FI67712C - TELOMERER SOM FOERNAETAS UNDER INVERKAN AV LJUS OCH FOERFARANDE FOER FRAMSTAELLNING DAERAV - Google Patents

Description

6771 2

Light-crosslinkable telomeres and their method of manufacture

The present invention relates to telomeres having one or more sequences, at least one of which has unsaturated lateral groups along its entire length, which are statistically distributed and which have the property of crosslinking by means of light.

This invention also relates to a process for the preparation of these telomeres.

Telomeres are organic synthesis products obtained by the so-called by a telomerization reaction in which an organic unsaturated compound X 1, called "taxogen", reacts with catalysts or initiators in the presence of another compound AZ, called "telogen", to condense and form n divalent bonds - ( X 1) -, and the telogen AZ is divided into two parts which are attached to the ends of the sequence to give a substance having the general formula: A- (X 2) -Z, called the telomer. This, in turn, can act as an actelelogen for another taxogen Y 1 to form bi-sequence co-telomeres having the general formula:

N - (Y) -N '- (X) -Z

n 'n where A' and A "are the result of the distribution of A.

Of particular interest are those products and derivatives thereof which are obtained by attaching unsaturated side chains to at least one sequence.

Low molecular weight molecules containing unsaturated groups are known in the art and are commercially available. For example, in the case of allyl side chains 267171 2, tetra-allyloxy-1,1,2,2-ethane is already available, and acrylates of diols, triols and tetraols are known from acrylic side chain substances. But these compounds have no more than four light-polymerizable groups.

Molecules with a molecular weight between 1000-3000 (telexel oligomers) and two acrylic groups at the chain ends are widely used in industry. These macromolecules are obtained, for example, from dihydroxy polyesters or polyurethanes.

High molecular weight polymers with substituted acrylic and / or allyl groups have been known for some time and their applications are still the subject of several patents and publications. Mention may be made, for example, of polyvinyl alcohols and glycol poly (meth) acrylates having acrylic groups as substituents of the Kinnayl, β- (2-furyl) acrylic or β- (pyridyl) acrylic type. Very few unsubstituted compounds with acrylic or allyl side chains of this type have been reported in the literature. However, mention should be made of French Patent No. 2,412,572, in which these side chains are obtained by means of carbonate bridges.

The idea of the invention is based on the fact that mono-sequence telomeres and bi-sequence telomeres or co-telomeres have been synthetically prepared, the lengths of which are determined and connected to them by special side chains, the number of which has been adjusted. As a result, new compounds have been obtained which have a number of interesting properties and which can be applied to various fields of technology.

In this way, substances with short sequences have been prepared, i.e. they have a relatively low molecular weight and a low viscosity, which makes them possible to use without a solvent.

Monosquence telomeres have also been developed which have a junction structure such that it is possible to attach a certain number of highly reactive groups, such as acrylic or allyl derivatives, which thus give them excellent crosslinking properties with light, but leave some sequence junctions free. , which still retain their own properties, such as joints with an acid or alcohol functional group which are more or less soluble in water or tend to adhere to metals.

When the invention has been extended to bi-sequence telomeres, depending on the structure of this second sequence, other properties may have been created or developed, such as improved surface properties in the presence of fluorine radicals or flexibility in the case of diene radicals or hydrocarbon resistance when using acrylic. radicals such as acrylonitrile.

The invention therefore relates to telomeres of the general formula R-CC 2 -ix ^ J - / χΛ -Z, in which the sequence of the - / xj - / ^ χΛ-x 1χχ \ R? / Y 'V ^ / y joints is derived from the same of a taxogen X 1 having a free functional group which is a primary alcohol, an acid or a secondary alcohol, and in which the linkages -fx 1 - correspond to the esterified form of X 1, R 1 is a radical of the group used in the esterification, RCC 4 - and - Z is a moiety of the telogen RCC 2 Z, wherein -Z is -H or -Cl, and R is a single radical or a macromolecular radical, and these telomeres are characterized in that X 1 is X 1, X 2, X 1 or X 4, of which X 1 is hydroxy- 2-ethyl acrylate 4 6771 2 ti or hydroxy-2-ethyl methacrylate, X2 is acrylic acid or methacrylic acid, is vinyl alcohol, X1 is allyl alcohol, and 0 <x <500, 1 <y <500, 1 <x + y <1000, and that the group used in the esterification has at least one photocrosslinkable double bond and is an acid or acid chloride in the case of X 1, X 1, X 4, and in the case of alcohol ^ 2.

According to a particularly preferred embodiment, the telomeres have a single sequence in which the taxogen has one free functional group, such as a primary alcohol function in hydroxy-2-ethyl acrylate and methacrylate and allyl alcohol, an acid function in acrylic and methacrylic acid and a secondary alcohol function in vinyl alcohol. The number of linkages in this sequence ranges from 1 to 1000, and all or at least half of them are esterified with acid or alcohol groups having at least one light-crosslinkable ethylene bond. These groups are statistically distributed along the sequence and allow the resulting telomer to use simultaneously the properties associated with the various non-esterified functional groups involved.

Depending on the structure of the taxogen forming the linkages of the sequence, different groups may be used to aid in esterification. In the case where the taxogen is X 1 or X 1 or X 1, and thus has an alcohol function, acrylic acid or methacrylic acid or cinnamoyl chloride is selected. In the case where the taxogen has an acid function represented by X 1, an alcohol such as hydroxy-2-ethyl acrylate, allyl alcohol or cinnamon alcohol is selected.

Z, which may be the radical -H or -Cl, preferably denotes the radical -Cl when the taxogen is of the type X1 and X2.

As for the radical R, it is a simple radical or a macromolecular radical. Such a macromolecular radical is derived from other telomeres containing a taxogen and thus results in the formation of bi-sequence co-telomers which have the advantage of the properties brought by both sequences.

The radical R can take different forms depending on the taxogen X. .

With X 1, R may be a simple radical belonging to the group consisting of -Cl, CH 2 -O-CO-, CF 2 -, which correspond to the telogens carbon tetrachloride, methyl trichloroacetate and trifluoro-trichloroethane.

R may also be a radical belonging to the group consisting of - ^ CF2_CFCl ^ n -Cl, where 1 <n ^ <10 CH3 \ - (CH2- <rH) -H '- (εΗ2-ίΗ) -cl <- ( CH 2 -i) n, -C 1 '0 n 2 O' n 2 V CO 0 H 2 1 I 2 c = c-ch 3 oc-ch 3 CH 3 - (CH 0 -C 1 -CCl, - (CH 2 -C = CH-CH 2) - Cl V 2> / 2 \ 2 IV n V Co2-CH3 * CH3 ^ 2 where 1 <n2 <500 i.e. these radicals are thus derived from telomeres respectively: chloro-trifluoroethylene-carbon tetrachloride, vinyl acetate-chloroform, vinyl acetate-carbon tetrachloride, methacrylic acid -carbon tetrachloride, methyl methacrylate-carbon tetrachloride, isoprene-carbon tetrachloride.

With X2, R can be a simple radical belonging to the group consisting of -Cl and -CF3, which correspond to the telogens carbon tetrachloride and trifluorotichloroethane, and also the macromolecular radical - (CF2-CFC1) -Cl, 2 n, where 1 <<10, i.e. that it is derived from the telomer chloro-trifluoroethylene-carbon tetrachloride.

With X 1, R may be a single radical belonging to the group consisting of -Cl, (C 2 H, -O) 2 ~ PO, or a macromolecular radical belonging to the group consisting of: - CH 2 -CH 'N -Cl , - ^ CH2-C = CH-CH ^ \ n -Cl, where 1 <n2 <500, 0 7n cH '2 1 2 3 0 = C-CH3, i.e. that these radicals are derived from telomeres, respectively; carbon tetrachloride, chloroform, diethyl hydrogen phosphonate, bromo-trichloromethane and, from telomeres, vinyl acetate and isoprene with telogen carbon tetrachloride and chloroform.

With X4, R may be a simple radical belonging to the group consisting of -CC12-CO2H, -CC12-CO2CH3, -CC13, (C1-O) TjPO-, i.e. they are derived from telogens, respectively: trichloroacetic acid, methyl trichloroacetate, chloroform, diethyl hydrogen phosphonate.

The invention also relates to a process for the preparation of telomeres having the general formula R-ccl - (χ) - (X Λ -Z, wherein X 1 is a subgroup X 1, X 2, X 3 or X 2, of which X 1 is hydroxy-2- ethyl acrylate or hydroxy-2-ethyl methacrylate, X 2 is acrylic acid or methacrylic acid, X 3 is vinyl alcohol, X 3 is allyl alcohol, and 0 <x <500, 1 <y <500, 1 <x + y <1000, R 1 is a group in which cm is at least one light-crosslinkable double bond and is an acid or acid chloride in the case of X 1, X 3 and X 1, and an alcohol in the case of X 2, Z is H or Cl and R is a simple radical or a macromolecular radical characterized in that the process is telomerized with telogen PCC12Z, wherein X1, R and Z are as defined above, in the presence of a catalyst and then esterified with the resulting telomer to attach a group R ', which is as defined above.

Il 7 6771 2

However, in some cases it is possible to carry out the esterification before telomerization.

But depending on the taxogen used in the telomerization or the taxogen involved in the macromolecular radical R involved in the bis-telomerization, the synthesis of each of these substances acquires its own special feature.

Thus, for example, in the case of a telomerization reaction and the taxogen used is of the vinyl, conjugated diene or allyl type, the telogen is selected from chloroform and the catalysis is peroxide catalysis (in which case benzoyl or azobisisobutyronitrile peroxide is used as initiator of telomerization). The cleavage that takes place is at C-H and in this case one of the tele-terminal ends is a group of trichloromethylClCl.

If the taxogen is of the acrylic, conjugated diene or chlorotrifluoroethylene type, then the telogen is carbon tetrachloride and the catalysis is of the oxidation-reduction type (FeCl 2 / benzoin pair is most used, but also other transition acetals and / or salts such as Mg, Cu, etc.). may be used). In this case, the cleavage of the telogen is of the C-Cl type, but as in the above case, there is always a trichloromethyl group at the end of the telomer.

In the case of a bis-telomerization reaction in which the telomeres of the type RCCl 2 obtained above act as telogenous substances, if the new taxogen is vinyl, this reaction takes place by peroxide catalysis (see above). All other taxogens: alkyl, conjugated diene, chlorotrifluoroethylene, have a catalysis type of oxidation-reduction.

When the taxogens are of the vinyl or allyl type, vinyl acetate and allyl acetate are used as the starting material for telomerization, respectively, and then hydrolysis is performed in the presence of sodium methanolate to give the alcohol functions, to which light-crosslinkable groups are then attached.

The number of linkages: x + y in the different sequences of the taxogens is given by the average degree of polymerization DPn and the polydispersity index DPq of the telomerization reaction, which depend on parameters already known in the literature.

MAYO has defined a general law for peroxide telomerization: -i- = —-- + CTr and BOUTEVIN et al for oxidation-reduction-catalytic telomerization: —— = C, .c + CTr DP ~ K n j0issac '(' focus and r = illroT 'CT and ckat are the transition coefficients for telogen and catalyst.

These laws have been applied within the scope of the invention and have made it possible to determine DPn values in advance in the desired various sequences. The results obtained in the closed tubes have then been extrapolated to a semi-industrial reactor for experimental operations. In the reactor, it was possible to perform steps 1 and 2 to access the bi-sequence co-telomeres, as one step when the second monomer was added to the reactor when the first step was completed (see Example 4).

With respect to esterification, various methods that existed for simple molecules or polymers have been applied to bi-sequence co-telomomers. The methods used depend on the groups to be attached and the structure of the taxogens.

In the case of taxogens of the type X1 and X4, which thus form polyol sequences, it has been seen above that the groups used in the esterification were either acids or acid chlorides.

9 6771 2

In the case of acrylic acid chlorides, such as cinnamic acid chloride, the working method used is the same as for pyridinium complexes in the activation or Schotten Bauman method.

In contrast, in the case of acrylic acid, azeotropic esterification can be used directly using paratoluenesulfonic acid or sulfuric acid as a catalyst. This esterification takes place with an aromatic solvent or a chlorinated type solvent such as: CH 2 Cl 2 or CHCl 3 when it has to take place at low temperature for fear of thermal polymerization.

In the case of type X2 taxogens, which thus form polyacid sequences, the activation of the acid functions above the coupling is carried out by converting them to the acid chloride using pure thionyl chloride under reflux conditions. The coupling then takes place in tetrahydrofuran or any other aprotic solvent protected from water under a nitrogen atmosphere.

The invention will be more readily understood by means of the following application examples.

The telomerization and / or co-telomerization reactions have been carried out in closed tubes or in a reactor under pressure and, if the boiling points of the taxogens and telogens are sufficiently high, they have been carried out in a pyrex reactor at atmospheric pressure. All the structures described in the examples have been determined by the following analytical methods: one hundredth analysis, proton magnetic resonance, gel filtration chromatography, viscosity measurement, infrared spectrophotometry.

Example 1: Telomerization of taxogen Χ ^: η: hydroxy-2-ethyl acrylate and telogen 1,1,1-trifluoro-trichloroethane.

10 6771 2 CH2 = CH-CO2-CH2-CH2OH + CF3CC13 -> cf3-cci2 / ch2-ch \ -ci \ CO2-CH2-CH2OH / n

174 g of hydroxy-2-ethyl acrylate are charged to the reactor; 281.25 g CF 2 CCl 2; 2.43 g ferric chloride; 3.15 g of benzoin 3 J ύ and 200 cm of acetonitrile. Heat with stirring for 12 h at 115 ° C and 4.4 bar. After completion of the reaction, the solvent is evaporated to give 272 g of a viscous substance.

In a separate reactor, at a pressure of 200 Torr, unreacted taxogen is removed. The degree of conversion to telomere is 90%. The monoaddition compound is separated by distillation (boiling point: 92 ° C at 0.5-10-2 Torr).

The crude reaction product is precipitated and the average degree of polymerization of each fraction is determined by one hundredth analysis. This gives: - soluble in ether: DPn $ 5 (3% of total weight) - soluble in chloroform: DPn = 9 (53% of total weight) - soluble in acetone: DPn = 11 (26% of total weight) - soluble in methanol: DPn = 18 ( 18% of the total weight).

Example 2:

Esterification of the telomer of Example 1 with acrylic acid. Take DPn = 9. Direct azeotropic esterification of this polyol in methylene chloride (CH 2 Cl 2) at 39.5 ° C and using paratoluenesulphonic acid as catalyst with excess acrylic acid. After purification, the following compound is obtained: 11 6771 2 CF3CC12-pCH2-CH) 4> 5- (CH2 - CH3 - Cl)

L C = 0 C = 0 'J

and i-O-CH2-CH2-OH-O-CH2-CH2-O-C-CH = CH2O

Example 3: Esterification of the telomer of Example 1 with cinnamoyl chloride.

Kinna-moyl chloride is added to the various fractions obtained in Example 1 according to the following procedure: freshly distilled pyridine is placed in a flask with two orifices and a flat bottom equipped with a condenser and a bromine ampoule and a magnetic stirring system. A drop of cinnamoyl chloride dissolved in carbon tetrachloride or toluene is administered dropwise via a bromine ampoule. After the addition, when a milky precipitate has appeared, the telomer is added dissolved in pyridine. Allow to react for 1/2 h at ambient temperature, at which point the first precipitate disappears and the second granular precipitate appears. Evaporate the pyridine to give a substance which is soluble in chloroform.

Of all the fractions of Example 1, a degree of incorporation of about 75% is always obtained. In the case of the fraction soluble in chloroform (DPn = 9), a compound of the formula is obtained: CF3CC12- jjCH2-CH> 2 - (CH2-CH) ^ 1-Cl

C = 0 c = o J

I I

O-CH2-CH2-OH o ch2-ch2-o-C-CH = CH-⁇ o Φ represents a benzene ring.

Example 4: Bis-telomerization of hydroxy-2-ethyl acrylate with telomer CCl 4 -isoprene and subsequent addition of acrylic acid to a 4.5 liter experimental reactor is charged with 773 g of hydroxy-2-ethyl acrylate; 103 g carbon tetrachloride; 683 g of acetonitrile; 12 6771 2 10.8 g of ferric chloride; 14 g of benzoin. The reaction is carried out at 110 ° C at a pressure of 4.4 bar for 4 h, after which the pressure drops (3.5 bar); then 907 g of isoprene are added directly. The reaction is continued for 6 h. Evaporation and work-up give 1095 g of the bi-sequence co-telomer. Acrylic acid is then added as described in Example 2 to give the final material:

Cl- (CH2-CH = CCH3-CH2) 2i? Cc12- [jCHj-CH)? - (CH2-CH) 6 ~ | -Cl CO, CO, I 2 I 2 CH, CH, -CH, -O-C-CH = CH, | 2 2 2 i, 2 ch2 0

OH

i.e., a bi-sequence hydroxy-2-ethylisoprene co-telomer with an degree of acrylic chain incorporation of about 45%.

Example 5:

Bis-telomerization of taxogen X2: acrylic acid and telomomer of carbon tetrafluoride and chlorotrifluoroethylene ci (cfci-cf2) 3 5-cci3 + (CH2 = CH) - * co2h

Cl- (CFCl-C1'2) 3 ^ 5-CCl2- (CH2-CH) 1λ 5-Cl

CO 2 H

2.5 liters of acrylic acid (180 g) are charged to a 1 liter pyrex reactor; 0.49 moles of Cl- (CFCl-CF 2) 35 δ-CCl 3 (77.5 g); 2.034 * 10 2 moles of ferric chloride (3.17 g); 1.95 · 10 2 moles of benzoin (4.14 g) and 200 g of butyronitrile. The reaction takes place under solvent reflux conditions for 24 h. The butyronitrile is evaporated off and unreacted telogen (14.5 g) is recovered to give 140 g of product. The rate of conversion to telomer is 50%. Fractionate to fractionate to give 100 g of a white solid which is soluble in acetonitrile (DPn = 44) and 40 g of a yellow solid which is soluble in ether (DPn = 11.5).

13 6771 2

Example 6:

Activation of the acid functions of the co-telomer of Example 5 The fraction DPn = 11.5 obtained in Example 5 is treated as follows.

27 g of this telomer are placed in a pyrex reactor equipped with a condenser. Pure thionyl chloride (SOCC12) is added. Heat under reflux for 114 h and stir vigorously the solution (magnetic stirring). The volatiles are eliminated to give 30.3 g of the following substance: ci- (cfci-cf2) 3 5-cci2- (ch2-ch) n 5-ci COCl, i.e. the conversion of acid functions to acid chloride functions is total.

Example 7:

Esterifier of the cotomomer of the above example with cinnamon alcohol.

One third of the weight of the material obtained in Example 6 (10.1 g) is dissolved in anhydrous tetrahydrofuran. A co-telomer and 19.4 g of cinnamon alcohol are placed in a flask equipped with a condenser, a bromine ampoule and a system by which a stream of nitrogen can be bubbled into the solution. The temperature of the reaction solution is raised to 40 ° C and monitored by the release of hydrochloric acid formed. When the release has ceased, the solvent is evaporated off and, after purification, a substance of the formula: ci- (cfci-cf2) 3 5-cci2- ^ (ch2-ch) 1 5- (ch2-ch) 10J -Cl CO2Hf < f = 0 0-CH2 ~ CH = CH-ip, i.e. the degree of crosslinking is 87%.

14 6771 2

Example 8:

Esterification of the co-telomer of Example 6 with allyl alcohol.

Allyl alcohol is added (15 g) to the second third of Example 6 (10.1 g) according to the procedure described in Example 7.

The following substance is purified: ci- (cfci-cf2) 3/5-cci2- £ "(ch2-ch) 2 ts ~ (ch2 ~ ch) gj -Cl C00H C = 0

2 I

0-CH2-CH = CH2, i.e. the degree of crosslinking is 71%.

Example 9:

Coupling of hydroxy-2-ethyl acrylate to the co-telomer of Example 6.

Hydroxy-2-ethyl acrylate (33.5 g) is added to the last third of Example 6 (10.1 g) according to the procedure described in Example 7, but this time at ambient temperature. The following compound is purified: C1- (CFCl-CF2) 35 5-CC12- [(CH2- <pn6f6- <cH2-YH) 4i ^] - ci CO9H c = o

2 I

0 CHo-CHo-0-C-CH = CHn 2 2 II 2

O

that is, the degree of networking is 43%.

ii 15 6771 2

Example 10:

Bis-telomerization of taxogen x ^: isoprene and telomer of vinyl acetate chloroform.

H- (CH - CH2) 30-CCl3 + CH2 = CCH3-CH = CH2 -> OCCHt

II -3 o H- (CH-CH2) 30-CCl2- (CH2-CCH3 = CH-CH2) n-ClO-CCH -3 li 3 -3

6.75 g (2.5 x 10 moles) of the telomer of vinyl acetate-chloroform (DPn = 30) are placed in a sealed tube; 6.8 g of methyl 2-butadiene-1,3 (0.1 mol) 0.13 g of ferric chloride; 0.17 g of benzoin and 30 cm of acetonitrile. After 12 hours of reaction at 90 [deg.] C., 13.8 g of a viscous substance are obtained. The degree of conversion of the co-telomer is thus 100%.

Example 11:

Hydrolysis and esterification of the co-telomer of Example 10.

H— (CH-CH ..) _ Λ — CCl-j— (CH. ·, —CCH-. = CH — CH ·%) - Cl + 30 Cl-C-CH = CH- <p | ^ jU * ä J £ Γ1 11

OH O

The material obtained in Example 10 is treated with sodium methanoate. Two substances are obtained: insoluble in methanol (70% by weight) and one soluble in methanol and chloroform (30% by weight). Cinnamoyl chloride is added to both substances as described in Example 3. 100% coupling and substances of the following formulas are obtained: Γ ----- 6771 2 16 70% H- (CH-CH2) 30-CCl2- (CH2-CCH3 = CH-CH2) 65-Cl (!> C- CH = CH-ip and 30% H- (CH-CH2) 3Q-CC12- (CH2-CCH3 = CH-CH2) 42-Cl C> C-Ch = CH-ip

S

Example 12:

Telomer Bis-telomerization of acrylic acid-carbon tetrachloride with isoprene.

ci- (ch-ch2) 40-cci3 + ch2 = cch3-ck = ch2

io2H

12.2 g of Cl (CH-CH 3) 4q-CCl 3 are placed in a glass tube

CO H

-3 Δ (4 x 10 moles) obtained synthetically as in Example 5, but using carbon tetrachloride as a telogen and acetonitrile as a solvent; 10.88 g isoprene (0.16 mol); 0.195 g of ferric chloride, 1.25-10-3 moles) and -3.26 g of benzoin (1.25-10 moles) and 100 cm of acetonitrile. 18.2 g of material are obtained, i.e. the degree of telomerization is 55%. 6 g of this substance is soluble in ether and 12 g is insoluble in it. Thus, compounds of the following formulas are obtained: 6 g of C1- (CH-CH2) 40-CC12- (CH2-CCH3 = CH-CH2) 50-C1c2h 12 g of C1- (CH-CH2) 40-CC12- (CH2-CCH3 = CH-CH2) 18-C1 co2h

Example 13:

Esterification followed by telomerization.

Cinnamoyl chloride is added to hydroxy-2-ethyl acrylate as described in Example 3. The following monomer is obtained: CHo = CH-C-O-CHo-CHO-O-C-CH = CH- <p 2 II 2 2 n

O O

17 6771 2 90% yield. This material (24.2 g) is then reacted in a pyrex reactor with the following materials: 15.4 g of carbon tetrachloride; 1.62 g of ferric chloride: 2.12 g of benzoin and 50 cm of acetonitrile.

The reaction is refluxed for 24 h by distilling off acetonitrile. 27 g of a substance corresponding to the formula are obtained: cci3- (ch2-ch) 10 ~ Cl c = o 0-CH0-CH-, -O-C-CH = CH-ip

2 2 II

o

Example 14:

Telomerization of allyl acetate.

A 1 mole% benzoyl peroxide, one mole of allyl acetate and 1 mole of telogen dissolved in 300 ml of benzene are charged to a 1 liter reactor. After removal of the monomer (evaporation and washing in petroleum ether), a viscous product is obtained (yield 80%) whose DPn values as a function of r and the telogens used are summarized in the following table: _ DPn r HPO (OEt) 2 HC12C-CC> 2CH3 CC13- CO 2 CH 3 1 2.4 3.45 0.5 4.5 5.9 2.6 0.25 8.5 12.5 5 0.2 10 13.5 6.3

Example 15:

Esterification of allyl acetate telomeres.

The compounds obtained in Example 14 are treated in the same manner as in Example 11. A 100% degree of incorporation is obtained in the corresponding light-crosslinkable telomeres.

Due to their water solubility, electro-solubility, flexibility, adhesion to metals, and durability of oils, the light-crosslinkable telomomers and co-telomeres according to the invention can be used both in printing: offset printing, chemigraphy, flexographic printing, printing circuits), as well as in the coating of some metallurgical materials.

il

Claims (21)

1 J co-ch3 where 1 <n2 <500. li 21 6771 2 1 I 2 o = c-ch3 o = c-ch3 f? H3 \ / \ - CH - C \ -Cl or -f CH „-C = CH-CH0] -Cl, where 1 <n0 <500. V 2 I Jn2 \ 2 I Vn 2 "2 V CO2 <2K ^ δ \ CH3 / * Telomeres of the general formula R-CCl 2 X 2 -Z, wherein the sequence of the linkages - (Xj - [X.] - is derived from the same V Vx \ r7V taxogen X 1 having a free functional group which is primary alcohol, acid or secondary alcohol, and wherein the linkages - (X Λ- correspond to the esterified form of X 1, \ R '/ R' is a radical of the group used in the esterification, RCCl 2 - and -Z are the telogen RCC 2 Z moieties wherein -Z is -H or -Cl, and R is a single radical or a macromolecular radical, characterized in that it is X 1, X 2, X 3 or X 1, of which X 1 is hydroxy-2-ethyl acrylate, or hydroxy-2-ethyl methacrylate, X 2 is acrylic acid or methacrylic acid, X 1 is vinyl alcohol, X 1 is allyl alcohol, and 0 <x <500, 1 <y <500, 1 <x + y <1000, and that the group , which is used in the esterification, is at least one photocrosslinkable double bond and is an acid or acid chloride in the case of X 1, X 1 and X 1, and an alcohol in the case of X 2. Telomeres according to Claim 1, characterized in that the group used for the esterification of X 1, X 2 and X 2 is acrylic acid, methacrylic acid or Cinnamoyl chloride. Telomeres according to Claim 1, characterized in that the group used for the esterification of X 2 is hydroxy-2-ethyl acrylate, allyl alcohol or cinnamon alcohol. Telomeres according to Claim 1, characterized in that when the taxogen is of the type X 1 and X 2, the radical -Z is predominantly only -Cl. 20 6771 2 Telomeres according to Claim 1, characterized in that, when the taxogen is of the type X 1, R is a single radical which is -Cl, CH 2 -O- or CF 2 - Telomeres according to Claim 1, characterized in that, when the taxogen is of the type, R is a radical which is: - (CF - CFCl) --Cl, in which 1 <n1 <10, * n1 / ίΗ3 \ - (CH-- CH) -H, - (CH »-Ch) -Cl, - [CHO-C] -Cl, 2. n '\ 2 | Ί n \ 2, n 0. O7 \ C0oH7 Telomeres according to Claim 1, characterized in that, when the taxogen is of the X 2 type, R is a single radical which is -Cl or -CF 3 · Telomeres according to Claim 1, characterized in that when the taxogen is of the type X 2, R is the radical - (CF 2 -CFCl) n, in which 1 <n ^ <10. Telomeres according to Claim 1, characterized in that when the taxogen is of the X 3 type, R is a single radical which is -Cl or (C 2 H 3 O) 2 PO-. Telomeres according to Claim 1, characterized in that when the taxogen is of the type X 3, R is a radical which is - (CH_-CH) -Cl or - (CH - C = CH-CH_) -Cl, 2 | 2 n » 0 CH- Telomeres according to Claim 1, characterized in that, when the taxogen is of the type X 1, R is a single radical which is -CO 12 -CCO> 2H, -CC12-CO 2 CH 3, -CC13 or (C 2 H 5 O) 2 "PO-. A process for the preparation of telomeres of the general formula R-CClO- (x.] -F X.) -Z, wherein X 1 is a subgroup X 1, X 2, X 2 or X 4, of which X 1 is hydroxy-2-ethyl -acrylate or hydroxy-2-ethyl methacrylate, X 2 is acrylic acid or methacrylic acid, X 1 is vinyl alcohol, X 1 is allyl alcohol, and 0 <x <500, 1 <y <500, 1 <x + y <1000, R ' is a group having at least one light-crosslinkable double bond and is an acid or acid chloride in the case of X 1, X 1 and X 2, and an alcohol in the case of X 2, Z is H or Cl and R is a simple radical or a macromolecular radical, characterized in that the taxogen X1 is telomerized with telogen RCC12Z, in which X1, R and Z have the same meaning as above, in the presence of a catalyst and then the resulting telomer is esterified to attach a group R 'having the same meaning as above. . Process according to Claim 12, characterized in that the telomer obtained is bistelomerized before esterification. Process according to Claim 12, characterized in that when the taxogen is of the vinyl or allyl type, the telomerization is carried out in the presence of a peroxide catalyst and chloroform is used as the telogen. 22 6771 2 Process according to Claim 12, characterized in that when the taxogen is of the acrylic type, of the conjugated diene type or of the chlorotrifluoroethylene type, the telomerization is carried out in the presence of an oxidation-reduction catalyst and carbon tetrachloride is used as the telogen. Process according to Claim 12 or 13, characterized in that if the novel taxogen is of the vinyl and allyl type, the bis-telomerization is carried out in the presence of a peroxide catalyst. Process according to Claim 12 or 13, characterized in that if the new taxogen is of the acrylic type, of the conjugated diene type or of the chlorotrifluoroethylene type, the bis-telomerization is carried out in the presence of an oxidation-reduction catalyst. Process according to Claim 14 or 16, characterized in that the taxogen used is an acetate which is hydrolysed with sodium methanolate so as to obtain alcohol functions to which light-crosslinkable groups are then attached. Process according to Claim 12, characterized in that when the esterification is carried out with acrylic acid chloride, the activation is carried out with pyridinium complexes. 19 6771 2 Process according to Claim 12, characterized in that when the esterification is carried out with acrylic acid, direct azeotropic esterification is carried out in the presence of paratoluenesulfonic acid and a solvent. Process according to Claim 12, characterized in that when a taxogen of the type is esterified, activation of the acid functions is carried out before the coupling by converting them to the acid chloride by means of thionyl chloride. 23 6771 2