JP2016524637A5

JP2016524637A5 -

Info

Publication number: JP2016524637A5
Application number: JP2016514128A
Authority: JP
Filing date: 2014-05-16
Publication date: 2017-06-29

Claims

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

(i) the azaphosphatran is present in an amount from about 0.025 weight percent to about 5 weight percent based on the total weight of the cyclic siloxane, or (ii) the azaphosphatran is the cyclic siloxane. 5. The process of any of claims 1-4, wherein the process 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 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 5 , wherein

The cyclic siloxene is octamethylcyclotetrasiloxane (D4), hexamethylcyclotrisiloxane (D3), octaphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, hexamethyl-1,1-diphenyl. cyclotetrasiloxane, decamethylpentacyclosiloxane, cyclopenta (methylvinyl) siloxane, cyclotetra (phenylmethyl) siloxane is selected from cyclopentasiloxane methylhydrosiloxane or a combination of two or more thereof, according to any of claims 1- 6 Process.

Two or more cyclic siloxanes include with silanol or methyl-terminated poly (dimethylsiloxane), wherein, with a size of at least two cyclic siloxanes are different from each other ring, to any of the claims 1- 7 The process described.

Adding a terminal blocker material selected from hexamethyldisiloxane; octamethyltrisiloxane; decamethyltetrasiloxane; dodecamethylpentasiloxane; tetradecamethylhexasiloxane; hexadecamethylheptasiloxane, or a combination of two or more thereof A process according to any of claims 1-8 .

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; and a material that neutralizes the catalyst further including the process of any of claims 1 9 and processing the product, or to be deactivated the catalyst by a combination of two or more thereof in.

The filtered reaction mixture by and optionally filtering the reaction mixture further comprises treating with charcoal, the process according to claim 10.

(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 12 , wherein

The azaphosphatran has the formula:

The composition of Claim 13 chosen from the compound of these, or its 2 or more types of combination.

15. A composition according to any of claims 12-14 , 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 in any one of Claims 12-15 which has this.

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 The composition according to any one of claims 12 to 16 , which is selected from trisilane; 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) alkyl) cyanurate, and tris (trialkoxysilylalkyl) isocyanurate, (epoxy) alkyl dialkoxy silanes, selected from (epoxy alkyl) trialkoxysilane or a combination of two or more thereof, of claim 12-17 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 12 to 18 , which has

20. A composition according to any of claims 12-19 , provided as (i) a one-part composition , or (ii) a two-part composition comprising a first part (P1) and a second part (P2). object.

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),
21. A composition according to any of claims 12-20 , which can be stored in the absence of moisture and is curable in the presence of moisture upon exposure to ambient air.

21. A method of providing a cured product comprising exposing the composition of any of claims 12-20 to ambient air.

Includes combining the previous SL first portion and said second portion, and curing the mixture, a method of providing a cured product from the two-part composition according to claim 20.

24. Formed from the composition or method of any of claims 12-23 in the form of an elastomeric seal, thermosetting resin seal, adhesive, coating, sealant, molded article, mold or impression material . Cured polymer.