DE1961555C3 - Resin-like polysiloxane molding compound or coating compound that hardens at room temperature - Google Patents

Description

'R ¹

I to the remaining Si atoms in the resinous poly |

; siloxane is 1: 3 to 1:20. - Si - OR *

f 3. Molding or coating compound according to An 40 i

_; Proverb ϊ or 2, thereby gckeimzeichiici that they _Ä ""

I as a curing catalyst ^{Dialkyldiacylzinnverbin- υκ} "

• fertilize, preferably dibutyltin dilaurate, in amounts of 0.1 to 5, preferably 0.5 to 3 weight - in which R ^{1 is} an alkyl or an aryl radical or contains percentages. 45 Interpretation of the group OR ⁸ hst and OR * eia alkoxy radical

: 4. Molding or coating compound according to one with 1 to 4 carbon atoms or the rest

or more of the preceding Assprüd », iqq jj 1 n & s

characterized in that it is in a solution ^l * "« ** "*

medium, preferably an aromatic solution, wherein R ^{3 is} an alkyl, preferably methyl ester, medium, in particular benzene, toluene or XyToI 50 and η has a value of Ϊ or 2, is free or mixtures thereof, is dissolved. of silanol groups and known metal

organic HSnoi ^ iii kauiyssieriü M? 5g "i van contains 0.1 'to 5 weight percent.

The curing of the molding compound according to the invention

j 55 or coating compound probably happens in the

Ii way that in the presence of air humidity and

jl under the action of the organometallic catalysts

ψ_ The invention relates to a hydrolyze under the action of the OR * -Gruppeo and then

- | Water, including humidity, in the event of room condensation.

1 temperature-curing resinous polysiloxane molding compound do As mentioned above, the remainder R ¹ can be

j or coating compound. have meaning of an alkyl radical. Are preferred

If resin-like polysiioxanes (also silicone hafers gs · dis atedersa alkyir residues, such as, for example, methyl or

ί; called) usually consist of mono-, di-, tri- and; Ethyl residue. However, higher alkyls can also be used

tetrafunctional silicon units. Your condensate residue. A silicone resin is described in a Befspcel

ij sation to higher molecular weight compounds and out Ss. in which the radical R ^{1 has} the meaning of an octad

^f curing is thereby effected in that silanes - cylrestes has!. However, these residues act on the resins

groups already softening each other with the elimination of water. This can be for special

1 condense. This requires the application of higher expressions to be desired. The remainder R ¹ can

also have the meaning of an aryl radical, where .the carried out according to the following reaction scheme is -phenyl radical is preferred. the:

The remainder OR ² can have the meaning of a lower

Have alkoxy radicals, which can have up to 4 carbon atoms = SiOH + Cl - SiR ¹ COR ² ) * -> = SiOSiRHOR ² J ₂ . Examples are the methoxy, 5

Ethoxy, n-propoxy, i-propoxy, n-butoxy or this reaction scheme is based on the principle

i-butoxy radical. The OR ² radical can also mean corresponding siloxanols with chlorosilanes to form an alkylene glycol monoether radical of the general formula which have at least two garbyloxy groups. The Ha that is released during the reaction. "Ogen-

lo hydrogen can be absorbed by acid acceptors such as ammo

[OC ₂ H ₄ I _n OR * niak. The reaction becomes purposeful

carried out moderately at elevated temperature.

to have. In this formula, η has a value of 1 or 2. Another, known manufacturing process is based

R ³ is an alkyl radical, preferably the methyl radical. suf the implementation of corresponding siloxanols with tri-

The content of the end groups 15 or tetraalkoxysilanes in the silicone resin: the formula

R ¹ R ¹

. ^R1 ■ 1

I = Si-OH + R ² O-Si-OR ³ -> ^ SiO-Si-OR *

- Si —OR ¹ ao I ■

The invention, under the action of

is variable within wide limits. From the tasks aj water, especially air humidity, in the case of a room for the expert from self-hardening resinous Ροί / siloxane form, that a masses or coating masses for crosslinking with curing can be used anywhere The necessary minimum number of such groups must be used where silicone resins have hitherto been available have to be. Those turns are particularly preferred. However, they are particularly beneficial there Silicone resins that use these groups in a molar 30 ratio, where higher temperatures are not used from 1: 3 to 1:20, based on the remainder. This is e.g. B. the case if borrowed Si atoms of the resin, ünthalUn. the substrate to be coated with the silicone resin

As organometallic hardening catalysts can be temperature sensitive or due to it in principle all from the state of the art (»chemistry dimensioning is not easy for the und Technologie der Silicones ”by Walter Noil, 35 making baking techniques suitable. So suitable Verlag Chemie GmbH, 1968, p. 340), the molding compositions or bonds according to the invention are known be taken, but the di- layering compounds z. B. for the coating of alkyldiacytin compounds, preferably dibutyl luminous tubes or shields, the resins tin diaurate, are preferred. These hardening catalysts can be pigmented with phosphors. Another Analyzers are the silicone resins at any 40, intended use is in the coating tech-time after their production in amounts of 0.1 niche papers, e.g. B, of foiocopy papers, which to 5 percent by weight, preferably in amounts of heat-sensitive pigments. 0.5 to 3 percent by weight added. The subject of the invention was in the following

The examples below are explained in greater detail with the exclusion of atmospheric moisture. The parts specified in the inventive molding compounds 45 examples containing the sator are parts by weight, or coating compounds are practically unlimited in terms of storage ⁽

stable. A particular advantage is that the shape. ...

^: compounds or coating compounds solvent-free dei game l

Can be stored and used provided they manufacture the silicone resin

inherently have a viscosity that their 50

_t work allowed. However, if the resins are for an In a 500 ml three-necked flask that comes with a

ί direct processing too highly viscous or is the reflux condenser, a stirrer, a dropping funnel

_ Applying solutions of synthetic resins from others. and an inlet pipe, 22S g

• Appropriate for reasons, the molding compounds or a 25% solution of a cohydrolyzate of meth-

\ Coating compounds in the compounds 55 thyltrichlorosilane up 'Dimethyldichlorsüan only one

; common solvents, preferably aromatic content of OH Grup _F s of 4.2 weight percent and

Solvents, esters or ketones. a molar ratio of CH _a : Si = 1.2: 1 in toluene. Examples of such solvents are benzene, toluene, weighed out. While stirring and at the same time

19 g of xylene, mixtures thereof, commercially available aromatic conduct from gaseous NH _{3 are added dropwise}

Distillates or solvents on ester and ketone 60 CeH ₈ Si (OCaH ₀ ) J ₁ Cl for 15 minutes at 50 ° C.

- basis, such as ethyl acetate, butyl acetate, ethyl- The molar ratio of OH groups of the vpr-

glycol acetate or methyl ethyl ketone. Cohydrolysates mentioned and Cl in the silane is 1: 1.

The silicone resins can be made from various Si compounds. Stirring is continued for a further hour

be built up. Examples of such units are NH _{3 introduced} at 50 ^° C. Then the

CH ₃ SiO ₃ /. ,, (CHa) ₂ SiO, C _e H heated for ₈ SiO _3/2, (C _e H _{B) a} SiO, 65 reaction mixture slowly to 10O ⁰ C and at

(CHa) ₃ SiO, SiO ₄ fa or (CH ₃ ) HSiO. this temperature was stirred for 1 hour. The received

The production of the silicone resins, which is part of the mixture, is made by filtration of the Ainmo

This invention is not claimed, e.g. B. exempted nickel chloride.

After a temperature load of 200 ⁰ C over

The molding compound according to the invention ₂ 4 hours give products 1 and 2 the cross-cut

The solution obtained is treated with 1% dibutyl values Gt 0.

tin flaurate, based on the solid content. Under Beisoiei 4

Absence of atmospheric moisture occurs no condensation ^y 5

lation, while the silicone resin is painted on a glass plate
and exposed to the influence of humidity

Product after several hours a solid Fflm 490.5 g of a 25 ⁰ / "igea toluene solution of a

forms. Part of the solution is cohydrolyzed by distillation of 135 parts of methyltrichlorosilane,

completely freed from the solvent The aus- io 17.5 parts of dimethyldichlorosflan, 17.5 parts of trim

The remaining ammonium chloride that falls is filtered off. The ihylchlorosilane, 23 parts of methjwichlorosilane and

liquid Dibutylzirmdilamrai "r'sltende 100 ° / ₀ sodium 17.5 parts Tetrachiorsilan containing

Resin remains with the exclusion of humidity and OH grapes of 1.15% are carried out analogously to Example 1

liquid, but condenses bä / * ττκ. / on air humidity- with 20 g CgHsSi (OC ₂ Hs) ₂ Cl corresponding to one

.keit to a fixed pr * '^ ;. 15 OH: Cl ratio of 1: 1 implemented

', ""., .... ErSndansseiaäßs molding compound

Manufacture « · *" of silicone resin

According to the method given in Example 1, although the filtered solution as well as that from the

wsrden 324geicer 25 ⁰ / intrinsically tcluoliscben solution of 20 solvents freed flüssigf dance remain after addition of Cohydrolysaits Methyltrichlorsibn and dimethyl · 1 ° / o Dibatylanndilaurat in the absence of dichlorosilane with a content of OH-groups of humidity liquid. The molding compounds condense 2.6 percent by weight and a molar ratio of sieren, painted on glass plates, with the ingress of CH ₃ : Si = 1.2: 1 with 19.5 g of CH ₃ (OCjHs) ₂ SiCl converted atmospheric humidity to solid films,
sets, corresponding to an OH: Cl ratio of 1: 1. «5

Molding compound according to the invention B e i s ρ i e 1 5

Both the crystalline solution and the solution from the production of silicone resins

Liquid resin freed from solvent remains after addition

of 1% dibutyl tin flaurate with the exclusion of air 30 240 g of a 25% solution of a cohydrolyzate moisture liquid. In the presence of atmospheric moisture, methyltrichlorosilane and dimethyldichlorosilane with hardens the silicone resin. a content of aa OH groups of 2.6 percent by weight

cent and a molar ratio of CH ₃ : Si = 1.2: 1

be i s ρ i e 1 ^ in toluene analogous to Example 1 with 25 g

u. 11 j οι-, t. 35 C ₁₈ H ₃₇ Si (OGjHs) ₂ Cl corresponding to an OH: U production of the silicone resin ratio of 1: 1 . The solution Jes arise-

According to the example! 1, the resin is liquid, the solvent-free product is 324 g of a 25% strength toluene solution of a wacns-like.
Cohydrolysates of methyltrichlorosilane and DimetFyl-

dichloroshan with an OH group content of 40 Molding compound according to the invention

2.6 weight percent and a molar ratio of

CH ₃ : Si = 1.2: 1 with 39 g of CH ₃ Si (OQH ₅ ) ₂ Cl ent- both solution and the solvent

corresponding to an OH: Cl ratio of 1: 2, the waxy resin that has been freed from it also changes after it has set (product 1). Addition of 1 ° / _? Dibutyltin dilaurate with the exclusion of

Using the same procedure, 153 g of 45 air humidity are rt ^ nt. But they condense at 25 ° / ₀ strength toluene solution of a cohydrolyzate glass plates coated, on admission of Luftfeuchtigvon methyltrichlorosilane and Dimethyldivhlorsilan with ness to solid films with greasy handle,
an ai> OH group content of 2.6 percent by weight and a Moi ratio of CH ₃ : Si = 1.2: ί. .
with 28 g QHsSiiOQH ^ Cl corresponding to a 50 examples
OH: Cl ratio of 1: 2 implemented (product I) - production of the silicone resin

The molding compound according to the invention _{In e} ; _NEM 500-mI three-necked flask is allowed to 20Og

OZW. uesememungsmassc _{thner 2} 5 "/ _o igen toluene solution of a Cohyärmy-

Products 1 and 2 are made with 1% dibutyltin sates of methylirichlorosilane and dimethyldichloro

added dilaurate and remain liquid even in the presence of silane with a content of OH groups of 2.6 Gs solvents with the exclusion of atmospheric moisture percent by weight and a molar ratio before = CH ₃ : Si. They condense on ingress of moisture = 1.2: 1 with 63.7 g tetraethoxysilane and 1.1 g of titanium

TO solid bodies. butoxide catalyst under reflux for 4 hours

Applied to deep-drawn trays, soaked in the air. Then the solvent is distilled,

films that have condensed out show the excess tetraethoxyilane and the resulting

Values given in the table. from which alcohol. 6.8 g of ethanol were formed

(theoretically 7.04 g ethanol).

⁶ 5 Molding compound according to the invention

The liquid resin freed from the solvent remains under even after the addition of 1% dibutyltin dilaurate

product Erichsenticfung Cross-cut Pencil hardness 1
2 8, ': mm
9.9 irm GtI
GtO 5H
2H

Exclusion of moisture in the air. The molding compound CH _{: |} : Si - = 1.2: 1 are condensed analogously to Example 1 with 117.8 g over, painted on glass plates, with addition CH ₃ S! (OC ₂ H ₄ OCH :,) ₂ Cl corresponding to an OH: CI-iritl from LuftJeücnliglccil to fixed films. Ratio of V: 2 implemented.

Example? S.

Manufacture of the silicone resin

■ 20Og cirtcr 25% toluene resin solution of a
Ctthydfolysatcsvon methyltrichlprsiian and dimethyldichlorosilane with a content of OH groups of Ίο 4.2 percent by weight and a molar ratio of inventive molding compound

Both the nitrated solution and the liquid resin, which has been freed from the solvent, remain _{nutty even after the addition of t / o} dibufyltin dilaurate with the exclusion of "air humidity".

Painted on glass plates, forming solid films when exposed to humidity.

Claims (2)

I 961 555 I ■ 1 2 temperatures. Silicone resins are therefore baked in in the patent claims: The condensation of the silanol groups can be 1. Under the action of water, including pointing silicone resins also cause that Humidity, 5 maa catalysts which cure at room temperature add such catalysts Resinous polysiloxane molding compounds br *, -beschich- are organometallic compounds such. B. sealing compound, characterized by butyltin dilaurate. The addition of curing catalyst the resinous polysiloxane end groups, the gate must be done immediately before processing, Structure as the mixtures only have a limited pot life ίο and already at room temperature within a short time R ¹ condense out time (»Chemistry and Technology of I Silicone «by Walter Noil, Verlag Chemie GmbH, - Si —OR * 1968, p. 357 ff.) - One can end prematurely counteract hardening by removing the resins OR * i ₅ in relatively large amounts of solvents dissolves and / or very small amounts of catalyst zasettL where R ^{1 is} an alkyl radical or an aryl radical, or Both process measures are, however, the meaning of the group OR * and OR * is a technically disadvantageous one. In the first case, the residual solvent ao medium amounts must escape from the alkoxy radical with 1 to 4 carbon atoms or the applied resin solvent layer, with very less films [OC ₂ H ₁ I _n OR ⁹ layer thicknesses arise that are also often porous are. Due to the small amounts of catalyst where R * is an alkyl radical and η has a value of then the curing of the films also follows ratio-1 or 2 has, silanol group free is moderately slow. and organometallic hardening systems known per se. The object of the invention is for space catalysts Curing in amounts of 0.1 to 5 weight temperature and despite the addition of a catalyst contains procert. excluding water, including air 2. Molding or coating compound after moisture, synthetic resins that can be stored for any length of time in. Claim 1, characterized in that the Mot- form of one-component systems to obtain the Group 30 ratio is storage-stable even in the absence of solvents yy _x stay. »1 Surprisingly, this task can be accomplished by a I 1 resinous polysiloxane in the invention ! - Si - OR * molding compound or coating compound are dissolved, I · '35 which end groups of the structure I OR *