323cm
-1, 1530cm
-1, be respectively the stretching vibration absorption peak of N-H and the flexural vibration absorption peak of acid amides II; 1720cm
-1Stretching vibration absorption peak for C=O; Above three stack features peaks are the charateristic avsorption band of amino-formate bond in urethane, can prove thus the successful preparation of rosinyl shape memory polyurethane.
The response rate of gained rosinyl shape memory polyurethane under 500% deformation is 90%, replys shape and becomes 450%.Testing method is: 1. on universal testing machine, be stretched to corresponding deformation with the rate of extension of 50mm/min, then use the cooled with liquid nitrogen sample, fix deformation.2. take off sample from universal testing machine and be placed under room temperature (25 ℃) and replied 3 minutes, the response rate of test deformation.Following examples are test in this way all.
Embodiment 8
With joining in reactor after the 1:5:0.001 mixing in molar ratio of poly butylene succinate dibasic alcohol (number-average molecular weight 1000), isophorone diisocyanate (IPDI), dibutyl tin laurate, react 3h under 65 ℃, obtain performed polymer.Then be warmed up to 100 ℃, add embodiment 2 gained rosinyl chainextenders (mole dosage of rosinyl chainextender is 4 times of poly butylene succinate dibasic alcohol mole dosage), reacted 5 hours, and added dry toluene (add-on be poly butylene succinate dibasic alcohol, isophorone diisocyanate, rosinyl chainextender and dibutyl tin laurate total mass 40%) adjusting viscosity in reaction process.After reaction finished, vacuum-drying was taken off solvent and is obtained the rosinyl shape memory polyurethane.The response rate of gained rosinyl shape memory polyurethane under 800% deformation is 96%, replys shape and becomes 768%.
Embodiment 9
After 1:3:2:0.005 mixes in molar ratio with the rosinyl chainextender of polyoxyethylene glycol (number-average molecular weight 2000), hexamethylene diisocyanate (HDI), embodiment 3 gained, stannous octoate, join in reactor, in 80 ℃ of reaction 3h, the centre adds anhydrous butanone (add-on be polyoxyethylene glycol, hexamethylene diisocyanate, rosinyl chainextender and stannous octoate total mass 20%) adjusting viscosity.After reaction finished, vacuum-drying was removed butanone and is obtained the rosinyl shape memory polyurethane.The response rate of gained rosinyl shape memory polyurethane under 400% deformation is 95%, replys shape and becomes 380%.
Embodiment 10
After 1:3:2:0.005 mixes in molar ratio with PTMG (number-average molecular weight 500), tolylene diisocyanate (TDI), embodiment 4 gained rosinyl chainextenders, stannous octoate, join in reactor, in 75 ℃ of reaction 3h, the centre adds anhydrous propanone (add-on be PTMG, tolylene diisocyanate, rosinyl chainextender and stannous octoate total mass 50%) adjusting viscosity.After reaction finished, vacuum-drying was removed acetone and is obtained the rosinyl shape memory polyurethane.The response rate of gained rosinyl shape memory polyurethane under 300% deformation is 93%, replys shape and becomes 279%.
Embodiment 11
With joining in reactor after the 1:4:0.001 mixing in molar ratio of polycaprolactone dibasic alcohol (number-average molecular weight 6000), dicyclohexyl vulcabond (HMDI), tetrabutyl titanate, react 3h under 65 ℃, obtain performed polymer.Then be warmed up to 100 ℃, add embodiment 5 gained rosinyl chainextenders (mole dosage of rosinyl chainextender is 3 times of polycaprolactone dibasic alcohol molar weight), reacted 5 hours, and added dry toluene (add-on be polycaprolactone dibasic alcohol, dicyclohexyl vulcabond, rosinyl chainextender and tetrabutyl titanate total mass 35%) adjusting viscosity in reaction process.After reaction finished, vacuum-drying was taken off solvent and is obtained the rosinyl shape memory polyurethane.The response rate of gained rosinyl shape memory polyurethane under 1000% deformation is 91%, replys shape and becomes 910%.
Claims (10)
1. the preparation method of a rosinyl shape memory polyurethane, is characterized in that, comprises the following steps:
Polyvalent alcohol, vulcabond and rosinyl chainextender are adopted single stage method or two step synthesis obtain the rosinyl shape memory polyurethane under catalyst action;
Described rosinyl chainextender is the compound of formula I structure or formula II structure;
Wherein, R
1Be selected from aromatic series segment or C
1～C
14The aliphatics segment; R
2Be selected from aromatic series segment or C
1～C
14The aliphatics segment; R
1With R
2Identical or different.
2. the preparation method of rosinyl shape memory polyurethane according to claim 1; it is characterized in that; described single stage method comprises: polyvalent alcohol, vulcabond, rosin chainextender and catalyzer are being reacted 3h～5h under the protection of shielding gas together under 50 ℃～150 ℃, after reaction finishes, discharging obtains the rosinyl shape memory polyurethane.
3. the preparation method of rosinyl shape memory polyurethane according to claim 1; it is characterized in that; described two-step approach comprises: at first polyvalent alcohol, vulcabond and catalyzer are reacted 1h～3h under 50 ℃～100 ℃ under the shielding gas protection; obtain performed polymer; then add the rosinyl chainextender to carry out chain extending reaction 3h～5h, after reaction finishes, discharging obtains the rosinyl shape memory polyurethane.
4. the preparation method of according to claim 1,2 or 3 described rosinyl shape memory polyurethanes, is characterized in that, described polyvalent alcohol, vulcabond, rosinyl chainextender three's mol ratio is 1:1.1～5:0.1～4.
5. the preparation method of rosinyl shape memory polyurethane according to claim 4, is characterized in that, the mole dosage of described vulcabond equals the mole dosage sum of polyvalent alcohol and rosinyl chainextender.
6. the preparation method of rosinyl shape memory polyurethane according to claim 5, is characterized in that, described polyvalent alcohol, vulcabond, rosinyl chainextender three's mol ratio is 1:3～5:2～4.
7. the preparation method of according to claim 1,2 or 3 described rosinyl shape memory polyurethanes, is characterized in that, the mol ratio of described catalyzer and polyvalent alcohol is 0.001～0.01:1.
8. the preparation method of according to claim 1,2 or 3 described rosinyl shape memory polyurethanes, it is characterized in that, described polyvalent alcohol is a kind of in polyester polyol, polyether glycol or two kinds, and wherein, the number-average molecular weight of the pure and mild polyether glycol of polyester polyols is 500～20000;
Described vulcabond is a kind of or two or more in aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate;
Described catalyzer is a kind of or two or more in organic tin urethane catalyst for synthesizing, titanate ester urethane catalyst for synthesizing, organo-bismuth class urethane catalyst for synthesizing.
9. the preparation method of rosinyl shape memory polyurethane according to claim 1, is characterized in that, adopts in single stage method or two step synthesis, adds the organic solvent adjusting viscosity, and adjusting viscosity organic solvent used is the good solvent of urethane.
10. the preparation method of rosinyl shape memory polyurethane according to claim 9, it is characterized in that, described organic solvent is one or more in acetone, butanone, ethyl acetate, DMF, N,N-dimethylacetamide, toluene.
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| CN105315424A (en) * | 2014-08-01 | 2016-02-10 | 中国科学院宁波材料技术与工程研究所 | Polyurethane-urea elastomer with low permanent deformation, preparation method and application 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 |
| CN114133517A (en) * | 2021-12-02 | 2022-03-04 | 无锡杰夫电声股份有限公司 | Rosin-based polyurethane and synthetic method thereof |
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| CN101921382A (en) * | 2010-09-17 | 2010-12-22 | 上海交通大学 | Method for preparing shape memory polyurethane resin |
| CN102002142A (en) * | 2010-09-21 | 2011-04-06 | 中国科学院宁波材料技术与工程研究所 | Biodegradable polyurethane and preparation method thereof |
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| US5652288A (en) * | 1994-06-06 | 1997-07-29 | Wood; Benny R. | Water dispersible polyisocyanate adhesive |
| CN101921382A (en) * | 2010-09-17 | 2010-12-22 | 上海交通大学 | Method for preparing shape memory polyurethane resin |
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| CN105315424A (en) * | 2014-08-01 | 2016-02-10 | 中国科学院宁波材料技术与工程研究所 | Polyurethane-urea elastomer with low permanent deformation, preparation method and application thereof |
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| CN114133517A (en) * | 2021-12-02 | 2022-03-04 | 无锡杰夫电声股份有限公司 | Rosin-based polyurethane and synthetic method thereof |
| CN114133517B (en) * | 2021-12-02 | 2023-09-01 | 无锡杰夫电声股份有限公司 | Rosin-based polyurethane and synthetic method thereof |
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