JP2016524637A - Catalyst for siloxane synthesis - Google Patents

Abstract

Compositions and methods for the production of siloxane materials using azaphosphatran as a catalyst. In one embodiment, a process is provided for the ring opening polymerization of cyclic siloxanes in the presence of azaphosphatran. In another embodiment, compositions and methods for condensation curing of moisture curable compositions using azaphosphatran are provided.

Description

Cross-reference of related applications

  This application claims priority and benefit of US Provisional Application No. 61 / 824,705, entitled “Siloxane Synthesis Catalyst,” filed May 17, 2013, the disclosure of which is hereby incorporated by reference in its entirety. Incorporated in the description.

  The present invention relates to a method of forming a siloxane using an azaphosphatolan material as a catalyst. Azaphosphatolan can be used as a condensation curing catalyst in a ring-opening polymerization reaction.

  Cyclic siloxanes are often used as starting monomers to form polysiloxanes. In general, polysiloxanes can be formed by ring-opening polymerization of cyclic siloxanes and appropriate end-capping units. The reaction is carried out in the presence of a catalyst.

  Various catalysts are known for cyclic siloxane polymerization. Examples include alkali metal hydroxides, alkali metal alkoxides or complexes of alkali metal hydroxides and alcohols, alkali metal silanolates, and phosphonitrile halides (sometimes referred to as acidic phosphazenes). Such polymerization can be carried out in bulk, solvents (such as nonpolar or polar organic solvents) or emulsions. Phosphazene bases and carbenes are described as suitable catalysts for ring-opening polymerization of siloxanes. Endblocking agents may be used to adjust the molecular weight of the polymer and / or to add functional groups. The polymerization may be terminated by using a neutralizing agent that reacts with the catalyst to render it inert. In most cases, catalyst residues remain in the polymer product and are desirably removed, such as by filtration.

  Solid-type catalysts can be used as catalysts for synthesizing polydimethylsiloxane (PDMS) fluids and PDMS functional fluids by ring-opening polymerization. Solid type catalysts exhibit high catalytic activity but produce solid waste. Solid waste is usually incinerated. In addition, solid waste can contain a significant fraction of the product, reducing overall yield and increasing manufacturing costs.

  Curable compositions, such as moisture curable compositions, also use a catalyst to promote curing and polymer network formation. In order to accelerate moisture assisted curing of non-silicone polymers having polyorganosiloxanes and reactive terminal silyl groups in room temperature vulcanized compositions, metal catalysts are typically used as condensation cure catalysts. Organotin, such as dibutyltin dilaurate (DBTDL), is generally used as a catalyst in such compositions. However, environmental regulators and directives have increased or are expected to increase restrictions on the use of organotin compounds in formulated products. For example, formulations containing more than 0.5% by weight of dibutyltin currently require reproductive 1B toxicity labeling, but dibutyltin-containing formulations will be phased in consumer applications over the next 4 to 6 years. It has been proposed to eliminate it completely.

  The use of alternative organotin compounds, such as dioctyltin compounds and dimethyltin compounds, can simply be considered a short-term correction plan as these organotin compounds may also be regulated in the future. Desirably, replacements for organotin catalysts should exhibit properties similar to organotin compounds in terms of cure, storage and appearance. The non-tin catalyst may also desirably initiate the condensation reaction of the selected polymer to complete this reaction on the surface and be in the desired time schedule in the bulk. Therefore, there are many proposals for replacing organometallic tin compounds with other metal compounds. These compounds include metals such as Ca, Ce, Bi, Fe, Mo, Mn, Pb, Ti, V, Zn and Y. These other metals have certain advantages and disadvantages in terms of complete replacement of the tin compound. Non-metallic catalysts are also of interest. Therefore, there is still a need to address the limitations of possible metal compounds as catalysts suitable for condensation cure reactions. The physical properties of the uncured and cured composition also justify the investigation, especially to maintain the ability to adhere to the surface of some substrates.

  The present invention provides compositions, methods and processes that form polysiloxanes and promote curing of curable siloxane compositions.

In one aspect, the present invention provides a process for forming a polysiloxane by ring-opening polymerization of a cyclic siloxane. The process includes contacting a cyclic siloxane with azaphosphatran.

［式中、Ｒ⁹、Ｒ¹⁰およびＲ¹¹は、水素、１から１０個の炭素原子を含む直鎖状または分岐アルキル、６から１２個の炭素原子を含む芳香族基、および窒素を含むまたは含まない置換リン基から独立して選ばれ；Ａは、水素、Ｒ¹²または（Ｒ¹³Ｒ¹⁴Ｐ−Ｎ＝）ｔから選ばれ、ここで、Ｒ¹²、Ｒ¹³およびＲ¹⁴は、水素、１から１０個の炭素原子を含む直鎖状または分岐アルキル、および６から１２個の炭素原子を含む芳香族基から独立して選ばれ；ｔは１から１０である。］のものである。 In one embodiment, azaphosphatran has the formula:

[Wherein R ⁹ , R ¹⁰ and R ¹¹ comprise hydrogen, a linear or branched alkyl containing 1 to 10 carbon atoms, an aromatic group containing 6 to 12 carbon atoms, and nitrogen, or Independently selected from substituted phosphorus groups not included; A is selected from hydrogen, R ¹² or (R ¹³ R ¹⁴ P—N═) t, wherein R ¹² , R ¹³ and R ¹⁴ are hydrogen, Independently selected from linear or branched alkyl containing 1 to 10 carbon atoms and aromatic groups containing 6 to 12 carbon atoms; t is 1 to 10. ]belongs to.

  In one embodiment, the azaphosphatran is about 0.05 weight percent to about 5 weight percent based on the total weight of the cyclic siloxane; further about 0.1 weight percent to about 0.00 weight based on the total weight of the cyclic siloxane. Present in an amount of 4 weight percent.

  In one embodiment, the process includes deactivating the catalyst. In one embodiment, deactivating the catalyst comprises heating the product of the process at a temperature of about 100 ° C. or higher after the reaction; treating the product with water; bubbling carbon dioxide into the product. Treating the product with a material that neutralizes the catalyst, or a combination of two or more thereof.

  In another embodiment, the process further comprises filtering the reaction mixture.

  In another embodiment, the process further comprises treating the filtered reaction mixture with charcoal.

  In another aspect, the present invention provides a method of forming such a composition comprising a curable composition and a catalyst comprising azaphosphatran.

In one embodiment, the present invention is a composition for forming a cured polymer composition comprising:
(A) a polymer having at least a reactive silyl group;
(B) a crosslinking agent or chain extender;
A composition comprising (C) a catalyst comprising an azaphosphatran compound; and (D) an optional adhesion promoter.

［式中、Ｒ⁹、Ｒ¹⁰およびＲ¹¹は、水素、１から１０個の炭素原子を含む直鎖状または分岐アルキル、６から１２個の炭素原子を含む芳香族基、および窒素を含むまたは含まない置換リン基から独立して選ばれ；Ａは、水素、Ｒ¹²または（Ｒ¹³Ｒ¹⁴ＰＮ＝）ｔから選ばれ、ここで、Ｒ¹²、Ｒ¹³およびＲ¹⁴は、水素、１から１０個の炭素原子を含む直鎖状または分岐アルキル、および６から１２個の炭素原子を含む芳香族基から独立して選ばれ；ｔは１から１０である。］のものである。 In one embodiment, the azaphosphatran has the formula:

[Wherein R ⁹ , R ¹⁰ and R ¹¹ comprise hydrogen, a linear or branched alkyl containing 1 to 10 carbon atoms, an aromatic group containing 6 to 12 carbon atoms, and nitrogen, or Independently selected from substituted phosphorus groups not included; A is selected from hydrogen, R ¹² or (R ¹³ R ¹⁴ PN =) t, wherein R ¹² , R ¹³ and R ¹⁴ are hydrogen, 1 Independently selected from linear or branched alkyl containing 10 carbon atoms and aromatic groups containing 6 to 12 carbon atoms; t is 1 to 10. ]belongs to.

  These and other aspects of the invention are further illustrated with reference to the following description.

Detailed Description of the Invention

Ring Opening Polymerization The present invention, in one aspect, provides a process for the ring opening polymerization of cyclic siloxanes. The method includes contacting a cyclic siloxane with an azaphosphatolan material. The inventor has found that azaphosphatolan materials can be suitable for catalyzing the ring-opening polymerization of cyclic siloxanes. The reaction can be carried out in a suitable solvent. The reaction can also be carried out in the presence of water to such an extent that the catalytic activity of the catalyst does not decrease.

［式中、Ｒ⁹、Ｒ¹⁰およびＲ¹¹は、水素、１から１０個の炭素原子を含む直鎖状または分岐アルキル、６から１２個の炭素原子を含む芳香族基、および窒素を含むまたは含まない置換リン基から独立して選ばれ；Ａは、水素、Ｒ¹²または（Ｒ¹³Ｒ¹⁴Ｐ−Ｎ＝）_tから選ばれ、ここで、Ｒ¹²、Ｒ¹³およびＲ¹⁴は、水素、１から１０個の炭素原子を含む直鎖状または分岐アルキル、および６から１２個の炭素原子を含む芳香族基から独立して選ばれ；ｔは１から１０である。］の化合物から選ぶことができる。適切なアルキル基は、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、オクチル、イソプロピル、イソブチルなどを含むがこれらに限定されない。適切な芳香族基は、フェニル、ベンジル、ナフチルなどを含むがこれらに限定されない。 The azaphosphatolan material has the formula (1):

[Wherein R ⁹ , R ¹⁰ and R ¹¹ comprise hydrogen, a linear or branched alkyl containing 1 to 10 carbon atoms, an aromatic group containing 6 to 12 carbon atoms, and nitrogen, or Independently selected from substituted phosphorus groups not included; A is selected from hydrogen, R ¹² or (R ¹³ R ¹⁴ P—N═) _t , wherein R ¹² , R ¹³ and R ¹⁴ are hydrogen, Independently selected from linear or branched alkyl containing 1 to 10 carbon atoms and aromatic groups containing 6 to 12 carbon atoms; t is 1 to 10. ] Can be selected. Suitable alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, isopropyl, isobutyl, and the like. Suitable aromatic groups include, but are not limited to phenyl, benzyl, naphthyl and the like.

およびその２種以上の組み合わせ［式中、Ｒ⁹−Ｒ¹⁴は上記の通りである。］の化合物から選ぶことができる。一実施形態において、アザホスファトラン材料は、式（２）−（４）［式中、Ｒ⁹、Ｒ¹⁰およびＲ¹¹は、メチル、イソプロピル、イソブチルまたはその２種以上の組み合わせから選ばれる。］の化合物から選ばれる。 In one embodiment, the azaphosphatolan compound has the formula (2)-(4):

And a combination of two or more thereof, wherein R ^{9 to} R ¹⁴ are as described above. ] Can be selected. In one embodiment, the azaphosphatolan material is of the formula (2)-(4), wherein R ⁹ , R ¹⁰ and R ¹¹ are selected from methyl, isopropyl, isobutyl or combinations of two or more thereof. ] Is selected from the compounds.

  It will be appreciated that one or more various azaphosphatran materials can be used as the catalyst material in the ring-opening polymerization process.

  The polymerization can be carried out in the bulk or in the presence of a solvent. Suitable solvents are liquid hydrocarbons or silicone fluids. The azaphosphatran catalyst can be diluted in a hydrocarbon solvent such as hexane or heptane or dispersed in a silicone fluid such as polydiorganosiloxane. If the azaphosphatolan catalyst is initially in a solvent such as hexane, the hexane can be removed by evaporation under vacuum, and the catalyst is dispersed in the silicone fluid to give a stable clear solution. The reaction can include a concentration of water that does not cause catalyst deactivation or degradation.

  The polymerization reaction can be carried out at ambient temperature or under heating. In general, heating can be carried out up to about 100 ° C. The catalyst can facilitate the reaction at low temperatures. Catalysts tend to decompose when heated above 100 ° C. In one embodiment, after completion of the reaction, the method includes heating the reaction system to a temperature greater than 100 ° C. to decompose and remove the catalyst from the system. This eliminates the neutralization step normally required with conventional catalysts.

  The time taken for polymerization depends on the activity of the catalyst in the system chosen and the desired polymer product. Azaphosphatolan catalysts are sufficiently active to convert cyclic siloxanes such as D4 to high molecular weight polysiloxane gums within hours.

The starting material is a cyclic siloxane (also known as a cyclic siloxane). Cyclic siloxanes are useful and commercially available materials. These have the general formula (R ¹⁵ R ¹⁶ SiO) _n , wherein R ¹⁵ and R ¹⁶ are independently selected from alkyl, alkenyl, aryl, alkaryl or an aralkyl group having up to 8 carbon atoms, Any of substitution and substitution may be used, and n represents an integer having a value of 3 to 12. ]. R ¹⁵ and R ¹⁶ may be substituted with a halogen such as fluorine or chlorine, for example. The alkyl group may be, for example, methyl, ethyl, n-propyl, trifluoropropyl, n-butyl, sec-butyl, and tert-butyl. Alkenyl groups can be, for example, vinyl, allyl, propenyl, and butenyl. Aryl and aralkyl groups may be, for example, phenyl, tolyl and benzoyl. In one embodiment, at least 80% of all R ¹⁵ and R ¹⁶ groups are methyl or phenyl groups. In one embodiment, the R ¹⁵ and R ¹⁶ groups are substantially all methyl groups. When R ¹⁵ and R ¹⁶ are methyl, the compound is referred to as Dn; for example, when n = 4, the compound is referred to as D4. The value of n may be 3 to 6, and in one embodiment is 4 or 5. Examples of suitable cyclic siloxanes are octamethylcyclotetrasiloxane (D4), hexamethylcyclotrisiloxane (D3), octaphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, hexamethyl-1 , 1-diphenylcyclotetrasiloxane, decamethylpentacyclosiloxane, cyclopenta (methylvinyl) siloxane and cyclotetra (phenylmethyl) siloxane. A particularly suitable commercially available material is a mixture of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

  In one embodiment, the reaction mixture includes two or more cyclic siloxanes. In one embodiment, the reaction mixture comprises a mixture of at least two cyclic siloxanes of various ring sizes. In one embodiment, at least one of the cyclic siloxanes includes one or more functional groups selected from vinyl, amine, and the like.

  The process can further include adding an end blocker material. The end blocker material is generally not limited and can be selected as desired for a particular purpose or end use. In one embodiment, the end blocker material is from hexamethyldisiloxane; octamethyltrisiloxane; decamethyltetrasiloxane; dodecamethylpentasiloxane; tetradecamethylhexasiloxane; hexadecamethylheptasiloxane, or a combination of two or more thereof. To be elected.

The reaction mixture is generally purged with an inert gas, preferably nitrogen, to remove dissolved CO ₂ prior to addition of the catalyst. Since it is a very fast reaction, the reaction mixture is vigorously mixed to ensure homogeneous dispersion of the catalyst. Insufficient mixing results in the catalyst being trapped in the rubber beads when added to the reaction, which then takes longer to diffuse out of the rubber particles and the reaction is slower. Become.

  The azaphosphatolan catalyst is about 0.025 weight percent to about 5 weight percent; 0.05 weight percent to about 4.5 weight percent; 0.1 weight percent to about 4 weight percent based on the weight of the starting cyclic siloxane material. 0.25 weight percent to about 3 weight percent; 0.4 weight percent to about 2 weight percent; and further about 0.5 weight percent to about 1 weight percent. In one embodiment, the azaphosphatolan catalyst is present in an amount of about 0.1 weight percent to about 0.4 weight percent based on the weight of the cyclic siloxane material. Again, as elsewhere in the specification and claims, numerical values can be combined to form new or undisclosed ranges.

  The method can further include deactivating the catalyst. Deactivating the catalyst can include removing the catalyst from the reaction system. In one embodiment, deactivating the catalyst can be accomplished by heating the reaction system to a temperature of about 100 ° C. or higher. In one embodiment, the catalyst can be deactivated by heating the reaction system to a temperature of about 110 ° C. or higher, 120 ° C. or higher, and 130 ° C. or higher. The catalyst can be deactivated by treating the reaction system with water, bubbling carbon dioxide into the system and / or treating with an agent that neutralizes the azaphosphatolan compound. Suitable acids that neutralize the catalyst include, but are not limited to, inorganic acids and ion exchange resins. It will be appreciated that one or more of the above deactivation operations can be used to deactivate the catalyst. The present catalyst offers advantages over other types of catalysts such as acidic clays that require filtration of clay particles dispersed in the reaction medium.

Following deactivation, the reaction system can be treated as desired or required to remove any coloration present in the system. Such treatment can include filtration of the sample, such as passing through a celite bed, treatment with charcoal and the like.
Moisture curable composition

  The present invention provides a curable composition using an azaphosphatolan catalyst as a condensation catalyst. In terms of accelerating moisture assisted condensation cure of silicones resulting in crosslinked silicones that can be used as sealants and RTVs (room temperature vulcanized rubbers), compositions comprising azaphosphatran materials use organotin compounds such as DBTDL. Compared with the composition, good curing characteristics can be exhibited. Given the stringent future regulations for organotin catalysts, the non-toxic nature of these compounds makes them more attractive and practical than organotin catalysts.

  In one embodiment, the present invention provides a curable composition comprising a polymer component (A) comprising a reactive terminal silyl group; a crosslinker component (B); and a catalyst component comprising azaphosphatolane compound (C And optionally an adhesion promoter component (D); an optional filler component (E); optionally an acidic compound (F) and optionally an auxiliary component (G).

  The polymer component (A) may be a liquid or solid polymer having a reactive terminal silyl group. The polymer component (A) is not particularly limited and may be selected from any silyl crosslinkable polymer that may be desired for a particular purpose or intended use. Non-limiting examples of suitable polymers for polymer component (A) include polyorganosiloxane (A1) or organic polymer (A2) that does not contain siloxane bonds, where polymers (A1) and (A2) are reactive Contains a terminal silyl group. In one embodiment, the polymer component (A) may be present in an amount from about 10 to about 90% by weight of the curable composition. In one embodiment, the curable composition comprises about 100 parts by weight of polymer component (A).

As noted above, polymer component (A) may include a wide range of polyorganosiloxanes. In one embodiment, the polymer component has the formula (5):
^{_{[R 1 c R 2 3-}} c Si-Z-] n- X-Z-SiR 1 c R 2 3-c (5)
One or more polysiloxanes and copolymers of R ¹ is linear or branched alkyl, linear or branched heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, linear or branched aralkyl, linear or branched heteroaralkyl, or two thereof You may choose from the above combination. In one embodiment, R ^1, C ₁ -C ₁₀ alkyl; one or more Cl, F, N, C replaced by O or S ₁ -C ₁₀ alkyl; phenyl; C ₇ -C ₁₆ alkylaryl C ₇ -C ₁₆ arylalkyl; C ₂ -C ₂₀ polyalkylene ether; or a combination of two or more thereof. Exemplary preferred groups are methyl, trifluoropropyl and / or phenyl groups.

R ² may be a group reactive to a protic agent such as water. Exemplary groups for R ² include OH, alkoxy, alkoxyalkyl, alkenyloxy, alkyloximo, alkylcarboxy, arylcarboxy, alkylamide, arylamide, or combinations of two or more thereof. In one embodiment, R ² is OH, C ₁ -C ₈ alkoxy, C ₂ -C ₁₈ alkoxyalkyl, amino, alkenyloxy, alkyloximo, alkylamino, arylamino, alkylcarboxy, arylcarboxy, alkylamide, It is selected from arylamide, alkylcarbamato, arylcarbamato, or a combination of two or more thereof.

Z is selected from the group of bonds, O _1/2 , hydrocarbons that can contain one or more O, S or N atoms, amides, urethanes, ethers, esters, urea units or combinations of two or more thereof. It may be a divalent linking unit. When the linking group Z is a hydrocarbon group, Z is connected to the silicon atom through a silicon-carbon bond. In one embodiment, Z is selected from C ₁ -C ₁₄ alkylene.

X is polyurethane; polyester; polyether; polycarbonate; polyolefin; polyester ether; and R ¹ ₃ SiO _1/2 , R ¹ ₂ SiO, R ¹ SiO _3/2 and / or SiO ₂ [wherein R ¹ Is defined as above. ] Is selected from polyorganosiloxanes having units of X is a siloxy unit linked via a terminal silyl group containing a reactive group R ² as described above through an oxygen or hydrocarbon group, or a silicon atom containing one or more reactive groups R ² as described above. Or a divalent or polyvalent polymer unit selected from the group of polyether, polyalkylene, polyisoalkylene, polyester or polyurethane units linked via a hydrocarbon group. The hydrocarbon group X contains one or more heteroatoms such as N, S, O or P and can form amides, esters, ethers, urethanes, esters, and / or ureas. In one embodiment, the average degree of polymerization (P _n ) of X is greater than 6, such as polyorganosiloxane, of R ¹ ₃ SiO _1/2 , R ¹ ₂ SiO, R ¹ SiO _3/2 and / or SiO _2. Must be a unit. In the formula (5), n is 0 to 100; preferably 1, and c is 0 to 2, preferably 0 to 1.

Non-limiting examples of the component of unit X include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyethylene-polyoxypropylene copolymer, polyoxytetramethylene, or polyoxypropylene-polyoxybutylene copolymer. Oxyalkylene polymers; ethylene-propylene copolymers, polyisobutylene, polychloroprene, polyisoprene, polybutadiene, copolymers of isobutylene and isoprene, copolymers of isoprene or butadiene and acrylonitrile and / or styrene, or hydrogenation of these polyolefin polymers Hydrocarbon polymers such as hydrogenated polyolefin polymers; produced by condensation of dibasic acids (such as adipic acid or phthalic acid) and glycols Ring-opening polymerization of the polyester polymer or lactone; polyacrylic acid ester prepared by radical polymerization of monomers such as acrylic acid C ₂ -C ₈ alkyl, vinyl polymers, such as acrylic acid esters (acrylic acid ethyl or butyl acrylate, etc. ) And acrylic acid ester copolymers of vinyl acetate, acrylonitrile, methyl methacrylate, acrylamide or styrene; graft polymers prepared by polymerization of the above organic polymers with vinyl monomers; polycarbonates; polysulfide polymers; ε-caprolactam ring opening Nylon 6 produced by polymerization, nylon 6-6 produced by polycondensation of hexamethylenediamine and adipic acid, nylon 12 produced by ring-opening polymerization of ε-laurolactam, Mer polyamides, including polyamide polymer such as polyurethane or polyurea.

  Particularly suitable polymers include polysiloxanes, polyoxyalkylenes, saturated hydrocarbon polymers (such as polyisobutylene, hydrogenated polybutadiene and hydrogenated polyisoprene), or polyethylene, polypropylene, polyester, polycarbonate, polyurethane, polyurea polymers, etc. Including but not limited to. In addition, saturated hydrocarbon polymers, polyoxyalkylene polymers and vinyl copolymers are particularly suitable because of their low glass transition temperatures and high flexibility at low temperatures, i.e. below 0 ° C.

The reactive silyl group of formula (5) is a known method using an unsaturated hydrocarbon by hydrosilylation, or SiOH, aminoalkyl or aryl in the prepolymer to be linked to the reactive silyl group by condensation or ring-opening reaction. Contains functional groups capable of reacting by reaction of HOOC-alkyl or aryl, HO-alkyl or -aryl, HS-alkyl or -aryl, Cl (O) C-alkyl or aryl, epoxyalkyl or epoxycycloalkyl groups Can be introduced by using silane. Examples of major embodiments include: (i) Can undergo a condensation reaction with silane (LG) SiR ¹ _c R ² _3-c , releasing leaving group (LG) and hydrogen addition products However, (LG-H), a siloxane prepolymer having SiOH groups thereby forming siloxy bonds ≡-Si-O-SiR ¹ _c R ² _3-c ; (ii) by hydrosilylation or radical reaction with SiH groups An unsaturated group capable of reacting, or a silane having a radical activating group of a silane or unsaturated group such as SiH; and (iii) an organic or OH, SH, amino, epoxy, -COCl, -COOH group Silane containing an inorganic prepolymer, epoxy, isocyanato, OH, SH, cyanato, carvone to which the reactive prepolymer should be linked to the organofunctional silane Silanes that can react complementary to acid halides, reactive alkyl halides, lactones, lactams or amines to give silyl functional polymers.

  Suitable silanes for process (i) are alkoxy silanes, in particular tetraalkoxy silanes, di- and trialkoxy silanes, di- and triacetoxy silanes, di- and triketoximo silanes, di- and trialkenyloxy silanes, di- And tricarbonamidosilane, wherein the residue at the silicon atom position of the silane is a substituted or unsubstituted hydrocarbon. Other non-limiting silanes for process (i) are vinyltrimethoxysilane, methyltrimethoxysilane, propyltrimethoxysilane, aminoalkyltrimethoxysilane, ethyltriacetoxysilane, methyl- or propyltriacetoxysilane, Alkyltrialkoxysilanes such as methyltributanone oximosilane, methyltripropenyloxysilane, methyltribenzamidosilane, or methyltriacetamidosilane. A suitable prepolymer for reaction under method (i) is a SiOH-terminated polyalkylsiloxane capable of undergoing a condensation reaction with a silane having a hydrolyzable group bonded to a silicon atom. Exemplary SiOH-terminated polyalkyldisiloxanes include polydimethylsiloxane.

Suitable silanes for process (ii) include alkoxysilanes, especially trialkoxysilanes (HSi (OR) ₃ ) such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane and phenyldimethoxysilane. Hydrogen chlorosilanes are possible in principle, but are less desirable due to the additional substitution of halogens by alkoxy, acetoxy groups and the like. Other suitable silanes include organofunctional silanes having unsaturated groups that can be activated by radicals such as vinyl, allyl, mercaptoalkyl or acrylic acid groups. Non-limiting examples include vinyltrimethoxysilane, mercaptopropyltrimethoxysilane, and methacryloxypropyltrimethoxysilane. Prepolymers suitable for reaction under process (ii) are vinyl-terminated polyalkylsiloxanes, preferably polydimethylsiloxanes, which can undergo hydrosilylation, or corresponding organics of silanes containing, for example, unsaturated hydrocarbons or SiH groups. Includes hydrocarbons with unsaturated groups capable of undergoing radical-induced grafting reactions with functional groups.

  Another method of introducing silyl groups into the hydrocarbon polymer may be copolymerization of unsaturated hydrocarbon monomers with unsaturated groups of silane. The introduction of unsaturated groups into the hydrocarbon prepolymer may involve the use of, for example, alkenyl halides as chain terminators after polymerization of hydrocarbon moieties that do not contain silicon.

The desired reaction product between the silane and the prepolymer includes the following structure:
—SiR ¹ ₂ O—SiR ¹ ₂ —CH ₂ —CH ₂ —SiR ¹ _c R ² _3-c , or (hydrocarbon)-[Z-SiR ¹ _c R ² _3-c ] _n

  Suitable silanes for method (iii) include, but are not limited to, alkoxy silanes, particularly silanes having organofunctional groups that are reactive with —OH, —SH, amino, epoxy, —COCl or —COOH.

  In one embodiment, these silanes include, for example, gamma-isocyanatopropyltrimethoxysilane, gamma-isocyanatopropylmethyldimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropylethyldimethoxysilane, gamma -Glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, beta- (3,4-epoxycyclohexyl) ethyltriethoxysilane, epoxy Limonyltrimethoxysilane, N- (2-aminoethyl) -aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma- Having isocyanatoalkyl group, such as amino propyl methyl diethoxy silane - amino propyl methyl dimethoxy silane, gamma.

In one embodiment, it is desirable to select either the blocked amine or isocyanate (Ζ′-Χ) _n -Ζ ′ first for thorough mixing and then for the next coupling reaction. Examples of blocking agents are disclosed in EP 0947531; other blocking procedures using heterocyclic nitrogen compounds such as caprolactam or butanone oxime or cyclic ketones are described in US Pat. No. 6,827,875. Both of which are incorporated herein by reference in their entirety.

Examples of prepolymers suitable for reaction under method (iii) preferably have a high molecular weight (M _w , weight average molecular weight> 6000 g / mol) and a polydispersity M _w / M _n of less than 1.6, Polyalkylene oxides having OH groups; including but not limited to urethanes having residual NCO groups (such as NCO functionalized polyalkylene oxides, particularly blocked isocyanates). The prepolymer can be reacted in a complementary manner with the epoxy, isocyanato, amino, carboxyhalogenide or halogenalkyl group of the corresponding silane with additional reactive groups useful for final cure -OH, -COOH, amino, epoxy Selected from the group of hydrocarbons having groups.

  Suitable isocyanates for the introduction of NCO groups into the polyether can include toluene diisocyanate, diphenylmethane diisocyanate, or xylene diisocyanate, or aliphatic polyisocyanates such as isophorone diisocyanate or hexamethylene diisocyanate.

The degree of polymerization of unit X depends on the viscosity and mechanical property requirements of the cured product. When X is a polydimethylsiloxane unit, the average degree of polymerization based on the number average molecular weight _Mn is preferably 7 to 5000 siloxy units, preferably 200 to 2000 units. In order to achieve a sufficient tensile strength of> 5 MPa, an average degree of polymerization P _{n of} > 250 is suitable where the polydimethylsiloxane has a viscosity of more than 300 mPa · s at 25 ° C. When X is a hydrocarbon unit other than a polysiloxane unit, the viscosity with respect to the degree of polymerization is much higher.

  Examples of a method for synthesizing a polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH, a polymerization method using a metal porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound, for example, US Patent 3,427,256; 3,427,334; 3,278,457; 3,278,458; 3,278,459; 3,427,335; , 696,383; and 6,919,293, including, but not limited to, polymerization processes using the double metal cyanide complex catalysts.

  When the group X is selected from hydrocarbon polymers, polymers or copolymers having isobutylene units are particularly desirable due to their physical properties such as excellent weather resistance, excellent heat resistance, and low gas and moisture permeability.

  Examples of monomers include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes and allyl silanes. Examples of copolymer components are 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether , Isobutyl vinyl ether, styrene, alpha-methyl styrene, dimethyl styrene, beta-pinene, indene and, for example, vinyltrialkoxysilanes such as vinyltrimethoxysilane, vinylmethyldichlorosilane, vinyldimethylmethoxysilane, divinyldichlorosilane, divinyl Dimethoxysilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallyldimethoxysilane, gamma-methacryloyloxypropyl Silane, and gamma - including methacryloyloxypropyl methyldimethoxysilane not limited thereto.

  Examples of suitable siloxane-free organic polymers are silylated polyurethane (SPUR), silylated polyester, silylated polyether, silylated polycarbonate, silylated polyolefin (such as polyethylene, polypropylene), silylated polyester ether And combinations of two or more thereof, but are not limited thereto. The siloxane-free organic polymer may be present in an amount of about 10 to about 90% by weight or about 100 parts by weight of the composition.

  In one embodiment, the polymer component (A) may be a silylated polyurethane (SPUR). Such moisture curable compounds are generally known in the art and include (i) isocyanate-terminated polyurethane (PUR) prepolymers having a hydrolyzable functional group such as alkoxy on a suitable silane, eg, a silicon atom. And secondly reacting with a silane having an active hydrogen-containing functional group such as a mercaptan, primary or secondary amine (preferably the latter), or (ii) a hydroxyl-terminated PUR (polyurethane) prepolymer, For example, it can be obtained by various methods including reacting with a suitable isocyanate-terminated silane having 1 to 3 alkoxy groups. Details of these reactions and details on the preparation of isocyanate-terminated and hydroxyl-terminated PUR prepolymers used therein are described in particular in US Pat. No. 4,985,491; US Pat. No. 5,919,888; 6,207,794; 6,303,731; 6,359,101; and 6,515,164; and US Patent Application Publication No. 2004/0122253. And US Patent Application Publication No. 2005/0020706 (isocyanate-terminated PUR prepolymer); US Pat. Nos. 3,786,081 and 4,481,367 (hydroxyl-terminated PUR). Prepolymer); U.S. Pat. No. 3,627,722; 3,632,557; No. 5,971,751; No. 5,623,044; No. 5,852,137; No. 6,197,912; and No. 6,310,170 (isocyanate). Moisture curable SPUR (silane modified / terminated polyurethane) resulting from reaction of a terminal PUR prepolymer with a reactive silane (eg, aminoalkoxysilane); and US Pat. No. 4,345,053; 625,012; 6,833,423; and US 2002/0198352 (wet curable SPUR obtained from the reaction of a hydroxyl-terminated PUR prepolymer with isocyanatosilane). The entire content of the aforementioned US patent document is incorporated herein by reference. Other examples of SPUR materials include those described in U.S. Pat. No. 7,569,653, the entire disclosure of which is incorporated by reference.

In one embodiment, the polymer component (A) has the formula (3):
R ² _3-c R ¹ _c Si—Z— [R ₂ SiO] _x [R ¹ ₂ SiO] _y —Z—SiR ¹ _c R ² _3-c (6)
Wherein R ¹ , R ² , Z and c are as defined above with respect to formula (6); R is C ₁ -C ₆ alkyl (exemplary alkyl is methyl); x is from 0 to about 10,000, and in one embodiment from 11 to about 2500; y is from 0 to about 10,000; preferably from 0 to 500. ] May be used. In one embodiment, Z in the compound of formula (6) is a bond or a divalent C ₁ -C ₁₄ alkylene group, particularly preferably —C ₂ H ₄ —.

In one embodiment, the polymer component (A) has the formula (7):
^{_{R 2 3-cd SiR 3 c}} R 4 d - [OSiR 3 R 4] x - [OSiR 3 R 4] y -OSiR 3 e R 4 f R 2 3-ef (7)
R ³ and R ⁴ may be the same or different at the same silicon atom, hydrogen; C ₁ -C ₁₀ alkyl; C ₁ -C ₁₀ heteroalkyl, C ₃ -C ₁₂ cycloalkyl; C ₂ -C ₃₀ heterocycloalkyl; C ₆ -C ₁₃ aryl; C ₇ -C ₃₀ alkylaryl; C ₇ -C ₃₀ arylalkyl; C ₄ -C ₁₂ heteroaryl; C ₅ -C ₃₀ heteroaryl C ₅ -C ₃₀ heteroalkyl aryl; C ₂ -C ₁₀₀ polyalkylene ether; or a combination of two or more thereof. R ² , c, x and y are as defined above; d is 0, 1 or 2; e is 0, 1 or 2; f is 0, 1 or 2.

  Non-limiting examples of suitable polysiloxane-containing polymers (A1) include, for example, silanol-terminated polydimethylsiloxane, silanol or alkoxy-terminated polyorganosiloxanes such as methoxy-terminated polydimethylsiloxane, alkoxy-terminated polydimethylsiloxane-polydiphenylsiloxane. Copolymers, and silanol or alkoxy-terminated fluoroalkyl-substituted siloxanes such as poly (methyl 3,3,3-trifluoropropyl) siloxane and poly (methyl 3,3,3-trifluoropropyl) siloxane-polydimethylsiloxane copolymers . The polyorganosiloxane component (A1) may be present in an amount of about 10 to about 90% by weight or 100 parts by weight of the composition. In one preferred embodiment, the polyorganosiloxane component has an average chain length in the range of about 10 to about 2500 siloxy units and a viscosity of about 10 to about 500,000 mPa.s at 25 ° C. It is in the range of s.

Alternatively, the composition may comprise a silyl-terminated organic polymer (A2) that does not contain siloxane units and that is cured by a condensation reaction comparable to that of the siloxane-containing polymer (A1). Similar to the polyorganosiloxane polymer (A1), the organic polymer (A2) suitable as the polymer component (A) contains terminal silyl groups. In one embodiment, the terminal silyl group has the formula (8):
-SiR ¹ _d R ² _3-d (8)
Wherein R ¹ , R ² and d are as defined above. ].

The polysiloxane composition may further contain a crosslinking agent or a chain extender as component (B). In one embodiment, the crosslinking agent has the formula (9):
R ¹ _d SiR ² _4-d (9)
Wherein R ¹ , R ² and d are as defined above. ]belongs to. Alternatively, the crosslinker component may be a condensation product of formula (9), wherein one or more but not all R ² groups are hydrolyzed and released in the presence of water. The intermediate silanol then undergoes a condensation reaction to give Si—O—Si bonds and water. An average degree of polymerization can result in compounds having 2 to 10 Si units.

In one embodiment, the crosslinker has the formula R ³ _d (R ¹ O) _4-d Si, where R ¹ , R ³ and d are defined above. ] Is an alkoxysilane. In another embodiment, the cross-linking agent is of the formula R ³ _d (R ¹ CO ₂ ) _4-d Si wherein R ¹ , R ³ and d are defined above. Acetoxysilane. In yet another embodiment, the cross-linking agent has the formula R ³ _d (R ¹ R ⁴ C═N—O) _{4 -d} Si, wherein R ¹ , R ³ , R ⁴ and d are defined above. . ] Is oximosilane.

  As used herein, the term crosslinker includes compounds comprising at least two hydrolyzable groups and an additional reactive component having less than 3 silicon atoms per molecule not defined in (A). . In one embodiment, the crosslinker or chain extender is an alkoxysilane, alkoxysiloxane, oximosilane, oximosiloxane, enoxysilane, enoxysiloxane, aminosilane, aminosiloxane, carboxysilane, carboxysiloxane, alkylamidosilane, alkylamidosiloxane, Arylamide silane, arylamide siloxane, alkoxyaminosilane, alkylarylaminosiloxane, alkoxycarbamatosilane, alkoxycarbamatosiloxane, imidatosilane, ureidosilane, isocyanatosilane, isothiocyanatosilane, and combinations of two or more thereof May be. Examples of suitable cross-linking agents are tetraethyl orthosilicate (TEOS); methyltrimethoxysilane (MTMS); methyltriethoxysilane; vinyltrimethoxysilane; vinyltriethoxysilane; methylphenyldimethoxysilane; Fluoropropyltrimethoxysilane; methyltriacetoxysilane; vinyltriacetoxysilane; ethyltriacetoxysilane; di-butoxydiacetoxysilane; phenyltripropionoxysilane; methyltris (methylethylketoximo) silane; vinyltris (methylethylketoximo) silane 3,3,3-trifluoropropyltris (methylethylketoximo) silane; methyltris (isopropeneoxy) silane; vinyltris (isopropeneoxy) silane; poly Dimethyl tetraacetoxydisiloxane; tetra-n-propyl orthosilicate; methyldimethoxy (ethylmethylketoxime) silane; methylmethoxybis (ethylmethylketoxime) silane; methyldimethoxy (acetoaldoximo) silane; methyl Dimethoxy (N-methylcarbamato) silane; Ethyldimethoxy (N-methylcarbamato) silane; Methyldimethoxyisopropeneoxysilane; Trimethoxyisopropeneoxysilane; Methyltriisopropeneoxysilane; Methyldimethoxy (but-2-ene) -2-oxy) silane; methyldimethoxy (1-phenyletheneoxy) silane; methyldimethoxy-2- (1-carboethoxypropeneoxy) silane; methylmethoxydi (N-methylamino) silane; Nyldimethoxy (methylamino) silane; Tetra-N, N-diethylaminosilane; Methyldimethoxy (methylamino) silane; Methyltri (cyclohexylamino) silane; Methyldimethoxy (ethylamino) silane; Dimethyldi (N, N-dimethylamino) silane Methyldimethoxy (isopropylamino) silane; dimethyldi (N, N-diethylamino) silane; ethyldimethoxy (N-ethylpropionamide) silane; methyldimethoxy (N-methylacetamido) silane; methyltris (N-methylacetamido) silane; Dimethoxy (N-methylacetamido) silane; Methyltris (N-methylbenzamido) silane; Methylmethoxybis (N-methylacetamido) silane; Methyldimethoxy (caprolactamo) Trimethoxy (N-methylacetamido) silane; methyldimethoxy (ethylacetimidato) silane; methyldimethoxy (propylacetimidato) silane; methyldimethoxy (N, N ′, N′-trimethylureido) silane; methyldimethoxy ( N-allyl-N ′, N′-dimethylureido) silane; methyldimethoxy (N-phenyl-N ′, N′-dimethylureido) silane; methyldimethoxyisocyanatosilane; dimethoxydiisocyanatosilane; methyldimethoxyisothiocyanato Lan; including but not limited to methylmethoxydiisothiocyanatosilane, or combinations of two or more thereof. In one embodiment, the crosslinking agent may be present in an amount from about 1 to about 10% by weight of the composition, or from about 0.1 to about 10 parts by weight per 100 parts by weight of polymer component (A). In another embodiment, the cross-linking agent may be present in an amount of about 0.1 to about 5 parts by weight per 100 parts by weight of polymer component (A). In yet another embodiment, the crosslinker may be present in an amount of about 0.5 to about 3 parts by weight per 100 parts by weight of polymer component (A). Again, as elsewhere in the specification and claims, numerical values may be combined to form new or undisclosed ranges.

The additional alkoxysilane in an amount exceeding 0.1% by weight of the component (A) not consumed by the reaction between the prepolymers Z′-XZ ′ and containing an additional functional group selected from R ⁵ It can also act as an adhesion promoter and is defined and counted under component (D).

  This curable composition further contains the catalyst (C) containing an azaphosphatran compound. The azaphosphatolan compound may be any suitable azaphosphatolan compound. In one embodiment, the azaphosphatolan compound can be selected from any of the compounds of formula (1)-(4) above. The catalyst component (C) can contain a plurality of azaphosphatran compounds. In one embodiment, catalyst (C) comprises an azaphosphatolane compound of formula (2).

  The catalyst component (C) containing the azaphosphatran compound (3, 4) is about 0.01 to about 7 parts by weight per 100 parts by weight of the polymer (A); In the curable composition in an amount of from about 0.1 to about 2 parts by weight per 100 parts by weight of polymer (A); and from about 0.2 to about 1 part by weight per 100 parts by weight of polymer (A). Can exist. Again, as elsewhere in the specification and claims, numerical values may be combined to form new or undisclosed ranges.

The composition optionally includes an adhesion promoter component (D) that is different from component (A) or (B). In one embodiment, the adhesion promoter (D) is not identical to the group R ⁵ , eg, an organofunctional silane including amino silane, and the silane of component (B) or is required to end-capping the polymer (A) Other silanes may be present in amounts exceeding the amount of silane. The amount of unreacted silane (B) or (D) in the reaction to make (A) is up to 200 ° C. so that the free silane exceeds 0.1% by weight of (A) after the end-capping reaction. It can be defined by evaporating at higher temperatures and higher vacuum up to 1 mbar.

  Although azaphosphatolan catalyst compounds can exhibit at least as good curing properties as tin catalysts, adhesion promoters should be added to promote adhesion of the resulting cured product to various substrates. Can do. The azaphosphatolan catalyst material can be used with various adhesion promoters without loss of catalytic activity, as seen with some metallic non-tin catalysts. The combination of an adhesion promoter with an azaphosphatolan catalyst can provide a composition that exhibits improved curing properties compared to the azaphosphatolan compound alone. Thereby, advantageously, several selected amines can be added to fine-tune the speed of azaphosphatran catalyzed condensation curing of silicone / non-silicone polymers containing reactive silyl groups as desired. .

In one embodiment, the composition has the general formula (10):
R ⁵ _g R ¹ _d Si (R ² ) _4-dg (10)
[Wherein R ⁵ is E- (CR ³ ₂ ) _h -W- (CH ₂ ) _h- ; R ¹ , R ² and d are as described above; g is 1 or 2; d + g = 1 to 2; h is 0 to 8, and may be the same or different. An adhesion promoter (D) comprising a group R ⁵ described by Non-limiting examples of suitable compounds include the following:
_{^{E 1 - (CR 3 2)}} h -W- (CH 2) h -SiR 1 d (R 2) 3-d (10a) or (10d)
_{^{E 2 - [(CR 3 2}} ) h -W- (CH 2) h -SiR 1 d (R 2) 3-d] j (10b) or (10f)
[Wherein j is 2 to 3. ].

The group E may be selected from either the group E ¹ or E ² . E ¹ is an amine, —NH ₂ , —NHR, — (NHC ₂ H ₅ ) _a NHR, NHC ₆ H ₅ , halogen, pseudohalogen, unsaturated aliphatic group containing up to 14 carbon atoms, up to 14 May be selected from monovalent groups including an epoxy group-containing aliphatic group, a cyanurate-containing group, and an isocyanurate-containing group.

E ² is a divalent or polyvalent group consisting of amines, polyamines, cyanurate-containing and isocyanurate-containing groups, sulfides, sulfates, phosphates, phosphites, and polyorganosiloxane groups that can include R ⁵ and R ² groups. W may be selected from a heteroatom group selected from a single bond, —COO—, —O—, epoxy, —S—, —CONH—, —HN—CO—NH— units. R ³ is as defined above, R ¹ may be the same or different as defined above, and R ² is defined above and may be the same or different. Good.

［式中、Ｒ¹、Ｒ²およびｄは上に定義された通りである。］。成分（Ｄ）の例は、式（１０ａ−１０ｌ）の化合物を含む。さらに、化合物（Ｄ）の式（１０ｂ）は、式（１０ｍ）の化合物を含むものとする：

［式中：Ｒ、Ｒ²、Ｒ⁵およびｄは上に定義された通りであり；ｋは０から６（一実施形態において望ましくは０）であり；ｂは上記の通り（一実施形態において望ましくは０から５）であり；ｌ＋ｂ≦１０である］。一実施形態において、Ｒ⁵は、

から選択される。 Non-limiting examples of component (D) include:

Wherein R ¹ , R ² and d are as defined above. ]. Examples of component (D) include compounds of formula (10a-10l). Further, formula (10b) of compound (D) shall include the compound of formula (10m):

[Wherein R, R ² , R ⁵ and d are as defined above; k is 0 to 6 (preferably 0 in one embodiment); b is as described above (in one embodiment] Desirably 0 to 5); l + b ≦ 10]. In one embodiment, R ⁵ is

Selected from.

  Exemplary groups of adhesion promoters are selected from the group consisting of amino group-containing silane coupling agents. The amino group-containing silane adhesion promoting agent (D) is an acidic compound having a group containing a silicon atom bonded to a hydrolyzable group (hereinafter referred to as a hydrolyzable group bonded to a silicon atom) and an amino group. Specific examples thereof include the same silyl group as the hydrolyzable group described above. Of these groups, methoxy and ethoxy groups are particularly suitable. The number of hydrolyzable groups may be 2 or more, and compounds having 3 or more hydrolyzable groups are particularly suitable.

  Examples of other suitable adhesion promoters (D) are N- (2-aminoethyl) aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, bis (3-trimethoxy Silylpropyl) amine, N-phenyl-gamma-aminopropyltrimethoxysilane, triamino functional trimethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methylamino Propyltrimethoxysilane, gamma-glycidoxypropylethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxyethyltrimethoxysilane, gamma-glycidoxypropylmethyl Dimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, beta- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, beta- (3,4 -Epoxycyclohexyl) ethyltriethoxysilane, beta- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, epoxylimonyltrimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropylmethyl Dimethoxysilane, beta-cyanoethyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, alpha, o Ga-bis (aminoalkyldiethoxysilyl) polydimethylsiloxane (Pn = 1-7), alpha, omega-bis (aminoalkyldiethoxysilyl) octamethyltetrasiloxane, 4-amino-3,3-dimethylbutyltrimethoxy Including, but not limited to, silane, N-ethyl-3-trimethoxysilyl-2-methylpropanamine and 3- (N, N-diethylaminopropyl) trimethoxysilane, combinations of two or more thereof.

  It is also possible to use derivatives obtained by modifying them, for example amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes and aminosilylated silicones. These amino group-containing silane coupling agents may be used alone or in combination of two or more thereof.

  The adhesion promoter (D) may be present in an amount of about 0.1 to about 5.0 parts by weight per 100 parts of the polymer component (A). In one embodiment, the adhesion promoter may be present in an amount of about 0.15 to about 2.0 parts by weight per 100 parts by weight of the polymer component (A). In another embodiment, the adhesion promoter may be present in an amount from about 0.5 to about 1.5 parts by weight of the polymer component (A). This defines the amount of (D) in the composition of (A), where the content of free silane coming from the end-capping of polymer (A) is less than 0.1% by weight.

The composition may further comprise a filler component (E). The filler component (E) may have different functions as used as a reinforcing or semi-reinforcing filler, i.e. to achieve a higher tensile strength after curing. The filler component may also have the ability to increase viscosity, establish pseudoplastic / shear thinning, and exhibit thixotropic behavior. Non-reinforcing fillers may act as bulking agents. Reinforcing fillers are characterized by having a specific surface area of the relevant BET surface of more than 50 m ² / g, whereby a semi-reinforcing filler having a specific surface area in the range of 10-50m ² / g. So-called bulking fillers preferably have a specific surface area of less than 10 m ² / g and an average particle size of less than 100 μm according to the BET method. In one embodiment, the semi-reinforcing filler is a calcium carbonate filler, a silica filler or a mixture thereof. Examples of suitable reinforcing fillers include but are not limited to fumed silica or precipitated silica, which can be treated partially or fully with organosilanes or siloxanes to make them less hydrophilic and contain water. The rate can be reduced or the viscosity and storage stability of the composition can be controlled. These fillers are termed hydrophobic fillers. Trade names include Aerosil (registered trademark), HDK (registered trademark), Cab-O-Sil (registered trademark), and the like.

  Examples of suitable bulking fillers are ground silica (Celite ™), precipitated and colloidal calcium carbonate (which are optionally treated with compounds such as stearate or stearic acid); fumed silica , Precipitated silica, silica gel and reinforced silica such as hydrophobized silica and silica gel; crushed quartz, cristobalite, alumina, aluminum hydroxide, titanium dioxide, zinc oxide, diatomaceous earth, iron oxide, carbon black, acrylonitrile, polyethylene, polypropylene, poly Including but not limited to powdered thermoplastics such as tetrafluoroethylene and clays such as graphite or kaolin, bentonite or montmorillonite (treated / untreated).

  The type and amount of filler added depends on the desired physical properties of the cured silicone / non-silicone composition. Thus, the filler may be a single species or a mixture of two or more. The bulking filler can be present from about 0 to about 300% by weight of the composition relative to 100 parts of component (A). The reinforcing filler may be present from about 5 to about 60%, preferably 5 to 30% by weight of the composition, relative to 100 parts of component (A).

  The composition of the present invention optionally comprises an acidic compound (F), which can be combined with an adhesion promoter and an azaphosphatolan catalyst to accelerate curing (in the absence of such compound). Compared to curing). Component (F) may be present in an amount from about 0.01 to about 5% by weight of the composition. In another embodiment, 0.01 to about 8 parts by weight per 100 parts by weight of component (A) (pt. Wt.), More preferably 0.02 to 3 parts by weight per 100 parts by weight of component (A) is used, Most preferably 0.02 to 1 part by weight is used per 100 parts by weight of component (A).

The acidic compound (F) may be selected from various phosphate esters, phosphonates, phosphites, phosphonites, sulfites, sulfates, pseudohalogenides, branched alkyl carboxylic acids, combinations of two or more thereof, and the like. Without being bound by any particular theory, acidic compound (F), in one embodiment, is useful as a stabilizer to ensure longer storage times when sealed in a cartridge prior to use in contact with ambient air. It can be. In particular, alkoxy-terminated polysiloxanes lose the ability to cure after storage in a cartridge and may exhibit low hardness under curing conditions. Thus, it may be useful to add a compound of formula (11) that can extend storage time or ability to cure beyond several months.
O = P (OR ⁶ ) _3-c (OH) _c (11)
Wherein c is as defined above; R ⁶ is a linear or branched and optionally substituted C ₁ -C ₃₀ alkyl group, linear or branched C ₅ -C ₁₄ cyclo. alkyl group, C ₆ -C ₁₄ aryl group, C ₆ -C ₃₁ alkylaryl group, a linear or branched C ₂ -C ₃₀ alkenyl radical or a linear or branched C ₁ -C ₃₀ alkoxyalkyl group, Marlophor (registered TM) C ₄ -C ₃₀₀ poly alkenylene oxide group, such as N5 acid (polyether), tri organyl silyl and diorganyl (C ₁ -C ₈₎ - is selected from the group of an alkoxysilyl group. ]. The phosphate can also include a mixture of primary and secondary esters. Non-limiting examples of suitable phosphonates include 1-hydroxyethane- (1,1-diphosphonic acid) (HEDP), aminotris (methylenephosphonic acid) (ATMP), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP), 1,2-diaminoethane-tetra (methylenephosphonic acid) (EDTMP), and phosphonobutanetricarboxylic acid (PBTC).

In another embodiment, a compound of formula O═P (OR ⁷ ) _3−g (OH) _g may be added wherein g is 1 or 2 and R ⁷ is R ⁶ or 1 or Defined as a divalent or polyvalent hydrocarbon containing multiple amino groups. ].

Another class is phosphonic acid compounds of formula R ⁶ P (O) (OH) ₂ such as alkyl phosphonic acids, preferably hexyl or octyl phosphonic acids.

In one embodiment, the acidic compound is a monoester of phosphoric acid of formula (R ⁸ O) PO (OH) ₂ ; a phosphonic acid of formula R ⁸ P (O) (OH) ₂ ; or a formula (R ⁸ O) P (OH) ₂ phosphorous acid monoester [wherein R ⁸ is C ₁ -C ₁₈ alkyl, C ₂ -C ₂₀ alkoxyalkyl, phenyl, C ₇ -C ₁₂ alkyl aryl, C ₂ -C ₄ poly Such as alkylene oxide esters or mixtures thereof with diesters. ] May be selected.

In another embodiment, the acidic compound is a branched C ₄ -C ₃₀ alkyl carboxylic acid, or a combination of two or more thereof, including C ₅ -C ₁₉ acid with an alpha tertiary carbon. Examples of such suitable compounds include, but are not limited to, Versatic ™ Acid, lauric acid and stearic acid. In one embodiment, the acidic compound may be a mixture comprising a branched alkyl carboxylic acid. In one embodiment, the acidic compound are predominantly a mixture of tertiary aliphatic C ₁₀ carboxylic acid.

  Generally, the acidic component (F) is added in a molar ratio of 1 or less with respect to the catalyst (C). In embodiments, the acidic component (F) is added in a molar ratio of (F) :( C) of 1:15 to 1: 1.

  The curable composition may also contain auxiliary substances (G) such as plasticizers, pigments, stabilizers, antibacterial agents, bactericides, biocides and / or solvents. Preferred plasticizers for the reactive polyorganosiloxane (A) are selected from the group of polyorganosiloxanes having a chain length of 10 to 300 siloxy units. 100 to 1000 mPa.s at 25 ° C. Trimethylsilyl-terminated polydimethylsiloxane having a viscosity of s is preferred. Optional solvent (dispersion medium or extender) options may have the role of ensuring uniform dispersion of the catalyst and thereby changing the cure rate. Such solvents include polar and nonpolar such as toluene, hexane, chloroform, methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidinone (NMP) and propylene carbonate. Contains an organic solvent. Water may be an additional component (G) that accelerates the fast-curing two-part composition RTV-2, for which reason water may be in one part of the two-part composition. Particularly suitable non-polar solvents include but are not limited to toluene, hexane, etc., where the solvent must be evaporated after curing and application. In another embodiment, the solvent comprises a high boiling point hydrocarbon such as alkyl benzene, phthalate ester, aryl sulfonate ester, phosphate trialkyl ester or phosphate triaryl ester, which have a low vapor pressure and volume The amount can be increased to provide a low cost. Examples cited by reference may be those of US Pat. No. 6,599,633; US Pat. No. 4,312,801. The solvent can be present in an amount of about 20 to about 99% by weight of the catalyst composition.

  In one embodiment, the composition according to the invention comprises 100 parts by weight of polymer component (A); about 0.1 to about 10 parts by weight of crosslinker component (B); about 0.01 to about 7 parts by weight of catalyst. Ingredient (C) is included. In one embodiment, the composition comprises from about 0.1 to about 5 parts by weight, and in one embodiment from 0.15 to 1 part by weight of the adhesion promoter component (D); from about 0 to about 300 parts by weight. Filler component (E); about 0.01 to about 7 parts by weight of acidic compound (F); optionally 0 to about 15 parts by weight of component (G), wherein components (B)-(G ) Are each based on 100 parts of polymer component (A). In one embodiment, the composition comprises component (F) in an amount of about 0.01 to about 1 part by weight per 100 parts by weight of component (A). In yet another embodiment, the composition comprises catalyst (C) in an amount of about 0.1 to about 0.8 parts by weight per 100 parts by weight of component (A).

  It will be appreciated that the curable composition may be provided as either a one-part composition or a two-part composition. A one-part composition refers to a composition comprising a mixture of the various components described above. The two-part composition may comprise a first part and a second part that are stored separately and then mixed together just prior to application to curing. In one embodiment, the two-part composition comprises a first part (P1) comprising a polymer component (A) and a crosslinker component (B), and a second comprising a catalyst component (C) comprising an azaphosphatolan compound. Part (P2). The first and second portions may include other components (D) and / or (E) and / or (F) and / or (G) as desired for a particular purpose or intended use. . For example, in one embodiment, the first part (P1) may optionally contain an adhesion promoter (D) and / or a filler (E), and the second part (P2) optionally comprises an auxiliary substance (G ), A curing rate modifying component (F) and water (G).

  In one embodiment, the two-part composition comprises (i) a first portion comprising a polymer component (A), optionally a filler component (E), and optionally an acidic compound (F); and (ii) a cross-linking agent. (B), comprising a second part comprising a catalyst component (C), an adhesion promoter (D) and an acidic compound (F), where applied to curing by mixing components (i) and (ii) Until then, parts (i) and (ii) are stored separately.

  An exemplary two-part composition comprises a first part (i) comprising 100 parts by weight of component (A) and 0 to 70 parts by weight of component (E); 0.1 to 5 parts by weight of at least one kind A second part (ii) comprising a cross-linking agent (B); 0.01 to 4 parts by weight of catalyst (C); 0.1 to 2 parts by weight of adhesion promoter (D); 02 to 1 part by weight of component (F).

  The curable composition is used as a material for sealing, mold making, glazing, prototyping, as an adhesive, as a coating, as a seal between different materials, for example as a sealant between a ceramic or inorganic surface and a thermoplastic resin. It may be used in a wide range of applications, including as a paper release, as an impregnation material, and the like. The curable composition according to the present invention comprising an amine compound as a catalyst has, for example, general purpose and industrial sealants, potting compounds, caulks, adhesives or coatings for architectural use, sheet glass fixed and sealed to a metal frame. Insulating glass, structural glazing; may be suitable for a wide variety of applications such as metal plates, car bodies, vehicles, caulking of electronic equipment, adhesives, etc. Furthermore, the composition may be used as either a one-part RTV-1 or two-part RTV-2 formulation and can adhere to a wide variety of metal, inorganic, ceramic, rubber or plastic surfaces.

Ring-opening polymerization Ring-opening polymerization of octamethylcyclotetrasiloxane (D4) using hexamethyldisiloxane is carried out using azaphosphatran of formula (2) in which R ⁹ -R ¹¹ are each isobutyl or methyl as catalyst. To do. The catalyst is prepared at a loading rate ranging from 0.1% to 0.4% by weight. The catalyst is added as a neat liquid or solid and is completely miscible in the reaction mixture. The comparative example uses a heterogeneous acid type catalyst and a soluble base type catalyst (Table 1).

  Example 1: Octamethylcyclotetrasiloxane (100 gm, 0.3365 mol) and hexamethyldisiloxane (0.82 gm, 5.03 mmol) were placed in a round bottom flask equipped with a water-cooled condenser. The catalyst isobutyl substituted azaphosphatran (2) (0.1 gm, 0.292 mmol) was added. The reaction mixture was kept in an oil bath maintained at 100 ° C. Samples were taken periodically and the volatile content of the sample was recorded to monitor the progress of the reaction. A volatile content of 69.1% was measured after 5 hours of reaction.

  Example 2: Octamethylcyclotetrasiloxane (100 gm, 0.3365 mol) and hexamethyldisiloxane (0.82 gm, 5.03 mmol) were placed in a round bottom flask equipped with a water-cooled condenser. The catalyst isobutyl substituted azaphosphatran (2) (0.4 gm, 1.168 mmol) was added. The reaction mixture was kept in an oil bath maintained at 100 ° C. Samples were taken periodically and the volatile content of the sample was recorded to monitor the progress of the reaction. A volatile content of 16.2% was measured after 2 hours of reaction.

  Example 3: Octamethylcyclotetrasiloxane (100 gm, 0.3365 mol) and hexamethyldisiloxane (0.82 gm, 5.03 mmol) were placed in a round bottom flask equipped with a water-cooled condenser. The catalyst methyl-substituted azaphosphatran (2) (0.4 gm, 1.85 mmol) was added. The reaction mixture was kept in an oil bath maintained at 100 ° C. Samples were taken periodically and the volatile content of the sample was recorded to monitor the progress of the reaction. A volatile content of 51% was measured after 4 hours of reaction.

  Example 4: Octamethylcyclotetrasiloxane (20 gm, 0.067 mol), silanol-terminated poly (dimethylsiloxane) (80 gm), and hexamethyldisiloxane (0.82 gm, 5.03 mmol) were fitted with a water-cooled condenser. Into a round bottom flask. The catalyst isobutyl substituted azaphosphatran (2) (0.4 gm, 1.16 mmol) was added. The reaction mixture was kept in an oil bath maintained at 100 ° C. Samples were taken periodically and the volatile content of the sample was recorded to monitor the progress of the reaction. A volatile content of 14% was measured 1 hour after the reaction.

  Example 5: Octamethylcyclotetrasiloxane (20 gm, 0.067 mol), silanol-terminated poly (dimethylsiloxane) (80 gm) and hexamethyldisiloxane (0.82 gm, 5.03 mmol) were fitted with a water-cooled condenser. Place in a round bottom flask. The catalyst isobutyl substituted azaphosphatran (2) (0.1 gm, 0.29 mmol) was added. The reaction mixture was kept in an oil bath maintained at 100 ° C. Samples were taken periodically and the volatile content of the sample was recorded to monitor the progress of the reaction. A volatile content of 20% was measured after 3 hours of reaction.

  Example 6: Octamethylcyclotetrasiloxane (20 gm, 0.067 mol), silanol-terminated poly (dimethylsiloxane) (80 gm) and hexamethyldisiloxane (0.82 gm, 5.03 mmol) were fitted with a water-cooled condenser. Place in a round bottom flask. The catalyst isobutyl substituted azaphosphatran (2) (0.05 gm, 0.145 mmol) was added. The reaction mixture was kept in an oil bath maintained at 100 ° C. Samples were taken periodically and the volatile content of the sample was recorded to monitor the progress of the reaction. A volatile content of 30% was measured after 3 hours of reaction.

  Example 7: Octamethylcyclotetrasiloxane (20 gm, 0.067 mol), silanol-terminated poly (dimethylsiloxane) (80 gm), and hexamethyldisiloxane (0.82 gm, 5.03 mmol) were fitted with a water-cooled condenser. Into a round bottom flask. The catalyst isobutyl substituted azaphosphatran (2) (0.025 gm, 0.0725 mmol) was added. The reaction mixture was kept in an oil bath maintained at 100 ° C. Samples were taken periodically and the volatile content of the sample was recorded to monitor the progress of the reaction. A volatile content of 28% was measured after 4 hours of reaction.

  Example 8: Octamethylcyclotetrasiloxane (100 gm, 0.3355 mol) and 1.3 divinyltetramethyldisiloxane (0.89 gm, 4.77 mmol) were placed in a round bottom flask equipped with a water-cooled condenser. . The catalyst isobutyl substituted azaphosphatran (2) (0.25 gm, 0.725 mmol) was added. The reaction mixture was kept in an oil bath maintained at 100 ° C. Samples were taken periodically and the volatile content of the sample was recorded to monitor the progress of the reaction. A volatile content of 13.1% was measured after 6 hours of reaction.

  Example 9: Silanol-terminated poly (dimethylsiloxane (93 gm) and methyl-terminated poly (dimethylsiloxane (viscosity-100 cst, 11.0 gm)) were placed in a round bottom flask equipped with a water-cooled condenser. Phosphatrane (2) (0.4 gm, 1.16 mmol) was added and the reaction mixture was kept in an oil bath maintained at 100 ° C. Samples were taken periodically and samples were monitored to monitor reaction progress. A volatile content of 12.3% was measured 1 hour after the reaction.

  Example 10 (Comparative): Octamethylcyclotetrasiloxane (100 gm, 0.3365 mol) and hexamethyldisiloxane (0.82 gm, 5.03 mmol) were placed in a round bottom flask fitted with a water-cooled condenser. . 0.4% by weight of base type catalyst was added. The reaction mixture was kept in an oil bath maintained at 100 ° C. Samples were taken periodically and the volatile content of the sample was recorded to monitor the progress of the reaction. A volatile content of 18.6% was measured after 5 hours of reaction.

  Example 11 (Comparative): Octamethylcyclotetrasiloxane (100 gm, 0.3365 mol) and hexamethyldisiloxane (0.82 gm, 5.03 mmol) were placed in a round bottom flask fitted with a water-cooled condenser. . 0.4% by weight of acid type catalyst was added. The reaction mixture was kept in an oil bath maintained at 100 ° C. Samples were taken periodically and the volatile content of the sample was recorded to monitor the progress of the reaction. A volatile content of 11.6% was measured after 4 hours of reaction.

  Example 12 (Comparative): Octamethylcyclotetrasiloxane (20 gm, 0.067 mol), silanol terminated poly (dimethylsiloxane (80 gm), and hexamethyldisiloxane (0.82 gm, 5.03 mmol) were water-cooled condensed. Placed in a round-bottomed flask equipped with a kettle, 0.4 wt% base type catalyst was added and the reaction mixture was kept in an oil bath maintained at 100 ° C. Samples were taken periodically to monitor reaction progress. The volatile content of the sample was recorded to achieve a 9.8% volatile content measured after 3 hours of reaction.

  Example 13 (Comparative): Octamethylcyclotetrasiloxane (20 gm, 0.067 mol), silanol terminated poly (dimethylsiloxane (80 gm), and hexamethyldisiloxane (0.82 gm, 5.03 mmol) were water-cooled condensed. Placed in a round-bottomed flask equipped with a vessel, 0.4% by weight acid type catalyst was added and the reaction mixture was kept in an oil bath maintained at 100 ° C. Samples were taken periodically to monitor reaction progress. The volatile content of the sample was recorded to achieve a volatile content of 13.7% was measured after 3 hours of reaction.

Table 1 illustrates aspects of the above reaction.

  The polymerization reached equilibrium in 2-4 hours with an azaphosphatolan catalyst, but with the same catalyst loading, the reaction took between 3 and 5 hours to reach equilibrium. . This indicates that using azaphosphatran as a catalyst in some cases can reduce cycle times by almost a factor of two. The volatile content using each catalyst after polymerization was 11.6% to 13.7% for the acid catalyst, 9.8% to 18.63% for the base catalyst, and 12% for the azaphosphatolan catalyst. 3% to 69.1%. Table 1 also shows that the polymerization can be successfully performed at a significantly lower catalyst loading when using an azaphosphatolan material as the catalyst.

  Using poly (dimethylsiloxane) containing silanol, octamethylcyclotetra-siloxane and hexamethyldisiloxane as raw materials, the equilibrium is reached when azaphosphatolan is used as a catalyst at a catalyst loading of 0.4 wt%. Reach in 1 hour. On the other hand, equilibrium is reached in 2.5 hours when an acid catalyst is used and in 3 hours when a soluble basic catalyst is used.

  The catalyst is deactivated in the system by heating the reaction system to a temperature higher than 120 ° C. The sample is then treated by passing it through a celite bed and then treated with charcoal to remove the yellow color from the product.

  Example 14 (Condensation Curing) To 4.0 g of silanol-terminated poly (dimethylsiloxane) and 0.5 g of methyltrimethoxysilane are added various amounts of isobutyl substituted azaphosphatran (3). The amount is varied from 10 mg to 40 mg and added as neat material. The reaction mixture is held at ambient room temperature and monitored for cure. A cured product is formed.

  Example 15 (Condensation Curing) To 4.0 g of silanol-terminated poly (dimethylsiloxane) and 0.5 g of methyltrimethoxysilane, various amounts of methyl-substituted azaphosphatran (3) are added. The amount is varied from 10 mg to 40 mg and added as neat material. The reaction mixture is held at ambient room temperature and monitored for cure. A cured product is formed.

  Example 16 (Condensation Curing) To 4.0 g of silanol-terminated poly (dimethylsiloxane) and 0.5 g of methyltrimethoxysilane are added various amounts of isobutyl substituted azaphosphatran (4). The amount is varied from 10 mg to 40 mg and added as neat material. The reaction mixture is held at ambient room temperature and monitored for cure. A cured product is formed.

  Example 15 (Condensation Curing) To 4.0 g of silanol-terminated poly (dimethylsiloxane) and 0.5 g of methyltrimethoxysilane are added various amounts of methyl-substituted azaphosphatran (4). The amount is varied from 10 mg to 40 mg and added as neat material. The reaction mixture is held at ambient room temperature and monitored for cure. A cured product is formed.

  While embodiments of the present invention have been described above, modifications and changes can occur to others upon reading and understanding this specification. The following claims are intended to cover all modifications and changes as long as they come within the scope of the claims or their equivalents.

Claims (30)

  A process for the synthesis of a siloxane polymer by ring-opening polymerization of a cyclic siloxane comprising contacting the cyclic siloxane with azaphosphatran. The azaphosphatran has the formula:

[Wherein R ⁹ , R ¹⁰ and R ¹¹ comprise hydrogen, a linear or branched alkyl containing 1 to 10 carbon atoms, an aromatic group containing 6 to 12 carbon atoms, and nitrogen, or Independently selected from substituted phosphorus groups not included; A is selected from hydrogen, R ¹² or (R ¹³ R ¹⁴ P—N═) t, wherein R ¹² , R ¹³ and R ¹⁴ are hydrogen, Independently selected from linear or branched alkyl containing 1 to 10 carbon atoms and aromatic groups containing 6 to 12 carbon atoms; t is 1 to 10. The process of claim 1, wherein The azaphosphatran is a compound of the following formula

The process according to claim 2, which is selected from a combination of two or more thereof. formula:

[Wherein R ⁹ , R ¹⁰ and R ¹¹ are independently selected from methyl, isopropyl or isobutyl. The process according to claim 1, comprising an azaphosphatolane compound of   The process of any of claims 1-4, wherein the azaphosphatran is present in an amount of about 0.025 weight percent to about 5 weight percent based on the total weight of the cyclic siloxane.   The process of any of claims 1-4, wherein the azaphosphatolan is present in an amount of about 0.1 weight percent to about 0.4 weight percent based on the total weight of the cyclic siloxane. The cyclic siloxane has the formula (R ¹⁵ R ¹⁶ SiO) _n , wherein R ¹⁵ and R ¹⁶ are hydrogen or optionally substituted alkyl, alkenyl, aryl, alkaryl having up to 8 carbon atoms or Selected independently from the aralkyl group, n represents an integer having a value of 3 to 12. The process according to any one of claims 1 to 6, wherein   The cyclic siloxene is octamethylcyclotetrasiloxane (D4), hexamethylcyclotrisiloxane (D3), octaphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, hexamethyl-1,1-diphenyl. 8. The method according to claim 1, which is selected from cyclotetrasiloxane, decamethylpentacyclosiloxane, cyclopenta (methylvinyl) siloxane, cyclotetra (phenylmethyl) siloxane, cyclopentamethylhydrosiloxane, or a combination of two or more thereof. Process.   9. Two or more cyclic siloxanes together with silanol or methyl-terminated poly (dimethylsiloxane), wherein at least two cyclic siloxanes have different ring sizes. The process described.   10. A process according to any of claims 1-9, comprising adding an end blocker material.   The terminal blocker material is selected from hexamethyldisiloxane; octamethyltrisiloxane; decamethyltetrasiloxane; dodecamethylpentasiloxane; tetradecamethylhexasiloxane; hexadecamethylheptasiloxane, or a combination of two or more thereof. Item 11. The process according to Item 10.   12. The process according to any of claims 1-11, further comprising deactivating the catalyst.   Deactivating the catalyst comprises heating the product of the process at a temperature above about 100 ° C. after the reaction; treating the product with water; bubbling carbon dioxide into the product 13. The process of claim 12, comprising: treating the product with a material that neutralizes the catalyst, or a combination of two or more thereof.   14. A process according to claim 12 or 13, further comprising filtering the reaction mixture.   15. The process of claim 14, further comprising treating the filtered reaction mixture with charcoal. (A) a polymer having at least a reactive silyl group;
(B) a crosslinking agent or chain extender;
(C) a catalyst comprising an azaphosphatran compound; and (D) comprising an optional adhesion promoter.
A composition for forming a cured polymer composition. The azaphosphatran has the formula:

[Wherein R ⁹ , R ¹⁰ and R ¹¹ comprise hydrogen, a linear or branched alkyl containing 1 to 10 carbon atoms, an aromatic group containing 6 to 12 carbon atoms, and nitrogen, or Independently selected from substituted phosphorus groups not included; A is selected from hydrogen, R ¹² or (R ¹³ R ¹⁴ P—N═) t, wherein R ¹² , R ¹³ and R ¹⁴ are hydrogen, Independently selected from linear or branched alkyl containing 1 to 10 carbon atoms and aromatic groups containing 6 to 12 carbon atoms; t is 1 to 10. The composition according to claim 16, wherein The azaphosphatran has the formula:

The composition according to claim 17, wherein the composition is selected from the following compounds or a combination of two or more thereof.   19. A composition according to any of claims 16-18, comprising from about 0.01 to about 7 parts by weight of the catalyst (C) per 100 parts by weight of the polymer (A). Wherein the polymer (A) has the formula ^{_{[R 1 a R 2 3-}} a Si-Z-] n -X-Z-SiR 1 a R 2 3-a
Wherein X is polyurethane; polyester; polyether; polycarbonate; polyolefin; polyester ether; and poly having units of R ₃ SiO _1/2 , R ₂ SiO, RSiO _3/2 and / or SiO ₂ Selected from organosiloxanes,
n is 0 to 100;
a is from 0 to 2,
R and R ¹ may be the same or different in the same Si atom, C ₁ -C ₁₀ alkyl; one or more _{Cl, F, N, C 1} -C 10 alkyl substituted with O or S; phenyl ; is selected from or a combination of two or more thereof,; C ₇ -C ₁₆ alkylaryl; C ₇ -C ₁₆ arylalkyl; C ₂ -C ₄ polyalkylene ether
R ² is OH, C ₁ -C ₈ alkoxy, C ₂ -C ₁₈ alkoxyalkyl, oximoalkyl, enoxyalkyl, aminoalkyl, carboxyalkyl, amidoalkyl, amidoaryl, carbamatoalkyl, or two or more thereof Selected from a combination of
Z is a divalent unit selected from the group of a bond, C ₁ -C ₈ alkylene or O. The composition according to any one of claims 16 to 19, which has   The crosslinker component (B) is tetraethyl orthosilicate (TEOS); methyltrimethoxysilane (MTMS); methyltriethoxysilane; vinyltrimethoxysilane; vinyltriethoxysilane; methylphenyldimethoxysilane; Trifluoropropyltrimethoxysilane; methyltriacetoxysilane; vinyltriacetoxysilane; ethyltriacetoxysilane; di-butoxydiacetoxysilane; phenyltripropionoxysilane; methyltris (methylethylketoximo) silane; vinyltris (methylethylketoximo) Silane; 3,3,3-trifluoropropyltris (methylethylketoximo) silane; methyltris (isopropeneoxy) silane; vinyltris (isopropeneoxy) silane; Dimethyltetraacetoxydisiloxane; tetra-n-propyl orthosilicate; methyldimethoxy (ethylmethylketoximo) silane; methylmethoxybis (ethylmethylketoximo) silane; methyldimethoxy (acetaldoximo) silane Methyldimethoxy (N-methylcarbamato) silane; ethyldimethoxy (N-methylcarbamato) silane; methyldimethoxyisopropeneoxysilane; trimethoxyisopropeneoxysilane; methyltriisopropeneoxysilane; methyldimethoxy (but-2) -En-2-oxy) silane; methyldimethoxy (1-phenyletheneoxy) silane; methyldimethoxy-2- (1-carboethoxypropeneoxy) silane; methylmethoxydi (N-methylamino) sila Vinyldimethoxy (methylamino) silane; tetra-N, N-diethylaminosilane; methyldimethoxy (methylamino) silane; methyltri (cyclohexylamino) silane; methyldimethoxy (ethylamino) silane; dimethyldi (N, N-dimethylamino); Silane; methyldimethoxy (isopropylamino) silane; dimethyldi (N, N-diethylamino) silane; ethyldimethoxy (N-ethylpropionamide) silane; methyldimethoxy (N-methylacetamido) silane; methyltris (N-methylacetamido) silane; Ethyldimethoxy (N-methylacetamido) silane; methyltris (N-methylbenzamido) silane; methylmethoxybis (N-methylacetamido) silane; methyldimethoxy (caprolactamo) ) Silane; trimethoxy (N-methylacetamido) silane; methyldimethoxy (ethylacetimidato) silane; methyldimethoxy (propylacetimidato) silane; methyldimethoxy (N, N ′, N′-trimethylureido) silane; methyldimethoxy (N-allyl-N ′, N′-dimethylureido) silane; methyldimethoxy (N-phenyl-N ′, N′-dimethylureido) silane; methyldimethoxyisocyanatosilane; dimethoxydiisocyanatosilane; methyldimethoxyisothiocyana 21. A composition according to any of claims 16-20, selected from: tosilane; methylmethoxydiisothiocyanatosilane, or a combination of two or more thereof.   The adhesion promoter component (D) is (aminoalkyl) trialkoxysilane, (aminoalkyl) alkyldialkoxysilane, bis (trialkoxysilylalkyl) amine, tris (trialkoxysilylalkyl) amine, tris (trialkoxysilyl) The alkyl) cyanurate, and tris (trialkoxysilylalkyl) isocyanurate, (epoxyalkyl) alkyldialkoxysilane, (epoxyalkyl) trialkoxysilane, or a combination of two or more thereof. A composition according to any one of the above. The polymer component (A) has the formula:
R ² _3-a R ¹ _a Si—Z— [R ₂ SiO] _x [R ¹ ₂ SiO] _y —Z—SiR ¹ _a R ² _3-a
[Where:
x is from 0 to 10,000;
y is 0 to 1000;
a is 0 to 2;
R is methyl;
R ¹ is, C ₁ -C ₁₀ alkyl; one or more Cl, F, N, C replaced by O or S ₁ -C ₁₀ alkyl; phenyl; C ₇ -C ₁₆ alkylaryl; C ₇ -C ₁₆ arylalkyl; C ₂ -C ₄ polyalkylene ether; or a combination of two or more thereof, other siloxane units may be present in an amount of less than 10 mol%;
R ² is OH, C ₁ -C ₈ alkoxy, C ₂ -C ₁₈ alkoxyalkyl, oximoalkyl, oximoaryl, enoxyalkyl, enoxyaryl, aminoalkyl, aminoaryl, carboxyalkyl, carboxyaryl, amide Selected from alkyl, amidoaryl, carbamatoalkyl, carbamatoaryl, or combinations of two or more thereof;
Z is —O—, a bond or —C ₂ H ₄ —. The composition according to any one of claims 16 to 22, which has   24. A composition according to any of claims 16-23, provided as a one-part composition.   24. A composition according to any of claims 16-23, provided as a two-part composition comprising a first part (P1) and a second part (P2). 100 parts by weight of component (A),
0.1 to about 10 parts by weight of at least one crosslinking agent (B);
0.01 to about 7 parts by weight of the azaphosphatran (C);
0.1 to about 5 parts by weight of an amino-containing adhesion promoter (D);
0 to about 300 parts by weight of filler (E);
0 to about 7 parts by weight of an acidic component (F);
0.01 to about 15 parts by weight of component (G),
26. A composition according to any of claims 16-25, which can be stored in the absence of moisture and is curable in the presence of moisture upon exposure to ambient air.   27. A method of providing a cured product comprising exposing the composition of any of claims 16-26 to ambient air.   26. A method of providing a cured product comprising combining the first portion and the second portion of claim 25 and curing the mixture.   A cured polymer formed from the composition or method of any of claims 16-28.   30. A cured polymer according to claim 29 in the form of an elastomeric seal, a thermosetting resin seal, an adhesive, a coating, a sealant, a molded article, a mold or an impression material.