**3.1 Applications of carbofunctional silanes**

The carbofunctional silanes XnSi(R'Y)4-n have found misceleneous practical applications thank to the presence of two kinds of the functional groups X and Y. In practice formation of chemical bonds with an inorganic material is possible, as a result of reactions of functional groups X, which most often are alkoxy groups. On the other hand the functional groups Y enable reactions with organic polymers. Most popular, available on market, are compounds of a structure (RO)3Si(CH2)3Y, in which as alkoxy substituents are present methoxy or

Modification of Thermoplastics with Reactive Silanes and Siloxanes 161

are utilized in a manufacture of glass-reinforced laminates. Silanes containing oxirane groups are applied for surface treatment of fillers which are used in epoxide composites. They are also utilized for the modification of novolac resins through reaction of hydroxyl groups of phenol with epoxy groups. Polycarbonates (PC) and polysulphones (PSU) form amide or sulphonamide bonds, and polyurethanes – urea bonds, respectively. This way modified polyamides, PC and PSU can be easier reinforced with the fillers, giving composite

For the modification of polymers most often are used (aminoalkyl)silanes. Chlorinated polymers, e.g. poly(vinyl chloride) (PVC), easily form quaternary salts with (aminoalkyl)-

Silane agents, terminating polymer chains ("*endcappers*"), were prepared by addition Michael reactions of (3-aminopropyl)trimethoxysilane to acrylates. They were used for an introduction of trimethoxysilane groups on chain ends of polyurethanes, enabling their cross-linking under action of atmospheric moisture. It established a base for elaboration of a technology of newer one-component, solventless adhesion materials ("*solvent-free*")

The carbofunctional silanes are also applied for the surface modification of the inactive fillers and polymers, e.g. in polyolefin composites filled with calcium carbonate or mica (Han et al., 1981; Okuno & Woodhams, 1975; Scott et al.; 1987; Trotignon et al., 1986). Polypropylene filled with CaCO3 is the fundamental plastic, from which are produced garden furniture. Two aminofunctional silanes were applied for improvement of a tensile strength and decrease of deformability of the polypropylene composites containing nonmodified CaCO3 and modified with silanes (Demjen et al., 1997, 1998, 1999; Pukanszky, 2005). The polycondensation of triethoxysilyl groups under process conditions takes place quickly as well and leads to a reinforcement of interactions between ingredients of the

Polyolefins are the most widely used group of commodity thermoplastics. A cross-linking is one of modification methods of polyolefins (PO) properties, such as high temperature

**Cl**

**(CH2-CH)n** 

**H-N**

 **(CH2)3**

 **+ HCl**

**Si**

materials showing very good mechanical properties (Arkles, 1977).

**Si(CH2)3-NH2 + (CH2-CH)n** 

**(CH2-CH)n** 

**H-NHCl- +**

 **(CH2)3**

**Si**

Scheme 5. Reactions of (aminopropyl)silane with PVC.

composite PP/CaCO3 (Demjen et al., 1997).

**3.1.3 Modification of polyolefins** 

silanes (Scheme 5).

(Nomura et al., 2007).

ethoxy groups, and as organic functional groups Y: amine -NH2, glicydyloxy -O-CH2-(CH-CH2O) or methacryloxy –O-CO-C(CH3)=CH2 groups.

#### **3.1.1 Processes sol-gel**

The carbofunctional silanes are often used in sol–gel processes for a preparation of hybrid organic–inorganic materials (Brinker, 1990; Schmidt, 1984, 1994). In sol–gel systems take place hydrolysis and condensation reactions of alkoxysilanes, described by equilibrium elementary reactions (4)-(6), which are catalyzed both by acids and bases:

$$\text{\ \#Si-OR} \quad \text{\ + \ H}\_2\text{O} \quad \Leftrightarrow \text{\ \#Si-OH} \quad \text{\ + \ \text{ROH}} \tag{4}$$

$$\text{=Si-OR} \quad + \text{ HO-Si=} \quad \Leftrightarrow \quad \equiv \text{Si-O-Si=} + \quad \text{ROH} \tag{5}$$

$$\text{\#Si-OH} \quad + \text{ \text{HO-Si}\equiv} \quad \Leftrightarrow \text{\#-O-Si} \quad + \text{ \text{H}\_2\text{O}} \tag{6}$$

In an acidic medium hydrolysis reactions undergo faster than condensation reactions, but in a basic medium condensation reactions are faster. Products of the sol–gel process of tetraethoxysilane are: silicagel, branched poly(ethoxysilicates) or silsesquioxanes, as it is presented on a Scheme 4 (Abe & Gunji, 2004).

Scheme 4. Products formed in the sol–gel process of tetraethoxysilane.

New 2,6-di-tert-butylphenol antioxidants and their derivatives containing trialkoxysilane linkages were prepared by the sol-gel method. They were applied for a stabilization of isotactic polypropylene (Nedelcev et al., 2007). The sol–gel technique is also applied in order to get organic materials with better properties, through an introduction of metal alkoxides.

#### **3.1.2 Modification of polymers properties by CFS**

The carbofunctional silanes have found wide applications in modifications of many organic polymers. For example, unsaturated polyesters modified with (methacryloxypropyl)silanes

ethoxy groups, and as organic functional groups Y: amine -NH2, glicydyloxy -O-CH2-(CH-

The carbofunctional silanes are often used in sol–gel processes for a preparation of hybrid organic–inorganic materials (Brinker, 1990; Schmidt, 1984, 1994). In sol–gel systems take place hydrolysis and condensation reactions of alkoxysilanes, described by equilibrium

In an acidic medium hydrolysis reactions undergo faster than condensation reactions, but in a basic medium condensation reactions are faster. Products of the sol–gel process of tetraethoxysilane are: silicagel, branched poly(ethoxysilicates) or silsesquioxanes, as it is

> **( <sup>x</sup> Si O OEt**

> > **O0,5**

**O Si**

**<sup>O</sup> <sup>R</sup> ONR4 4NO**

**O O**

**O**

**Si O Si**

**O**

**ONR4**

**O Si**

**Si O Si**

New 2,6-di-tert-butylphenol antioxidants and their derivatives containing trialkoxysilane linkages were prepared by the sol-gel method. They were applied for a stabilization of isotactic polypropylene (Nedelcev et al., 2007). The sol–gel technique is also applied in order to get organic materials with better properties, through an introduction of metal alkoxides.

The carbofunctional silanes have found wide applications in modifications of many organic polymers. For example, unsaturated polyesters modified with (methacryloxypropyl)silanes

**Si**

**O**

**O**

**) (**

**<sup>y</sup> Si O )z <sup>n</sup> O0,5**

**ONR4**

**ONR4**

**O0,5 ( film,**

 **fibre, casting )**

**SiO2 (powder)**

**Si O**

**OEt**

**( ) OEt**

**Si**

**R4NO**

**O**

**R4NO**

Scheme 4. Products formed in the sol–gel process of tetraethoxysilane.

**3.1.2 Modification of polymers properties by CFS** 

**R4NO**

Si-OR + H2O Si-OH + ROH (4)

Si-OR + HO-Si Si-O-Si + ROH (5)

Si-OH + HO-Si Si-O-Si + H2O (6)

elementary reactions (4)-(6), which are catalyzed both by acids and bases:

CH2O) or methacryloxy –O-CO-C(CH3)=CH2 groups.

presented on a Scheme 4 (Abe & Gunji, 2004).

**R4NOH**

**Si(OEt)4**

**3.1.1 Processes sol-gel** 

are utilized in a manufacture of glass-reinforced laminates. Silanes containing oxirane groups are applied for surface treatment of fillers which are used in epoxide composites. They are also utilized for the modification of novolac resins through reaction of hydroxyl groups of phenol with epoxy groups. Polycarbonates (PC) and polysulphones (PSU) form amide or sulphonamide bonds, and polyurethanes – urea bonds, respectively. This way modified polyamides, PC and PSU can be easier reinforced with the fillers, giving composite materials showing very good mechanical properties (Arkles, 1977).

For the modification of polymers most often are used (aminoalkyl)silanes. Chlorinated polymers, e.g. poly(vinyl chloride) (PVC), easily form quaternary salts with (aminoalkyl) silanes (Scheme 5).

Silane agents, terminating polymer chains ("*endcappers*"), were prepared by addition Michael reactions of (3-aminopropyl)trimethoxysilane to acrylates. They were used for an introduction of trimethoxysilane groups on chain ends of polyurethanes, enabling their cross-linking under action of atmospheric moisture. It established a base for elaboration of a technology of newer one-component, solventless adhesion materials ("*solvent-free*") (Nomura et al., 2007).

Scheme 5. Reactions of (aminopropyl)silane with PVC.

The carbofunctional silanes are also applied for the surface modification of the inactive fillers and polymers, e.g. in polyolefin composites filled with calcium carbonate or mica (Han et al., 1981; Okuno & Woodhams, 1975; Scott et al.; 1987; Trotignon et al., 1986). Polypropylene filled with CaCO3 is the fundamental plastic, from which are produced garden furniture. Two aminofunctional silanes were applied for improvement of a tensile strength and decrease of deformability of the polypropylene composites containing nonmodified CaCO3 and modified with silanes (Demjen et al., 1997, 1998, 1999; Pukanszky, 2005). The polycondensation of triethoxysilyl groups under process conditions takes place quickly as well and leads to a reinforcement of interactions between ingredients of the composite PP/CaCO3 (Demjen et al., 1997).

#### **3.1.3 Modification of polyolefins**

Polyolefins are the most widely used group of commodity thermoplastics. A cross-linking is one of modification methods of polyolefins (PO) properties, such as high temperature

Modification of Thermoplastics with Reactive Silanes and Siloxanes 163

**O C**

**OR**

**- H2O**

Scheme 6. Basic reactions involved in silane grafting onto PE and further cross-linking of PE

An alternative method to the silane grafting is a one-step random copolymerization of ethylene with vinyltrialkoxysilanes at high pressure (150-350 MPa) and temperature (180-290 C) in the presence of free radical initiators (usually peroxides), which was developed by Union Carbide and Mitsubishi Petrochemicals. This process has some advantages, since the silane units (< 5 wt. %) can be randomly and homogeneously distributed in the polymer chain, so it was possible to achieve a certain degree of cross-linking with a small amount of the silane incorporated in the polymer. There is also no limitation in the choice of antioxidants as in the case of peroxide and silane grafting cross-linking process (Eagles, 1990; Munteanu, 1997).

A copolymer of ethylene with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, a poly(ethylene-*co*divinylsiloxane), was synthesized in a high pressure reactors at 180-220 °C and p 1300 bar

A hydrosilylation of terminal double bonds in polyolefins through reactive processing is a

**OR**

**C Me**

**Me**

**Me**

**Me**

**Dicumyl peroxide**

**C. + CH2 CH Si OR**

**C C C Si OR H H**

**OR**

**H H**

**H H**

(Morshedian & Hoseinpour, 2009).

(Smedberg et al., 2004).

**3.1.3.2 Hydrosilylation of polyolefins** 

next important modification method of these thermoplastics:

**C C C Si OH** 

**OR**

**OR**

**OR**

**H H**

**2**

**heat**

**Me**

**.**

**2 O**

**Me**

**C C C Si OR** 

**OR**

**CCC**

**H**

**H**

**RO H**

**RO H**

**+ ROH**

**OR**

**H H**

**OR**

**OR**

**H H**

**OR**

**OR**

**C C C Si O Si** 

**H H**

**H H**

**H H**

**H H**

**O O C**

**C + CH3**

**+ H.**

**+ H2O C C C Si OH** 

**CH + CH C. + CH4 <sup>3</sup> .**

**. <sup>O</sup> .**

**Me**

stability, chemical and stress cracking resistance, and also as shape memory. It can be done by different methods: irradiation, peroxide process, azo process, and moisture curing of silane-functionalized polyolefins (Munteanu, 1997; Morshedian & Hoseinpour, 2009). The last technique (SIOPLAS technology) was developed in the late 1960s, and modified in the late 1980s. Both irradiation and peroxide cross-linking processes have some disadvantages such as high costs for irradiation equipment, the possibility of pre-curing in peroxide crosslinking processes, the inability to crosslink PP through tertiary-bonded carbon atoms and the formation of voids in cable insulations.

#### **3.1.3.1 Silane-crosslinked polyolefins**

The new cross-linking SIOPLAS technology, patented by Dow Corning, is a two-step process, based on the chemistry of organofunctional silanes, which are first grafted on polyolefins chains. In a second post-reactor step the siloxane cross-linkages (Si-O-Si) are formed. Alkoxysilanes, most often vinyltrimethoxysilane (VTMS), are melt grafted on polyolefins in processing equipment, usually extruders, in the presence of small amounts of peroxides as radical initiators. Vinyltriethoxysilane (VTES), and especially 3-methacryloxypropylsilane have limited application. Usually, about 2 % of silanes are used, and dicumyl peroxide as the initiator is used (5-15 wt. %). The silane grafting reaction is very fast and it allows the choice of reactive processing to be the industrial synthetic method. Within a few minutes of the residence time of all components in the extruder, very high grafting yields are obtained (at least 80 % of the added silane is grafted onto PE) in an optimized industrial process. The possibility of silane homopolymerization may be almost excluded under the conditions of reactive processing. The reactive processing techniques enable silane grafting onto any kind of olefin homopolymer (LDPE, linear LLDPE, HDPE, very low density VLDPE, PE waxes, all kinds of PP), PO blends or copolymers (EVA, EP and EPDM elastomers), and polyisobutene (Munteanu, 1997).

The silane-grafted POs are still thermoplastic cross-linkable products, which are processed in the usual way in finished goods subsequently subjected to cross-linking in the presence of moisture. The alkoxysilyl groups hydrolyse to form silanol groups Si-OH, which condense to generate the siloxane bonds responsible for the formation of the three dimensional network. Before the moisture cross-linking step a master batch containing 0.05-0.15 wt. % (and even 2.0-3.6 wt. %) of an organotin catalyst is melt mix with the silane-grafted PO in order to achieve cross-linking rates of practical importance. Cross-linking takes place beside the production line in hot water tanks or steam chambers, most often at 60-90 C. Under these conditions the curing time is in a range from a few hours or days.

The silane cross-linking has many advantages among curing technologies. Most of those advantages are the consequence of separating the cross-linking step from the shaping step and the specific structure of the network as well, the latter feature is responsible for better thermomechanical properties in comparison with peroxide cross-linked networks.

A modified one-step version of this technology, called as MONOSIL process, appeared few years later. All the components, i.e. polyethylene + silane + grafting initiator + cross-linking catalyst, were added in a high-shear mixing extruder wit a longer screw (Thomas & Bowrey, 1977; Swarbrick et al., 1974).

stability, chemical and stress cracking resistance, and also as shape memory. It can be done by different methods: irradiation, peroxide process, azo process, and moisture curing of silane-functionalized polyolefins (Munteanu, 1997; Morshedian & Hoseinpour, 2009). The last technique (SIOPLAS technology) was developed in the late 1960s, and modified in the late 1980s. Both irradiation and peroxide cross-linking processes have some disadvantages such as high costs for irradiation equipment, the possibility of pre-curing in peroxide crosslinking processes, the inability to crosslink PP through tertiary-bonded carbon atoms and

The new cross-linking SIOPLAS technology, patented by Dow Corning, is a two-step process, based on the chemistry of organofunctional silanes, which are first grafted on polyolefins chains. In a second post-reactor step the siloxane cross-linkages (Si-O-Si) are formed. Alkoxysilanes, most often vinyltrimethoxysilane (VTMS), are melt grafted on polyolefins in processing equipment, usually extruders, in the presence of small amounts of peroxides as radical initiators. Vinyltriethoxysilane (VTES), and especially 3-methacryloxypropylsilane have limited application. Usually, about 2 % of silanes are used, and dicumyl peroxide as the initiator is used (5-15 wt. %). The silane grafting reaction is very fast and it allows the choice of reactive processing to be the industrial synthetic method. Within a few minutes of the residence time of all components in the extruder, very high grafting yields are obtained (at least 80 % of the added silane is grafted onto PE) in an optimized industrial process. The possibility of silane homopolymerization may be almost excluded under the conditions of reactive processing. The reactive processing techniques enable silane grafting onto any kind of olefin homopolymer (LDPE, linear LLDPE, HDPE, very low density VLDPE, PE waxes, all kinds of PP), PO blends or copolymers (EVA, EP and EPDM

The silane-grafted POs are still thermoplastic cross-linkable products, which are processed in the usual way in finished goods subsequently subjected to cross-linking in the presence of moisture. The alkoxysilyl groups hydrolyse to form silanol groups Si-OH, which condense to generate the siloxane bonds responsible for the formation of the three dimensional network. Before the moisture cross-linking step a master batch containing 0.05-0.15 wt. % (and even 2.0-3.6 wt. %) of an organotin catalyst is melt mix with the silane-grafted PO in order to achieve cross-linking rates of practical importance. Cross-linking takes place beside the production line in hot water tanks or steam chambers, most often at 60-90 C. Under

The silane cross-linking has many advantages among curing technologies. Most of those advantages are the consequence of separating the cross-linking step from the shaping step and the specific structure of the network as well, the latter feature is responsible for better

A modified one-step version of this technology, called as MONOSIL process, appeared few years later. All the components, i.e. polyethylene + silane + grafting initiator + cross-linking catalyst, were added in a high-shear mixing extruder wit a longer screw (Thomas & Bowrey,

thermomechanical properties in comparison with peroxide cross-linked networks.

these conditions the curing time is in a range from a few hours or days.

the formation of voids in cable insulations.

elastomers), and polyisobutene (Munteanu, 1997).

1977; Swarbrick et al., 1974).

**3.1.3.1 Silane-crosslinked polyolefins** 

Scheme 6. Basic reactions involved in silane grafting onto PE and further cross-linking of PE (Morshedian & Hoseinpour, 2009).

An alternative method to the silane grafting is a one-step random copolymerization of ethylene with vinyltrialkoxysilanes at high pressure (150-350 MPa) and temperature (180-290 C) in the presence of free radical initiators (usually peroxides), which was developed by Union Carbide and Mitsubishi Petrochemicals. This process has some advantages, since the silane units (< 5 wt. %) can be randomly and homogeneously distributed in the polymer chain, so it was possible to achieve a certain degree of cross-linking with a small amount of the silane incorporated in the polymer. There is also no limitation in the choice of antioxidants as in the case of peroxide and silane grafting cross-linking process (Eagles, 1990; Munteanu, 1997).

A copolymer of ethylene with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, a poly(ethylene-*co*divinylsiloxane), was synthesized in a high pressure reactors at 180-220 °C and p 1300 bar (Smedberg et al., 2004).

#### **3.1.3.2 Hydrosilylation of polyolefins**

A hydrosilylation of terminal double bonds in polyolefins through reactive processing is a next important modification method of these thermoplastics:

Modification of Thermoplastics with Reactive Silanes and Siloxanes 165

The membranes were prepared from the crosslinked copolymer composed of elastomeric glassy styrene-isoprene prepolymer and oligo- or polyhydrosiloxanes (Kerres & Strathmann, 1993; Kujawski et al., 2003). The pervaporation properties of the membranes, used for pervaporation of water–methyl acetate and water–methyl *tert*-butyl ether mixtures, depend on the siloxane content in the membrane and were much better than properties of

High molar mass copolymers of ethylene or propylene with -olefin macromonomer, monovinyl-functional silsesquioxane cage 1-(9-decenyl)-3,5,7,9,11,13,15-heptaethylpentacyclo-[9.5.1.13,9.15,15.17,13]octasiloxane, were obtained in the presence of metallocene catalysts, activated with alumoxanes. These copolymers, contained up to 25 wt. % (1.2 mol. %) of spherosilicate pendant units, which accounted for a decrease of the melting temperature by 18 K with respect to PE. A thermostability under air was improved in the poly-

The carbofunctional polysiloxanes are most often used for syntheses of hybrid siliconeorganic copolymers and for the modification of many polymers and plastics. This way,

The graft copolymers of polysiloxane with styrene, methyl metacrylate, and chloroprene were synthesized by a radical polymerization from the commercial carbofunctional poly-

Block copolymers comprised of chemically distinct polymers covalently joined together selforganize in bulk into well-defined nanoscopic structures including lamellar, cylindrical, and spherical morphologies. There are a lot of block copolymers based on styrene monomers with reactive alkoxysilyl groups. A series of well-defined poly(3-methacryloxypropyltriethoxysilane)-*b*–polystyrene (PMAPTES-*b*-PS) diblock copolymers was prepared via sequential RAFT polymerization (Zhang et al., 2007). Poly(acryloxypropyltriethoxysilane)-*b*polystyrene (PATPES-*b*-PS) diblock copolymers were prepared by the nitroxide-mediated polymerization (NMP) using alkoxyamine initiators (Gamys et al. 2010). The core-shell particles prepared by emulsion polymerization of styrene and subsequent addition of MPTMS have been used to produce hybrid nanocapsules (Ni et al., 2008). A series of welldefined rod-coil block copolymers poly(dimethylsiloxane-*b*-poly{2,5-bis[(4-methoxyphenyl) oxycarbonyl]styrene} (PDMS-*b*-PMPCS) containing a CO2-philic block PDMS was synthesized through ATRP (Shi et al., 2011). The nanostructure of these copolymers changed from lamellae (LAM) to hexagonally packed cylinders (HEX) according to the volume fraction of PDMS in block copolymers. The microemulsion photocopolymerization of styrene and butyl acrylate in the presence of silane coupling agent, such as MAPTMS, using 2-hydroxy-2-methylpropiophenone as photoinitiator was carried out as well (Wan et al., 2009). The copolymer particles were nearly spherical and were very uniform with the

siloxanes containing side and terminal mercaptopropyl groups (Fawcett et al., 2001).

numerous new polymeric materials with profitable properties were obtained.

the commercially available hydrophobic membranes.

**3.2 Applications of carbofunctional polysiloxanes** 

**3.2.1 Modification of vinyl and acryl polymers by CFPS** 

number average particle size of 25.5 nm and Mw/Mn of 1.11.

**3.2.1.1 Polystyrene** 

ethylene copolymer in comparison to PE (Tsuchida et al., 1997).

### Si-CH=CH2 + H-Si Si-CH2-CH2-Si

Polypropylene containing terminal double bonds was modied with a hydride-terminated polydimethylsiloxane (PDMS) at three different temperatures through a hydrosilylation reaction, catalyzed by Karstedt's platinum catalyst in the melt phase (Malz & Tzoganakis, 1998; Long et al., 2003, 2004). The double bonds were formed by peroxide initiated degradation of PP in an extruder or a batch mixer. An organic peroxide, Lupersol 101, was used in concentrations of 0.5-5 wt. %. A hydride-terminated polydimethylsiloxane was used as a substrate hydrosilylating the terminal double bonds of the degraded polypropylene (DPP). Reactive processing experiments were carried out in a hot press, a batch mixer, and a single screw extruder. The reaction time of the hydrosilylation reaction was short enough to be completed in a screw extruder. This made possible the simultaneous extrusion and modification of polypropylene.

Two different reaction mechanisms were used to initiate the hydrosilylation reaction: a radical chain addition mechanism and a platinum catalyzed mechanism using platinum Karstedt's catalyst. It was found that both reactions, degradation and hydrosilylation, could be performed simultaneously, by using high peroxide concentrations, while previously degraded polypropylene could be hydrosilylated with catalytic amounts of a peroxide. For the catalytic mechanism, the required stabilization of the platinum colloid formed in this mechanism was accomplished by adding *t*-butylhydroperoxide as a co-catalyst.

The hydrosilylation of polybutadiene (PB) with hydrosilanes is catalyzed by rhodium and platinum catalysts, and platinum-nanoclusters and it is a source of silyl derivatives of PB, many of them have functional group and can find useful applications (Guo et al., 1990; Iraqi et al., 1992; Chauhan & Balagam, 2006; Chauhan et al., 2008).

A comprehensive study on the surface characteristics of hydrosilylated polypropylene was conducted by combining macroscopic thermodynamics, microstructure, and chemical composition measurements (Long et al., 2003, 2004). A positive effect of a poly(dimethylsiloxane) modied polyolen additive on the processing and surface properties of linear low density polyethylene (LLDPE) was observed (Zhu et al., 2007). A polydimethylsiloxane (PDMS) modied polyolen, obtained by reacting an ethylene-ethyl acrylate-maleic anhydride (EEAMA) copolymer with an amine terminated PDMS in the melt phase, was used as a processing aid to facilitate the extrusion of LLDPE. Surface properties of hydrosilylated polyolens could be further modified by annealing in supercritical carbon dioxide (Zhu & Tzoganakis, 2008). Two hydrosilylated polypropylenes (PP) and polyethylenes (PE) were obtained by reacting with di- and multi-functional hydride terminated poly(dimethylsiloxane). Processing properties of polypropylene were improved by the addition of a small amount (~2 wt. %) of silicone oil (Zhang et al., 2010).

A PDMS grafted copolymer, which can be potentially applied as a processing agent or a surface property modier, was synthesized via reactive melt mixing of ethylene–ethyl acrylate–maleic anhydride terpolymer (EEAMA) and aminopropyl terminated PDMS (McManus et al., 2006).

Crosslinked styrene-isoprene-siloxane copolymers were applied for a preparation of membranes useful for pervaporative removal of volatile organic compounds from water. The membranes were prepared from the crosslinked copolymer composed of elastomeric glassy styrene-isoprene prepolymer and oligo- or polyhydrosiloxanes (Kerres & Strathmann, 1993; Kujawski et al., 2003). The pervaporation properties of the membranes, used for pervaporation of water–methyl acetate and water–methyl *tert*-butyl ether mixtures, depend on the siloxane content in the membrane and were much better than properties of the commercially available hydrophobic membranes.

High molar mass copolymers of ethylene or propylene with -olefin macromonomer, monovinyl-functional silsesquioxane cage 1-(9-decenyl)-3,5,7,9,11,13,15-heptaethylpentacyclo-[9.5.1.13,9.15,15.17,13]octasiloxane, were obtained in the presence of metallocene catalysts, activated with alumoxanes. These copolymers, contained up to 25 wt. % (1.2 mol. %) of spherosilicate pendant units, which accounted for a decrease of the melting temperature by 18 K with respect to PE. A thermostability under air was improved in the polyethylene copolymer in comparison to PE (Tsuchida et al., 1997).
