WO2004046156A1 - Silane coupling agent, process for the preparation of a silane coupling agent, use of said silane coupling agent in a composite or on a substrate, nanoparticles and use thereof in a coating. - Google Patents

Silane coupling agent, process for the preparation of a silane coupling agent, use of said silane coupling agent in a composite or on a substrate, nanoparticles and use thereof in a coating. Download PDF

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Publication number
WO2004046156A1
WO2004046156A1 PCT/NL2003/000787 NL0300787W WO2004046156A1 WO 2004046156 A1 WO2004046156 A1 WO 2004046156A1 NL 0300787 W NL0300787 W NL 0300787W WO 2004046156 A1 WO2004046156 A1 WO 2004046156A1
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Prior art keywords
coupling agent
silane coupling
agent according
composite
carbon atom
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PCT/NL2003/000787
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French (fr)
Inventor
Jacobus Antonius Loontjens
Bartholomeus Johannes Margretha Plum
Rolf Mulhaupt
Steffen Maier
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Dsm Ip Assets B.V.
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Priority to AU2003279627A priority Critical patent/AU2003279627A1/en
Publication of WO2004046156A1 publication Critical patent/WO2004046156A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages

Definitions

  • SILANE COUPLING AGENT PROCESS FOR THE PREPARATION OF A SILANE COUPLING AGENT, USE OF SAID SILANE COUPLING AGENT IN A
  • the invention relates to a silane coupling agent.
  • a coupling agent is in this application understood to mean an agent that is used to bind an inorganic filler to an organic matrix or an agent by means of which an organic material can be bound to an inorganic substrate, or a combination of these agents. Through the silane coupling agent a better bond between filler and matrix or organic compound and substrate is obtained.
  • the above mentioned coupling agent is used in for example a composite consisting of an inorganic filler and an organic compound used as dental filling material. The better bond as obtained through the use of the coupling agent results is a higher strength of the composite.
  • a known coupling agent that is often used in for example dentistry is isocyanatopropyl trimethoxysilane.
  • a disadvantage of this known silane coupling agent is that the attainable strength of the composite is limited and not sufficient for applications demanding high strength.
  • the aim of the invention is to provide a silane coupling agent through which a higher strength of a composite can be attained.
  • the compound according to Formula (I) therefore comprises a lactam blocked isocyanate group in which the lactam group comprises 3 to 15 CH 2 units as well as an amide group, the Y chain already mentioned and a silane group.
  • Y in the coupling agent according to Formula (I) preferably is composed of an alkane chain with from one to ten CH 2 units.
  • the raw materials for these compounds are readily available on a commercial scale. More preferably the number of CH 2 units in Y is 3. Given the cost price of the raw materials it will in this latter case be possible to produce cheaper compounds according to Formula
  • silane coupling agent according to the invention it is possible to obtain composites with higher strength than through the use of the hitherto known silane coupling agents.
  • the silane reacts with the inorganic substrate and the lactam blocked isocyanate is capable of reacting with a component of the composite, for example a hydroxy functional polymer.
  • the additional reactive group in the Y chain in the compound according to Formula (I), can react with specific components present in a composite. If the additional reactive group is an amine group, it may react with for example epoxy functional organic compounds whereas, if the additional reactive group is a hydroxyl group, it may react with organic compounds containing isocyanates or blocked isocyanates.
  • An improved durability means a better retention of strength in time.
  • a further advantage is that due to the presence of the additional reactive group, it is possible to react the coupling agent according to Formula (I) by two or more independent polymerization mechanisms. Such reaction by a plurality of independent polymerization mechanisms is also known as dual cure.
  • An embodiment of dual-cure consists in reacting an amine as additional reactive group with an epoxy resin and simultaneously or successively, optionally at elevated temperature, reacting the lactam blocked isocyanate group with a hydroxy functional organic compound, for example a hydroxy functional polymer.
  • the use of the urethane nitrogen present in the coupling agent according to Formula (I) besides the lactam blocked isocyanate group in order to carry out the reaction with for example an epoxy proves virtually ineffective in practice.
  • a composite in this description is understood to be a composition consisting of a filler or reinforcing agent in an organic compound or binder.
  • a filler or reinforcing agent may for example be an inorganic oxide or a mineral. Examples of inorganic oxides are silicon oxide, titanium dioxide and glass fibres, glass beads or glass flakes. Examples of minerals are talc, mica, clay and wallostonite.
  • Organic compounds are preferably polymers and coatings.
  • Polymers are here understood to be a thermoset or a thermoplast.
  • Thermosets may for instance be epoxies, polyesters, poly(meth)acrylates, for example U V-curable acrylates that are often applied in dentistry.
  • Thermoplasts may for instance be polyamides, polyester, polypropylene, polyethers, cellulose, starch, polyvinyl alcohol or poly(meth)acrylates.
  • Exemplary inorganic substrates are metals, including aluminium and steel, but also glass, minerals, including hydroxyapatite, inorganic oxides including for example TiO 2 or other additives commonly used in the polymer industry.
  • the invention also relates to the use of the coupling agent according to the invention in a composite e.g. in a dental application or on an inorganic substrate.
  • An advantage of the use of the compound according to the invention in dental filling materials is not only better adhesion between filler and organic compound but also better adhesion to hydroxyapatite as the main component of teeth.
  • a further advantage of the use of the coupling agent according to the invention in dental applications is that this coupling agent is substantially less toxic than the known, isocyanate-based isocyanatopropyl trimethoxysilane.
  • the compound according to the invention can be prepared according to the process described in WO-A-00/17169 by reacting a carbonyl bislactamate with a silane compound containing at least one amino group.
  • This amino group in the silane compound preferably is a primary amino group.
  • the temperature at which the carbonyl bislactamate reacts with a silane compound that contains at least one amino group is lower than 150°C in which process a blocked isocyanate is formed and a lactam is split off.
  • the silane compound may also contain an additional reactive group.
  • This group will in general be so chosen that it exhibits lower reactivity than the at least one amino group mentioned. This ensures that the reaction of the carbonyl bislactam with the at least one amino group mentioned comes first. Due to the selection of the temperature as mentioned above and the selection of the quantity of the carbonyl bislactam relative to the quantity of at least one amino group and the additional reactive group in the silane compound it is possible to control a quantity of as yet unreacted groups. This ensures that the latter group is available for the reaction with other components in a composite.
  • the invention also relates to nano particles, in particular nanosilicate particles obtained by reaction, for example hydrolysis, of the coupling agent according to the invention and in particular to the use of these particles in a coating or a thermoset.
  • nanosilica particles for improvement of the scratch resistance of a coating is known. This is subject to good dispersion of the particles in the coating.
  • TEOS tetraethoxysilane
  • a problem of the known nano particles is their mediocre adhesion to the coating, as a result of which the particles are easily abraded from the coating.
  • the aim of the invention is also to provide nanosilicate particles with improved adhesion to the coating.
  • nanosilicate particles obtained by hydrolysis of the coupling agent according to Formula (I), optionally in the presence of TEOS.
  • An added advantage of the use of the nano particles according to the invention is that it results in more homogeneous dispersion in a coating.
  • a further advantage of the nano particles according to the invention is that the additional reactive amine or hydroxy group may also function as a crosslinker in a coating or a thermosetting polymer composition.
  • a crosslinker is used in these systems in order to cure the coatings or the thermosetting polymer.
  • By using the nano particles of the invention less extra crosslinker or no extra crosslinker needs to be added to the coating or the thermoset. It has also proved possible to prepare nano particles according to the invention by adding the coupling agent according to Formula (I) to very fine particles, for example metal oxides, such as SiO 2 and TiO 2 .
  • the reaction between the metal oxide and the silane coupling agent according to Formula (I) is not limited to fine particles or nano particles. Larger particles, for example with an average size up to 50 ⁇ m, similarly react with the silane coupling agent according to Formula (I) and also exhibit the advantage that, because of the at least one additional reactive group, they can operate as a cross linker.
  • Silane compounds including the known ⁇ -aminopropyl trimethoxy silane, are also often used for coating substrate surfaces. It is known to treat the surfaces of minerals such as kaolin, mica and talc with this compound in order to improve the adhesion of these minerals in a polymer composition.
  • silanes are often used as part of a sizing composition.
  • Such a sizing composition is often used in the production of glass fibres for the purpose of treating the surface of glass fibres.
  • the compound according to formula (I) is particularly suitable for treating mineral and glass substrates. Therefore, the invention also relates to the use of the compound according to formula (I) for the purpose of treating mineral and glass substrates.
  • Example III Preparation by dual cure of a composite based on an epoxy and the compound obtained via Example II
  • the mould was heated to 100°C and kept at that temperature for 1 hour.
  • the temperature was increased to 180°C and kept at that temperature for 30 minutes, in which period a reaction took place between the hydroxyl group - that had formed in the reaction of the epoxy and the secondary amine in the silane compound - and the caprolactam blocked isocyanate.
  • the mould was cooled to room temperature and the tensile strength of the test bar obtained was determined in a tensile test; it was 75 MPa.
  • Comparative experiment B Preparation of an epoxy-based composite 68 grams of an epoxy resin (Epikote ® 828), 6.6 grams (0.05 mol) of the compound obtained via Example I and 34 grams of SiO 2 filler (Aerosil ® ) were mixed at room temperature to form a mixture. This mixture was transferred into a mould whose cavity had the form of a tensile test bar according to ISO 527/1 A. The mould was heated to 100°C and kept at that temperature for 1 hour. Subsequently, the temperature was increased to 180°C and kept at that temperature for 30 minutes. The mould was cooled to room temperature and the tensile strength of the test bar obtained was determined in a tensile test; it was 55 MPa.
  • an epoxy resin Epikote ® 828
  • SiO 2 filler SiO 2 filler

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

The invention relates to a novel silane coupling agent according to Formula (1) below, wherein Y = a chain composed of aliphatic, cyclic or aromatic groups, furthermore comprising an additional reactive group chosen from the series of a secondary amine, a amine linked to a secondary or tertiary carbon atom or a hydroxyl group linked to a primary, secondary or tertiary carbon atom. R, R'= CH3 or C2H5, n = 3-15, q = 1, 2 or 3 and p = 3-q. The invention also relates to the use of the coupling agent according to the invention in a composite, for example in a dental application. The invention further relates to a process for the preparation of a silane coupling agent by reacting, at a temperature lower than 150° C, a carbonyl bislactamate with a silane compound containing at least one amino group. The invention moreover relates to nano particles, in particular nano silicate particles, obtained by hydrolysis of the coupling agent according to the above formula in the presence or absence of tetraethoxysilane and to the use of such particles in a coating.

Description

SILANE COUPLING AGENT. PROCESS FOR THE PREPARATION OF A SILANE COUPLING AGENT, USE OF SAID SILANE COUPLING AGENT IN A
COMPOSITE OR ON A SUBSTRATE. NANOPARTICLES AND USE THEREOF
IN A COATING
The invention relates to a silane coupling agent. A coupling agent is in this application understood to mean an agent that is used to bind an inorganic filler to an organic matrix or an agent by means of which an organic material can be bound to an inorganic substrate, or a combination of these agents. Through the silane coupling agent a better bond between filler and matrix or organic compound and substrate is obtained. The above mentioned coupling agent is used in for example a composite consisting of an inorganic filler and an organic compound used as dental filling material. The better bond as obtained through the use of the coupling agent results is a higher strength of the composite.
A known coupling agent that is often used in for example dentistry is isocyanatopropyl trimethoxysilane.
A disadvantage of this known silane coupling agent is that the attainable strength of the composite is limited and not sufficient for applications demanding high strength.
The aim of the invention is to provide a silane coupling agent through which a higher strength of a composite can be attained.
This aim is achieved by a silane coupling agent according to Formula (I)
Figure imgf000002_0001
where
Y = a chain composed of aliphatic, cyclic and/or aromatic groups, further comprising at least one additional reactive group chosen from the series of a secondary amine, an amine linked to a secondary or tertiary carbon atom and a hydroxyl group linked to a primary, secondary or tertiary carbon atom, R, R' = CH3 or C2H5, n = 3 -15, q = 1 , 2 or 3 and p = 3-q
The compound according to Formula (I) therefore comprises a lactam blocked isocyanate group in which the lactam group comprises 3 to 15 CH2 units as well as an amide group, the Y chain already mentioned and a silane group.
Y in the coupling agent according to Formula (I) preferably is composed of an alkane chain with from one to ten CH2 units. The raw materials for these compounds are readily available on a commercial scale. More preferably the number of CH2 units in Y is 3. Given the cost price of the raw materials it will in this latter case be possible to produce cheaper compounds according to Formula
(I).
Through the use of the silane coupling agent according to the invention it is possible to obtain composites with higher strength than through the use of the hitherto known silane coupling agents. The silane reacts with the inorganic substrate and the lactam blocked isocyanate is capable of reacting with a component of the composite, for example a hydroxy functional polymer.
The additional reactive group in the Y chain in the compound according to Formula (I), can react with specific components present in a composite. If the additional reactive group is an amine group, it may react with for example epoxy functional organic compounds whereas, if the additional reactive group is a hydroxyl group, it may react with organic compounds containing isocyanates or blocked isocyanates.
An additional advantage is that through the use of the coupling agent according to formula (I) an improved durability of a composite is obtained.
An improved durability means a better retention of strength in time.
A further advantage is that due to the presence of the additional reactive group, it is possible to react the coupling agent according to Formula (I) by two or more independent polymerization mechanisms. Such reaction by a plurality of independent polymerization mechanisms is also known as dual cure. An embodiment of dual-cure consists in reacting an amine as additional reactive group with an epoxy resin and simultaneously or successively, optionally at elevated temperature, reacting the lactam blocked isocyanate group with a hydroxy functional organic compound, for example a hydroxy functional polymer. The use of the urethane nitrogen present in the coupling agent according to Formula (I) besides the lactam blocked isocyanate group in order to carry out the reaction with for example an epoxy proves virtually ineffective in practice. Accordingly, a dual cure with the coupling agent according to Formula (I) without an additional reactive group in the chain Y proves virtually impossible in practice. A composite in this description is understood to be a composition consisting of a filler or reinforcing agent in an organic compound or binder. A filler or reinforcing agent may for example be an inorganic oxide or a mineral. Examples of inorganic oxides are silicon oxide, titanium dioxide and glass fibres, glass beads or glass flakes. Examples of minerals are talc, mica, clay and wallostonite.
Organic compounds are preferably polymers and coatings. Polymers are here understood to be a thermoset or a thermoplast.
Thermosets may for instance be epoxies, polyesters, poly(meth)acrylates, for example U V-curable acrylates that are often applied in dentistry.
Thermoplasts may for instance be polyamides, polyester, polypropylene, polyethers, cellulose, starch, polyvinyl alcohol or poly(meth)acrylates.
Exemplary inorganic substrates are metals, including aluminium and steel, but also glass, minerals, including hydroxyapatite, inorganic oxides including for example TiO2 or other additives commonly used in the polymer industry.
The invention also relates to the use of the coupling agent according to the invention in a composite e.g. in a dental application or on an inorganic substrate.
An advantage of the use of the compound according to the invention in dental filling materials is not only better adhesion between filler and organic compound but also better adhesion to hydroxyapatite as the main component of teeth. A further advantage of the use of the coupling agent according to the invention in dental applications is that this coupling agent is substantially less toxic than the known, isocyanate-based isocyanatopropyl trimethoxysilane.
The compound according to the invention can be prepared according to the process described in WO-A-00/17169 by reacting a carbonyl bislactamate with a silane compound containing at least one amino group. This amino group in the silane compound preferably is a primary amino group. In this way, a rapid reaction with the carbonyl bislactamate is achieved. The temperature at which the carbonyl bislactamate reacts with a silane compound that contains at least one amino group is lower than 150°C in which process a blocked isocyanate is formed and a lactam is split off.
The silane compound may also contain an additional reactive group. This group will in general be so chosen that it exhibits lower reactivity than the at least one amino group mentioned. This ensures that the reaction of the carbonyl bislactam with the at least one amino group mentioned comes first. Due to the selection of the temperature as mentioned above and the selection of the quantity of the carbonyl bislactam relative to the quantity of at least one amino group and the additional reactive group in the silane compound it is possible to control a quantity of as yet unreacted groups. This ensures that the latter group is available for the reaction with other components in a composite. The invention also relates to nano particles, in particular nanosilicate particles obtained by reaction, for example hydrolysis, of the coupling agent according to the invention and in particular to the use of these particles in a coating or a thermoset.
The use of nanosilica particles for improvement of the scratch resistance of a coating is known. This is subject to good dispersion of the particles in the coating.
A known process for the preparation of such nanosilica particles involves controlled hydrolysis of tetraethoxysilane (TEOS).
A problem of the known nano particles is their mediocre adhesion to the coating, as a result of which the particles are easily abraded from the coating.
The aim of the invention is also to provide nanosilicate particles with improved adhesion to the coating.
This aim is achieved by nanosilicate particles obtained by hydrolysis of the coupling agent according to Formula (I), optionally in the presence of TEOS.
This results in nano particles containing a silicate core with blocked isocyanate groups at the surface of the core. With the nanosilicate particles thus obtained, used in a coating, an improved scratch resistance of the coating is achieved.
An added advantage of the use of the nano particles according to the invention is that it results in more homogeneous dispersion in a coating. A further advantage of the nano particles according to the invention is that the additional reactive amine or hydroxy group may also function as a crosslinker in a coating or a thermosetting polymer composition. A crosslinker is used in these systems in order to cure the coatings or the thermosetting polymer. By using the nano particles of the invention less extra crosslinker or no extra crosslinker needs to be added to the coating or the thermoset. It has also proved possible to prepare nano particles according to the invention by adding the coupling agent according to Formula (I) to very fine particles, for example metal oxides, such as SiO2 and TiO2. This results in a coupling agent with a "built-in" metal oxide such as TiO2. It has also been found that the reaction between the metal oxide and the silane coupling agent according to Formula (I) is not limited to fine particles or nano particles. Larger particles, for example with an average size up to 50 μm, similarly react with the silane coupling agent according to Formula (I) and also exhibit the advantage that, because of the at least one additional reactive group, they can operate as a cross linker. Silane compounds, including the known γ-aminopropyl trimethoxy silane, are also often used for coating substrate surfaces. It is known to treat the surfaces of minerals such as kaolin, mica and talc with this compound in order to improve the adhesion of these minerals in a polymer composition. It is also known to treat glass surfaces, including glass fibres, with this type of silanes. In the case of glass fibres, these silanes are often used as part of a sizing composition. Such a sizing composition is often used in the production of glass fibres for the purpose of treating the surface of glass fibres.
It has been found that the compound according to formula (I) is particularly suitable for treating mineral and glass substrates. Therefore, the invention also relates to the use of the compound according to formula (I) for the purpose of treating mineral and glass substrates.
This ensures improved adhesion of mineral and/or glass additives in polymers. An added advantage is that the mineral and/or glass substrates treated with the compound according to formula (I) are less susceptible to hydrolysis. As a result, these additives retain their properties in a moist or aqueous environment for a longer period of time.
Example I
Preparation of caprolactam blocked γ-isocvanatopropyl trimethoxysilane 17.9 g (0.1 mol) γ-aminopropyl trimethoxysilane and 25.2
(0.1 mol) carbonyl biscaprolactamate were dissolved in 300 ml toluene. The mixture was heated for 3 hours at 75°C. After the mixture had cooled down to room temperature it was transferred into a film evaporator in which the toluene and the caprolactam that had formed were evaporated at 100°C and 0.1 bar absolute pressure. There was formed a compound according to the following structural formula:
Figure imgf000007_0001
A quantitative yield was obtained and the purity as determined by 1H-NMR was 98%.
Example II Preparation of caprolactam blocked N-(2-isocvanatoethyl)-3-aminopropyl trimethoxysilane
22.2 g (0.1 mol) N-(2-aminoethyl)-3-aminopropyl trimethoxysilane and 25.2 (0.1 mol) carbonyl biscaprolactamate were dissolved in
300 ml toluene. The mixture was heated at 75 °C for 3 hours. After the mixture had cooled down to room temperature, it was transferred into a film evaporator in which the toluene and the caprolactam that had formed were evaporated at 100°C and 0.1 bar absolute pressure. There was formed a compound according to the following structural formula:
Figure imgf000008_0001
A quantitative yield was obtained and the purity as determined by 1H-NMR was 98 %.
Example III Preparation by dual cure of a composite based on an epoxy and the compound obtained via Example II
68 grams of an epoxy resin (Epikote® 828), 6.6 grams (0.05 mol) of the compound obtained via Example II and 34 grams of SiO2 filler (Aerosil®) were mixed at room temperature to form a mixture. This mixture was transferred into a mould whose cavity had the form of a tensile test bar according to ISO
527/1 A. The mould was heated to 100°C and kept at that temperature for 1 hour.
Subsequently, the temperature was increased to 180°C and kept at that temperature for 30 minutes, in which period a reaction took place between the hydroxyl group - that had formed in the reaction of the epoxy and the secondary amine in the silane compound - and the caprolactam blocked isocyanate. The mould was cooled to room temperature and the tensile strength of the test bar obtained was determined in a tensile test; it was 75 MPa.
Comparative experiment A Preparation of an epoxy-based composite
68 grams of an epoxy resin (Epikote® 828), 6.6 grams (0.05 mol) of the compound obtained via Example I and 34 grams of SiO2 filler (Aerosil®) were mixed at room temperature to form a mixture. This mixture was transferred into a mould whose cavity had the form of a tensile test bar according to ISO 527/1 A. The mould was heated to 100°C and kept at that temperature for 1 hour. The mould was cooled to room temperature and the tensile strength of the test bar obtained was determined in a tensile test; it was 53 MPa.
Comparative experiment B Preparation of an epoxy-based composite 68 grams of an epoxy resin (Epikote® 828), 6.6 grams (0.05 mol) of the compound obtained via Example I and 34 grams of SiO2 filler (Aerosil®) were mixed at room temperature to form a mixture. This mixture was transferred into a mould whose cavity had the form of a tensile test bar according to ISO 527/1 A. The mould was heated to 100°C and kept at that temperature for 1 hour. Subsequently, the temperature was increased to 180°C and kept at that temperature for 30 minutes. The mould was cooled to room temperature and the tensile strength of the test bar obtained was determined in a tensile test; it was 55 MPa.

Claims

C L A I M S
Silane coupling agent according to Formula (I)
Figure imgf000010_0001
where
Y = a chain composed of aliphatic, cyclic or aromatic groups, further comprising at least one additional reactive group chosen from the series of a secondary amine, a amine linked to a secondary or tertiary carbon atom and a hydroxyl group linked to a primary, secondary or tertiary carbon atom
R, R' = CH3 or C2H5, n = 3 -15, q = 1 ,
2 or 3 and p = 3-q 2. Coupling agent according to Claim 1 , wherein n = 5, q=3, R = CH3, or
C2H5 and Y contains 3 CH2 units.
3. Use of the coupling agent according to Claim 1 or 2 in a composite or on a substrate.
4. Use of a composite according to Claim 3 in a dental application.
5. Process for the preparation of a silane coupling agent by reacting at a temperature lower than 150 °C, a carbonyl bislactamate with a silane compound containing at least one amino group.
6. Process according to claim 5 whereby the at least one amino group is a primary amino group 7. Process according to either one of claims 5-6, whereby the silane compound contains at least one additional group chosen from the series of a secondary amine, a amine linked to a secondary or tertiary carbon atom and a hydroxyl group linked to a primary, secondary or tertiary carbon atom. Nano silicate particles obtained by hydrolysis of the coupling agent according to Formula (I), optionally in the presence of tetraethoxysilane. Use of nano silicate particles according to Claim 8 in a coating.
PCT/NL2003/000787 2002-11-20 2003-11-10 Silane coupling agent, process for the preparation of a silane coupling agent, use of said silane coupling agent in a composite or on a substrate, nanoparticles and use thereof in a coating. WO2004046156A1 (en)

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WO2007113082A1 (en) * 2006-04-06 2007-10-11 Wacker Chemie Ag Process for preparing polyamide-polysiloxane block copolymers
EP2307517A2 (en) * 2008-07-29 2011-04-13 E. I. du Pont de Nemours and Company Surface active blocked isocyanates and coating compositions thereof
EP2384885A1 (en) * 2010-03-15 2011-11-09 Manville, Johns Polymerization initiators for fiber-reinforced polymer composites and materials made from the composites
CN103694270A (en) * 2013-12-20 2014-04-02 福建师范大学 Functional siloxane containing phenazine and synthetic method thereof
EP2813533A1 (en) * 2013-06-11 2014-12-17 Johns Manville Sized glass fibers for fiber-containing composite articles and methods of making them
US20150148498A1 (en) * 2013-11-22 2015-05-28 Johns Manville Fiber-reinforced composites made with thermoplastic resin compositions and reactive coupling fibers
WO2016113240A1 (en) * 2015-01-12 2016-07-21 Semperit Ag Holding Adhesion promoter for integrally bonding a polymeric organic material to an inorganic substrate and method for integrally bonding a polymeric organic material to an inorganic substrate by means of the adhesion promoter

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