DE2164260A1 - New polyesters and processes for their manufacture and use - Google Patents

Description

Dr Micha6irUiß | 4260

Patent attorney 635 Bad Nauheim

Burgallee 12 b T «Won (0 6032) 6Jt 37

December 22, 1971 H / E W (394) 4849

PPG Industries, Inc., Pittsburgh, Pa., USA

NEW POLYESTERS AND METHODS FOR THEIR MANUFACTURING AND USE

Unsaturated polyester resins are used extensively to coat substrates of very different types. If these resins can also be used to produce solid and chemically resistant coatings, then on the other hand there are difficulties in producing these coatings for certain To apply substrates, especially in the case of metallic substrates, firmly adhering.

It has now been found that with modified unsaturated polyester resins firmly adhering coatings are obtained on substrates if the coatings are ionizing with Treated with rays or actinic light. The modified polyester resins according to the invention essentially consist of a modified unsaturated polyester and a polymerizable, ethylenically unsaturated monomer.

The modified unsaturated polyester is produced by reacting an unsaturated polyester with polyphosphoric acid.

The polyesters of alpha, beta-ethylenically unsaturated polycarboxylic acids are used as unsaturated polyesters and polyhydric alcohols.

209830/1096

Examples of suitable ethylenically unsaturated polycarboxylic acids are, in particular, dicarboxylic acids such as Maleic acid, fumaric acid, aconitic acid, mesaconic acid, citraconic acid, Itaconic acid and its halogen and alkyl derivatives called these acids. Of these acids, maleic acid is preferably used. Unless there are these Acids are anhydrides, these of course also fall under the term "acid", because the acid and their anhydride receives essentially the same polyester. The ethylenically unsaturated dicarboxylic acids are used, based on the total content of acid in the polyester usually in an amount of about 10 mol.% to about 100 mole percent, preferably in an amount of about 20 mole percent to about 80 mole percent.

For the production of unsaturated polyester resins, polyhydric alcohols, especially dihydric alcohols, for example ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, Polypropylene glycol but also higher quality alcohols such as glycerine, neopentyl glycol, pentaerythritol, trimethylol propane and trimethylolethane are suitable. The for the purpose of Polyols preferably used in the invention have a molecular weight less than about 2000 and consisting essentially of carbon, hydrogen and oxygen. Man generally uses the polyhydric alcohols in an amount corresponding to the totality of the acid components Amount or in a slight excess thereto, for example in an excess of about 5 mol.%.

209830/10 9 6

For the production of the unsaturated polyester resins one can use in connection with the unsaturated acids or their anhydrides also use saturated dicarboxylic acids. These acids extend the polyester chain, without creating additional networking points. This is desirable with some polyesters.

As examples of suitable dicarboxylic acids that are either saturated or only aromatically unsaturated, be succinic acid, adipic acid, suberic acid, azelaic acid, Sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid and hexachlorendomethylenetetrahydrophthalic acid called. As with the ethylenically unsaturated acids, in this case too the The term "acid" optionally includes the anhydrides of the acids mentioned, because here too the polyesters obtained with them the polyesters obtained with the acids are equal to sin ^. Further For the purposes of the invention, the aromatic nuclei of acids such as phthalic acid are generally considered to be saturated considered, since the double bonds do not react like ethylenic groups by addition. Hence where the phrase "saturated Dicarboxylic acid "is used, it includes the aromatically unsaturated dicarboxylic acids. Such" saturated carboxylic acids " can also be referred to as "non-olefinically unsaturated" polycarboxylic acids.

The unsaturated polyesters according to the invention are modified by reaction with polyphosphoric acid.

The unsaturated polyesters can with the polyphosphoric acid are implemented under conditions which vary within a wide range. Temperatures are preferably used between 20 and about 150 ° C and pressures between about 5 mm Hg and about 7 atmospheres. A catalyst is not required.

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The polyester can be reacted with the polyphosphoric acid in any ratio, but in general one equivalent of the functional hydroxyl groups of the polyester is used for one equivalent of the phosphate. It is sometimes advisable to use the hydroxy equivalent in a slight excess.

The modified unsaturated polyester has the formula

Il

- P

0 -

ROC-R ¹ -

0 - L. - R Tl O U ~ Il CO OP •

OH

In the formula is R is an alkyl radical or the radical R "(OR"), R "is an alkyl radical and R ^{1 is} an unsaturated alkyl radical;

furthermore, in the formula η is 1 or 2; m is 1 or 2, η + m 3, L is 2 to about 20, and q is 0 to about 15.

More precisely, R is an alkyl radical with any number of Carbon atoms, preferably from about 2 to about 20 Carbon atoms, for example methyl, ethyl, propyl, Isopropyl, butyl, neopentyl, hexyl, ethylhexyl, octyl, Decyl or dodecyl.

R can also be a radical of the formula R "(OR") q, where R "is an alkyl radical having preferably 2 to about 8 carbon atoms, such as ethyl, propyl, octyl and the like, and q is 0 to 15. If more than one R" radical is present, these radicals can be the same or different.

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R * is an unsaturated alkyl radical such as, for example Ethylene, propylene, butylene or cyclohexene and preferably contains from about 2 to about 15 carbon atoms.

Both η and a are either 1 or 2, where η is 1, when a is 2 and η is 2, when m is 1; the sum of η and m * 3, L is a number from 2 to about 20 and c [a Number from 0 to 15.

From the modified unsaturated polyesters one can then prepare the coating compounds with crosslinking, ethylenically unsaturated monomers.

Examples of vinyl monomers suitable for this purpose are styrene, alphamethylstyrene, divinylbenzene, vinyl acetate, allyl acetate, diallyl phthalate, diallyl succinate, diallyladipate, Diallylsebacate, methyl acrylate, methyl methacrylate, hexyl acrylate, octyl acrylate, octyl methacrylate, diallyl itaconate, Diallyl maleate, dialyl fumarate and triallyl cyanurate. It is preferred to use monomers which are liquid and soluble in the polyester components.

The monomer or monomers can be used in a wide range of quantities. They are generally used in a lesser amount by weight than the polyester. The amount of the monomer or monomers should be so large that one a liquid, flowable, copolymerizable mixture receives. The proportion of the monomer normally makes up about 10 to about 60% by weight, preferably about 20 to about 50% by weight the total mixture consisting of the polyester and the monomer.

As the polycater component of the copolymerizable mixture is often highly viscous and even solid at ambient temperatures, the monomer is preferably set at one temperature

209830 / 109b '

- ο -

to, in which the polyester is the one for union with the Monomers has required fluidity. For this purpose, a temperature of about 100 to about 120 ° C is usually suitable, which is high enough to cause premature gelation in the absence of gelation inhibitors, if that Monoaere is introduced into the system. This also applies in the event that no free radical catalysts are present.

A gelation inhibitor is therefore preferably added to one or both components of the mixture. Suitable inhibitors of this type are those of the quinone = or phenol series, as well as quaternary ammonium salts and amino salts, especially amine-halide salts. Suitable inhibitors of the quinone and phenol series are p-benzoquinone, Chlorine III, hydroquinone, 3-isopropylcatechol, 4-tert.-butylcatechol, 3-methylcatechol, 4-ethylcatechol, 4-isopropylcatechol and others Examples of inhibitors are trimethylamine hydrochloride, trimethylamine hydrobromide, dimethylaniline hydrochloride, triethylamine hydrochloride, tri-n-butylamine hydrochloride, tribenzylamine hydrobromide and N-benzylaniline hydrochloride. Suitable quaternary ammonium salts that can be used as inhibitors are, for example, trimethylbenzylanmonium oxalate, Trimethylbenzylammonium chlorid, di (trimethylbenzylammonium) oxalate, trimethylbenzylammonium maleate and trimethylbenzylammonium tartrate. Other ammonium compounds that can be used and amine-halogen salts are described in US patents 2 593 787 and 2 646 416 mentioned. The quaternary ammonium salts and the amine halide salts are used with the new System used with preference as inhibitors, although inhibitors of the phenol and quinone series are also satisfactory Results.

209830/1096

The gelation inhibitors remain in the solution of the Polyester and the monomer existing copolymerizable mixture and prevent the mixture in the Storage gelled before use. The amount of the inhibitor to be added to the mixture varies within wide limits. She lies, Based on the polyester component of the mixture, expediently in the range from 0.001 to about 0.1% by weight. One can copolymerizable mixtures of polyesters from alpha, beta-ethylenically unsaturated dicarboxylic acids and monomers, the contain an inhibitor of the type described for long periods of time, for example for weeks or even months, store without premature gelling.

Other substances, such as fillers, pigments and the like, can also be added to the coating composition.

The coating composition can be applied by known coating processes, for example by rolling on or by dipping or by spraying onto the substrate.

With the coating composition according to the invention, firmly adhering coatings are obtained on substrates of any type, for example those made of metal, wood, paper, fabric and plastics. Since it has been particularly difficult up to now, metal substrates with firmly adhering coatings of unsaturated To provide polyester resins, the novel process according to the invention is preferably used for coating or coating of metal.

In order to give them the necessary adhesive strength, the coatings are treated with ionizing radiation or subjected to actinic light.

209830 / 109b

In the context of this description, "radiation" means high-energy radiation and / or the secondary radiation resulting from the conversion of electron energy or other particle energy into neutron or gamma radiation, the energies used being at least about 30,000 electron volts. If principle other radiations are suitable for the purposes of the invention, such as X-rays and gamma and B _e tastrahlen so has irradiation with be-ε "tfileunigten energy electrons because of their efficiency and good results achieved particularly proved useful. Without With regard to the type of ionizing radiation and the apparatus used for its generation and application, its use for the purposes of the invention must then be regarded as falling within the scope of the invention if its energy corresponds to at least about 30,000 electron volts.

Albeit one in theirs for the purposes of the invention Strength up to unlimited electron energy can be used, so in practice it has been shown that about 20,000,000 electron volts need not be exceeded. Generally speaking, the electron energy the deeper it penetrates into the massive structure of the substances to be treated, the larger it is and that in correspondingly shorter treatment times to achieve the dei desired results are required. For other types of radiation, such as gamma rays and X-rays, energies in the aforementioned electron volt range are appropriate.

209830/1096

The term "radiation" should also be understood to mean what is referred to in technology as "ionizing radiation" and is defined as radiation that has at least such energy that it can generate ions and is chemical Able to break ties. It therefore also includes radiation such as "ionizing particle radiation" and radiation like "ionizing electromagnetic radiation".

The term "ionizing particle radiation" denotes the emission of electrons or highly accelerated nuclear particles, such as protons, neutrons, alpha particles, deuterons, beta particles or their analogues that are so directed are that the particles are thrown into the mass to be treated. You can get charged particles through the production of voltage gradients with devices such as accelerators with resonance chambers, Van der Graaff generators, Accelerate betatrons, synchrotrons, cyclotrons, etc. Neutron radiation can be generated by using a Selected light metal, for example beryllium, bombarded with positive particles of high energy. One can get a particle radiation also from a nuclear reactor or with the help of radioactive isotopes or other natural ones or synthetic radioactive substances.

An "ionizing electromagnetic radiation" is obtained when using a metallic target, for example a target made of tungsten, bombarded with electrons of suitable energy. The electrons get their energy from an accelerating voltage of over 0.1 million electron volts. This type of radiation, commonly known as X-rays, can also be used obtained from a nuclear reactor or manufactured with natural or synthetic materials, for example with cobalt 60.

209830 / 1Ü9Ö

Various types of high-performance electron linear accelerators are commercially available available, e.g., that from High Voltage Engineering Corporation of Burlington, Massachusetts, Developed traveling wave accelerators of the ARCO type working with 3 to 10 million electron volts, Model Mark I. Satisfactory results are also obtained with other accelerators, for example with the accelerators according to US Patent 2,763,609 and British Patent 762,953.

The polyester resin coating can be cured and firmly bonded to its substrate at an exposure dose of about 2 to about 50 Mrad. The "rad" is the amount of radiation of 100 ergs per gram of the material to be treated. An "Mrad" is 10 ⁶ rad. The radiation dose is the total amount of radiation absorbed by the coating.

The coatings can also be cured and firmly bonded to their substrates in such a way that they can be treated with actinic or short-wave light, for example with ultraviolet light, irradiated. The fabrics to be treated speak responds to short-wave light generally at a wavelength of about 1800 to 4000 8. For the irradiation of the coatings Various means are available with short-wave light, e.g. quartz lamps, mercury vapor lamps, carbon arcs and high-power flashlight lamps.

Photosensitizers can be added to the coating compositions in order to reduce the hardening effect that the short-wave light has on the Coating has to reinforce, for example benzoin, benzoin thy lather or benzophenone. The coating compounds can the photosensitizers are added in an amount of about 0.1 to about 5% by weight.

209830/1096

Short-wave waves are used to treat the coatings Light with a wavelength of about 1800 to about 6000 Å.

The coated by the process of the invention Substrates can be used as roofing panels, panels for building cladding, and the like. One can also manufacture pipe linings from the preparations. The coated panels are preferably used as roofing material.

The invention is described in more detail in the following examples using specific exemplary embodiments. she is however, it is not restricted to these embodiments, but allows numerous modifications. Both in the description as well as in the examples, all parts and percentages are unless otherwise stated, parts by weight and percent by weight.

example 1

A modified polyester is put on the following Way:

797 g of isophthalic acid, 1997 g of neopentyl glycol, 467 g of diethylene glycol and 784 g of maleic anhydride are poured into one Reaction vessel, the mixture is heated to 210 ° C, it is kept at this temperature for about 7 hours, leaving the unsaturated Cool the polyester for 3 hours and then modify it by adding 404.5 g of polyphosphoric acid over the course of one hour added at 80 ° C.

It is made from 70 parts of the modified unsaturated Polyester, 30 parts of styrene and 0.02 part of methylhydroquinone produce a resin preparation. The resin has a Gardner-Holdt viscosity of Zlplus and the acid number 71.8.

209830/1096

Example 2

A modified polyester is made in the following way:

797 g of isophthalic acid, 1997 g of neopentyl glycol, Put 467 g of adipic acid and 784 g of maleic acid in a reaction vessel, heat the mixture to 210 ° C. and hold it for 9 hours at this temperature, the polyester formed, which has an acid number of 7.72, is allowed to cool and modify for one and a half hours then by adding 404.5 g of polyphosphoric acid and heating to 80 ° C. for one hour.

A resin preparation is made from 70 parts of the modified polyester, 30 parts of styrene and 0.02 part of methylhydroquinone here. The resin has a Gardner-Holdt viscosity of Y and an acid number of 73.2.

Example 3

100 parts of the compound prepared from 12 moles of neopentyl glycol, 3 moles of isophthalic acid, 5 moles of maleic acid and 2 moles of adipic acid are used Polyester with 7.4 parts of polyphosphoric acid and is made up of 65 parts of the modified unsaturated Polyester, 35 parts vinyl toluene and 1% benzoin methyl ether a resin preparation.

The resin is applied in a 0.0127 mm thick layer to a plate of cold-rolled steel treated with iron phosphate and the coating is cured with ultraviolet light by moving it 6 times at a speed of 3 m per minute under a 4000 watt, 30, 5 cm long high-pressure mercury vapor lamp ^ 2.54 cm from the tube, passes through. In order to test the adhesive strength of the coating, scratch it, cover it with cellophane tape at this point and pull the tape off. No parts of the coating are lifted off with the tape. This indicates that the coating is firmly adhered to the substrate. 209830/1096

216426Q

Examples 4 to 7

Four modified polyester resins are produced by « 14 parts of titanium dioxide, 7 parts of silica, 8 parts of black tint and 11 parts of vinyl toluene to 60 parts the resin formulations consisting of 30 parts of vinyl toluene and 70 parts each of one of the following modified polyesters gives:

At- polyester mole polyester- polyphosphorus-

game (parts) acid (parts)

4 neopentyl glycol 12 92.6 7.4 isophthalic anhydride 3 maleic anhydride 5

Adipic acid 2

5 neopentyl glycol 12 94 isophthalic anhydride 3 maleic anhydride 5 Adipic acid 2

6 neopentyl glycol 12 96 isophthalic anhydride 3 maleic anhydride 5 Adipic acid 2

7 neopentyl glycol 12 98 isophthalic anhydride 3 maleic anhydride 5 Adipic acid 2

The polyesters are applied to cold-rolled steel plates and the coatings are exposed to ionizing radiation, by passing them under an electron beam to a dose of 12 Mrad. Every film has in the dry Condition a thickness of about 0.01 mm.

The coatings are then tested for adhesion by the reverse impact test and the scribe test.

In the scratch test, the coatings are scratched in the shape of a hatch and then pasted over the incised areas with cellophane tape. The tape is then lifted from the cover. The coating fails if parts of it can be lifted off the steel plate with the tape. 209830/1096

In the reverse impact test, weights are dropped from various heights onto one of the coating to be tested Lying steel balls with a diameter of 1.27 cm fall until the coating shows damage. The results of the Reverse Impact Tests, expressed in the ratio of "inches" to "pounds", are the product of that used Weight in "pounds" and the distance from which the weight is dropped in "inches".

The results of the two tests are shown in the following table:

Example scratch test, reverse impact resistance test

("inches - pounds")

4th no detachment 80 5 no detachment 50 6th no detachment 20th 7th no detachment 10

The test results show that the invention provides excellent adhesive strength for coatings can achieve.

For comparison, a coating made of a mixture of the same but unmodified polyester and toluene diisocyanate is worn as an adhesion accelerator like the coatings used in the above experiments on a plate of cold-rolled Steel and irradiated it with an electron beam at a total dose of 12 megarads. This coating when subjected to the impact resistance test, gives a value of less than 20.

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Claims (1)

New Claimsι 1. An unsaturated polyester of the formula 0 _ 0 0 ¹¹ Γ r HO Γ Γ "" Ί "Γ Ί HO - P 1 - 0 - IR 0 C : - R '- CO - R OP OH L- -J _n «L. * - ^J L -Ίη 'LJ _n in which R stands for an alkyl radical or a radical of the formula R "(0R"), in which R "stands for an alkyl radical and q is a number from about 0 to about 15, and in which R ^{1 is} an unsaturated alkyl radical, η and m for the numbers 1 or 2, η + m for the number 3 and L for a number from 2 to about 20. 2. The unsaturated polyester according to claim 1, characterized in that R is neopentyl, R ^{1 is} ethylene, η 2, m 1 and L 5. 3. The unsaturated polyester according to claim 1, characterized in that R is propyl, R ^{1 is} ethylene, η 2, m 1 and L 6. 4. The unsaturated polyester according to claim 1, characterized in that R is ethyl, R 'ethylene, η 2, m 1 and L 10 . 5. An unsaturated polyester according to claim 1, characterized by a content of a polymerizable ethylenic unsaturated monomers. ■ 6. An unsaturated polyester according to claim 5, characterized in, that the monomer is styrene. Ij) Process for the production of an unsaturated polyester firmly adhering to substrates, characterized in that an unsaturated polyester is reacted with polyphosphoric acid. ORfGiNAL I 209830 / 1Ü9b rs? n- 8. The method according to claim 7, characterized in that
an unsaturated polyester is used, which by
the reaction of maleic acid, isophthalic acid and neopentyl glycol was produced. 9. Use of the unsaturated polyester according to one of the claims 5 or 6 for the production of firmly adhering coatings on substrates. 10. Use according to claim 9, characterized in that that the coatings are hardened by ionizing radiation ™. 11. Use according to claim 10, characterized in that the coatings with a total radiation dose of about 2 to to be hardened about 50 Mrad. 12. Use according to one of claims 9 to 11, characterized in that that metal is used as a substrate. 13. Use according to claim 9, characterized in that the coatings are cured with actinic light. 14. Use according to claim 13, characterized in that the substrate used is metal. 209830/1096