DE1917788A1 - Radiation sensitive telomerized polyesters - Google Patents

Description

Radiation Sensitive Telomerized Polyesters This invention relates to generally radiation sensitive polymers. In particular, the invention relates viscous, soluble and flowable polymers of relatively low molecular weight, which, when subjected to ionizing radiation, are insoluble and infusible will. More specifically, the invention is concerned with telomerized Polyesters that when irradiated into three-dimensional, cross-linked, insoluble and infusible Polymers are converted, with relatively low doses of an ionizing agent Radiation are required.

The polyesters used in the practice of this invention are linear polyesters formed by the condensation of saturated or unsaturated aliphatic, including the cycloaliphatic, polycarboxylic acids with a saturated or unsaturated aliphatic, including the cycloaliphatic, polyhydric alcohol; the end groups with acryloxy groups that are very sensitive to radiation.

and glycidyl acrylates0 These telomerized polyesters have the very radiation3-sensitive acryloxy group with the formula as end groups Accordingly, the radiation-sensitive telomerized polyesters have the formula e.g. CH2 = CHCOOCH2CH2OOCCOOCH2CH2OOCCH = CH2, In these formulas, R represents a divalent saturated or unsaturated aliphatic (including cycloaliphatic) hydrocarbon radical having from 0 to 10 carbon atoms; R 'is a divalent, saturated or unsaturated aliphatic (including cycloaliphatic) hydrocarbon radical having from 2 to 10 carbon atoms; R "is hydrogen or a methyl radical; R1- is a divalent saturated or unsaturated aliphatic (including cycloaliphatic) hydrocarbon radical with 2 to 10 carbon atoms or CH2CHCH2; X is hydrogen or an acyl radical of the formula R 'CO ox and rutile is hydrogen or an aliphatic Hydrocarbon radical with 1 to 18 carbon atoms The radical -OOCRCOO- can be defined as the radical of a dicarboxylic acid which is derived from unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like.

These very radiation-sensitive telomerized polyesters are made from suitable acrylic derivatives such as glycidyl esters, produced by reaction with carboxylic acids or unsaturated or saturated aliphatic polyesters with terminal carboxyl groups or polyhydric alcohols with end groups which are sealed with acrylic radicals by reaction of a diol with an acrylic acid. in cases where a glycidyl acrylate is used, the glycidyl acrylate, which is a derivative of trivalent glycerol, forms linear esters containing a free, unreacted hydroxyl group. The reaction of one mole of a dicarboxylic acid with two moles of a glycidyl acrylate corresponds to the reaction of one mole of a dicarboxylic acid with two moles of an acrylic acid and two moles of glycerol, which acts as a dihydric alcohol, to form a radiation-sensitive polyester with a terminal hydroxyl-substituted one Form acrylic esters according to the following equation: Similarly, a saturated or unsaturated aliphatic polyester with two terminal carboxyl groups can be reacted with glycidyl acrylate to obtain radiation-sensitive linear hydroxyl-substituted polyesters according to the following formula: first (n + 1) R (COOH) 2 + n Rt (oH) 2 i> HOOCRGO OR1OOCRtCOnOH then HOOCRCO 1 f CX2 = C-COOCH2CHCE200CRCO OR 'OOOROO OCH2CHCH200C-C-CH2 OH OH (same lb) This second class of oligomers can be represented by the formula of equation lb, which includes equation la when n = 0 and also includes the higher molecular weight oligomers when n = 1 to 14. The hydroxy-substituted oligomeric polyesters with Terminal acrylic groups, as represented in a general manner by equations la and lb, have specific and improved properties, especially when they are polymerized in the presence of cellulose such as wood, paper, fibers, fibreboard and the like to make coatings, impregnants or adhesives form. The presence of the alcoholic hydroxyl groups causes an improved wetting of the cellulose and because of the hydrogen bonding of the hydroxyl group with the cellulose, an improved adhesion compared to unsubstituted oligomeric polyesters is achieved0 In those cases where the presence of these hydroxyl groups is undesirable or detrimental to properties such as the dielectric constant or the power factor, the hydroxyl groups can be converted to ester groups by acylation with aliphatic acids of the formula R "" COOH, in which R "" is H or an aliphatic saturated or unsaturated hydrocarbon radical having 1 to 18 carbon atoms, such as formic acid, acetic acid, propionic acid , Butyric acid, acrylic acid, methacrylic acid, oleic acid, stearic acid and the like, or the anhydrides of these acids, forming a class of oligomeric polyesters which are also advantageous products according to this invention. These conversions proceed according to the following equations: (Same as ¢ 2a) Rt R " CH2 = COOCH2CHCH200C-R-CO lOR '' OOCRC OCH2CHCH200O = CH2 1 "nI L OOCR «OOCR PGequ, 2) The radiation-sensitive oligomeric polymers of equations 2a and 2b are particularly suitable in a mixture with other unsaturated polymeric alkyd esters such as polyethylene glycol maleate, polyethylene glycol fumarate and the like.

The acrylation of the hydroxyl-substituted telomerized polyesters of equation lb with the aid of an acrylic acid or its anhydride or chloride leads to a class of telomerized, radiation-sensitive polymers which, because of the increased number of acrylic groups, are even more sensitive to ionizing radiation. Such a conversion takes place according to the equation: OH OH CH2 = CCOOCH2CHCH200CRCO [OR'OOCRCO] OCH2CHCH200CC = CH2 + 2 (CH2 = C-C0) 20 B "OH R" CH2ClcoOCHZCHCH200CRCO E0R '0OCRC03OCH2CHCH20OC = CH2 CH, -b-cI Rj # (equation 3) 2 O-OC-C = CH2 Simple telomerized polyesters according to this invention can be prepared by reacting two moles of an unsaturated aliphatic dicarboxylic acid of the formula R (COOH) 2 and one mole of a diol of the formula R '(OH), and two moles of a glycidyl acrylate of the formula can be prepared, whereby a product of the following general formula is obtained: Instead of the free acids R (COOH) 2, suitable derivatives of such acids such as the anhydrides, acid chlorides or omega-hydroxyalkyl esters can also be used for the synthesis of these polyesters; likewise, the corresponding alkylene oxides can be used instead of the diols R '(OH) 2 - if these exist, where R "'is H or an alkyl group with 1 - 10 carbon atoms0 Telomerized polyesters with a larger number of repeating segments or units, which consequently have a higher molecular weight than the simplest polyesters, can be produced are made by increasing the ratio of the n poles of the diol and the n + 1 moles of the dioarboxylic acid to the 2 moles of glycidyl acrylate to keep the mole ratio of diol: dicarboxylic acid: glycidyl acrylate at n: (n + 1): 2. The simplest Polyester is consequently obtained from one mole of a diol, 2 moles of a carboxylic acid and 2 moles of the glycidyl diacrylate. If the value of n for the diol is increased to 2, the value for the dicarboxylic acid becomes 3 and that for the acrylic function remains constant at 2 .

The linear polyesters can be prepared by various types of standard reactions used to prepare esters, starting with acids or their anhydrides or their acid halides and glycols or alkylene oxides. The conditions used are those which are suitable for the normal reactions of alcohols with acids, acid anhydrides and acid halides to produce esters and those which are normally used for the reaction of glycidyl groups with acids. For example: This product can be converted to compounds in which X represents an acid residue by reacting it with a suitable acid halide such as acrylic chloride or an acid anhydride such as acetic anhydride to obtain the desired acid derivative.

Another example of such a reaction using an acid anhydride is represented by the following formulas: Another example of such a reaction using an acid chloride results from the following formulas: base 2 RiCOC1) 2 + R '(OH) 2>ClOCRCOOR'O0CRCOCl CH2-CH-CH2 Bas g 2 1 OH OH OH CH2-CH-CH20OCRCOOR 'OOCRCOOCH2-CH-CH2 1H AH bs HH 2 2 CH2 = CCOC1 base J CH2 = C-COOCH2CHCH200CRCOOR'OOCRCOOCH2CRCH200C-C = CH2 1 1 OH OH In the above formulas, the derivatives of the glycidyl acrylate component are by the structure shown. It is clear, however, that the oxirane ring of the glycidyl group also converts to the isomeric structure can implement. Therefore, it is intended in the present invention that both isomeric structures are represented by the various formulas.

Oligomers in which the value n is greater than 1 are easily obtained by the same reactions as explained above by changing the ratio of the diol to the desired value of n and that of the dicarboxylic acid to n + 1 and at the same time the molar proportion of the acrylic component remains at 2. This corresponds to the equation: Depending on the nature of X, R 'and R ", the viscosity of these telomerized polyesters increases from about 100 to 9,000 centistokes at 200 ° C. as n increases from 1 to 14. The molecular weight of these telomerized esters also changes depending on the values of n, R 'and R "from about 275 for the lowest molecular weight at a value of n = 1 to about 8800 for n = 14 when decenedicarboxylic acid is the dicarboxylic acid and dodecanediol is the diol.

Some illustrative examples of the various HO-R-OH alcohols which can be used in the synthesis of the telomerized polyesters according to this invention are: ethylene glycol, trimethylene glycol, 2t3 dihydroxybutane, 1,4-dihydroxybutane, 1,4-dihydroxy-2 Ethylbutane, 1,6-dihydroxyhexane, 1,8-dihydroxyoctane, 2,10-dihydroxydecane, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, 2,2-diethylpropanediol-1,3, 2,3-dimethyl -propanediol-1,3, 3-methylpentanediol-1,4, 2,2-diethylbutanediol-1,3, 4, 5-dihydroxynonane, pentamethylene glycol, heptamethylene glycol, nonamethylene glycol, decamethylene glycol, digethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol -2-diol-1,4, 2,7-dihydroxy-n-hexene-4, 2,7-dihydroxy-2,7-dimethyl-n-hexene-4, 2-ethylhexanediol-1,3 and the like alkylene oxides can can also be used to give the corresponding glycol derivatives, for example propylene oxide, ethylene oxide, 2,3-butylene oxide and the like. As illustrative examples of the various acids of the Formula HOOC-R-COOH, which can be used for the production of telomerized polyesters according to the invention, are maleic, fumaric, itaconic, citracon, mesaconic, acetylenedicarbon, aconite, alpha-methyl-itaconic, alpha-alpha-dimethyl-1,2-tetrahydrophthalic, 1,3-tetrahydrophthalic, 1,4-tetrahydrophthalic, trans-1,4-cyclohexenedicarbonic, oxalic, amber, adipic, glutaric, sebacic , Methyl amber, pimeline, 2,3-dimethyl amber, suberine, hexyl amber, 1,3-hexahydrophthalic, 1,4-hexahydrophthalic, 1,1-cyclobutanedicarbonic, trans-1,4-cyclohexanedicarbonic, 3t3-diethylglutaric, 3,3-dimethylglutaric, 2,2-dimethylglutaric, 2,2-dimethylsuccinic, 2-ketoglutaric, diglycollic acid or acids u0 dgl0 In those cases in which the carboxylic acid with a polyhydric alcohol with end groups which have been capped with an acrylic radical is reacted, the simplest telomerized polyesters are those which result from the reaction of 1 mol of a saturated or unsaturated a lipatic carboxylic acid of the formula R (COOH) 2 (including oxalic acid in which R does not contain a carbon atom) with 2 moles of a diol of the formula R '(OH) 2 and of 2 moles of an acrylic acid of the formula arise and which the general formula to have.

In the case when n = 1, the synthesis of these telomerized oligomers can be achieved by any of the following reactions, since it is immaterial in which order the starting materials are combined with one another: (Equal 1h) (Equal to 1j) or 1 'R "RR"' R "' R (COOH) 2+ HOHCH200CC = CH2; CU2 = C00-CH2H00C-R-C00-C1HCH2- 2., OOCC = CHiCHCB2- OOC = CH2 (Equal. Lc) - CH2 = C-COOR'OCC-R-COOR'OCC-C = CH2 (equal to 0 ld) or 2 CH2 = COCl R (CO) 20 + 2 R '(OH) 2 - + HOR'OOC-R-COOR'OH base base R "ß" CH2 = C-COOR'OOC-R-COOR'OOCC = CH2 (Equal. Le) or R (COC1) 2 + 2 R (OH) 2 Base 'HOR'OOC-R-COOR'OH 2 b B "B" CH2 = C-COOß'OOC-ß-COOR'OOCC = CH2 (Equ. 1f) R11 or RItl R ''' 1 2 C R (COOH) + Rt'CHCH2 -jtHOCHCE200C-R-COOCH2CHOH 0 R "- R"'R"R" CH 2 = C-COOCHCH20OCRCOOCH2OHOOC- = CH2 (Equ.) Oligomers in which the value n is greater than 1 can easily be prepared by the same reactions as given above, simply by changing the ratio of the dicarboxylic acid to the desired value of n and that of the diol to n + 1 , whereas the molar fraction of the acrylic component remains at 2, so that the following equation is applicable: I. n R (COOH) 2 + (n + 1) R '(OH) 2>HOR'OloCRCOOR 4 2 CM, = C-COOH R "R" CH2 = E-COOR'O COCRCOOR "OJnOCC '= CH2 (Equ. 2b) The same alcohols and polyoarboxylic acids can be used as in the pall when the polycarboxylic acid or the polymer of the polycarboxylic acid and the polyhydric alcohol are reacted with a glycidyl ester. It is very important that the various classes of those used in the practice of the invention telomerized polyesters contain aliphatic hydrocarbon structures in their polyearboxylic acid and polyhydric alcohol segments. Because of this aliphatic character, the telomerized polyesters are very sensitive to ionizing radiation. that this is no longer of economic interest.

As an example it should be noted that the polyethylene glycol maleate of the formula telomerized with dimethacrylic radicals cross-linked at about 2 megarads, whereas the corresponding phthalic acid derivative of the formula and the corresponding xylyl derivative of the formula require 12 and 14 megarads respectively to become insoluble and infusible.

This difference is particularly astonishing since you three telomerized Polyesters all with radical initiators like with 1 benzoyl peroxide, in about 90 to 95 seconds at 100 ° å and with redox systems of cobalt acetate and Cure tert-butyl hydroperoxide in 3 to 3 1/2 hours at room temperature.

This difference appears to be due to the fact that the aromatic ring compounds, such as phenyl, naphthyl compounds and the like, as energy converters for the radiation work.

As used herein, the term "radiation11" means radiation of high energy or very high energy radiation and / or the secondary energies, resulting from the conversion of these electron or other particles or corpuscular energy in neutron or gamma radiation, with such energies at least about 100,000 electron volts are equivalent0 It is true that there are different types of radiation suitable for this invention, such as X-ray, Gamma and B-eta rays, it has been found shown, however, that the radiation with accelerated electrons of high energy, easiest to use and most economical to get very satisfactory results to obtain. Regardless of the type of radiation and the type of equipment used for the generation or application of radiation, any radiation comes into play for the invention into consideration as long as the ionizing radiation is about 100,000 electron-volts equivalent is.

While there is no upper limit to the electron energy that can be used with Advantage can be applied; However, in order to achieve the desired effects To obtain the invention, it is not necessary to exceed an upper limit of about 20,000,000 electron volts to go. In general, the higher the electron energy used, the greater the penetration depth into a massive structure of the material to be treated and the shorter the required Exposure time, to achieve the desired result. For other types of radiation, such as gamma and x-rays, are beneficial to energy systems to be used which are equivalent to the aforementioned range of electron volts.

The term "radiation" used includes what is known in the art Prior art has been referred to as "ionizing radiation", and what is called a radiation has been defined which has an energy which is at least sufficient is to generate ions or to break chemical bonds0 As a result Such radiation includes both radiations and the ionizing particles or corpuscular radiation «as well as the" ionizing electromagnetic radiation " known radiation.

The term "ionizing particle or corpuscular radiation" is has been used to reduce the emission of electrons or highly accelerated nuclear particles, such as protons, neutrons, alpha particles, deuterons, beta particles or their analogues to denote, these particles are oriented so that the particle in the mass to be irradiated penetrates. Charged particles can be generated with the help of voltage gradients are accelerated by such devices or accelerators as resonance chambers, Van de Graaff generators, betatrons, synchrotons, cyclotrons etc. A neutron radiation can by bombarding a certain light metal, such as beryllium, with positive Particles of high energy are generated. Corpuscular radiations were lying down also by using a nuclear reactor, radioactive isotopes or others natural or synthetic radioactive materials obtained0 an 'ionizing electromagnetic radiation "is generated when a metallic anticathode, such as Tungsten, with electrons is bombarded by suitable energy. Such energy is given to the electrons by voltage accelerators of over 0.1 million electron volts (MEV) granted. Except for these types of radiations that Usually referred to as X-rays, it can be an ionizing electromagnetic Radiation suitable for practicing the invention by means of nuclear reactors or by using natural or synthetic radioactive materials, e.g. from cobalt 60.

There are several types of linear electron accelerators from high energy commercially available, e.g. the ARCO-type accelerator with advancing Wave, Model Mark I, operating at 3 to 10 million electron volts and from the High Voltage Engineering Corporation, Burlington, Massachusetts, U.S.A. or other types of accelerators such as those described in the U.S. Patent 2,763,609 and British Patent 762,953 are all of these Accelerators are well suited for practicing the invention.

In the following examples the dose of radiation is given in megarads indicated, where such a unit corresponds to 1 a00 000 rad. A "wheel" becomes defined as the absorbed dose and corresponds to 100 ergs per gram.

One already has numerous monomers and also polymers of the ionizing Subjected to radiation in order to convert them into improved or modified products. The irradiation methods were, however, in the first / of scientific interest and there is very little use in industry of such irradiations made of polymers. This is in primarily because of the cost ionizing radiation.

due to economic factors for the system to be treated. For example, the well-known and cheap polyester system consists of roughly the same Parts by weight of monomeric styrene and unsaturated alkyd resin based on maleic or fumaric anhydride, phthalic anhydride and ethylene glycol or diethylene glycol. This system can be made more economical by initiators that form free radicals, are polymerized than by ionizing radiation, at which about 25 to 40 megarads are required depending on the formulation.

Such systems can be improved somewhat in this regard, by eliminating the phthalic anhydride in the formulation of the polyester and by replacing the styrene with the more expensive monomeric acrylic esters. But also in such systems are unfavorable, and not just because of, the economic factors the much higher cost of the mixture, but also because of the easier volatility the acrylic or methacrylic esters used. In such cases, too, an irradiation dose is used from 18 to 20 megarads are required and the systems are also powered by oxygen very strongly inhibited. By adding such substances as acetone or methyl ethyl ketone, you can reduce the radiation dose to 9 to 12 megaradsO But even then you can own it the products have the offensive odor of unpolymerized acrylic monomers0 In contrast in addition, the polyesters telomerized with aoryl radicals form according to this invention crosslinked, insoluble and infusible polymers, if one considers the polyester of an ionizing Radiation in doses less than 8 megarads and in some cases 0.5 Subjects to megarads or less, with preferred irradiation dosages of at least about 1 megarad radiation doses are used in-this: area but are economical.

In addition, it is advantageous that the acrylic component telomerized in them Polyesters are at the end of the polyester chain, making them more effective crosslinking can. More importantly, the acrylic component is only a small fraction of the Preparation makes up what is economically particularly advantageous if the value of n in these telomerized polyesters is at least two. Since also that Molecular weight of the telomerized polyesters much higher than that of the corresponding ones simple monomers such as methyl methacrylate or ithylacrylate can make these products act as both monomers and polymers in a molecule.

This advantageous crosslinkability of the telomerized polyesters after the invention with economical irradiation dosages is also retained, when using the telomerized polyesters with unsaturated alkyd resins alone or also mixes in the presence of other polymers, provided that the unsaturated Alkyd resins and the other polymers are of a non-aromatic type, doh. that they are free of aromatic rings, which act as energy converters and delay the crosslinking reaction. Another advantage of this diacryl-polyester is their compatibility with different types of resins, especially with polyesters of the alkyd resin type.

As some illustrative examples of suitable polymers disclosed in the telomerized polyesters according to the invention-together with unsaturated alkyd resins can be dissolved or mixed with, are non-aromatic polymers, such as polyvinyl acetate, Polyethyl acrylate, polymethyl methacrylate, cellulose acetate, Cellulose butyrate, Ethyl cellulose, polyethylene glycol adipate, polyethylene glycol aceleate, polydecamethylene succinate, Polydecamethylene sebazate etc. The telomerized polyesters are also made with polyvinyl chloride tolerated, especially after applying moderate heat.

The telomerized polyesters of this invention are particularly useful as Coating compositions suitable for all types of substrates including cellulose in their various forms such as paper, wood, paper panels, wood panels, Wood pulp, regenerated cellulose in film or fiber form, laminated bodies of various Types including those made of fibrous fillers with urea, melamine, Epoxy and polyester resins as binders, plasterboard, cement in its various Shapes, such as plates, blocks and the like. They can also be used as an impregnating agent for porous bodies can be used, as from the aforementioned preparations, as well for synthetic or natural sponges and the like are of particular interest they are used as binders and adhesives for solid, porous and foamed bodies. she can also be polymerized alone or as a mixture with one another or with others Monomers, unsaturated or saturated polymers in the absence or in the presence of dyes, pigments, plasticizers and the like. When using them for coatings, as impregnating agents or as adhesive preparations, you can, in case the presence of small amounts of solvents in the hardened Bulking is not undesirable with volatile or non-volatile solvents of a non-aromatic nature, the solvent being so chosen will find that it is best suited for the particular application that will be made after the irradiation products obtained from the telomerized polyesters according to this Invention can vary in their properties from the soft flexible bodies up to hard, stiff masses The telomerized, radiation-sensitive polyesters according to the ser invention are particularly suitable for the production of copolymers with unsaturated alkyd resins. In performing this embodiment of the invention is an esterification product of a polyhydric alcohol and a alpha, beta-unsaturated polycarboxylic acid first in accordance with the well-known Process made.

Any aliphatic polyhydric alcohol that has at least two esterifiable contains aliphatic hydroxyl groups, or mixtures of such alcohols can be used in the manufacture of the unsaturated alkyd resins. Examples of such polyhydric alcohols are ethylene glycol, di-, tri- and tetra-ethylene glycol, Thiodiglycol, glycerine, pentaerythritol, 1,4-dihydroxy-butene-2, dimethylolcyclohexane, Dihydrocyclohexane and the like. Any non-aromatic alpha-unsaturated, alpha, beta-polycarboxylic acid or mixtures of such acids can be used with the polyhydric alcohol. or the polyhydric alcohols are reacted to form the unsaturated alkyd resin.

Examples of such polycarboxylic acids are maleic, fumaric, citraconic, Mesaconic, acetylenedicarboxylic, aconitic, cyclohexenedicarboxylic acid and the like, itaconic acid and their homologues, e.g.

alpha-methylitaconic acid, alpha, alpha-dimethylitaconic acid u.

The like. Anhydrides of these polycarboxylic acids can also be used will.

In some cases you can replace unmodified, unsaturated Alkyd resins use an unsaturated alkyd resin that has been internally modified is by replacing a part ZOB. up to 75 moles, the unsaturated Polycarboxylic acid by saturated aliphatic polycarboxylic acids, such as succinic, Adipic, glutaric, pimelic, sebacic, azelaic, suberic, tricarballylic acid and the like.

Anhydrides of these acids can also be used, if they occur will. The term "polyearboxylic acid", as it is used here, is meant that it also includes the anhydrides of acids.

The esterification products of polyhydric alcohols with ethylenic alcohols Polycarboxylic acids or polycarboxylic acids with aliphatic polycarboxylic acids can be modified further be. This can be done by introducing a starting material during manufacture the alkyd resins of one compound or more compounds that are only one esterifiable Group included, in particular by introducing a saturated or unsaturated one normal or isomeric monohydric alcohol or mixtures thereof or a saturated one or unsaturated monocarboxylic acid or mixtures thereof or both of these Compounds with only one esterifiable group or by using hydroxycarboxylic acids.

Examples of non-aromatic monohydric alcohols used for modification of the alkyd resins that can be used are propyl, isopropyl, butyl, isobutyl, Amyl, isoamyl, hexyl, octyl, decyl, dodecyl, tetradecyl, cetyl, octadecyl, Cyclohexyl, cyclopentyl alcohol and the like The use of methyl and ethyl alcohol is not excluded, but such alcohols are generally less so suitable because they have very low boiling points. As monobasic acids can e.g. unsubstituted saturated and unsaturated normal or isomeric Monocarboxylic acids are used that contain only one esterifiable group, such as Vinegar, propion? Butter to stearic acid including, hexahydrobenzoic, hexahydrotoluyl, Furancarboxylic acids and the like

The compounds with only one esterifiable group can be used before, during or after the esterification of the polyhydric alcohol with the polycarboxylic acid Conditions which the transesterification of the incompletely esterified product from polyvalent Alcohol and polycarboxylic acid favor being introduced. This means that the connection which has only one esterifiable group is introduced into the reaction mass, before all acid groups of the polycarboxylic acid and all alcohol groups of the polyvalent Alcohol have been esterified.

The term "dysaturated non-aromatic alkyd resin" as it is As used herein in the description and in the claims, both unmodified esterification products of a non-aromatic polyhydric alcohol with a non-aromatic alpha-unsaturated, alpha, beta-polyearboxylic acid and Esterification products of these components that have been modified, e.g., as above briefly stated. As an alternative term, "unsaturated aliphatic Alkyd resin "can be used, this term denoting the cycloaliphatic compounds includes.

The interpolymerization of the unsaturated alkyd resins with the telomerized To effect polyesters according to this invention it is necessary to first use a solution or a mixture of the unsaturated alkyd resin in dom or with the telomerized To make polyester. The interpolymerization of the components of the mixture wiyd intoxicating and advantageously by ionizing radiation zOBO with a nuclear reactor or by cobalt 60 or by electrons of high Energy obtained from a linear electron accelerator.

Typical examples of unsaturated alkyd resins are: Alkyd resin A - Ethylene glycol itaconate parts by weight Ethylene glycol 23 Itaconic acid 52 The components are mixed and slowly over the course of an hour from room temperature to 1900 C while maintaining an inert nitrogen atmosphere. At this The temperature of the reaction mass is maintained for 3 to 5 hours.

Alkyd resin B - ethylene glycol maleate parts by weight of ethylene glycol 31 Maleic anhydride 32 The components are mixed and used as in the manufacture of the alkyd resin A heated to 180 ° C and at this temperature for 4 to 6 hours held.

Alkyd resin C - Diethyl en1yko1-Male inat modified with acetic acid Weight of steep diethylene glycol 106 maleic anhydride 88 acetic anhydride 10 The components are mixed and refluxed for one hour in an inert Heated nitrogen atmosphere, after which the reaction mixture is heated to 1900 C ~. This temperature is maintained for 4 to 6 hours.

It is clear that, of course, the invention is not limited is based on the use of specific unsaturated alkyd resins, as mentioned earlier have been mentioned, and that a wide modification of the nature of the interpolymer is possible is made using other unsaturated aliphatic alkyd resins or mixtures of such resins. As illustrative examples of other unsaturated alkyd resins the following esterification products can be used as alkyd resins D to I. The aromatic alkyd resin J is included for comparison.

Alkyd Resin Components (Parts) D Diethylene Glycol (160) Maleic Anhydride (147) E diethylene glycol (106) itaconic acid (130) F glycerine (18.4) itaconic acid (39.0) G ethylene glycol (6.0) maleic anhydride (19.6) hydroxypropyl acrylate (26.0) H ethylene glycol (20) maleic anhydride (29.4) succinic acid (3.3) 1 diethylene glycol (30w6) maleic hydride (17.6) Itaconic acid (15, Q) J Diethylene glycol (30.3) Maleic anhydride (13.2) Phthalic anhydride (21.7) In some balls it is possible to polymerize instead of a single telomerized polyester with a single unsaturated alkyd resin Blends of two or more telomerized polyesters with a single one unsaturated aliphatic alkyd resin or a single telomerized polyester with two or more unsaturated alkyd resins or mixtures of two or more telomerized polyesters with two or more unsaturated aliphatic alkyd resins use. Comonomers can be used in conjunction with the alkyd resins, which are copolymerizable with the telomerized polyester or with the unsaturated polyester Alkyd resin or both, zoB; one or more telomerized polyesters can can be used in conjunction with one or more unsaturated aliphatic alkyd resins and in association with methyl methacrylate.

In addition to or instead of methyl methacrylate, other comonomers can be used or mixtures of comonomers can be used, e.g., vinyl esters such as vinyl acetate and vinyl esters of saturated and unsaturated and aliphatic monobasic and polybasic acids and, more specifically, the vinyl esters of the following Acids: propionic, isobutter, valerian, caprylic, capric, oil, stearinWp acrylic, Methacryl ", croton, oxal, malon, bernatein, glutar, adipine, suberine, azelaine, Maleic, fumaric, itakonic, mesakonic, hexahydrobenzoic, citric, trimesic acid and the like. Like. And also the corresponding allyl, methallyl and like esters of those mentioned above Acids.

Other suitable comonomers are acrylic and alkacrylic acids and their Derivatives, such as their esters, amides and the corresponding nitriles, e.g. 3. Acrylic acid, Methyl acrylate, butyl acrylate, allyl acrylate, ethylene glycol diacrylate, acrylonitrile, Methacrylonitrile, Methacrylic acid, methyl methacrylate and dglo; the Itaconic acid monoesters and diesters, such as the methyl, ethyl ", allyl, dimethallyl ester, the maleic and fumaric acid monoesters, diesters and their amides and nitriles, such as ethyl allyl maleate, Fumarditrile, dimethallyl fumarate and the like; unsaturated ethers, such as methallyl allyl ether, Vinyl allyl ether, vinyl methallyl ether, allyl crotyl ether, vinyl crotyl ether; Cyanuric acid derivatives such as diallyl cyanurate, triallyl cyanurate, trivinyl cyanurate or, in general, triazine compounds with at least one polymerizable or copolymerizable unsaturated Group that is directly or indirectly bound to the triazine ring, and also partially, soluble or meltable polymers of the monomers listed here and the like.

The modified unsaturated aliphatic alkyd resins of this invention can be used alone or with fillers, dyes, pigments, opacifiers, lubricants, Plasticizers, natural and synthetic resins or other modifying agents Materials are used, e.g. for casting, deforming in the production of laminated bodies and as adhesives, impregnating agents and protective coatings.

When coating, impregnating and similar applications, the mixed monomeric or partially copolymerized materials without addition a solvent applied to the object to be treated and polymerized there become, with or without the application of heat and pressure, 1xm as the end product the insoluble Generate polymeric product "in situ".

These new synthetic materials can be used as waterproofing agents for numerous porous bodies, such as cork, pottery, felt or other bodies with spaces in between, like the coils of electric snakes, net-shaped fibers, interwoven fiber-shaped cotton or glass materials and the like can be used.

They are also suitable for making oversize on wires and spoolable tapes and for protective coatings on impermeable bodies such as Metal or as coatings and impregnating agents for articles such as paper, wood, textiles, Glass fibers in matted, woven or other form, cement, linoleum, plastic boards and the like. These new synthetic materials can also be used to make laminated to produce fibrous layer materials, with superimposed layers of textiles, paper, glass fabrics or mats and the like new preparations are connected.

It is also possible to telomerize these mixtures from at least one Polyester according to the invention and at least one unsaturated aliphatic alkyd resin, with or without modifiers, to be cast under pressure and irradiated in the process.

In the preparation of the interpolymerization products from the unsaturated aliphatic alkyd resin and the telomerized polyester may be the unsaturated Alkyd resin represent up to 98 or 99% by weight of the total mass. In other cases the telomerized polyester can be used alone or as a mixture with aliphatic comonomers or modifiers up to 98 to 99 wt.

of the entire mass.

In general, the proportions of the components used in the particular Preparation used on the special properties of the desired copolymer depend. For most applications it is preferred to have 30 to 90% of the unsaturated to use aliphatic alkyd resin and 10 to 70% of telomerized polyester, because within this range the most useful copolymers for most commercial ones Applications are obtained.

The new copolymers have a broad range within this range Range of properties. So can the new copolymers with regard to their Hardness, rigidity and resistance to solvents as a function of the particular telomerized polyester or blend of telomerized polyesters with the special unsaturated aliphatic alkyd resin, the special proportion thereof, the polymerization conditions such as temperature, pressure, presence or absence of additives and the like, the dose of irradiation and the degree of polymerization vary.

Some of the intermediate stages of interpolymerization can also be used Forms of liquid preparations of various viscosities can be used. For coating or impregnation where the presence of small amounts of solvents The mixed starting component cannot be objected to in the cured mixture mixed with volatile or non-volatile solvents or diluents will be best suited for the particular application. Then after that Applying the solution to the particular item being coated or impregnated or is to be impregnated and coated, the polymerization is to be carried out, By suitable selection of the starting materials and the conditions for the copolymerization mixed polymers are obtained that are insoluble, infusible and practically resistant against attack by other chemicals, such as acids, bases, salts, solvents, Swelling agents u0 dglo If one considers the properties of the polymers of the telomerized If polyester is to be modified according to the invention, this can be achieved by copolymerization a mixture of at least one telomerized polyether and at least one copolymerizable unsaturated ethylenic or acetylenic compound with a hydrocarbon radical. In particular, compounds with a CH2 = C radical, such as vinyl, allyl, Methallyl or vinylidene radical or copolymerizable compounds which the Contains -CH = CH- or -CH = C # or # groups, e.g. vinylidene fluoride, vinylidenecyanide5 Vinyl propionate, maleic anhydride or their esters and amides, methyl maleic anhydride, Tetrafluoroethylene and the like.

Further examples of copolymerizable comonomers are monomers or partially polymerized vinyl esters such as vinyl acetate, vinyl propionate and the like; Vinyl ketones, methyl vinyl ketones, olefin nitriles, such as acrylonitrile, methacrylonitrile, Fumaronitrile, beta-cyano-ethyl acrylate, acrylic and methacrylic esters, e.g. methyl acrylate, Ethyl acrylate, propyl acrylate, butyl acrylate, ethyl methacrylate propyl methacrylate, butyl methacrylate, Octyl methacrylate, glycol dimethacrylate, allyl methacrylate and the like; Itaconic acid ester, e.g., dimethylitaconate, diethylitaconate, diallylitaconate; Olefin amides, e.g. acrylamides, Itaconamides, the maleic acid mono- and -diamides and the corresponding imides u. like; the vinyl ethers, e.g. vinyl butyl ether, vinyl isobutyl ether, vinyl cyclohexyl ether; the dienes and the like> e.g. butadiene, isoprene, dimethylbutadiene and the like.

In the preparation of the copolymers of telomerized polyester with other polymerizable comonomers such as methyl methacrylate, acrylonitrile and the like, the telomerized polyester can represent as little as 0.1% by weight of the total, whereas in other cases the telomerized polyester alone can much, like up to 98 to 99% of the total. As in the production of mixed polymers with unsaturated aliphatic alkyd resins, the proportion of the components in the particular preparation depends on the particular comonomers used and, in particular, on the desired properties of the copolymer. The polymers and copolymers can be produced very easily by ionizing radiation. Numerous embodiments for carrying out the invention are illustrated in the following examples. These examples serve only to illustrate the invention and do not restrict the invention in any way. The parts and percentages here and in the description are always in weight, unless expressly stated otherwise If the temperature is set, 284 parts of glycidyl methacrylate, 9 98 parts of maleic anhydride and 2 parts of hydroquinone are added, the mixture is heated to 1,100 ° C. for 18 minutes while stirring in a nitrogen atmosphere. The following product is obtained: Example 2 When 256 parts of glycidyl acrylate are used in the reaction of Example 1 with maleic anhydride instead of 284 parts of glycidyl methacrylate, a product of the following formyl is obtained: Example 7; A mixture of 375 parts of the product from Example 1, 204 parts of acetic anhydride and 1 part of tributylamine are refluxed for 1 hour in a nitrogen atmosphere. The acetic acid formed as a by-product is then removed by distillation under reduced pressure at 5 mm and 497 parts of the product of the formula remain in the reaction vessel Example 4 The procedure of Example 3 is repeated, using molar equivalents of appropriate suitable anhydrides of the following acids: methacrylic, stearic, methoxyacetic, acetic, acrylic and butyric acid. The product of Example 1 is easily converted into the following derivatives: Example 5 When other unsaturated aliphatic dicarboxylic acids such as fumaric, dodecenedicarboxylic, tetrahydrophthalic acid and the like are used in place of maleic and itaconic anhydride in Examples 1 and 2, the corresponding hydroxy-substituted polyesters with acrylic terminal groups are obtained. Similarly, when other aliphatic diols such as hexamethylene glycol, diethylene glycol, dihydroxycyclohexane, hexahydroxylylidene glycol and the like are used in place of ethylene glycol, the corresponding hydroxy-substituted polyesters having terminal acrylic groups are obtained. These hydroxy substituted polyesters can be readily acylated by the procedures shown in Examples 3 and 4.

Example 6 The telomerized, hydroxy-substituted polyesters of Examples 1 and 2 and the acyl substituted polyester of Example 3 are shown in irradiated an aluminum plate in the presence of air, each at 1.9, Connect 2.0 and 1.85 megarads.

The telomerized polyesters of Examples 4b ', 4c, 4d' and 4f 'are used similarly irradiated and all become insoluble and infusible at doses in the range of 2.0 to 2.8 megarads.

Example 7 Alkyd Resin A 80 parts of telomerized polyester according to the example 3 20 parts The alkyd resin A and the telomerized polyester are carefully to mixed with a uniform mass and then subjected to ionizing radiation> turning them into an insoluble and infusible hard product, at one dosage can be converted from 3.3 megarads.

If you add fillers such as wood flour, alpha cellulose, crushed cellulose derivatives, Asbestos, paper, textiles, sands, silicon dioxide, calcium sulfate and the like with the mixture coated or impregnated and the mass hardened by irradiation, is obtained Objects of good appearance and excellent physical properties and improved heat resistance.

In order to improve the heat resistance even further, this can be done Modify the procedure so that a higher proportion of telomerized Polyesters and less unsaturated alkyd resin used: Alkyd resin A 50 parts telomerized Polyester 50 parts and alkyd resin A 75 parts telomerized polyester 25 parts preparations of the type explained in this example have the advantage that they do not generate radicals Contain initiators and can be kept for long periods of time. Still they are cured in a simple manner without adding a catalyst by they are subjected to respiration.

Example 8 In a suitable reactor equipped with a stirrer a reflux condenser, an inlet for an inert gas, a heating mantle, and a Temperature control device is provided, 284 parts of glycidyl methacrylate, 146 parts of adipic acid and 2 parts of hydroquinone were added. This mixture is under Stirring in a nitrogen atmosphere, heated to 1300 ° C. for 18 minutes.

The following product is obtained: Example 9 A mixture of 415 parts of the product from Example 8, 204 parts of acetic anhydride and 1 part of tributylamine is heated to boiling for one hour under reflux cooling in a nitrogen atmosphere. The acetic acid formed as a by-product is then removed under a reduced pressure of 5 mm and 497 parts of the following product remain in the reaction vessel: Example 10 The procedure of Example 9 is repeated with the exception that instead of acetic anhydride, 252 parts of acetic anhydride, the 1% tert. Contains butyl alcohol. The following product is obtained: Example 11 In a number of corresponding experiments, corresponding amounts of ethylene glycol and succinic anhydride are placed in the reactor of Example 8 and reacted at 180 ° C. for ó hours. A series of products of the general formula HOOC (CH2) 2CO [OCH2CH2OOCCH2CH2CO] OH, in which n corresponds to 1, 3, 5t 10, 12, 14 and 15, will behave. These products are in turn reacted with 2 molar fractions of glycidyl methacrylate, 7 products being obtained each with the following general formula: In this formula, n = 1 for sample a 'n = 3 for sample b' n = 5 for sample c 'n = 10 for sample d' n = 12 for sample e 'n = 14 for sample f' n = 15 for Sample g 'Example 12 The procedure of Example 11 is repeated several times using molar equivalents of glycidyl acrylate in place of glycidyl methacrylate. 7 products of the following general formula are obtained: -OOCCH = CH2 In this formula n = 1 for sample a 'n = 3 for sample b' n = 5 for sample c 'n 2 10 for sample d' n = 12 for sample e 'n = 14 for sample f' n = 15 for sample g 'Example 13 The procedure of Example 11 is repeated, using equivalent amounts of an aromatic dicarboxylic acid, phthalic anhydride, instead of the aliphatic dicarboxylic acid, succinic anhydride. A series of products of the general formula is obtained: In this formula, nn = 1 in sample a9 n E 5 in sample b 'n = 10 in sample cn = 12 in sample d' Example 14 The procedure of Example 11 is repeated using equivalent amounts of the aromatic dialcohol p-xylylidene glycol of the formula HOCH2C6H4CH2OH can be used instead of ethylene glycol. A series of products of the general formula is obtained: In this formula, n = 1 in sample a 'n = 5 in sample b' n I 10 in sample c 'n. 15 in sample d 'Example 15 The seven telomerized polyesters of Examples 11al to 11g' inclusive are subjected to radiation. These polyesters have different n values and with increasing n value the radiation dosage required for crosslinking also increases, 2 megarads being required for n = 1 and 4.6 megarads for n = 14. Bür.n = 15 cross-linking occurs at 6.7 megarads, from which it follows that the. economically interesting limit for the n values is less than 15 If, however, an average value of less than 15 for n can be achieved by using mixtures with a polyester whose n value is less than 15, e.g. n = 1 to 12, polyester with n = 15 can also be crosslinked economically.

ZoBo one can use a polyester with n = 15 each with polyesters Mix n- = 1 or 5, with crosslinking occurring at 3, 1 or 4.2 megarads.

Irradiation of the seven telomerized samples 12a 'to 12gV inclusive leads to similar results, with n = 14 determined as the economically upper limit will.

Example 16 A cellulose sponge is made with the telomerized polyester of Example 11a ', which was dissolved in an equal amount by weight of acetone is, so that after evaporation of the acetone at 250 C, the sponge 18 wt.% Of the polyester contains0 A tough, solid product with a low density is obtained by irradiation.

Example 17 A printed cover sheet with a wood grain print is made with various blends of telomerized polyesters. impregnated. The telomerized polyester (1) 11a '50 parts are used; (2) 11c ' 20 parts and (3) lld 'lO parts; if n = 2 5 parts and from the alkyd resin G 15 parts; so that the impregnated cover sheet consists of 60 parts of the polyester mixture and consists of 40 parts of the cover sheet.

This impregnated cover sheet is placed on a wood fiber board and irradiated the whole thing with 4 megarads. The end product obtained is a plate which has the appearance of a fine wood grain and has a glossy varnish coating, which is resistant to water, alcohol, acetone and most organic solvents is.

Example 18 A mixture of 80 parts of wood fibers as used in To manufacture fibreboard used 12 parts of the telomerized polyester of Example 13b ', 1 part of zinc stearate and 7 parts of linseed oil is until equilibrium worked through, pressed into a plate and irradiated with 4.8 megarads.

A well-bonded hard panel is obtained that can easily be painted over Paint in organic solvents or with aqueous emulsion paints leaves.

Example 19 4 parts of the polymer of Example lle 'becomes 10 parts Added water containing 0.5% sodium dioctyl sulfosuccinate as an emulsifier. The mixture is emulsified in a colloid mill. The emulsion of the telomerized Polyester is added to 50 parts of pre-expanded polystyrene beads and the mixture obtained is agitated until all the pearls are uniformly coated. Man then lets the water evaporate from the coated foam-like beads, which easily stick together. The coated foamed beads are then placed in a container given, e.g. a cardboard box and irradiated with a dose of about 4 megarads. At this How it works you get a foam-like structure in which all the pearls come together connected by an infusible product. The shape corresponds to the shape of the each container used.

Example 20 A uniform blend of 40 parts of the diacrylic polyester is obtained of Example 11 a 'and 60 parts of a plastisol-type polyvinyl chloride with a Molecular weight of about 25,000 produced. This mixture is extruded into tubes and irradiated at a dose of 3 megarads. The polyvinyl chloride is through this narrow dose does not break down and duroh the treatment the tube becomes insoluble and infusible, so there is hot water of 990 C and hot saturated salt solutions of 101.70 C without softening. Also against hot solutions of acetic acid, Toluene, carbon tetrachloride and the like.

the pipes are resistant.

Example 21 Into a suitable apparatus equipped with a stirrer, a Reflux condenser, an inlet for inert gas, a heating mantle and a device is equipped for temperature control in the reactor, 28.8 parts of 2-Hydroxypropylmethaorylatp 20 parts of succinic anhydride and 0.25 parts of hydroquinone were added. The apparatus first becomes oxygen-free by purging with dry oxygen-free nitrogen made; then a slow stick material flow through the apparatus during the Implementation headed.

The mixture is heated to 125-130 ° C for 30 minutes, 9 where the Pro is the formula in quantitative yield arises. Then 6 parts of ethylene glycol are added and the reaction is continued for about 4 hours or until the acid number is essentially zero. The telomerized oligomer of the formula is obtained which is a slightly viscous, light colored, oily product.

If the methacrylate is replaced by an equivalent amount of the 2-hydroxypropylene acetate, a viscous product of the following formulas results EXAMPLE 22 The procedure of Example 21 is repeated ten times, with the following compounds being used in the stated amounts instead of 28.8 parts of 2-hydroxypropyl methacrylate: a: 26.0 parts of 2-hydroxyethyl methacrylate b: 23.2 parts of 2- Hydroxyethyl acrylate cs 26.0 parts 2-hydroxypropyl acrylate d: 26.0 parts 3-hydroxypropyl acrylate e: 28.8 parts 3-hydroxypropyl methacrylate fs 2X, 0 part diethylene glycol monoacrylate gt 28.8 parts diethylene glycol monomethacrylate h: 39.0 parts 1.4 Hexahydroxylylidene glycol monoacrylate i: 33.0 parts of 1,4-cyclohexanediol acrylate j: 45.6 parts of 1,10-decamethylene glycol acrylate The products of the following formulas are obtained in each case.

j ': CH2 = CHCOO (CH2) 10OOCCH2CH2COOCH2CH2OOCCH2CH2COO (CH2) 10OOCCH = CH2 Example 23 The procedure of Example 21 is repeated six times, the following products being used in the specified amounts instead of the 6 parts of ethylene glycol: a: 9 parts of butylene glycol b : 17.4 parts of decamethylene glycol c: 11.8 parts of hexamethylene glycol d: 7.6 parts of propylene glycol e: 11.6 parts of 1,4-cyclohexanediol f: 14.4 parts of 1,4-hexahydroxylylidene glycol g: 15.0 parts of triethylene glycol the products of the following formulas are obtained in each case.

EXAMPLE 24 The procedure of Example 21 is repeated, the following products being used in the stated amounts instead of 20 parts of succinic anhydride: a: 22.8 parts of glutaric anhydride b: 30.8 parts of 1,2-hexahydrophthalic anhydride c: 22, 8 parts of methylsuccinic anhydride d: 25.6 parts of dimethylsuccinic anhydride The products of the following formulas are obtained in each case: Example 25 All of the radiation-sensitive acrylic-terminated polyesters of Examples 21 through 25 can be prepared by alternative methods such as those described in Methods A and B below for the synthesis of * If other starting materials than in Examples 21, 22, 23 and 24 are used, methods A and B also give the desired products.

Method As The reactor of Example 21 is fitted with a 'tDean-Stark' pad equipped to collect the condensed water, and in the reactor are 26 Parts of 2-hydroxyethyl methacrylate, 0.2 parts of hydroquinone and 20 parts of succinic anhydride given and the mixture can be prepared for 20 minutes at 1300 C.

puts. Then 6 parts of ethylene glycol, 0.15 parts of toluene sulfonic acid and 100 parts of toluene are added and the mixture is refluxed until no more water is condensed in the "Dean-Stark" trap. The mixture is then neutralized with solid sodium bicarbonate, filtered and removing the toluene by distillation at a pressure of 15 mm to give the product of the following formula: Method B: The procedure of method A is repeated with the exception that the order in which the starting materials are added is different. The 20 parts of succinic anhydride and the 6 parts of ethylene glycol are first reacted at 1300 a, then hydroquinone, toluene, toluenesulfonic acid and hydroxymethyl methacrylate are added and the reaction continues until no more condensation is collected, then the toluene is removed by distillation, the same being done Product obtained as in Example 22a 'and in method A of Example 25o Example 26 A sample of the liquid polyester 21a' is placed in a layer thickness of 1.27 cm in an aluminum beaker and in the open air a jet of 1 MEV from a Van der Graaff accelerator suspended. An increase in viscosity at 1 megarad is observed, and at 2.1 kegarad the product is completely crosslinked. If the same sample is exposed to an electron beam from an Arco Mark 1 linear accelerator with a microwave operating at a beam energy of 8 MRV, the sample will also become insoluble and infusible at the same dosage, resulting in these telomerized polyesters being independent are of the type of radiation.

However, if the polyester of Example 21b 'is terminated with the acetyl groups in the same way and also at the same dosage or at dosages up to is irradiated to 50 megarad, one observes a degradation and no crosslinking in Agreement with the information in "Report NASA-SP-58, Office of Technical Services, Department of Commerce, Washington, D. C. ".

Example 27 The procedure of Example 26 is repeated seventeen times, where in each case the samples of Examples 22 a ', b', c ', d', e ', f', g ', h', i '; , j j 'and 23 a', b ', c', d ', e', f ', g' can be used. Samples 22a 'and 22b' network at between 1.75 and 1.8 megarads and all the others except for the Sample 23g 'at 2 to 2.4 megarads, whereas 23g1 cross-linked at 2.9 megarads.

The properties of the products vary from hard to rubbery Masses as a function of the length of the alkylene groups.

Example 28 The procedure of Example 26 is repeated four times, using samples 24 a ', b', c ', d'. All products network at Radiation dosages ranging from 1.95 to 2.55 megarads. The products fluctuate in their properties from hard to ductile masses depending on the Length and nature of the carbon chain.

Example 29 50 parts of the telomerized polyester from Example 21 are diluted with 10 parts of glycol dimethacrylate, with this mixture is a about 0> 3 cm thick cement board impregnated and with a dose of 3.5 megarads irradiated. A water-impermeable plate is obtained.

Example 30 A uniform blend of 40 parts of the diacrylic polyester of Example 21 and 60 parts of a plastisol-type polyvinyl chloride having a molecular weight of about 25,000 is prepared. This mixture is extruded into a tube and subjected to a radiation dose of 3 megarads. The polyvinyl chloride is not degraded at this small radiation dose and the treatment renders the pipe insoluble, infusible, so that it can withstand hot water at 99 ° C. and hot saturated saline solution at 101.7 ° C. without softening. The tube is also resistant to hot solutions of acetic acid, toluene, carbon tetrachloride and the like. Example 31 In a suitable reaction apparatus equipped with a stirrer, a reflux condenser, an inlet for inert gas, a heating jacket and a device for temperature control in the reactor 28.8 parts of 2-hydroxypropyl methacrylate 20 parts maleic anhydride and 0.525 parts hydroquinone are added. The apparatus is first freed of oxygen by purging with dry nitrogen-free nitrogen; then a long stream of nitrogen is passed through the apparatus during the reaction. The mixture is heated to 125-1300 ° C. for 30 minutes, the product of the following formula in quantitative yield 6 parts of ethylene glycol are then added and the reaction is continued for about 2 hours or until the acid number is essentially 0. A telomerized oligomer is obtained which is a slightly viscous, light-colored, oily product and has the following formula: If an equivalent amount of 2-hydroxypropylene acetate is used in place of the methacrylate, a viscous product of the following formula results: EXAMPLE 32 The procedure of Example 31 is repeated, the following anhydrides being used in the stated amounts instead of 20 parts of maleic anhydride: as 22.5 parts of citric anhydride to 30> 8 parts of 1,2-tetrahydrophthalic anhydride ct 22.5 parts of itaconic anhydride 22.5 parts of mesaconic anhydride Zs are each obtained products of the following formulas: Example 33 26 parts of hydroxymethyl methacrylate, 50 parts of carbon tetrachloride, 0.5 part of hydroquinone and 8 parts of sodium hydroxide, dissolved in 50 parts of water, are placed in the reactor of Example 31. 15.3 parts of fumaric dichloride, dissolved in 50 parts of carbon tetrachloride, are slowly introduced into this mixture at 200 ° C. over the course of one hour, while stirring. The reaction mixture is then washed four times with 100 parts of water, dried over anhydrous sodium sulfate, filtered, and the carbon tetra-chloride is separated from the reaction product by distillation at 15 mm pressure. A product of the formula is obtained If 28.8 parts of 2-hydroxypropyl methacrylate are used in this process instead of 26 parts of hydroxyethyl methacrylate, the product of the following formula results: EXAMPLE 34 24 parts of ethylene glycol and 49 parts of maleic anhydride (or 58 parts of maleic acid) are added to the reactor of Example 33 and the mixture is reacted for 6 hours at 180 ° C. or until titration of a sample with sodium hydroxide indicates that essentially one product of the formula HOOC (CH2) 2CO [OCH2CH2OOCCH = CHCO] 4OH is then the product is then transferred to an I2Dean-Stark reactor, in which 26 parts of 2-hydroxyethyl acrylate, 0.5 part of toluenesulfonic acid, 150 parts of toluene and 1 part of hydroquinone are added werden0 The mixture is heated to boiling under reflux cooling until no more water of condensation separates out in the trap.

The mixture is then treated as in Example 25-B and a product of the following formula is isolated: Example 35 The procedure of Example 34 is followed except that 54 parts of ethylene glycol and 98 parts of maleic anhydride are used in place of 24 and 49 parts, respectively.

A product of the following formula is obtained: Similarly, using 66 parts of ethylene glycol and 118 parts of maleic anhydride, a product of the following formula is obtained: With 84 parts of ethylene glycol and 147 parts of maleic anhydride, a product of the following formula is formed: Changing these ratios also gives the product of the following formula: Example 36 The procedures of Examples 34 and 35 are repeated using equivalent amounts of the aromatic dicarboxylic acid, phthalic anhydride, and corresponding multiples thereof, in place of the aliphatic dicarboxylic acid, maleic anhydria. A series of products of the general formula is obtained In this formula, n has the following meaning n = 1 in sample al n = 5 in sample b 'n = 10 in sample c' n = 12 in sample d '.

Example 37 The procedures of Examples 33 and 34 are repeated, using equivalent amounts of the aromatic dialcohol p-xylyideglycol of the formula HOCH2C6E4CH20H and corresponding multiples thereof in place of ethylene glycol. A series of products of the general formula below is obtained.

In this formula, n has the following meaning: n = 1 in sample a 'n = 5 in sample b 'n 3 10 in sample c n = 15 in sample d'.

Example 38 The samples from Examples 35 a ', b', c ', d' and 36 a ', b ', ¢', d 'are irradiated according to the procedure of Example 37. It is no signs of networking at 1, 2, 5, and 10 megarads. A certain Increase in viscosity is noted at doses higher than 15 megarads, and the crosslinking becomes evident at about 23 megarads for the samples of Example 35 and at about a0 megarads for the samples of Example 36. This gives the Influence of the aromatic nuclei on the required radiation dose.

Example 39 The telomerized polyesters of Example 35 are made up Heated to 80 ° C and poured into glass ampoules. Then they are allowed to come to room temperature cool and expose them to an ionizing beam from a 0.450 MEV electron accelerator the end. All products become insoluble and infusible at the following dosages: Sample 35 a 'n = 10 4.2 megarads Sample 35 b' n = 12 4.6 megarads Sample 35 e 'n = 15 6.8 megarads sample 35 d 'n = 14 5.2 megarads These values show that a value of n less than 15, i.e.

of 14 or less is an economic upper limit for this telomerized Represents polyester. This value of less than 15 can be obtained as an average be by zOB. equal amounts by weight of the sample from Example 34, in which n = 5, and the sample from Example 35c 'in which n = 15, mixes. Such a mixture networked at a dose of 3.7 megarads.

If a mixture of 9 parts of the polymer from Example 2a 'and 1 part of the polymer of Example 35c 'is mixed, crosslinking will result Irradiation observed at 2.6 megarads.

Example 40 Alkyd Resin A 80 parts of the telomerized polyester of Example 31a '20 parts The alkyd resin A and the telomerized polyester are thorough mixed to a uniform mass and then subjected to ionizing radiation0 An insoluble, unmeltable, hard product is created at a dose of 3.15 megarads.

It is possible to use precipitants> such as wood flour, alpha cellulose, cellulose derivatives, Asbestos, paper, textiles, sand, silicon dioxide, calcium sulfate and the like with this Coating or impregnating mixture, which hardened when irradiated Obtaining bulk, the articles of good appearance and excellent physical Properties and an improved heat resistance represent.

You can do that to improve the heat resistance even further Modify the above procedure so that one has a higher proportion of telomerized Polyester used in relation to the unsaturated alkyd resin. You can do the following Use mixtures: Alkyd resin A 50 parts Delomerized polyester 50 parts and Alkyd resin A 75 parts Telomerized polyester 25 parts.

Mixtures of this type have the advantage that they do not generate any radicals Contain initiators and can be stored for long periods of time. Still can they can be cured quickly and without the addition of a catalyst by using a Subjects to irradiation.

Example 41 The procedure of Example 40 is repeated with the Exception that instead of alkyd resin A, alkyd resin B is used. It will infusible and insoluble masses at 2.8-3.8 megarads obtained by irradiation.

The mixtures of Examples 39 and 40 can be used in conjunction with glass mats or glass fabrics are used as binders for the production of laminated bodies where you can work at room temperature and low pressure.

It goes without saying that this invention does not apply to copolymerization of alkyd resins A and B with the telomerized polyesters of Example 31a ' and that other polyesters telomerized with acrylic radicals, alone or in combination can be used, e.g., the telomerized polyesters of Examples 32 bis 34 inclusive.

In contrast, it is necessary to use radiation dosages 18 megarads to use to remove hard, infusible polymers from the telomerized aromatic polyesters of Examples 35 and 36 to obtain.

Similarly, high radiation dosages are over 16 megarads Required if the aromatic alkyd resin J is used with the acrylic residues telomerized polyesters in contrast to the use of alkyd resins C, D, E, F, H and I which become infusible and insoluble in the range of 3.8 to 4.0 megarads.

The use of the unsaturated alkyd resin G, which is an unsaturated Alkyd resin with terminal acrylic radicals is, in mixture with the aliphatic telomerized Polyesters with terminal acrylic groups, e.g. with the polyester of Example 31, is of particular interest since the crosslinking is already in the range from 1.6 to 2.0 Megarad takes place.

Example 42 A mixture of 80 parts of wood fibers as used in manufacture used by Saser plates, 12 parts of the telomerized polyester of Example 34b ', 1 part zinc stearate and 7 parts linseed oil is used until uniform mixed and pressed into a plate which is irradiated at 4.3 megarads. It will Get a well-bonded, hard panel that can easily be coated with paints Can be painted in solvents or aqueous emulsions.

Example 43 4 parts of the polymer of Example 34b 'becomes 10 parts Water containing 0.5 sodium dioctyl sulfosuccinate as an emulsifier was added and this mixture is then emulsified in a colloid mill. The emulsion of the telomerized Polyester is added to 50 parts of expanded polystyrene beads and these Mixture is agitated until the pearls are evenly coated. Then you leave that Water evaporate from the coatings of the foamed beads, which easily stick together be liable. The coated hemmed beads are then placed in a container, e.g. a cardboard box, and irradiated at a dose of about 3.6 megarads. at This procedure results in foam structures in which the beads are all bonded with an infusible binder, the Porm the each the container used.

This invention has been described in numerous embodiments0 It is clear, however, that many other modifications of the invention are possible without to move away from its subject matter and there is no intention of the invention to be limited to the details of the embodiments shown here.

Claims (1)

Patent claims: 1. Radiation-sensitive telomerized diacrylic polyester of the formula characterized in that n has a value of 0-14; m has a value from 1 to 14; R is a divalent saturated or unsaturated aliphatic hydrocarbon radical having 2 to 10 carbon atoms; R 'is a divalent saturated or unsaturated aliphatic hydrocarbon radical having 2 to 10 carbon atoms; R "is hydrogen or a methyl radical; R1 is a divalent saturated or unsaturated hydrocarbon radical having 2 to 10 carbon atoms or; X is hydrogen or an acyl radical of the formula R "" CO and R "" is hydrogen or an aliphatic hydrocarbon radical having 1 to 18 carbon atoms. 2. Telomerized diacrylic polyester according to claim 1, characterized by the formula 3o telomerized diacrylic polyester according to claim 1, characterized by the formula 4. Telomerized diacrylic polyester according to claim 1, characterized by the formula 5. Telomerized diacrylic polyester according to claim 1, characterized by the formula 6o telomerized diacrylic polyester according to claim 1, characterized by the formula 7. Telomerized diacrylic polyester according to claim 1, characterized by the formula 8. Telomerized diacryl polyester according to claim 1, characterized by the formula CH2 = CHCOOCH2CH2OOCCH = CHCOOCH2CH2OOCCH = CHCOOCH2CH2OOCCH = CH2 9o Telomerized diacryl polyester according to claim 1, characterized by the formula 10. Telomerized diacrylic polyester according to claim 1, characterized by the formula llo telomerized diacrylic polyester according to claim lS characterized by the formula 12. Telomerized diacryl polyester according to claim 1, characterized by the formula CH2 = CHCOOCH2CH2OOCCH2CH2COOCH2CH2OOCCH2CH2COOCH2CH2OOCCH = CH2 13o telomerized diacryl polyester according to claim 1, characterized by the formula 14. Telomerized diacrylic polyester according to claim 1, characterized by the formula 15o telomerized diacrylic polyester according to claim 1, characterized by the formula 16. Telomerized diacryl polyester according to claim 1, characterized by the formula i7. Telomerized diacrylic polyester according to Claim 1, characterized by the formula 18. Process for the preparation of an improved polyester resin composition by irradiating a polyester, characterized in that a radiation-sensitive telomerized diacryl polyester of the formula in which n has a value from 0-14; m has a value from 1 to 14; R is a divalent saturated or unsaturated aliphatic hydrocarbon radical having 2 to 10 carbon atoms; R 'is a divalent, saturated or unsaturated aliphatic hydrocarbon radical having from 2 to 10 carbon atoms; R "is hydrogen or a methyl radical; R1 is a divalent saturated or unsaturated hydrocarbon radical with 2 to 10 carbon atoms or CH2CHCH2; Ox X is hydrogen or an acyl radical of the formula R" 2tCO and R is hydrogen or an aliphatic hydrocarbon radical with 1 to 18 carbon atoms, irradiated with at least about 0.5 megarads and no more than about 8 megarads of high energy ionizing radiation, which radiation is at least 100,000 electron-volts equivalent. 19o method according to claim 18, characterized in that the diacryl polyester is mixed with a copolymerizable monomer and the diacryl polyester 1-99% by weight of the copolymerizable mass and the polymerizable monomer 99 - 1 Gew0 make up the copolymerizable mass. 20. The method according to claim 18, characterized in that the diacryl polyester is mixed with an unsaturated aliphatic alkyd resin and that this mixture 10-70% by weight of the diacrylic polyester and 30-90% by weight of the aliphatic alkyd resin contains. 21. The method according to claim 18, characterized in that the diacrylic polyester has the formula hat0 22. The method according to claim 18, characterized in that the diacryl polyester has the formula Has. 23. The method according to claim 18, characterized in that the diacryl polyester has the formula hat0 24. The method according to claim 18, characterized in that the diacryl polyester has the formula vv CH2 CH2 = CHCH2COOCH2CHCH20OCCH2C11CO COCH2CH200CCH2CCO3 nCH2CHCH2OOCH = CH2 has 0 OH OH 25. The method according to claim 18, characterized in that the diacryl polyester has the formula Has. 26. The method according to claim 18, characterized in that the diacryl polyester has the formula hat0 270 method according to claim 18, characterized in that the diacryl polyester has the formula CH2 = CHCOOCH2CH2O0CCH = CHCOOCH2CH2OOCCH = CHCOOCH2CH2OOCCH = CH20 280 method according to claim 18, characterized in that the diacryl polyester has the formula Has. 29. The method according to claim 18, characterized in that the diacryl polyester has the formula Has. 30. The method according to claim 18, characterized in that the diacryl polyester has the formula Has. 31. The method according to claim 18, characterized in that the diacryl polyester has the formula CH2 = CHCOOCH2CH2OOCCH2CH2COOCH2CH2OOCCH2CH2COOCH2CH2OOCCH = CH2. 32 ,. Process according to Claim 18, characterized in that the diacryl polyester has the formula Has. 33. The method according to claim 18, characterized in that the diacryl polyester has the formula Has. 3,4., - Method according to claim 18, characterized. that the diacrylic polyester has the formula Has. 35. The method according to claim 18, characterized in that the diacryl polyester has the formula Has. 36. The method according to claim 18, characterized in that the diacryl polyester has the formula Has. 37. The method according to claim 18, characterized in that the Diacr-oil polyester has the formula 38. The method according to claim 18, characterized in that the diacryl polyester has the formula hat0 39. An irradiated polymeric Produl {t? produced by the method of claim 18. 40. An irradiated polymeric product obtained by the process according to Claim 19 was made. 41. An irradiated polymeric product 9 produced by the method according to Claim 20 was made.