DE2152270C3 - Process for the preparation of equilibration products of organosiloxanes n - Google Patents

Description

The invention relates to a method for making a wide range of organopolysiloxanes by Rearrangement of siloxanes using a packing of macro-linked sulfonic acid groups containing cation exchange resin having a specific pore volume of at least about 0.01 cc / g. One embodiment of the invention relates to rearrangement or, in particular, to equilibration from organopolysiloxanes with low molecular weight to ovganopolysiloxanes with higher Molecular weight, such as oils, resins and rubbery products, being the organosiloxanes low molecular weight by a package containing a macro-crosslinked sulfonic acid group Cation exchange resin with a specific pore volume of at least about 0.01 ccm / g flow be left. Another embodiment of the invention is the rearrangement of organopolysiloxanes high molecular weight, e.g. B. solvated rubbery products, solvated resins, oils, fats or gels to form cyclic and linear organosiloxanes with a lower molecular weight, such as volatile organosiloxanes or oils, being solvated high molecular weight organopolysiloxanes flow through the bed of the macro-crosslinked, sulfonic acid group-containing cation exchange resin be left.

In particular, the invention relates to a continuous process for the rearrangement of solvated Organopolysiloxanes, which consists in allowing organopolysiloxanes to react as above, the solvated restructured organopolysiloxanes are separated from the ion exchange resin and that Product is separated to isolate a product with the desired boiling point range and the undesired fractions are continuously returned to the process.

The invention also relates to the process mentioned, wherein the outflowing organosiloxane in is in a state of equilibrium of chemical bonds.

It is known that organopolysiloxanes by rearrangement reactions can be produced, the silicon-oxygen-silicon bonds being practical be arbitrarily rearranged. Rearrangement reactions of organopolysiloxanes are triggered by strong Bases and strong acids catalyzed. The siloxane l'mlaeerunticn catalyzed by strong acids and strong bases are often used in the technical Her position of organopolysiloxanes with a higher Mr Lekularuewicht from Organosüoxanen with lower Molecular weight and vice versa.

The catalysts used so far are strong bases, such as the alkali metal bases (e.g. lithium oxite Sodium hydroxide, potassium alkoxides, potassium silanolate and cesium hydroxide), the quaternary bases, wi Tetraalkylammonium hydroxide and alkoxide and tetraalkylphosphonium hydroxide and alkoxide. soii strong acids, such as the complex Lewis acids, hydrohalic acids, sulfuric acid. Bnrsäun and trifluoromethylsulfonic acid. It was made for dii Rearrangement of siloxane bonds also as suitable catalysts certain acids on support prescribed how acid treated carbon, acid treated silicates, acid treated Clays and synthetic "gel-like" cation exchange resins.

However, each of the above catalysts have process limitations. which are surprisingly avoided when the specific macro-crosslinked ion exchange resin according to the invention is used as a catalyst. For example, the alkali metal bases require temperatures above 100 ° C. and the quaternary bases work at temperatures above about 90 ° C. At these high catalytic temperatures, the carbon-silicon bond is cleaved in a number of organosilicon compounds, causing undesirable side reactions. In addition, the high temperatures in catalysis require structurally complex high-pressure containers for the cyclic volatile substances, which have a high vapor pressure. The use of acidic catalysts offered only minimal improvement in the rearrangement of siloxanes with the exception of complexes of ice (III) chloride-hydrogen chloride and sulfuric acid, both of which allow siloxane rearrangement below 10 () ^r C. It will be readily apparent, however, that the presence of such acidic catalysts necessitates chemical neutralization of the effluent, thereby requiring additional procedures and steps to separate the effluent from the catalyst and reagents. In addition, sulfuric acid is required in high concentrations of 7. B. two parts per 100 parts of siloxane.

In the case of acidic catalysts on a support. d. H. Catalysts that are physically in at least the Surface of a carrier particle are incorporated, the catalyst can be separated from the effluent product and the isolated catalyst particles can then be regenerated for reuse will. The carrier substances for the acids vary in terms of particle size. By decreasing Particle size could increase the rearrangement rate. Carriers with small particle size, like clays, are impractical because of the pressure drop in the catalyst bed for economic Manufacturing is too high. The use of small particle size carriers also increased the extent to which the catalyst was carried over into the effluent, which in turn makes an additional separation stage necessary.

In U.S. Patent 28310OS is one method for the production of certain silicone oils described, wherein a cyclic siloxane with a compound that Contains monofunctional silyl groups, in the presence

> incs of dilute acid treated solid catheter are generally on the order of only a few The exchange resin, which is in a fine dispersion, is available for minutes. Therefore, the invention

is implemented.

In this patent the use of Fine-grained KatjonausiauschstoffTc treated with dilute acid. like carbon. Kaolin, montmorillonite / quartz, charcoal, fuller's earth unrl

Process considerable economic opportunities. The terms "macro networking" and "macro networking" as they have been used up to now and in the description, the examples and the claims are used refer to a porous mi-

• Described in an ucl-like synthetic resin. crospheric structure. This particular structure is

Defined in Examples 1 and 2 of the subsequent US Pat. No. 3,037,052. To the Writing is a comparison of the effectiveness of an io in the case of the catalyst used according to the invention macro network. The structure used to define sulfonic acid groups is referred to herein as cation exchange resin in relation to the unreal reference to this patent specification, contain the abundance of gel-like sulfonic acid groups- Thus the expression »resin with macro-

the ion exchange resins under the same re-crosslinked structure "or even shorter" contain macro processing conditions. The Reaktionsbedin- i _{5-crosslinked} resin "on a resin are a network of _un2en in Examples 1 and 2 moderate compared with microscopic channels possesses and by a loading <~ prescribed reaction conditions with sonderes polymerization Jen been obtained high temperature (100 to 200 ⁰ C) with long reac- is. This particular polymerization process lasts (4 to 9 hours) of the USA patent is that the monomer mixture is in the presence of 28 31008. In addition, the effluent 20 of a precipitant is polymerized, which has a - "- ■ 1 - = - ■ - «· _-: _.-_ ,. ■■., Is a liquid that (a) acts as a solvent for the monomer mixture and is chemically inert under the polymerization conditions and (b) is present in such an amount and has such a low solvation 25 has an effect on the crosslinked copolymer product that a phase separation of the product takes place, as follows from the fact that the copolymer product is cloudy when it is exposed to a liquid

with a different refractive index

according to the invention practically free of resin while the finely dispersed resins of the USA. Patent can easily be carried along into the oil obtained as a product, which is a special process step of filtering makes it necessary.

In US Pat. No. 33 22 722 there is an exchange of alkoxy groups for acyloxy groups
described in the case of siloxanes by batchwise reaction using strongly acidic catalysts. In
of this patent are known strong acids such as 30 mixed. Sulfuric acid, with sulfonated macrovcrnetzlen Kai- The cation exchange resin is of the mn type

ion exchange resins (Amberlysi 15) equated. Sulfonic acid substituted nuclei. These resins can

Furthermore, the siloxane-alkoxy / ÄcyloxVAus- z. B. by sulfonation of a network-like copolymer exchange when using a sulfonated resin sate of styrene and a polyvinylidene monomer. according to this patent for periods of about 35 such as divinylbenzene, trivinylbenzene or Pclyvinyi-12 up to 60 hours at temperatures of 20 to 100 C ether of polyhydric alcohols, such as divinyloxy

Example 13 below is the siloxane-alkoxy ester interchange using a packing with the catalyst according to the invention with a batch Implementation according to US Pat. No. 33 22 722 compared. As it turns out, is the dwell time according to the known method greater than

11 25 hours at 80 to 90 ⁰ C, while the dwell

time suitable to the used in the invention catalytic converters _45, which is a specific pore volume of tor 14 minutes at 27 ° C, by the same at least about 0.01 cc / g and preferably accessible by the degree of exchange, which is a highly surprising improvement .

It has been found that when using organosiloxanes,. . .

through a pack of a macro-networked shark, the method by introducing mercury are summarized in the following table in the flow with a pore volume of over 0.01 ccm / g. This allows rearrangement to occur at a surprisingly high rate at moderate temperatures;
in many cases the balance was in less than
one hour at a temperature below 100 ^° C. at ₅₅
Low molecular weight siloxane feeds
achievable.

While many resins have heretofore been used for catalyst bed packing, it was surprising to find such a large increase in the rate of reaction. The time spans for establishing equilibrium according to the prior art of 12 to 60 hours at temperatures of 80 to 100 ^° C. have been drastically reduced to 30 minutes or less at 60 ° C. In the actual technical implementation, if the desired outflowing product is a mixture that is not in the same state, the residence

üthane and trivinyloxypropane can be obtained. The sulfonating agent can be concentrated sulfuric acid. Be oleum, sulfur trioxide or chlorosulfonic acid. Not all macro-linked cation exchange resins with sulfonic acid groups are equally suitable according to the invention. It was found that only such macro-crosslinked sulfonic acid cation exchange resins in practicing the invention

0.03 ccm / g. Various macro-crosslinked resins and their corresponding specific pore volumes, measured according to the porosimetric method

IWIkV.llUV.ll li.mt.iiui ■ .J w · · ~ - .. -. . . . . . .

also reproduced a similar product:

Miikrovcrnclzlcs H; ir /

*! Ambcrliie-200

*) Ambcrlite-252

*) Ambcrlite-lR-120 (gel-like)

*) Amberlysi-15
**) Dowcx-70
**) D0WCX-5OW-X8

Average volume

0.0213 0.0041 0.0033 0.0325 0.0231

lliias Co .. Philadelphia.

* | Goods / calibration of the company Rohm &

Penna. LISA. . . ,

♦ I goods / calibrations from Do «Chemical Co. Midland. Me.

In the figure, the measurement results are on some of these resins.

The macro furrows given in the table were obtained Resins contribute to a siloxane rearrangement 60 C with the same feed as follows! use:

(a) A mixture of 1960 g of cyclic dimethylsiloxanes and 40 g of Hxamethyldisiloxan (2.4 cSl at 25 C) was through a column of 1 cm diameter given that a dry sulfonic acid-Kalionenaiistauschcrharz (62 ecm) with an average internal pore volume of 0.0325 ecm g (Amberlysl 15), at 60 C. The viscosity at 25 C of a sample which, after 8 minutes of dwell time in the Acid had been withdrawn. had risen to 120 cSl.

(b) A second, equal amount of the same starting mixture was passed through a bed of a dry sulfonic acid potassium ion exchange resin with an average internal pore volume of 0.0231 ccm / g (Dowex 70th H 'form) under the conditions given by experiment (a). The viscosity at 25 C reached 97 cSt after a residence time of 26 minutes.

(C) A third, equal amount of the above feed was passed through a bed with a dry Sulphonic acid chalk ion exclusion resin. that an average internal pore volume of 0.0213 ecm g (Amberlitc 200) under the conditions of the experiment (a) given. The viscosity at 25 C reached 94 cSt after 30 minutes of processing.

(d) A fourth, equal amount of the above feed was through a bed of dry sulfonic acid cation exchange resin with a average internal pore volume of 0.0041 ccm / g (Ambcrlilc 252) under the conditions given by experiment (a). The viscosity at 25 C reached only 2.7 cSl after a residence time of 90 minutes.

The weather wedges were (.lurch the change in viscosity per cell unit change in each of the resins mentioned is determined and carried out by the curve (du df) is shown, the viscosity being plotted against the line. The measured rearrangement speeds were then used as a function the specific pore volumes in the various resins shown in the figure. The symbols used in the reverberation of one har (s) were as follows:

I l; ir / Sjnih.i! il 1 ;;. l

Amber! Ite-2 (Xr G

Amberlile-252 ^k

Amberlite-lR-120 "(gel-like)

Amberlyst-15 ¹ <; T \

Dowex-70 "

As can be seen from the figure, resins with pore volumes below about 0.005 ecm g showed no change in viscosity and therefore no period for rearrangement while resins have pore volumes over Approximately 0.01 ecm g of measurable degrees of rearrangement showed. The larger the pore volume, the larger it was Rearrangement of the siloxanes. Macro-network resins with specific pore volumes above 0.03 ecm g are Im best suited to technical work.

The high transfer rates. which can be achieved when carrying out the invention, are measured by the dwell time, i.e. H. currently, during which the organosiloxane is in contact with the resin. In a continuous process the flow rate through a bed packed with the resin during one pass is calculated as follows:

Dwell time =

OriMiiosiloxane

Volumetric feed rate Pack 11 η s; svo! u men (ecm I

(ecm mini

Other arrangements of the catalyst bed, such as a Flow bell, stationary reactors and packings that are recycled naturally have a modified one Equation. For example, the residence time in a stationary bell reactor is equal to the reaction time.

As mentioned, under equilibrium there is equilibrium the chemical bond, i.e. the point at which the rearrangement of individual compounds is favored in the same way. In the case of equilibrium rearrangement, this is the case in practice Equilibrium measured as the end point of viscosity as this represents the point at which equilibrium is reached sew while another viscosity add-on is too slow. to be measured yet. This Point is determined when the viscosity is plotted against the cell and as an asymptotic viscosity designated. The equilibrium dwell is d: snn the time it takes to reach equilibrium or to reach the F.iuK iskosilät.

In Example 4 it is made clear that a mixture \ on predominantly cyclic siloxanes. when equilibrated according to the invention, an equilibrium dwell time from 65 minutes at 60 (hai

Λιιν Example 2 shows that a mixture \ on i: \ clischen Siloxanen tiiiii Hcxamclhvldisiloxan. if it is rearranged, an equilibrium dwell of about 10 minutes at 41 C "hai.

From Example 15 it can be seen that low molecular weight liquid silicones, the "'- phenylpropylsiloxane can achieve a rearrangement of about 5.5 hours at 25 C.

As a result, organosiloxanes have that contain lower alkylresles, extremely short equilibrium residence times. while such with free-hanging aromatic radicals as phenylethyl groups. have considerably longer equal dwell times. It is believed to be a animal disorder by the freely hanging aromatic groups

caused during rearrangement in the microscopic pores of the macro-crosslinked resin.

Organosiloxanes that only contain alkyl groups with 1 to

Have 5 carbon atoms, store up to equilibrium in periods of less than about 2 hours at 60 ° C. while those that only have alkyl groups Have 1 to 3 carbon atoms, until equilibrium in cell spaces under one hour at 60 (' rearrange.

Organosiloxanes that have aromatic groups with I to IK carbon atoms reach equilibrium by initial storage in periods of less than about ^ hours at 60 C.

The invention is not, and is, limited to any particular group of organopolysiloxanes applicable to all organosiloxanes in which the organosiloxanes are a mixture or a compound represent at least one structure of the formula

(Y) _n SiO ₄ _ "

"2

wherein Y is hydrogen, a substituted or unsubstituted monovalent hydrocarbon group or a divalent hydrocarbon group and α has the value from 1 to 3 inclusive. Preferably Y contains 1 to about 30 carbon atoms. The groups represented by Y can be the same or different in a given siloxane unit.

The organosiloxanes which can be used according to the invention are preferably free from siloxy ester bonds, such as Silylalkoxy or silylacyloxy groups, however, may optionally contain such groups.

The organosiloxanes as such or in solvation Form only traces of the known poisons for sulfonic acid ion exchange resins, such as strongly ionic compounds, residues containing functional silane halogen atoms and strong bases because of the siloxane rearrangement is inhibited by undesirable and relatively large amounts of these toxins.

With regard to the molecular weight of the organosiloxanes which can be used according to the invention, there is none Restriction. The only practical limitation of the mixture fed is the viscosity, which to allow a flow through the resin bed, wherein high pressure losses are to be avoided. the Viscosity can of course be controlled by properly metering the solvent. It was found, that feed mixtures of organosiloxanes with viscosities up to about 10000 cP are practical Results give and viscosities in excess of 10,000 cps are not considered useful in the process will.

The process conditions for carrying out the invention are not critical within narrow limits. at Atmospheric pressure, the reaction temperature is from about 10 to about 100 C. Lower temperatures can be used but do not provide any significant benefit. Temperatures above 100 "C can be used even if the catalyst is somewhat at temperatures above about 150 "C decomposed. The reaction can be carried out at atmospheric pressures, but pressures can also be used can be used above or below atmospheric pressure.

The siloxane rearrangement is a reversible process; that is, the low molecular weight organopolysiloxanes are convertible to high polymers and high polymers to siloxane compounds with a Conversely, lower degree of polymerization can be converted. Such rearrangements are in the present a suitable rearrangement catalyst continued until an equilibrium mixture of different siloxanes has been formed. For example, in systems that mainly contain such equilibrium mixtures consist of diorganosiloxy units with or without triorganosiloxy units, in general a relatively small amount of cyclic siloxanes as well as higher molecular weight linear siloxanes. However, the quantitative ratio of cyclic siloxanes varies by weight from system to system System, largely dependent on the nature of the organic substituents on the silicon atom of the rearrangement Siloxane depends. As long as substances that have a catalytic effect on the rearrangement remain in the system, create cyclic siloxanes removed from the system, a disruption in equilibrium, and another rearrangement occurs, which helps to replenish the removed amount of cyclic substances and restore equilibrium adjusts. Continuous removal of the

ίο cyclic substances may possibly be the largest Use up part or all of the siloxane in the system. Diluting the system with a solvent also favors the formation of cyclic substances in the equilibrium mixture. When on the other hand, the catalyst becomes inactive when the equilibrium mixture is reached or during the Rearrangement before or after reaching the equilibrium mixture Can relatively low-boiling substances including cyclic substances by extraction with a solvent, by rinsing, or by stripping in vacuo with no further formation of cyclics Substances are removed.

High molecular weight organopolysiloxanes can be depolymerized in solvated form. The decrease the siloxane concentration of a feed by adding a diluent gives one Increase in the ratio of cyclic rearranged structures to linear rearranged structures. With increasing ratios of cyclic to linear structures, the mean continues to be average Decrease in molecular weight of the linear rearranged organopolysiloxanes.

The solvents that are useful as diluents in the process of the invention are inert organic solvents. The solvent chosen depends on the organosiloxane used away. Preferred are the non-hygroscopic organic solvents including, for example aromatic hydrocarbons such as xylene, toluene. Benzene and naphthalene, and aliphalicc Hydrocarbons such as η-hexane, n-octane, n-nonane, n-dodecane and white spirit. Hygroscopic solvents such as ethers (e.g. diethyl ether, di-n-butyl ether. Tetrahydrofuran and dioxane). Amides (e.g.

N, N-dimethylformamide and N, N-dimethylacetamide). Ketones (e.g. acetone, dimethyl ketone, methyl ethyl ketone and methyl isobutyl ketone), esters (e.g. ethyl acetate, isopropyl acetate, isobulyl acetate and methyl propionate) can be used when appropriate drying or dewatering operations are provided flocks.

One embodiment of the invention relates to the rearrangement or, more precisely, the equilibration of Organopolysiloxanes with low molecular weight

weight, especially volatile organopolysiloxanes, with organosiloxanes with a higher molecular weight, how oils, rubbery products and resins are formed. Those flowing out of the reaction zone Substances can be distilled or fractionated in order to separate off the no longer volatile organopolysiloxane.

Another embodiment of the invention relates to the rearrangement or, more precisely, the depolymerization of solvated high-molecular organo-

polysiloxanes, with low-boiling organosiloxanes, like volatiles and light oils. are formed. The effluent from the reaction zone Substances can be distilled or fractionated to

609 6Π / 215

9 ίο

the volatile substances and / or those in a medium

Separate area boiling fractions. Mü ^ hcnwciic

The invention can be easily in a continuous manner _lmm) inulin i "" i
be carried out with the feed mixture

from organosiloxanes in solvated form or as 5

pure substances, the temperature of which is determined by heat ^ex- ~ Ό · ^ ^{+ ΌΑ} ~ -. «) + 40 IO

exchange devices is kept constant by -0.42 + 0.297 -40 + 50 5.7

a horizontal or vertical ion exchange diameter of 0.297 mm

Resin bed is passed, in which the siloxane charge- _{(50 me} ^ _h) | _jeb , _{Qa / iTm}

tion takes place The substances running off are then _{I0 Geh} , _{an en Kömern} , ^.

by chemical separation processes such as moisture removal below 1 percent by weight

strips of solvent, distillation, the _c ",, £ no c / - ■ L ,, -"", -. t

fractional distillation and / or the solvent- ^ ^eststoff ^ ^e ". ··, ■ ⁹⁸ ' ^{5 GcwIchls} P ^rozcnt

run through extraction to remove the fraction with hydrogen ion concentration

to separate the desired product. Then, ₅ J ™ ¹¹⁰ ? T ^ f ^{rockcn) 4} " ⁹

the unwanted fractions are in the hydrogen ion concentration

drive circuit zurückge- for reprocessing ^{stepped 'on mac} l ^{/ ml (columns'} _Ί

leads. The catalyst can be regenerated to _Q ^P P ₄ , ^U u ⁸ '~ ü''"■■' i I, - - _n ■ ·

Allowing the continuity of the process given- Specific surface .. 40 to> 0 nr g

at least caused by the fact that parallel beds ₂₀ ° ™ ^suat · ^ml ' ^oren ' ^ml

be provided that can be bridged. _n corner _: ··· ■ - ·· lUU to IU>

In the following examples the average pore size used is

Macro-linked sulfonic acid - cation exchanger - _c diameter. A. 200 to 600

Resin Amberlyst 15, hereinafter also referred to as macro-specific pore volume 0.029 to 0.03S cm g

crosslinked resin is referred to. Amberlyst 15 has the 25 In the following examples the following typical properties are used: Abbreviations used: M is (CH ₁ J ₃ SiOi: TD is

Typical particle size distribution as a percentage, (CH ₃ J ₂ SiO; D 'is CH ₃ (H) SiO; T is CH ₃ SiO-I :; Q is that is retained on a USA standard sieve: SiO _2. D _x . Is the number of units D according to the above

Definition, where χ is equal to 0 or an integer ₃ o is greater than 0, whereby the value refers to linear organo-

M-ischcmvciic siloxane refers to, commonly referred to as MD _x M

and D _v is the number of units D izc

^{lmml lmcshl} '""' as defined above, where y is an integer greater than O

is and where the value is based on cyclic organo-

119 16 I ₄ 35 refers to siloxanes, which are commonly referred to as Dy

_i'iQxnx4 _16-i -> o ήΊ ^dcn - ^{The v} crweilzcit is the time during which the

'·'''"" ° ': " ~ !; - Organosiloxanes in contact with the catalyst

-0.84 + 0.59 -20 + 30 47.9. It is given by the equation

^Dwell time = ^{V <il} ii ^ ^r i scne .. flow rate
Volume catalyst packing

definitely. . setting of the product and the feed in Gc-

The equivalence time is the time during which the weight percentage is compared. The viscosity is given in eSt an-Organopolysiloxane in contact with a milli- 45,
are equivalent to hydrogen ions. Me, means TbH 1
Milliequivalent of H ⁺ . The control conditions relate to a catalytic reaction lasting 4 hours at 25 ° C, using 2% "" ■ Pn >> inU
equivalent sulfuric acid (based on the weight of the feed
the organosiloxanes), unless otherwise stated

The viscosity is in the usual way according to Ost- ^Vlskos »:» t (cSt) 29.1 4.176

Wald determined at 25 ° C and in centistokes (cSt) Hxamcthylcyclotrisiloxan (D ₃ ) 0.2 not
reproduced. All analyzes of the mixtures found in the

Examples were 55 octamethylcyclotctrasiloxane (D ₄ ) 34.5 5.1

8 ^efuhrt · decamethylcyclopentasiloxane 9 I 3.8

Example 1 (D ₅ )

There were 6 g of the macro-crosslinked resin in a D ° ^dccame thylcyclohexasiloxan 2.1 1.4

Flask given 50 g of neutralized hydrolyzate 60 ⁶

of dirnethyldichlorosilane. The Siloxangc- Emc second feed, which is produced in the same way

The mixture consisted mainly of Dy and HODH, was tanned in a flask that weighed 44 g

measured table I. The mixture was 1 hour at 68 C DOWex 50W-X 8 (Har.doc drawing of the company

touched. The mixture was then removed from the resin. Dow Chemical Co) contained an eclartipcs sulfone

trated using a pressure filter according to 65 acidic ion exchange resin 'The "mixture was

Kruger made of stainless steel with an asbestos agitated 16 hours at 65 ° C. The subsequent

filling. Analysis revealed no change in composition

In the following Table I the combination of the Einspcisgemisches. * "

Example 2

Hin was part of a mixture of 1984 g of cyclic siloxanes Dy and 496 g of linear siloxanes MM by a column 20 mm in diameter and 300 mm long, connected to 30 a 'of a niakrovernctzien Resin was filled, passed through at 41 ° C. Samples of the leakage were taken and analyzed. The composition in percent by weight is

Table II

given in Table II. The column was emptied, cleaned and filled again with 30 ecm of a gel-like resin Amberilc IR 120 (5.0 meq H ⁺ , 0.8% H ₂ O). The remainder of the mixture produced was passed through the column at 41 "C and a sample of the final substances was also analyzed. The composition is also shown in Table II for comparison purposes.

addition product 11.5 10.0 60.0 On ben Uc 0.98 0.85 5.1 IR 120 (11) Amhcrlysl 15 6.4 6.4 6.5 Dwell time (min.) 13th - 18th Equivalence time (min.) 1.2 3.8 3.9 3.9 2.3 Viscosity (cSt) 1.4 6.4 2.8 2.1 2.3 1.4 D, (weight percent) 11.3 0.6 0.6 0.6 11.5 D ₄ (weight percent) 66.2 4.4 2.0 1.9 1.9 65.2 D _s (weight percent) 0.9 2.5 3.4 3.2 3.2 0.9 D ₁ , (percent by weight) ■ - 0.6 3.9 3.8 3.7 - MM (weight percent) 21.4 2.0 4.0 3.8 4.1 20.6 MDM (weight percent) - 3.2 4.0 4.1 4.0 0.1 MD ₂ M (weight percent) 3.7 4.0 3.9 4.0 0.1 MD ₁ M (weight percent) - 4.0 - MD ₄ M (weight percent) - 4.0 72.0 72.5 72.3 MD, M (weight percent) 3.9 - Components with higher Molu weights 72.1 1.5

Example 3

It was a mixture of hydroxamethyldisiloxane and cyclic dimethylsiloxanes and a flow rate of 0.35 cnr \ min. (Vcrwcilzcit 25 minutes) passed through a column filled with 11 g Ambcrlyst 15 was filled. Water at 86 ° C. was circulated through a jacket on the outside of the column calmly. A comparison of the properties of the product with those of the inclusion mixture in Weight percent is shown in the following table :

l-.inspcisiirm

Tetradccamylhoxasiloxane
(MD ₄ M)

Components with longer 9.5
gas chromatographic cr
Retention

product

2.4
1.0

1 inspeisunii

Hexamethylryclolrisilox.ji 2.8

Octamethylcyclotetrasiloxane 16.2

Decamethylcyclopentasil- no

oxane (D ₅ ) found

Dodecamethylcyclohexa-

siloxane (D _h )

Tctradccamcthylcyclohepia-

siloxane (D ₇ )

Hexamethyldisiloxane | MM) 68.0

Octamethyltrisiloxane 2.4

(MDM)

Dccamethyltetrasiloxane 1.1

(MD ₂ M)

Dodccamethylpentasiloxane

(Mn, Mt

product

in the following Examples 4 and 5, mixtures were used from MM and Dy passed through a filled column according to Example 3, with different reaction conditions have been complied with. The results are given in the following tables, where the percentage values in percent by weight wicdcrb id

not SO! ItgCIJCII S T IU. Example 4 IS c Prodtikl / iisammcnsctziini! 1 MD., Viscose \1 1599 found Rcakiions- Feed 2985 α (Weight percent 1 UiI (cSn 1995 5.4 bciiinuunjicn D ₄ \\ MDA ND 2110 Λ Ο MM 6o duration ND 55 η 6.2 3.9 ND ND 1938 3.3 30 min. 6.1 3.8 ND 65 min. 5.7 3.9 ND ND 1.8 ₆₅ 130 min. comparison Tempe 5.1 3.7 ND 37.6 4h rature ND Niirhl Found 23.3 60 ° C 60 C 11.2 60C 5.2 2SC

Example 5
feed

MM D,.

210 g 8790 g

Reaklionsbedinjuinjicn length of time

temperature

3 min.

4 min.
8.5 min.

13 min.
67 min.

30 C 30 "C 30 "C 30 "C 30 C

Example 6

product

viscosity

(cSl |

12th
19th
50
79
137

liiiispcisuni! Product

HjSO ₄

Dwell time
temperature
Viscosity (cSt)

Hxamethyldisil-

oxane (MM)

(Weight percent)

Hxamethyl-

cyclotrisiloxane

not

definitely

11.0

9.1

4.0 hours 25 ± 2 "C not definitely

0.4

Ambcrlyst 15

0.3 hours
25 + T C
14.3

0.4

I'.inspcisuiii! Product ii, SO ₄

57, p

22.1

2.9

0.3 0.4

96.4 97.9

Amherlw 15

1.4

. This example shows the possibility of using highly viscous liquid silicones in the presence of a non-reactive Prepare diluent.

A mixture of 7.5 g MM, 1493 g D ,. and 355 g of hexane passed through a column of 30 mm diameter and 800 mm height, which was filled with 250 ecm Amberlyst 15, at 60 ° C and 45 minutes residence time. The resulting liquid had a viscosity of 8 · 10 ³ cSt. After stripping off volatile constituents up to 220 ° C. at atmospheric pressure, the viscosity was 89 · 10 ³ cSt.

Example 7

This example demonstrates the ability of a macro-crosslinked resin to form methylhydrogensiloxane linkages rearrangement and copolymers of dimethylsiloxane-methylhydrogensiloxane to manufacture.

A mixture of 166 g of methyl hydrogen polysiloxane with trimethylsiloxy end groups and a viscosity of 30 cSt (Union Carbide Silicone L-31), 55 g of MM and 435 g of D _y was passed through a column which was filled with 11 g of macro-crosslinked ion exchange resin.

A 100 g sample of the feed mixture was mixed with 2 g of concentrated sulfuric acid at room temperature mixed and then neutralized with sodium bicarbonate and filtered. A comparison of the Samples taken from the ion exchange column, the sample treated with sulfuric acid and the feed mixture is shown in the following table.

Octamethylcyclotetrasiloxane
(D ₄ )

Sym. Heptamethyitrisiloxane
(MD'M)
Higher molecular compounds

The following Examples 8 to 10 show the preparation of methyl hydrogen siloxane-dimethylsiloxane copolymers by siloxane rearrangement on macro-crosslinked exchange resins. Mixtures of MD ' _X M, D, and MM were passed through a glass column 2.54 cm in diameter and 60 cm in height containing 250 cm ^{3 of} the macro-crosslinked resin.

The feed mixtures were also treated with 2 percent by weight sulfuric acid for 4 hours at 25 ° C treated. The properties of the samples treated with sulfuric acid are shown as comparative samples.

Example 8

liinspcisiiiii! Anal) se the

tinspcisunj;

(i! |! weight

percent)

MM MD ', M

412
974

3285

viscosity

RCfiktiiinsbcdinpuni'cn
length of time

8.7%

ν = 3.9.8% ν = 4. 62.3% y = 5.1.1% 4.4 cSt

31 min.

14 min.

23 min.

Product use (Percent by weight!

Temperature MM D ₄ viscosity

(O IcSlI

4 hours

25th
25th
25th

25th

0.4
0.4

comparison
0.4

1.6 1.8

1.7

16.5 16.4 16.7

15.8

Example 9 feed

MM 124 g

MD'Jvl 25Og

D, 4611 g

Viscosity 2.4

Rcaklion ^ vcliiiüun.ücn PrniHikl / iivimmensel / iinL · Kcaktiiinshcdinüimucn Pi.iiUikl / usamincnM-lAiiiü

Kiewichl-.pro/enii "* iGciuchlspro / ciiil

Duration icnipci.mii IV!), D ₄ V ^ bisi · ;; ·. Wmc. Tempera- MM MfVM MIXM N) IV ₁ M

I (Ί IcSn ^{5 Ulr}

(Cl

12 min. 25 0.5 9.9 60.5

37 min. 25 0.9 4.1 84.3 4 min. 25 41.9 27.0 12.3 5.0

30 min. 25 0.8 4.6 79.3 io 8.5 min. 25 37.1 30.9 16.1 6.8

Comparison comparison

4 SId. 25 0.9 4.5 76.4 _{4 Sld 2} 5 36.2 30.3 18.1 7.8

ExampleO, ₅ The following examples 11 and 12 show

p; , ·. _t suggest that Amberlyst 15 for the rearrangement of diphenyl

-.nspeisuni. siloxane bonds is useful. Next will be the

MM 1620 a shown the possibility of low molecular weight cyclic slruk-

MD'jM 600 g doors made from high molecular weight linear structures

D ₁ Ou 2o deliver.

B ι: i s ρ i e 1 11

A solution of 193 g of a neutra en 25 was a solution with 20 percent by weight of organosiloxane

Diphenyldichlorosilane hydrolysates, 78 g neutral. to echo, mixed and guided through a column,

The volatilized hydrolyzate of the 250 cm 'Amberlyst 15 among the following

Dimethyldichlorosilane and enough toluene to fill conditions.

/ \ nal \ se lies hinspcisunesuemisclies Kicuichtspro / cnl)

Toluene I) ₄ Π, I). high molecular weight

Siloxanes

Mixture 80.1 0.2 0.2 0.1 19.4

Normalized

Composition of

Organosiloxanes I | 0.5 97.5

Reaklioiisbciliii (Uini: cn toluene O ₄ l \ Π, |). Ι1Ί1, IVO ₄ I) I),

Duration Tcmpera-

Iu r

56 min. 60 C 77.5 3.0 1.4 0.4 0.1 0.3 0.2 0.1 17.0 percent by weight

normalized
Organosiloxane composition 13 6 2 0.5 1.5 I 0.5 75

I) "- l) iphen \ lsilo \ an.

Example 12

There was a gummiarligcs silicone Ausgangsmatcrial mil high molecular weight, which was devolatilized and about 15 weight percent Diphcnylsiloxy-Einhciten and 85 weight percent (CHOzS'O-liinheilcn acid (20 g). 80 g of toluene, and HH) cm ¹ Ambcrlysl 24 hours stirred at room temperature. The properties of the product are summarized in the following table.

l'rotlukl Kiewicluspm / L-mi

Toluene D, I) ₁ IX IV Π D ₄ DD, DI », DD

K7 0.1 6.2 3.1 0.9 0.3 0.1 1.1 0.7 0.2

Normalized composition of the
nn.i.nnsiloxane 0.8 47.7 23 »6.9 2.4 0.8 p.5 5.4 1.7

Example 13

Equal parts of 47 g each of a mixture of 20 g of tetraethyl orthosilicate and 450 g of cyclic dimethylsilicone (98% cyclic tetramers) were placed in a 100 cm ³ flask. The flask was fitted with a mechanical stirrer and a nitrogen inlet tube with an outlet bypass. The flask was ^{heated to 80 °} C. and the temperature was set thermostatically to 80 to 90 _{° C.)} 1 g of Amberlyst 15 were added with continuous stirring. Samples were taken periodically from the flask and analyzed for the percentage content of tetraethylorthosilicate. After 11.25 hours, the tetraethyl orthosilicate content had fallen from 4.7 to 1.2% initially.

The residue of the prepared mixture was divided into equal parts and passed through a column of 10 mm diameter and 80 mm height, was filled with 60 cm 'Amberlyst 15 °. The TeHe were passed through the column with alternating residence times. The mixture was kept at 27 ° C. With a residence time of 14 minutes, the analysis for tetraethylorthosilicate showed 0.2 percent by weight of this substance. No tetraethylorthosilicate was found with a residence time of 38 minutes.

Dimethylsiloxane
meren used.

- methylhydrogensiloxane -

Example 15

Example 14

A mixture of 1458 g of tetraethoxysilane and 455 g of hexamethyldisiloxane was passed through a column 1.9 cm in diameter and 92 cm in height, which was filled with 230 cm 'Amberlyst 15 which was moistened with ethanol. given with a Verwcilzeit of 32 minutes. The product obtained contained the following components:

Geuk'lilspro / enl

Hexamethyldisiloxane 1.0

Trimethylalhoxysilane if>, 0

1,1,1-Trimethyl ^ JJ-triethoxydisiloxane 28.7 1,1,1 Ä5,5-hexamethyl-3,3-diethoxytri-

siloxane 2,3

Tetraithoxysilane 49.0

in Examples 15 and 16 below, Amberlyst 15 for the rearrangement of phenylalkylsiloxanes and for the production of phenylalkyl-methyl-siloxane-Es a mixture of 30.1 g of MM. 898 »D 67.9 g of methylhydrogensiloxane with trimethylsiToxyJ End groups (liquid) and 643.4 g of the neutral hydrolyzate of / -'- PhenylpropyKmethyljdichlorsilan with a viscosity of 25 cSt passed through a column of 30 mm in diameter and 800 mm in length, the was filled with 250 ecm Amberlyst 15. Hs was at a temperature of 25 "C and a 5.5 hour residence time worked on balance. The resulting liquid had a final viscosity of 150 cSi.

Example 16

A mixture of 13 g of liquid methylhydrogensiloxane with trimethylsiloxy end groups (viscosity 30 cSt) and liquid phenylethyl methyl siloxane dimethylsiloxane with trimethylsiloxy end groups (viscosity 375 cSt) was passed through a column 30 mm in diameter and 800 mm in length , which was ^{filled with 250 cm 3 of} Amberlyst 15. The experiment was carried out at room temperature and with a residence time of 5 hours. The resulting liquid had a viscosity of 545 cSt.

B e i s ρ i e 1 17

This example shows the possibility of not using the Organopolysiloxanes in equilibrium in any distribution through the mechanical Reücluni » the dwell time.

A mixture of HOu hexamethyldisiloxane and 620 g of octamethylcyclotetrasiloxane was carried out given a column filled with 11 g of Amberlyst 15 was. Samples were made at different contact times and temperatures taken.

A 100 g sample of the feed mixture was stirred with 2 g of sulfuric acid for 4 hours and then neutralized with sodium bicarbonate and fileted. This sample was called the comparative sample.

A comparison of the starting mixture, the samples taken from the column and that with sulfuric acid treated mixture is shown in the following table.

Katiilysiilnr

Dwell
(Min.)

temperature
(C)

viscosity
fcSt)

feeding

1.7

79.8
0.7
0.9

comparison product I5i 1.4 track 4.7 8.8 3.2 12th (H ₂ SO ₄ ) (Aiiiberlvs! 85 25.6 85 85 25 ± 2 2 5 i 240 0.4 5.5 3.1 8.4 9.2 4.2 8.6 26 4: 2 85 Composition in 0.8 Weight percent 5.5 5.5 0.1 0.2 0.1 0.1 track track 44.8 0.1 8.8 5.3 34.3 7.5 track 2.2 3.1 3.0 2.1 2.9 5.0 0.8 0.8 0.8 0.5 0.9 2.3 0.2 0.2 0.2 0.2 0.1 0.5 0.1 0.1 0.1 0.1 () I. 0.2 0.1

Hortsct / ung

19th

20th

111, SO ₄ I.

product

I5 |

MD ₂ M MD ₃ M MD ₄ M MD ₅ MMD ₁ , M MD ₇ M MU ₈ M MD ₉ M MD ₁₀ M MD _n M MD ₁₂ M MD ₁₁ M MD ₁₄ M MD ₁₅ M MD ₁₁₁ M

19.5

Composition in percent by weight

0.1 1.3

2.0 2.4 2.5 3.6 2.9 2.8 2.9 2.8 2.4 2.2 2.0, 7 .5, 3

, 0

track track track 0.9 2.9 1.7 1.7 2.1 2.0 2.2 2.3 2.4 2.4 2.8 2.9 4.7 11.5 7.6 2.8 3.0 1.6 3.1 2.4 2.9 2.8 2.4 2.9 3.2 3.0 3.0 2.6 1.8 2.3 2.4 1.5 2.3 2.1 1.4 2.0 1.9 1.3 1.9 1.6 1.0 1.6 1.6 0.9 1.4 I 2 0.8 1.3 1.1 0.6 1.0

track track track 1.3 1.7 1.3 2.1 2.0 1.9 2.4 2.3 2.3 2.7 2.7 1.3 3.0 8.6 3.4 2.8 2.9 2.9 2.8 2.6 3.1 2.8 2.5 2.9 2.8 2.8 2.9 2.6 1.0 3.1 2.4 1.7 2.6 2.4 2.3 1.6 1.8 1.4 2.9 1.7 2.1 1.2 1.9 1.0 2.6 1.2 1.6 0.9 2.2

example

This example shows the production of liiissiuen Dimethylsiloxanes on an industrial scale.

It became a mixture of 450 kg of cyclic dimethyl silicone and 3.28 kg of hexamelhyldisiloxane at 80 ° C on a stainless steel column 46 cm in diameter and 245 cm in length extending to a depth of cm was filled with Amberlyst 15 ion acoustic resin, at a rate of 79.5 kg per hour given. The substances running off from the column had a viscosity of 130 oCSt and contained 9.5 percent by weight cyclic dimethylsiloxanes.

1 sheet of drawings

Claims (1)

Claim: Process for the production of equilibration products of organosiloxanes by rearrangement of the siloxane bond on a calcium ion exchange resin, characterized in that the organosiloxane or organosiloxane mixture used as starting material is allowed to flow at a temperature of about 10 "C to about 100 C through a packing which, as a cation exchange resin, is a macro-crosslinked Cation exchange resin containing sulfonic acid groups with an average pore volume of at least about 0.01 enr ¹ / «.> 5