CN104650333A - Polylactic acid/hydrogenated polybutadiene thermoplastic supramolecular elastomer and preparation method thereof - Google Patents
Polylactic acid/hydrogenated polybutadiene thermoplastic supramolecular elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high molecular thermoplastic elastomer technology, and aims to provide a polylactic acid/hydrogenated polybutadiene thermoplastic supramolecular elastomer and a preparation method thereof. The polylactic acid/hydrogenated polybutadiene thermoplastic supramolecular elastomer contains a PLA-PEB-PLA triblock copolymer containing a PLA block and a PEB block as a basic unit; and the terminal group of the basic unit is a 2-carbamido-4[1H]-pyrimidone group capable of forming quadruple hydrogen bonds. According to the high molecular thermoplastic elastomer technology, by adjusting the proportions of PLA and PEB, the intensity and the modulus of the elastomer are easy to adjust; because a UPy group is used as the structural unit, the elastomer is high in binding force and has reversibility; the prepared elastomer has better mechanical property; simultaneously, the elastomer also has the functions of memorizing shapes, self-repairing and the like; PLA is used as the hard section of the supramolecular elastomer; PLA can be prepared on the basis of renewable biomass resources and degraded after being used; and the polylactic acid/hydrogenated polybutadiene thermoplastic supramolecular elastomer is low in pollution to the environment, environmentally friendly and resource-saving.
Description
Technical field
The invention relates to macromolecular thermoplastic elastomeric technology field, particularly based on the supramolecule elastomerics and preparation method thereof of poly(lactic acid)/hydrogenated butadiene polymer.
Technical background
Supramolecule elastomerics is the novel polymer materials of a class, different from by the traditional polymer elastomerics of covalent bonding, and in supramolecule elastomerics, all or part of structure is combined by non covalent bonds such as hydrogen bond, Coordination interaction, pi-pi accumulation interactions.Wherein, the supramolecule thermoplastic elastomer formed by hydrogen bonding, not only there are the snappiness of conventional elastomer, rheological property etc., simultaneously due to the reversibility of hydrogen bond, this kind of polymer materials shows the premium propertiess such as such as environment-responsive, shape memory, selfreparing, receives extensive concern and the research of people.In hydrogen-bonded supramolecule elastomerics, 2-urea groups-4 [1H]-pyrimidone (UPy) holds functionalized polymer elastomer to attract most attention, UPy holds functionalized polymkeric substance easily to prepare, Quadrupolar hydrogen bond can be formed between this group interact, linkage force, close to covalent linkage, is therefore prepare the elastomeric ideal building blocks of hydrogen bonding supramolecule.
At present, the UPy group that can form Quadrupolar hydrogen bond is introduced into be prepared thermoplastic elastomer in small molecules or high polymer and has been reported.But the emphasis of most of literature research UPy group is directly modified the end of the chain in soft section of polymkeric substance or interchain, although this method can prepare supramolecule elastomerics, the supramolecule elastomerics intensity obtained and modulus are too low, and strength and modulus is difficult to regulate.After part soft section of polymkeric substance is directly modified by UPy group, be difficult to obtain that there is stable shaped elastomerics, thick material can only be obtained.In addition, at the end modified UPy group of line style small molecules (as oligosiloxane), although small molecules can be assembled into " long-chain " supramolecule by multiple hydrogen bonding, but fail effectively to be cross-linked between these supramolecular long-chains, thus be difficult to show usual elastomeric performance (Abed et al.Polymer Bulletin, 1997,39,317-324).
Thermoplastic elastomer is can be used as by hard section, the soft section of ABA type triblock copolymer formed, it has the workability of elastomeric superior elasticity and thermal plastic high polymer concurrently, and the hard section of thermoplastic elastomer is usually by semicrystalline polymer or have high glass-transition temperature (T
g) polymkeric substance form.When being used as thermoplastic elastomer, require that the molecular weight of segmented copolymer is higher, be usually greater than 50,000, but molecular weight being higher and the more difficult preparation of ABA type triblock copolymer that molecular weight distribution is more homogeneous.But when molecular weight, film-forming properties and the processability of ABA type triblock copolymer are poor, directly elastomer material can not be used as.So utilize UPy end group to modify low-molecular-weight ABA type triblock copolymer, not only can improve the molecular chain length of polymkeric substance, thus prepare supramolecule elastomerics, also can give physical properties and the function of supramolecule elastomerics uniqueness, as environment-responsive, shape memory, self-repairability etc. simultaneously.
In aliphatic polyester, poly(lactic acid) (PLA) has higher intensity, modulus, excellent environment friendly and biocompatibility, and it becomes one of the most promising bio-based, biodegradable plastic.Lactic acid has opticity, therefore there are D-ALPHA-Hydroxypropionic acid, Pfansteihl two kinds of optically active isomers, poly (l-lactic acid) (PLLA) and the D-ALPHA-Hydroxypropionic acid (PDLA) with isotactic structure are crystallizable, the ploy DL lactic caid (PDLLA) with random structure is not crystallizable, but has higher T
g.Therefore, PLA can be used as the hard section of thermoplastic elastomer, by changing stereochemical structure and the elastomeric over-all properties of crystallinity controllable of PLA segment.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, provides a kind of poly(lactic acid)/hydrogenated butadiene polymer thermoplasticity supramolecule elastomerics and preparation method thereof.The present invention prepared part based on bio-based, Biodegradable high-molecular, PLA/ hydrogenated butadiene polymer (PEB) supramolecule thermoplastic elastomer that performance is easily adjusted.
For technical solution problem, solution of the present invention is:
A kind of poly(lactic acid)/hydrogenated butadiene polymer thermoplasticity supramolecule elastomerics is provided, be with the PLA-PEB-PLA triblock copolymer containing PLA block (i.e. the hard section of PLA) and PEB block (i.e. soft section of PEB) for elementary cell, and the end group of elementary cell is 2-urea groups-4 [1H]-pyrimidone group that can form Quadrupolar hydrogen bond;
This poly(lactic acid)/elastomeric concrete structure of hydrogenated butadiene polymer thermoplasticity supramolecule, is shown below:
In formula,
Wherein, the molecular weight of PEB block is 2000 ~ 6000g/mol, and the molecular weight of single PLA block is 400 ~ 5000g/mol.
Invention further provides preparation aforementioned poly(lactic acid)/elastomeric method of hydrogenated butadiene polymer thermoplasticity supramolecule, being take stannous octoate as catalyzer, the 2-urea groups-4 [1H]-pyrimidone (UPy-NCO) modified by hydroxy-end capped poly(lactic acid)-hydrogenated butadiene polymer-poly(lactic acid) (PLA-PEB-PLA) triblock copolymer of both-end and isocyano reacted, to obtain product; Its concrete preparation process is:
Add PLA-PEB-PLA triblock copolymer and UPy-NCO in Xi Dingke pipe after, repeatedly carry out gas displacement and make to be finally argon atmosphere in Xi Dingke pipe; Dry toluene and stannous octoate is added, stirring reaction 6 ~ 48h at 80 ~ 120 DEG C in Xi Dingke pipe; Filtered by reaction mixture after reaction terminates, utilize the solvent in rotary evaporation removing filtrate, the solid obtained is poly(lactic acid)/hydrogenated butadiene polymer thermoplasticity supramolecule elastomerics;
The consumption of each reactant is: the mol ratio of PLA-PEB-PLA triblock copolymer and UPy-NCO is 1: 2.2 ~ 10; The quality of toluene is 5 ~ 20 times of PLA-PEB-PLA triblock copolymer amount, and the quality of stannous octoate is 0.5 ~ 10 ‰ of PLA-PEB-PLA triblock copolymer amount.
In the present invention, can after obtaining poly(lactic acid)/hydrogenated butadiene polymer thermoplasticity supramolecule elastomerics, vacuum-drying 12h under 25 DEG C of conditions, for subsequent use.
In the present invention, in PLA-PEB-PLA triblock copolymer, described PLA block be following any one: the poly (l-lactic acid) of hemicrystalline, poly-D-ALPHA-Hydroxypropionic acid, or non-crystalline racemize gathers D, Pfansteihl, by corresponding L-rac-Lactide, the ring-opening polymerization of D-rac-Lactide and D, L-rac-Lactide prepares.
Compared with prior art, technological merit of the present invention is:
1, the present invention adopt that PLA is hard section, PEB be the PLA-PEB-PLA triblock copolymer of soft section as elastomeric primary structure, by the adjustment of PLA, PEB ratio, elastomeric strength and modulus is easily adjusted;
2, the present invention adopts the UPy group that can form Quadrupolar hydrogen bond as the structural unit of supermolecule polymer, this Quadrupolar hydrogen bond linkage force is strong, there is reversibility, so prepared supramolecule elastomerics has good mechanical property, also will have the function such as shape memory, selfreparing simultaneously;
3, the present invention adopts PLA as the hard section of supramolecule elastomerics, and PLA can be prepared based on biomass renewable resources, use rear degradable, and the pollution produced environment is little, and environmental protection, economizes on resources.
Accompanying drawing explanation
Fig. 1 is the tensile stress-strain curve of embodiment 3 ~ 5 sample.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail.The following examples can make professional and technical personnel's comprehend the present invention of this specialty, but do not limit the present invention in any way.
In the following embodiments, the PEB purchased from American Sartomer of the both-end hydroxyl modified used.Rac-Lactide used is purchased from Purao AS, and in ethyl acetate, recrystallization removes impurity, and at 60 DEG C, vacuum-drying is to constant weight;
The structural formula of UPy-NCO of the present invention is:
UPy-NCO is according to document (Sontjens et al.Macromolecules; 2008; 41:5703-5708) described method preparation; concrete grammar is as follows: be added in 500ml there-necked flask by 2-amino-4-hydroxy-6-methylpyrimidine (20.0g); 1h is vacuumized at 50 DEG C; applying argon gas is protected; add 180.3g hexamethylene diisocyanate (HDI) and 6.5g methyl-2-pyrrolidone is catalyzer; wherein HDI mole number is 7 times of 2-amino-4-hydroxy-6-methylpyrimidine mole number, and catalyzer is containing 3% of total reactant.Stirring reaction 16h at 100 DEG C, product is added dropwise in the mixed solution of 1200ml normal heptane and 200ml isopropyl ether, precipitation, filters.Solid product is put into 50 DEG C of dry 10h of vacuum drying oven, for subsequent use.
The structural formula of the PLA-PEB-PLA triblock copolymer that both-end of the present invention is hydroxy-end capped is:
The hydroxy-end capped PLA-PEB-PLA triblock copolymer of both-end presses reference (Huang et al.RSC Adv., 2014,4:47965-47976) described method synthesis: with the hydroxy-end capped PEB of both-end for macromole evocating agent, stannous octoate is catalyzer, is prepared by the ring-opening polymerization of rac-Lactide.Concrete grammar is as follows: in Xi Dingke pipe, add the hydroxy-end capped PEB of the both-end of predetermined design mass ratio and rac-Lactide, adopt rac-Lactide to can be L-rac-Lactide, D-rac-Lactide or racemic D, L-rac-Lactide.Then argon gas is filled with after being vacuumized by Xi Dingke pipe, and carry out gas displacement 3 times (namely repeatedly vacuumizing and be filled with argon gas 3 times), be argon atmosphere in final Xi Dingke pipe, dry toluene and stannous octoate is added again in Xi Dingke pipe, and the interpolation quality of toluene is 10 times of PEB quality, it is 5 ‰ of rac-Lactide quality that stannous octoate adds quality.Stirring reaction 12h at 110 DEG C.After reaction terminates, the reaction mixture in Xi Dingke pipe is added dropwise to 5 times in the ethanol of volume of toluene, obtains solid after filtering separation and be PLA-PEB-PLA triblock copolymer, vacuum-drying 12h under 25 DEG C of conditions, for subsequent use.
The molecular weight of multipolymer and wherein PLA block by nucleus magnetic resonance (
1h NMR) measure, molecular weight of copolymer dispersion index (PDI) is measured by gel permeation chromatograph (GPC).By changing the mass ratio of the molecular weight of both-end hydroxy-end capped PEB, rac-Lactide kind, PEB and rac-Lactide, prepare the PLA-PEB-PLA that different molecular weight and copolymerization form.Specific structural features is as table 1.
The preparation of table 1:PLA-PEB-PLA and structural performance
PLLA in table
400-PEB
2000-PLLA
400the M of PEB block in segmented copolymer
nfor 2000g/mol, the M of single PLLA block
nfor 400g/mol.
NMR tests: utilize nuclear magnetic resonance analyser (Bruker company, 400MHz) to test segmented copolymer
1h NMR spectrogram, and then calculate its Mn.Probe temperature is room temperature, and solvent is deuterochloroform, and chemical shift is corrected by solvent peak.
Molecular weight calculation specifications: according to
1on H NMR collection of illustrative plates, the theoretical molecular of peak area ratio and PEB segment calculates the M of segmented copolymer
nand the M of wherein poly(lactic acid) block
n.Represent the proton resonance peak of methyl in PEB main chain at the chemical shift resonance peak that is 0.76ppm place, represent the proton resonance peak of methyl on PLA main chain in multipolymer at the chemical shift resonance peak that is 1.50ppm place.The molecular weight of PLA block in triblock copolymer is calculated according to the methyl of PEB unit and the methyl proton peak area ratio of PLA unit.
Molecular weight distribution is tested: molecular weight of copolymer distribution adopts GPC (model Waters 1525/2414) test, and probe temperature is 30 DEG C, and moving phase is tetrahydrofuran (THF), and standard model is monodisperse polystyrene.
In embodiment 1 ~ 7 below, prepared the PLA-PEB-PLA supramolecule elastomerics of UPy end-blocking by the reaction of hydroxy-end capped PLA-PEB-PLA triblock copolymer and UPy-NCO, specific as follows:
PLA-PEB-PLA triblock copolymer and the UPy-NCO of predetermined design mol ratio is added in Xi Dingke pipe, then argon gas is filled with after being vacuumized by Xi Dingke pipe, and carry out gas displacement 3 times (namely repeatedly vacuumizing and be filled with argon gas 3 times), be argon atmosphere in final Xi Dingke pipe, dry toluene and stannous octoate is added again in Xi Dingke pipe, the interpolation quality of toluene is 5 ~ 20 times of PLA-PEB-PLA block copolymerization amount, and it is 0.5 ~ 10 ‰ of PLA-PEB-PLA block copolymerization amount that stannous octoate adds quality.Stirring reaction 6 ~ 48h at 90 ~ 120 DEG C.
After reaction terminates, reaction mixture is filtered, utilize the solvent in rotary evaporation removing filtrate, obtain solid and be UPy-PLA-PEB-PLA-UPy supramolecule elastomerics, vacuum-drying 12h under 25 DEG C of conditions, for subsequent use.
The mol ratio of described PLA-PEB-PLA triblock copolymer and UPy-NCO is 1/2.2 ~ 1/10.
By changing the kind of PLA-PEB-PLA, preparation is containing the supramolecule elastomerics of different soft, hard section composition.Utilize
1h NMR determines the terminal hydroxy group reactivity of PLA-PEB-PLA segmented copolymer.Concrete preparation condition is as table 2.
The elastomeric preparation of table 2:UPy-PLA-PEB-PLA-UPy supramolecule
Terminal hydroxy group reactivity calculation specifications: according to
1on H NMR collection of illustrative plates, chemical shift peak area ratio calculates terminal hydroxy group reactivity.The proton resonance peak of the methyl of PEB main chain is represented at the chemical shift resonance peak that is 0.76ppm place, represent the proton resonance peak of C-NH-C in UPy group at the chemical shift resonance peak that is 13.1ppm place, calculate the reactivity of terminal hydroxy group according to the methyl of PEB unit and the imino protons peak area ratio of UPy group.
As shown in table 2, in reaction, the ending ratio of UPy group is higher, close to 100%, between 87% ~ 95%, show that in PLA-PEB-PLA multipolymer, all terminal hydroxy group all there occurs reaction with the isocyano in UPy-NCO substantially, illustrate that the method effectively can prepare the supramolecule elastomerics of UPy end-blocking.
UPy-PLA-PEB-PLA-UPy supramolecule elastomerics prepared by embodiment 1 ~ 7 is dissolved in methylene dichloride (concentration is 50g/L), then by solution casting in ptfe surface ware, make solvent evaporates at ambient temperature, then by sample dry 8h in 60 DEG C of vacuum drying ovens.The state of visual inspection solution casting film and transparency.
The solvent cast film of embodiment 1 ~ 7 sample is cut to the dumbbell shaped batten of standard, batten length is 50mm, cross-sectional width 4.0mm, and thickness is about 0.5mm.Utilize SANS universal testing machine to carry out individual event Elongation test, rate of extension is 20.0mm/min.Each sample at least parallel testing five times, then gets its mean value.
In comparative example 1 ~ 3, respectively by PLLA
600-PEB
3600-PLLA
600, PDLA
1300-PEB
3600-PDLA
1300, PLLA
2200-PEB
3600-PLLA
2200be dissolved in methylene dichloride (concentration is 50g/L), then by solution casting in ptfe surface ware, make solvent evaporates at ambient temperature, then by sample dry 8h in 60 DEG C of vacuum drying ovens.The state of visual inspection solution casting film and transparency.
The test result of the film-forming properties of embodiment 1 ~ 7, comparative example 1 ~ 3 sample, the transparency and mechanical property is as table 3.
Table 3: the film-forming properties of embodiment 1 ~ 7 and comparative example 1 ~ 3 sample, the transparency and mechanical property
The transparency and the film-forming properties of embodiment and comparative example are as shown in table 3: in solution casting, and UPy-PLA-PEB-PLA-UPy supramolecule elastomerics all has good film-forming properties and the transparency, and film is smooth, soft and flexible, substantially completely transparent.And the PLA-PEB-PLA triblock copolymer matter sample of comparative example can not film forming, more crisp, and opaque, the test of further mechanical property cannot be carried out.This shows the group modified Be very effective of UPy of PLA-PEB-PLA triblock copolymer end.
As shown in table 3, supramolecule elastomerics has higher elongation at break, and the elongation at break of most of batten is greater than 100%.Along with the increase of PLA content, the elastomeric tensile strength of supramolecule and Young's modulus increase, but elongation at break reduces; Along with the increase of PEB block molecule amount, the elastomeric tensile strength of supramolecule and Young's modulus reduce, and elongation at break increases.Therefore, by changing the length of PLA and PEB block in supramolecule elastomerics, can the elastomeric mechanical property of Effective Regulation supramolecule.
Finally, it should be noted that above what enumerate is only be described preferred embodiment of the present invention.Obviously, the invention is not restricted to above embodiment, a lot of distortion can also be had.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (4)
1. poly(lactic acid)/hydrogenated butadiene polymer thermoplasticity supramolecule elastomerics, it is characterized in that, be with the PLA-PEB-PLA triblock copolymer containing PLA block and PEB block for elementary cell, and the end group of elementary cell is 2-urea groups-4 [1H]-pyrimidone group that can form Quadrupolar hydrogen bond;
This poly(lactic acid)/elastomeric concrete structure of hydrogenated butadiene polymer thermoplasticity supramolecule, is shown below:
In formula,
Wherein, the molecular weight of PEB block is 2000 ~ 6000g/mol, and the molecular weight of single PLA block is 400 ~ 5000g/mol.
2. prepare poly(lactic acid)/elastomeric method of hydrogenated butadiene polymer thermoplasticity supramolecule described in claim 1, it is characterized in that, be take stannous octoate as catalyzer, undertaken reacting to obtain product by the hydroxy-end capped PLA-PEB-PLA triblock copolymer of both-end and UPy-NCO; Its concrete preparation process is:
Add PLA-PEB-PLA triblock copolymer and UPy-NCO in Xi Dingke pipe after, repeatedly carry out gas displacement and make to be finally argon atmosphere in Xi Dingke pipe; Dry toluene and stannous octoate is added, stirring reaction 6 ~ 48h at 80 ~ 120 DEG C in Xi Dingke pipe; Filtered by reaction mixture after reaction terminates, utilize the solvent in rotary evaporation removing filtrate, the solid obtained is poly(lactic acid)/hydrogenated butadiene polymer thermoplasticity supramolecule elastomerics;
The consumption of each reactant is: the mol ratio of PLA-PEB-PLA triblock copolymer and UPy-NCO is 1: 2.2 ~ 10; The quality of toluene is 5 ~ 20 times of PLA-PEB-PLA triblock copolymer amount, and the quality of stannous octoate is 0.5 ~ 10 ‰ of PLA-PEB-PLA triblock copolymer amount.
3. method according to claim 2, is characterized in that, after obtaining poly(lactic acid)/hydrogenated butadiene polymer thermoplasticity supramolecule elastomerics, and vacuum-drying 12h under 25 DEG C of conditions, for subsequent use.
4. according to the method in claim 2 or 3, it is characterized in that, in PLA-PEB-PLA triblock copolymer, described PLA block be following any one: poly (l-lactic acid), poly-D-ALPHA-Hydroxypropionic acid or racemic poly-D, Pfansteihl.
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| CN109206570A (en) * | 2017-06-30 | 2019-01-15 | 翁秋梅 | A kind of compliant physical split-phase supermolecule dynamic aggregation object and its application |
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| CN105017779A (en) * | 2015-07-06 | 2015-11-04 | 浙江大学 | Steric compound crystal controlled polylactic acid/hydrogenated polybutadiene supermolecular elastomer |
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| CN106221100B (en) * | 2016-07-21 | 2018-09-18 | 天津大学 | A kind of preparation method of the optical drive selfreparing film based on ethylene-butylene copolymer |
| WO2018137507A1 (en) * | 2017-01-25 | 2018-08-02 | 翁秋梅 | Physical separate-phase dynamic polymer and use thereof |
| CN109206570A (en) * | 2017-06-30 | 2019-01-15 | 翁秋梅 | A kind of compliant physical split-phase supermolecule dynamic aggregation object and its application |
| CN109251311A (en) * | 2018-11-01 | 2019-01-22 | 杭州聚合顺新材料股份有限公司 | Quick discoloration selfreparing intelligence nylon 6 of power and preparation method thereof |
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| CN110423337B (en) * | 2019-07-08 | 2022-06-07 | 浙江大学衢州研究院 | Temperature-sensitive supramolecular polymer regulated and controlled by multiple hydrogen bonds and preparation method thereof |
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