synthesis, properties and applications of inorganic-organic polymers

Current Opinion in Solid State and Materials Science 4 (1999) 571–580

Synthesis, properties and applications of inorganic–organic copolymers(ORMOCER s)

*Karl-Heinz Haas , Herbert Wolter¨ ¨Fraunhofer-Institut f ur Silicatforschung, Neunerplatz 2, D-97082 Wurzburg, Germany

Abstract

Hybrid inorganic-organic polymers based on organically modified heteropolysiloxanes have found widespread attention and applicationas materials with adjustable properties using tailor-made precursors. The chemical structures of monomers and their modified sol-gelprocessing method are described. An overview is given for the control of various properties (mechanical, electrical, optical) of thematerials on a molecular scale. Successful material developments and industrial applications are described. 2000 Elsevier ScienceLtd. All rights reserved.

1. Introduction materials [3] with strong covalent bonds between inorganicand organic moieties. During sol–gel processing of

Organic copolymers – defined as polymers derived from ORMOCER s the inorganic network is formed first andmore than one species of monomer – have found wide- the organic crosslinking is the final curing step. The basic

spread applications as polymer materials. The basic idea structural elements of ORMOCER s are shown in Fig. 2.behind the formation of copolymers is that properties The precursors used for these molecular composites cansuperior to homopolymers can be achieved. As silicon be categorized as follows:based copolymers polyorgano–polysiloxane block copoly-mers with mainly linear Si–O–Si links are well-known [1]. • Forming inorganic silica type networks based onNew types of copolymers using monomers which form Si–O–Si bonds: Type Iinorganic network polymers (glass-like) and organic net- • Forming inorganic oxidic networks other thanworks have been developed which can be described as Si–O–Si: Type IIinorganic–organic copolymers. They are prepared by the • Modifying the inorganic network by (nonreactive)sol–gel process starting from liquid precursors [2]. This organic functionalities: Type IIIleads to molecular composite materials which cannot be • Formation of organic networks /crosslinking: Type IVprepared by conventional means like, for example mixing

of glass with organic polymers because of temperature Beside ORMOCER s a wealth of various other types ofrestraints. Molecular composites have the potential tocombine certain structural properties of different classes ofmaterials in ways not accessible by mixtures of macro-scopic phases as this is the case in classical composites(e.g. glass-fibre reinforced polymers). The intimate mixtureof structural elements which results from their formationby chemical processing (polymerization reactions) canprevent the formation of separate phases. In the case of

inorganic–organic hybrid copolymers like ORMOCER s(Trademark of Fraunhofer-Gesellschaft in Germany) thepossible combinations of properties are shown in Fig. 1.

ORMOCER s belong to the so-called class II hybrid

*Corresponding author. Tel.: 149-931-4100-500; fax: 149-931-4100-559. Fig. 1. Relationship of ORMOCER s to silicones, organic polymers,

E-mail address: [email protected] (K.-H. Haas). glasses and ceramics.

1359-0286/00/$ – see front matter 2000 Elsevier Science Ltd. All rights reserved.PI I : S1359-0286( 00 )00009-7

572 K.-H. Haas, H. Wolter / Current Opinion in Solid State and Materials Science 4 (1999) 571 –580

Fig. 2. Structural elements of ORMOCER s (based on type I–type IV precursors).

nanocomposite /molecular composite materials are de- Beside the variation of type and number of organicpolymerizable groups (see precursors /10-13/ in Table 2),scribed in the literature [3–8].the inorganic network forming reactions are controlled byIn the following sections the precursors and the basic

the number of Si–OR units. Non-reactive type organicnetwork forming reactions of ORMOCER s are describedfunctions (see precursors Table 1) and the type (seewith some properties controlled by the use of distinctprecursors /12,13/ in Table 2) and length of the spacerstructural elements with the focus on mechanical prop-

groups used in the ORMOCER precursors are also usefulerties. An overview of applications of ORMOCER s willtools to control the structures formed and the propertiesconclude this contribution.connected to them.

2. Precursors

3. Basic network forming reactionsThe monomers used for the synthesis of ORMOCER sare silicon alkoxides, organically modified silicon alkox-

3.1. Formation of inorganic networkides, various other metal alkoxides and in some cases alsoorganic monomers. Type I precursors are e.g. Si(OMe) or4

The reactions for forming the inorganic network ofSi(OEt) , type II precursors are metal alkoxides of Al, Zr,4 ORMOCER s are the classical inorganic sol–gel-process-Ti, Sn etc. often used as alkoxides with chelating agents ining reactions:order to slow down the very high hydrolysis and condensa-

tion reaction rates of alkoxides from elements with higher Hydrolysis:electronegativity than Si. Examples for type III and type ; SiOR 1 H O → ; SiOH 1 ROH2IV precursors are shown in Tables 1 and 2. These types ofprecursors are compounds with alkoxy groups for inor- Polycondensation:ganic network formation and either organic functionaliza-

; SiOH 1 HO–Si ; → ; Si–O–Si ; 1 H O2tion (type III) or organic crosslinking (type IV).; SiOH 1 RO–Si ; → ; Si–O–Si ; 1 ROHFor the formation of organic networks by crosslinking

reactions of monomers different from those shown in These reactions do not occur consecutively because theTable 2, pure organic (not Si-based) monomers like polycondensation reactions start as soon as the firstacrylates or di-epoxy-compounds are also used in some hydrolyzed species are present. The influence of variouscases. In order to widen the possibilities for organic pH-conditions, amount of water, solvent, temperature etc.crosslinking reactions multifunctional (meth)acrylate al- for simple alkoxide compounds is well described [2].koxysilanes have been synthesized ([9,10]). The organiccrosslinking can be increased by using two or more 3.2. Organic crosslinking reactionsreactive organic polymerizable groups per monomeric

silane precursor. The high variability of ORMOCER The second step of ORMOCER synthesis is theprecursors is shown in Fig. 3. organic crosslinking during the final curing step. Depend-

K.-H. Haas, H. Wolter / Current Opinion in Solid State and Materials Science 4 (1999) 571 –580 573

Table 1Examples of alkoxysilanes for organic functionalization of inorganic network (type III)

ing on the nature of the reactive organic groups present in their insolubility. NMR and Raman spectroscopy resultsthe ORMOCER precursor different reaction types known especially concerning the reaction of epoxysilane based

from organic polymer chemistry can be used to create a ORMOCER s have been published recently ([14–16]).linear or a three-dimensional polymer structure connectedwith the basic inorganic oxidic network.

(Meth)acrylate alkoxysilanes can react by radical poly- 4. Shaping processesmerization or in combination with multifunctional amines

by a covalent nucleophilic polyaddition type reaction. Due to the formation reaction of ORMOCER s fromReduced polymerization shrinkage can be achieved solution the resulting sols, mainly constituted of organical-through the use of systems polymerizing by a ring-opening ly modified inorganic oligomers, are often used for coat-polymerization mechanism ([11] and [12]). A radical ings. The processing of these lacquers is described e.g. in

polyaddition type reaction is observed in thiolene [17]. No special techniques are required for ORMOCERORMOCER systems [13]. SH-groups are added to the coatings. They can be processed by typical wet-coating

double bonds resulting in a thioether linked ORMOCER techniques (spin-on, spray coating, dip-coating etc.). Typi-network (Precursors /8 / and /9 / see Table 2). An cal film thickness of the cured systems is in the range of

important advantage is that in some cases no photoinitiator 5–15 mm. The processing of ORMOCER s is also pos-is necessary leading to enhanced photostability and resist- sible as resins which often contain no solvents. Bulkance to weathering. samples, fibres, foils /membranes and composites (intro-

Epoxysilane based ORMOCER systems react by the duction of fillers, see chapter 5) can be prepared. Theformation of polyether linkages. These reactions can be UV-curing equipment for the preparation of ORMOCER

catalyzed by the addition of amine compounds like in hollow fibres is shown in Fig. 4.many conventional organic epoxide systems. In general ORMOCER resins can also be used to create submic-

ORMOCER s can be cured either thermally (120–2008C), ron-structures by embossing methods followed by UV-by UV-/visible light or redox-initiation. curing. Embossed ORMOCER structures are useful for

Since the inorganic–organic crosslinked materials are planar optical waveguides [18] and antireflective coatingsduroplastic materials (thermosets) the structural characteri- [19]. Due to the possibility of UV-curing ORMOCER s

zation of the cured materials is not straightforward due to can also be used for dielectric multilayers and optical


Table 2Examples of alkoxysilanes for organic crosslinking/network forming (type IV)

waveguides due to their negative resist behaviour [18,20]. 5. Basic properties of ORMOCER sThe crosslinked parts of the selectively UV-cured

ORMOCER becomes insoluble and the parts not ir- The synthesis principle for the preparation ofradiated stay soluble and can be removed by appropriate ORMOCER s has some general consequences concerning

solvents (e.g. alkaline solutions). their properties. ORMOCER s are homogeneous materi-


Fig. 3. Schematic structures of multifunctional silanes for ORMOCER synthesis (Precursors: type III – organic modification R’- and type IV-organicnetwork forming/crosslinking).

2als, they are transparent and show duroplastic behaviour dense materials and show no porosity (,1 m /g accordingdue to the organic network/crosslinking (thermosets). to BET measurements). Organically modified silicates,Experiments conducted so far to identify inorganic or however, with an appreciable amount of inorganic struc-organic phases by electron microscopy or X-ray methods tures and no organic crosslinking show porosity which canhave resulted in the confirmation of their amorphous be controlled by the amount of inorganic /organic struc-

behaviour with no detectable phase separation. tures [21]. The density of ORMOCER lies in the range of31.1 and 1.6 g/cm which is slightly above the range for

5.1. Porosity and density organic polymers, but well below the density of oxide3materials (e.g. SiO 52.2 g/cm ). Some basic relationships2

Classical ORMOCER s with organic crosslinking are between density and the amount of organic crosslinking /

Fig. 4. UV-curing equipment for manufacturing of ORMOCER hollow fibres (including electron micrograph of an ORMOCER hollow fibre).


modification of the silica network have shown that density compounds can also be used as low shrinkage polymeri-decreases with increasing amount of network modifying zation materials with excellent mechanical properties [12].organic elements (based on type III precursors) and

5.3. Mechanical propertiesincreases with increasing amount of heterometallic oxidestructures (based on type II precursors) [22]. 5.3.1. Young’s-modulus and thermal expansion

coefficient5.2. Shrinkage during curing process

The mechanical and thermomechanical propertiesOne basic drawback for preparing materials by sol–gel (Young’s modulus and thermal expansion coefficient) of

processing – especially in the case of bulk materials – is ORMOCER bulk materials can be controlled by thetheir high volume shrinkage (more than 50%) during amount of inorganic and organic network density and byremoval of the solvents and the curing /network densifying the spacer-length connecting the inorganic and organicsteps. This often leads to mechanical stresses e.g. in thicker crosslinking sites of bifunctional monomers (see Fig. 3).coatings, laminates or molded articles (bulk materials). As an example Fig. 5 shows the influence of the organicLoss of dimensional precision (problems with near-net- crosslinking density of various multi(meth)acrylate based

shape processing), crack formation, reduced mechanical ORMOCER s on Young’s modulus and the thermalstability, delamination or other defects may be the conse- expansion coefficient [24]. As can be expected Young’squence. The use of organic crosslinking reactions as the modulus increases with increasing organic crosslinkingactual curing step to form the inorganic–organic copoly- density by using various multi(meth)acrylate alkoxysilane

mer structure of ORMOCER s makes this shrinkage much precursors. At the same time the thermal expansionless pronounced due to the pre-formation of the inorganic coefficient decreases. The correlation between the numberSi–O–Si network. of inorganic network modifying Si–C bonds and the

Polymerization of (meth)-acrylate alkoxysilane based thermal expansion coefficient clearly shows [22] theORMOCER s results in a dramatically reduced shrinkage increase of the thermal expansion coefficient at higher

(2–8 Vol.%) as compared to pure organic polymerized amounts of Si–C bonds containing ORMOCER s (type III(meth)-acrylates (often above 20 Vol.%). By the incorpora- and IV precursors).tion of fillers a further shrinkage reduction is possible. In The mechanical data of SiO /SiO(CH ) type materials,2 3 2

some cases near zero-shrinkage ORMOCER s can be which were prepared by cocondensation of TEOS withobtained by using spiroorthoester silanes (Precursor /12 / polydimethylsiloxane–oligomers (PDMS) [25] showssee Table 2) with a volume change during the poly- another example for the variability of Young’s modulusmerization step of below 0.5% [11]. Norbornene type between rubbery materials at high PDMS contents andsilanes in combination with thiolene type polyaddition hard materials at low PDMS contents. However in this

Fig. 5. Young’s modulus and thermal expansion coefficient of bulk ORMOCER s based on the variation of the number and type of organic polymerizablegroup of multi(meth)acrylate alkoxysilanes [24].


case some porosity remains at high amounts of SiO , since thermally curable types showing higher abrasion resist-2

the densifying reactions for the inorganic Si–O–Si net- ance. The influence of heteroatoms (Al, Zr, Ti) waswork cannot be completed due to temperature restraints. investigated in epoxysilane-based ORMOCER s showing

The variability of mechanical data of multiacrylate that Al–O containing ORMOCER s show the highestbased ORMOCER s is further increased due to the use of abrasion resistance [27,28]. Another interesting result

precursors with different spacer lengths between the concerning epoxysilane-based coatings on polycarbonateinorganic and organic network forming groups as shown in substrates was presented by [29]. There it was shown thatFig. 6. A drastic increase of Young’s modulus from – in contrast to other expectations – the Young’s modulus70 MPa to more than 2000 MPa can be detected by of epoxysilane compositions containing nano-silica par-decreasing the spacer length from 20 to 11 atoms connect- ticles was lower than in compositions based oning inorganic and organic crosslinking sites. epoxysilane–Si(OEt) cocondensates, the latter being real4

Using various types of multi(meth)acrylate alkoxysilane molecular composite materials.precursors a range of Young’s moduli from around 1 MPaup to 4000 MPa and thermal expansion coefficients from 5.4. Optical properties

26 21184 to 67310 K (temperature range: 0–508C) can becovered [10,24]. The mechanical properties of ORMOCER s are colourless materials showing no

ORMOCER s can be further modified by using fillers of absorption in the visible spectrum. The refractive indexvarious types and amounts. The thermal expansion coeffi- depends especially on heteroelements (Ti, Zr) used in the

26 21 cient can be lowered to values of 17310 K and the ORMOCER compositions. Increasing e.g. the amount ofYoung’s modulus increased up to values of around Zr–O or Ti–O-containing structures in epoxysilane based

17000 MPa at filler contents of 79 wt.%. ORMOCER s also increases the refractive index from1.48 up to 1.68 [30]. Bulk materials based on multiacrylate

5.3.2. Abrasion resistant coatings alkoxysilanes with various spacer groups containing noORMOCER s are especially useful as abrasion resistant heteroelements also have been developed with the possi-

coatings for various substrates [26,27]. Abrasion resistance bility to increase the refractive index from 1.52 with linearis often characterized by the taber-abraser method, measur- aliphatic to 1.56 with aromatic or 1.60 with halogenateding the increase in haze on transparent substrates if their aromatic spacer groups [31]. A decrease of the refractive

surface is treated by an abrader wheel. The lower the index of ORMOCER systems at optical wavelengths (toincrease in haze, the higher is the abrasion resistance of the around 1.45) is possible using special multifunctional

respective coating. For ORMOCER s thermally and UV- acrylate systems [32] or fluorinated silanes. The use ofcurable coatings are available for abrasion resistance, the specially designed perfluorarylsilanes ([33] and [34]) leads

Fig. 6. Young’s modulus and thermal expansion coefficient of bulk ORMOCER s based on multiacrylate alkoxysilanes with various spacer lengths definedas number of atoms between inorganic and organic network forming groups [24].


to very low absorption losses (,0.3 dB/cm) in the NIR- very attractive materials for coating applications are theirregime at 1310 and 1550 nm (optical communication transparency, their good adhesion to various substrates,range). their chemical stability and their good abrasion resistance

due to the inorganic structures in ORMOCER s [26]. As5.4.1. Electric and dielectric properties industrial products two abrasion resistant coatings ([42]

Most ORMOCER s are highly insulating materials with based on thermal curing ORMOCER and [13] based on13 16 bulk resistivities in the range of 10 –10 V cm. There- UV-curing thiolene addition type ORMOCER ) and a

fore they show good passivation properties for electronic decorative dish-washer resistant ORMOCER coating onapplications [35,36], due to their good adhesion to most of lead-crystal glasses [17] could be realized. Antiadhesivethe interconnection materials and good barrier properties. (antisoiling), antifogging, antistatic and antireflective coat-Their low dielectric constant (around 3) makes them good ings with good basic abrasion resistance were also de-

candidates for interlayer dielectrics in electrical and optical veloped (see chapter 4). The use of ORMOCER s asinterconnection technology [18]. Some special barrier layers for food packaging applications especially in

ORMOCER types can be synthesized with ion-conduct- connection with inorganic oxide layers (SiO ) is anotherx1 1ing properties for Li and H -ions. In these cases anions vital area of material development [40]. Further coating

are covalently bound to the inorganic /organic network of applications are in the field of microsystem technologyORMOCER s in order to generate mechanically stable [18] and as materials for chemical sensors [32,43].

solid polymer ion conductors ([37] and [20]).6.2. Bulk materials, composites5.4.2. Surface properties and polarity

Since ORMOCER s have important applications as As shown in chapter 4 ORMOCER s show an enorm-coating materials, the control of the surface polarity oftenous variability to adjust material properties like Young’splays an important role. By choosing polar or unpolarmodulus, thermal expansion coefficient, gas permeability,functional groups (type III precursors) the surface energyrefractive index etc. Because of additional advantages likecan be increased or decreased. Using fluorosilane modifiedhigh flexural strength and hardness, transparency, com-ORMOCER s hydrophobic and oleophobic surfaces canparably low shrinkage during the curing process, biocom-be generated showing low polar and low dispersivepatibility (confirmed by cytotoxity tests) and the possibilitycontributions to surface energy. It could be shown that – of incorporation of fillers, ORMOCER s anddepending on the nature and amount of fluorosilanes used ORMOCER composites are an interesting alternative– PTFE-like surface polarity can be achieved with as littlebeside the classical bulk materials (organic polymers,as 1 mol-% of appropriate fluorosilane [38].glasses) especially when very complex requirements haveThe incorporation of ionic silanes especially increasesto be realized. For example a light curable dental fillingthe polar contribution of the surface energy, therebycomposite has been developed meeting the essential in-lowering the wetting angle for water (antifogging-effect;vitro requirements necessary for an effective amalgam[39]) and decreasing the surface resistivity (antistaticalternative [9]. Some basic dental applications and prop-behaviour; [28]). erties of ORMOCER s are shown in Fig. 7.Since the polarity modifying units are covalently bound Products either using ORMOCER s as one of the matrixto the inorganic–organic ORMOCER network the stabili- TMcomponents (Definite ) or using a functionalizedty towards leaching of polar compounds, often found e.g. ORMOCER based light-curable dental composite inin antifogging or antistatic-coatings is greatly reduced. combination with ORMOCER based bondingsAlso the basic abrasion resistance of ORMOCER coat- TM(Admira ) are on the market. Special carboxy modifiedings is not adversely affected in most cases. ORMOCER s are promising matrix materials for the

5.5. Barrier properties and corrosion resistance development of light curable glass ionomer cements[23,24]. Further investigations showed that injection mold-Due to the possibility of controlling the inorganic and able, flame retardant ORMOCER composites with highorganic network density and the organic functionality of

impact strength are also possible.the ORMOCER s it could be shown that effective barrierlayers for flavours, gases, water and ions could be prepared

6.3. Fibres and foilsby using ORMOCER s ([40] and [17]) as coatings onpolymers and glasses and also as corrosion resistant layers Due to the sol–gel processing of ORMOCER s com-for metals [41].

plex rheological requirements necessary for the fibredrawing process can easily be realized. New types of

unsupported hollow fibres based on ORMOCER s with a6. Applicationsmechanical behaviour from brittle glass-like (Young’smodulus 5 GPa) to flexible rubber-like (elongation at6.1. Coatingsrupture up to 30%) can be used for membrane and material

transport applications. Their properties can be adjusted byThe basic properties of ORMOCER s which make them


Fig. 7. Application and properties of ORMOCER s as dental materials.

varying the composition, the synthesis parameters of the materials which can be tailored for various applications byORMOCER condensates and the spinning parameters controlling their molecular structures. This material syn-

(UV-induced curing, Fig. 4). The oxygen permeability can thesis principle based on sol–gel techniques using bifunc-be varied between 0.02 and 250 barrer (1 barrer5 tional silane based monomers has left the state of pure

21 310 cm /cm3s3cm Hg) as well as the dimension of the scientific interest and has successfully entered industrialfibres (outer diameter: 90 mm–5 mm; wall thickness: applications. Due to the large variability of structural

22 15 mm mm). The manufacturing of solid fibres and foils combinations the most fruitful time for ORMOCERis also possible. applications has just begun and further scientific and

The three-dimensional inorganic skeleton of the industrial interest will surely follow.ORMOCER matrix is an ideal starting-point for manufac-

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