BE468991A - - Google Patents

Description

       

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  Process for the preparation of novel polymerizable organic materials, products obtained by this process, their polymerization and resulting polymers.



   The present invention relates to a process for preparing novel polymerizable organic materials, to the products obtained by this process, to the polymerization of these products and to the resulting polymers. The invention relates more especially to the preparation and polymerization of novel polymerizable organic materials containing two unconjugated CH2 = C # groups in the molecule.



   In English Patent No. 423,790, a process for the preparation of new polymerizable products is described, in which either acrylic acid or acid is reacted.



  Methacrylic on an alcohol, divalent under ordinary conditions

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 nally applied in esterification to form a diacidic ester but adding, if desired, a pro-
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 The polymerization is started, and the resulting polyuzeresis product is isolated. Organic materials, such as glycol amethylacrylate, which contain two unconjugated ël '() Ul, H ;;: llents OH 2 = :: 0 <in the molecule, can generally be transformed by polymerization, free of volatile matter, hard intusiolous solids and practically insensitive to solvents. The polymers prepared from these materials do not exhibit the property of cold casting and, due to their hardness, they are not easily scratched.

   These properties
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 make organic -.1ilateral containing two unconjugated OH2 = C groups in the molecule very suitable for bonding other materials to each other under application of low pressure, for example to bond sheets of fibrous materials. one to another by coating or impregnating the sheets with the organic materials in question and by polymerizing these organic materials after assembly of the sheets.

   The hardness and solvent resistance of organic materials completely
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 polymerized containing two CH 2 ".E <i'LOn-COnàU6ués groups in the molecule, make these polymers, when they are free of materials which make them opaque, suitable for use by
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 example for the manufacture of aircraft and automobile windshields, level tools, lenses and card sheaths. The organic materials in question are suitable or well for incorporation into coating or coating compositions intended to be subjected to surface polymerization conditions.



   Many organic materials containing two group-
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 mente CH2 0 <unconjugated in. molecule are however difficult to polymerize because they tend to crack or crack.

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 to break down during the final stages of the polymerization, in particular when their polymerization is carried out in the absence of a diluent or of a filler. Many of these materials, when polymerized to an infusible, solvent resistant state, are brittle and permanently deformed, so that they cannot be shaped or molded to. hot.

   The polymerization of many organic materials containing two unconjugated CH2 = C <groups in the molecule is prevented by air, and this fact greatly diminishes the ease of use of these materials in the manufacture of products of a high quality. great utility.



   The present invention aims to provide: new polymerizable organic materials containing two unconjugated CH2 = C <groups in the molecule; such organic material which is likely to polymerize with a low risk of cracking or breaking; organic materials of the kind resulting in the formation of infusible polymers, resistant to solvents and at the same time relatively tough and possessing a certain degree of thermoplasticity; such organic materials which can be satisfactorily polymerized in the presence of air; an economical process for the preparation of these organic materials.



   According to the present invention these objects are achieved by a process in which acrylic acid, as defined below, or a derivative thereof, is reacted under conditions leading to the formation of diacid esters. esters, for example its diacid chloride, its anhydride or its methyl, ethyl, propyl or butyl ester, with the

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   hydroxyl groups of a divalent polyester formed from a divalent alcohol and a dicarboxylic acid or one or more of their ester-forming derivatives, from a mixture of tele esters or from a mixture of a or of several such esters ac a divalent alcohol, this ester or these mixtures contained between 2,

  5% and 25% by weight of hydroxyl groups. The expression "conditions which lead to the formation of diacidic esters" means in the present description the conditions of erication in which the proportions of the materials participating in the reaction and the reaction times are such that the formation of crystals is formed. diacrylic esters.

   It will be appreciated that, since in these esterification reactions the esters themselves constitute participants in the reaction, the reactions should not be carried out under conditions leading to saponification, because otherwise one arrives at low yields of the products object of the present invention, i.e., the reaction mixtures must be maintained in a substantially water-free state when the reactions occur at elevated temperatures.



  It will also be appreciated that since the materials participating in these reactions and the products resulting therefrom are materials which tend to polymerize rapidly at elevated temperatures, the reaction which is the object of the present invention must be carried out in the presence of. of a suostance capable of inhibiting the polymerization if the reaction is to be carried out at an elevated temperature and without polymerization of part of the contents of the reaction vessel taking place.



   The new polymerizable materials formed have a content of acrylic groups corresponding to a content of hydroxyl groups of 2.5% to 25% by weight and are constituted by one or more acrylic esters of divalent alcohols and dicarboxylic acids present. or in the absence of one or more acrylic esters of divalent alcohols.

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   Throughout the present description and the claims forming part of it, the term "acrylic" relates only to unsubstituted acrylic groups, methacrylic groups and alphahaloacrylic groups.



   Mixtures are obtained containing the above-mentioned divaive polyesters and divalent alcohol, mixtures having a content of hydroxyl groups of between 2.5% and 25% by weight and suitable for use in the process under consideration. of the present invention, by reacting together? under conditions conducive to the formation of esters, suitable molecular portions of divalent alcohols, the hydroxyl groups of which are separated by a chain of x atoms, and dicarboxylic acids, of which the carboxyl groups are separated by y atoms, 1 plus 1 being equal to 3 or more.

   It will be appreciated that a small amount of ether is formed during this reaction and that the mixture obtained when ester formation appears to be substantially complete (as indicated by the reaction byproduct released , i.e. in this case water) contains a certain amount of free carboxyl groups.

   or, the divalent polyesters can be prepared from derivatives, resulting in the formation of esters, of these acids and alcohols, although it is understood that in some cases there will be no divalent alcohol in the mixture. reaction product and that the product may be a divalent polyester alone, for example when reacting ethylene-chlorohydrin with a salt of a dicarboxylic acid, molecular portions such as such participants in the reaction as the hydroxyl groups of divalent alcohols or their equivalents, minus the hydroxyl groups or their lost equivalents,

   during the reaction forming the subject of the present invention lead to obtaining

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 diapers having the desired content of hydroxyl groups, correction often being necessary because a certain amount of divalent alcohol is removed, together with the reaction by-product, for example water, from the reaction mixture during the reaction. reaction.

   The divalent polyesters themselves or mixtures of divalent polyesters can be obtained by repairing the ingredients of the mixtures of divalent polyesters and divalent alcohol by such methods as tractor wash or distillation separation. The fractional distillation of these mixed leads to the formation of a certain quantity of ethers leading to the formation of diva-polyesters with very high molecular weight if high temperatures are applied.

   so that it must be carried out at low pressures and temperatures so that this formation of ethers is low.



   A simple method for measuring the aforementioned hydroxyl contents is as follows:
A reagent is prepared consisting of:
200 ml of pyridine 'A R1 dried over KOH and distilled between 1140 C. and 116 C,
27 ml of acetic anhydride 'A R' distilled between 138 and
142 C,
0.7 ml. of water, adding the water to the pyridine and vigorously stirring them together, after which the acetic annhydride is added and vigorous stirring again.



   Then introduced and weighed in a pressure resistant flask 1.5 gr. sample that lion wants to try and add 40 ml. reagent. 40 µl of the reagent is also added to another pressure resistant vial. These pressure bottles are sealed and placed for 2 1/2 hours in a bath.

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 of boiling water, cool them until they are quite cold, open them and add to each 100 ml. of water.



  We reseal them, we put them back in the boiling water bath for half an hour, we cool them completely and we transfer the contents of each into one liter bottles, in which we also pour the liquid adhering to the walls. pressure bottles and removed from them by rinsing with water. The contents of the 1 liter vials were titrated with sodium hydroxide Nil using as an indicator an abundant amount of phenolphthalein. The hydroxyl content of the sample is calculated from the difference between the control and the sample, correcting the titrations for the acid number of the sample.



    @ Dicarboxylic acids, or their ester-forming derivatives, which lion can very suitably react with divalent alcohols before preparing the new polymerizable compounds which are the subject of the present invention, are maleic, adipic, sebacic acids, phthalic, terephthalic and diglycolic, or their ester-forming derivatives. Malonic acid can also be used, but it tends to decompose into carbon dioxide and acetic acid on heating, although esters of malonic acid do not suffer from this drawback.

   Suitable divalent alcohols are glycols such as ethylene-, trimethylene-, pentamethylene- and diethyleneglycol, the preferred alcohol being ethylene glycol because of its low cost.



   The choice of dicarboxylic acid and di- valent alcohol, or of their ester-forming derivatives, and the molecular proportions in which they are made to react with each other, regulate the hydroxyl content of said divalent polyester, or of said metal. -

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 mixture of divalent polyesters, the viscosity of the polymerizable materials prepared by the process forming the object of the present invention and the properties (including the price) of the polymers ob
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 held by the polymerization of these polymerizable materials forming the subject of the present invention.

   The viscosity of these materials po-
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 polymerisable, their degree of polymerization as well as the hardness and scratch resistance of the polymers obtained therefrom depend primarily on the hydroxyl content of the aforementioned di-valent polyesters or mixtures thereof. if divalent alcohol
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 used is ethylene glycol and lucid dicarboxylic acid is 1 <1 Niq.ae, the alcohol: acid molecular ratio can be only 11:10 to obtain a divalent polyester, or a mixture of such. esters, containing not less than 2.5% by weight of hydroxyl groups.

   At the other end of the range of divalent polyesters provided by the present invention, the malonate which contains only one malonic residue in the molecule has a hydroxyl content of 17.7% by weight. It has been found in the preparation of divalent polyesters that when divalent alcohols and dicarboxylic acids, or their ester-forming derivatives, are reacted with each other in a molecular ratio greater than unity, a mixture is formed. of divalent alcohol and divalent polyesters, mixture in which the polyesters have an average alcohol ratio:

   acid residue less than said ratio, and that the amount of uncombined alcohol
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 4.at ti: up to 7.5 (7) by weight of the total mixture, when the contribution.). OlculcÜe of the alcohol: acid is not more than 2: 1. In the tests (the preparation of mixtures in which the polyester .tivalrlt, showing a jt-appoit alcohol: acid residue of: 1, that is to say 1 predominant ester, one mixed 3 molecules dtYll, 'tl ^ -Z; IyCOI to.



  1 molecule was added to the phthalic acid and subjected to ion conditions, and 2.5 molecules were treated in a similar fashion.

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 of ethylene glycol with 1 molecule of malonic acid. The mixtures obtained after these reactions had hydroxyl contents of 21.5% and 23% by weight respectively and glycol contents of 25% and 20% by weight respectively.



   Both mixtures are suitable for use in the process which is the subject of the present invention. The preferred hydroxyl contents of these divalent polyesters, or of their mixtures with divalent alcohols, are between and 17% by weight to be most suitable for the accomplishment of the object of the present invention, for the purposes of the invention. preparation of polymerizable materials having suitable viscosities for ease of handling, especially when used to bond other materials together and in the preparation of hard scratch resistant polymers.

   Thus, if the di-valent alcohol is ethylene glycol and the dicarboxylic acid is maleic acid, the alcohol: acidic molecular ratio reacting is preferably 2: 1 4: 3.



   The choice between an acid. dicarboxylic or a derivative thereof depends mainly on the relative prices of these reaction participants and the expense of their reaction for the preparation of the polymerizable materials object of the present invention, other factors such as that the toxicity of the materials used, their flammability, the corrosion of the apparatus, must also be taken into account. The acid chlorides of dicarboxylic acids have more than hydrochloric acid, formed as a by-product of the reaction with divalent alcohol, spontaneously evaporates from the reaction mixture if this mixture is free of water, and the reaction tends continue until all the acid chloride is converted to an ester.

   Evaporating this acid

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 EMI10.1
 The hydrochloric acid of the reaction mixture can be accelerated and made complete by boiling the llléidll or by passing a stream of gas, for example air, through the mixture. However, these acid chlorides are normally expensive. Acids and anhydrides, when they can be obtained,
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 For example, pntalic and maleic anhydrides are preferred because of their relatively low price.

   To facilitate and complete the conversion of acids and anhydrides to esters, water can be quickly removed from the reaction mixtures by distilling it from them.
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 when these mixtures have relatively high temperatures, for example 200 C., or by azeotropic distillation. The distillation from a reaction mixture having a high temperature is more economical than azeotropic distillation, while the latter produces a less colored product.



  Methyl, ethyl, propyl and goal alcohols are removed from the waste ester reaction mixtures, containing the material involved. reacting with a methyl, ethyl, polyopyl or butyl ester, most suitably by fractional distillation with the aid of a liquid forming an azeotropic mixture.



  If a suitable fractionation column is not used
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 for aistillation from a mixture (the reaction having a high ?: t: ", Ù.JH, tU: r8 or from a reaction mixture of e-CHe \ .IlgO of esters, it It may happen that, due to the reaction mixture, a certain proportion of substances participating in the reaction, for example dtthY18ne-glycol, must be taken into account, and the resulting change in the molecular yield must be taken into account; Parti- cipct-nts a id. reaction * We can mix acrylic a.CidE; B as defined more nautical, or their aerated .orumirt aes 0st. ;;;

  .!., ct.u proault obtained

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 by reacting the mixture of dicarboxylic acid and divalent alcohol, and reacting them until the amount of the reaction by-product, for example hydrochloric acid, water or methyl alcohol , ethyl, propyl or butyl indicates that acrylic acid, or its derivative, has completely reacted. The extent to which the reaction object of the present invention takes place and the speed of this reaction can be increased to some extent by the removal of reaction by-products, which removal has been carried out. any of the known ways, as described above with respect to the reaction of dicarboxylic acids, or their derivatives with divalent alcohols.

   However, distillation from a reaction mixture at an elevated temperature, such as 2000 C, does not generally give satisfactory results because of the tendency of the contents of the reaction mixture to polymerize.



   Preferably there. the presence of small amounts of an esterification or ester exchange catalyst, for example hydrochloric acid, or sulfuric or tOluenesulfonic acid, in reactions between dioarboxylic acids or their methyl or ethyl esters , propyl or butyl, and divalent alcohols, or in the reactions forming the object of the present invention in which, as raw material, acrylic acid or alpha-substituted acrylic acid, or their esters are used. methyl, ethyl, propyl or butyl.

   Sodium methoxide is another ester exchange catalyst with good results,
The strong acid catalysts most suitable for use in these esterification or ester exchange reactions are the side reaction ingredients described in British Patent Application No. 26882/45, for example.

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 ae hydioquinonedisulfonic acid, because these strong acids are polynterization agents and suppress the tendency of the reaction mixture ingredients to be the subject of the.
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 present invention to polymerize and melt gels.

   These polymerization initiators are most effective in the presence of dissolved oxygen, so normally
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 pa.s, eY an air current through the mixtures3 ad, 1'1; ' which one uses the innibitors entering 1100jet a4 the \, aemandë of o .L'0vet angltB 3 26dd2 / 45.

   These polymerization irilbites have the particular advantage, among other polymerization materials, of being easily removed from organic liquids by washing with water or washing. by means of weakly alkaline aqueous solutions, or, preferably / by stirring with alkali an-
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 hydra, than with sodium carbonate, and filtering off the salt of the inhibitor thus formed, as this avoids the formation
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 water / organic liquid aluuulsions tion. These treatments also remove, at least in part, the excess of acidic materials participating in the reaction.



   To minimize the certainly in products forming the subject of the present invention by the formation of emulsions during
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 1 "removal of the polymerization inhibitors by washing, it is possible to dilute these products with a strong or low density solvent, for example with trichlol'thYlèn0 (high den- located) or auoenzene (low density), from so that the density of the solution differs significantly from that of the washing liquid.



  These solvents can be removed subsequently by distillation. We
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 These solvents can also be used for the azeotzapic distillation of by-products, eg water or lower apalcools formed during product-forming reactions.

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   There may be presence of a small amount of polymerization inhibitor, for example 0.025% by weight of hydroquinone calculated with respect to the amount of the products forming the subject of the present invention present in the mixture. , to stabilize these products during the removal of said solvents by evaporation. These small amounts of stabilizer can conveniently remain dissolved in the products to stabilize them during storage, transport, etc. Preferably, the solvent is evaporated off at reduced pressure so that this operation can be carried out at a relatively low temperature.



   Preferably the reaction object of the present invention is carried out in glass or enamel coated vessels, because some steels are attacked to a great extent at reaction temperatures.



   Another characteristic of the invention lies in carrying out the polymerization of the new organic materials which are the subject of the present invention in one or more stages, preferably in the presence of a polymerization catalyst. We can. The polymerization is to be carried out successfully in the presence of low quantities of a polymerization inhibitor provided that a sufficiently high temperature is applied and / or a sufficient concentration of polymerization catalyst is used.

   Normally, therefore, it is not necessary to remove added inhibitors to prevent polymerization during storage and transport, and the effect of any inhibitor contained in materials coming into contact with organic compounds during. polymerization seldom causes difficulty.

   In the present entire description, the term "polymerization" means the formation of a compound with a high molecular weight, a formation which is achieved by reacting the molecules of a compound, containing the group CH2 = C #, so that these groups react to each other,

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 this reaction being able to be carried out if it is unsuccessful, in the presence
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 one or more other unsaturated organic compounds which
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 contain the group <:. Jl1kmt) CC <whose molecules do not react with the molecules of said compound containing 10 group = - mf.it Ul {2 C [, and which are associated with formal high molecular weight eoiiipoôas and / or in the presence of one or more other unsaturated organic compounds which polyidëriaent .;

  i1il.ultanéJ.ent is born which does not COliJ.OÜ10nt to the high weight compound 1JJ.Olculdir \; J * Thus, the new organic matter making i 'ooju.1 of the. pre! - swnte invention can 3tre., f01YlliéJ.'Üt; iS Q-: 111es, or in the presence of one another, or in the presence of other unsaturated ort ;; cu1.ic compounds containing 14 groups O.rr2 = C <such as dU3Cinate â.l- (dllylglYColylique), glycol ciïltnacxyldte, aetyacrylate aë .lldtny'.JÇ, uutyq.-e methacrylate, le; c1110.i. u: n, vinyl, vinyl acetate or styrene; or in the presence of a morning containing ii group C C, such as al1.nyd.ri- .a maijique or polyesters of malic or ihzuaric acid and divalent alcohols.

   It is also possible to incorporate into the novel organic materials which are the subject of the present invention, during their polyitiization, accessory ingredients such as heaters and pigments, carbonates, reinforcing materials and polymers.
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 thermoplastics.



  New organic materials covered by the
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 The present invention is particularly suitable for the binding of fiorue3 materials together, for example for the manufacture of lamelleea sheets in fioreusss materials. The exposure points of these new organics allow the polymerization of the latter to be carried out without appreciable volatilization at reduced pressures and elevated temperatures, for example at a res.sion of 20 nua of mercury and at 100 C, often applied fi

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 in the manufacture of laminates or lamellae products, and under these conditions the materials in question polymerize with particularly great rapidity. The linked products have excellent mechanical properties.



   The following examples, in which all parts are by weight, illustrate the execution of the invention without limiting the latter.



     EXAMPLE 1.



   We heat together to 2000 C, while stirring vigorously:
250.5 parts of ethylene glycol (containing 2.5 parts of water) i.e. 4 moles of glycol,
299 parts of phthalic anhydride (containing 3 parts of water) i.e. 2 moles of anhydride, 'in an enamelled container from which the water can be removed by disti11at1on using a fractionation column which prevents .. the departure of ethylene glycol. In this way, 45 parts of water are rapidly distilled off. The reaction mixture is then cooled and a viscous product is obtained containing 13.4% of hydroxyl groups.



   The product is transferred to an enamelled container in which it is vigorously stirred, this container being designed for the removal of water by azeotropic distillation, and 300 parts of trichlorethylene, 360 parts of methacrylic acid (containing 16 parts of water) and 20 parts of nydroquinone-disulfonic acid (containing 2 parts of water). This mixture is refluxed with stirring and a continuous stream of air bubbles passing through it, and the water of reaction (together with the other water present) is removed by distillation. azeotropic with trichlorethylene which is returned to the container after condensation.

   When 90 parts of water have been removed, we cool

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 this reaction mixture at room temperature.



   25 parts of anhydrous sodium carbonate are added and the resulting mixture is stirred for half an hour. We filter the
 EMI16.1
 After mixing with a small filter, 0.2 part hydroquinone is added to the filtrate and the trichlorethylene is distilled off at reduced pressure so that the temperature does not rise above 80 c. We obtain a viscous liquid
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 consisting essentially of dimetnaoryl esters of phthala, your low molecular weight dihydroxyglycolics.

   The hydroquinone previously added stabilizes this liquid effectively against polymerization at room temperature.



     EXAMPLE 2.



   We mix together:
 EMI16.3
 100 parts of the prepared product: uir.xzt Example 1 and 1 part of benzoyl peroxide alsous in 10 parts of uutyl metnacrylates, until a uniform solution is obtained. This solution is spread evenly over sheets of glass flora tissue, prior to
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 bl ('Jl12nt cnauffées at 210 C. during) neures to rid them of fat. The sheets of fabric are placed on top of each other so as to obtain a laminated product having a thickness
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 ú.0 1, 2? nW1 (50/1000 inch) taking care to avoid the entrapment of air vents.

   This laminated product is placed between two sheets of cellophane and heated for 15 minutes in an oven at 100 ° C. A strong plate is obtained which is suitable for coating airplanes.



    EXAMPLE 3.
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  Ensmaole is heated to 200 ° C., while stirring ener:; i- q.ùe ..;:> iit;

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 EMI17.1
 498 parts of ethylene glycol (containing 2 parts of water) i.e. 8 moles of glycol, 596 parts of a, phthalic hydride (containing 4 parts of water)) i.e. say 4 moles of anhydride, in an enameled vessel from which the water can be removed by distillation, without fractionation. In this way, a mixture consisting of 82 ,? parts
 EMI17.2
 water and 11.3 parts of ethylene glycol.

   The reaction mixture is cooled and 1000 parts of a product wdsqueux having a content of 12% of hydroxyl groups, an acid number of 27 mgr. of KOH per gr. and an ethylene glycol content of 10%, the remaining 90% consisting essentially of a mixture of divalent polyesters containing 7.2% of hydroxyl groups.



  1 The product is transferred to an enamelled container in which it is vigorously stirred, this container being arranged, for the removal of water by azeotropic distillation, and added
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 600 parts of trichlorethylene, 640 parts of diethylacrylic acid (containing 32 parts of water) and 40 parts of dihydroquine-disulphonic acid (containing 4 parts of water). We treat this mixture
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 reflux, while stirring and passing through it, continuously a stream of air bubbles, and the water of reaction (together with the other water present) is removed by azeo-distillation. tropic with trichlorethylene which is returned to the container after condensation.

   When 168.5 parts of water were removed
 EMI17.5
 this reaction mixture is cooled to room temperature.



  Hydroquinonedisulfonic acid, unattacked acid reactants and trihlorethylene were removed as in Example 1 to give a viscous liquid consisting essentially of the diluethacrylic esters of low molecular weight dihydroxyglycol phthalates.

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     EXAMPLE 4.heating ---------- while stirring '
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 cnaufce onseaole 240-250Q all d.gitcl.11t. c; nc: rbiqua "nt: 212 parts of diethylene glycol (2 moles),
98 parts of maleic anhydride (1 mole), in a glass vessel from which the water can be distilled off using a fractionation column. In this way, 18 parts of water are rapidly distilled off.



  The reaction mixture is cooled to room temperature and a viscous product is obtained which contains 11.0 hydroxyl groups.



   The product is transferred to an enamel container in which it is vigorously stirred, this container being arranged for the removal of water by azeotropic distillation, and added.
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 300 parts of trichlorethylene, 163 parts of methacrylic acid (which corresponds to the above-mentioned content of hydroxyl groups) and 8 parts of nydroquinoriedisulfoniquu acid. this mixture is refluxed, while stirring it and continuously passing a stream of air bubbles through it, and the water is removed
 EMI18.3
 reaction by azeotropic distillation with t: ric! l10retny1ene - which returns to the vessel after condensation.

   When 34.1 parts of water have been removed, this reaction mixture is cooled to 1d. room temperature * 15 parts of carbonate are added
 EMI18.4
 sodium dJ.1.Zlydre and the resulting mixture is then stirred for half an hour. The mixture is filtered through a small pressure filter, 0.1 part of hydroquinone is added and the tri-
 EMI18.5
 pure chlorethylene distillation at reduced pressure so that the temperature of this solution does not rise above 30o C. A liquid is ooti (the viscous consisting essentially, because of dimethaeryl esters of .1lct.lâates âihyàroxyàiàtnyiéne- YCOliqU6 à èi'oi1 = moléould.ire weight.

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 EMI19.1
 



  E1 # .I '/ IPLE .5. ----------
 EMI19.2
 Together, while stirring vigorously, 124 parts of ethylene glycol (2 moles) and 146 parts of adipic acid (1 mole) are heated to 2000 ° C. in a glass vessel from which the water can be removed. by distillation using a fractionation column. In this way 36 parts of water are rapidly distilled off. The reaction mixture is cooled to room temperature and a viscous product is obtained which contains 14.0% - of hydroxyl groups.

   The product is transferred to an enamelled container in which it is agitated enargiqupiiierit, this container being arranged for the removal of water by distillation.
 EMI19.3
 azeotropic reaction, and 300 parts of trichloroetaylene, 155.5 parts of methacrylic acid (which corresponds to the above-mentioned hydroxyl content) are added. and 8 parts of nydroquinoDOdisUlfonic acid. This mixture is refluxed while stirring and continuously passing a stream of air bubbles through it, and the water of reaction is removed by azeotropic distillation with trichlorethylene which is returned to the vessel. after con-
 EMI19.4
 sensation. After 34.6 parts of water had been removed, this reaction mixture was cooled to room temperature.



  Hydroquinonedi6ulfonic acid, unattacked acid reaction participants and tricinorethylenene coram were removed in Example 4, and a viscous liquid was obtained consisting essentially of dimethacrylic esters of low weight aixlydroxyglycol adipates. molecular.



     EXAMPLE 6.



   ----------
 EMI19.5
 We heat together at 240-250 ° C., while stirring vigorously:
124 parts of ethylene glycol (2 moles)
202 parts of sebacic acid (1 mole),

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 EMI20.1
 ClJ3 un r cc i j 1; : i t e ii V <:: 1): l '<.:; to which 1 dl, j, J'ut Ù t 1 <z ....: nluvdi ;: by Cl.istill "" ti0 ± la the aiae <at <unà column fj, ..;: .t'J. dction, h; ¯!,.; l1t..o. "otte., lc, uier,:; we hunted rpid ..) nt by ùiE'tiLiation 5t? lJC9.r 'li a'eau.



  0 ,; : ¯-iiOJ.l.l7.t the "lèlaJ.16i3 of inaction at ld ls, .vl, W, '. DtLllLC' ù.JuÍ1J,; Ül'i.;: And on JCîl: 7..ilt a proault visqù wà qui 3! J 8ùllQi2.'i8 a.1, L.;. do ::,:; t which contains lL, 2 µ% of grùuJ, :: l; 1tlts Ylyu1'O, l; s. We tra1Js.ter <: ;; 1% produces QdJ18 un: t - ;: cij), Gnt .ùêÜllé in 1 <qu, à1 OJ has it: -;) 4âxiq.z; ::: lc: ilt, ce i ec 1 a 1 to nt being arranged for 1 'removal, icnt of 1 1 e,? ci.!' There are 1 st 11 and 1 ozotropic '', and 300 petTtiea of t: dci1107ct.l1Y1ÈHJe, 105 d.rtic3 of Altriacryliqu4 acid (which corresponds to said content ':; 11. 11Y <. hydroxyl) are added. and t 8.> ar 'l 1> 1 acid 1iyài' where 1 Aone to 1 sul roni q uoe This mixture is treated under reflux, while stirring it and continuously passing a stream of bubbles through it. air, c, t is removed 1 te in uû the reaction by azeotropic distillation with t. ::

  ic nJ.oT0tuYlènr ;; that 1 oa returns in 1 container after C0nú.i.;: l1; 3éL: l: .ion. When 5 -9, 5,. a1 t 1 # of water the reaction nest is cooled at t: lx-dtur; orull1air ,.



  The hydrocui7or1di3ulÎOlüqu. Acid, the reaction stimulants and the unattacked acid and tiienlor-ltiaylene CO "IT: 18 in Example 4 were removed and a waxy solid formed essentially was obtained. , 10nt by diëtnacryliquMS esters of low molecular weight dinydroxyglycolic acid.



  EXAMPLE 7.



  We cnarge and we shake enLr.queûl.aat:
 EMI20.2
 2, parts of concentrated sulfuric acid,
 EMI20.3
 124 parts of ethylene glycol (2 violated), 148 parts of phthalic anhydride (1 mole),) 00 parts of trichlorethylene, dct / 1S a container ::: 11 to which water can: 1tl ',:; .l.Gv4c; by azeotropic uiBtillation, the tricLllorethylene was returned to the living vessel after condensation. After, 11 / lèvelàl; .it of 14 parts 1 '\

 <Desc / Clms Page number 21>

 of water the reaction mixture is cooled to ordinary temperature and 172 parts of methacrylic acid and 8 nettles are added
 EMI21.1
 nyàroquinonedisulronic acid. The aze-tropic distillation is continued while bubbling a current of air through the neianéw until all the water (36 parbies) has been removed.



  20 parts of anhydrous sodium carbonate are added and
 EMI21.2
 the mixture obtained is stirred for half an hour. The mixture is filtered using a small pressure filter and the mixture is transferred.
 EMI21.3
 filtrate in a drained container from which the triciilor is removed;

  - ethylene by distillation at reduced pressure, so that the temperature of the mixture does not exceed 50 C. is obtained. a pale yellow viscous liquid consisting mainly of
 EMI21.4
 Low iiiolecultivate dinydroxyglyoolic phthalate dimethacrylic esters.

     EXAMPLE A 100 parts of the product prepared according to Example?
 EMI21.5
 1 part of benzoyl peroxide is mixed until the benzoyl peroxide is underneath, The operation is carried out in a cell, consisting of two glass plates separated by an elastic lining, the polymerization of this solution by subjecting this
 EMI21.6
 you last at a temperature of 60-? 0 C., during b neurea and then at a temperature of 100 C. during 3 hours. The glass plates were removed from the cell in a bath. dteauw to 90-95 ° C. and gradually cooled to 60 ° C. A lightly colored sheet suitable for use as a sleeve for cards is obtained.



     EXAMPLE * 9
To 90 parts of the product prepared according to Example 1 is mixed 1 part of benzoyl peroxide dissolved in 10 parts
 EMI21.7
 of butyl methacrylate so as to obtain a lioiiio-

 <Desc / Clms Page number 22>

 
 EMI22.1
 gn3. The solution obtained was uniformly spread out on sheets of canvas. The coated sheets are placed l JU111 .--- on the other of .üa..nièr0 to hold a laminated or lamination product: wl <i; llÔ,? Os5édd.nt a thickness of 3xl? ÌLi1 (1/8 inch) that one places I:> ntI'8 two sheets of cel10} rldne and that one heats in an oven endajit 30 -1inute at 100 C.

   We oti; lnt a resistant plate l) lOl) re to be used in the manufacture of dlétuiz or kits EXAMPLE 10t We heated together 13. 200 C, while stirring vigorously ôlioiiit 2f + u parts CJ.ttnY1èn - <: slycOl (4 lI1011 :: 5), 24 parts ua3y, raxiàe iuai éiqui (j .L110ldS), dd.l1.s a receptacle to which lt: a peu.t 3tru all: v: e by (Jl: -; til1c. tloll using 0.a. column il.xd, Ctl.Otl: l: .W.: t. ih; cett \ 3 .'Ic: w: 1iel '; on C1,;,> :) S0 rapiaenisnt par d.lstJ.l1ation 54 parts G'éaà, On 18.i..rùla.i the alldlac of roaction ..: t on o.otii;, .. 1t a viscous product containing 0, 5? ':; (, .e grou.!? 8Jlk: nts nydroxylés.

   The mixture is transferred to an ìo1Joillé container in which it is stirred energy- qU: 2lllr; nt, this container; both arranged for the removal of water by nitrogen distillation, .Jiqu3, and 330 parts of trichloroetoylam, io0 parts of methacrylic acid (which corresponds to 1ctdi t8 hydroxyl content and 8 parts of nydroquinonedi-
 EMI22.2
 sulfonic. This mixture is treated under reflux, while stirring it and
 EMI22.3
 \ ;;) 11 by continuously passing a stream of air vents through it, and the water of reaction is removed by azeotropic distillation with tx ic> 1oï't: alene which is returned to l8.l ' eci..vi.: mt after condensation. Lorequ-'on removed 33.5 parts by cooling this reaction mixture to room temperature.



  The hydroqùinonedis-ùlroniqu13 ltacid is removed, participating in the unattacked acid leactlon and the tricn10r13tnylene 1 \

 <Desc / Clms Page number 23>

 as in Example 4, and a viscous liquid consisting essentially of dimethacrylic esters of low molecular weight dihydroxyglycol maleates is obtained.



   EXAMPLE 11 ----------
We heat together to 2000 C., while stirring vigorously:
186 parts of ethylene glycol (3 moles),
296 parts of phthalic anhydride (2 moles), in a glass vessel from which the water can be removed by distillation using a fractionation column. In this way 36 parts of water are rapidly distilled off, after which the reaction mixture is cooled and a viscous product is obtained containing 7.0% of hydroxyl groups. The product is transferred to an enamel container in which it is vigorously stirred, this container being arranged for the removal of water by azeotropic distillation, and 350 parts of trichlorethylene, 159 parts of methacrylic acid (this is added). which corresponds to said hydroxyl content) and 8 parts of hydroquinonedisulfonic acid.

   This mixture is refluxed while stirring and continuously passing a stream of air bubbles through it, and the water of reaction is removed by azeotropic distillation with trichlorethylene which is returned to the vessel afterwards. condensation. When 33.3 par ..., t of water have been removed, this reaction mixture is cooled to room temperature.



   The hydroquinonedisulfonic acid, the unattacked acid reaction participants and the trichlorethylene were removed as described in Example 4, and a viscous liquid was obtained consisting essentially of dimethylacrylic esters of low molecular weight dihydroxy glycol phthalates.

 <Desc / Clms Page number 24>

 



   EXAMPLE 12.



   -----------
We cook together at 2000 C., while stirring vigorously:
208 parts of pentanediol (2 moles),
98 parts of maleic anhydride (1 mole), in a glass vessel from which the water can be distilled off using a fractionation column. In this manner, 18 parts of water are rapidly distilled off, after which the reaction mixture is cooled and a viscous product containing 11.0% of hydroxyl groups is ooticnt.



  The product is transferred to a scaled container in which it is vigorously stirred, this container being arranged for the removal of water by azeotropic distillation, and 350 parts of trichlorethylene, 161 parts of methacrylic acid are added. (which corresponds to said hydroxyl content) and 8 parts of hydroquinonedisulfonic acid. This mixture is refluxed while stirring and continuously passing a stream of air bubbles through it, and the water of reaction is removed by azeotropic distillation with trichlorethylene which is returned to water. the container after condensing.

   When 33.7 parts of water have been removed, this reaction mixture is cooled to room temperature.



   The nydroquinonedisulfonic acid, the participants in the reaction unattacked acids and the tricnlorethylene are removed as in Example 4, and a viscous liquid is obtained consisting essentially of dimethacrylic esters of: low molecular weight dinydroxypentamethylenic maleates. .



    EXAMPLE 13.



   ------------
We heat together to 200.0 O., while stirring vigorously:

 <Desc / Clms Page number 25>

 
 EMI25.1
 124 parts of ethylene glycol (2 moles),
148 parts of phthalic anhydride (1 mole), in an enameled vessel from which the water can be removed by distillation using a fractionation column. In this way 18 parts of water are rapidly distilled off, after which the reaction mixture is cooled and a viscous product is obtained containing 13.0% by weight of hydroxyl groups.



   The product is transferred to an enamel container in which it is vigorously stirred, this container being provided with a fractionation column, and 300 parts of trichloride are added.
 EMI25.2
 retylene, "4b parts of methyl alpha-chloroacrylate and 12 parts of hydroquinonedisulfonic acid diacid. This mixture is subjected to gentle heating while passing through it; a stream of air until all the binary mixture of methyl alcohol-trichlorethylene The product is then cooled to room temperature, 30 parts of anhydrous sodium carbonate are added and the whole is stirred for half an hour.

   After filtration using a small pressure filter, 0.1 part of hydroquinone is added and the volatiles including the excess of methyl alpha-chloroacrylate are removed by vacuum distillation, while taking care that the temperature of the mixture does not exceed 80 C.



   A resinous liquid is obtained which consists essentially of
 EMI25.3
 ment by di-alphacloracrylic esters of low molecular weight dihydroxy-glycol phthalates.



  EXAMPLE 14.



   Mix while shaking vigorously:
 EMI25.4
 170 parts of a mixture of low molecular weight dihydroxyclycOl phthalates and 12% hydroxyl ethyleneglycol prepared as described in, 3,

 <Desc / Clms Page number 26>

 
240 parts of methyl methacrylate,
12 parts decides nydroquinonedisulfonic,
200 parts of trichlorethylene, in a glass vessel fitted with a fractionation column.



  The mixture was refluxed with stirring and air bubbling through it, and the binary methanol-trichlorethylene mixture (bp 60-70 ° C.) was distilled off.



  When all of the binary mixture has passed, the product is cooled to room temperature and the hydroquinonedisulfonic acid and 1 remaining trichlorethylene removed, as in Example 4.



  A viscous liquid is obtained consisting essentially of dliuétliacryliques esters of low molecular weight dihydroxyglycolic phthalates.



   EXAMPLE 15.



   -----------
We heat together to 2000 C., while stirring vigorously:
245 parts of maleic anhydride (2.5 moles),
188.5 parts of ethylene glycol (3 moles) containing
2.5 parts of water, in a glass vessel from which the water can be distilled off using a fractionation column. In this way 47.5 parts of water are rapidly distilled off.



  The reaction mixture is cooled to give a viscous product containing 4% hydroxyl groups. We transfer it. produced in an enamelled container in which it is stirred vigorously, this container being arranged for the removal of water by azeotropic distillation. and we. add 35 parts of trichlorethylene, 78.5 parts of methacrylic acid (which corresponds to the said hydroxyl content) and 4 parts of hydroquinone-disulfonic acid. This mixture is treated at reflux while stirring it and continuously passing a stream of air bubbles through it.

 <Desc / Clms Page number 27>

 and the water of reaction is removed by azeotropic distillation with trichlorethylene which returns to the vessel after condensation.

   When 16.5 parts of water have been removed, this reaction mixture is cooled to room temperature.



   Hydroquinonedisulfonic acid, the non-attacked acids and trichlorethylene are removed, as in Example 4, and a viscous liquid is obtained consisting essentially of dimethacrylic esters of low molecular weight dihydroxyglycol maleates. .



   EXAMPLE 16.



   -----------
We heat together to 200 C., while stirring vigorously:
188.5 parts of ethylene glycol (3 moles) containing,
2.5 parts of water,
148 parts of phthalic anhydride (1 mole), in a glass vessel from which the water can be removed by distillation using a fractionation column. In this way, 20.5 parts of water are rapidly distilled off, after which the reaction mixture is cooled and a product is obtained containing 21.5% of hydroxyl groups.



   The product is transferred to an enamel container in which it is vigorously stirred, this container being arranged for the removal of water by azeotropic distillation, and 350 parts of trichlorethylene, 344 parts of methacrylic acid ( which corresponds to said hydroxyl content) and 16 parts of hydroquinonedisulfonic acid. This mixture is refluxed with stirring and continuous steaming with an air bubble purifier, and the water of reaction is removed by azeotropic distillation with trichlorethylene which is returned to the water. the container after condensation.

   When 72 parts of water have been removed

 <Desc / Clms Page number 28>

 this reaction mixture is cooled to room temperature.
 EMI28.1
 



  The nyoroquinonedieulfonic acid, the non-attacked acids and the COOld18 triciiioretylylene were removed in Example 4, and a viscous liquid was obtained consisting essentially of dimethyl esters of low molecular weight dinydroxyglycolic phthalates. - EXAMPLE 17.



   ----------- Mix while stirring vigorously:
 EMI28.2
 170 parts of a mixture of low molecular weight ilihydroxyglycolic phthalates and diethyl,> ne-glycol, with a content of 312 1b dtnydroxyl (and prepared as described in Example 3, 240 parts of methyl methacrylate ,
 EMI28.3
 12 parts of paraphenylenediamine,
500 parts of benzene, in a glass container fitted with a fractionation column.
 EMI28.4
 



  The reflux liquid is treated with stirring with air permeation, and a solution containing 2.5% is slowly added thereto. of sodium; ul '- <l18SOUS in 25 parts of W t3ia, nol. The binary mixture lU.0th¯, nol - oen; ene (point of 1 é "oul- lition 58 C.) is distilled off and when all the oinair mixture has been removed the product is cooled to room temperature and we still add
 EMI28.5
 250 parts of Denién ;. The resulting solution is read three times with an extended solution of hydrochloric acid and twice with water, in order to remove the excess alkali participants in the reaction.

   Then 0.1 part of hydroquinone is added and the volatiles, including excess methyl methacrylate, are removed by vacuum distillation, taking care that the temperature does not exceed 80 C. A temperature is obtained. viscous liquid made up
 EMI28.6
 predominantly low molecular weight dimthacryli.ques esters of diriy-droxyglycolic phthalates.


    

Claims (1)

CLAIMS EMI29.1 --7 ------------------------ 1.- Process for the preparation of new polymerizable organic materials containing two CH2 = C <npn- groups conjugated in the molecule, characterized. # In that it is reacted, under conditions leading to the formation of diacidic esters, of acrylic lucid, as defined above, or a derivative of the latter, forming esters, with the hydroxyl groups of a divalent polyester formed from a divalent alcohol and a dicarboxylic acid or their ester-forming derivatives , of a mixture of such esters or of a mixture of one or more of such esters with one or more divalent alcohols, this ester or these mixtures containing between 2, 5% and 25% by weight of hydroxyl groups. 2.- A method according to claim l, characterized in EMI29.2 what divalent alcohol is ethYlene glycol. 3. A method according to either of the preceding claims, characterized in that the dioarboxylic acid, or its ester-forming derivative, is phthalic acid or one of its ester-forming derivatives. 4. A method according to any one of the preceding claims, characterized in that the dicarboxylic acid derivative, forming esters, is an anhydride. 3. A process according to any one of the preceding claims, characterized in that the divalent polyester, or the mixture of such esters, or their mixtures with one or more divalent alcohols, contain between 7% and 17% by weight, of hydroxyl groups. 6. A process according to any one of the preceding claims, characterized in that acry- acid is reacted. EMI29.3 lic as defined above, or its armydride or methyl ester <Desc / Clms Page number 30> EMI30.1 that, ethyl, propyl.or butyl, and the reaction mixture is removed by azeotropic distillation, water or alcohol set free. 7. A method according to any one of the preceding claims, characterized in that the reaction is carried out in an acidic medium and that the substance capable of inhibiting the polymerization. EMI30.2 tion is a substance of the genus: t'd.iSàllt 1'o-J = t of the aemcuine to English patent N 26882/45. 8.- Process for the preparation of new organic materials EMI30.3 lJOll1érisables containing two nonconjugated 2 = C <groups in the molecule, in substance as al; 1cri above, nota. with reference to the cited examples. 9.- A titi :; new industrial products, ma- EMI30.4 tJ.è: r6; 3 Polyiaxi, ables characterized in that they have contents of 2; rOU <2ll, acrylic mts corresponding to group contents, slow hydroxyls of 2.5 to 25% by weight , and consist of one or more acrylic esters, as defined above, of poly EMI30.5 divalent ester of divalent alcohols and cic acids, 'oxyliquc; s en. presence or absence of one or more acrylic esters, EMI30.6 cornas defined more r1. <.: mt, divalent alcoholsa. 10. Polymerizable materials according to claim 1, characterized in that. the divalent polyester (s) are polyesters <a <elinyane-ìy-a1 and (, (tUl1 or (10 alu5i; urs dicarboxylic acids. ll- polymeric acids according to 1ü, claim 9 or 10, characterized, 311 this qU'l ;; ll "., 3 0: 1 un. # content of aCl'yl groups \ -; :: 3 corresponding to a tensur, ;;: 11; ßcuja.rlvntc hydroxyl CO ,, 1, dYi .. 38 between 7 3t 17 Cli in weight. 12.- Preparation process 1.1.3 new organic materials J? OlY ,, 101es, characterized in that one 1> ily., Iàx ise a material <Desc / Clms Page number 31> polymerizable obtained by the process according to any one of claims 9, 10 or 11. 13. A process according to claim 12, characterized in that the sheets of fibrous material are bonded to one another or to each other by the polymerization of a film of the polymerizable material located between these. leaves. 14.- The method of claim 13, characterized in that the sheets of fibrous material are sheets of glass fabric released from fat. 15. A process for the preparation of novel polymeric organic materials, in substance as described above, especially with reference to the cited examples. 16. As new industrial products, organic polymeric materials prepared by the process according to any one of claims 12 to 15.