CN104650333B - Polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer and preparation method thereof - Google Patents
Polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer and preparation method thereof Download PDFInfo
- Publication number
- CN104650333B CN104650333B CN201510058848.4A CN201510058848A CN104650333B CN 104650333 B CN104650333 B CN 104650333B CN 201510058848 A CN201510058848 A CN 201510058848A CN 104650333 B CN104650333 B CN 104650333B
- Authority
- CN
- China
- Prior art keywords
- pla
- peb
- triblock copolymer
- elastomer
- polylactic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The present invention relates to macromolecular thermoplastic elastomeric technology, it is desirable to provide a kind of polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer and preparation method thereof.This product is with the PLA PEB PLA triblock copolymer containing PLA block and PEB block as elementary cell, and the end group of elementary cell is 2 urea groups 4 [1H] the pyrimidone groups that can form Quadrupolar hydrogen bond.Inventing the regulation by PLA, PEB ratio, intensity and the modulus of elastomer are easily adjusted；Using UPy group as construction unit, its bonding force is strong, has reversibility, and prepared product has preferable mechanical performance, also has the function such as shape memory, selfreparing simultaneously；Use PLA as supermolecule elastomer hard section, PLA can be prepared based on biomass Renewable resource, uses after degradable, the pollution to environment generation is little, and environmental protection economizes on resources.
Description
Technical field
The present invention is about macromolecular thermoplastic elastomeric technology field, particularly to based on polylactic acid/hydrogenated butadiene polymer
Supermolecule elastomer and preparation method thereof.
Technical background
Supermolecule elastomer is not the polymeric material that a class is novel, and by the traditional polymer elastomer of covalent bonding not
With, in supermolecule elastomer, all or part of structure is non-by hydrogen bond, Coordination interaction, pi-pi accumulation interaction etc.
Covalent bond combines.Wherein, hydrogen bonding the supermolecule thermoplastic elastomer (TPE) formed, not only there is conventional elastomer
High resiliency, rheological property etc., simultaneously because the reversibility of hydrogen bond, this kind of polymeric material show such as environment-responsive,
The premium properties such as shape memory, selfreparing, receives extensive concern and the research of people.At hydrogen-bonded oversubscription bullet
In gonosome, the polymer elastomer of 2-urea groups-4 [1H]-pyrimidone (UPy) end functionalization attracts most attention, UPy end official's energy
The polymer changed easily is prepared, and can form Quadrupolar hydrogen bond and interact between this group, and bonding force, close to covalent bond, is therefore
Prepare the ideal building blocks of hydrogen bonding supermolecule elastomer.
At present, it is introduced to the UPy group that can form Quadrupolar hydrogen bond in little molecule or macromolecule polyalcohol prepare thermoplastic elastomehc
Gonosome has been reported.But, major part literature research it is important that UPy group is directly modified in the chain of soft section of polymer
End or interchain, although this method can prepare supermolecule elastomer, but the supermolecule elastomer intensity obtained is the lowest with modulus,
And intensity and modulus are difficult to regulate.After soft section of polymer of part is directly modified by UPy group, it is difficult to obtain that there is stable shape
The elastomer of shape, can only obtain thick material.It addition, the end in the little molecule of line style (such as oligosiloxane) is repaiied
Decorations UPy group, although by multiple hydrogen bonding little group of molecules can be dressed up " long-chain " supermolecule, but these supramolecular length
Fail between chain effectively to cross-link, thus be difficult to show usual elastomer performance (Abed et al.Polymer Bulletin,
1997,39,317-324)。
Be can be used as thermoplastic elastomer (TPE) by hard section, the soft section of ABA type triblock copolymer formed, it has elastomer concurrently
Superior elasticity and the machinability of thermal plastic high polymer, thermoplastic elastomer (TPE) hard section is generally by semicrystalline polymer or have
High glass-transition temperature (Tg) polymer constitute.When as thermoplastic elastomer (TPE), it is desirable to dividing of block copolymer
Son amount is higher, typically larger than 50,000, but the ABA type triblock copolymer that molecular weight is higher and molecular weight distribution is more uniform
More difficult preparation.But when molecular weight, film property and the processability of ABA type triblock copolymer are poor, it is impossible to
It is directly used as elastomeric material.So utilizing UPy end group to modify the ABA type triblock copolymer of low-molecular-weight, not only
The molecular chain length of polymer can be improved, thus prepare supermolecule elastomer, also can give supermolecule elastomer unique simultaneously
Physical property and function, such as environment-responsive, shape memory, self-repairability etc..
In aliphatic polyester, polylactic acid (PLA) has higher intensity, modulus, excellent environment friendly and life
The thing compatibility, it has become one of the most promising bio-based, biodegradable plastic.Lactic acid has optical activity, because of
This has D-ALPHA-Hydroxypropionic acid, two kinds of optical isomers of Pfansteihl, has poly (l-lactic acid) (PLLA) and the D-ALPHA-Hydroxypropionic acid of isotactic structure
(PDLA) crystallizable, the ploy DL lactic caid (PDLLA) with disordered structure is the most crystallizable, but has higher Tg。
Therefore, PLA can be used as the hard section of thermoplastic elastomer (TPE), by changing stereochemical structure and the crystallinity of PLA segment
The combination property of controllable elastomer.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, it is provided that a kind of polylactic acid/hydrogenation polybutadiene
Olefinic thermoplastic supermolecule elastomer and preparation method thereof.The present invention has prepared and has been based partially on bio-based, biodegradable
PLA/ hydrogenated butadiene polymer (PEB) the supermolecule thermoplastic elastomer (TPE) that high molecular, performance is easily adjusted.
For solving technical problem, the solution of the present invention is:
A kind of polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer is provided, is so that (i.e. PLA is hard containing PLA block
Section) and the PLA-PEB-PLA triblock copolymer of PEB block (i.e. soft section of PEB) be elementary cell, and basic
The end group of unit is 2-urea groups-4 [the 1H]-pyrimidone group that can form Quadrupolar hydrogen bond；
The concrete structure of this polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer, 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 400～5000
g/mol。
Invention further provides the method preparing aforementioned polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer, be
With stannous octoate as catalyst, by the hydroxy-end capped polylactic acid-hydrogenated butadiene polymer-polylactic acid of both-end
(PLA-PEB-PLA) the 2-urea groups-4 [1H]-pyrimidone (UPy-NCO) that triblock copolymer is modified with isocyano
React, to obtain product；Its concrete preparation process is:
After adding PLA-PEB-PLA triblock copolymer and UPy-NCO in the pipe of uncommon Dinke, gas is repeated and puts
Change in making uncommon Dinke pipe final for argon atmosphere；Dry toluene and stannous octoate is added, 80～120 in the pipe of uncommon Dinke
Stirring reaction 6～48h at DEG C；Reactant mixture is filtered after terminating by reaction, and utilize that rotary evaporation removes in filtrate is molten
Agent, the solid obtained is polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer；
The consumption of each reactant is: the mol ratio of PLA-PEB-PLA triblock copolymer and UPy-NCO be 1: 2.2～
10；The quality of toluene is 5～20 times of PLA-PEB-PLA triblock copolymer quality, and the quality of stannous octoate is
The 0.5～10 ‰ of PLA-PEB-PLA triblock copolymer quality.
In the present invention, can be after obtaining polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer, under the conditions of 25 DEG C
Vacuum drying 12h, standby.
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 the poly-D of non-crystalline raceme, Pfansteihl, by corresponding L-lactide,
D-lactide and D, the ring-opening polymerisation of L-lactide prepares.
Compared with prior art, the technological merit of the present invention is:
1, the present invention use PLA be hard section, PEB be that the PLA-PEB-PLA triblock copolymer of soft section is as elasticity
The primary structure of body, by the regulation of PLA, PEB ratio, intensity and the modulus of elastomer are easily adjusted；
2, the present invention uses the UPy group that can form Quadrupolar hydrogen bond as the construction unit of supermolecule polymer, this quadruple
Hydrogen bonding power is strong, has reversibility, so prepared supermolecule elastomer has preferable mechanical performance, the most also will
There is the function such as shape memory, selfreparing；
3, the present invention use PLA as supermolecule elastomer hard section, PLA can be prepared based on biomass Renewable resource,
Using rear degradable, the pollution producing 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.
Detailed description of the invention
With detailed description of the invention, the present invention is described in further detail below in conjunction with the accompanying drawings.The following examples can make this
The professional and technical personnel of specialty is more fully understood the present invention, but limits the present invention never in any form.
In the following embodiments, the PEB of the both-end hydroxyl modified used is purchased from Sartomer of the U.S..Used third hands over
Ester is purchased from Purao AS, and in ethyl acetate, recrystallization removes impurity, is dried under vacuum to constant weight at 60 DEG C；
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: added to 500ml there-necked flask by 2-amino-4-hydroxy-6-methylpyrimidine (20.0g),
Evacuation 1h at 50 DEG C, applying argon gas is protected, and adds 180.3g hexamethylene diisocyanate (HDI) and 6.5g methyl
Ketopyrrolidine is catalyst, and wherein HDI molal quantity is 7 times of 2-amino-4-hydroxy-6-methylpyrimidine molal quantity, catalysis
Agent contains the 3% of total reactant.Stirring reaction 16h at 100 DEG C, product is added dropwise to 1200ml normal heptane and 200ml isopropyl
In the mixed liquor of ether, precipitation, filters.Solid product is put into 50 DEG C of vacuum drying ovens are dried 10h, standby.
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 press list of references (Huang et al.RSC Adv.,
2014,4:47965-47976) described method synthesis: with the hydroxy-end capped PEB of both-end as macromole evocating agent, octanoic acid is sub-
Stannum is catalyst, is prepared by the ring-opening polymerisation of lactide.Concrete grammar is as follows: add predetermined design in the pipe of uncommon Dinke
PEB that the both-end of mass ratio is hydroxy-end capped and lactide, used lactide can be L-lactide, D-lactide or
The racemic D of person, L-lactide.Then will be filled with argon after the pipe evacuation of uncommon Dinke, and carry out gas displacement 3 times (i.e.
Repeatedly evacuation and be filled with argon 3 times), be argon atmosphere in the pipe of final uncommon Dinke, then addition be dry in the pipe of uncommon Dinke
Toluene and stannous octoate, and interpolation quality is PEB mass 10 times of toluene, it is the third friendship that stannous octoate adds quality
The 5 ‰ of ester quality.Stirring reaction 12h at 110 DEG C.Reactant mixture in the pipe of uncommon Dinke is dripped after terminating by reaction
Enter in the ethanol of 5 times of volume of toluene, obtain solid after filtering separation and be PLA-PEB-PLA triblock copolymer,
12h it is vacuum dried under the conditions of 25 DEG C, standby.
The molecular weight of copolymer and wherein PLA block by nuclear magnetic resonance, NMR (1H NMR) measure, molecular weight of copolymer divides
Cloth index (PDI) is measured by chromatograph of gel permeation (GPC).By change the hydroxy-end capped PEB of both-end molecular weight,
Lactide kind, PEB and the mass ratio of lactide, be prepared for different molecular weight and the PLA-PEB-PLA of copolymerization composition.
Specific structural features such as table 1.
The preparation of table 1:PLA-PEB-PLA and architectural characteristic
PLLA in table400-PEB2000-PLLA400The M of PEB block in block copolymernFor 2000g/mol, single
The M of PLLA blocknFor 400g/mol.
NMR tests: utilize nuclear magnetic resonance analyser (Bruker company, 400MHz) test block copolymer1H NMR
Spectrogram, and then calculate its Mn.Test temperature is room temperature, and solvent is deuterochloroform, and chemical shift is carried out school by solvent peak
Just.
Molecular weight calculation specifications: according to1The Theoretical molecular gauge of peak area ratio and PEB segment on H NMR spectra
Calculate the M of block copolymernAnd the M of wherein polylactic acid blockn.It it is the formant generation at 0.76ppm in chemical shift
The proton resonance peak of methyl in table PEB main chain, is that the formant at 1.50ppm represents PLA in copolymer in chemical shift
The proton resonance peak of methyl on main chain.Methyl and the methyl proton peak area ratio of PLA unit according to PEB unit calculate
The molecular weight of PLA block in triblock copolymer.
Molecular weight distribution is tested: molecular weight of copolymer distribution uses GPC (model Waters 1525/2414) test, surveys
Examination temperature is 30 DEG C, and flowing is oxolane mutually, and standard sample is monodisperse polystyrene.
In following embodiment 1～7, by hydroxy-end capped PLA-PEB-PLA triblock copolymer and UPy-NCO
Reaction be prepared for UPy end-blocking PLA-PEB-PLA supermolecule elastomer, specific as follows:
PLA-PEB-PLA triblock copolymer and the UPy-NCO of predetermined design mol ratio is added, so in the pipe of uncommon Dinke
After will be filled with argon after the pipe evacuation of uncommon Dinke, and carry out gas displacement 3 times (the most repeatedly evacuation and be filled with argon 3 times),
It is argon atmosphere in the pipe of final uncommon Dinke, then adds dry toluene and stannous octoate in the pipe of uncommon Dinke, the interpolation of toluene
Quality is 5～20 times of PLA-PEB-PLA block copolymer quality, and it is PLA-PEB-PLA that stannous octoate adds quality
The 0.5～10 ‰ of block copolymer quality.Stirring reaction 6～48h at 90～120 DEG C.
Reactant mixture is filtered after terminating by reaction, utilizes rotary evaporation to remove the solvent in filtrate, obtains solid and be
UPy-PLA-PEB-PLA-UPy supermolecule elastomer, is vacuum dried 12h under the conditions of 25 DEG C, standby.
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 different soft, the supermolecule elastomers of hard section composition.Utilize1H NMR determines the terminal hydroxy group response rate of PLA-PEB-PLA block copolymer.Concrete preparation condition such as table 2.
The preparation of table 2:UPy-PLA-PEB-PLA-UPy supermolecule elastomer
Terminal hydroxy group response rate calculation specifications: according to1On H NMR spectra, chemical shift peak area ratio calculates terminal hydroxy group reaction
Rate.It is the proton resonance peak that the formant at 0.76ppm represents the methyl of PEB main chain in chemical shift, at chemical potential
Move the proton resonance peak representing C-NH-C in UPy group for the formant at 13.1ppm, according to the first of PEB unit
The imino protons peak area ratio of base and UPy group calculates the response rate of terminal hydroxy group.
As shown in table 2, in reaction, the ending ratio of UPy group is higher, close to 100%, between 87%～95%, and table
In bright PLA-PEB-PLA copolymer, all terminal hydroxy groups the most all there occurs reaction with the isocyano in UPy-NCO,
Illustrate that the method can effectively prepare the supermolecule elastomer of UPy end-blocking.
UPy-PLA-PEB-PLA-UPy supermolecule elastomer prepared by embodiment 1～7 is dissolved in dichloromethane (dense
Degree is 50g/L) in, then solution is cast in ptfe surface ware, makes solvent volatilize at ambient temperature,
Then sample is dried in 60 DEG C of vacuum drying ovens 8h.The state of perusal solution casting film and transparency.
The solvent cast thin film of embodiment 1～7 sample is cut to the dumbbell shaped batten of standard, a length of 50mm of batten,
Cross-sectional width 4.0mm, thickness is about 0.5mm.SANS universal testing machine is utilized to carry out individual event extension test,
Rate of extension is 20.0mm/min.Each sample at least parallel testing five times, then takes its meansigma methods.
In comparative example 1～3, respectively by PLLA600-PEB3600-PLLA600、PDLA1300-PEB3600-
PDLA1300、PLLA2200-PEB3600-PLLA2200It is dissolved in dichloromethane (concentration is 50g/L), then by solution
It is cast in ptfe surface ware, makes solvent volatilize at ambient temperature, then by sample at 60 DEG C of vacuum drying ovens
In be dried 8h.The state of perusal solution casting film and transparency.
Embodiment 1～7, the test result such as table 3 of film property, the transparency and mechanical performance of comparative example 1～3 sample.
Table 3: embodiment 1～7 and film property, the transparency and the mechanical performance of comparative example 1～3 sample
Embodiment is as shown in table 3 with the transparency of comparative example and film property: in solution is poured into a mould,
UPy-PLA-PEB-PLA-UPy supermolecule elastomer is respectively provided with good film property and the transparency, and thin film is smooth, soft
And flexible, the most transparent.And the PLA-PEB-PLA triblock copolymer sample of comparative example can not film forming, relatively
Crisp and opaque, it is impossible to carry out the test of further mechanical performance.This shows PLA-PEB-PLA triblock copolymer
The group modified effect of UPy of end is notable.
As shown in table 3, supermolecule elastomer has higher elongation at break, and the elongation at break of major part batten is more than
100%.Along with the increase of PLA content, the hot strength of supermolecule elastomer and Young's modulus increase, but extension at break
Rate reduces；Along with the increase of PEB block molecule amount, the hot strength of supermolecule elastomer and Young's modulus reduce, and
Elongation at break increases.Therefore, by changing the length of PLA and PEB block in supermolecule elastomer, can effectively adjust
The mechanical performance of control supermolecule elastomer.
Finally it should be noted that listed above is only that the preferred embodiment to the present invention is described.Obviously,
The invention is not restricted to above example, it is also possible to have many variations.Those of ordinary skill in the art can be open from the present invention
Content in all deformation of directly deriving or associating, be all considered as protection scope of the present invention.
Claims (3)
1. the method preparing polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer, it is characterised in that be with
Stannous octoate is catalyst, is entered with UPy-NCO by the PLA-PEB-PLA triblock copolymer that both-end is hydroxy-end capped
Row reaction is to obtain product；Its concrete preparation process is:
After adding PLA-PEB-PLA triblock copolymer and UPy-NCO in the pipe of uncommon Dinke, gas is repeated and puts
Change in making uncommon Dinke pipe final for argon atmosphere；Dry toluene and stannous octoate is added, 80～120 in the pipe of uncommon Dinke
Stirring reaction 6～48h at DEG C；Reactant mixture is filtered after terminating by reaction, and utilize that rotary evaporation removes in filtrate is molten
Agent, the solid obtained is polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer；
The consumption of each reactant is: the mol ratio of PLA-PEB-PLA triblock copolymer and UPy-NCO be 1: 2.2～
10；The quality of toluene is 5～20 times of PLA-PEB-PLA triblock copolymer quality, and the quality of stannous octoate is
The 0.5～10 ‰ of PLA-PEB-PLA triblock copolymer quality；
Described polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer, with containing PLA block and PEB block
PLA-PEB-PLA triblock copolymer is elementary cell, and the end group of elementary cell is the 2-urea that can form Quadrupolar hydrogen bond
Base-4 [1H]-pyrimidone group；
The concrete structure of this polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer, 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 400～5000
g/mol。
Method the most according to claim 1, it is characterised in that obtaining polylactic acid/hydrogenated butadiene polymer thermoplasticity
After supermolecule elastomer, under the conditions of 25 DEG C, it is vacuum dried 12h, standby.
Method the most according to claim 1 and 2, it is characterised in that at PLA-PEB-PLA triblock copolymer
In, described PLA block be following any one: poly (l-lactic acid), poly-D-ALPHA-Hydroxypropionic acid or racemic poly-D, L-breast
Acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510058848.4A CN104650333B (en) | 2015-02-05 | 2015-02-05 | Polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510058848.4A CN104650333B (en) | 2015-02-05 | 2015-02-05 | Polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104650333A CN104650333A (en) | 2015-05-27 |
| CN104650333B true CN104650333B (en) | 2016-08-24 |
Family
ID=53242003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510058848.4A Expired - Fee Related CN104650333B (en) | 2015-02-05 | 2015-02-05 | Polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104650333B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496490A (en) * | 2016-11-01 | 2017-03-15 | 浙江大学 | A kind of method for preparing polyurethane elastic body containing Stereocomplex crystallization |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017779A (en) * | 2015-07-06 | 2015-11-04 | 浙江大学 | Steric compound crystal controlled polylactic acid/hydrogenated polybutadiene supermolecular elastomer |
| 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 |
| CN108342049B (en) * | 2017-01-25 | 2023-08-22 | 厦门天策材料科技有限公司 | Physical split-phase dynamic polymer and application thereof |
| CN109206570B (en) * | 2017-06-30 | 2023-04-25 | 厦门天策材料科技有限公司 | Flexible physical split-phase supermolecular dynamic polymer and application thereof |
| CN109251311B (en) * | 2018-11-01 | 2021-02-09 | 杭州聚合顺新材料股份有限公司 | Force-sensitive color-changing self-repairing intelligent nylon 6 and preparation method thereof |
| 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 |
| CN114479093B (en) * | 2022-03-07 | 2023-01-20 | 扬州惠通生物新材料有限公司 | Low molecular weight metal coordination supermolecule triblock copolymer thermoplastic elastomer film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2323626A2 (en) * | 2008-08-05 | 2011-05-25 | Coretherapix Slu | Parenteral composition comprising microspheres with a diameter between 10 and 20 microns |
| WO2012168392A1 (en) * | 2011-06-07 | 2012-12-13 | Technische Universiteit Eindhoven | Hydrogelator with shape-memory properties |
-
2015
- 2015-02-05 CN CN201510058848.4A patent/CN104650333B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2323626A2 (en) * | 2008-08-05 | 2011-05-25 | Coretherapix Slu | Parenteral composition comprising microspheres with a diameter between 10 and 20 microns |
| WO2012168392A1 (en) * | 2011-06-07 | 2012-12-13 | Technische Universiteit Eindhoven | Hydrogelator with shape-memory properties |
Non-Patent Citations (5)
| Title |
|---|
| A modular and supramolecular approach to bioactive scaffolds for tissue engineering;Dankers, PYW;《NATURE MATERIALS》;20050730;第4卷(第7期);568-574 * |
| Combining block copolymers and hydrogen bonding for poly(lactide) toughening;Delgado, PA;《RSC ADVANCES》;20140221;第4卷(第26期);13266-13273 * |
| Polylactide-b-poly(ethylene-co-butylene)-b-polylactide thermoplastic elastomers: role of polylactide crystallization and stereocomplexation on microphase separation, mechanical and shape memory properties;Huang, YF;《RSC ADVANCES》;20140915;第4卷(第89期);47965-47976 * |
| Preemptive Healing through Supramolecular Cross-Links;Wietor, JL;《MACROMOLECULES》;20090908;第42卷(第17期);6640-6646 * |
| Supramolecular polymer materials: Chain extension of telechelic polymers using a reactive hydrogen-bonding synthon;Folmer, BJB;《ADVANCED MATERIALS》;20000616;第12卷(第12期);874-878 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496490A (en) * | 2016-11-01 | 2017-03-15 | 浙江大学 | A kind of method for preparing polyurethane elastic body containing Stereocomplex crystallization |
| CN106496490B (en) * | 2016-11-01 | 2019-02-01 | 浙江大学 | A kind of method for preparing polyurethane elastic body of the crystallization containing Stereocomplex |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104650333A (en) | 2015-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104650333B (en) | Polylactic acid/hydrogenated butadiene polymer thermoplasticity supermolecule elastomer and preparation method thereof | |
| Lavilla et al. | PET copolyesters made from ad-mannitol-derived bicyclic diol | |
| US5461139A (en) | Biodegradable optically active copolymers and processes for producing the same | |
| Cai et al. | Surface biodegradable copolymers—poly (D, L-lactide-co-1-methyl-1, 3-trimethylene carbonate) and poly (D, L-lactide-co-2, 2-dimethyl-1, 3-trimethylene carbonate): preparation, characterization and biodegradation characteristics in vivo | |
| CN109054056A (en) | A kind of interlocking network cross-linked polymer and its preparation method and application based on reversible covalent bonds | |
| CN102161768A (en) | Polysiloxane-polyphenyl ether crosslinked block copolymer and preparation method and use thereof | |
| Jiang et al. | Synthesis and characterization of biocompatible poly (ethylene glycol)-b-poly (L-lactide) and study on their electrospun scaffolds | |
| Hou et al. | Biomedical segmented polyurethanes based on polyethylene glycol, poly (ε-caprolactone-co-D, L-lactide), and diurethane diisocyanates with uniform hard segment: Synthesis and properties | |
| CN104130365B (en) | A kind of linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA and its preparation method and application | |
| CN105368023B (en) | Supermolecule stereoblock polylactic acid that easily Stereocomplex is crystallized and preparation method thereof | |
| CN103087298A (en) | Multi-arm block copolymer, preparation method and application of multi-arm block copolymer in improvement of mechanical property of poly-L-lactic acid thereof | |
| CN102432852A (en) | Polylactic-acid-based isotactic compound crosslinking copolymer and preparation method thereof | |
| CN103172855B (en) | A kind of Lactic acid-amino acid copolyester amide and preparation method thereof | |
| Jia et al. | Influence of well-defined hard segment length on the properties of medical segmented polyesterurethanes based on poly (ε-caprolactone-co-L-lactide) and aliphatic urethane diisocyanates | |
| Teng et al. | Synthesis and degradability of a star-shaped polylactide based on l-lactide and xylitol | |
| CN113817148B (en) | Polylactic acid copolymer, preparation method and application thereof, and preparation method of blend film | |
| Aboueimehrizi et al. | Synthesis of high-modulus thermoset PUs of PCL-PTMG/CNW biomaterials with different soft domain architecture and composition for high shape memory performance | |
| CN106459569B (en) | It include the polymer composition of the block copolymer based on polylactide-polybutadiene | |
| Phetsuk et al. | Physical and thermal properties of l‐lactide/ϵ‐caprolactone copolymers: the role of microstructural design | |
| Gao et al. | A biobased aliphatic polyester derived from 10-hydroxydecanoic acid: molecular weight dependence of physical properties | |
| Chen et al. | Bio-based and biodegradable electrospun fibers composed of poly (L-lactide) and polyamide 4 | |
| CN105017779A (en) | Steric compound crystal controlled polylactic acid/hydrogenated polybutadiene supermolecular elastomer | |
| CN103613743B (en) | A kind of biodegradable succinic acid-oxalic acid-butanediol copolymer and preparation method thereof | |
| Zhong et al. | Preparation and characterization of polylactide‐block‐poly (butylene adipate) polyurethane thermoplastic elastomer | |
| CN109320694B (en) | Preparation method of stereocomplex polylactic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160824 Termination date: 20220205 |