[go: up one dir, main page]

WO2018009989A1 - Procédé d'obtention de nanocomposites de poly(l-lactide) sans inertisation ni solvants - Google Patents

Procédé d'obtention de nanocomposites de poly(l-lactide) sans inertisation ni solvants Download PDF

Info

Publication number
WO2018009989A1
WO2018009989A1 PCT/BR2017/000067 BR2017000067W WO2018009989A1 WO 2018009989 A1 WO2018009989 A1 WO 2018009989A1 BR 2017000067 W BR2017000067 W BR 2017000067W WO 2018009989 A1 WO2018009989 A1 WO 2018009989A1
Authority
WO
WIPO (PCT)
Prior art keywords
fact
clay
inertization
poly
polymers
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.)
Ceased
Application number
PCT/BR2017/000067
Other languages
English (en)
Portuguese (pt)
Inventor
Ana Flávia PATTARO
Maria Ingrid Rocha Barbosa SCHIAVON
André Luiz Jardini MUNHOZ
Rubens MACIEL FILHO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universidade Estadual de Campinas UNICAMP
Original Assignee
Universidade Estadual de Campinas UNICAMP
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Universidade Estadual de Campinas UNICAMP filed Critical Universidade Estadual de Campinas UNICAMP
Publication of WO2018009989A1 publication Critical patent/WO2018009989A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters

Definitions

  • This invention relates to the field of chemistry, more specifically to the field of tissue and packaging engineering biomaterials, discloses a process for obtaining poly (L-lactide) (PLLA) nanocomposites, including use of reaction medium inert gas: in solve t s.
  • PLLA poly (L-lactide)
  • Synthetic materials used in biological (biomaterial) applications may be classified as metals, ceramics, polymers and composites.
  • This class of biomaterials has two main advantages when compared to non-biodegradable biomaterials.
  • the first advantage is that they do not cause permanent foreign body reactions, as these materials are gradually absorbed 1 by the body and leave no trace of residues: permanent in the places where the implants were performed.
  • the second advantage is that some specific types of biomaterials are capable of regenerating tissues through their interaction with immune cells. Based on the behavior of polymeric bioreactors in living tissues, they can be divided into biostable, bioabsorbable, partially bioabsorbable, or bioreactors.
  • bioabsorbable, partially bioabsorbable or fooreactive materials are more appropriate than biostable polymeric materials.
  • the bioabsorbable or bioreactive surgical materials are suitable for temporary internal fixation when the tissue has been traumatized, as the implant preserves the tissue structure in its early healing phase, such as bones, tendons or skin. As the implant gradually decomposes, the stresses are also gradually transferred to the healing tissue. The time required depends on the type of matter, molar mass and structural properties, as well as where the implant is inserted.
  • bioabsorbable or more resorbable in living tissues are considered bioabsorbable or more resorbable in living tissues.
  • the most important surgical bioresorbable polymers are aliphatic polyesters (polymers and copolymers derived from the hydroxy acids. Most of them are thermoplastic polymers, partially crystalline or fully amorphous.
  • Table 1 shows some synthetic and natural polymers.
  • Table 1 Examples of synthetic and natural polymers used as biornaterials.
  • poly (lactic acid) is among the few clinically used.
  • the interest in these types of polymers is the fact of them have already approved for a number of clinical applications by the US Food and Dr g Administration ⁇ FDA) t body responsible for the release of food and drugs in the US.
  • Poly (lactic acid) (PLA) is expected to have a wide range of applications from use with biodegradable plastic, but also as a material for biomedical applications, because of its excellent mechanical properties and for being highly hydrolysable in the human body.
  • PLA can be prepared by two types. polymerization methods: direct condensation of lactic acid and ring opening polymerization of the cyclic lactide dimer.
  • Both lactic acid and cyclic dimer lactide have chiral carbons, and lactic acid has two stereoisomeric forms, L- and D-lactic acid.
  • the lactide . what. is the cyclic diester of lactic acid, has four different isomers: L-lactide, D-laetid the racemic mixture D, L-lactide and the optically inactive mesoacid. High purity mesolactid is difficult to prepare and is therefore rarely mentioned in the literature.
  • Lactic acid may be a precursor to totally amorphous materials as well as highly crystalline materials.
  • Poly (L-lactic acid) is a semi-crystalline polymer with melting temperature (Tm) of about 180 ° C.
  • D-poly (lactic acid) has the same properties as L-poly (lactic acid; OD, L-poly (lactic acid) to attic is an amorphous material with glass transition temperature between 45 ° and 60 ° C).
  • D, L-poly (lactic acid), which contains long blocks of D and L units, may have similar properties to those of optically pure polymers.
  • Poly (L-lactic acid) as well as its lactitic cyclic dimer shows good mechanical strength, thermal plasticity, processability and can undergo chain disruption in the body: human resulting from oligomers and finally monomeric units of lactic acid, which are fully resorbable as a natural intermediate to metabolism, in particular L-isomer is a biological metabolite of the human body.
  • Pallimeric kanocomposites are defined as materials composed of more than one phase where at least one of the constituents of one of these phases, commonly a nanocharge, has a nanometric dimension (1-100 nmj) and its properties exhibit substantial improvement.
  • nanoscale loads used in the polymers produce composite materials with improved mechanical, electrical, ethical, thermal and magnetic properties.
  • Clay minerals which are part of the group of 2: 1 phyllylicates are mainly made up of monmormononite, beidelite, nontronite, volconscoite, saponite, sauconite, hectorite. They consist of two sheets of tetrahedral silicate, with an octahedral central leaf, joined together by common oxygen to the leaves. These sheets are continuous in the directions of axes a and b and are stacked randomly on top of one another in some types and in some order in others.
  • bentonite are used and without any information as to the geological origin or the mineral mineral composition.
  • montinorilonite Since montinorilonite has the highest swelling capacity in aqueous medium, it is a great option for obtaining polymeric compounds.
  • Polymerization processes including the process of obtaining the poly L TM Lactldec, comprise a step of inerting the reaction medium to avoid counting with 0; and, when the process is in solution, the addition of solvent: these steps may require time, use of specific equipment and also promote the emission of toxic agents to the environment.
  • the present invention relates to a process for obtaining a poly.
  • (L-Lactide) comprising 1 the addition of nanocarb of clay after complete fusion of the monomer and without the use of inertia gas from the reaction medium and solvent, producing a material that can be applied as a biomaterial.
  • the material obtained in such a document has a completely different concept from the present invention, since it does not use an inorganic filler but rather a polymeric matrix, in addition to the use of another polymer as nanocarbon.
  • the present invention suggests a simpler process of obtaining PLLA nanocomposites without the use of inerting gas and pressure increase without the use of any solvent: in the reaction medium, besides allow the slow and continuous addition of nanocargo allowing better homogenization of the charge with the polymer matrix, further simplifying the process and avoiding the emission of toxic agents into the environment.
  • the present invention relates to a process for obtaining poly (L-lactide) (PLLA) iranocompounds using: the I-Laetrdeo monomer by : ring opening polymerization in situ without inertization and without use of solvents,
  • FG 1 shows 03 JTTIR spectra for PLLA / Clay nanocomposites synthesized using the in situ p-ligation process with reaction medium inertization;
  • FIG. 2 shows the FTI spectra for the PLL & Clay nanocomposite synthesized using the in situ polymerization process without inertization of the reaction medium;
  • FIG. 3A shows the G curves referring to thermogravimetric analysis of the three PXL polymers with reaction medium inertization and clay addition;
  • FIG. 3B shows the DTG curves for the terraogravimetric analysis of the three PLLA polymers with the reaction medium inertization and clay addition.
  • the Fie. 4A shows the TG curves for the radiographic analysis of the .PLLA polymer without inerting the reaction medium with clay addition.
  • FIG. B shows the DTG curves .Referring to thermographic analysis: of PLLA polymer without inertization: of reaction medium with clay addition
  • the F1G. SA shows DSC curves for second heating performed for NanoPLLA 1 polymer synthesized with medium: reaction inertization;
  • FIG. 5B shows, a. DSC curve. referring to the second heating performed for the Nano PLLA 2 polymer synthesized with reaction medium inertization;
  • the FI. 5C shows the DSC curve for the second heating performed for the NanoPLLA 3 polymer synthesized with reaction medium inertization
  • FIG. 5D shows the DSC curve for second heating 1 performed for NancPL.
  • LA polymer 4 synthesized without inertization: reaction medium;
  • FIG. 5E shows the DSC curve for the second heating performed for PLL9 polymer synthesized without addition of clay
  • FIG. 6 shows the diff atograma the x-ray NanoPLLA 4 using sation polymerization process without inerting and compared: the one obtained for the Algiers organophilizated CN-40 with 12 to inododecanó acid: acid.
  • the present invention describes a process for obtaining polymer (L-lactide ⁇ nanocomposites by in situ ring opening polymerization without reaction medium inertization, comprising the following solvents: following: steps;
  • the L-lactide inonomer adds 0.51 to 4.0%: of a catalyst belonging to the group of titanium IV alkoxides, preferably 1.5 of the tin octanoate catalyst and then add 5 to 80 ⁇ l primer belonging to the protieog solvent group.
  • the 1-dodecancl to the reactor under agitation was a range ranging from 2700 rpm to 5000 rpm, preferably 3000 rpm, until complete melting;
  • organophilic clay preferably 12-aminododecanoic acid organofluorinated bentonite, in a proportion of 1.0 to 12% of the amount of monomer used in the synthesis, under continuous agitation and slowly and continuously, and not to be added just one time ;
  • bentonite clay commercially known as Algiers C-40 (natural sodium clay; Table 2 shows the analytical characteristics of the clay studied.
  • Modification of bentonite clays is a key point for: application of this material in polymeric matrices, as the use of: modifying agent (organophilizing agent in the case of organophilic clays; suitable may significantly alter the intercalation length of the between the interlabellar spacing of the clay due to the interaction between polymer and the functional groups of the modifying agent.
  • modifying agent organophilizing agent in the case of organophilic clays; suitable may significantly alter the intercalation length of the between the interlabellar spacing of the clay due to the interaction between polymer and the functional groups of the modifying agent.
  • the tin catalyst ootanoate (95% purity) and the 1-dodecanol initiator (98% purity) were used.
  • the clays used as nanocarbons were obtained through the organophilization process.
  • a soil disperser was used for the process of organofilization of the bentonite clay.
  • 600 ml of distilled water at a temperature of 100 ° C to facilitate the solution of the amino acid was placed in the soil disperser container. and then 25 g of clay was slowly added to the vessel under constant stirring at a speed of S000 rpm. After complete addition of the clay, the stirring speed was increased to 12000 rpm and kept constant for 2 : 0 minutes for complete clay dispersion.
  • the mixture was stirred at 9000 rpm for 20 minutes. After this period, the stirring speed was increased to 12000 rpm and held for 10 minutes. The mixture was then transferred to a poker where it was left to stand for 24 hours at room temperature. After this period, vacuum filtration was performed using a Bucbner e-itate funnel to remove excess exits. In this step, 2000 mL of distilled water was used to wash the material.
  • the reactor silicone bath was kept at a constant temperature: 140 ° C.
  • 50g of L-Lactide monomer 0.5 to 4.0%, preferably 1.5% of Tin Octanoate catalyst and 5 to 80 pL, preferably 57 ⁇ , of 1- Dodecanol primer.
  • the monomer, catalyst and initiator were constantly stirred within a range of 2700 rpm to 5000 rpm, preferably 3000 rpm, until complete melting.
  • the addition of 12--3ml & dodecan-oic acid organophilized benonite was started in the ratio 1.0 to 12%, preferably 0.5% of the amount of Kionomer used in the synthesis, under stirring.
  • the FXGs. 1 and 2 show the FTI spectra of the synthesized polymers to obtain the nanocomposites.
  • Table 3 shows the initial mass loss temperature (Ti)., Degradation temperature ( ⁇ ; > .. 3 ⁇ 4), and mass loss final temperature (T>) for the polymers produced with the addition. of clay with and without inertization of the reaction medium and which refer to the thermogames present in FIGS. 33 ⁇ 4, 3B and 4,4B.
  • Table 3 Temperatures obtained from thermal degradation for PLLA polymers without inertization of. reaction medium and clay addition, and PLLA9 polymer produced without clay addition.
  • the E'IGs. SA-5P presents the DSC graphs of the second heat for the clay-added PXilA polymers using the colorless processes and inertization of the reaction medium.
  • FIG. 5E presents the DSC graph of the second heat for the PLL & 9 polymer synthesized in clay addition.
  • Table 4 shows the values of glass transition temperature (T ⁇ ;, Melting temperature (T ;;;) and cold crystallization temperature (t:,:) for all polymers synthesized PLLA and using the processes with and without inertization of the reaction medium, and the polymer synthesized without the addition of clay.
  • NanoPLIA 1 (with N 2 ) 51.0: 2.164.84, 5.14
  • NanoPLlA 3 (with N) 51.80 171, 96 91, 25
  • NanoPLIA 4 (no N s) 43.80 3.71 27 92 13
  • DRX X-ray Scanning
  • the XRD technique is commonly used to verify the structure of a nanocomposite. By monitoring the position, shape 1 and intensity of the basal reflection distributions of the silicate layers, the structures of a nanocomposite. ⁇ interspersed or exfoliated ⁇ can be identified.
  • FIG. 6 presents the diffractogram for PLLA 4 and its comparison with that obtained for argel CN-40 orga clay . nofili zat ⁇ a with 12-arcd.nododecanoic acid.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Composite Materials (AREA)
  • Dispersion Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un procédé d'obtention de nanocomposites de poly(L-lactide) par polymérisation par ouverture de cycle in situ, sans inertisation du milieu réactionnel et sans utilisation de solvant. La présente invention se différencie par la suppression de l'étape d'inertisation, par la non-utilisation de solvants et par l'addition lente et continue de l'argile, favorisant un procédé simplifié, avec une meilleure homogénéisation entre la charge et la matrice polymère, et évitant l'émission d'agents toxiques dans l'environnement. La présente invention trouve une application dans le domaine de la chimie, et plus particulièrement dans le domaine des biomatériaux pour le génie tissulaire et les emballages.
PCT/BR2017/000067 2016-07-12 2017-06-29 Procédé d'obtention de nanocomposites de poly(l-lactide) sans inertisation ni solvants Ceased WO2018009989A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRBR2020160161720 2016-07-12
BR202016016172 2016-07-12

Publications (1)

Publication Number Publication Date
WO2018009989A1 true WO2018009989A1 (fr) 2018-01-18

Family

ID=60952259

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/BR2017/000067 Ceased WO2018009989A1 (fr) 2016-07-12 2017-06-29 Procédé d'obtention de nanocomposites de poly(l-lactide) sans inertisation ni solvants

Country Status (1)

Country Link
WO (1) WO2018009989A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111574855A (zh) * 2020-06-09 2020-08-25 新疆大学 改性蛋白土、改性蛋白土复合材料及其制备方法和应用

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100656986B1 (ko) * 2005-09-28 2006-12-14 한국과학기술원 전단 담화와 강인성이 향상된 신규한 폴리락티드/클레이나노 복합체의 제조방법
KR100683941B1 (ko) * 2006-01-06 2007-02-16 한국과학기술원 전단 담화와 강인성이 향상된 신규한 폴리락티드/클레이나노 복합체의 제조방법
BRPI0515822A (pt) * 2004-12-01 2008-08-05 Akzo Nobel Nv argila compreendendo ìons orgánicos de balanceamento de carga e materiais nanocompósitos compreendendo os mesmos
WO2009130205A1 (fr) * 2008-04-21 2009-10-29 Purac Biochem Bv Composition de polymère comprenant un polylactide
KR20110053006A (ko) * 2009-11-13 2011-05-19 현대자동차주식회사 폴리유산-나노클레이 복합재 조성물 및 이를 포함하는 친환경 자동차 내장재
CN102260405A (zh) * 2011-05-17 2011-11-30 淮阴工学院 聚乳酸/凹凸棒石粘土复合材料的制备方法
CN102391627A (zh) * 2011-08-24 2012-03-28 淮阴工学院 聚乳酸/聚丁二酸丁二醇酯/凹凸棒石粘土复合材料的制备方法
US8829110B2 (en) * 2010-02-11 2014-09-09 Fpinnovations Nanocomposite biomaterials of nanocrystalline cellulose (NCC) and polylactic acid (PLA)
US20140363598A1 (en) * 2012-03-07 2014-12-11 Huhtamäki Oyj Essentially biobased, thermoformable composition and containers formed thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0515822A (pt) * 2004-12-01 2008-08-05 Akzo Nobel Nv argila compreendendo ìons orgánicos de balanceamento de carga e materiais nanocompósitos compreendendo os mesmos
KR100656986B1 (ko) * 2005-09-28 2006-12-14 한국과학기술원 전단 담화와 강인성이 향상된 신규한 폴리락티드/클레이나노 복합체의 제조방법
KR100683941B1 (ko) * 2006-01-06 2007-02-16 한국과학기술원 전단 담화와 강인성이 향상된 신규한 폴리락티드/클레이나노 복합체의 제조방법
WO2009130205A1 (fr) * 2008-04-21 2009-10-29 Purac Biochem Bv Composition de polymère comprenant un polylactide
KR20110053006A (ko) * 2009-11-13 2011-05-19 현대자동차주식회사 폴리유산-나노클레이 복합재 조성물 및 이를 포함하는 친환경 자동차 내장재
US8829110B2 (en) * 2010-02-11 2014-09-09 Fpinnovations Nanocomposite biomaterials of nanocrystalline cellulose (NCC) and polylactic acid (PLA)
CN102260405A (zh) * 2011-05-17 2011-11-30 淮阴工学院 聚乳酸/凹凸棒石粘土复合材料的制备方法
CN102391627A (zh) * 2011-08-24 2012-03-28 淮阴工学院 聚乳酸/聚丁二酸丁二醇酯/凹凸棒石粘土复合材料的制备方法
US20140363598A1 (en) * 2012-03-07 2014-12-11 Huhtamäki Oyj Essentially biobased, thermoformable composition and containers formed thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SILVINO A.C. ET AL.: "Polylactide/clay nanocomposites: a fresh look into the in situ polymerization process", JORNAL OF APLLIED POLYMER SCIENCE, vol. 124, 10 December 2011 (2011-12-10), pages 1217 - 1224, XP055456781 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111574855A (zh) * 2020-06-09 2020-08-25 新疆大学 改性蛋白土、改性蛋白土复合材料及其制备方法和应用

Similar Documents

Publication Publication Date Title
Castillo et al. Crystallization and morphology of biodegradable or biostable single and double crystalline block copolymers
Zheng et al. Shape memory properties of poly (D, L-lactide)/hydroxyapatite composites
Hofmann et al. Knowledge‐based approach towards hydrolytic degradation of polymer‐based biomaterials
Bigi et al. Hydroxyapatite-gelatin films: a structural and mechanical characterization
US8507614B2 (en) Multiphasic absorbable compositions of segmented l-lactide copolymers
Li et al. Stereocomplex crystallite network in poly (D, L-lactide): formation, structure and the effect on shape memory behaviors and enzymatic hydrolysis of poly (D, L-lactide)
PT98203A (pt) Processo para a preparacao de um copolimero absorvivel segmentado obtido a partir de monomeros de ester ciclico
Dos Santos et al. Manufacturing and characterization of plates for fracture fixation of bone with biocomposites of poly (lactic acid-co-glycolic acid)(PLGA) with calcium phosphates bioceramics
Fan et al. Injectable thermosensitive hydrogel composite with surface-functionalized calcium phosphate as raw materials
Fabbri et al. New fully bio-based PLLA triblock copoly (ester urethane) s as potential candidates for soft tissue engineering
Oyama et al. Biologically safe poly (l-lactic acid) blends with tunable degradation rate: microstructure, degradation mechanism, and Mechanical Properties
Zhao et al. Polylactide (PLA)/layered double hydroxides composite fibers by electrospinning method
BR102013034085B1 (pt) Compósitos biocompatível e reabsorvível para osteossíntese e seu método para fabricar
Renouf-Glauser et al. A degradation study of PLLA containing lauric acid
Bachtiar et al. Structure-property relationships in 3D-printed poly (l-lactide-co-ε-caprolactone) degradable polymer
Jin et al. Precise and controllable assembly of block copolymers
Shuai et al. Montmorillonite reduces crystallinity of poly‐l‐lactic acid scaffolds to accelerate degradation
Hosseini et al. Effect of crystallization process on the electrical, and piezoelectric properties of PLA scaffolds
WO2018009989A1 (fr) Procédé d'obtention de nanocomposites de poly(l-lactide) sans inertisation ni solvants
Janeczek et al. Poly (L-lactide) liquid crystals with tailor-made properties toward a specific nematic mesophase texture
Wilberforce et al. A comparative study of the thermal and dynamic mechanical behaviour of quenched and annealed bioresorbable poly-L-lactide/α-tricalcium phosphate nanocomposites
Silva et al. Evaluation of hydrolytic degradation of bionanocomposites through fourier transform infrared spectroscopy
Ciferri Translation of molecular order to the macroscopic level
Yang et al. Crystallization and rheological properties of the eco-friendly composites based on poly (lactic acid) and precipitated barium sulfate
EP0933089A2 (fr) Matériel pour la fixation des os et méthode de préparation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17826698

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17826698

Country of ref document: EP

Kind code of ref document: A1