DE1810157C - Process for the production of organosilicon resins - Google Patents

Description

useless. _{0> 3g bjs QM Vl} ny | groups,

0.75 to 0.96 phenyl groups and

1.94 to 1.99 phenyl, vinyl and methyl groups

The present invention relates to a method for having and 10 groups each C _e H ₅ SiOi, ₅ ,

_{Production of 5 to 9 groups} that can be used without solvents (CH ₃ J ₃ SiO ₀ "

and stable organosilicon _{resins by hydro 25 to 50} groups (C _e H ₆ ) _a SiO;

_{Analysis of alkylchlorosilanes} , arylchlorosilanes and _{3Q to 50 groups} (CH ₃ ) (CH ₂ - = CH) SiO.

y.nylchlorsilanen and condensation, the overall characterized a _{5 2 BJS 12 Gru} pp _GU nts (CH _{3) 2} SiO
is characterized by the fact that a mixture is used for hydrolysis

from included.

10 moles of phenyltrichlorosilane, _A ^Di _u ^e resins prepared according to the invention will :.

5 to 9 months! Trimethylchlorosilane, ^d » ^Tch , mixed hydrolysis and mixed condensation of

25 to 50 moles of diphenyldichlorosilane, 3 ° phenyltrichlorosilane, Tr.methylchlorosilar D.pheny di-

30 to 50 moles of methyl vinyldichlorosilane and chlorosilane, methylvinyldichlorosilane and dimethyldi-

2 to 12 moles of dimethyldichlorosilane chlorosilane in the above for the corresponding groupings given molar ratios obtained,

used. This operation can be carried out according to the usual

It is known that various types of organic driving are performed. For example, it is possible to use silicon resins for a wide variety of purposes, to develop a mixture of organochlorosilanes in one. It is also known which diluents are suitable, such as Diteil, to be able to dispose of resins which can be used without ethyl ether, toluene, xylene, cyclohexane or methyl with the aid of a solvent, to dissolve cyclohexane, the whole thing in motion to and you know that the resins that hold a certain 4 ° and add the hydrolysis water.
Conversely, one can also add the organic solution liciumatome, a very special one of the organochlorosilanes to interest in suitable motion due to the suitability of these groups for holding water.

Crosslinks in the warmth and improvements The hydrolysis temperature is not critical and can

the properties that can be varied within wide limits for certain applications. This enables

purposes can have. use of a diluent with a little

These flowable resins with vinyl groups can boiling point, such as diethyl ether, the

belong to the linear type, such as those in simple reflux of the reaction mixtures, the

the French patent 1 166 405 described reacti η to control effectively.

new, or of the crosslinked type, such as 50 The amounts of diluent used

wise those in French patent specification 1,059,884 should be sufficient to use the organochlorosilanes

described. and to make their mixed condensates soluble. the

The previously known products of the actual amount of water can be crosslinked in a very large excess Type drawn from the condensation of the number of groups to be hydrolyzed Represent the hydrolysis of silanols 55 Si - Cl derived from halosilanes. When all organochlorosilanes with are obtained, however, are only at the expense of an un- which are brought into contact with water for hydrolysis, complete condensation flowable. the mixture will generally remain in for some time

On the one hand, this leads to a lack of storage stability. Movement, then the acidic aqueous

with the formation of an excessively condensed and removed for fractions, and the solution of the organosilicon

Use of the product as such uncured mixed condensate is achieved with water until it is neutral

netcn state and on the other hand washed to a release.

of water in the course of the Umwan.dlungsbchand- These mixed condensates in solution

during the formation of products on which are then made of polymers with low molecular weight

Based on such resins. weight, the linkages Si - O - Si and numerous

I ^{7 For} certain purposes, the products contain 65 groups Si - OH. You have to be into polymers

require the excellent properties to be converted as clck- with higher molecular weight,

have Irish insulation and considerable mc- which practically no longer contain any Si - OH groups,

chanischu stresses with sometimes increased which are then storage-stable.

3 4

In order to carry out this process of "continuing production of switch-off parts, insulation cylinders, stepping", the solution of mixed condensates can be used for fuse links, molded and extruded parts, after adding a catalyst, such as intermediate layers for transformers and plates with sodium hydroxide, potassium hydroxide or a connection terminal , to use. The isolation quaternary ammonium or phosphonium hydroxide, cylinder can be heated by winding glass fibers, sulfuric acid, phosphoric acid or an earth activated by a catalyzed resin coated onto a strong acid. That from the mandrel, which is rotated at the desired speed, the condensation of the groups Si - OH are produced. It is sufficient to then cross-link the whole thing by means of other water, which is then heated to a degree. Removed the liners for transsein formation. to formators and the plates with terminals

If the organosilicon diluent is used, glass fabric / resin can be made from laminates.

mixed condensates have a slightly increased boiling point.

It is advisable to replace it at this stage of the ^r The laminates can be replaced by another dilution method after the usual methods of preparation of the resins, by stacking one on top of the other with medium with a higher boiling point, so that one layer of catalyzed Resin coated has a reflux temperature of at least 100 ° C. Glass fabric pieces and subsequent pressing in

p g

dj: _ _o .._ _o «_" i "i _o . a: ~ «" ckiiHntio A ** HwU / ärmc under oerineem pressure and the following

Resin much faster, and the water is then heated in a ventilated drying cabinet for comparison in For η of the binary mixture of water - completion of the hardening process,
thinning agent removed or carried along by this 30 The mechanical properties of this layer the latter. fabrics are excellent, in particular the remains

It is preferable to work with a very low flexural strength, measured at 150 ° C., over 10 kg mm ² .

Amount of diluent. The electrical properties are also good. So

mixed at greatly increased temperatures, for example the dielectric strength is well over 10 kV / mm

200 to 250 C, heat without diluting even after immersing the laminates for 24 hours

medium to be handicapped, which allows the duration of the in water at room temperature (25 ° C). The spe-

Reduce heating accordingly. Preferably specific volume resistance is in the size

Do not exceed 250 ° C. Order of 10 ¹⁵ II-cm and remains above 10 ¹⁰ i2-cm

As before, the water formed is removed with the aid of the diluent from its formation after the laminates have been immersed in manure for 24 hours. There 3 ° water at room temperature. The water absorption can be separated in a separator, and these materials is after 24 hours of a diluent can wiet ^J r Mischkonden- the dip in distilled water sowed at room temperature are added. less than 0.1 percent by weight of the laminates.

The amount of catalyst introduced is not The following examples illustrate the invention,
critical. In general, amounts between 35 _R are suitable. _c . ,.
1 and 5 parts by weight per 1000 parts by weight to be treated. Example 1
the Harz Mountains. After all of the condensate has escaped, the heating is stopped in a 6-1 condenser with a device, which is preferably equipped with a weak and cooler and a dropping funnel for agitation, a thermometer, a reflux solution , volatile acid or base, depending on the type of catalyst, is added to diethyl ether, 169.2 g (0.8 mol) of C ₆ H ₅ SiCl ₃ , neutralized and then filtered, and the 708 g (2, 8 mol) (C _e H ₅ ) ₂ SiCl ₂ , 452 g (3.2 mol) (CH ₃ ) diluent is obtained by distillation in vacuo (CH ₂ = CH) SiCl ₂ , 82.6 g (0.64 mol) (CH ₃ ) ₂ SiCl ₂ and removed. 60.8 g (0.56 moles) of (CH ₃ ) ₃ SiCl.

When the reaction takes place with practically no dilution In this agitated mixture one brings medium, it is advantageous to take 2 liters of water within 30 minutes using the Add a certain amount of diluent to the dropping funnel. It is held in neutralization for a further 30 minutes and to facilitate filtration. movement, then removes the aqueous layer and

The resins produced in this way according to the invention are washed away with the remaining ether layer three times

Liquids with a viscosity of 3000 to 100 OOOcSt per 300 cm ^{3 of} water,

at 20 ⁰ C can vary. 50 The ether of the ethereal layer becomes subsequently

The liquid resins prepared according to the invention by distillation initially by heating under

can with the help of a peroxide, such as atmospheric pressure up to a temperature of

Dicumyl peroxide, tert. - Butyl perbenzoate or di- 100 ⁰ C in the mass and then removed in vacuo,

tert-butyl peroxide, are cured. taking the distillation under a reduced

The amount of peroxide used is in general 55 pressure of 25 mm Hg at a temperature of

mean 0.5 to 3 percent by weight of the resin, 150 ⁰ C removed in the residue.

Fillers can be introduced in order to reduce the viscosity. 50 cm ^{3 of} toluene are added to the residue

to improve mechanical properties. You can add 1.5 g of crushed potassium hydroxide and add it

in this regard glass fibers, glass fabric and glass spheres, then the whole thing for 2 hours under nitrogen

pyrogenic or precipitated fine atmosphere at 200 ⁰ C, whereby that from the condenser

shared silicas, diatomaceous earths, calcium carbonate, sation of the groups Si - OH originating from one another

Soot, the various natural silicates, asbestos, water azeotropically towed away and in one compartment

Name quartz powder and cork powder. Per 100 weight that is collected. After cooling the mass on

parts of resin can be filled up to 300 parts by weight - about 100 ° C, 3 g of acetic acid are added and the mixture is stirred

add substance. 65 Whole 1 hour, keeping the temperature constant

The resins produced according to the invention are mainly held at 100.degree.

The residue neutralized in this way is made by adding

offers for the formation of insulation, for example ^{diluted to 500 cm 3 of} toluene. After adding animal

Charcoal is refluxed for a few minutes and filtered. The toluene of the filtrate is then removed by distillation under reduced pressure, initially at 15 mm Hg and then at 4 mm Hg, the heating temperature gradually reaching 200 ° C. in the mass. There remain then 1005 g uncolored oil which virtually no groups Si-OH has more enthäU and a viscosity of 10,800 cSt at 20 ⁰ C and its atoms and groups to be present in accordance with the amounts of the starting materials used in the following ratios and proportions:

(CH, + C, H, + CH, = CH) / Si = 1.97 CHJSi = 0.8 CH, = CH / Si = 0.4

Dielectric loss factor tg <5:
ASTM D 257-58 standard

Dielectric constant : ASTM standard D 257-58 BeJS-IO ¹ Hz Beil 10 Hz 5 _{Bü 20} o _C 3.3
6th 3.3
3.9 After a 24 hour hold
in water of 20 ⁰ C ...

VinvleruDDen 8.1

° / ₀ groups C ₆ H ₅ SiO ₁₆ iu

o / ₀ groups (C _e H ₅ ) ₂ SiO 35

° / ₀ groups (CH ₃ ) (CH ₂ = CH) SiO ... 40

° / ₀ groups (CH ₃ ) ₂ SiO 8

° / ₀ groups (CH ₃ ) ₃ SiO _{0> 5} 7

The properties of the resin produced according to the invention can be seen from the following tests:

Eleven squares with dimensions of 15-15 cm in the direction of the weft and warp are cut out of a desized glass fabric with a satin weave with a specific weight of 308 g / m ". An amount of dicumyl peroxide equal to 1.5 ° / ₀ accounts for its weight to. then, bringing the thus catalyzed resin in a layer on each square on, assigns the eleven squares then successively in exactly identical manner, ie in matching directions of warp and weft, it is brought into a press and heated for 2 hours under a pressure of 5 bar at 150 ⁰ C. The curing is terminated du.ch 4stündiges heating in a ventilated oven at 200 ° C.

From the laminate thus obtained, which has a thickness of 3 mm and contains about 36.5 percent by weight of silicone resin, parallelepiped test specimens with dimensions of 25 × 65 × 3 mm are cut out in the direction of the chain. Measuring the flexural strength to fracture in accordance with ASTM D-790-63 at 2O ⁰ C and 150 ⁰ C and receives results here as 31.5 and 11 kg / mm *.

The dielectric properties of these laminates are as follows:

Dielectric strength: ASTM D. 149 standard

at 20 ° C 15 kV / mm

after 24 hours of immersion in
Water at 20 ^° C. 11.5 kV / mm

Volume resistivity: ASTM standard

D 257-58

at 2O ⁰ C 1-10 "Ω-cm

after 24 hours of immersion in
Water at 20 ° C for 2 x 10 ^u Ω · cm

10 40

40 3 7 8.1

The water absorption after immersion in water at 20 ^° C. for 24 hours is 0.05 ¹ V ₀ .

Example 2

Following the procedure of Example 1, a second resin is made from the same organochlorosilanes the following features:

ir-H. 4- CH. 4- CH. = CH) / Si = 1.97

C ₆ H ₆ ZSi = u, *

CV ₁ = CH / Si = 0.4

% Groupings CeH ₆ SiO ,,,

% Groupings (C _e H _s ) _a SiO

° / ₀ groupings

(CH ₃ ) (CH ₂ - CH) SiO

° / ₀ groupings (CH ₃ ) ₂ SiO

⁰ Z ₀ groupings (CHj) ₁₁ SiO ₀₁₅

Weight percent vinyl groups

Viscosity at 20 ° C 27 200 cSt

As described in Example 1, B, laminates are produced with this resin. The characteristics of this Laminates, determined according to the same standards as in Example 1, B, are the following:

a) Mechanical properties:
Flexural strength to break

at 20 ⁰ C 30.3 kg / mm ²

Flexural strength to break

at 150 ⁰ C 11.5 kg / mm ²

b) Electrical properties:
Dielectric strength at

20 ⁰ C 19.5 kV / mm

Dielectric strength according to
24 hour immersion in

Water at 2O ⁰ C 16 kV / mm

Specific volume resistance at 20'C 1 · 10 «Ω · αη

Specific volume resistance after 24 hours
Immersion in water at 20 ⁰ C 1.7 x 10 ^{ΙΟ Ω} · cm

Dielectric loss factor tg <5:

Keep
° C "" At. <· 10 'St. ax • 10 ⁶ Hz At 2O ⁰ C. 4.5
300 ΙΟ- ³
ΙΟ- ³ 2.5
90 • ΙΟ " ³
• ΙΟ- ³ After 24 hours
in water from 20

Dielectric constant

Keep
"C ... At 5 • ΙΟΉ7 At 1 • 10'Hz At 20 "C 9
240 • ΙΟ ³
• ΙΟ ³ 3
47 • ΙΟ- ³
• ΙΟ " ³ After 24 minutes
in water from 20

At 20 ° C

After holding for 24 hours
. 10-3 ⁵ in water at 20 ° C

At 5-10 »Hz

3.5

9.5

BeU-IO ⁶ Hz

3.45

5.15

c) Water absorption after immersion in water at 20 ° C. for 24 hours 0.07%.

Claims (1)

Temperatures are able to endure, after all Claim: the previously known products, both the those of the linear type as well as those of the Process for the production of non-solvent type, not yet satisfactorily usable and stable organos. . silicon resins produced by the hydrolysis of alkyl chlorine according to the claimed process silanes, arylchlorosilanes and vinylchlorosilanes Organopolysiloxane resins are solvent-free and condensation, dadur.h identifiable and storage-stable and allow, exceptionally, that a mixture for hydrolysis is used for the production of products, which at the same time from ίο good mechanical and electrical properties 10 moles of phenycrichlorosilane, J? * ": / ¹ " ^si f ^M maintained elevated temperatures. 5 to 9 moles of trimethylchlorosilane. ^^ ^Resins ^ ^{marry from} groupings of the formulas 25 to 50 moles of diphenyldichlorosilane, C, H _s SiO, _t , (C, H _s ) £ iO, (CH,), SiOe. _s , 30 to 50 moles of methyl vinyl dichlorosilane and (CH ₃ ) (CH ₁ = CH) SiO and (CH ^ iO. 2 to 12 moles of dimethyldichlorosilane ' ⁵ ...... _L. ο ι where £ ie on average per silicon sodium