DE1493328A1 - Organosilicon compounds containing isocyanate groups and processes for their preparation - Google Patents

Description

DH. ING. F. WDKSTHOFF 4 / ft «S O β Ο« MÜNOHKN 9O DIPL. ING. G. PULS I H 9 3 J Z 8 SCHWIiaiUTIABSI ·

DH.K.T.PKCHMANN - DB. ING. D. BKHBKNS

P 14 3'j 320.9

(U 11 009 IVb / 12 o)

1Λ-28 5;> 7

Be a honor ibu η g on the patent application

UKIOM CARBIDE CORPORATIOIJ Hew York, ΪΪ.Υ., U. S. A.

concerning

Organosilicon compounds containing isocyanate groups and methods of making them

The present invention relates to new silanes and siloxanes which contain organofunctional isocyanate groups, and a method for their production.

It is known that silanes and siloxanes, which are characterized by the presence of one or more organofunctional Irjocyanatgruppen are modified, very desirable silicon compounds are what is mainly due to the reactivity of the isocyanate group with other functional ones Groups, such as a hydroxyl, amino, sulfhydryl, carboxyl, amide group and similar groups,

. *; Documents ca * 7 u a & sji ».1 sau 3 * ·

BAD OftiriiM *

909817/0746

which contain active hydrogen atoms · Up to now, however, there are few methods of producing these Compounds are known, most of which are unsatisfactory.

DAS 1 066 562 describes a process for the production of silicon-containing isocyanates, according to which organosilicon compounds containing amino groups of the group = Si-0-11- (NII ₉ ) are reacted with phosgene. However, owing to the oxygen bridge between the silicon atom and the radical R, these compounds are easily hydrolyzable and can therefore only be used to a limited extent for certain purposes.

The new silicon compounds according to the invention are (A) silanes of the general formula

^R 'b

(I) (OC3J-R) _a Si - X ^

in which -It is a divalent hydrocarbon radical, R ^{1 is} a monovalent hydrocarbon radical, XV / hydrogen,] ?, Cl or a (-0R ¹ ) group and in which a is an integer from 1 to 3ιb inclusive, b is an integer from 0 up to and including 2, provided that (a + b) is 1 up to and including 3:
(B) Organosiloxane homopolymers of the formula:

? V

(II) (OCff-R) _a Si - 0 ₄ _

909817 / 074S

BATH

in which R, R ¹ , a, b and (a + b) have the same meaning as in

of formula I above and

(C) Siloxane mixed polymers, which are essentially composed of

0.1 to -99.9 moles -> of units according to formula II

and in addition to this from ^; J9.9 to 0.1 col-v * of units

the general formula

(Ill) H "

composed, in which R "is hydrogen or a group such as R ¹ in formula I 1st and c has a value from" 0 to 3 inclusive ·

Examples of divalent hydrocarbon radicals R in formula rif. And II are straight-chain or chain-branched alkylene radicals such as methylene, ethylene, propylene, n-butylene, isobutylene, n-amyiene, decylene, n-octadecylene, 2 -Ethylhexylene radical; divalent arylene radicals with a benzene-like ring such as the p-3-phenylene, xylylene, ethyl-p-phenylene radical; fused divalent ring-shaped aryl radicals such as the naphthylene radical ;. bieyelic divalent ions such as p, p ^l -biphenylene; Gyoloalkylene radicals such as cyclopentylene and cyclohexylene, R preferably contains 3 to 10 carbon atoms and is "(; most preferably a phenylene radical (OgH,), a radical -CH-CpIL or a polymethylene chain (-GIIp-), where η is a We ^ t ϊςη 3 _: up to and including,. £ = ■, · has · "

S098177O7 46. bad original

Examples of monovalent hydrocarbon radicals !! Ii 'and ii "in formula I, II and III are straight-chain or chain-branched alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, η-butyl, isoarayl, hexyl, decyl and octadecyl -itest, the cyclic alkyl radicals such as the cyclopentyl, cyclohexyl and bicycloheptyl radical, the aryl radicals such as the phenyl, itfaphthyl, p-phenylphenyl and alkaryl groups such as neophyl, tolyl and xylenyl and the aralkyl groups such as benzyl and phenylethyl radical. R ' ¹ is preferably an alkyl radical with 1 to 10 carbon atoms or a thenyl group, ie C, -IL-. II * is preferably a ethyl radical.

Examples of 3ilanes according to Formula I are Isocyanatophenyl (methyl) dichlorosilane, isocyanatophenyltrichlorosilane, Isocyanatophenyldimethylchlorosilane, ß-Isocyanatophenyläthyldiäthoxyfluorsilan, <J-isocyanatobutyl (methyl) difluorosilane, Y-isocyanatopropyl (butoxy) dichlorosilane and isocyanatocyclohexyldifluorosilane.

Examples of siloxanes according to formula II and III are:

1 7/0746

colorless and odorous liquid, bp>27i> ^u 0 / I mn Jig, Vickofiitilt ^j u. [> .jLit bei jö ⁰ : "

BAD OWGINAL

colorless and odorless

Delivery
Bp, ~ 1 68 ° C / 0.1 i viscosity ro. 30 cSt at JO ⁰ C

(c) | (CH ₅ ) ₃ Si-O

I!

Si - (CH ₂ ). NOO

colorless liquid with a slightly pungent odor,
Bp. 175 ° C / 45 mm Hg _n visc. 6 cSt at 25 ° C

OOii

ITOO

colorless liquid

with weak biting

the smell,

Bp 230 ° C / 0.5 mm Hg

Vis. Rd. 2 cSt at

100 ⁰ C

Si-O

- SiO - I

CH ₉

HC-CH ₅

NCO

903817/0746 color- and odorless liquid,
Kp.260 ^ö C / 0.20 mm Hg viscosity 3.5 cSt at 10O ⁰ C

BATH ORIGINAL

Vic der Pnclmann olui.i further recognizes, the Lljolapolynerisate and no ^ cpolTTnericate $ o according to the functionality of the Koiaponentoneinlieiten in the form of cyclic compounds, linear riioI3racdion, branched flow medion, ii etc /. present

".Vie go-tunden v / ardorj. Itonnto, can be dia Xicwys. 7crbindiaivr-Ä onno further according to cinom procedure hor-, v.'onach. A." ^ Ilnohydrocarbylsilan or Aaino-

loxan nit Ihoc ^ sn, axif desires if it is present an inert organic locus medium with formation dor £ ev / äncchton Isocyanatailiciumverbindungen uacocotzt

Λ13 Output substance for the manufacturing million Pre-opening in accordance with Regulation I above iu'-iiLohydrocarbylsilane of the general iToriael

(IV) (H ₂ IT - ^ - Gi -

V <a * b)

uses "" in the H ₁ i.1 ¹ , a and b the same meaning v; io in Tornol I iiaben, "and in the Q 'Vasseratoff or a (-02') - Crruppo iGt · on a similar '.veiso let the Ilü ^ opolynoriaato and Hischpolynerisate entaprochond formula II and III from the Auasanrjssubstansen the general formula

(V) (H ₂ HR) ^ i - 0

4_ _(nrt0

- 7 -909817 / 07A6

BATH ORIGINAL

or from Aminohydrocarbyloiloxan-Mischpolymerisateii accordingly the general formula

Il

IiIL

- (a + b)

IV SiO c

produce, in which R, R ¹ , a, b and c have the same meaning as in formula II and III, and in which d and e are an integer such that the units of the formula j-ΐ. ¹ , oiü.,

0.1 to 99 »9 mol-'j of the copolymer.

The quantitative ratio of phosgene to the aminohydrocarbyl silicone is not a strictly critical parameter.However, in order to achieve an effective and complete conversion, approximately one to five times the amount of phosgene required is preferably used. Btoichiometrically, one half of phosgene is required to convert a (-HH ₀ ) group into a (-1I = G = O) group. For each Hol Aminohydrocarbylsilicone the theoretically required molar amount of phosgene is numerically the same

9 09817/074

BAD OR! C! N ¹ AL

" ³ "

the average 2aiii of (-2T alkyl or aminoarylsilicon molecule

per anino

V.cnn also, the ftealitionßnaehanisaus not g

1: 1: ir, it can nevertheless be on ^ enonmon that the reaction of the Λϋίη, οalkyl or aminoarylsilicon precursor with ihos-Sen. Above a second stage reaction takes place, the products of the first reaction being a corbasiyl chloride and a hydrochloride, which are converted into intermediate products through the further addition of the host in each case in the desired luccyanate bond this ITnoetaunücn (Ii is an alkylene or arylene half) are j *

O η

(2) IiCl

- It I "

Sis

Cl C - EH 2 - Sis

+ COC1 ₂ ^ ~> HCl-

+ COCIo-> 2 OCN-E-SiS + M- HCl

Me erate reaction (1) is at a relatively low temperature of the order of generally from -20 ° C begünsstiEt bit 25, while the second reaction (2) ixi a.ll ccusinen _u "is beeünstist at elevated temperature · Ia the case of Aioinoalkylsiliconen werdon optimal in alliseneinen! results achieved in the second Reaktionostufe at a temperature in the range of 100 to 200 ° C and preferably at ungofälir ■ 175 ° O. in the case of Aminoarylöilpxanen a temperature of 50 to 1OO is ^east C preferably so

909817/0746

bad original

a splitting of the siloxane bonds and a reduction in Ö.ZZ '-usbeuto do not occur. It is therefore advantageous to first bring the aininoiloxone into contact with l'hosgon at a low temperature and to increase the reaction temperature v /; Virend doo Ej.Tl "!; Io ~ 3rr is complete.

7. As can be seen from the following examples, the reaction of phosgene with the amino group of the AucsansssiliciunverbindunG especially at low temperatures re ^ onubor of the same-zoitis proceeding unset-zu ^ von ihosgon ini'b one also in the eiche AuscangjßsubstAnzon independent hydrocarbonoxy group bonded to silicon is favored. At the temperature at which an optimal © U_i3ot £ UD £ the speed is reached, but rare in the generally some Ilydrocarbonoxyubstituenten in chlorine substituents converted, whereby a mixed reaction product \ .v; j arises, which can easily be separated in a known manner, for example by distillation. Bonded to silicon Chlorine can be readily obtained by reacting a chlorine-containing product with sodium fluorosilicate at moderate levels Replace temperature with fluorine.

A preferred procedure for achieving thorough contact between the reaction participating substances is the use of an inert organic solvent mode in which at least

- 10 -

90 9 817/0746 bad original

dec IliOs ^ L'ii iir.- "; vorzu ^ svoiee also the .'jainohydrpcfirbyl-

löülich isj-fe. Representatives of such common LÖSUB33 are toluene, eensol, chlorobenzene, ^ -chloroethylbenzene, xylene and carbon tetrachloride. iüoll dio Ciedoteriiporatur an ijevninGchten LÖ nictola zur .Grroiclruns einor optimal TTsisetaijns tur {je et eifert v; ^f ground, then überataocphärendruclc lcann t: be iijc "nvijidt Tierden, vrobei separated from the Seaktionscyotsia however IIc1 nut The Umsctzun2 ertolst in ixll ^ eiioinan under normaloza atmospheric pressure" or under slightly vc-i'i'iR ^ locate egg ¹ KLA '. untci "* L ^ archleit an inert gas vd.e

Helium.

The crude product © can be converted into hellish lolynere by their reaction riuii ^ sn loocyanatjjruppc v / er dcij. Yes-;. They can be hardened with the compounds known from other compounds, namely olycarbonic acid, polyalcohols or polyclycolone or olymors such as polyester or polyether.

The process is illustrated by the following example n "'hor, but in no way by the same

909817/0746 _ΘΑ ο

i: .- HJ .. '5r; ial 1 "

ICO ül xoluol and 1C0 g'i ' · filled nohsen The ilccQctionsGe- U £.! l and 36in content vmrden then to approximately -20 ° C cooled, after which 43 t5 (0.135 ZOI) KXD ₂ -J A-oi (CHj) ₂₎ 'o in 100 ml toluene Course of about 20 liin · laniscam additions

cii · The obtained mixture was ^{heated to "1} C under nitrogen, uia {appropriate gases to be separated · Then. * 3 toluene from ^ eotrippt and the product distilled. It

/ * ν

RU? Lo / t) CH- ' ^: A-Gi (CH ^) ₂ Z ₂ O ¹ ^ * a boiling point of

° C "at 0.09 iam H-j · in a yield of 70 LIol-% 36 g) received

In a reaction vessel equipped essentially in Example 1, 50 5 (0 >> 5 I> "ol) 3 ows and 100 ail 1.4 chloroethylbenzol. The reaction vessel and pure contents were cooled and added to the Rcalction Giso vial of 150 g of a silicone liquid of the average ToBaruaensetzus

909817/0746 bad original

- 12 -

Γ ⁵

C-Si-O-

CH

CH

-Si

7th CH J r 3 I. I. CH 3.

65

CH-

ι -

-Si

(average molecular weight about 5,300) with a viscosity of 97 cSt in the range of about -10 ° to -3O ⁰ C. The paste-like reaction mixture obtained was then heated at 160-Ms 170 ⁰ C and continue to phosgene was obtained until a clear Heaktionsmasse. This was followed by the removal of low-boiling products while passing through nitrogen and vacuum stripping at 200 ^° C. under reduced pressure of approximately 1 mm Hg. 134 g of a somewhat opaque oil with a viscosity of 120 cSt and an average composition of

OH-.

CH ^ -Si - Ο

CH,

CH ₅

Si - ΟΙ CH ₂ ) ₄

HCO

I * -Si - ΟΙ

CH,

-Themselves,

CH ₅

obtain.

Isocyanate group content: calculated 2.94 wt. 5 »NCO

Found 2.9% by weight for NGO

909817/0746

BAD OW ^ NAL

Example 3 ,

100 ml of toluene and 115 g of phosgene (1.15 mol) were placed in a reaction vessel essentially as described in Example 1. The temperature of the reaction vessel and its contents were reduced to approximately -10 0 and maintained for 30 minutes, during which time 40 g ( 0.14 mol) of 1,3-bis (/ \ -aminobutyl) tetramethyldisiloxane, which were treated with toluene diluted to approximately 100 ml were slowly added. A white paste-like Heaktiona mass formed. The toluene diluent was removed and replaced with 200 ml of p-chlorotoluene. The mixture was then heated to 170 to 180 G and phosgene was slowly introduced into the reaction vessel in the course of 21/4 hours. By distilling the crude product, 7 g of OCN- (CH ₂ ) ₄ Si (CH ₅ ) ₂ Cl and 30 g of 1,3-bis (A-isocyanatobutyl) tetramethyldisiloxane of the formula were obtained

v OH,

I I

OCN - (CH ₂ ) ₄ - Si - 0 - Si -

CH ₅ OH ₃

obtained of bp 140 ° C / 17 mm Hg.

Analysis;

Calculated C, 51.2; H 8.6; Si 17.1; N 8.5; NCO 25.6 # Found C 50.9; H 8.5; Si 16.9; N 8.3; IiCO 24.9 ° / <>

909817/0746 ~ "o" a.N ".

H93328

In a lieaktionssöfüß au3 glass ait a ^ ü ^ Qü of 1 1, the zd / fc oiiusu liüiirör, a gas inlet uags · roar. ,, üiiiOGi ilioriioncitor υϋα. cinpa 2iic I'rociiöneis ^ afeüiilijoa 2.UIiIj ^ · aua ^ c-instead of v / ar, vrardca. 4Ό g (0.4; üol) riipegen, which in 100 tu. ioluol ^ olöst v / aron, G ^ iüllen · The lieaktiozisüoräß un * coin IrJialt were cooled to -10 ° C. This teayporatiir wuri- .1 ^ -wj.d im ^ oXäto £ 0 iiia · "retainedon" during which since 20 & (0.05 i-ol) dos cyGlischon xotrameren the Gtruk-

-'3

CIL

0 - Sj

• 4

slowly starts up vnrcdoa. · The temperature of this under ütiskotofi Dtohendeia I ^ iu ealctionssemisches.wurde then over a period of 3 · 3td lanssam to 100 ° C gosteiGört · Di © RcinicnjnG dös ßeaktionsproduktes yielded 21 5 ₁ S (93 üol-> i yield) of the entsprechendon Isocyanatsiliciumverbindung the Fomol. .. · .-

909817/0748

BATH

Bp 97-98 ° G / O, 035 mm Hg.

Analysis:

Calculated 0.41.4; H 6.2; Si 29.2; H 3.5; NCO 10.4 Found- C 42.0; H 6.4; Si 27.9; N 3.6; NGO 10.5

Example 5

(A) By adding 88.4 g (0.4 mol) of α-aminopropyltriethoxysilane to 190 g (1.9 mol) of phosgene diluted with toluene to 260 ml of phosgene, b- isocyanatopropyl (ethoxy) dichlorosilane was prepared in the course of 1 hour , the temperature at -50 + 10 ⁰ C was kept. The temperature was then gradually increased to 109 ° C. over the course of 2 hours. The product was isolated by distillation in a yield of 61.5 g (67 mol%). Bp 75-80 ° C / i, 0 in Hg.

909817/0746 ^BAD

(B) The (J-Isocyanatopropyliäthoxyjdichlorsilan from part (A) was made by treatment with 165 g of thionyl chloride and j), 0 g triphenylphosphine under reflux in one yield of 98 mol - '/ o converted into O -Iaocyanatopropyltrichlorosilane. Bp. 61 - 63 ° C / 1.7 - 2.5 mm Hg.

(G) The 6 -Icocyanatopropyltrichlorsilan from part (B) by reaction with a 50 '/ o-molar excess of ITatriumfluosilicat at a temperature of 90 C to 142 ⁰ C, until no evolution of SiF. more took place, in a yield of. 90 mol- $ converted into d-isocyanatopropyltrifluorosilane · bp. 142 ⁰ O / 753 mm Hg.

Analysis;

Calculated 0 20.4; H 3.6; Si 16.6; IT 0.3 ^l / o Found 0.28.3; H 5.9; Si 15.8; IT 0.4> «

Example 6

200 ml of toluene and 80 g (0.0 g) of phosgene were introduced into a 1 liter three-necked flask with a mechanical stirrer, dropper, thermometer, and dry ice cooler with a stream of dry nitrogen passed through. ^{The stirred reaction mixture was cooled to -2O 0} O by means of a dry ice bath and 45 g (½, 2 hol) of ilgJ-10 ^ Jt ^ -JiOII (OOgii ^) ,; tru-pfenweifse over 50 Hin · added, 'Hr, was.,' ijtd. v / eitor agitated, v; obei die Tomperatiu- on ', -t <' \ l '- "n.'jtieg ·: jui'j'Inti'ernung von üderwohüssigei.'i Phcgcii unu tJiiiorwas ^ er.'jt 'jff' .. 'U'd »the G-cmirjoh under otiekotoff-

9Ü9817 / 07A6

BATH ORIGINAL

introduction heated to 110 ⁰ O · The clear, colorless crude product was distilled through a 30 cm Vigreux column with an internal diameter of 1.27 cm and 41 g of a mixture of isocyanatophenylmethylchlorethoxysilanes with a boiling range of 129 ° C / 10 mm Hg to 132 ° C / 11 mm Hg, which were identified by infrared spectrometry.

When the product was heated under reflux for 1 hour with 60 g of distilled thionyl chloride and 1 g of triphenylphosphine until the evolution of gas had subsided and then distilled, 36.5 g (0.16 mol) of O = G = II-C ₆ H ₅ - SiGn ₇ obtained in a yield of 80 '/ o of theory. Bp. 96 ⁰ G / 0.7 mm Hg.

Calculated for C ₈ H ₇ SiWOGl ₂ : G 41.4; H 3.0; Si 12.1; N 6.9 ^c / <> Found: C 41.1; H 3.7; Si 11.8; F 6.5 'i *

The new silanes and siloxane homopolymers according to the invention and copolymers are valuable hydraulic fluids, coating resins, elastomers and finishing agents for paper, textile and glass fibers similar to the silicone precursors from which they are derived.

The superior effect of the isocyanate-modified according to the invention Organosilicon compounds as sizing agents for cellulosic materials the following comparative tests:

BATH

909817/0746

H93328

From about 20 parts by weight of one containing isocyanate groups Silicone compound, about 1 part by weight of polyoxyethylene esters of a mixture of fatty acids and resin acids, about 1.1 parts by weight H-getylethyl morpholine ethosulfate and about 78 parts by weight Water an emulsion was made.

For comparison with this, an emulsion was also prepared which contains a silicone oil of the general formula (CH _v ) _v -SiO- / I ^- OH ₃ ) HSiO / _5O __ _4O Si (CH ₃ ) ₃ in an amount of about 40 wt. Parts, polyoxyethylene ester of a mixture of fatty acids and resin acids in an amount of about 4 parts by weight, about 56 parts by weight of water and such an amount of acetic acid that this resulted in a pH of about 4.5.

Two suitable catalyst emulsions were found for both of these approaches manufactured. The first catalyst emulsion consisted of a mixture of about 37 »5 parts by weight of dibutyltin dilaurate, about 2.96 parts by weight of polyoxyethylene sorbitan monooleate, a mixture of mono- and diglycerides of fat-forming fatty acids in an amount of about 0.74 parts by weight and about 57 * 8 parts by weight v / ater. The second catalyst emulsion consisted of a mixture of about 39 parts by weight Zinc octoate, about 3.12 parts by weight of polyoxyethylene aorbitan monooleate, a mixture of mono- and diglycerides of fat-forming fatty acids in an amount of about 0.78 parts by weight and from about 57.1 parts by weight of water.

9 0 9 817/0746, _BAD original

Appropriate baths were then prepared from the above-mentioned batches by diluting the silicone-containing emulsions with water to a silicone content of about 2 de \ r, - ⁽ / o and adding a catalyst emulsion, so that the catalyst concentration given in the table below was obtained Cellulosic materials were then passed through these baths.

The thus treated cellulosic materials were then repeatedly washed in a washing machine with detergent, a little water and a temperature of about 71 ⁰ G. After each wash cycle, the fabric was air dried. The test results are shown in the following table.

Tabel

90 9 8 ι 7/0 7 A6 ^b * d original

Tabel

Silicone

Catalyst based on silicone

Drying.

Output 3 worth ^ aschvor- Waschä operations

Pibutylsinn dilaurate

5 min at

10O ⁰ G

100

80

80

O CO OO

nothing

min. 10O ⁰ C +

at
3 min. 16O ⁰ C

at

100

80

80

Comparison

(CHj) ₅ SiOf (CH ^) HSiOJ J _0-40 Si

11 Qew, -jt zinc octoate

5 rain ". At 100 ^° C + 3 min. At 160 ^° C

100

50

CO CO

The tests show that the compounds according to the invention are more washable than can be achieved with conventional silicone oils. The water resistance also occurs after a shorter period of time, the use of curing catalysts does not impair the service life of the finish, and the presence of alum does not have any disadvantageous effects, as is the case with conventional silicone-based sizing agents of the l < ^l alj. is.

ta t- gn tadas priioh e

BATH ORIGINAL

Claims (1)

Claims or homopolymers of the general formula or, Oopolymei'e with 0.1 to v9 »9 M0I- / 3 units of the general Pormel II and 99.9 to 0.1 Iol - '/ o units of the general formula III where in the formulas R is an aweiv / ertiger carbon radical, S ^{1 is} a monovalent hydrocarbon radical, E ".hydrogen or a monovalent hydrocarbon radical, X is hydrogen or a fluorine or chlorine atom of one group (-QB. ¹ ..) is, a is 1,2 or 3 and b is 0,1 or 2, where (a + b) has a value 1, 2 or 5 toad c has a value 0, 1,2 or 5. 909817 / Ö746 BATH ORIGINAL 2. organosilicon compounds according to claim 1, characterized in that R in formulas I and II a divalent hydrocarbon radical with 3 to 10 Means carbon atoms. 5, organosilicon compounds according to claim 2, characterized indicated that R in the formulas has a reads (-GH ₀ -) - means, where η 'means J ₃ 4 or | 3. <L η 4-. Process for the production of the organo si lic ium compounds according to claim 1, characterized in that g e k e η η ζ ei without t, that you can phosgene with a silicon compound of the general Formula. T * I (U ₂ S - RL - Si - VXa + b) or with a polymer of the general formula II (VI ₂ H - R> _a - Si - 0 ₄ _ _{(a + b)} or with a copolymer consisting in we sent borrowed from 0.1 to 'jj, 9 ^ HoI- according to units of formula II and from 99.9 to 0.1 fetch io of units of the general formula III R "- Si-O ORIGINAL 9 0 9-81 7 / Q.7 4-.6 ". ■ £, {,,. composed, converts, where in the formulas Ii, H ', Ii. ", a, b, (a + b) and c have the meaning mentioned and (..
Hydrogen or a (-ϋί: ί ^Γ ) group means. 5. The method naoli claim 4 »thereby geke η η draws t that the; Jubstituent U is a divalent hydrocarbon rer ^ t lait 3 to 10 Lohleiistoffatoiion. 6. The method according to claim 5, characterized ge Ic e η η draws t that it has the structure (~ CI-Ip -) - r -, where η is an integer of 5 _t 4 or 5. 7. The method according to claim 4 to 6, characterized in that g -e k e η η-draws, that you can implement in an inert liquid organic reaction chemicals ö. The method of claim 4 to 7 _f characterized in that the reaction with phosgene zuei'st carries out at low temperature and the reaction temperature during the reaction increases. 9. The method according to claim 4 to 8, characterized in that g e k e η η-draws | that phosgene is used in abundance ^ 3 to 5 times the stoichiometric required Amount corresponds to 76XXVI δ O 3 8 1 7 / O 7 U 6 _BATH