Polymers

Polymerization Synthetic polymers used in dentistry
Pavel Bradna Institute of Dental Research

1
Inorganic - gypsum products, investment materials, cements, ceramics Metals denture frameworks, supraconstructions, implants, amalgams, orthodontic brackets, wires Organic (polymer-based) materials
2
Dental materials
(C) Institute of Medical Biochemistry, 1st Faculty of Medicine, Charles University, and Institute of Dental Research in Prague
Typical applications of polymers in dentistry

Dentures (bases, artificial teeth, relining materials) Filling materials (composites, cements, adhesives) Impression materials Obturation materials (endodoncy) Equipment (spatulas, measures, etc)
3
What is the lecture about?

Terms and definitions Structure of polymer chains Polymers in dentistry Polymerization Methyl methacrylate polymers Typical dimethacrylate resins
4
Definition
Polymer a chemical compound consisting of giant molecules MACROMOLECULES formed by union of many POLY small repeating units mers
MONOMER molecules POLYMER chain, macromolecule
polymerization
covalent bond
What controls polymer properties?

1. Chemical composition of polymers type of monomer, its structure
CH2=CH Vinyl polymers R Examples: R = H : polyethylene hydrophobic, semicrystalline polymers R = OH : poly(vinyl alcohol), hydrophilic water soluble polymer with gelling properties
2. Topology of polymer chains Linear polymers

A-A-A-A-A-A-A-
Nonlinear (branched) polymers

Branches
Polymer (linear) backbone

7
Cross-linked polymer (polymer networks)

A-A-B-A-BA-B-B-AA-B-A-B-B-A-A-B- A-B-A-B-B-A-A-BA-B-A-B-B-AA-B-B-A- A-B-A-B-B-A-
Cross-links (permanent connections between chains restricting motion of chains rigidity) Temporary cross-links entanglements 8
3. Monomer distribution in copolymer chains

Homopolymers (one type of monomer - A)
A-A-A-A-A-A-A-
linear/branched
Copolymers (2-3 comonomers)

A-B-A-B-B-B-A-
statistical (random) block alternating
A-A-A-B-B-B-B-A-AA-B-A-B-A-B-A-A-A-A-A-A-
graft/branched
-B-B-B-B-B
4. Polymer molecular weight

Simple compounds composed of identical molecules
-number average -weight average
Molecules of polymer strongly differ (vary by many monomer units)
Polymers are characterized by molecular weight/polymerization degree average 10
Definitions of molecular weight averages

Number average, Mn Mn= Mi ni/ni=Mixi
xi states for molefraction of molecules with Mi -number average -weight average
Weight average, Mw Mw= Mi (ni Mi)/ni Mi =Mi (mi/mtotal)=Mi wi

wi states for weight fraction of molecules with Mi
Polymerization degree Pw= Mw/Mo Mo states for molecular weight of repeating unit
Polydispersity Mw/ Mn
11
5. Supramolecular structure (molecular organization) Amorphous polymers coiled irregular (random) shape of polymer chains Semicrystalline polymers domains with regular (crystalline) structures acting as
special type of cross-links

Amorphous domains
Crystallites
12
C C C C
C C C C H H
C N
N C O
(CH2)5 C N O H
(CH2)5 N C O
Van-der-Waals interactions
H-bridges
Typical for polyamides, polyethylene, polypropylene etc.

13
Influence of cross-links on physical properties of polymers

Linear or branched polymers - flow when heated, can be easily reshaped upon heating - thermoplastic polymers (usually soluble in organic solvents) Cross-linked polymers - they cannot be reshaped on heating, do not melt, but decompose on heating, insoluble in organic liquids (thermosetting polymers).
14
Glass transition (softening temperature) Temperature Tg

Temperature at which rigidity of polymer decreases Glass Rigid Range of Tg High degree of cross-linking
Rigidity
Rubbery state
Low degree of cross-linking Linear
Liquid Plastic Temperature

15
Polymers used in dentistry

Natural polymers
- polysaccharides (agar and alginates) - poly(isoprene)
2-methyl-1,3-butadiene
guttapercha
Trans-poly(1,4-isoprene) - (obturation points)
natural rubber
Cis-poly(1,4-isoprene) - (impression materials)
16
Polymers used in dentistry

Synthetic polymers
Prepared via polymerization reactions:

Addition (chain-growth) polymerization of monomers with a double bond Step-growth polymerization of
bifunctional monomers, frequently with release of low molecular compounds (analogous reaction to low molecular weight compounds)
17
Addition polymerization Characteristics

Starts from an active center (only these molecules are capable to react) -bond of monomer is converted to -bond in the polymer Monomers add sequentially to the end of a growing chain Is very fast and exothermic Produces high molecular weight polymers
18
Types of addition polymerizations:

Free-radical polymerization active center is a radical (contains unpaired electron) and the propagating site of reactivity is a carbon radical. Cationic polymerization - the active center is an acid, and the propagating site of reactivity is positively charged Anionic polymerization - the active center is a nucleophile, and the propagating site of reactivity is negatively charged
19
Few common polymers prepared via addition polymerization

Name(s) Formula Monomer Properties
Polyethylene low density (LDPE)

Polyethylene high density (HDPE)
Polypropylene (PP) different grades
Poly(vinyl chloride) (PVC)
Polystyrene (PS)
(CH2-CH2)n
(CH2-CH2)n
[CH2-CH(CH3)]n
(CH2-CHCl)n
ethylene CH2=CH2
ethylene CH2=CH2
propylene CH2=CHCH3
vinyl chloride CH2=CHCl
styrene
soft, waxy solid

rigid, translucent solid
atactic: soft, elastic solid isotactic: hard, strong solid
strong rigid solid
hard, rigid, clear solid soluble in organic solvents
[CH2-CH(C6H5)]n CH2=CHC6H5
Polytetrafluoroethylene (PTFE, Teflon)

Poly(methyl methacrylate) (PMMA, Lucite, Plexiglas)
cis-Polyisoprene natural rubber
(CF2-CF2)n
[CH2C(CH3)CO 2CH3]n
tetrafluoroethylene CF2=CF2
resistant, smooth solid
methyl methacrylate hard, transparent solid CH2=C(CH 3)CO 2CH3
[CH2-CH=C(CH3)- isoprene CH2=CHCH2]n C(CH 3)=CH 2
soft, sticky solid
20
10
Step-growth polymerization Characteristics

reactions (condensation, addition)
Proceeds by conventional functional group
Needs at least 2 functional groups per reactant Any monomer molecule has the same probability to react After an elementary reaction ability to grow remains Combines two different reactants in an alternating structure
21
Polymers are formed more slowly than by addition
polymerization
Polymers are generally of lower molecular weight
Types of step-growth polymerization

Polycondensation Polyaddition
22
11
Few common polymers

Formula Type polyester Mylar polycarbonate Components Phthalic acids (Bisphenol A) phosgene Tm C Instruments, matrices Artificial teeth, Veneering shells, Prefabricated crowns, orthodontic brackets Surgical suture materials
~[CO(CH2)4CONH(CH2)6NH]n~ ~[CO(CH2)5NH]n~
polyamide Nylon 66 polyamide Nylon 6 Perlon polyamide Kevlar
HO2C-(CH2)4CO2H H2N-(CH2)6-NH2
Surgical suture materials
para HO2C-C6H4CO2H para H2N-C6H4NH2 HOCH2CH2OH
Fibre reinforced splints
Toluene diisocyanate
Die materials
23
A. Stages of free radical polymerization

1. Initiation/induction process starts
- Primary radical formation
In - In Initiator T, h In. + In. (activation) Free radicals
Addition of primary radical on the double bond of monomer

In. + M In-M.
24
12
to an active center (free radical) to generate a new active center

In-M. In-M-M. + + M M
yM
2. Propagation - the addition of monomer
In-M-M. In-M-M-M. In-M-M-M-.. My.
In-M-M-M. +
3. Termination the growing chain is stopped

- Radical coupling/recombination (most common) In-Mx. + .My-In In-Mx-My-In
25
4. Chain transfer An atom is transferred
to the growing chain, terminating the chain growth and starting a new chain.
1. Chain termination
-M-M-M. + XB -M-M-M-X + B.
Chain transfer agent Chain transfer radical
2. New chain growth starts

B. + M BM.
Consequences Mol. weight decrease Branching Mol. weight regulation Polymerization is stopped XB Monomer Polymer Chain transfer agent Retarder/Inhibitor
26
13
A retarder is a substance that slowly reacts with a radical to form products nearly incapable of reacting with monomer. An inhibitor is a retarder that reacts rapidly with active radicals to form stable compounds (BX.) unable of addition to monomer completely stops or inhibits polymerization.
B. Anionic polymerization
phenyl, cyano or carbonyl
X-
Initiated with e.g. n-butyllithium, alkaline metals Used in superglues for methyl 2-cyanoacrylate 27 polymerization
+ H2C=CH(CN)
X-H2C-CH(CN)-
C. Cationic polymerization
H+ + H2C=CHR
H+ strong acids R - alkyl, phenyl or vinyl H C-CHR+
3
28
14
Step-growth polymerization
Polycondensation
nH2N(CH2)6NH2 + nHOOC(CH2)4COOH
Hexamethylene diamine Adipic acid
-2n H2O (-HN(CH2)6NH-CO(CH2)4CO-)n

Polyamide 66
Water release from the reaction mixture: 1. controls mol. weight, 2. contributes to contraction of the system
1. Setting reaction of C-silicone impression materials

O
..O
Si
O
OH
+ Si(OCH3) 4
O HO Si O
..O
..O
Si
O
OH
..O
O Si O
2. Setting reaction of epoxies

Diglycidyl ether bisphenol A
Diamine
Root canal sealers, die materials
Polyaddition
1. Production of polyurethanes
O=C=N-R1-N=C=O
+ O
HO-R2-OH Diol
O=C=N-R1-N-C-O-R2-OH
H
Alkyl, aryl diisocyanate
polyurethane
..O
..O
HO Si
-4CH3OH
..O
Si
O
O Si
O Si O
Si O
..O
29
30
15
2. Setting reaction of A-silicone impression materials
Vinyl terminated polysiloxane prepolymer
Addition of -H on vinyl double bond
Methylhydro-dimethylsiloxane a cross-linking agent
31
Most frequently used group of polymers in dentistry

Why? Because these materials can be easily adopted to individual purposes (fillings, prostheses) and can be in contact with human body
Methyl methacrylate (MMA) polymers
Suitable manipulation/processing properties (easy to mix, shapable, simple to process and cure) Good mechanical properties (rigidity, strength, wear resistance) Biocompatible (tasteless, odourless, non-toxic or non-irritating, resistance to microbial colonization) 32
16
Aesthetic properties translucency and transparency (colour and optical properties of tooth tissues) Chemical resistance in oral environment, to disinfectants etc. Acceptable cost of both material and processing method
33
Properties of MMA
Melting point -48oC CH =C Boiling point 100.3oC C=O Density 0.945 g/mL O CH Heat of polymerization 54.3 kJ/mol (!! exothermic reaction !!) Colourless liquid Immiscible with water but miscible with organic solvents Irritant !! Flammable !!
2
CH3
34
17
Properties of poly(methyl methacrylate)

Transparency and high clarity Low absorption of visible and UV light (to 250 nm) Density 1.19 g/cm3 (causes polymerization contraction/shrinkage app. 22 vol %) Compression strength 90 100 MPa Very rigid - elastic modulus above 2.4 GPa Water sorption up to app. 1.0 wt % Temperature resistance Tg = 120 125oC Soluble in organic solvents (MMA, acetone, toluene, etc.)
35
Methyl methacrylate polymers in dentistry

First applications for dentures (thermoplastic compression molding) of molten PMMA powder (too expensive and complicated) 1936 Kulzer: powder/liquid system
Powder PMMA prepolymer with residuals of DBP Liquid MMA monomer and additives
- When mixed workable plastic mass
(dough) is formed and polymerized in plaster individually fabricated mold Decreased polymerisation shrinkage
(app. 6 vol %)
36
18
PMMA prepolymer beads

Prepared by suspension polymerization
Average particle size 0.005-0.100 mm

Acrylics and Other Synthetic Resins Used in Dentistry
37
Initiation
Polymerization scheme of MMA monomers
Decomposition of dibenzoyl peroxide (DBP) during heating

heat
O O
2
O
O O
.+ CH =C
2
CH3 O CH2-C C=O O
CH3
C=O O
O CH3
CH3
38
19
Thermal decomposition of peroxides

C = concentration of peroxide k = kinetic constant t = time
Effect of temperature
T=const.
The temperature dependence of kinetic constant is given by an Arhenius law : with : k(T) = kinetic constant at temperature T (K) Ea = Activation energy R = Gas constant T = Temperature in K
The higher T the higher k and higher conc. of radicals 39
Propagation
CH3 O-CH2-C O
2
. + n(CH =C)
C=O CH3
CH3 O (CH2-C O
CH3
CH3 CH2- C
C=O O CH3
)n
C=O
C=O O
O CH3
CH3
Chain termination
CH3 R1-H2C- C
. +.
CH3
CH3 C CH2-R2 R1- H2C -C
CH3
CH3 C CH2-R2
C=O O
C=O O CH3
C=O O CH3
C=O O CH3
40
20
Chain transfer to MMA monomer

CH3 R CH -C .
2
CH3 + CH2=C C=O O
CH3 R- CH2=C C=O O +
CH3 CH3- C
C=O O CH3
C=O O
CH3
Chain transfer to phenolic inhibitors

-MX CH2-CH2. + HO-OH
CH3
CH3
-MX CH2-CH3 +HO-
-O
Hydroquinone (HQ)
Stable hydroquinone radical will not propagate/stop other chain radical

41
HO
OCH3
Methoxy phenol (hydroquinone monomethyl ether) MEHQ
C(CH3)3 HO C(CH3)3 CH3
2,6-di-tert-butyl-4-methylphenol (Butylated hydroxytoluene - BHT)
Sterically hindered phenols less efficient but reduced colour change after polymerization - Synergic mixtures HQ + MEHQ
Oxygen inhibition
Mx I
+ O2
MxIOOH
Stable hydroperoxide
Oxygen-inhibited layer on the composite/adhesive surfaces
42
21
Why polymer inhibitors are added?

Usually 0.01 0.005 wt %
1. To extend monomer shelf life by restricting spontaneous polymerization 2. Decrease sensitivity to ambient light 3. To prolonge working time
Note: Eugenol = phenol (inhibits polymerisation)
4-Allyl-2-metoxyfenol
43
Negative interaction with Zinc oxideeugenol materials
Modifications of PMMA for dental applications

Cross-linking
- improves hardness and stiffness (increases mol. weight) - increases crazing resistance (small cracks originating at the teeth-denture margin), wear and solvent resistance, but increases brittleness - increases thermal resistance (polymers are easily finished - grinded and polished without melting)
44
22
Example: MMA cross-linked with ethylene glycol dimethacrylate (EGDMA)

CH3 CH2 =C C=O O CH3 CH3 CH3 CH3 CH3
CH2 =C C=O O
CH2 =C C=O O
-CH2 -C -CH2 -C -CH2 -CC=O O C=O O C=O O
CH3
CH2
CH3
CH3
CH3
CH2
CH3 O
CH3
MMA
Cross-link
CH3 C=O O
O C=O CH2 =C CH3
C=O
-CH2 -C -CH2 -C -CH2 -C-
CH3
C=O O
CH3
CH3
CH3
Ethylene glycol dimethacrylate (EGDMA)
45
copolymerization (with acrylic and methacrylic monomers, PVC, PVAc, butadiene) disturbs regular intermolecular order of a homopolymer decreases softening temperature - improves fatique and impact resistance - increase dissolution rate in MMA blending of various MMA polymers increase rate of dissolution in MMA - decreases softening temperature
CH2=CH C=O O CH3
Methyl acrylate
46
23
Glass transition temperature (softening) of various methacrylic polymers

rigid
Methacrylate
methyl ethyl n-propyl n-butyl
Soft, faster dissolution
Polymer Tg oC
125 65 38 33
CH3 CH2=C C=O O CH3 (ethyl, propyl, butyl)
47
plasticizing high-boiling compounds swelling the polymer (phthalates dibutyl/dioctyl phthalates) - to reduce stiffness, hardness and softening point - to prepare flexible polymers (acrylic relining materials combinations of MMA copolymers with plasticizers)
48
24
Classification of polymers/resins according to initiation reactions (activation)

Heat activated (heat cured/heat curing resins)
(two component systems)
- Chemically activated (self cured/curing, cold curing, autopolymerizing, fast curing) resins
(two component systems) (one component system)
- Light activated (LC/UV cured) resins

Note
Dual-cure (a combination of chemically and light activated materials, LC modified GIC, luting materials) Tri-cure (a combination of acid-base setting reaction, LC and chemical activation [peroxide/amine] activating system)
49
(denture base resins, resins for artificial acrylic teeth, crown and bridge polymers)
Composition: powder: PMMA prepolymer with dibenzoyl peroxide (up to 0.5 - 0.6 wt %) liquid: MMA, cross-linking agent (app. 1- 6 wt %), inhibitors, additives (plasticizers), regulators
Heat activated resins
Volume mixing ratio (powder/liquid): 3-2.5/1.0
Regulators decrease the rate of polymerization heat release

Enable fast curing process
1-methyl-4-(1-methylethenyl)cyclohexene)
50
25
MMA vapours release
porosity in a denture
MMA boiling point
Too fast Standard polymerization Starts at 60oC
Temperature changes in PMMA during denture polymerisation in hot water

Lower temperature decreased risk of porozity MMA boiling point
Directly to 100oC Heated to 100oC
51
Typical porosity of heat activated denture base resin
Properly polymerized
Phillips Science of dental materials
Too fast heating

52
26
Chemically activated resins

(denture reparations, relining, orthodontic appliances, pouring resins)
Composition: powder: PMMA prepolymer or copolymer (fine particle size), dibenzoyl peroxide liquid: MMA, cross-linking agents, inhibitors, accelerators (1-4 wt %), UV absorbers Accelerators 1. Tertiary aromatic amine 2. Barbituric acid derivatives combined with aliphatic amine (lower colour change) and Cu cations 3. Sodium p-toluene-sulfinate (for systems 53 containing methacrylic acid), Cu cations
Scheme of DBP decomposition accelerated by tert. amine
CH3 H3C -N CH3 +

O O
CH3 + -N. CH3
.
Free radical
N,N-dimethyl-p-toluidine (DMPT); N,N-di(hydroxyethyl)-p-toluidine
Compared to heat activated resins: Lower molecular weight Higher amount of free monomer 3-5 wt %, heat activated app. up to 1 % Less colour stability due to oxidation of aromatic amine accelerators
54
27
Light activated resins

(light cured composite materials, adhesives, light cured glass-ionomer cements)
Composition (usually one component): 1. Dimethacrylate resin, light initiating system camphorquinone (CQ) - amine, inhibitors 2. Filler particles Light activation
amine
.. .
H 55
CQ
Free radicals
Typical dimethacrylate resins

BIS-GMA 2,2-bis[4-(2hydroxy-3-metakryloyloxypropoxy) fenyl]propane (Bowen monomer, 1955)
higher molecular weight less polymerization shrinkage
56
28
Capable of Hbridge formation high viscosity
Meth.
CH CH 3 H H3
Hindered rotation of C-C bond rigid part of a molecule
Meth.
H H
HH
HH
H H
Less polymerization shrinkage app. 5-6 vol %

57
2. Urethane dimethacrylate (UDMA) (2,2,4-trimethylhexamethylebis-(2-carbamoyl-oxyethyl)dimethacrylate)
Also of high viscosity
3. Triethylene glycoldimethacrylate TEGDMA (low viscosity diluent)
4. 1,6 hexane dioldimethacrylate
58
29
5. Ethoxylated bis-GMA
n=1-5
Low viscosity monomer
59
Other polymers - alternatives to

acrylic denture base polymers
Thermoplastic semicrystalline polymers/injection molding at high temperatures
Poly(formaldehyde) acetic acid
polyacetal
HO2C-(CH2)4-CO2H + H2N-(CH2)6-NH2 adipic acid
~[CO(CH2)4CO-NH(CH2)6NH]n~
hexamethylene diamine
polyamide Nylon 66
60
30
Few monomers used in dental adhesives

2-hydroxyethyl methacrylate
N-phenylglycine 4-acryloxyethyl trimelitic acid anhydride
4-methacryloxyethyl trimelitic acid anhydride/acid
61
N-phenylglycine glycidyl dimethacrylate
2-methacryloxyethyl phenyl hydrogen phosphate
Glycerophosphoric acid dimethycrylate
62
31
Dipentaerythritol penta acrylate monophosphate
10-methacryoloyloxydecyl dihydrogenphosphate
Polymers and monomers for GIC

Maleic acid
Polyacrylic acid with pendant methacrylate groups
Itaconic acid
63
Standards on synthetic polymers and resinous materials

EN ISO 4049: Dentistry Polymer-filling, restorative and luting materials EN ISO 10477: Dentistry Polymer-based crown and bridge materials EN ISO 1567: Dentistry Denture base polymers
SN EN ISO 10477: Stomatologie Korunkov a mstkov pryskyin materily SN EN ISO 4049: Stomatologie Vplov, rekonstrukn a fixan polymern materily
EN ISO 6874: Dental resin-based pit and fissure sealants

SN EN ISO 6874: Dentln pryskyin materily pro peetn jamek a fisur
SN EN ISO 1567: Stomatologie Bazln protzov pryskyice
64
32
Summary
1. Polymers, characterization, properties (molecular structure) 2. Polymerization addition (free radical, ionic); step-growthpolycondenzation and polyaddition 3. Phases of free radical polymerization 4. Properties of MMA, polymerization of PMMA 5. Types of activation reactions, inhibitors 6. Characteristics of heat, chemical and light activation systems 7. Dimethacrylate resins used in composite materials 8. Other monomers and polymers
65
33

Polymers

Caricato da

Informazioni sul documento

Descrizione originale:

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Polymers

Caricato da

Copyright:

Formati disponibili

Polymerization Synthetic polymers used in dentistry

Pavel Bradna Institute of Dental Research

Typical applications of polymers in dentistry

What is the lecture about?

What controls polymer properties?

2. Topology of polymer chains Linear polymers

Nonlinear (branched) polymers

Polymer (linear) backbone

Cross-linked polymer (polymer networks)

3. Monomer distribution in copolymer chains

Copolymers (2-3 comonomers)

statistical (random) block alternating

4. Polymer molecular weight

-number average -weight average

Molecules of polymer strongly differ (vary by many monomer units)

Polymers are characterized by molecular weight/polymerization degree average 10

Definitions of molecular weight averages

Weight average, Mw Mw= Mi (ni Mi)/ni Mi =Mi (mi/mtotal)=Mi wi

special type of cross-links

Typical for polyamides, polyethylene, polypropylene etc.

Influence of cross-links on physical properties of polymers

Glass transition (softening temperature) Temperature Tg

Low degree of cross-linking Linear

Liquid Plastic Temperature

Polymers used in dentistry

Polymers used in dentistry

Prepared via polymerization reactions:

Addition polymerization Characteristics

Types of addition polymerizations:

Few common polymers prepared via addition polymerization

Polyethylene low density (LDPE)

soft, waxy solid

Polytetrafluoroethylene (PTFE, Teflon)

resistant, smooth solid

methyl methacrylate hard, transparent solid CH2=C(CH 3)CO 2CH3

[CH2-CH=C(CH3)- isoprene CH2=CHCH2]n C(CH 3)=CH 2

soft, sticky solid

Step-growth polymerization Characteristics

Polymers are formed more slowly than by addition

Polymers are generally of lower molecular weight

Types of step-growth polymerization

Few common polymers

polyamide Nylon 66 polyamide Nylon 6 Perlon polyamide Kevlar

Surgical suture materials

para HO2C-C6H4CO2H para H2N-C6H4NH2 HOCH2CH2OH

Fibre reinforced splints

A. Stages of free radical polymerization

Addition of primary radical on the double bond of monomer

to an active center (free radical) to generate a new active center

2. Propagation - the addition of monomer

In-M-M. In-M-M-M. In-M-M-M-.. My.

3. Termination the growing chain is stopped

4. Chain transfer An atom is transferred

2. New chain growth starts

-2n H2O (-HN(CH2)6NH-CO(CH2)4CO-)n

1. Setting reaction of C-silicone impression materials

2. Setting reaction of epoxies

Root canal sealers, die materials

Alkyl, aryl diisocyanate

2. Setting reaction of A-silicone impression materials

Vinyl terminated polysiloxane prepolymer

Addition of -H on vinyl double bond

Methylhydro-dimethylsiloxane a cross-linking agent