department of chemistry and technology of polymers cracow university of technology ul. warszawska 24...

DEPARTMENT OF CHEMISTRY DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSAND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY

ul. Warszawska 24ul. Warszawska 2431-155 Krakow Poland31-155 Krakow Polandwww.pk.edu.plwww.pk.edu.pl

DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSCRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY

Profile :Profile :

Department of Chemistry and Technology of Polymers Department of Chemistry and Technology of Polymers (hereafter called “Department”) is a part of Faculty of (hereafter called “Department”) is a part of Faculty of Chemical Engineering and Technology at the Cracow Chemical Engineering and Technology at the Cracow University of Technology. In the Department there are 3 full University of Technology. In the Department there are 3 full professors, 1 associate professor, 9 adjuncts and 4 professors, 1 associate professor, 9 adjuncts and 4 members of staff. members of staff.

Faculty members of the Department are involved in Faculty members of the Department are involved in teaching and research in the area of polymer chemistry and teaching and research in the area of polymer chemistry and technology, including materials science issues. At the post-technology, including materials science issues. At the post-graduate level 45 students are trained within the graduate level 45 students are trained within the specialisation “technology of polymers”, performing at the specialisation “technology of polymers”, performing at the final semester M.Sc. works under supervision of faculty final semester M.Sc. works under supervision of faculty members at the Department. members at the Department.

Most of the research works is performed together with 12 Most of the research works is performed together with 12 Ph.D. students who are working towards their doctorates at Ph.D. students who are working towards their doctorates at the Department, being funded by Ministry of National the Department, being funded by Ministry of National Education and Science in Poland.Education and Science in Poland.


Activities :Activities :

Education: the main teaching profile is technology and Education: the main teaching profile is technology and engineering engineering

of polymeric materials (polymers, copolymers, blends, of polymeric materials (polymers, copolymers, blends, (nano)composites, plastics, hybrid materials, etc.) and their (nano)composites, plastics, hybrid materials, etc.) and their application as innovative products in modern materials application as innovative products in modern materials engineering. engineering.

Research: synthesis, processing, characterisation and Research: synthesis, processing, characterisation and optimization optimization

of properties of polymeric materials for advanced applications. of properties of polymeric materials for advanced applications. Design Design

of structure / properties relationships in polymer of structure / properties relationships in polymer nanocomposites to fabricate value-added products and nanocomposites to fabricate value-added products and technologies.technologies.

Cooperation: established links with Polish polymer industry to Cooperation: established links with Polish polymer industry to develop jointly new products and technologies as well as to offer develop jointly new products and technologies as well as to offer training possibilities and research expertize. training possibilities and research expertize.


Expertise on following materials:Expertise on following materials:

• polymerspolymers• copolymerscopolymers• blendsblends• (nano)composites(nano)composites• hybrid materialshybrid materials


Actual research domains concerning materials Actual research domains concerning materials technology /Competences :technology /Competences :

Activities :Activities :

Research works performed at the Department focus on the Research works performed at the Department focus on the following areas:following areas:

• Synthesis of novel polymers for special applications (e.g. Synthesis of novel polymers for special applications (e.g. biodegradable polymers,biodegradable polymers, polymers from renewable polymers from renewable resources, polymer nanohydrogels),resources, polymer nanohydrogels),

• Preparation of polymer blends and nanomaterials for Preparation of polymer blends and nanomaterials for thermal energy storage materials,thermal energy storage materials,

• Polymer nanocomposites with enhanced thermal Polymer nanocomposites with enhanced thermal properties,properties,

• Recycling of polymers and plastics, particularly PVC Recycling of polymers and plastics, particularly PVC wastes,wastes,

• Flame retardancy of polymeric (nano)materials,Flame retardancy of polymeric (nano)materials,• Application of novel techniques in polymer synthesis and Application of novel techniques in polymer synthesis and

characterisation, e.g. MT-DSC, microwaves, thermovision.characterisation, e.g. MT-DSC, microwaves, thermovision.DEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERSDEPARTMENT OF CHEMISTRY AND TECHNOLOGY OF POLYMERS

CRACOW UNIVERSITY OF TECHNOLOGY CRACOW UNIVERSITY OF TECHNOLOGY

POM/MMTPOM/MMT


Polyoxymethylene (POM) - engineering Polyoxymethylene (POM) - engineering thermoplastic polymerthermoplastic polymer

Properties:Properties:high mechanical strength, high mechanical strength, chemical resistance,chemical resistance,thermal resistance,thermal resistance,good electrical properties.good electrical properties.

Applications:Applications:gears, conveyors, gears, conveyors, elements of pumps, belt elements of pumps, belt fasteners, etc.fasteners, etc.

POM share in the worldwide POM share in the worldwide production of engineering production of engineering thermoplasticsthermoplastics

PC

POM

Other

PA


Polymer/layered silicate nanocompositesPolymer/layered silicate nanocomposites

Advantages over classic compositesAdvantages over classic composites

Improved material performance at low filler loading Improved material performance at low filler loading (below 10 wt%, usually 3 -5 wt%)(below 10 wt%, usually 3 -5 wt%) d due to small ue to small interparticle distances and the conversion of a large interparticle distances and the conversion of a large fraction of the polymer matrix near their surfaces into an fraction of the polymer matrix near their surfaces into an interphase of different properties as well as to the interphase of different properties as well as to the consequent change in morphology.consequent change in morphology. Enhancement Enhancement ofof a variety of properties a variety of properties,, e e.g..g. mmechanical echanical strength, thermal stability, chemical resistance, barrier strength, thermal stability, chemical resistance, barrier propertiesproperties..Elimination or reduction of processing problems, such as Elimination or reduction of processing problems, such as substantialsubstantial changes in rheological properties, changes in rheological properties, deterioration of surface appearance.deterioration of surface appearance.


Structures of ammonium compounds used Structures of ammonium compounds used for MMT modificationfor MMT modification

N

CH3

CH3

CH3

ClR N

CH3

R2

CH3

ClR1

N

H2C

CH3

H2C

ClR

CH2OH

CH2OH

OH CH2 N

CH2

R

CH2

CH2

CH2

OH

OH

Cl

N

CH3

CH3

CH3

ClR

1R3M 2R2M

RM2Et RB2Et

RA3M, where R contains amide group


Structure of organo-modified MMTStructure of organo-modified MMT (o- (o-MMT)MMT)

XRD diffractograms of sodium MMT and o-MMT modified with different amounts of ammonium modifier (50 and 100% of cation exchange capacity of MMT).

6,55

5,85,0

2 7 12 172 theta, degree

Inte

nsi

ty

Na+MMT

MMT-RA3M, 50% CEC

MMT-RA3M, 100% CEC

(i) changing the hydrophilic character of montmorillonite into organophilic one thus allowing macromolecules to intercalate into MMT galleries, and, (ii) increasing the distance between montmorillonite layers and simultaneously weakening electrostatic forces responsible for MMT stack cohesion.

More effective in dispersing the polymer matrix were o-MMT More effective in dispersing the polymer matrix were o-MMT with higher interlayer distances since organic compound with higher interlayer distances since organic compound facilitates exfoliation byfacilitates exfoliation by


Melt blending of MMT into POM matrixMelt blending of MMT into POM matrix

Previous research on thermoplastic polymers indicated Previous research on thermoplastic polymers indicated that the degree of exfoliation/intercalation of MMT is that the degree of exfoliation/intercalation of MMT is favoured byfavoured by

Longer time of mixing Longer time of mixing Higher speed of rotorsHigher speed of rotors Higher melt viscosity (higher molecular weight of Higher melt viscosity (higher molecular weight of

polymer)polymer)

Since POM is susceptible to thermomechanical Since POM is susceptible to thermomechanical degradation the optimization of processing degradation the optimization of processing parameters is required.parameters is required.


Nanocomposite structure characterization

WAXD diffractograms ofWAXD diffractograms of: :

a- pristine MMT, a- pristine MMT,

b - organo-modified MMT (MMT-2M2R),b - organo-modified MMT (MMT-2M2R),

c - POM/MMT-2M2Rc - POM/MMT-2M2R nanocomposite nanocomposite..

5.5

6.355.2

2 4 6 8 10 12 142θ, degrees

inte

nsity

, a.

u.

c

b

a

2θ peak at ca. 5.5º 2θ peak at ca. 5.5º indicatindicateses the presence of the presence of unintercalated stacks of unintercalated stacks of organomodified MMT organomodified MMT layers. However, taking layers. However, taking into account the weak into account the weak intensity of these peaks, intensity of these peaks, partial exfoliation of partial exfoliation of montmorillonite can be montmorillonite can be considered. considered.


Model of structure of POM/MMT Model of structure of POM/MMT nanocompositenanocomposite


Structure of nanocmposites Structure of nanocmposites

SEM microphotographs – homogenic distribution of MMT SEM microphotographs – homogenic distribution of MMT stacks and layersstacks and layers

POM/MMT-2R2M.POM POM/Na+MMT


Core-shell structure of nanocomposite Core-shell structure of nanocomposite injection mouldinginjection moulding

SEM microphotographsSEM microphotographs of criofractured injection of criofractured injection moulding samplemoulding sample

247 μm


Influence of MMT on crystallization Influence of MMT on crystallization process of POMprocess of POM

SampleSample

Enthalpy of meltingEnthalpy of meltingHHmm

[J/g][J/g]

Crystallinity Crystallinity degreedegree

CC%%

[%][%]

Core Core regionregion

Shell Shell regionregion

Core Core regionregion

Shell Shell regionregion

POMPOM 135.1135.1 133.7133.7 41.441.4 41.041.0

POM/NaPOM/Na++MMTMMT(microcomposit(microcomposit

e)e)145.4145.4 136.8136.8 44.644.6 41.941.9

POM/MMT-2R2M POM/MMT-2R2M (nanocomposite(nanocomposite

))168.0168.0 137.6137.6 51.551.5 42.242.2


POSS – polyhedral oligomeric POSS – polyhedral oligomeric silsesquioxanessilsesquioxanes


POSS – polyhedral POSS – polyhedral oligomeric silsesquioxanessilsesquioxanes

Structures of POSS occurring most often: a – T6, b – T8, c – T10, d i e

– T12.

Within the latter class of materials increasing interest lies in the usage of functional polyhedral oligomeric silsesquioxanes (POSS) with a general formula (RSiO1.5)n having natural silica-type nanoparticles with a well defined structure and topology

as an inorganic phase. Cubic structural compounds (completely and incompletely condensed silsesquioxanes) are commonly

illustrated as T6, T8, T10 and T12, based on the number of silicon atoms present in cubic structure.

POSS nanostructured chemicals, with sizes of from 1 to 3 nm in diameter, can be thought of as the smallest possible particles

of silica

Cubane cage of POSS (RSiO1,5)8


Polyhedral oligomeric silsesquioxanesPolyhedral oligomeric silsesquioxanesCharacteristic and properties of POSS

Si O Si

O

Si O Si

O

O

O

SiOSi

O

SiOSi

O

O

O

XR

R R

R

R

R

R

Unreactive organic (R) groups for solubilization and compatibilization

One or more reactive groups for grafting or polymerization

Thermally and chemically robust hybrid framework. Precise three-dimensional

structure for molecular level reinforcement of polymer

segments and coils. 1 - 3 nm (~0,5 nm)

POSS Properties: They occur in the form of crystalline solids, waxes and oils.

Soluble in organic solvents such as THF, toluene, chloroform and hexane.

They have relatively low melting point.

Due to the presence of Si-O bonds are rigid and resistant to nucleophilic and electrophilic agents.


Polymeric nanohybrid materialsPolymeric nanohybrid materialsDefinitionsDefinitions

Hybrid materials – mixtures of two or more materials with new properties

created by new electron orbitals formed between each material, such as covalent bond between polymer and silanol molecules in

inorganic/organic hybrids. Hybrid compositeHybrid composite Hybrid polymerHybrid polymer

The composite material in which two or more

high-performance reinforcements are

combined.

Understood as the polymer where an organic part is combined, on the molecular level, with an

inorganic part.


Nanohybrid materialsNanohybrid materials POSS/PolymerPOSS/Polymer

Hybrid organic-inorganic materials based on incorporating of polyoctahedral oligomeric silsesquioxanes (POSS) into polymeric matrices have received a

considerable attention.A variety of POSS nanostructured chemicals contain one or more covalently bonded reactive functionalities that are suitable for polymerization, grafting,

surface bonding, or other transformations.

Covalently bonded POSS nanocomposites exhibit:

improved thermal and mechanical stability,

improved elasticity,

increased the resistance to oxidation,

increased the resistance to UV radiation,

reinforcement of the surface,

increased glass-transition temperature value,

reduced flammability,

enhanced mechanical strength,

System of POSS-polymer.


Synthesis of PU - POSSSynthesis of PU - POSS

I STEP: Synthesis of PU prepolymer:

• 4,4 -methylenebis(phenylisocyanate) (MDI)

• poly(tetramethylene glycol) (Terathane 1400) (PTMG)

• 1,2-propanediol-heptaisobutyl-POSS (PHIPOSS)

• Temperature: 80°C• Atmosphere: N2

II STEP: Synthesis of PU elastomer:

• 1,4-butanediol


MorphologyMorphologyPU-POSS

Lateral force AFM images for PU/POSS

WAXD diffractograms of PU/POSS polymers


Thermal analysisThermal analysisPU-POSS

Normalized DSC thermograms recorded with polyurethane matrix and the hybrids

Normalized TSDC thermograms for PU and hybrid PU/POSS

Composite TGA mass loss plots for PU/POSS hybrid systems


Thermal analysisThermal analysisPU-POSS


ACRYLATE HYDROGELSACRYLATE HYDROGELS


AcrylateAcrylate hydrogelshydrogels – – polymerpolymer matrix matrix

Hydrogels matrix have some different properties Hydrogels matrix have some different properties such as their capacity to allow controlled release, such as their capacity to allow controlled release, changing their swellability by ionic strength, pH , changing their swellability by ionic strength, pH , temperature, chemical activity to interact with temperature, chemical activity to interact with adsorbates and selectivity to some species (i.e., adsorbates and selectivity to some species (i.e., metal ions, proteins and enzymes)metal ions, proteins and enzymes)

Applications:Applications:medical applications, medical applications, including drug delivery including drug delivery systems, scaffold materials systems, scaffold materials to organize cells into to organize cells into a a three-dimensional three-dimensional architecture, tissue architecture, tissue replacements, wounds replacements, wounds dressings and immobilization dressings and immobilization of proteins, cells, of proteins, cells, agriculturalagricultural applicationsapplications


Crosslinking reaction of acrylic acid Crosslinking reaction of acrylic acid with N,N`-methylenobisacryloamide with N,N`-methylenobisacryloamide

Swelling of hydrogels


SEM microphotographs of swollen SEM microphotographs of swollen acrylic matrix acrylic matrix


Available research infrastructure :Available research infrastructure :

• fully-equipped polymer processing laboratory (extrusion, fully-equipped polymer processing laboratory (extrusion, Brabender mixing, injection moulding, compression Brabender mixing, injection moulding, compression moulding, pressing, pelleting, grinding, etc),moulding, pressing, pelleting, grinding, etc),

• thermal analysis laboratory (TG, DSC, MT-DSC, DMA, thermal analysis laboratory (TG, DSC, MT-DSC, DMA, TG/DSC),TG/DSC),

• FTIR, FTIR microscopy, UV-Vis, NMR, AFM, GC/MS, GPC, FTIR, FTIR microscopy, UV-Vis, NMR, AFM, GC/MS, GPC, HPLC, HPLC,

• mechanical properties testing machines,mechanical properties testing machines,• LOI, thermovision camera, UL-94.LOI, thermovision camera, UL-94.


Contact person:Contact person:

Prof. Krzysztof PielichowskiProf. Krzysztof Pielichowski

Head of DepartmentHead of Department

Tel. : +48-12-6282727Tel. : +48-12-6282727

Fax : 6282947Fax : 6282947

e-mail : e-mail : [email protected]


Thank Thank yyou ou

ffor or your ayour attentionttention

department of chemistry and technology of polymers cracow university of technology ul. warszawska 24...

Documents

biodegradable polymers

recycling of polymers

department focus

synthesis of novel polymers

area of polymer chemistry

polymer nanocomposites

polymer synthesis

following materials