FR2472592A1 - COMPOSITIONS OF POLYORGANOSILOXANES CURABLE UNDER THE ACTION OF A RADIATION - Google Patents

Abstract

COMPOSITIONS THAT DO NOT RELEASE ACETIC ACID ON CURING. THEY INCLUDE: A.100PARTS OF A POLYORGANOSILOXANE WITH SILANOL TERMINATIONS ESSENTIALLY CONSTITUTES REASONS RESPONDING TO THE FORMULA: (CF DRAWING IN BOPI) B. FROM 2 TO 200 PARTS OF AN ALCOXYSILANE MEETING THE FORMULA: (CF DESIGN IN BOPI) . FROM 0.1 TO 20PARTS OF AN ONIUM SALT OF AN ELEMENT OF GROUP VB, GROUP VIB OR GROUPEVIIB, AND D. FROM 0 TO 20PARTS OF AN ACTIVE ORGANIC COLOR; KNOWING THAT, IN THE FORMULAS, R IS CHOSEN FROM THE GROUP CONSTITUTED BY MONOVALENT HYDROCARBON RADICALS AND MONOVALENT HALOGENATED HYDROCARBON RADICALS, R IS CHOSEN FROM THE ALKYL RADICALS IN C1-C12, WHICH R IS CONSIDERED IN THE LITTLE GROUP REPRESENT R AND GLYCIDYLALKYL RADICALS IN C1-C8, A REPRESENTS A WHOLE NUMBER BETWEEN 2 AND 4 INCLUDED, B REPRESENTS A WHOLE NUMBER BETWEEN 0 AND 2 INCLUDED AND THE SUM OF A AND B IS EQUAL TO 4. APPLICATION TO THE COATING MANUFACTURING.

Description

Prior to the present invention, composites

  polyorganosiloxane compositions which can be vulcanized at ambient temperature.

  As described in U.S. Patent No. 3,070,555, the present invention was based on the moisture curing of a mixture of a silanol-terminated polydiorganosiloxane and an acyloxysilane. Although it has been found that these polyorganosiloxanes can be used

  curable in the presence of moisture for various applications

  during hardening, they release acetic acid

  tick that gives off an unpleasant odor, and reacts

  with various substrates. We have achieved better results

  results when it was found, in accordance with U.S. Patent No. 3,816,282, that radiation-curable polyorganosiloxanes could be cured using a polymercaptosiloxane and a source of radicals.

  free. It was found that one could use as catalyst

  onium salts of elements of groups Vb, VIb and VIIb

  for the condensation of hydrolysable silanes under

  ultraviolet light as indicated in the patent

  United States of America No. 4,101,513.

  The present invention is based on the discovery that one

  can obtain hardened polyorganosiloxane compositions

  sands by radiation which do not give off an odor of acetic acid and which are curable by both UV and visible light, using a mixture of a polydiorganosiloxane with silanol and an alkoxysilane in combination with an onium salt of a group Vb, VIb or VIIb element. Unlike the compositions of the United States patent

  No. 3,616,282, the hardened polyorganosiloxane compositions

  The radiation sands of this invention are based on the condensation of the silanol groups. In the case where it is desired to harden under the action of the

  visible light, an active organic dye can be used.

  suitable in combination with the onium salts indicated above. The present invention provides radiation-curable polyorganosiloxane compositions which comprise: (A) 100 parts of a silanol terminated polyorganosiloxane consisting essentially of chemically combined diorganosiloxy units having the formula: (1) R2SiO (B) from 2 to 100 parts of an alkoxysilane having the formula: (2) (R10) a (R2) bSi, (C) from 0.1 to 20 parts of an onium salt of a member of group Vb, group VIb or group VIIb, and (D) from 0 to 20 parts of an activating organic dye,

  since in the formulas R represents a hydrocarbon radical

  monovalent bond or a halogenated monovalent hydrocarbon radical, R1 represents a C1-C12 alkyl radical, R2 is chosen from the group consisting of the radicals that can represent R and the glycidyl-C1-C8 alkyl radicals, a represents an integer inclusive between 2 and 4 inclusive, b represents an integer between 0 and 2 inclusive and the sum of a and

of b is equal to 4.

  Among the radicals that may be represented by R in formulas (1) and (2), for example, monovalent aryl radicals, monovalent halogenated aryl radicals, such as phenyl, xylyl, chlorophenyl or naphthyl groups; aralkyl radicals, such as benzo, phenylethyl;

  aliphatic and cycloaliphatic radicals such as

  alkyl, alkenyl, cycloalkyl and chloroalkyl groups such as methyl, ethyl, propyl, chloropropyl, vinyl, allyl, trifluoropropyl, cyclohexyl, etc., and cyanoethyl, cyanopropyl, cyanobutyl, etc. For example, among the radicals that may represent R 1, methyl, ethyl, propyl, and the like. The onium salts used in the practice of the present invention have the formula:

(3) [Y], [J] -

  wherein J represents a non-nucleophilic counter-ion (counter-ion) which will be better defined below, and Y represents a cation selected from the group consisting of an aromatic halonium cation: (4) (R) (Rd) D]

L J

  an aromatic cation of the group Vb, (5) (R3) f (R5) g (R6) h E] and an aromatic cation of the group VIb, [R3) j (R7) k (R8) m G1, L (3) k

  knowing that in the formulas, R represents a radical radical

4-

  monovalent aromatic acid, R represents a radical radical

  divalent aromatic acid, R and R7 represent

  monovalent aliphatic organic dyes selected from the group consisting of alkyl, cycloalkyl and

  substituted alkyls, R and R represent radicals

  polyvalent ganics, chosen from the group consisting of

  aliphatic radicals and aromatic radicals formally

  mantle a condensed heterocyclic or cyclic structure,

  with E or G, D represents a halogen radical such as I, E

  present an element of the group Vb selected from N, P, As, Sb and Bi, G represents a group VIb element selected from S,

Se and Te.

  "c" represents an integer equal to O or 2 "d" represents an integer equal to O or 1 and when c is equal to O, d is equal to 1, and when d is equal to O, c is equal to 2 "f" represents an integer between 0 and 4 inclusive, "g" represents an integer between 0 and 2 inclusive, "h" represents an integer between 0 and 2 inclusive, and the sum of " f "+" g "+" h "is equal to 4 or the combination value of E," j "represents an integer from 0 to 3 inclusive," k "represents an integer from 0 to 2 inclusive , and "m" represents an integer equal to 0 or 1, and the sum of "j" + "k" + "m" is equal to 3 or the combination value of G. R3 may represent identical radicals or different carbocyclic or heterocyclic aromatics having 6 to 7 carbon atoms, which may be substituted with 1 to 4 monovalent radicals selected from alkoxy radicals

  C1-C12, C1-C12 alkyl, nitro, chloro, etc .; R rep-

  More particularly, phenyl, chlorophenyl, nitrophenyl, methoxyphenyl, pyridyl and the like. We can cite

  among the radicals that can represent radical R4 radicals

  Slow as: R5 and R7 may represent C1-C12 alkyl radicals, such as methyl, ethyl, etc., alkyl radicals

  substituted as -C2H4OCH3, -CH2COOC2H5, -CH2COCH3, Q 'is -

  as defined below, etc., R6 and R8 may represent structures such as: R'-N

N N

THIS

  R 'wherein Q' is selected from the group consisting of -O-, (-CH2-) n ,, = NR 'and -S-, n represents an integer from 1 to 4 inclusive, Z is selected from R 'group consisting of -O-, -S- and, and R' is selected from the group consisting of hydrogen, C1-C8 alkyl radicals, C6-C13 aryl radicals, etc. Among the non-nucleophilic opposing ions, it can be mentioned that in the formula (3)

  MQd, where M is a metal or a metal

  loide, Q represents a halogen radical, and d represents

  an integer, for example between 4 and 6 inclusive.

  In addition, J may also represent, in formula (3), non-nucleophilic counterions such as perchlorate, CF 3 SO 3 - and C 6 H 4 SO 3 -, etc. J may also represent, in the formula (3) a halide counterion such as Cl-, Br-, F-, etc., or nitrate, phosphate, etc. Among the metals or metalloids that may be represented by M, in the formula MQd indicated above, for the non-nucleophilic anion that can be represented by J in formula (3), transition metals such as Sb, Fe, Sn, Bi, Al, Ga, In, Ti, Zr, Sc, V, Cr, Mn, Cs, rare earth elements such as lanthanides, and for example Cd, Pr, Nd, etc.,

  actinides and for example Th, Pa, U, Np, etc., and

  talloides like B, P, As, etc. Among the complex anions which can be represented by MQd ', for example, BF 4, PF 6, AsF 6, SbF 6, FeC 5 SnCl 6, SbCl 6, BiC 15 etco, mention may be made, for example, of halonium salts.

  corresponding to formula (3) and comprising cations corresponding to

in formula (4):

CH3

+ - + _

  t BF PF NO2 etc. For example, among the onium salts

  of elements of group Vb corresponding to formula (3) and comprising

  cation having the formula (5): CH CH3

-N-CH-C

CH3 BF4 SbF6

+ (I "2- C -BF4,

CH2 ,,. C.-.- BF4-,

'PF4,

(<EP-CH 2-Ct AsF.

  (C 1 -C 2 COOC 2 H 5 Pr 6 (P + t) 4 BF 4 OH BF 4 OH As + BF 4

CH3 O

Q C H 2 1 BF4

vt Bi-CH2-C BF4, etc.

  For example, among the onium salts of

  Group VIb with formula (3) and comprising

  cations corresponding to formula (6).

CH3

-CH2- S BF4-,

CH3

3- -CH2-S PF6-

02N Q C-CHjS) AsF6

/ '?, ± ,.

I o OTDqS

- z m- o o-

LI '/ + o

Cuo -

o-H - s

SZ HD-.

1: '.Q

91Don-

d9-f -MaDU a = ID li u

he -

Q C-CH2Se 3 PF6, etc.

  Examples of polyorganosiloxanes with terminal

  silanol compounds consisting essentially of chemically combined units of formula (1), linear polydiorganosiloxanes having the formula

(7) R

HO - + Si0- H 1 q R

  wherein R is as defined above and q represents

  an integer whose average value is included

  between about 5 and 3000 inclusive. This fluid presents, pre-

  Preferably, a viscosity of from about 2000 to about 50,000 centipoise at 25 ° C. These silanol-terminated fluids can be prepared by treating a high molecular weight polyorganosiloxane, for example a polydimethylsiloxane.

  with water, in the presence of a mineral acid, or a cat-

  basic polymer to bring the viscosity of the polymer into the

  desired range. The processes for the preparation of these polyorgano-

  High molecular weight siloxanes used in the production of the silanol terminated polydiorganosiloxane of formula (7) are well known. For example, diorganohalosilanes such as dimethyldichlorosilane, diphenyl-dichlorosilane, methylvinyldichlorosilane and the like can be hydrolyzed. or mixtures thereof to produce a low molecular weight hydrolyzate. It can then be equilibrated to obtain a polyorganosiloxane of higher molar mass. Balancing of cyclic polysiloxanes

  cyclic octamethyltetrasiloxane, octaphenyltetra-

  cyclic siloxane, or mixtures thereof, will also make it possible to obtain high molecular weight polymers. These polymers are preferably removed from the equilibrium catalyst by conventional methods prior to use as described in US Pat.

3,153,007.

  Silanol-terminated polyorganosiloxanes having viscosities of less than 1200 centi-

  by treating polyorganosiloxanes consisting essentially of

  essentially of units of formula (I) chemically combined with pressurized water vapor. We will find others

  processes that can be used to prepare polyorgano-

  silanol-terminated siloxanes, described in greater detail in US Pat.

2,607,792.

  For example, among the alkoxy silanes of formula (2), methyltrimethoxysilane,

  dimethyldimethoxysilane, methyl orthosilicate, ortho-

  ethyl silicate, n-butyltrimethoxysilane, trimethyl

  methoxysilane, methyltriethoxysilane, phenyl trimethoxy

  silane, diphenyldiethoxysilane, and condensation products

  a higher molar mass, such as dimethyltetra-

  methoxydisiloxane, glycidyl-2 trimethoxysilane.

  For example, among the organic dyes

  which can be used in the practical application of the

  vention, acridine orange, acridine yellow, phos-

  phine R, benzoflavine, hematoporphirine, 9,10-diethyl anthracene, Michler's ketone, tetoflavin T, perylene, coronene, etc. In the practice of the invention, it is possible to mix together the various constituents of the mixture, such as the silanol-terminated fluid, the alkoxysilane, and the salt.

  onium. In the case where onium salt and palydiorgano

  If the silanol-terminated siloxane or "silanol-terminated fluid" does not form a solution, the onium salt can first be dissolved in a liquid diluent which is inert to the components of the mixture. Suitable inert diluents include ethanol, ethyl acetate,

  ethers, acetonitrile, etc. We can add the alkoxysi-

  lane before or at the same time as the onium salt to the silanol fluid. In cases where it is desired to cure under the action of visible light, the organic dye can be added to the constituents in total or partial darkness for

  minimize the premature activation of onium salt.

  Various fillers or pigments may be incorporated into the radiation-curable composition, such as, for example, silica, talc, mica, titanium dioxide, gypsum, iron oxide, alumina, sawdust, glass fibers, graphite, carbon black, dust, etc. The amount of charge that can be used can vary widely. However,

  the choice of the load and its quantity can affect the effi-

  This increases the curing rate of the mixture, and the amount can therefore vary widely, depending on the application requirements and the length of curing that can be tolerated. A conventional mixture will include, for example, from 1 to 30 parts

  charge per 100 parts of silanol terminated fluid.

  The compositions of this invention can be used.

  as sealants for construction, caulking compounds, etc. The compositions of the present invention can be stored for an unlimited period of time. However, in the case where an organic-activating dye is used in

  the mixture, the polyorgano-

  curable siloxane away from daylight for

  minimize the activation of onium salt.

  In order for those skilled in the art to more easily put the invention into practice, the following examples are given for illustrative purposes, but they are not meant to limit

  the invention. All parts are by weight.

Example 1

  A mixture of 10 parts of a poly-

  silanol terminated dimethylsiloxane having a

  of 35,000 centipoise and an OH content of 0.09% of ethyl orthosilicate, and 0.3 part of di (4-n-butyl) phenyl iodonium hexafluoroarsenate in the form of 0.0762 mm-on a glass slide and irradiated using a GE H3T7 medium pressure mercury vapor arc lamp at a distance of 17.78 cm. After an irradiation time of 20 seconds we have

got a rubbery film.

  A copper wire is immersed in the U.V. curable polyorganosiloxane above, and the coated wire is exposed to ultraviolet light as previously described. An adherent coating of elastomeric silicone rubber is obtained which can serve as an insulating coating

  on the wire after 10 seconds of exposure.

Example 2

  The procedure of Example 1 was repeated except that

  used methyltri-thoxysilane instead of orthosilane

  ethyl licate. The hard silicone composition was spread in the form of a 0.0254 nm film on a coverslip

  of glass and irradiated at a distance of 17978 cm.

  In the process of Example 1, a cross-linked rubber film was obtained after 10 seconds of rradiation. At this point, the same composition of curable silicone was applied to the resin in the form of a film of 0.degree. In spite of the fact that it has been hardened in the manner indicated above, there is no permanent use of paper coated with adhesives which are resistant to the kraft paper. The coating was not coexistent. It was not removed by rubbing. A solution comprising 0 g of hexafluoro-rbz was prepared. (5) Polyvinyl chloride. 1.0 g of fluid was added to the mixture. Difunctional hydroxy salts: - have a viscosity of 35,000 cps, and! The orthosilicate of the mixture will be set with the above mixture in the form of a film of 0.0254 mm -1 on an aluminum plate and ventured at a distance of 7.662 cm -1. a lamp GE H3T70 Fifteen

  seconds of irradiation were enough to lead to a

  Example 1 A polymeric mixture was prepared using a hydroxyl terminated polydimethylsiloxane fluid having a viscosity of 47,000 cp, 5 parts of 2-glycidyl trimethoxysilane, and a portion of a salt having a viscosity of 47,000 cp. Phenylthiotriphenylsulfonitum having the formula: S SQ AsF6- When the above mixture was irradiated for 1.0 minutes, in the form of a 0.0254 mm film deposited on a glass slide, there was obtained a transparent hard film. Irradiation was carried out using a steam arc lamp

  of GE H3T7 medium pressure mercury.

  The phenylthiotriphenylsulfonium salt prepared

  As follows: A mixture of 19.6 parts of 86% potassium hydroxide, 33 parts of thiophenol and about 120 parts of dimethylacetamide was heated to a temperature of 120.degree.

  stirring, to remove the water. When we have collected

  After 6.5 parts of water, 26.3 parts of para-dibromobenzene were added to the resulting mixture and the mixture was heated to reflux. After 6 hours of refluxing, the mixture was allowed to cool and 300 parts of water were added. A tan colored solid was obtained which was filtered and washed with water several times. The product was then dried. 34.7 parts of 14-dithio-14-phenylbenzene were obtained from the preparation process. A mixture of 7.35 was heated

  parts of the previous disulphide, 11.75 parts of hexafluoro-

  arsenate of diphenyliodonium and 0.2 part of benzoate

  of copper for 3 hours at 120 C. The mixture was washed several times

  resulting reaction mixture with about 50 parts of diethyl ether and the remaining solid was recrystallized from its 95% ethanol solution. We obtained a 45% return

  crystalline product of very light tan color

  with a melting point of 69.75, and the elemen-

  next: Calculated C: 51.3%, H: 3.50%, S: 11.43%, Found C: 51.21%, H: 3.59%, S: 11.37%. According to the process

  of preparation, a triarylsulfonium salt having

  dant in the formula: \ Q S Q S AsF6 Example 5

  0.02 parts of perylene used as

  to the reaction mixture of Example 4. Then,

  The mixture was placed on a glass slide and another glass slide was placed on the first to make a glass-glass bond. After irradiating the mixture through the glass

  for 1.5 minutes, using a bright light projector

  GE EBR 375W, a permanent link was obtained.

Example 6

  One part of a polydimethylsiloxane was

  hydroxy compounds having a viscosity of 47,000 centipoises

  and 0.1 part of didodecylphenyliodo hexafluoroantimonate

  4 parts of ethyltrimethoxysilane. The solution was

  in the form of a film of 0.0508 mm on an aluminum board.

  and irradiated with a GE H3T7 medium pressure mercury vapor arc lamp placed at a distance of 24 cm. The film hardened to turn into a hard film

  transparent after one minute of continuous irradiation.

Example 7

  0.01 part of perylene was added to the solution of Example 6 and the film was deposited in the foregoing manner on an aluminum panel. The panel was irradiated with visible light using a GE EBR 374 W projector.

  got a hard transparent film after a minute of irra-

  diation using the lamp above placed at a distance

10.16 cm.

Example 8

  Example 6 was repeated except that the photoinitiator was replaced by

16 -

  (0eS SbF6 A cure time of 1.5 minutes was required for

  obtain a non sticky hard coating.

  Although the examples above only relate to

  some of the very many hard silicone compositions

  cissable under the action of radiation in accordance with

  In the present invention, it is to be understood that the present invention relates to a much greater variety of silanol-terminated polydiorganosiloxane silicone compositions comprising units of formula (I),

  aromatic onium as indicated in the foregoing description of

  and optionally an activating organic dye.

Claims (9)

  A radiation-curable polyorganosiloxane composition characterized in that it comprises: (A) 100 parts of a silanol terminated polyorganosiloxane consisting essentially of units having the formula: R2SiO, (B) of 2 to 200 parts of an alkoxysilane having the formula: (R) (R2 (C) from 0.1 to 20 parts of an onium salt of a Group Vb, Group VIb or Group VIIb element and (D) from 0 to 20 parts of an activating organic dye, wherein in the formulas R is selected from the group consisting of monovalent hydrocarbon radicals and halogenated monovalent hydrocarbon radicals, R1 is selected from the group consisting of C1-C12, R2 is selected from the group consisting of radicals that can represent R and C1-C8 glycidylalkyl radicals, a represents an integer between 2 and 4 inclusive, b represents an integer between 0 and 2 inclusive; and the sum of a and b is equal to 4.   2. Composition according to claim 1, characterized in that the silanol-terminated polydiorganosiloxane is   a silanol terminated polydimethylsiloxane.   3. Composition according to claim 1, characterized in   that the alkoxysilane is ethyl orthosilicate.   4. Composition according to claim 1, characterized in   what the onium salt is hexafluoroarsenate di (n-bu- 4-tylphenyl) iodonium.   5. Composition according to claim 1, characterized in that the onium salt is: c'soL @ PF 6 6. Composition according to claim 1, which the onium salt is characterized in SbF 7. Composition according to the claim that the onium salt is: (12H25 I +   8. Composition according to the claim   what the dye is perylene.   9. Composition according to the claim   that the dye is Mitchler's ketone.   6, characterized in SbF6 1, characterized in 1, characterized in that