DE1770262A1 - Novel perhalo isoalkoxyalkyl alcohols and acrylates and methacrylates and polymers thereof - Google Patents

Description

It iat known that au "a number of known ev fluorinated alcohols folymethaorylate Shuren _# acid derivatives and polyacrylates and, dfe ala TenBlde and means, etc. for example, Texkiller. Oil" patch "and faen MZV-water resistant to, can be used Can be prepared, In these Pclymeren let uine pluoroalkylkettö bonded to an active acrylic cell. The oleophobicity and hydropobicity of these polymers can be attributed at least in part to the low surface energy of the fluoroalkyl chain of the molecule would be the bond to the surface of the carrier ", or perhaps one! TextHi ₄ . in a physical or chemical way through the active aero-layer, wi * tl. HLoAA known all of these

2098U / 1623

BATH ORIGINAL

fluorinated acrylates and methacrylates are capable of the surface to give a wearer both bi-repellent and stain- and water-repellent properties. Even more essential It makes a difference that the means lire when washing or chemising can be easily removed "which is obviously due to the fact that the binding of these materials to the Carrier is unstable.

From the new polyhalo-isoalkoxyalkyl alcohols of the invention can now agents with surprisingly superior surface activity and oil, stain and water repellency, especially the acrylates, methacrylates, polyacrylates and polymethacrylates of the invention. The alcohols themselves are also used as surfactants and as solvents for polymerizations In Solution usable.

The novel compounds of the invention have the formula

in which R is a radical of the formula

^R l

(I ^L

FC ₁ = R ₁ PCOA-

B ₁

2098U / 1623

BATH ORIQINAL

In which each of the radicals R-, which can be the same or different, is a fluorine or chlorine atom or an alkyl radical having 1 to 9 carbon atoms and is unsubstituted or substituted by one fluorine, chlorine or bromine atom or more such atoms; or two radicals R 1 together form a divalent alkylenate with a maximum of 18 carbon atoms which is unsubstituted or substituted by a fluorine, chlorine or bromine atom or several such atoms, with the proviso that no more than three of the radicals R 1 haloalkyl radicals and no more than xwei of the radicals R _{1 are} alkyl radicals; A is a remainder of the formula

in which each of the radicals R, and R ^, which are the same or different can be a hydrogen or a fluorine atom and R- is a hydrogen "fluorine" chlorine or bromine atom or is a perfluoroalkyl radical,

each of the radicals C and D, which are the same or different can be a remainder of the formula

In the 1st) Z ₁ , Zg, Z * and Z ^, which can be the same or different, a hydrogen, fluorine ", chlorine"

2098U / 1623

BATH ORIGINAL

or is a bromine atom with the proviso that not more than two of the radicals Z _14, Z ₂ , Z ~ and Z ^ are chlorate and not more than one of these radicals is a Broiatco, or 2) any other radicals Zj, Z ₂ , Z »And Z ^, which can be equal or hidden. Are hydrogen or fluorine atoms and the other two, which are identical or different

a) Hydrogen, fluorine, chlorine or bromine atoms «are with the MaSgate that not both are bromine atoms, or

b) radicals of the formula -C (X _{ft) v} ^{In the} E ^ach of the radicals different \ r "dlt same or a fluorine or bromine atom .. chlorine * fc," ind or

o) Zj and Z. together or Zy and Z ^ Susanne form a divalent aliphatic bed, or 5) jtdsr of the rents Z ₁ and Z ,, which can be the same or different, a hydrogen or fluorine atom and each of the radicals Z ₂ and Z ^, which can be identical or different, is a radical of the definition given in a) or b) above, or

d) a radical of the formula -CF ₂ X ₁ ,, -Y ₁ -OY ₂ , -Y ₁ -Y ^ or -0-Y4, in which X _{b is} an alkyl radical with 1 to 8 carbon atoms, which is unsubstituted or with a Fluorine, chlorine or bromine or several solitary atoms is substituted, is,

Y _{1 is} a saturated alkylene radical which is unsubstituted or has one or more fluorine, chlorine or broa atoms

BAD ORIGINAL 2098U / 1623

of such atoms is substituted: Y. _? a hydrogen atom is an alkyl group, Y «is an aryl group and
Y ^ is an alkyl group
e) Ζ «and Ζ, together a» white aliphatic

Remainder form j

with the proviso that the carbon atom to which the radical X is bonded * is also bonded to r.wei Waesei -stffatoate, & 0 or an integer from "> to 15 "

η O or a whole ^ number ron '»to 7 ^, mß. preferably

ν O or? is / with the proviso = that the Susiei * iron m ,, η

and ν is at least i ^ and Xi is a residue of i'oraiöl

-OH wire

0CCH ₃

0 M.
in the M a hydrogen atom or * a methyl radical iat. _;

The radicals C and D can be olefinically unsaturated Telomerizable connections derive! Russians, however do not derive from such compounds, although they are preferably obtained also from such compounds.

Particularly preferred radicals C and D are GP ₃ CF ₂ , CH ₂ CH ₂ , CPgCHg, CPgCClP, CP ₂ CF (CF. *) and in particular the first two. In a preferred class of compounds, C is the Reet CFgCF ₂ i'nd D the remainder CHgCHg.

2098U / 1623

BATH ORIGINAL

If the radical A contains alkyl or perfluoroalkyl radicals, these sub-substituents preferably contain a total of 1 to 6 carbon atoms. Specific examples of radicals A are -CP ₂ CF ₂ - * -CP ₂ CH ₂ - and -CHgCHgp. The radical A is preferably perfluorinated.

The radicals R, in the new compounds are preferred all fluorine atoms or perhaloalkyl, especially perfluoroalkyl, radicals.

Of the four radicals R- are preferably not more than three haloalkyl radicals. All radicals R ^ are preferably fluorine atoms or perhaloalkyl, in particular perfluoroalkyl radicals, in particular those with 1 or! 2 carbon atoms. If the radicals R ₁ and R ₂ are substituted with halogen atoms other than fluorine atoms or contain hydrogen atoms, they preferably contain so many fluorine atoms that the atomic ratio of fluorine to other halogen atoms, to hydrogen atoms or to the total number of other halogen atoms and hydrogen atoms is at least 1 : 1 is.

Examples of radicals R or R- (C) _n , - (D) _n - (CH ₂ ) _v - are

List e A

? ^P 3? ^P 3

PCO- CP ₂ CH ₂ PCO- CP ₂ CF ₂ CH ₂

2098U / 1623

BATH ORIGINAL

CP ₀ Cl

β 2 5 ^Ρ 3.

PCO CP-. -CO- (CPg) ₁₀ (CHg) ₁₀

CP

g ₃
PCO- CPgCPHCPHCHClCHgCHgCHgCH ₂

C)

₅
(CCIg) ₈

F-C-O CF,

PCO- CPgCPgCPHCPBrCHgCH ₂ CP,

CF,
FCO-CF, (h - 1-10) F -

? ^F 3 CO-

(h - 1-10)

CP

PCO- (CF ₂ CFCl) ₁₁ CH ₂ CHg F - C - 0 - CP ₂ CP ₂ (CH ₂ CH ₂ ) J ₁

CF

3 (h - 1-10) CF

3 (h «1-10)

FCO- (CPgCP (CP ₃ )) _h CHg ^CP 3 (h - 1-10) P - C 2 0 ■ CPgCPgCPgCH ₂ CP,

2098U / 1623

BAD ORiGlNAl.

CF, CF,

FCO- CP ₂ CP ₂ CHgCH ₂ PCO CPj CFj

CF, CF,

9 3 β 2

CF ₂ Cl

FCo- (CFp) ₂ (CHpK FCO CFj CFj

CF, CF ₁

PCO- (CFg) ₅ (CHg) ₂ PCO-

CFj CFj

CFj CF ₂ Cl

CFj 'CF ₂ Cl

PCO- (CFg) ₂ Q (CHg) ₂ FCO-CFj CF,

F (CFg) j FCO- CFHCH ₂ FCO- CFgCPgCHgCHg

^CF 3? ^F 2

F (CFg) J
FCO- CFgCFgCFgCFgCHgCHg

2098U / 1623

BATH ORIGINAL

F (CPCl) ₄

? ^F 2
ρ - CO- CP ₂ CFgCPgCPgCFgCPgCHgCH ₂

9 ^P 2
F (CFCl) ₄

Ά.

CF ₂ > C - O - CFgCPgCF ₂ CH ₂ CH ₂

pCo- CP ₂ CFgCPgCPgCHgCHg

C χ- O ** CffrtCFCPrtUPpCiioCno

CF,

β *

pC-0 Cp ₂ CPCH ₂ CH ₂ CH ₂ CH ₂

• ⁵ 9 * ·

(CF ₂ ) ₃ Αϊ-0- CP ₂ CP ₂ CHgCH ₂

CP ₂

^CP 2

p * C - 0

^CH 3 2098U / 1623

BATH ORIGINAL

P-C-O-CPgCPgCH-CH-CHg

F-C F -C-O-P-C-F

CP-,

8 2

P-C-CP

FCO-CF ₂

P-C- CF *

2098U / 1623 _{MD 0RI (3INAL}

^{0 5}
PCO- CP ₂ CH ₂ CHCH ₂ CB ₂

PP P

βο ι

P = C-C - C-P

0 1. »

PCO- CPgCPgCPgCPgCHgCH ₃

? * 2

CP ₅

H - C - CP _{5 2}

CP ₀ CP ₀ ρ. C - O - CPgCPg-CP -— CP-CHgCH ₂

CP ₀
HC- CP ₁ .

(CPg) ₈ P

PCO- CPgCPgCPgCPgCPgCPgCPgCP ₂ CHPCHgOHPCH ₂ (CPg) ₈ P

2098U / 1623

BATH ORIGINAL

CP-.
FC-CP

FCO- CPgCPCPgCFgCF ₂ CFgCH ₂ CH ₂ CHg

B t

CF, CF - CP ₅ CF *

(CF ₂ CPgCl FCO

⁽ ? ^P 2 ^} 9

F - C - O -

⁹ CF

A group of compounds "which are particularly suitable for the production of polyacrylates and -ethaorylates with oil, flake and water-absorbing properties" are those in which the radical A- (C) _n (D) _n - (CH ₂ ^ -, - (CFg) _x - (CHg) _y OH, in which χ and y, which can be the same or different, are whole numbers from 1 to 20, the sum of χ and y preferably not being more than 16 and In particular, less than 10

2098U / 1G23 BAD ORIGINAL

amounts to. In a preferred class of compounds, χ is 1 to 20, in particular 1 to 10 and y »1 to 10, in particular 1. In a further preferred class of compounds, χ is an integer from 2 to 16, in particular 2 to 10, in particular if y is an integer from 2 to 16, in particular 2 or 3 or 3 to 10. In a further preferred class of compounds is χ is an integer from 2 to 10, and y is 2 or 3 * In a further preferred class of connects ™ fertilize 1st χ an odd number of 1 to 10 and y is an odd or even number from 4 to 10. η of this group of compounds are preferably all radicals R ₁ fluorine atoms or perhaloalkyl radicals, in particular those with a maximum of 19 carbon atoms in which all halogen atoms are fluorine or chlorine atoms and at least one fluorine atom is bonded to each carbon atom, the perfluoroalkyl radicals being particularly preferred when y is 2 or greater than 2.

The length of the carbon chains is only determined by the requirement that the products obtained are those for the desired ones Application have required or desired solubility.

The new alcohols of the invention can be obtained from the corresponding telomeric compounds of the Po in the el

R -

2098U / 1623

BATH ORIGINAL

in which E is an iodine or bron atom, provided that the carbon atom to which B is bonded does not have two halogen atoms, by reacting with sulfur oxide to form the corresponding acid halide, the acid is "halogen" it is an "alkenol" at temperatures In the range of about 0 to 25% to the corresponding ester and subsequent reduction of the ester with a mild reducing agent such as Llthluualunlnlunhydrld In ether to the desired alcohol. Another process for the preparation of the new alcohols consists in the (dehydration of a telomeric compound of the formula R- (C) _m > (D) _n - (CH ₂ J ₇ -E, in which E is iodine or bromine, with the proviso that , if ν »0, the carbon atom to which the radical E is bonded, carries a hydrogen atom, an alkyl group, an alkylene group, a haloalkyl group or one or more haloalkylene groups, with sulfur trioxide to form the corresponding polyulfates and these then at about 1 <XÄ hydrolyzed to the desired alcohol with 35 to 50 liters of sulfuric acid.

The telomeric starting materials for these conversions and the preparation of the polysulphate from these telomeric compounds is described in the patent (patent application

P 17 68 288..L-43J of the same registration in dated

described the same day.

2098U / 1623 ^ÖAD

We ft creating the tei "ner * Output Ever bonds preferred ung""Ä.vigt _e telom" r * i. * rbare connections "UP ₂ CF _2, CF ₂ CH _2, CF ₂ -CC ^ * CF," CF «CF _g and CHg-CHg. Further suitable tele "ri"i> _r ^ re unsaturated compounds and: CCl ₂ -CH ₂ , CfH-CH ₂ , CfIH-CH ₂ , OFH-CF ₂ 'CFH-CFH, CClH-CClH, CF ₂ -CFBr, OF ₂ ClCF-CFj, CF ₅ CH-SCF ₂ , CF ₅ CCIaCF ₂ , CF ₃ CF-CFCl, CF ₅ CH-CTl, CFCl-OFCl, CF ₁₃ OF-CH ₂ CF ₂ BrCF-CF ₂ , CF ₅ CF- ^ CF ₅ , CHF-CFCiCl ₂ , CHF-CFCF ₅₁ CH ₅ , Cf ₂ -CFCHCICH ₅ , CF ₂ «CF <C ₆ H ₄ Cl), CP ₂ -CF (C ₆ H ₄ (CH ₅ )), CF ₂ -CF (C ₆ H ₄ (CH ₂ Cl)), CF ₂ -CHOF ₂ CH ₅ , OF ₂ «CHCF ₂ CH ₂ C1, OF ₂ -CHOF ₂ (C ₆ H ₅ ), OF ₂ ^ HCF ₂ (C ₆ H ₄ Ol), OF ₂ «CHC :? ₂ (C ₆ H ₄ (OH ₅ ) X CF ₂ -CHCF ₂ (C ₆ H ₄ (CF ₂ Cl)), CH ₂ -OjJF ^ JF ₂ Br, CW ₂ -C (CF ₅ ) CF ₂ (C ₅ H ₇ ) CHCl-CFCF ₅ , CH ₂ -OlCF ₂ CH ₅ ,

CF-CF CFCl-Cl (F ₀ -CCl CFdHOF OF-CF CHF-CF CF ₂ -CFBr, CF ₂ -CF, CF ₂ -CF, CTOL-CF, CF ₂ -CF ₂ , CHF-CF,

P »2 CF ₂

CF ₉ "· ^z ♦ ·

CH ₂ -C (C ₂ Hj) ₂ , CH ₂ ^ OH-C ₆ H ₅ , CH ₂ -CHCH ₂ CH (OC ₂ H ₅ I and (OH ₂ -CHCH ₂ ) ₂ a

2098U / 1623

BATH ORIGINAL

A number of these compounds are in the US patent specification 3143222 listed. The Paöhmann, however, has a far greater responsibility for such connections, the the above definitions are available.

Which process is preferably to be used for the preparation of the preferred compounds according to the invention, in which -A- (C) _n - (D) _n - is the radical (ΟΡ ₂ ) _χ (ΟΗ ₂ ) _ν , depends on which Values χ and y have:

1) When χ is an odd number from 1 to 19 and y is 1, the alcohols can be prepared by reacting the perhaloisoalkoxy alkyl iodide * in which χ is an even number from 2 to 20 and y equals 0, i.e.

PCR ₉

P-CCO - (CP ₂ ) _X (CH ₂ ) _O J

PCR _n

with sulfur trioxide to a mixture of the acyl fluoride and des Perhalogehalkoxyfluoroalkylpyrosulfurylfluorid !, Reacting this mixture with an alcohol such as methanol, ethanol

209814/1623 ^ ₀ OR ₁ GINAl

I7 -

u * dgl «, to the corresponding ester and reducing the Esters with lithium aluminum hydride to the alcohol can be obtained * The reactions can be illustrated as follows will:

C -
I. H ₂ X * number SO ₃ C -
t O - ( C -
t B ₂ [CFg) _x CF ₂ J 1-19 ^E 1 * odd

^R 1 C

C »

?1

-R,

-R

- (CF ₂ ) _x cr + ρ

^H 1

OSO ₂ F

- O - R ₂ -CO- (CF ₉ ) C ^

- CR ₉ ^ P R,

■ ι

-CR ₉

- C - 0 - (CFg) _x CF ₂ OSO ₂ OSO ₂ F "- \ j '- ΧΙλ Rl

2098U / 1623 "~

• 0xCH _x OH

BATH ORIGINAL

-. 18 -

P-

CR ₂

FCOF - C - R ₂ ^ OCH ₃

FCR ₂

1o) FCO- (CF ₉ ) ^ C "+ LiAlH.

te '

FCR ₂ R ₁

FCR ₂

FCO- (CF ₂ ) ₂ CH ₂ OH

ζ »odd number from 1-19

2) If χ is an even number from 2 to 20 and y is 1, the alcohol can be converted into a compound with the desired appearance by converting the iodide. Groups -CF ₂ - and svei groups

2098U / 1623 bad original

- with alcoholic potassium hydroxide with formation of the Perhalogenisopropoxyfluoralkyläthens by cleavage of iodine, Oxy Ii er en dee Athene with Kaliumpenianetnat to the Acid, converting the acid into a low molecular weight allyl ester and reducing the ester with lithium aluminum hydride to the desired alcohol. This procedure is as follows:

P 2a) ρ

- σ - «2 ClI ₉ CH ₉ J + EOH + alcohol, -C- O - (ΟΪ ₉ ) _ I. -Ο
ι V ^Ε 1

R,

-C-O-

P -

C ~

R ₄

P-C-

P -

CO- (CPg) _x COOH + CHjOH GR ₀

2098U / 162 3

BATH ORIGINAL

ρ «. c - O ρ - σ «

3) If χ an even number from 2 to 20 and y an odd or even number from 3 to 20, the alcohol can be obtained by reducing the corresponding iodine alcohols with lithium aluminum hydride oil with zinc and alcohol «Iodide with groups CP ₂ in the alkyl chain bit an allyl alcohol with x-2 (ie 1 to 17) groups OH ₂ in the chain attached to the terminal hydroxyl group. These implementations are illustrated by the following equations:

PCR ₉

PCO- (CP ₂ ) _X J + CH ₂ = CH (CH ₂ ) _y - ₂ OH + catalyst _ FCR ,,

2098Vi / 162 3

BATH ORIGINAL

3b) PCO- (CPg) _x CHgCHJ (CH ₂ ) gOH + Zn and alcohol PCR ₉

FOE ₂

3o) Ϊ - C - 0 - (OTG) _x OH ₂ OH ₂ (OH ₂ Jy _{-. 2} 0H, _{d h.}

g - 0 - H ₂

fc

P - β - O - (CPg) _x (CHg) ₇ OH PCR ₉ -

R ₁ (y «3 to 19)

4) If χ is an odd number from 1 to 19 and y is an even or odd number from 4 to 19, the alcohols can be converted into a perhalogenoalkoxycarboxylic acid with an odd number of groups CP ₂ in the fluoralkane chain with Ag ₂ O to the silver salt, reacting the bilber salt with iodine

2098U / 1623

BATH ORIGINAL

the perhalogenoalkoxyperfluoroalkyl iodide, Umaetsen of the perhalogenoalkoxyperfluoroalkyl iodide with a unsaturated alcohol (such as allyl alcohol) and separating of iodine, for example, with zinc and alcohol, as illustrated by the following equations:

4a) P
P.

- C - R ₉ -CO- (CF ₂ J _x (CH ₂ ) ^ OH + ~ eR ₂

R,

H ₂

Ag ₂ O

6QK

P »
4b) p -
P - C -
t
C -
J
C -
9 R ₂
0
R ₂ ^R 1 P - C -
J R ₂

-0 ~

odd number from 1-19,

+ CH ₂ = CH (CH ₂₎ i2 ° H η

ioo «c

catalyst

2098U / 1623

BATH ORIGINAL

F.
P.
P.

-CR ₉

-CO- (CPg) _x (CH ₂ ) CHJ (CH ₂ ) ^ ₂ OH + Zn + alcohol

-CR ₉ ^fi 1

P.
P.

CR ₀

t «

CO- (CFg) _x CH ₂ CHg (CHg) ₁

C - R "R.

^R 1

P.
P.
P.

-CR ₂

-C-O-

-0 -E ₂

, (CH ₂ ) _y OH

5 and 6). If χ is an even number from 2 to «20 and y am 1 3, the alcohols can be removed by hosing the corresponding Jcdids with sulfur trioxide to the pyroaulfate or with oleum to the hydrogen sulfate and hydrolysis of the Plucr-

2098U / 1623

SAO ORIGINAL

177U2K2

at.ii or · - »IiydiOipinauiratu tail

Acid to the Λ1 ioho3 can be obtained I) Jenrc Umne become by ^ h dif-: fjigenden Gloi ohmi / ron ■ voranoahouli «? 1j1:

5a) animal dao Hu I fat:

51 »)

F.
3

(J

F - C ~ Hr, Γ O- 0 «

Γ> ■ 0 - Jin

RO,

0 ί V / Hrrae and i'erdtinutc

5o)

6) In addition to hydrogen sulfate

9 0 U / Ui?

BATH ORIGINAL

F-C- Rr

t * ■

6a) F-C-O

I.
FC-Rr

ρ « R ₁ Ro si P - C - 0 F - J R ₂ 6b) C - I.

H ₁

- C - R «

P -

σ - ο

CR, ^R 1

F.
P.

- R "

C -

0 - (CF ₂

Marg

770262

(H ₂ SO ₄ + SO ₃ ) oleum

so

rardUnnte H ₉ SO,

U ₀ O (25-753>) '* (heat 90-100 ⁰ C)

even number from 2-20, y *!

0 ^ H Mf M) 2 3

BATH ORIGINAL

In particular, alcohols according to the invention of any desired -CH ₂ chain length with two or more carbon atoms can be obtained by reacting a corresponding telomeric iodide with ethylene or an ethylenically unsaturated alcohol such as allyl alcohol, as illustrated by the following equations 7 and 8:

PC no
ι ^Ä

PO- 0 - CP ₂ CP ₂ (CP ₂ CP ₂ ) _U J + OH ₂ «CH ₂

POR ₉

'j * R ^

^R 1

CR ₀ σ-0- CP ₂ OP ₂ (CP ₂ CP ₂ ; σ-ο

^R 1
POR ^

c - 0 - CP ₂ CP ₂ (CP ₂ CP ₂ ) _U J + CH ₂ 0 - Ro

■ Γ

U a 0-10

Y = J-9

CH (CH ₂ J ₁ OH -

2098U / 1623

BATH ORIGINAL

17 7 η? ß

71 -

P - C -
ι, R _? Pg) _n CH ₂ -CHI (OH P - r O = P - O « H ₂

Alcohols having an odd number of -OPj, - Groups can Umaetsen einee rei ⁱ lmlogMiieoall'oiyp ^<i * i3w ^Iji '· alkyljodido mil an even number van "- (Γ *, - Gi'iippcn with sulfur trioxide, VerciHorn (Ipp Iloa1r1innnprofluli1fin _f Heduzioren dee Eetoro ru dem Allu> Iiol, as in equations 1) goaisst and convert the alcohol π rail jj-toluene sulfonylohlorid and el mmiiwvm HmX to the iodide with m-1 -Cpo ^ groups and a -OHg- hnrgtS ".

The compounds of the invention in which h the heel

Il t

0 M.

means can implement dee appropriate Alcohols in which there is a hydroxyl group instead of L, with an aoryl bond of the formula

M o

“Il

HpC = 0 - G - Q

2098U / 10.7 3

BATH ORIGINAL

in which M is hydrogen or a methyl group and Q Is chlorine, a hydroxyl group or a methoxy group. The acrylic compound can also be used in the form of their anhydride, which can be formed in situ, be used, 3 Inlern one an acrylic acid and perfluor there is acid anhydride at a temperature below React room temperature with the alcohol "

The molar ratio of the reactants is not essential. In two ways, about 0.1 to 10 moles of alcohol per mole of aoryl compound are used and the best yields are obtained when the reactants are about stoichiometric
Quantities, ie in a molar ratio of about 1: 1, are used.

The reaction proceeds smoothly even in the absence of a solvent. However, as usual a solvent as a diluent and in order to facilitate the implementation of the reaction at an elevated temperature au, can be used. Anyone can do this Solvent which is inert under the reaction conditions can be used. Examples of suitable Solvents are: Beneol, Pyridine, Quinoline, Hitrobensol, Pearethyl anlinine, irifluoroacetic acid, beoalin

2098U / 1623

BATH ORIGINAL

- 29 and 1 »1., 2 trifluoro-1,2 _v 2-trichloroethane.

To reduce the reaction time, any of the known esterification catalysts such as pyridines can be used Quinoline, p-toluenesulfOA acid,

Phosphoric acid, sulfuric acid or C ^ prichlor! D can be used. The amount of catalyst used is not essential; it can be between about 1.0 and 200 percent, -. ^ are the alcohol used, if Aorylyl- Methaorylylohlorid or ₉ is used will act as a catalyst, preferably pyridine or quinoline, which, if used in sufficient amount to harden as a solvent, * In addition, pyridine and ghinoline have low boiling points and can therefore be easily separated from the reaction mixture by simple distillation. Pyridine and quinoline are generally used in an amount of about 0.10 to 2.00 parts, preferably 0.5 to 1.5 parts, per part of alcohol used.

The reaction temperature can be in a wide range, for example between room temperature and the boiling point of the reaction mixture vary. Usually

2098U / 1623

BATH ORIGINAL

«30 -

a temperature between about room temperature and 10O ⁰ C is applied, and the reaction mixture is gently stirred. If the acrylic acid is used in the form of its anhydride, the reaction mixture is preferably kept at about room temperature, ie between about 10 and 30 ^° C. and in particular below about room temperature «

The esterification is preferably carried out in the presence of a small amount of a customary polymerisation inhibitor, like hydroquinone, o ^ pinene and p-tert.-butyloatechin, to premature polymerization, which can take place in particular at elevated temperatures avoid"

The reaction times depend on the reactivity of the aoryl compound used, whichever is used Catalyst and other factors, such as the temperature from »It is generally between about 30 minutes to a few hours «.

Recovery and purification of the esters formed can be carried out by the usual measures, such as solvent extraction, multiple washes with water and ansohlieSendee

2098U / 1623 ^ ₀ original

- 31 drying or ordinary distillation take place «

According to the above methods, one can monomeric fluorinated aoryl compounds or, called mixtures of All-season alcohols are used, Oemiaohe such Connections are obtained.

The invention also relates to the homopolymers and copolymers including the new aorylates and methaorylates can be obtained and repeating units of the formula

CH ₂

included and also units that are calibrated by others oopolymerizable ethylenically unsaturated monomers Derive connections, can contain «

You can polymerize in any usual way, for example as solution polymerization, Maaaenpolymeriaation, Emulsion or suspension polymerization take place. Sine Kaaaenpolymeriaation can under beat irradiation with light

2098U / 1623

BATH ORIGINAL

or when used as a "free radical-forming agent" Catalyst-based initiator takes place. For «Ina LSeungapolymeriaation Can any suitable LtSaungMlttel * like Trlfluorethyltrlfluorooetat or a halogen-containing carbon dioxide, such as 1,1,2-TrlehlortrltluorMthan or 1,3-bis (trifluoro »ethyl) benzene and a catalyst like a Peroxide can be used as initiator.

Yorsugftwelee the Polyaerlaatlon takes place in wftBrlger anulaion. Oaa Polyaer is ala Latex or «1 · alB Oealaoh from obtained koagullrteai polymer and latex. Dia attachment can by Zueats Oblloher anlonlaoher, nioht-ionlaoher or cationlaoher official agent. Oeelgoete teulglermittel are beiaplelaweiaei sodium auryl sulfate, daa Kalluaaalx of Perfluoreulfonelure, Trlaethyltetradeoylaomonlumohlorid, latriuBlauryleulfoauoolna * and Ethylenoxldkondenamte of alkylphenols or alkylanines

The Polynerlaatlon in wiflrlger fculaion and dia polymer Ieationtn with other Tarfanren take place before aweiae in Oegenwart a ·· Katalyeatora, ntoliöh ainea organ cells or aaorgan cells forming free radicalsea Catalyst dea * eroxidtype. Dleet Katalyaatoran aind

209814/1623

ORIGINAL

known. Examples of suitable such catalysts are: benzoyl peroxide, lauryl peroxide, acetyl peroxide, suocinyl peroxide, potassium pereulfate, hydrogen peroxide, a, o ⁹ -Äa »bie · .Lsobutyronitrile, 2» 2'-azodiisobutyramidine dihydrochloride, cumene hydroperoxide and the like.

Various conventional additives can also be added to the recipes for the polymerization, for example chain transfer agents such as carbon tetrachloride and mercaptans, crosslinking agents such as divinylbenzene and alkylene glycol dimethacrylates, water-soluble organic solvents such as ethylene glycol, Ethyl alcohol and acetone, and inorganic salts such as chlorides, carbonates, acetates, phosphates and borates, which act as electrolytes and buffers.

The polymerization is usually carried out at a temperature between room temperature and about 10O ⁰ C. The time required for the polymerization depends mainly on the temperature employed, the monomer compounds used and the catalyst used. It is usually about 1 to 72 hours.

The polymerization can be followed by clicking on

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1770252

the formation of a rubbery or hard-like material or watch out for the onset of coagulation or the formation of an emulsion.

The new monomeric compounds of the invention can be mixed with any other ethylenically unsaturated monomers Compounds, especially those with terminal double bonds, are polymerized. Examples of this are the vinyl compounds, for example vinyl esters such as vinyl stearate, vinyl butyrate, vinyl acetate,

Vinyl halides such as vinyl fluoride, vinyl chloride, vinylidene fluoride, and tetrafluoroethylene; Vinyl alkyl ketones such as Vinyl methyl ketone; Vinyl alkyl sulfones such as vinyl isopropyl sulfoni Vinyl ethers such as methyl vinyl ether; H-vinyl urea; Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene; aromatic compounds with olefinically unsaturated groups such as styrene and methyl styrene; other acrylic compounds such as acrylic and methacrylic acid and their esters and amides such as methyl aorylate, methyl methaorylate, Butyl aorylate, 2-ethylhexyl acrylate, 2-ethylhexyl methaorylate, Deoxy aorylate, lauryl methacrylate, stearyl acrylate, hydroxyethyl aorylate, hydroxypropyl methacrylate, tert-butylaminoethyl acrylate, Ν, Ν-diethylamino-

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ethyl methacrylate, glycidyl acrylate, acrylamide, methacrylamide, I-Hethylolaoryiamid »I-Methylolaethaorylaaid, H-Isopropylaorylaaidi other unsaturated Beter, such as methyl oretonate, methyl maleate, diethyl famarate, allyl acetate and allylo acrylate. Other fluorinated monomeric aoryl compounds can be mixed with the new monomeric Compounds of the invention co-polymerized «ground.

You can temendet new polymers of the invention «Earth to make surfaces oil-, fleoken- and water-repellent oooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooo For example, if the polymers are obtained by bulk or suspension polymerization, can al · directly from their solution in a suitable organic solvent applied to a frager "earth. The organic solvent can do that in which the polymerization took place «Venn that Polymer obtained in the form of an aqueous emulsion the supernatural can be established »by The emulsion obtained has been diluted with water or another solvent to such an extent that it can be used as a transfer agent suitable. The optimum solids content of the dispersion or solution of the polymer depends on the

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The polymer itself, the coating on the carrier provided and. other actuators.

You lOlymerdispereion or solution can according to usual Methods such as spraying, painting or immersion applied to the carrier. The old coated surfaces can then be dried be to the water, solvent or bisperion medium to separate.

The new polymers can be applied to a wide variety of materials, in particular porous materials, textiles, other fiber materials, tides, fabrics of natural or synthetic origin, for example fabrics made of cotton or Ijlon, and on non-porous substrates such as paper, BoIs ₉ metal and the like. Like., be applied, including making these oil, stain and water repellent su.

The new polymers of the invention can also be used by other means, for example old other textile or paper equipment, «le Lelmungs- and Sole sealants, means sub Knivterfeetmaohen Clay textiles, diluents * sur reduction

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Cost of equipment, means of making water tight and the like can be used to combine some of these agents with the novel polymers of the invention gives a synergistic effect in terms of oil and water repellent. Suitable scattering agents are other homopolymers and copolymers of the above-mentioned, with the new monomeric compounds of ^

Invention of copolymerizable IS compounds, preferably non-fluorinated polymerizable unsaturated Compounds such as alkyl acrylates and methaerylates, for example methyl aorylate, ethyl methacrylate, isopropyl aorylate, Butyl methacrylate, 2-ethylhexyl aorylate, 2> ethylhexyl methaorylate, 3,5,5-trimethylheiylacrylate, Lauryl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate And the like. Other polymers suitable for this purpose are also the homopolymers and copolymers of N-methylolacrylamide, N-methylolmethacrylamide, Acrylonitrile and methacrylonitrile, Auoh waxes and condensation products based on formaldehyde can be used can be added to the coating oases to increase the durability to improve the coatings.

Preferred aoryl polymers of the invention, which are composed of the

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Preferred monomeric fluorinated aory! Compounds of the invention, contain repeating units of the formula

^R 1

O CH ₅ Γ

PCO- (CP ₂ ) _x (CH2) _y - 0 - C - CK PCR ₂
R ₁

in which Η *, R ₂ , χ, y and M have the meanings given above.

Purely the production of the preventive copolymers of the Br « The following coaonomers are presumed to be found used. Methyl acryl at, methyl ethacrylate, methacrylic acid, 2-XthylheJcylacrylat, Hydroxylakyleethacrylat, Dieethyleeiino-Mthylmethaerylat, 2-Xthylhexyl ethaorylate, 2-methylnexyl-

aorylate, K-methylolacrylamide, hydroxypropyl methacrylate, Butyl aorylate, butyl methaorylate, tert-butylaeinoäthylmethaorylat, n-Ootyla aorylate, n-Ootylaethaorylate, Ieodeoylaorylate, Ieodecyl methaorylate, glyoidyl aorylate, Slyoidyl methaorylate, ethylene acrylate, and ethyleiuwthaorylate.

209814/1623 bad original

Fluorinated monomeric acrylates of the invention which are particularly suitable for a copolymerization or copolymerization of other monomeric compounds are:

) ₀ CF0CF ₂ PF ^ CF ^ CF ^ CH ₂ PH ₂ 0C0C (CH ₅ ) -CH ₂ and (CP ₅ ) ^ F0CF ₂ CF ₂ (CF ₂ PF ₂ ) ₂ qH ₂ CH ₂ 0COC (CH ₅ ) -CH ₂ . Example "for Interpolyeere of the fiery dunes are"

25-50% (CF ₃ ) ₂ «» OCF ₂ CF ₂ CF ₂ CF ₂ cE _? CH ₂ 0C0C (CB ₅ ) -CH ₂ (S) 25-55-1 / 55 *

Example «for StreokunflMittel» those in the Upper LapaMJiin are used kSonen "are the foleendwi FolTawren" HoMopoljaer too n-Octjlaetheoiylet «HoBopoljMer from rt-Butyl • orjrlwt «HoBpolyawr from Ieodecylaethaorjlet» Copolya · «mus n-Ootylaetbeoxylat and V-Mettqrlolaoryleaid, Copolyaer pu n-Steerylaetbeor / lat and V-Methylolaerf leaid «Copolap ^ r from n-Butylaetheoiylet and M-Methylolaerjrlaaid, Copolyaer «us Ethyl aorylate it V-Methylolaorylaaid, CopolyMr au · Matliyl- ■ ethaerylat alt S-Hetlqrlolaeiylaaid, CopolyMr from n ■ jttheorylat ait M-Methyloleorylaald, Copolyaer aua n-I Ttthaorylat "with OydroXypropylaethmprylftt, Copolymer aua

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n-lauryl methacrylate with methyl methacrylate «copolymers n-Lauryl methaorylate with dimethylaminoHtiyl methacrylate, copolymer from 2-ethylhexyl methacrylate with N-methylolacrylamide, Copolymer of xsodecyl methaorylate with N-methyl aorylate, Copolymer of xsodeoyl methaorylate with hydroxypropyl methaorylate, Copolymer of isodeoyl methaorylate with hydroxyethyl methacrylate, copolymers of xsodeoylaethaorylate and n-butyl aorylate and N-methylolaerylamine, copolymer of xsodeoylnethaorylate nlt methyl methacrylate and N-Metfcylolaorylaald, Copolymers of iodecyl methaorylate and n-butylaethacrylate and N-methyl aorylaid, copolyner from methyl methacrylate old N-Methylolacrylainid, copolymers from Ieobutylaethaorylat nlt N-Me t hy 1 oil acrylamide and copolyner from Ieodeoyl methacrylate nlt N-methylol aorylate and xethylene glycol / methyl aorylate.

The following examples are intended to further illustrate the invention. Details in parts relate to the Oevloht, eof em not specified others.

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ÖAD ORIGINAL Example 1

In a reaction vessel equipped with stirrer, thermometer, and Rüekfluflkühler 51 g of bis (1,1,2,2-tetrahydro ~ ο c tafluor-6-heptafluorisopropoxyhexyl) pyr ο sulfate and 15 g of acrylic acid placed ₀ The mixture was 24 hours on 105 ⁰ C heated, during which time two liquid phases formed. The liquid was cooled to room temperature and the two phases were separated, the lower, water-insoluble phase (45 g) was distilled to give 38 g ($ 70) of 1,1,2,2-tetrahydrooeta-luoro-6-hepta-luoroisopropoxyhexyl acrylate formula

0-0-CHeCH ₂ , bp 48 - 51 ⁰ C / 1.5 mm.

10 g of CF ₂ OF ₂ OF ₂ CF ₂ CH ₂ OCOCHsC ^, 60 g of deionized water, 6 g of 24 / t aqueous solution of ethyldlmethylanionium acetate and 0.3 g of 2.2 ^l -hydrochlorld introduced. The flask was purged with nitrogen

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-42. 1770282

and the reaction mixture was heated to 6O ⁰ C

and held at this temperature for 6 hours. Included

An aqueous polymer emulsion was formed.

Example 3

17 g (0.052 Hol) 3 β 3 »4» 4-tetrafluoro-4- (heptafluoroisopropoxy) -1-butanol _t (OFa) ₂ OPOCP ₂ CF ₂ OH were placed in a 50 ml porridge shark flask equipped with a stirrer, reflux condenser and thermometer ₂ CH ₂ OH, 0.09 g of hydroquinone and 12 g (0.13 mol) of aorylylochloride, CH ₂ * CHCOC1. About 0.1 g of CuCl _{2 was} used for each catalyst. The mixture was slowly warmed ^{to 30 ° C.} After the evolution of hydrogen chloride began, the heating was stopped. The temperature of the mixture was then increased to 40 ^{° C. within 1 hour and to 75 °} C. within a further 3 hours. The reaction mixture was then cooled and the product was distilled using a sliver column. Überrechtteeigee-Aerylylehiorid wurÜ ^ W i. Flash evaporated and the residue was distilled. 13 g (yield 65.3 #) of (CFj) ₂ CFOCF ₂ CF ₂ CH ₂ CH ₂ OCOCH »CH _{2 were obtained} .

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1770252

Example 4

In a 100 ml three-neck flask, 2.5 g of GF ₂ CP ₂ CH ₂ GH ₂ OCOOH = Ch ₂ with 20 g of deionized water, 0.17 g of 30% hydrogen peroxide solution and 0.9 g of an emulsifying agent (prepared by mixing of 6 parts of cetyl-dimethylamine, 2 parts of glacial acetic acid and 24 parts of water). The flask was purged% with nitrogen. The temperature of the reaction mixture was increased to 55 ^° C. and a stable polymer emulsion was formed within 4 hours.

Example 5

68 g (0.207 mol) of 3,3,4,4-tetrafluoro-4- (heptafluorieoprop- * oxy) -1-butanol, (OPj) ₂ CIOCr ₂ CF ₂ CH ₂ CH ₂ OH, introduced together with 18 g (0.210 mol) of methacrylic acid, 0.7 g of concentrated sulfuric acid (96%), 2 g of hydroquinone and 150 ml of benzene. This mixture was refluxed with stirring. After about 6 hours, 2.9 g (0.16 mol) of water had collected in the Dean-Stark trap and the reaction mixture was transferred from the flask to a distillation flask.

2098U / 1623

The benzene was evaporated off, and there were obtained 4 g (0.012 mol) of starting alcohol and 67 g (0.17 Hol, conversion 82%, yield 88 £) of the methacrylic acid ester (CPi) ₂ CPOCF ₂ CF ₂ OH ₂ CH ₂ OCOC ( CHj) -CH ₂ from Kp 61 bit 63 ° 0/4 mm.

Example 6

The methacrylic acid ester obtained in Example 5 was polymerized according to the method of Example 4. A stable aqueous polymer emulsion was obtained.

Example 7

In a 100 ml three-necked flask equipped with a stirrer, reflux condenser and thermometers were 46 g (0.038 moles) of the

* Pyrosulfate

1.0 g hydroquinone and 15 g (0.20 mol) aoryl acid, CH ₂ -CHOOCH, brewed. The Oemisoh was heated to 100 to 110 ⁰ O and kept at this temperature for 15 hours. Danaoh was distilled da · Oemisoh using a sliver column. This gave 19 ff (0.023 Viol, conversion 42 *, yield 79 *) (OFJ) ₂ OFO OF ₂ OF ₂ (OF ₂ OF ₂₎ 2 OH ₂ O ₂ OOOOH-OH _2, Xp 82-83 ⁰ O / 2

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Calculated for O ₁₄ P ₁₉ H ₇ O ^:

O 28 ₈ 77 P 61.81 H.1 _p 20 ₀ Found: C 29.34 P 62.71 H 1.05.

Example 8

2.8g 1,1,2,2- -

Tetrahydrododeeafluoro-S-heptafluoroisopropoxyocylacrylate, 20 g of deionized water, 1.8 g of an emulsifier (prepared by mixing 6 parts of cetyldimethylamine, 2 parts of glacial acetic acid and 24 parts of water) and 0.6 g of 30% strength hydrogen peroxide solution were introduced. The mixture was purged with nitrogen and heated for 6 hours at 55 ⁰ Q. Then 0.09 g of sodium lauryl sulfate and 0.05 g of ^K 2 ³ 2 ° 8 were added, and the mixture was heated for a further 2 hours. The solid polymer obtained was further coagulated with methanol, dried in vacuo and dissolved in 1,3-bis- (trifluoroethyl) benzene dissolved,

Example ?

31 g (0.057 mol) of (OPj) ₂ OPO CP ₂ CP ₂ CP ₂ OP ₂ CH ₂ Ch ₂ J, 20 g (0.10 mol) of AgO03C (CH ₃ ) = CH ₂

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and 40 g of CH ₂ -C (CH ₅ ) COOH. Bas mixture was heated to 10O ⁰ O and maintained for 16 hours at this temperature. After that it was washed old water, dried and distilled. 12.5 g (0.025 mol}, yield 44 #) (CT ₃ ] CF ₂ CH ₂ CH ₂ OOOC (CH ₃ ) »CH ₂ , boiling point 69 to 70 ⁰ O / 1.5 mm were obtained.

Calculated for C ₁₃ P ₁ CHoO ₃ :

0.31.35 P 57.25 H 1.81. Found: 0 32.10 F 56.94 H 1.72.

Example 10

_{38 g of (CP 3} ) ₂ OFO CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ OOOO (Ch ₃ ) KCH ₂ , 20 g of deionized water, 0.2 g of 30% hydrogen are placed in a 100 ml three-neck flask peroxide solution and 9.9 pounds of an emulsifying agent, prepared by mixing 6! dents of ethyldimethylamine, 2 (dents of glacial acetic acid and 24! dents of water, introduced) The reaction mixture is flushed with nitrogen and ^{heated to 55 °} C. After 6 hours, about 0.5 g of K ₂ S ^ O ₈ and 0.5 g of sodium lauryl sulfate were added, after which the polymerization took place within 1/2 hour. A granular polymer was obtained. This polymer was coagulated with methanol, in vacuo

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dried and dissolved in 1 _f 3-bis- (trifluoivue "Shyl) benzene.

Example 11

To a 250 ml three-neck flask was added 124 g (0.23 mol) of (CP ₃ ) ₂ 0POCP ₂ 0P ₂ (0P ₂ CF ₂ ) ₂ CH ₂ CH ₂ 0H, 75 g (0.75 mol) of methyl methacrylate, 4th grade -, Og concentrated sulfuric acid and 1.0 g phenothiazine introduced. The flask was fitted with a distillation column with a fractionation head. The mixture in the flask was then heated ^{to 100 ° C. with stirring.} The Rückflußrerhältnie was adjusted so that the head temperature nioht auf.über 9O ⁰ C increased. The composition of the distillate (methanol and methyl ethyl aorylate) and of the reaction mixture was followed by Qaaohrotiatographi. The conversion was 87.5 * in 6 to 7 hours. Methyl methacrylate and ethanol formed as a by-product were then distilled off from the reactants.

110 g (0.17 mol) of (CF ₃ JgCPOCP ₂ CF ₂ (CP ₂ CPg) ₂ -CHgOH ₂ OOOO (PH ₃ JaCH ₂ , bp 63 ° C./1 mm) were obtained.

Calculated fttr O ₁₅ P ₁₉ H ₉ O ₅ :

C 30.11 P 60.36 H 1.50. Found: C 31.12 P 61.17 H 1.74.

Example 12 10 g (CP ₃ J ₂ CFO- CP ₂ , CP ₂ (CP ₂ CPg) ₂ CH ₂ CH ₂ OOOC (CH ₃ ) «CH ₂ , 55 g deinized a

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Vaeeer, 7.5 g of acetone, 6 g of cetyldimethylimmunium acetate and 0.15 g of aluminum persulfate were introduced. The mixture was flushed with nitrogen and ^{heated to 55 0} O and kept at this temperature for 5 hours. A polymerization took place during which a stable aqueous emulsion with 10.5 ow.jt of solid polymer was formed. The conversion was

Example 13

A 100 ml three-necked flask was filled _{with 4.0 g of CP 2} CP ₂ CH ₂ CH _{2 OCOCHeCH 2} , 4.0 g
OCOCHeCH ₂ , 2.0 g (CPJ) ₂ CPOCP
30 g of deionized water, 2.0 g of cetyldimethylammonium acetate (prepared by mixing 5 parts of cetyldimethylamine, 2 parts of glacial acetic acid and 24 parts of water) and 2.0 g of 30% hydrogen peroxide solution are charged. The mixture was heated to 55 ° C for 6 hours under a blanket of nitrogen. Then about 0.1 g of lauroyl peroxide was sugesetst. The polymerization took place within 1 hour. A latex and a coagulate were obtained. The loagulate was separated from the latex, further coagulated with methanol, dried in vacuo and in 1,5-Bia-

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(trifluoromethyl) benzene dissolved «,

Example 14 A 100-in-1 mash neck flask was placed at 1.35 g

515 g of deionized water, 0.59 g of emulsifying agent (prepared by mixing 6 parts of ethyldimethyl amine, 2 parts of glacial acetic acid and 24 parts of water), 0.31 g of a 60% aqueous solution of N-methyl acrylamide and 0.11 g of 30% # -ige hydrogen peroxide solution introduced. The mixture was purged with nitrogen and heated to 55 ⁰ O. Polymerization took place after 2 hours and a stable aqueous emulsion was obtained.

Example 15

In a 100 ml three-necked flask was 6.5 g ^ JgCFOCP ^ PgCHgCHjgOCOCiCC ^ J-CI ^, 0.325 g

Methyl methacrylate, 1.8 g of cetyldimethylanimoniuincetat and 0.8 g of 30 ^ hydrogen peroxide solution introduced. The mixture was heated for 4 hours at 55 ⁰ O. A stable aqueous polymer emulsion was obtained.

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Example 16

In a 200 ml three-necked flask were 6.25 g (OTf ₃ ) 2CTOOI ₂ OV ₂ OE ₂ OE ₂ OOOg BoCH ₂ , 0.325 g 2-ethylhexyl aorylate, 50 g deionized water, 1.8 g cetyldimethylammonium acetate and 0.8 g 50 pounds -ige hydrogen peroxide solution introduced. The Reaktionsge-r mixture was purged with nitrogen and heated for 3 hours at 55 ⁰ O. A stable polymer emulsion was obtained.

Example 17

38 g (CP ^ CKJCPgCPgCHgCHgOCOCiCH ^ -C ^ and 2 g HOCH ₂ CH ^ Ch ₂ OCOC (CH ^) »CH ₂ were dissolved in a mixture of 95 g CPCl ₂ CP ₂ Cl ₂ and 35 g CPCl ₂ CPOl ₂ solution was purged with nitrogen for 1 hour and then heated to reflux inter a protective layer of nitrogen. to the solution were in Abstäncten of 3 hours in three equal portions infgesamt as initiator 0.15 geCfjQ-Azoblsisobutyronitril zi'gesetzt while the solution at 74 ⁰ C was stirred.! / After the addition of the initiator was completed, the solution was further ^{heated to 76 to 78 °} C. The total

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since the heating including the time required for the addition of the initiator was 12 hours. A sample of the solution was then taken and weighed, the solvent was reduced under reduced pressure The pressure was evaporated and the solid polymer contained therein was isolated and weighed. Ss was a quantitative one Conversion of the monomeric compounds to polymer takes place. The polymeric product had a composition setting that the quantitative ratio of the starting monomers corresponded. Analyzes C 52.9 *. P 31.5 * t H 2.60 *.

Example 18

As described in Example 17, a mixture of 38 g (CFj ^ CPOOPgOPgCB ^ OHgOCOCCCH ^ CHg ^ ^{4 12 β} CHj (CH ₂ ) JOOOO (CHj) SOH ₂ in a mixture of 95 g CPCl ₂ CFCl ₂ and 35 g OPCl ₂ Dissolved OP ₂ Cl. The polymerization was carried out as described in Example 1? «Analysis of the polymeric product! 0 41.3 *, P 40.0 *» H 4.40 *.

Example 1? As in example 1? described was a mixture

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from 30 g (CiygCFOOFgCFgCHgCHgOOOOiOHjJ-CIHg and 12 g HNC (CH ₃ ) ₃ -GH ₂ 0H ₂ OCOC (CH ₃ ) ^ CH _{2 dissolved} in a mixture of 95 g CFCl ₂ CFCl ₂ and 35 g CFgOlCFCIg. The polymerization was carried out as in Example 17. Analysis of the product showed that its composition corresponded to the quantitative ratio of the monomers used.

Example 20

To a 100 ml three-necked flask was 6.5 g (CF.) g CF ₂ CF ₂ CH ₂ OHgOCOC (CH ₃ ) «CHg, 0.3 * 5 g methyl methacrylate, 1.8 g cetyldimethyliamonlunacetai (prepared by mixing 6 Parts of cetyldimethylamine, 2 parts of glacial acetic acid and 24 parts of water) and 0.8 g of 30 # hydrogen peroxide were introduced. The Genisoh was heated to 55 ⁰ C and held for 4 hours at this temperature. Polymerization took place to form a stable aqueous emulsion.

Example 21

6.25 g (CFj) ₂ CFOCFgCFgCHgCH ₂ OOOO (CH ₃ ) »CHg, 0.325 g 2-ethyl-

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hexyl acrylate, 50 g deionized water ₄ 1 _} 8 g

Cetyldimethyluoumiuaaoetai (manufactured by Ve? -

Misohen of 6 ropes of cetyldimethylamine, 2 ropes

Glacial acetic acid and 24 ropes of water) and 0 * 8 g of £ 30 igei Wasθerρeroxid introduced * Bas mixture was with Purged nitrogen, ^{heated to 55 0} O and 3 hours

held at this temperature. It happened aiie

Polymerization to form a stable aqueous

Emulsion. ™

Example 22

A reaction vessel was filled with 146.2 ropes (CfO ₂ GFO CP ₂ OF ₂ OH ₂ CH ₂ OOOC (Oh ₃ ) SOH ₂ , 3 ropes of ButylacryXate, 1 _S 25 ropes of a 60 ^ strength aqueous solution of N-methylolacrylamide, 598 ropes deionized water, 210 ropes of aoeton and 40.7 ropes of cetyldimefaylaaeonium = - aoetat (made by mixing 6 parts of the like

Cetyldiaethylamine, 2 ropes of vinegar and 24 ropes of water). Bas Gemisoh was purged with nitrogen and heated to 55 ⁰ C. 1 »13 g of K ₀ S ₀ Oo were then reacted and the mixture was ^{kept at 55 0} O for 4 hours. Ee polymerization occurred to form a solution containing

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'i5r> on solid polymer * Example 23

A reaction vessel was filled with 36 parts of (CF ») _{2 0FO-CF 2} CF ₂ CH ₂ CH ₂ OCOo (CH ₅ )« GH ₂ , 4 parts of dimethyl ainoethyl methacrylate, 175 parts of deionized water, 25 parts of acetone and 9.75 parts of a 24 £ -lgen aqueous solution of cetyldimethylamonium acetate (prepared by mixing 6 parts of cetyldimethylamine, 2 parts of glacial acetic acid and 24 parts of water) 'charged. The mixture was flushed with nitrogen and heated ^{to 55 ° C.} 0.27 g of X ₂ S ₂ Oq were then added, and the temperature of the reaction mixture8 was ^{kept at 55 °} C. for 4 hours. Thereafter, a further 0.27 g were K2 ^S 2 ° ^to 8 e ^eee 'i ^fczt etc. * ^dae Reaktionsgemiich was kept for another 4 hours at 55 ⁰ O. It was then found that polymerization had taken place. A solution containing 13.2 pounds of solid polymer was obtained.

Example 24 A reaction vessel was filled with 146.2 parts (OFj) ₂ OFO

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J 3 parts of butyl acrylate, 598 parts of deionized water, 210 parts of acetone and 40.7 parts of a 24 # strength aqueous solution of cetyldimethylammaniumaoeta (prepared by mixing 6 parts of cetyldimethylamine, 2 parts of glacial acetic acid and 24 parts of water) are charged. The reaction mixture was flushed with nitrogen and heated ^{to 55 ° C.} Then 1.13 g ^ S ₂ O _{8 were} added

setst, and the temperature of the reaction mixture was ^{held at 55 0} O for a further 3 hours. Thereafter, it was found that polymerization had occurred. A solution containing £ 15.2 of solid polymer was obtained.

Example 25

A reaction vessel was filled with 13 »5 parts of CP ₂ OF ₂ OH ₂ CH ₂ OOOO (CHj) = OH ₂ , 19.8 parts of isodecyl methacrylate, 2.7 parts of hydoxypropyl methacrylate, 200 parts of deionized water and 9» 75 parts of a 24 aqueous solution of Oetyldimethylammonlumaceta (prepared by mixing 6 parts of cetyldimethylamine, 2 parts of glacial acetic acid and 24 parts of water) charged. The Reaktlonsgemlsch was rinsed with nitrogen and heated to 49 ⁰ C.

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Then O ₉ 27 g of ^K 2 ^S 2 ° 8 ^ζυ · β ^θββ * ^ζΐ ί and the reaction mixture was ^{kept at 49 to 57 0} O for a further 96 minutes. Polymerization had then taken place and a solution with a solid polymer content of $ 14.3 had formed.

Examples 26-38

The polymers according to the invention were tested for their suitability as textile treatment agents for the textiles To make oil and water repellent, tested. The water repellency was determined according to ASTM D-583-58 » Water is sprayed onto the tightly stretched tissue under controlled conditions, and it becomes creates a wetting pattern that depends on the degree of water repellency. This pattern becomes permanent Compared with standard samples.

The wash fastness of the treated fabric was determined according to Method 61-1961 (Test II A) determined by the Amerioan Association of Textile Chemists and Colorists. This method is on pages 105-106 of the "Technical Manual and Yearbook "of this society, volume described. The results of this experimental method

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BATH ORIGINAL

are comparable to the results of rünf ordinary careful hand washes at a temperature of 49 ⁰ C

The effects of repeated dry cleaning were determined by American method 85-1060T Association of Textile Chemists and Colorista. This method is described on pages 87 to 88 of the "Technical Manual and Yearbook" of this company, Born in 1961, described. This test is based on a large number of laboratory tests which have shown that the test is three ubiquitous dry cleans at 4 # load using perchlorethylene as a solvent is comparable.

The determination of the oil repellency is for example in "Textile Research Journal", April 1962, pages 323-324. Doing so will focus on the treated Tissue carefully varying in drops of mixtures of mineral oil ("Nujol") and n-heptane Applied proportions. The drops are left on the treated tissue for 3 minutes. Thereafter it is determined visually whether the oil smells the Tissue is graded and penetrated. The number of the Gemisohes with the highest content of heptane,

2C98U / 1623

BATH ORIGINAL

that does not penetrate or wet the tissue, is called the oil repellency value of the fabric.

The hydrophobicity of the treated fabric was according to method 22-1961 of the American Association of Textile Chemiete and Coloriete beatlast Biese Method 1st, for example, in "Teohnical Manual and Yearbook "this Genellsohaft vintage 1961, pages to 153.

The results of the examinations are presented in faballen I to III. Vase and oil deterioration were determined on the finished fabric and after repeated vials and chemical cleaning. The fabric was a cotton printfeottonbloth τοη two by two meters. For preparing samples, the dor Baumwolltuoh was saturated with the test solutions and then 5 minutes at 10O ⁰ O dried, cured for 5 minutes at 160 ⁰ O and then pressed and ror checking allowed to stand still for 50 minutes.

The polymers to be tested became aqueous in the form Emulsions or solutions as used in some of the above Examples obtained are applied. In the tables, the polymer values are given in the example in which they are produced, identified.

2098U / 1623

BATH ORIGINAL.

T a b e 11 e

Po
ly,
mer Examination of the polymers At first
Wa OA 100 on water and 5 10 15th OA WA Oa WA Oil rejection O A. 70 from in order to treated tissue OA 10 OA 15th OA WA 20th O 80 at
game MLymer
on d.
Qewebe 50 100 Number of washes MA OA UA 80 0 80 O 80 Number of dry cleanings 90 WA 90 Wa 90 OA O 80 26th 6th 6.9 50 100 0 90 0 90 0 80 So O 70 «> 100 O 90 O 90 O 80 27 14th 5.7. 50 120 50 100 25th 90 0 80 O WA 90 50 90 O 80 28 10 *, 6 70 130 50 100 0 50 O O ° 29 8th 3.8 70 100 50 co
-30 15th 2.0 80 110 90 50 90 ^ 31 16 0.60 80 90 60 100 ? Ϊ32 0.70 80

WA «water repellency
OA »Oil rejection

Polymer 4 «homopolymer of (CP ₅ J ₂ CPOCF ₂ CP ₂ CHgCHgOOOCHsCHg Polymer 6 * homopolymer of (CPj) ₂ CPOOP ₂ CPgCHgOHgOOOO

Polymer 14 ■ Copolymer of (CPj) ₂ CPOCP ₂ CPgOHgCHgOCOCHeCHg

and N-Methylolaerylamld Polymer 10 «homopolymer of (CPa) ₂ CPOOPgOPgCPgOHgCHgOOOC

Polymer 8 ■ Homopolymer of (CP ₅ J ₂ CPOCP ₂ CP ₂ CF ₂ CP ₂ CPgCPgCHgCHg · B OCOC (CH ₅ J = CH ₂

Polymer 15 * Copolymer of (CP ₅ J ₂ CPOCP ₂ CP ₂ CH ₂ CH ₂ OCOCHeCHg

and methyl methacrylate
Polymer 16 * Copolymer of (CP ₅ JgCPOCPgCPgCHgCHgOCOCH (CHg) -CH ₃

and 2-ethylhexyl torylate.

2098U / 1623

Tab 11 <Π

Examination of the polymers Butt Weight #
polymer on 110 Water and oil repellent 90 - of tissue treated with it 90 10 Cleanings at
game mer on "d.
tissue 110
80 Number of washes 80 60 - Number of chemical: 100 OA 2Ö 2 0.8 At first
WA UA 90 2 _ä_ 1 ° ²⁰
OT "OA OTT US" ² 5
OA OK 90 OA 33 13th
17th 1.0 50 90 90 90 50 90 · ■ 60 IO 34
35 18th 0.1 70 110 100 90 - 90 90 098U 36 20th 0.80 - - 90 - - *** 77 21 0.70 70 «Μ σ>
»Ο 38 80

WA - Wasse rabtfeisuns
OA - oil repellency

Polymer 2 «homopolymer of

OCOCH = CH ₂
Polymer 13 = interpolymer of

CH ₂ , (CP ₃ ) ₂ CFOJP ₂ CP ₂ CP ₂ CP ₂ CH ₂ CH ₂ OCOCHe CH ₂ and (cp *) ₂ σpoσp ₂ σp ₂ (σP ₂ CF ₂ ) ₂ CH ₂ CH ₂

OCOCHsCH ₂
Polymer 17 * copolymer τοη

(CH «)« CH ₂ and hydroxypropyl etharylate polymer 18 * copolymer τοη

KOH ₂ and Butyia Ethmorylat Polymer 20 * Copolymer of () ₂₂

MCH ₂ and Itethylaethaerylat Polymer 21 »Copolymer τοη (J) ₂₂₂

₂ and 2-ethylhexyl acrylate.

Examples 39-41

In these examples, the monoester to be tested was introduced into a reaction to improve the oil and water repellency. The recipes were:

Weight *

MMMH

Test polymer 0.4

"NALAH W" ¹ 2.0

"MSLTRON 80» ² 2.0

2098U / 1623

Catalysr "PCC" ⁵ 1.0

Water 94.6

= Thermosetting resin from E.I. duPont deNemours and Company, used to make fluorocarbon equipments what to do repellent.

«Syrup-like melamine / formaldehyde condensate der

Crown Chemical Corporation, used to make Aus ™

to make armaments measurements permanent.

* at Crown Chemical's modified zinc nitrate catalyst Corporation.

The pH of the Hasse was adjusted with glacial acetic acid to 3.8 The cotton cloth samples of 2 χ 2 m were familiar with the testing solutions saturated, such that hits it you could pick up 75 $ moisture. Then the Ä

Samples heated 4 minutes IUF 120 ⁰ C and 2 minutes at 125 ⁰ C, and then pressed and allowed to stand for 30 minutes before they were tested.

The results of the tests for oil and water repellants with the masses given above are summarized in Table III.

2098U / 1623

\ t \

ill!

CVI

w4 I

O
CO

· I

8th . fc

o \ o \

«Hi CK Ch

S S ο

«Η« 4 Cn

8 8 8

»·« O O O

St 0 S

RSS

I R

2098U / 1623

SAD ORIGINAL Polymer 22 »Eerpolymer from gggg OH ₂ butyl acrylate and N-methylol acrylamide Polymer 23 * Copolymer of OH ₂ and dimethylaminoethyl methacrylate

Polymer 24- «Copolymer of _{I 2} CH ₂ and butyl acrylato

Example 42 4

Production of 1.1 _{t of} 2,2-tetrahydro-3,3,4,4 ~ tetrafluoro-4-heptafluoroisopropoxybutyl acrylate.

Xn a Reaktlonsgefäfi with stirrer, reflux condenser and Thermometers were 25 β Β1β- (1,1,2,2-ΐβίΓβ ^ άτο-3,3,4ι4 · -

tetrafluoro-4-heptafluoroisopropoxybutyl) pyrosulfate

and 14 β acrylic acid introduced. That Gemisoh became

Heated to 105 ° 0 for 24 hours, during which time g

two liquid phases formed. The Semisch was cooled to room temperature, and the two of them

liquid shafts were separated from each other. the lower, water-insoluble layer (25 g) was distilled to give 10 g (yield 95 #) 1,1,2,2-tetrahydro-3,3,4,4-

tetrafluoro ^ -heptafluoroisopropoxybutyl acrylate, (CF ₃ J ₂ OFOOP ₂ CF ₂ OH ₂ CH ₂ OOOOh-OH ₂ , bp 56 ° C / 4 mm.

209814/1623

BATH ORIGINAL

- 66 Example 45

Preparation of 1,1,2,2-Τθtrahydrooctafluoro-6-heptafluoroisopropoxyhexyl acrylate.

51 g of BIs- (1,2,2-tetrahydrooetafluoro-6-heptailuorieopropoxy}] exyl) pyroexafate and 15 g of acrylic acid were placed in a BeaktlonegefK * bit stirrer, reflux condenser and thermometer. The mixture was ^{heated to 105 0} O for 24 hours. Ee formed eioh svei liquid phases. The geaisoh was cooled to goat tea temperature and the two liquid phases were separated from one another. The lower, waeserunlusuche PhaBe (45 g) was distilled and gave 38 g (yield 70Ji) 1,1,2,2-Tetrahydroo-tafluoro-6-heptafluorieopropoxyhexylaorylate,

₂₂₂₂₂₂ , tob Kp 46 to 51 ° E / 1.5 mm.

Example 44

Manufacture of 3,3,4,4-tetrafluoro-4-heptafluoriaopropoxybutyl aorylate.

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BATH ORIGINAL

25 g of bis (3t2 »4,4-tetrafluoro-4-heptafluoroisopropoxybutyl) pyrosulfate and 14 g of acrylic acid were placed in a reaction vessel equipped with a stirrer, reflux condenser and thermometer. The mixture was kept at 10 ^ ⁰ C for 24 hours. Two liquid phases formed. The mixture was cooled to room temperature and the two liquid phases were separated. The lower, water-insoluble phase (25 g) was distilled and gave 10 g (yield 95S <) 3,3,4,4-tetrafluoro-4-heptafluoroisopropoxybutylaorylate, (CPJ) ₂ GPOGP ₂ CP ₂ GH ₂ CH ₂ OCOCh = CH ₂ rom Kp 56 ⁰ C / 4 mm «

Example 45

Production of rcra 3 _t 3,4,4-tetrafluoro-4-heptafluoroisopropoxy-1-butanol.

A 250- ^ al-Mreihal »flask with stirrer, dropping funnel, thermometer and a condenser ^{leading to a trap kept at -78 0} O was filled with 38 g (0.086 mol) of heptafluoroisopropoxytetrafluorobutyl iodide ((CP ^) gCPOCFgCFg CH ₂ CH ₂ J), bp 85 up to 87 ° C / 100 mm, stitched. Then slowly 0.344 Hols of stabilized sulfur trioxide were added while the reaction temperature was at

209814/1623

177Ü262

35 to 40 ⁰ C was held. A reaction took place immediately with liberation of iodine. After completion of the addition of the sulfur trioxide, the mixture to 70 ⁰ O was heated and the end of the formation of £ yrosulfate 2 hours at this temperature and then (O about 25 ⁰⁾ cooled to room temperature. In order to hydrolyze the pyrosulfate formed as an intermediate compound ((CFjJgCFOOF ^ FgCI ^ OHgOSOgJgO from the alcohol jbu, 100 ml 35 # sulfuric acid were added to the mixture. In addition, a small amount of sodium sulphate was added to remove elemental iodine. Then the (mixture 1 hour to 105 ⁰ O heated to complete the hydrolysis * the mixture was allowed to stand, with two layers trained. ORGANIC · layer was separated and the aqueous layer was extracted with anhydrous Ithyläther. Organic layer and extract were combined and The main component was identified as 3 »^ f4» 4 ~ tetrafluoro-4 · -h · ptafluoroisopropoxybutanol · (CPj) ₂ -CPOCP ₂ Or ₂ OH ₂ OH ₂ OH. The yield was 19 g or 0.06 mol (70Ji), bp 84 ° 0/59 mm.

2098U / 1623

Found 9 24, 6th 62, 55 1,

Analysis for Calculated

C 25.45

Γ 63.33

H 1.55

Example 46

Preparation of 3,3,4,4 »5» 5,6,6-0ctafluoro-6-heptafluoroisopropoxy-1-hexanol.

In a 2-1 three-necked flask with heating device, Stirrer "dropping funnel, thermometer and condenser were 200 g: 20 l oleum introduced. The flask was heated to 90 ° C and within 15 minutes were 100 g (0.185; moles) 3,3,4,4,5,5,6,6-ootafluoro-6-hβptafluoro-I

ibojpropoxy-1-hexyl iodide was added while the temperature was kept ^{at 90 to 100 0 O as the mixture.}

The Gem. '. SCV. ^{was stirred at 100 0} O for 1 hour and then cooled ^{to 25 0} O in an ice bath. Then 840 g of water were slowly added, the temperature rising ^{to 70 0 O.} The mixture was ^{heated to 100 0} O and kept at this temperature for 16 hours. Then it was washed _{with Ha 2} S ₂ O _{5 to}

2098U / 1623

BATH ORIGINAL

177Ü262

to separate elemental iodine. The water-insoluble layer was separated, dried and distilled. 50.2 g (0.117 mol) of 3,3,4,4,5,5,6,6-octafluoro-6-heptafluoroisopropoxy-1-hexanol, (CFj) ₂ CFOCF ₂ CF ₂ CF ₂ OF ₂ CH _{2 were obtained} CH ₂ OH with a boiling point of 63 ° C./4 mm, corresponding to a conversion of 63 £ and a yield of

analysis for C ₉ F ₁₅ H ₅ O ₂
Calculated 25th , 12 C. 66 , 28 F. 1 , 16 H example 47

Found 48 24, 41 66 21 1,

Production of 1,1-dihydro-2,2-difluoro-2-heptafluoroisopropoxyethanol, (

A 500 ml three-neck flask was filled with 100 ml of anhydrous diethyl ether and 3.5 g (0.091 mol) of lithium aluminum hydride. The mixture was cooled in an ice bath and a solution of 23 g (0.078 mol) of 2,2-difluoro-2-heptafluoroisopropoxyethyl acetate in 100 ml of ether was slowly made tea. The garrison was ^{stirred at 35 °} C. for 2 hours. Then before

2098U / 1623

BATH ORIGINAL

20 ml of 95% igea

Sights ^ "Methanol added to the complexes Destroy the SBU, whereupon 20 ml of 10 # hydrochloric acid are added were to make the lithium and aluminum compounds Dissolve all chlorides bu.

The organic layer was dried and separated

and distilled »15 g (0.052 mol) of 1,1-dihydro-2» 2-difluoro ^ -heptafluoroisopropoxy-i-ftthanol were obtained, boiling point 109 to 111 ⁰ O, corresponding to a yield of

analysis for Cj ₅ PgHjO ₂ : 48 Found Calculated 22 _V 2 σ 22.56 64.0 P. 64.29 1.0 H 1.13 Example

Manufacture of (CF ^) ₀ CPOCP ₀ CPACP ₉ CF ₀ J ₀ CH ₀ CH ₉ OH.

A 2-1 three-necked flask was filled with 1005 g of 20% oleum

2098U / 1623

BATH ORIGINAL

charged «Then within 1 1/2 hours at an oil temperature between 95 and 10O ⁰ C 615 β (0.96 mol) (OF ^) ₂ OFOCF ₂ OPg (OFgCFg) ₂ CHgOHgJ were added. The mixture was ^{kept at 100 °} C. for a further 11/2 hours and then added to 2200 ml of water containing 145 g of Na ₃ S ₂ O _{5 in} order to bring about hydrolysis to the alcohol and to remove iodine. The mixture was then ^{heated to 100 °} C. for 1 hour. After cooling, the organic phase was taken up in ether and dried. The ether was evaporated. By distilling the oily residue, 368 g (0.69 mol) of (OF ^) ₂ CFOCF ₂ CF ₂ (CF ₂ OFg) ₂ CH ₂ CH ₂ OH with a boiling point of 80 ° to 82 ° C./4 mm were obtained Alcohol was 72 "53 *.

analysis for C 11 * 1 4? 91 Calculated 11 C. 24, 94 F. 68, H ο, example

found

25.02

68.52

.12

Production τοη (OFj) ₂ OFOOFgCFg (OPgOPg) ₅ CH ₂ OHgOH.

2098U / 1623

BATH ORIGINAL

A 1-1 three-necked flask was charged with 380 g of 20% oleum. 190 g (0.26 mol) of (CP ₃ ) ₂ CK> CF ₂ OF ₂ (OP ₂ OP ₂ ) _{3 were} then slowly added within 2 hours, while the temperature was between

about 90 and 100 ^° C. · Sas mixture was transferred with stirring to a flask _{containing 1245 g of water and 25 g of Na 2} S ₂ Oe, in order to effect the hydrolysis to the alcohol and to remove iodine. The mixture was then ^{kept at 100 °} C. for a further 3 hours. After cooling, the organic phase was taken up in ether and dried, and the ether was evaporated. By distillation of the oily residue were 126 g (0.20 Hol) (OP ₃₎ 2OPOOp ₂ OP ₂ (OP ₂ OP ₂ J ₃ OH ₂ OH OH _2, bp 99 to 101 of ⁰ C / 4 mm obtained, conversion and yield of Cheating alcohol #

Analysis for O ₁₃ P ₂₃ H ₅ O ₂ Calculated ^s Found 24.76 24 _S 44 O 69.05 69.53 P. 0.79 0 ₉ 92 H

2098U / 1623

Example 50 Production of A 250-l-mash-neck flask was filled with 210 g (0.41 mol)

(OP ₃ ) ₂ CIOC? ₂ 0? 20 * 2 ^C? 2 ^J '^ * ^(O ' ⁵³ " ⁰ ^ ^ ndecylenalcohol and 1 g of cT, α'-Azobisiaobutyronltril charged as a catalyst. The mixture was ^{heated to 70 to 75 0} C and kept at this temperature for 12 hours 32 g (0.062 mol) (CFj) ₂ CTOCy ₂ Cr ₂ Cf ₂ OP ₂ J tob Ep 40 to 43 ° C / 25 mm, 34 g (0.2 mol) undecylene alcohol with a bp 90 to 100 ° C / 2 mm and 228 g (0.33 mol) (CF ₃ ) 2CPOCP ₂ OP ₂ CF ₂ GF ₂ CH ₂ CHj (CH ₂ ) ₉ OH were obtained with a bp above 100 ° 0/2 mm. The conversion and yield of the iodine alcohol were 81, 5 + or 96,

analysis for C. »Ρ λ eHo οJO j Found Calculated 31.54 C. 31.67 41.02 F. 41.78 3.21 H 3.22 17.75 J 18.62

2098U / 1623

Example 51 Production of

A 2-1 three-necked flask was charged with 500 ml of anhydrous diethyl ether and 32 g (0.86 mol) of lithium aluminum hydride. 228 g (0.41 mol) of (CP ^ gCPOCFgCl ^ CPgOP ^ H ^ HJiCHg J ₉ OH ^{in 30} ° ^{g of} free ethyl ether were slowly added to the resulting slurry. The mixture was then refluxed overnight. Ethyl acetate and then sulfuric acid were added. Two liquid phases formed. The upper phase was separated off and dried, and the ether was evaporated. 131 g (0.29 Hol) (CP ₃ J ₂ OPSCP ₂ CP ₂ CP ₂ CP ₂ (CHg) ₁₁ OH of IP 110 ° C / 0.5 mm and 32 g (0.05 mol) of starting iodo-alcohol were obtained, the conversion and yield of alcohol were 71% and 81%, respectively.

Analysis for ^c i8 ^P 15 ^H 23 ° 2 ^J Calculated Found

0 30.84 38.52

F 5126 51.75

■ 1 4.14 4 "82

2098U / 1623

- 76 Example 52

Manufacture of (OP ₃ J ₂ CPOOP ₂ OP ₂

An 850 ml three-necked flask was filled with 210 g (0.34 mol) (0F ₃ ) ₂ CF0CF ₂ 0P ₂ (CP ₂ 0F ₂ ) ₂ J. 75 g (0.44 mol) undecylene alcohol and 1 g, α, α ¹ -Azobisisobutyronitril charged as a catalyst. The mixture was heated to 70 to 75 ⁰ O and kept at this temperature for 5 hours. By Deetillation of the reaction mixture were added 10 g (0.016 mol) of unreacted iodine / 25 mm, bp 69-79 ° 0, 22 g (0.13 mol) ündeoylenalkohol, bp 80 to 9O ⁰ C / 1 mm and 227 g (0.29 Mol) (0P ₅ ) ₂ 0P00P ₂ 0P2 (CP ₂ CP2) 20H2CHJ (0H2) ₉ 0H from bp 150 to 155 ⁰ O / 1mm. The conversion and yield of iodine alcohol were 84.5 / »and 89, respectively.

analysis for ° 20 ^! 'i9 ^H 21 ^J0 2 Found Calculated 31.04 σ 30.69 45.92 P. 46.16 2.75 H 2.83 16.39 J 16.24

2098U / 1623

BATH ORIGINAL

- 77 Example 53

Production of (OP ₃ ) ₂ OPOCP ₂ CP ₂ (CP ₂ OP ₂ J ₃ OH ₂ CHJ (GH ₂ ) ₉ 0H

A 250 ml three-needle flask was filled with 210 g (0.295 mol) (OP ₃ J ₂ CPOCP ₂ CP ₂ (CF ₂ CP ₂ ) ₃ J, 70 g (0.41 mol) undecylene alcohol and 1 g ^, _f ec'- azobisisobutyronitrile ale catalyst charged. the mixture was heated 12 hours 70 to 75 ⁰ C. distillation of the mixture was added 14 g (0.02 mol) of unreacted iodine, bp 40 mm to 42 ° 0/2, 30 g (0, 17 mol) undecylene alcohol, bp 90 Ws 100 ° C / 2 mm and 213 g (0.24 mol) (CP ₃ ) ₂ CP0CP ₂ 0P ₂ (CP ₂ CP ₂ ) ₃ CH ₂ CHJ (CH ₂ ) ₉ 0H with a Kp obtained over 100 ⁰ C / ?. mm. conversion and yield of the Jodalkohol amounted to 8256 or «

Analysis for ^u 22 ^? 23 ^H 22 ^J0 2 ^:

Calculated Found σ 30, oo 31.07 P. 49.54 49 »24 H 2.49 2 _y 56 j 14.39 14.75

2098U / 1623

Example 54 Preparation of (g? 3 ⁾ 2 ^CP00g 2CP ₂ (CP ₂ CP ₂ ) ₂ (C ^) ₁₁ 0H.

A 2-1 three-necked flask was charged with 500 ml of diethyl ether and 20 g (0.53 Hol) of lithium aluminum hydride. To this slurry was added 217 grams (0.276 Hol) (CP,) ₂ CPOCP ₂ CP ₂ (OP ₂ OP ₂ ) ₂ CH ₂ CHJ (CH ₂ ) _g OH. Then the mixture was boiled overnight on the RüoksluB. Ethyl acetate and then sulfuric acid were added to decompose excess lithium aluminum hydride. Two phases formed as well. The upper phase was separated and dried and the ether was evaporated under reduced pressure. By distilling the oily residue, 59 g (0.09 mol) of (CP ₃ J ₂ CPOCP ₂ CP ₂ (CP ₂ CP ₂ J ^ CH ₂ J ₁ with a boiling point of 115 ° C / 0.5 mm and 102 g (0, 13 Hol) starting iodine alcohol with a boiling point of 135 ° C / 0.5 mm was obtained.

Analysis for ° 2O ^? 19 ^H 23 ° 2 ^:

2098U / 1623

Calculated Found σ 36.58 37.12 P. 55.03 55.62 H 3.5t 3.72 Example 55

Preparation of (CPj) ₂ CPOCP ₂ CP ₂ (CHg) ₁₁ OH.

A 3-1 three-necked flask was charged with 750 g of anhydrous diethyl ether and 62 g (1.67 Mo3) of lithium aluminum hydride. 500 g (0.86 Hol) (CP ₅ ) ₂ OPOCP ₂ CP ₂ CH ₂ CHI (CH ₂ ) ₉ OH in 250 ml of ether. The reaction was exothermic and the iodine alcohols were added in such a way as to keep the mixture at a gentle reflux. After the addition of the iodine alcohols was complete, the mixture was refluxed over Kaoht. The flask was then cooled in an ice bath and sufficient water was added to decompose excess lithium aluminum hydride. Then 25% sulfuric acid was added to the solution. They formed an essential and an oily splint,

2098U / 1623

ORIGINAL

that have been separated from each other. By distilling the oily layer, 182 g (0.40 mol)

CP ₂ CP ₂ (CH ₂ J ₁₁ OH with a bp of 92 to 95 ° C./4 mm and 120 g (0.25 mol) of Auegange-dodal alcohol with a bp of 125 to 130 ⁰ O / 4 mm were obtained. Conversion and yield of the desired alcohol were $ 47.5 and $ 67, respectively.

analysis for C ₁ ZP ₁ -HoTrO 56 CVl Found Calculated 43.01 C. 42.11 46.12 P. 45.82 5.52 H 5.04 example

Preparation of 3,3,4,4-tetrafluoro-4-heptafluorieopropoxy-1-butanols

A flask was charged with 680 g of 20 ^ -1 mixture of oleum. Then, within 1 hour at 25 ⁰ C, 440 g (1.0 mol) of 3,3 _t of 4,4-tetrafluoro-4-heptafluorleopropoxybutyljodid added. The mixture was at 50 ^° C. for 1/2 hour

2098U / 1623

BAD ORJGJNAL

- 8i -

heated to complete the formation of the hydrosulfates * Then, 2331 g of water was added, and the mixture was heated for 16 1/2 hours at 82 ⁰ C to hydroIisieren to the hydrochloride sulfate to the alcohol. The solution was filtered and 61 g (0.23 hol) iodine was recovered. The filtrate was decolorized with 45 g of Na ₂ S ₂ Oe, and the water-insoluble oil was separated off, combined with methylene chloride extracts from the aqueous phase, dried and distilled. 9.6 g (0.022 mol) of starting iodide and 281 g (0.85 mol) of 3,3,4,4-tetrafluoro-4-heptafluoroisopropoxy-1-butanol were obtained, corresponding to a conversion of 85 # and a yield of 87 $.

Example 57

Proof of the surface _{activity of (cr 3} ) ₂ 0J? 0C? ₂ 0P ₂ CH ₂ OH ₂ OH.

About 5 al (CP ^) ₂ CPOCP ₂ CP ₂ CH ₂ OH ₂ OH were shaken with 100 ml of distilled water. The Gemisoh was transferred to a Soheidetrlohtter and the insoluble alcohol (the sohwere oily Sohloht) was

2098U / 1623

BATH ORIGINAL

separated from the aqueous phase. Practically all of the alcohol was recovered. The surface tension of the aqueous phase was found to be EU 58.8 dyn / cm at 25 ^° C. The surface tension on untreated distilled water is 72.9 dyn / om ^{under the same conditions (35 ° C.).}

Example 58

Use of (CP ₅ ) ₂ 0P0CP ₂ CP ₂ CH ₂ 0H ₂ 0H as a solvent for a polymerization in solution.

A 100-al three-halo flask was filled with 54 g (C7 >>) ₂ C70 CP ₂ CP ₂ OH ₂ CH ₂ OH as solvent, 10 g (07 ^) ₂ CTO CP ₂ OF ₂ CH ₂ OH ₂ OCOO (OHj) -OH ₂ charged as monomers and 0.15 g of α, ο · -Aaobisisobutyronitrile as a catalyst. The solution was flushed with nitrogen for 1 hour and then ^{heated to 75 to 80 0} O and kept at this temperature for 12 hours under a protective layer of nitrogen. The alcoholic solvent was evaporated from a weighed sample of the solution under atmospheric pressure, and the solid polymer was isolated and weighed. The solids content of the solution had

2098U / 1623

15.0 G-ew _s "-? £", i.e. "96.5 $ of the monomeric compound had been converted into a polymer * With 100% conversion the solids content would have been 15" 6 $ ".

Analysis: Calculated: C 33.16 52.51 H 2.26. Found: C 33.75 P 52.84 H 2 _? 45.

2098U / 1623

If the radical is C or D by telomerization of an asymmetric When the unsaturated compound is obtained, the telomerization takes place predominantly in such a way that in the the radical derived from the unsaturated compound, the carbon atom closest to the group R is the one » which carries the lower weight of substituents. However, the telomerization can also be reversed to a lesser extent Expire way. When η or m is 2 or above, can telomerize the residues in an arbitrarily alternating order. In order to simplify the form, the residues C and D were given as they were in the case of the predominantly expiring one Telomerization are arranged in the products. However, the formulas should also include the other products.

If, therefore, telomerizable ethylenically unsaturated compounds CZ ₁ Z ₂ -CZ-ZjJ, in which Z ₁ and Z _{2 are} not the same as Z 1 and Z 2, are used, the product consists mainly of telomers in which the functional groups - (CZ ^ ZgCZ ^ Z ^) - are arranged in such a way that the sums of the atomic weights of Z ^ and Z ^ are greater than those of Z ₁ and Z ₂ . Correspondingly smaller quantities are present in the product Teloners in which the substituents Z ₁ to Z ^ and X ₁ to X ^ are arranged in reverse order or in arbitrarily alternating order.

2098U / 1623

BA ORIGINAL

Claims (1)

Claims 1. Compound of the general formula in the right a thatch of the Foreel ? P-C- CR ₁ PCOAPCR ₁ R. ^ 4 new 2098U / 1623 _{BAD 0RlG1NAL} in which each of the groups R ₁ , which can be equal or different, is a fluorine or chlorine atom or an alkyl group of 1 to 9 carbon atoms and is not titled or substituted with a fluorine, chlorine or bromine atom or several equal atoms or xwei groups Rj together is a divalent universal radical with a maximum of 18 carbon atoms, which is unmentioned or substituted with a fluorine, chlorine or bromine atom or several such atoms, with the notion that not more than three of the Reete Rj haloeneallreete and not more than one xwel of the chain R ₁ Alkylreato elndj A is a radical of the formula in each of the Reete R * and R ^, which are gleloh or versohieden «Is a hydrogen or fluorine atom and R- is a hydrogen, fluorine, chlorine or bromine atom or is a perfluoroalkyl radical, each of the residues C and 0, which are the same or separate its know a remainder of the formula in the 1st) Z ₁ , Z ₂ , Z ^ and Z ^, which can be identical or unified, a hydrogen, fluorine, chlorine 2098U / 1623 ÖAD ORIGINAL or is a bromine atom with the proviso that no more than two of the radicals Z ₁ , Z ₂ , Z, and Z ₁ ^ are chlorine atoms and no more than one of these radicals is a bromine atom, or 2) two of the radicals Z ₁ * Z ₂ , Z, and Z ^, which can be the same or different, are hydrogen or fluorine atoms and the remaining two, which can be the same or different a) radicals of the formula -C (X _a K # in which each of the radicals X _a , which can be identical or different, is a fluorine, chlorine or bromine atom, is or b) Z ₁ and Z * together or Z ₁ . and Zj, together form a divalent aliphatic radical, or 3) Each of the radicals Z ₁ and Z «, which can be identical or different, is a hydrogen or fluorine atom, and each of the radicals Z ₂ and Zh, which can be identical or different, is a radical as defined in a) above 1st or d) a radical of the formula -CF ₂ X ^, -Y ₁ -OY ₂ , -Y1-Y3 or -0-Y ^, in which X _{b is} an alkyl radical with 1 to 8 carbon atoms that is unsubstituted or with a fluorine, Chlorine or bromine atom or several such atoms is substituted, is, Y _{1 is} a saturated alkylene radical which is unsubstituted or has one or more fluorine, chlorine or bromine atoms 2098U / 1623 BAD ORIGJNAi. such atoms is substituted; Yg is a water off at oh or an alkyl group .iet _v Y, is an aryl group and
Yj is an alkyl group or
e) Zg and Z * e together form a divalent aliphatic Form the rest » with the hatred that the carbon atom to which the radical L is bound * also bound to two hydrogen atoms let « m 0 or a whole number from 1 to 75 1st ,, η is O or a whole number from 1 to 75, and preferably ν is 0 or 1 / with the proviso that the sum «of η * η and ν is at least 1 «and L is a radical of the formula -OH or -0-C-OCH ₉ 0 H
in the M a hydrogen atom or a Methylreet let «let 209814/1623 0AD ORIGINAL 17702B2 2 compound according to claim Ί, daduroh characterized; that the radicals C have the formula Cy ₂ CP ₂ , GH ₂ CH ₂ * CP ₂ COl? or) have. 3 ο compound according to claim 1 or 2, marked by the fact that any beds D that are present have the formula CP ₂ CF ₂ , CF ₂ CClF or CF ₂ CF (CF ₅ ); to have" 4 method according to claim 1 "characterized in that the radicals C and optionally present radicals D have the formula CFgCF ₂ or CH ₂ OH ₂ , 5. A compound according to any one of the preceding claims, characterized in that A is a perfluorinated radical » 6 «connection according to claim 5, characterized in that A is the remainder 0? ₂ CF ₂ is 7 ο compound according to one of the preceding claims, characterized in that each of the isste R _{1 is} a fluorine atom or a ferhalogenalkal group » 8 »Compound according to claim 7» characterized in that each of the radicals R _{1 is} a fluorine atom or a perfluoroalkyl radical 2098U / 1623 BATH ORIGINAL 9o compound according to Anepruoh 8, daduioh characterized _p that each of the radicals R _{1 is} a fluorine atom » 1O ₃ compound according to one of claims 1 to 4, characterized in that the radical R or the radical R- (O) - (D) _n - (OH _{2 has} one of the formulas given in list A _o 11, compound according to one of claims 7 to 9 »characterized in that the radical -A- (C) _n - (D) _m ~ (CH ₂ ) _v . the formula (OFg) _x ^ H ₂ ) - * in which χ and y, which can be the same or different, are integers from 1 to 20 12ο connection according to claim 11, characterized in that that the sum of χ and Yy is not greater than 16o 13ο connection according to claim 12, characterized in that the sum of χ and y is not greater than 10 iet _s 14, connection according to one of claims 11 to 13, since «* by indicating that χ is 1 to 20 and y is 1 to 10 » 1So connection naoh Anepruoh 14, daduroh markedο that y is equal to 1. 2098U / 1823 BATH ORIGINAL 16ο connection according to one of claims 11 to 13, characterized marked that χ is an even number from 2 to 16 let «, 17, connection according to claim 16, characterized in that that y is an integer, from 2 to 16 " 18ο connection according to claim 17, characterized in that it is marked that y is 2 or 3 19o connection according to claim 17 »characterized by that y is 3 to 10. 20, connection according to one of claims 11 to 13 _f characterized _{ that .c is an odd number from 2 to 9 and y is an integer from 4 to 10 * 2098U / 1623 BATH ORIGINAL 21o connection according to one of the preceding claims, characterized by the fact that they are listed here by name eats. 22. A method of making a compound of the in one of the preceding claims, in which L is -OH, characterized in that one 1) a telogen of the general formula II [CP (R ₁ ) ₂ ] ₂ CF-0-A- (C) _p - (DJq- (CH ₂ ) ^ B in which R ₁ , A, C and D have the meaning given in claim 1, E is an iodine or bromine atom, ρ and q are m and n, respectively, as defined in claim 1, and r O is and the carbon atom, to which B is bound, is still bound to two halogen atoms, is reacted with sulfur trioxide and the product of this onset is reacted with an alkenol to form the corresponding ester, which is then reduced, or 2) a telogen of the general formula II, In which R ₁ , A, C and D have the meaning given in claim 1, E is an iodine or bromine atom and p, q and r equal m or η and v, as in Arspruch 1 is defined and the carbon atom to which E is bonded is still bonded to two hydrogen atoms, is reacted with sulfur trioxide or oleum and the product is then hydrolyzed, or 3) a telogen of the general formula II, in which R ₁ , A, C and D have the meaning given in claim 1, 2098U / 1S2 3 BATH ORIGINAL the terminal group C or D is the group -CHgCHg, E is an iodine or bromine atom, R is O and ρ and q are m and n, respectively, as defined in claim 1, and ρ plus q is equal to m plus η plus 1, to the corresponding Olefin * in which the terminal group -CHxCHg is, dehydrohalogenated, the olefin to the corresponding acid in which the terminal group is a carboxyl group is, oxidized and the acid is reduced to a compound of the general formula Ϊ, in which ν is 1, or 4) a telogen of the general formula II, in which R ^, A, C and D have the meaning given in claim 1, E is an iodine or bromine atom and p, q and r equal m or η and v are as defined in claim 1 and ρ plus q plus r is [(m + η + ν) -5] with an appropriate one Allyl alcohol converts and the product of this reaction then desired or required reduced. 23. A method for the preparation of a compound as defined in any one of claims 1 to 21, in which L -OCOC (M) = CHg, characterized in that one 1) a compound according to one of claims 1 to 21, in which L is OH, with an acrylic compound of the general formula CH ₂ = C (M) COQ, in which Q is Cl, OH or OCH, reacts, the acrylic compound, when Q is OH, it can be used in the form of an anhydride; 2098U / 1623 6AD ORIGINAL 2) the telogen defined in claim 22 with an Ac ry! Compound of the above definition unset et ι 3) the product of the implementation of Te Io ge na is sulfur trioxide or oleum according to 1) or 2) of claim 22 with an acrylic compound as defined above. 24. The method according to claim 23, characterized in that dafi the starting material for (1) by a process according to Claim 22 is made. 25. Polymer, characterized in that it is recurring Units of the formula R- (C) _m - (D) _n - (CH ₂ ) _v -OCCM 0 CH ₂ which differ from a connection, as in one of the Claims 1 to 21 defined, in which L -0C0C (M) derive «CH2, contains. 26. Polymer naoh claim 25, characterized in that it consists of these units. 27. Polymer according to claim 26, characterized in that it consists of nothing but identical units. 2098U / 1623 BATH ORIGINAL 28. Polymer according to claim 25 »characterized» that besides these units there are still others, from another, contains copolymerizable monomer derived units. 29. Polymer according to claim 28, characterized in that these other units differ from one or more derive the monomers specifically mentioned herein. 30. Polymer according to claim 28, characterized in that these other units differ from non-fluorinated acrylates or methacrylates. 31. Polymer according to claim 25, characterized in that it is specifically listed herein. 32. A method for producing a polymer as defined in one of claims 25 to 31, characterized in that at least one compound as defined in one of claims 1 to 21, in which L is -OCOC (M) -CH ₂ , if necessary. polymerized together with one or more other copolymerizable ethylenic unsaturated compounds. 33. Surface, characterized by the fact that it is a Coating made of a polymer as defined in any one of Claims 25 to 31. 2098U / 1623 34. Fiber material, characterized in that it is with a Coating made of a polymer which is coated in one of the specifications 25 to 31 given. 35. Textile material, characterized in that it is made with a polymer according to the one given in one of claims 25 to 31 Definition is overdone. 36 * Porous material, characterized in that it has is coated with a polymer as defined in any one of claims 25 to 31. 37 · Use of a compound according to one of Claims 1 to 21, in which L is -OCOC (M) -CH ₂ , for the production of a polymer as defined in one of Claims 25 to 31, by polymerizing the compound, if necessary. together with one or more other copolymerizable methylene-unsaturated compounds. 38. Use of a polymer according to one of the claims up to 31 for the production of coatings on objects, for example textile fiber «, to this oil, fleoken and make it water-repellent. 2098U / 1623