DE1800373A1 - Oligomers, processes for their preparation and their use as conductive agents - Google Patents

Description

Dr. D. Thomsen H. Tiedtke G. Bühling Dlpl.-Chem. Dipl.-lng. Dipl.-Chern.

8000 MONKS 2

VAL 33

TELEPHONE 0811/226894

TELEGRAM ADDRESS: THOPATENT

Munich October 1, 1968 T 2838

Uniroyal, Inc.
New. York, Ή. Y. (USA)

Oligoraere, processes for their preparation and their use as conductive agents

The. Invention relates to a method of polymerization for the production of oligomers and on the oligomers produced by the process. In particular refers to the. Invention to a reductive polymerization 'process in an aqueous medium, in which a bisulfite salt as Reducing agent is used and the resulting oligomers with a terminal Sulp'honät. The invention relates also refer to the use of bisulfite-regulated oligomers as conductive agents, particularly theirs Use as a conductive agent for the conductive barrier layer on photo-electrostatic copy paper or other photo-electrostatic Rendering elements. Certain oligomers with terminal

909820 / 122.6

Oral · Agreements, especially by telephone, require written confirmation Dresdner Bank Manchen Account 1 «103 ■ Post check account Munich 11M 74

permanent bisulf-i% - according to the invention are also valuable for a wide variety of other uses, including wrinkle finishing, as antistatic agents for Blankets and carpets and as chelating agents for metal ions and for other purposes.

It has recently been proposed to use an oxidation initiator such as hydrogen or alkyl or acyl peroxides, persulfates or hydroperoxides, and a reductive activator such as NaHSO ₅ , Na ₂ S ₂ O ₅ , Na ₂ S ₂ O. or sodium formaldehyde sulfoxylate. In such processes the oxidative initiator is used in much larger amounts than the reductive activator and the former is part of the original batch, while the latter can be part of the original batch or can be added in increasing amounts during the polymerization. In the present context, these processes are referred to as "oxidative polymerization" processes. · ..

In the "reductive polymerization" process according to the invention, this is first in much larger quantities added material, i.e. the initiator, a reducing chemical substance, especially a bisulfite salt, e.g. NaHSO, while that during the polymerization in smaller

. 9 0 98 i Q / 1 2 2.6

Quantities of material added, i.e. the activator, an oxy-

The dative chemical substance is, e.g. (ITaH.,) ρ ^ 9 ^ 8 * ^ ^eses process is referred to herein as "reductive polymerization"".

In contrast to the above-described oxidative polymerization, reductive polymerization facilitates production of oligomers with a comparatively low and precisely regulated "degree of polymerization. This is from various Reasons beneficial.

According to the invention, a reductive polymer -sationsverfahren for the production of oligomers with terminal sten- ■ created a sulphonate, which consists in the fact that 1 or several alpha-, beta-ethylenically unsaturated monomers in one aqueous medium in the presence of water-soluble bisulfite as a reductive initiator emulsion-polymerized.

According to the invention are also oligomers terminated with sulphonate and their water-soluble salts with a Basic structure of 8 to 500 carbon atoms, to which one hydrophilic group each respectively. 2 carbon atoms in the backbone is bound, created.

In general, the "bY" average molecule of Oligomers are represented by the following formula:

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H-

Γ * ¹ t I. - C C. λ 1 X _Η.

1
γ

SO ₃ M

this formula of course, not the actual one Structure of the compounds obtained as final product represents as the structural units

R '

I χ

Jrtid

II

in which molecules are randomly distributed,

In the general formula above, M is a

1 "2 3
water-soluble cation of the bisulfite salt, R .., R, E ^ and R- are hydrogen, methyl or ethyl groups, Y represents one or more hydrophilic groups which, when bound to a vinyl group, form a water-soluble homopolymer
form, namely, · ^; .

-OOOH, -COlTH ₀ , -OCH- ,, -OCJI ₁ - and ^ 2 i 25

GH ₉ - CH _0/2 ., 2

- CH ₀ 2

and X represents one or more 'hydrophobic groups which, when attached to a vinyl group, form a water-insoluble homopolymer, namely -COOCgH.OH, -COOC ₅ HgOH,

-CONHCH ₀ OH, -COlHdH _x . -C01THC _{or similar}

² # 0 9 8 0 ^2/2 I

H, r, - CONHCzHr ₇

2 6 ^{3 7}

, - CONHC ₈ H ₁₇ ,

- 5 - '■■ ·, ■■■■

-COOCH ₅ , -COOC ₂ E ^ -CH, -0OCCH ₅ J-OOCC ₂ H ₅ or -OOHHO (GH ₃ ) ₂ -CH ₂ COCH ₅ .

Taking into account the water solubility of the above mentioned homopolymers. in the "preferred cases the water-soluble homopolymer one-such with a .Water solubility of over $ 10 and the water-insoluble hanopolymer one with a water solubility of less than $ 10.

In order to ensure that the oligomers according to the invention or the salts of which are soluble in water, there must always be at least one hydrophilic group, X, which is required however, a hydrophobic group, X, does not have to be present.

The subscript "a" used in the above formula · represents the total moles of the hydrophobic group or groups each Molecule and the subscript "b" the total moles of the hydrophilic Group or groups per molecule. The degree of polymerization a + Td is in a large range preferably between 4 and 25Ö, more preferably between 10 and 100. The molar fraction of the monomer with the functional group X = · - ■■ can from 0.0 to Oi 6, preferably the. Molar fraction smaller than 0.4 and most desirably less than 0.3, however, the limit of this value becomes with Mle-r respective hydrophobic group vary and should preferably not be so large that a macrophase of sticky polymer is formed The ratio of a to b can, as desired by the person skilled in the art, vary

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are, depending, most importantly, on the desired water solubility of the oligomer or its salts.

For an oligomer of the formula H- (acrylonitrile) -ν. - (Acrylic acid) -, - SO ^ iTa at a value of a + b of 20 or greater, the value for a / (a + b) should be less than 0.32, but preferably less than 0.25. When a + ' h is 16 or less, the value for a / (a * + b) can be on the order of 0.5. ·

Jedooh, on the other hand, is for the oligomer, H- (methyl acrylate) - (Acrylic acid) -u-S0-, Ha at a + b = '20 the upper limit for a / (a + b) between 0.3 and 0.4.

In summary it should be said that in 'the formula H- (X) - (acrylic acid). -S0JP · the individual symbols are as follows

Ot ' tJ 2

Have meaning: '-.

X '. a '+ b-. a / (a 4- b) maximum

Acrylonitrile

Acrylonitrile

Methyl acrylate

Isodecyl acrylate

H-isooctylacrylamide

2-ethylhexyl acrylate

Ethyl acrylate

Hydroxypropyl acrylate

Methoxyethyl acrylate

20th or greater 0.32 - 0 * 25 0.067 16 or smaller 20th .0.5 or greater 0.05 . Ί? V - ' . 0.4-0.3 21 \ · less than > and 0.25 15th about 0.05 0.25 . 20th less than 20th about 0.2 20th between 0, i 90982 0/12 26th less than

Any MonoiSer-e, especially those with hydrophobic Groups must be considered as separate and the broad and preferred areas determined ". The Oligomers contain only a trace of unreacted SOp or of unreacted bisulfite reducing agent.

The reductive polymerization according to the invention can be carried out with very different monomers with alpha, beta double bonds which have a hydrophilic group. A mixture of such monomers or one or more such monomers can be used in conjunction with a further monomer which has a hydrophobic group. The monomers used generally have a water solubility of at least 1 wt .- ^ at 24 ⁰ C.

The polymerization can · for the production of either (T) a clear, single-phase product or (2) a cloudy or milky, two-phase product, which is stirred, temperature-controlled and after neutralization of any acid groups which the Y or X position in the average Occupy molecule, can be made clear, can be carried out. Mixtures of monomers which can lead to the formation of a macro-phase of sticky polymers must be avoided, since such polymers stirring ^s oind temperature control hinder during polymerization and are not readily soluble after neutralization. ■ ·

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Examples of monomers with hydrophilic groups are: Acrylic acid, methacrylic acid, alpha-ethyl acrylic acid, beta Λ Methylacrylic acid, alpha, "be ta-dimethylacryic acid, hydoxyethyl acrylate, Acrylamide, methacrylamide, vinyl ethyl ether, vinyl methyl ether, vinyl pyrrolidone and allyl alcohol. ',

Monomers with hydrophobic groups are acrylonitrile or KIe thy! acrylonitril ,. Ethy! Acrylonitrile, methyl acrylate, Ethyiacrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, Hydroxypropyl acrylate, methoxyethyl acrylate, Hydroxyethyl methacrylate, hydroxypropyl methaorylate, vinyl acetate, Vinyl propionate, N-isopropyl acrylamide, U-ethyl acrylamide, ■ IT-methylacrylamide, IT-isooctylacrylamide, N-methylolacrylamide and diacetone acrylamide.

Further in accordance with the invention it has been found that oligomers of the following general formula is particularly valuable as conductive agents, especially for. photoelectrostatic. Playback sheets are: ·

πηπΜ / / πττ πττ " ¹ / / <? λ μ

'1'"'''■"' ■ " ^: ■" ■■ 3 "· '-"' 4 '' ■ "■ where M and M are water-soluble cations, R and R are hydrogen or a methyl group. ', Z is a -CU or -CONH ₂ group, c + d 10 Ms 60, preferably 15 to 40 »d / c + d 0.1 to 0.4 and preferably δ.15 Ms 0.15. ...

98 20/12

In general, the Ollgomerisationstemperatur is between "5 ° and 9O ⁰ G, preferably 20 ° and 65 ⁰ O-gehalten. This can easily depending on the reaction -jeweiligen," to be determined.

The oligomerization is "expediently in aqueous Medium in the presence of a relatively large amount of bisulfite as a reductive initiator. · Im

in general, the amount of the reductive initiator is

expressed as moles of T-monomer / g 1 formula weight (GFV7) of the reductive initiator, between 4 and 250, however, this value is preferably in the range -between 10 and 100. The ratio of moles of the monomer to the g] "W of the reductive initiator" determines the degree of oligomerization. Using the viscosity of the reaction product as an indication of the molecular weight Effect of the relative amount of the reductive initiator listed in the following table:

! Table I - Effect of NaHSO ^ on the viscosity of polyacrylic acid

Moles of acrylic acid ■ - viscosity, relative to water / water, g]? W ITaHSO, ■ -van. ' 10bigem reaction product

20 '' 1.86

40. 5.38

60 ^: 3.86 909820/1226

- ίο -

Regarding the protective initiator, the "are preferred Materials the water-soluble bisulfite salts, in particular Sodium or potassium salts, but other bisulfite salts can be used can be used, e.g. lithium, cesium, rubidium, ammonium, monomethylammonium or monoethanol ammonium salts.

In the practice of the invention, sufficient oxidative activator is used to effect 100% conversion of the monomers to the oligomer. The amount of such activator, expressed as g ¥ (I activator / glW initiator, can range from 0.0001 to 0.5, but is normally within the limits of 0.001 to 0.1. Any convenient conventional water-soluble oxidant can be used as Activator used v / earth. Examples of such oxidative activators are "ammonium persulfate, sodium persulfate, potassium persulfate and hydrogen peroxide."

The reductive polymerization products according to the invention have a comparatively low molecular weight and form aqueous solutions of low viscosity. The molecular weight of the compounds is generally less than 25,000, most desirably 500 to 4000. The viscosity for these materials in 10biger aqueous solution is often below 50Ov ₀ Ps at 22 ⁰ C, - but often also in the range from 1.5 to 100 cps at 22 ⁰ C. The aqueous

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Solutions can be neutralized with generally known hydroxides, 2.B. KaOH ₁ oxides, carbonates or free "bases, e.g. UH ~ Y if acid groups occupy the X or Y position of the average molecule listed above. These salt solutions of the oligomers also have low viscosity and are valuable masses.

The acid form of the oligomers of Formula II, i.e. where M'Hydrogen can also be obtained by the above-described bene reductive polymerization procedures can be produced. The acid form of the oligomer can then of the water-soluble conductive agents according to the invention be neutralized. Various alkaline materials, which neutralize the acidic oligomer and form a water-soluble oligomer salt can be used. Alkali and ammonium hydroxides and carbonates are suitable as such. Most of them are salts of the alkali metals having an atomic number of 19 or less is preferred. .Practically

Of these, the potassium salts are most desirable.

The conductive barrier layer can expediently be on the backing can be applied by any conventional technique. Since the oligomers regulated with bisulfate in aqueous solution can be prepared and there the Eeaktion leads to essentially complete conversion, the polymer can be used directly as a coating after neutralization.

S 0 9 8 2 0/1 2 2 6

- .12 -

.be usedT * -It is not a double processing, e.g. the Removal of solvent or unreacted monomer, required. '·..' '-.- .;

To reduce cost and / or stickiness The resulting coating can contain pigments, waxes and poly! mere to be added. The following. Table shows the Composition of typical coating solutions.

. '' Table II ■ ....

Ingredients Parts by weight / 100 parts oligomer

Pigments'. ; 0 to 200

Stickiness reducing agents. · .0 to 5 _;

Polymers. 0 to 400

V / ater. . . 200 to 1000

Generally all of the solids are in the

aqueous solution between 10 and 60 percent by weight. The viscosities of these solutions. are 10 to 20,000 cps, a range the easy application of the coating to the base paper permitted. ·.

Extenders, v / ie other polymers and pigments, can to improve the properties of the coating and to

.909820 / 1226 .-. _r: "

Reduction-of-cost may be admitted. Examples of pigments that can be used are clay, titanium dioxide, calcium carbonate, hydrated alumina and talc. Other polymers, both conductive and non-conductive, are, for example, carboxylated styrene-butadiene rubber latexes, acrylate latexes and water-soluble polykai ^ -oniscfae iblymere. Starch can also be added. Ammonium stearate, calcium. stearate and Carbowax (polyethylene glycol or epoxy resin having a molecular weight of 200 to 7000, a density of 1.0 to 1.16 to a melting point of -15 to 63 ^{0 O} O) are examples of the anti-tack agent, which may be added . . ;

- The invention is based on the following case. games explained in more detail.

Example 1 .

A 1 liter reaction vessel. was added with a stirrer, thermometer, reflux condenser, addition funnel and a gas inlet pipe, which goes into the vapor phase leads, equipped. The reaction vessel was placed in a bath maintained at 31.8 ° C.

The reaction vessel was filled with 3.12 g of HaHSO ₃ (0.03 gW), 159.0 g of water, 90.72 g of acrylic acid (1.26 mol) and 12.7 g of acrylic

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- 14 ■:

nitrile '(0.24 mol.) -. charged. The molar ratio of monomers to giW IaHS ₃ T3e _was "5 _{O and the} molar fraction of acrylic acid was

attracted to all monomers, .0.84 ·. - '

Nitrogen gas was passed into the reaction vessel through the gas inlet tube "at" a rate of 100 cm / minute. After the contents of the flask had reached 31.4 ⁰ C, accessories were added 0.25 ml batches of 1 $ aqueous (HEL) ₂ S ₂ O ₀ in the course of three hours through the addition funnel. A total of 3.25 ml (HH.) ΡSpOq were added. The reaction temperature varied zwischen.32, O and 36.8 ⁰ C. Finally was allowed to stand, the reaction mixture Geesthacht. The next morning the weight of the clear reaction product was 269.2 g. It had $ 39.2 solids indicating a 99.0 conversion. The viscosity of the product was 7700 cps. The oligomer produced can be represented as H- (ft.crylnitril) "- (acrylic acid KgSO ^ Ha .. /

Example 2

Following the general procedure of Example 1, (HH ^) HSO- "was used as an initiator for the production of H- (acrylonitrile) r, _κ - (acrylic acid"')', ™ j - SO-, HH. used. (HH.) ₂ S ₂ "0 _a was again used as activator. The reaction yielded 95 $ conversion of the monomer used. The solids at 100 $ ethyl sales amounted to 34.9 ^. The viscosity

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tat "was 1010 eps 'compared with. 1450' cps for the corresponding Oligomers produced with HaHSO., as initiator.

• Example 3

The general procedure of Example 1 was followed using 3.47 grams of HaHSO .; as initiator and 0.04g (NEL) ₂ "SpOo as activator per mole of monomer" was followed. The monomers used were as shown below. In "both" trials, "the" conversion was over $ .98 · The viscosity of an aqueous solution containing about $ 35 solids is shown below. '

Table III

Oligoineres ■ Viscosity, cps

H- (acrylonitrile) ₅ ^ (acrylamide) ₂ q- ■

(Acrylic acid) ₂₂ V-SO ₅ Na 1800

! ^ Acrylamide) ,, _c (acrylic acid) _{oo π} -

SO ₅ Na 1300

Example 4 "'"

"■. ■■ · ■ ^x o- ·· '

This Beiapiel serves to demonstrate the effect of storage

to indicate the viscosity of the reaction product. the The general procedure of Example 1 was used for preparation

90 9 82 0/1226

of, oligomers, applied, all.- reactions resulted in a Monomer conversion of. about 95 $ · -The formula that arises Oligomers can be used as H- (acrylonitrile), - (acrylic acid) ^, -S0.vM - can be specified. The following table shows the results obtained:

ammonium Tabel IV , - ammonium $ - solids
at. $ 100
sales Viscosity, cps
how won / ~
after 3 weeks Initiator ■ activator
HSO_ cation S _o 0 _q ■ potassium ■ 3200/2950 Sodium· ammonium / $ 50 73OO / 73OO sodium Potassium-. 5P $; . 6080 / - sodium potassium "$ 50 3780 / -. ' sodium ·. $ 45 1.1.00 / 1.150 Potassium ■ . $ 50 ■ 2300/2450 ' potassium Example 5

Using the general procedure of · Example 1 some other oligomers of the invention were derived from that represented by the 'general formula H- (acrylonitrile) - (acrylic acid),

a - υ

SCUNa described type 'manufactured. GO (degree of oligomerization) is given by (a + b), but is calculated from moles · monomer / gFW reducing initiator. In this procedure, GO is from 16 to 60, the molar fraction 'of acrylonitrile, a / (a + b ) from 0, 500 to 0.0 and the percentage of solids from .10 to _Q 6CK. varies. ■> ·. ·

ÖplQINAL INSPECTED

- 17 - ■ '

The effect of these variables on the viscosity, expressed centipoises is shown in the following table: '/ "... ·:

a / (a + b)

GO 1o ■ - '. "·

Pests. 0.500 0.333 0.250 0.176 0.000

16 35 $ · · "" · - 186 cps

60 $ 100M cps "■" "

$ 20 10 ■ ■ . .1.5 cps

35 $ '. ... '2-phase 296 cps 378 cps

'"3200 cps 150 cps

¹ 7300 cps.

30 .35 $ 2-phase 1450 cps' 1120 cps

$ 10. ,. 2-phase 2.7 cps

40 $ 30 ■ 2-phase

35 $. . 7500 cps 9600-cps 4000 cps

50 30 $ 2-phase

■ 35 $ ■ 2-phase 7700 cps

$ 40. 30M cps. 12M-. ops

60 $ ■ ν 4OM cps * ■

60 10 $, ν 2-phase 3.1 cps

35 / '3OM cps

If two phases were formed, neither was the conversion the viscosity is still determined. "The above -data-

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show that the üiedrige viscosity especially with ratios of a / (a + b) below 0.233 and at values of GO of 30 or less is obtained. It 'is, however, further note that low viscosities at low Solids levels, e.g. $ 10, can even be obtained there where the GO 60th cheated. In any case, there was where two phases were formed, after neutralization a homogeneous one Get solution. . - ■

Example 6

A four liter reaction vessel equipped in the same way as the 1 liter vessel of Example 1 was charged with 1707 g of water, 265 g of acrylonitrile, 1080 g of acrylic acid and 52 g of ITaHSO. The reaction vessel was placed in a ^{water bath maintained at 29.8 0} G and a stream of nitrogen was passed through the vapor phase of the reaction vessel. The initiator, 1 g (HHj) pSpO ₈ in 68 g water, was added slowly so that 10 g of the solution had been added to the reaction vessel after four hours. The temperature of the reaction components rose to 41 g. The reaction mixture was then allowed to stand overnight and had $ 44.9 solids and a viscosity of 74,000 cps. 33% aqueous KOH solution was then added to the reaction product in an amount sufficient to neutralize 95% of the acrylic acid groups present.

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■ - • 19 -

The disfiguring salt solution contained 37.8% solids a viscosity of 1: 300 cps and a pH of 6.5 and was "clear and colorless. The oligomer product was about 95 $ des Potassium salt of the formula H- (acrylonitrile) ljq- (acrylic acid Wq-SO J9a shown oligomers.

' Example 7 ' ■ "■ ■

The general procedure of Example 6 was followed except that the oligomer produced was the potassium salt of H- (acrylonitrile) c- (acrylic acid) ^ - SO, Na. The unneutralized reaction product had 44 * 6 $ solids and a viscosity of 4950 cps and was clear and colorless. If there is enough 33% aqueous KOH for neutralization. of '95 $ 'of acrylic acid had been added to this reaction product, a salt solution of the oligomer was used. obtain. This solution was clear and colorless, had 37 solids, a viscosity of 230 ^r cps, and a pH of 6.4.

''"■" .. "■ '- ^.; ■■ Example 8 ■ /. ■ -. ·. ■.,

• ^; The oligomers represented by the formula H- (methyl acrylate) _a - (acrylic acid) - ^ SO-ITa * are modified according to the general procedure of "Example- 1 uijte.r appropriate changes

82: 0712 26 '.

More monomers and NaIISOV to make the desired special To obtain oligomers, prepared. Enough water has been used to make about $ 45 solids at an iOÖ ^ ig turnover of the monomers used as "starting materials".

■ ""'■' - ■ ^; ■■■■■■ - ■ ". Table VI ■" - '"' - ^: '' · V"

Versüch-HrJ. ' a 'b ä / (a' - + b) '^ conversion ^: viscosity of the''-'

· ... ,, -. ·. · Product

. 0.2: ~ '■ - 9 &, 3i °.,. . Χ3Ί0- cps. ■: O _r 3 ■ ..- "ν. · ..98-i.2j * '>.: 20 ^ 5: cps

■ - ■ · ■■■: Example 9 -. ■ - ■ ". · ■ - · ■■. ·; ·. ■

Represented by the formula 'H-ClT Isooctylacrylamid) ^ (acrylic acid) ₂₀ -S0J! Ia shown Oligqinere was in a 1 liter resin flask equipped with a feinlaß Stickstof, a Rüclcflußkondensator, Tharinometep * ^ stirrer. ;and ; equipped with an addition funnel · -was “made”. 3 flask was placed in a ·. , 'kept at-58 ⁰ Q: water bath brought The flask was,. - with 7y8 "'g; ITaIISO * and ^ 9. ^ yZ: g -Water, charged. J) he ,, addition funnel contained a homogeneous solution of 12.25 g M-Iaq - - ,. octylacrylamide in 108 g ,, Ae ^ ry | säi; geu. The 'activator solution -._ · .--. -consists of 7-: g _; (ITH *). ₉ S "O _ftt , in; 50 _: gf: water .., if the content

CS Ä \

Substances of the piston * had reached a temperature of 58 ⁰ C, everything except 45.1. g of the mixed monomers to the flask allowed to flow, and at the same time 0.33 g "was added to the activator solution. The temperature of the reactants rose to 180 ⁰ C at Vind fell auf'die temperature of the bath after 20 minutes. The 'remainder of the mixture of monomers was then added, however, there was no more '"exothermicreaction" instead, were added to 2.3 g HaHSOJ in.10g water and 0.33 g activator solution. at this time, the temperature of the Reaktionskomponeten rose to ■ 67 ⁰ G. Another addition of activator solution (2 g) produced no exothermic reaction. The reaction product had 31% solids, "indicating 100% conversion. The viscosity of the reaction product was 220 eps and this would have a milky appearance. ·. ··

Example 10..

The oligomer represented by the formula H- (hydroxyethyl acryrate)., Q- (acrylic acid) .Q-SO ^ Ha was prepared in the apparatus described in Example 1 and using the general procedure of Example 1, except that the bath at 48 , 2 ⁰ C was held. The batch consisted of 10.4 g

_5, 368.4 g of water, 72 g'Acrylsäure un'd 11.6 g Hydro ^ yäthylacrylat. "Addition of 0.8 g of 1 $ aqueous (NH,) 2 ^ p ^ 8 during hours resulted in a exothermen.Erwärmung 'to 56 ⁰ C, during the next 40 minutes 1.4 g of 2Q $ iges

S ₂ O ₈ added. leading to an exotfiermen 909820/1226 '

Warming to 8OUQ ^ led, whereupon a drop to bath temperature took place. The reaction product had $ 34.3 solids, what a 98 $ conversion of the raw materials used Indicated monomers. The viscosity of the resulting clear solution was 370 cps.

Example 11

The oligonere represented by the formula H- (ethyl acrylate), - (acrylic acid) ^ g-SOvITa and its ammonium salt were prepared in the apparatus described in Example 1 and using the general procedure described in Example 1. The water bath was kept at 29.5 ° C. The batch consisted of 13.g UaHSO, -, 144 g acrylic acid, 50 g ethyl acrylate and 253 g water. The addition of 1.6 g of 20 $ aqueous (HH.XgS ₂ Og in the course of time of two hours führte.zu an exothermic heating at 37 ⁰ G. The Beaktionsproduktzeigte a 98 $ strength implementation and had a viscosity of 1600 cps It was a cloudy solution. The addition of 14.4 g of 28% HIL ₅ to 54.8 g of this reaction product resulted in a clear solution of the ammonium salt of this oligomer.

12th

The oligoiaere represented by the formula H-acid.) * C-SO-Ha and "its ammonium

90 9 820/1226

salt were; in dec. iii prepared as "apparatus described .1 and using the allgemeien procedure described in Example 1. The water bath was maintained at 50.0 ⁰ C. The batch consisted of 10.4 g of NaH ₂ -SO ,, J.08 g of acrylic acid, 65 g of hydroxypropyl acrylate and 340.6 g of water. The addition of 1.6 g of '{inferred aqueous ^ "(HH,) ₂ S ₂ Oo over two hours and 40 minutes resulted in exothermic heating. to 58 G. Subsequent addition of 2 g of 20% aqueous SpOrv over two and a half hours. produced a slight exothermic warming .: The reaction product had a YiBliOBity of 1560 cps and was spawned cloudy. The monomer conversion was 99%. Ueütralisiert- with leonzentrierter wäsörigen.- ammonia, the resulting salt solution was clear. - -

■ '- ■ - "■ : -' ■ · - ^:. ""■■'- ■ Example 13 : .-

y. The oligomers represented by the formula H- (methoxyethyl acrylate) c ~ (acrylic acid) ^ ri-rSO ^ ITa 'were described in the direction described in Example 1 and using the methods described in Example 1 general working method established; The, .Bath was held at:, 5Qi-OC. The batch consisted of 10.4 g of ITaHSO ₇ , 108 g of acrylic acid, 65 g of ethoxyethyl acrylate and 340.6 g of water. The addition of 1.8 g of 1 $ aqueous

) ₀ S ₀ O for one hour, leads to an exothermic heating to 7O ⁰ C. This is followed by the addition of 1.2 g of 2Obigem

909 82% / tZ2 a,. ,, » _{ii £ f}

aqueous (lih. ^ S ^ Qg during 30.Minuten led to a '/ exothermic heating to 54 ⁰ O. The reaction product was allowed to stand · .Hacht and separated SiOH during this time in zwei'flüssige phases. The addition of sufficient concentrated triertem HH, to neutralize the acrylic acid present, gave a 1-phase solution of the salt.

The following examples ^ relate to the conductive ones Properties of certain oligomers produced by the process according to the invention.,

Example 14 · - ■

Both sides of a G-round paper material were made with aqueous solutions of oligomers according to the invention in an amount of 0.907 kg per 279 m coated. The waiter-' The surface resistance of the coating was measured with a Kiethly conductivity device measured at a potential of the electrode of 100 volts. The investigated oligomers had the formula ■ ·

H H .— b H H I. i i · I. C. - C C - C. 1 I. t - «- I. H X H COOK

-SO ₃ Na

The following table shows the values of X, a + b, b / a + b and the "Specific" resistance in megohms at

909820/122 6

and 50 $ relative humidity (before baw. after Mark). '"'

0.5 Tabel VII 0.0 Acrylamide
0.25 X
b / a + Ta
. a + b 000/11 Acrylonitrile
0.25 0.16 ' 16 24 '2000/25 ·. - 270 / 9.5 . 680/14 20th - ' • 120/1 6 240/11 " 40 110 / 7.9 50 • 280 / 8.3 . "73 / 8.8. 60 - - 1 50/1 6

Example 15

This example illustrates the effect of the cationic group on the conductivity of the dried oligomer film. In general, the larger the cationic group, the better the conductivity will be. The acid form of an oligomer of the formula N (CH ₂ CHGOOH)., C (CH ₂ GHCH) ^ SO ^ ITa was neutralized with alkali or ammonium hydroxides to a pH of 7.5 and applied as a layer on a West Virginia rcolophony-equipped electrofax material applied as a base. The leaves were cut up at

909820/1226

conditioned the desired "relative humidities, and ' their resistance values were measured. The results * are shown in the following table. '.

■ · Table VIII ' ^:

Total coating surface megohms /

Coating weight lcg / 279m resistance unit area (ibö. / 500.0 ft. ² ). 20 $ relative F. 50 $ rel. · ■

. Li ' 1.77 (5.9) 1 600 ooo - 55 000. · HH ₄ _ 1.22 (2, -7) ; ■ ι 100 000 ' 28 000 N / A.' ■ 1.72 (3.8) 7th 200 510 K. 1.65 (3, -6) 500 20th Rb 2.18 (4.8) 140 16 Cs. 1.68 (5.7) 92 ·. 51 Example 16 ;

With H- (CH ₂ CHCOOK) ₅ (CH ₂ CHCN) ₅ S0,1a coated paper samples were heat aged for 96 · hours at ⁰ C 1QO. There was very little discoloration. Similar sheets were light-aged in the Fadeaneter (lightfastness tester) for 96 hours with little or no discoloration. ■ ■ '- \ ..,

The coated sheets were using on top coated with a photosensitive zinc oxide and then were

909820/12 26

! '! I Β! 9Μβ ISB ¥ "I"ST'"?'pi>; ■ "■ .- -J- ■. ■,» ■ c- - r, -j,,. - -. ,. ", _F ,, ,,. ,

45 days at 22.2-2 pounds. Aged (72 ⁰ P) and 50 $ relative humidity. These sheets looked good when the electrostatic copier (Model SCM33 from Smith Corona) was used. This shows that no oligomer migration occurs during storage of the sheet. . "■. · '.

Films made from these oligomers were obtained at 22.2 ° C. Aged (72 ⁰ P) and 50% relative humidity for 5 weeks with apparently no migration within the filine or any deleterious effects on the film. The film had good solvent resistance to mineral spirits and toluene and was odorless. ·

909820/12 26

Claims (1)

· Claims . 1) Reductiyes polymerization process for production of oligomers with terminal 'sulphonate or their salts', characterized in that one or more alpha, beta-ethylenic unsaturated monomers in an aqueous medium in the presence of a water-soluble, reductive bisulfite initiator emulsion-polymerized and then optionally 'existing Acid groups neutralized. . '2) Method according to claim 1', characterized-characterized, that you get 1 g-Pormelgewicht "■ '" · - of the water-soluble. '· Bisulfite - 4 to 250 moles of alpha, beta-ethylenic, unsaturated Monomer used. 5). Method according to one of the preceding claims, characterized in that 1 g formula weight of the water-soluble Bisulfite used per 10 to 100 moles of alpha, beta-ethylenically unsaturated monomer. ' 4) Method according to one of the preceding claims, characterized in that it is used as a water-soluble bisulfite Sodium bisulfite 'used. 5) Method according to one of the preceding claims, characterized in that the water-soluble bisulfite 909.820 / 1 226 - 29 -. ■ Lithium, cesium ^, rubidium, ammonium, monomethylamminium. or monoethanolammonium bisulfite is used. . , 6) Method according to any one of the preceding claims, characterized in that 0.0001 Ms 0.5 g formular weight of the oxidative activator present per G-ramm Pormelgewicht reductive initiator used. 7) Method according to one of the preceding claims, characterized in that one 0.001 to 0.1 g formula weight of the oxidative activator present per gram weight of porcelain reductive initiator used. '' '8) .Method according to one of the preceding claims, characterized in that · the oxidative activator ammonium persulfate, sodium persulfate, potassium persulfate or Hydrogen peroxide used. '· 9) Method according to one of the preceding claims, characterized in that it is carried out at a temperature of 5 ° Ms 90 ⁰ C. '. \ 10) Method according to one of the preceding claims, characterized in that man''es at a temperature of 20 ° to 6 5 ⁰ O executes. - ' 909820/12 2'6 ■ 11) method- ^ according to one of the preceding claims, characterized in that one oligomer with a. * Produces basic structure of 8 to 500 carbon atoms. 12) Method according to one of the preceding claims, characterized in that one. Oligomer of the formula • c R I C IP · - so. / b where M is a cation, ft. ^1,. R, Ή? and Ir r are identical or different and represent hydrogen, a methyl or ethyl group, Y represents one or more hydrophilic groups and X represents one or more hydrophilic groups, a + b «4 to 250 and a / a + b« 0.0 to 0 , 6 are. 13) Process-according to one of the preceding'Ansprüche, characterized in that an oligomer of the formula I is prepared in which Y is the group -COOH ,. -COHH ₂ , -OCH ₃ , -OC ₂ H ₅ 'or' ■ · ■ · ■ "' CH ₂ - CH ₀ -I i. - CH _r represents.- 909820/12 14) Process according to one of the preceding claims, characterized in that an oligomer of the formula I is prepared in which Y is the group -COOC ₂ H.OH ', -COOC ₅ H ₆ OH, -COlHC ₈ H ₁₇ , - COIHCH ₅ , -COKHC ₂ H ₅ , -COlTHC ₃ H ₇ , -COMC ₃ H ₁₇ , . Represents -COOCH ₃ , -COOC ₂ H ₅ , -CI, -0OCCH ₃ , -0OCC ₂ H ₅ or COIHC (CHJ ₂ 'CH ₂ COCH-. ■.. 15) Process according to one of the preceding claims, characterized in that an oligomer of the formula I. where a / a + Td is less than 0.4. 16) Method according to one of the preceding claims, characterized in that one oligomer of the. Herstellti formula I wherein a / a + \> .is less than 0.3. 17) Method according to one of the preceding claims, characterized in that an oligomer of the formula I is prepared in which a = 0. 18) Method according to one of the preceding claims, characterized in that an oligomer of the formula I is prepared in which a + "b is 10 Ms 100. 19) Method according to "one of the preceding claims, characterized in that a salt of an oligomer of the formula I is prepared by 1) acrylic acid or methacrylic acid with 2) acrylonitrile, ilethacrylonitrile, acrylamide or 909820/12 26 - 32 - ■ ·. ■■ -. Methacrylamide polymerizes and then at least some of the acid groups are neutralized to produce of an oligomer of the formula HZCH ₂ CR ⁵ COOMJZ ₀ ZoH ₂ CR ⁴ Z ^ SO ₃ M ¹ . II ' 1 '"3 where M and M are water-soluble cations, R and R ^{4 are} hydrogen or a methyl group, Z is a -ClT- or -CONH ₂ group, c + d >> 10 to .60 and d / c + d = 0.1 to 0.4 are. 20) Process according to one of the preceding claims, characterized in that an oligomer of the formula II where c + d * is 15 to -30. 21.) Method according to one of the preceding claims, . characterized in that one oligomer of the formula II ■ 1 '■ · produces, wherein M and M represent alkali or ammonium groups. 22) Method according to one of the preceding claims, characterized in that an oligomer of the formula II is prepared, wherein.R and R ^ represent hydrogen. 23) Oligoineres with a terminal sulphonate with a basic structure of 8 to 500 carbon atoms, on which a hydrophilic group for every 2nd carbon atom in the backbone 9 0 9 8 2 0/1226 - is bound, and - its. Salts. ■ 24. Oligomer according to claim 23, characterized by the formula. . R 'ι -C ι R-i where M is a cation, R, R **, R and R ^ "are identical or different and represent hydrogen, a methyl or ethyl group!" represents one or more hydrophilic groups, X represents one or more hydrophobic groups, a + Td * 4 Ms 250 and a / a + Id = O ₁ O to 0.6. 25. Oligomer according to one of the preceding claims, characterized by the formula I, 'wherein Y is the group -COOH, -CONH ₂ , -OCH ₃ , -OC ₂ H ₅ , -CH ₂ OH or CH ₂ - CH ₂ -35F C Il - CH _r means. 26. Oligomer according to one of the. preceding .Ansprüche, known by the formula I, wherein Y is the group -COOC ₂ H ₄ OH, -COOC ₃ H ₆ OH, -CONHC ₈ H ₁₇ , - CONHCH ₃ ', -COlTHC ₂ H ₅ , -COMiC ₃ H ₇ , -CONHC ₀ H ₁₇ , -COOCH ₃ , COOC ₂ H ₅ , -CN, -0OCCH ₃ , -0OCC ₂ H ₅ or -COInIC (CH ₃ ) ₂ CH ₂ COCH ₃ . 90 98 20/1226 27) oligomers according to one of the preceding claims, characterized by the formula I, wherein a / a + b is smaller al is 0.4. '·. ' 23) oligomer according to one of the preceding claims, characterized by the formula I, wherein a / a + b is less than 0.3. ' ·. . ". 29) oligomer according to one of the preceding claims, characterized by the formula I, wherein a. = 0 is. ■ · 30) oligomer according to any one of the preceding claims, characterized by the general formula I, wherein a + b 10 "to 100 is /. 31) oligomer or a salt thereof according to one of the preceding claims, characterized by the formula SO ₃ M ¹ -II where M and M are water-soluble cations, R and R are hydrogen or a methyl group, Z is a -CH- or - (group, c + d * 10 to 60 and d / c + d >> 0 , 1 to 0.4 32) oligomer according to one of the preceding claims, characterized by the formula II, wherein c. + d «is 15 to 30. 909820/1226 - .35 - 35) Oligomere'S "according to one of the preceding claims, characterized ¹ by the formula II, in which M and · M- represent alkali or ammonium groups. '' · 34) oligomer according to one of the preceding claims, characterized by the formula II, 'wherein R and R water · represent fabric '. . 35) Oligomer according to any one of the preceding claims, characterized by the resulting bisulfite or a salt thereof or an aqueous solution of the oligomer or its salt. . 36) Conductive composition, characterized in that it is an oligomer terminated with bisulfite or a A salt thereof according to any one of the preceding claims together with an extender. 37) Composition according to claim 36, characterized in that that it contains a salt of an oligomer according to claim 31 as oligomer. 58) Photoelectrostatic display element, labeled by a metallic'e.s · 'G-round sheet with a conductive Barrier layer on at least one side of the G-round sheet and a light-sensitive layer on the barrier layer or layers, v / whether the barrier layer is an oligomer or 909820/1226. -.36 - whose salt contains according to the preceding claims. - '. 39) display element according to claim 38, characterized in that that the barrier layer is a salt of an oligomer according to claim 31 contains. 9 09820/1226