DE2135401A1 - Malleable and / or thermoformable acrylic polymers and processes for their preparation - Google Patents

Description

Dr. Michael Hann

Patent attorney _Λι . _{T,. ΛΟ} . _Π Λ

635 Bad Nauheim ¹ ^ ^{July 19? 1} 2 135401

Burgallee 12 b Tetphone (0 60 32) 62 37

H / He (357) 69-105-GER Rohm and Haas Company, Philadelphia, PA, USA

Malleable and / or thermoformable acrylic polymers and processes for their preparation

This invention relates to a method for making crosslinkable and crosslinked polymers and di-polymers itself. In particular, the invention relates to the Production of polymers of an alpha, beta-unsaturated Carboxylic acid and another monomer, with a radical polymerization of the monomers in the presence of a certain types of diepoxides, resulting in products that are very uniformly distributed Epoxide groups and / or also in very evenly distributed groups contain the conversion products of Expoy groups and carboxy groups are.

The known crosslinked acrylic resins can generally be used divide into two groups. The first group, which has so far been of greater importance, includes polymers, made of an acrylic monomer such as methyl methacrylate, in copolymerization with a crosslinking monomer such as ethylene glycol dimethacrylate. To the Another group includes polymers that are obtained by making a linear acrylic polymer that has reactive groups contains, reacts with a polyfunctional compound, whose reactive groups are capable of reacting with the reactive groups of the polymer. As an an example for this group a reaction product of an acidic copolymer with a diepoxide may be mentioned, like this one for example, in U.S. Patent 3,027,357. Such crosslinked resins either have only very slight improvements over thermoplastic ones Aeryl resins, such as poly (methyl methacrylate), or are with has the disadvantage that in their application and / or Processing very narrow limits must be observed. One of

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The main disadvantages of the known crosslinked acrylic resins of the first group are that most of the curing, i. the final networking, take place in the final form must, since only a very limited change in shape after initial hardening is possible.

In the known, deformable and / or in the heat Mouldable polymers of the second type have significant disadvantages in that the crosslinking material is not uniform is present in them and in the cured end products. You therefore have a number of known products Deficiencies, such as differences in the refractive index and undesired clouding phenomena · Another problem is posed the irregular diffusion of the structure from the polymers and the crosslinker during the deformation and the subsequent Curing.

The present invention is based on the object of deformable and / or thermoformable aoryl polymers create which do not have these disadvantages and a uniform distribution of the crosslinkable sites and / or crosslinked Have groups, the polymers being in a state that they are still deformable and / or in the Heat are malleable.

This object is achieved according to the invention by a new polymerizable Preparation and the polymerization of this preparation dissolved.

The invention relates to a polymerizable preparation, which after the addition of a free radical initiator is capable of being deformed at 20 to 80 ° G and / or to form thermally malleable, viscous to solid polymer, this preparation characterized in that it is a mixture of

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a) a monomeric material

1) 40 to 95 wt. # _{Of a (C 1} -C ₄ ) alkyl methacrylate or cycloalkyl methacrylate or styrene or substituted styrene or a mixture thereof and

2) 5 to 60 wt. # Of an alpha, beta-monoäthylenisoh unsaturated acid

b) a 3, ^ Epoxycyclohexyloarbinyl · ^, 4-epoxycyclohexanecarboxylate, component b) being present in such amounts that O ₉ I to 2.0 Epoxy groups per carboxylic acid group are present in component 2) of a).

The one obtained from such a polymerizable preparation. Polymers have the advantages already mentioned in the description of the task. In addition, the curable acrylic plastics according to the invention are distinguished by the fact that, in the fully cured state, they have considerable advantages over the thermoplastic polymers of methyl methacrylate. Resistance to solvents, hardness and resistance to the occurrence of stress cracks under the action of solvents g should be mentioned as particularly advantageous properties. In addition, the compounds have a particularly good deformability of the invention, as the polymerization product of the present invention in the initial state may be a viscous liquid having a viscosity of at least about 10 poise at tree temperature (25 ⁰ C). In the partially cured or partially crosslinked state, the compositions according to the invention can be solids. In all of these cases, however, the compositions according to the invention can still be thermoplastic or at least be malleable under heat. If the partially cured or crosslinked polymeric compositions according to the invention are solids, they can be in the form of granules or powder or as a shaped body, for example a plate, where

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one such plate into another simple or complex one Shape can be deformed.

Both the liquid starting materials and the viscous, partially polymerizing and / or reacted materials according to the present invention can be hardened in the desired final shape in a single step by two-stage heating. It is of particular advantage that the hardening can be interrupted in any phase between the original liquid state and that of the fully hardened crosslinked product, so that any intermediate state of the material or the consistency of the material can be achieved In most areas of application, the polymerized masses according to the invention have a viscosity of at least 10 poise at about 25 ^° C. These masses and also the deformable and / or thermally formable solid masses according to the invention are more versatile than the known dimensions, since they can be transformed into a large number of very complicated and irregular shaped bodies much more easily than the previously known curable acrylic compositions. The fully cured materials according to the invention have a high transparency, a light color and good weather resistance, as is typical for thermoplastic acrylic plastics is.

In characterizing the present invention, the following definitions are used:

A "thermoplastic" is a polymeric material that is completely or is largely soluble in a solvent and that, when heat and pressure are applied, has a liquid flow behavior shows.

A "crosslinked polymer" is a polymeric material that is completely or largely insoluble in all solvents and none when heat and pressure are applied shows liquid pilling behavior.

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2135AO1

A "deformable mass" is at least »temporary thermoplastic mass, which may contain various auxiliaries or additives during the shaping process can.

A "thermally malleable mass" is a hate that can be formed, or if it is already in its initial state in a special shape, e.g. as a plate, be reshaped at least once using heat and pressure can, but such a mass is not necessarily thermoplastic.

From these definitions it follows that a · in warmth malleable Hasse can still be shaped, but has a higher degree of crosslinking than a malleable · Mae »·.

The thermally formable aryl polymers are obtained of the present invention by copolymerization of (a) about 40 to 95 »preferably 50 to 85% by weight of« ine »monomers from the group of the alkyl methaorylates, cycloalkyl methacrylates, styrene and substituted styrenes and (b) about 5 to 60, preferably 15 to 50 wt. ^ of an alpha, beta-monoäthyleniseh unsaturated acid ·, the mixture of these monomers an initiator capable of forming free radicals and a diepoxide of the following formula I contains:

B,

(D

In this formula, R ₁ denotes hydrogen, halogen or a lower alkyl radical having 1 to 4 carbon atoms, R ₂ ,

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_f R ^, R ^ and Rg denote hydrogen or a lower alkyl radical having 1 to 4 carbon atoms.

The amount of this diepoxide is in accordance with the invention Mass chosen so that 0.1 to 2.0, but preferably 0.5 to 0.9, epoxy groups per acid group in the acid according to (b) are present, with pesticides being in the preferred range develop.

Among the monomers according to (a) are the (C ₁ -C ^) alkyl methacrylates, in particular methyl methacrylate, cyclohexyl meth-P acrylate, methyl, dimethyl, and triethyl-cyolohexyl methacrylates, styrene and yiny! Toluene (o-, m- or p- ) preferred.

Preferred acidic monomers according to (b) are acrylic acid, methacrylic acid and itaconic acid, although alpha-chloroaryl acid, monomethyl itaconate, 4-pentenoic acid, methacryloxyacetic acid and acryloxypropionic acid and numerous other monomers which correspond to the definition can also be used.

In addition to at least one monomer (a) and at least one monomer (b), the polymerizable compositions can contain a or several other monomers (c) up to a total of of about 5 wt.? i, based on the total weight of monomers (a), (b) and (c). Although one or more of these additional monomers are only in small amounts can be used, the polymer can thereby be given special properties, whereby one can improve a particular property such as weather resistance, resistance to ultraviolet light and The like. Examples of such monomers include vinyl chloride, vinylidene chloride, trichlorethylene, chlorotrifluoroethylene, vinylidene fluoride and the like; Vinyl esters such as vinyl acetate, vinyl lactate, vinyl oleate and the like; olefinically unsaturated nitriles such as acrylonitrile, methacrylonitrile and the like; aliphatic olefins such as ethylene, propylene, butene, butadiene, isobutylene, piperylene and the like;

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Amides of acrylic acid such as acrylamide, Ν, Ν-dimethylacrylamide, N, N-Diäthylacrylamid and the like, and various other polymeriBierbare olefinic compounds, such as dibutyl maleate, Vinylcyclohexyläther, methyl vinyl ketone, allylidene diacetate, acrolein, vinylpyrrolidone, Athylthioathylmethacrylat and the like, (C _1.. - Cj) alkyl acrylates, for example ethyl or butyl aorylate.

Examples of particularly suitable diepoxides of the formula I include the following compounds 3, ^ epoxyoyolohexylmethyl ^ i ^ epoxyoyolohexanoarboxylate; 3,4-epoxy-1-methyloyolohexylmethyl-3,4-epoxy-1-ethylcyclohexane carboxylate;

3,4-epoxy-2-ethylcyclohexylmethyl-3 , 4-epoxy-2-ethylcyolohexane carboxylate;

3,4-epoxy-6-methylcyclohexylmethyl-2 ^ -epoxy-δ-ethylcyclohexanecarboxylate;

3 ^ -epoxy-1-chlorocyolohexylmethyl ^, 4-epoxy-1-chloroylclohexane carboxylate;

3,4-epoxy-1-bromocyclohexylmethyl-3,4-epoxy-1-broacyclohexanecarboxylate;

4,5-epoxy-1-chloro-2-methyloyclohexylmethyl-4 | 5- »poxy-1-chloro-2-methlycyclohexanoarboxylate and the like

When referring to the diepoxides of the formula I, the -CH ₂ part of the -CH ₂ OC- group can be called “methyl” or “carbinyl”.

The copolymerization can be carried out in the presence of a solvent for the monomers, but is preferred worked in the absence of a solvent.

The radical initiators used in the process according to the present invention are preferably those which are usually used in bulk polymerization. There is also agreement with the known prior art with regard to the amounts of these initiators.

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In general, the initiators are used in amounts of from about 0.01 to 1.0, preferably from about 0.05 to 0.4% by weight based on the weight of the mixture to be polymerized.

The polymerization reaction can be stimulated both by initiator systems of the thermal type and also of the redox type will. Examples of thermal initiators include the following compounds: organic peroxides, such as Benzoyl peroxide, substituted benzoyl peroxide, acetyl peroxide, Lauroyl peroxides, t-butyl hydroperoxide, di-t-butyl hydroperoxide; Peresters such as t-butyl peroxypivalate; Asotype initiators, such as azobis-isobutyronitrile; Persulfates, such as sodium, potassium or ammonium persulfate and peroxyphosphates, such as sodium, potassium or ammonium peroxyphoephate. Suitable redox systems can include, for example, the following compounds include: a combination of a hydroperoxide such as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, Diisopropylbenzene hydroperoxide and the like. Old a suitable reducing agent, such as sodium, potassium or Ammonium bisulfite, metabisulfite or hydrosulfite, sulfur dioxide, Hydrazine, iron (II) salts, isoasoorbic acid, Sodium formaldehyde sulfoxylate and the like in the polymerization chain transfer agents such as mercaptans, polymercaptans and polyhalogen compounds can also be used be, these additives in the polymerizing Mix in the usual amounts, as s.B. $ 0.1 to $ 2 or more, based on the total weight of the monomers, are present.

The mixture of monomers, initiator and diepoxide can also contain the usual additives and auxiliaries, which may be of interest depending on the particular application. Such additives can e.g. lubricants or mold lubricants such as soaps of fatty acids; Dyes, pigments and Fillers, being both powdered minerals as auoh

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organic or inorganic fibrous materials can be used. Other additives to consider are adsorbents for infrared light and modifiers for impact resistance, which can be addition polymers or condensation polymers. These Aids are used in the usual amounts.

The polymerization time can vary within wide limits, but is usually from 1 to 24 hours or even a longer period, for example at 40 to 50 hours, preferably about 20 to 80 ⁰ C is polymerised. The reaction is usually carried out at atmospheric pressure, although increased or decreased pressures can also be used, for example pressures of 14.0 kg / o * (200 psi) or 30 mm Hg. It is preferred to operate at atmospheric pressure. It should be noted that the polymerization temperature in the present invention determines the extent of the reaction between the carboxy groups and the epoxy groups during the initial polymerization, which on the other hand significantly affects the consistency of the material produced by the polymerization reaction. Other factors which favor the formation of viscous liquids compared to solids are the use of more than sufficient amounts of epoxide for the presence of g a ratio of one epoxy group to one carboxy group, smaller amounts of acid, e.g. only 5 to 15% in the Starting mixture of the monomers and the use of very small amounts of initiator, bB 0.001? *, Lied to all monomers, or the interruption of the copolymerization before essentially complete conversion of the monomers has taken place.

It is believed that during the polymerization of the monomers, some reaction between the diepozide and the acidic monomer and / or with the acidic groups of the copolymer occurs immediately after its formation. By a

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thorough mixing of the diepoxide with the monomers un _r indirectly before the polymerization or during the polymerization, it is achieved that the crosslinking material is uniformly dispersed in the polymerizing mixture. The resulting copolymeric composition can contain various components, for example an acidic copolymer whose carboxyl groups have not reacted with the diepoxide, a copolymer of the monomeric acid with the monomeric ester or the vinylaromatic compound in which some of the acidic groups with one of the epoxy groups of the diepoxide have reacted, so that the units of the copolymer contain epoxy groups for a later reaction with carboxyl groups of the same or a different acidic copolymer, and also a component in which the copolymeric molecules are crosslinked with each other with the reaction of acidic groups with Eiioxygruppen from the diepoxide. It is also assumed that a substantial proportion of the dieposide is unreacted at the end of the polymerization reaction, provided that the starting mixture to be polymerized contains the diepoxide and the acidic monomer within the limits already given.

The preparations containing the monomers, the initiator and the diepoxide can be poured and the polymerization can be brought about and then cured in the mold by heating to elevated temperatures, for example at temperatures of 120 to 220 ^° C. or higher, but preferably at 150 to 180 ^° C. The times that can be considered for this are around 15 seconds to 20 hours, depending on the construction or size and shape of the device in which the casting is carried out. The amount of diepoxide in relation to the number of acid groups in the polymerizing mixture is preferably selected so that hardening in the elevated temperature range just mentioned leads to an essentially complete conversion of the epoxy groups, whereby an insoluble, essentially completely hardened one · »Polymeric pro-

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product is formed that contains no or only insignificant amounts of oxygen in an oxirane group.

In an alternative and preferred embodiment of the invention, the mixture of monomers, initiator and diepoxide with or without additives is subjected to the polymerization under such conditions that a deformable or thermally formable viscous or solid material is formed, which is in a granulate, a plate or can be converted into extruded tablets. The polymer obtained in this case has not yet-uugesetzte * epoxy groups, since under the temperature conditions (20 to "80 ⁰ C) of the polymerization occurs only incomplete reaction of diepoxide with the acid groups. In the extent that the polymer which forms more viscous , a slowing down of the reaction between epoxy groups and carboxy groups occurs until the polymer has reached a solid state, after which the mentioned reaction comes to an almost complete end.Generally the most preferred starting mixture for the polymerization contains 0.5-0.9 Epoxy groups per acid group of the acidic monomer in the mixture of polymerizable starting materials from which the copolymer is prepared, and the extent of the reaction between the epoxy groups and the carboxyl groups jj is such that a malleable or thermally malleable mass is formed which contains Oxirane oxygen from 0.5 to 7 wt. % Contains, whereby it is insignificant whether the copolymer is in the form of granules, a plate or an extruded tablet or in another form. As a rule, compounds containing an oxirane content of about $ 5 to $ 7 are malleable; those with an oxirane content of 0.5 to 1% by weight are heat moldable, whereas those with an oxirane content of 1 to 5% are deformable and heat moldable. With the preferred ratio of epoxy groups to acid groups, it is avoided that the products obtained tend to discolour or show hardness and / or aging.

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The preferred copolymers in the heat moldable to 10% of methacrylic acid and 3,4-Epoxycyclohexylcarbinyl-3,4-epoxy-cyciohexancarboxylat obtained from a mixture of 45 to 70 wt. # Of methyl methacrylate, to 25 wt. In an amount such that 0, 5 to 0.9 epoxy groups are present per carboxyl group, the extent of the reaction between carboxyl groups and epoxy groups being adjusted during the polymerization so that a polymer which can be thermoformed with an oxirane content of about 1.0 to 3 »8% by weight is formed based on the weight of the polymer.

When the polymerization in the presence of chain transfer agents such as mercaptans and at low ambient temperatures, preferably at about 20, auegeführt to 50 ⁰ C, may be a solid, but still thermoplastic product are obtained, which only very contains few residual olefinic double bonds. This material is particularly good as a molding compound in view of the essentially uniform distribution of (l) any remaining diepoxides and (2) converted epoxy carboxy groups in the polymerized product. Suitable molding compounds can be produced from this product by granulating the solid product . A certain content of residual olefinic bonds is advantageous in such molding compositions, since this reduces the melt viscosity, but care should be taken that this content of olefinic bonds is not too high, otherwise the product will shrink during the shaping process. The molding compositions can be processed by the known methods for the squandering or transfer molding or injection molding, with temperatures of about 120 to 220 ⁰ C or higher, but preferably of 150 to 180 ⁰ C, and the usual pressures from 70 to 352 kg / cm ² ( 1000-5000 psi) in compression and 703-1406 kg / cm (10,000-20,000 psi) in transfer molding and injection molding.

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-IT-

The molding cycle can range from about 15 seconds to about 15 minutes or more, this period of time depending heavily on the degree of curing of the polymer in the molding compound. A cycle of about 1 minute up to 2 minutes is in most cases well suited for practicing the invention. If the polymers according to the present invention are converted into plate-like or film-like structures with the aid of customary processes, they can be stretched at elevated temperature, whereby a number of their properties are improved; but they can also be converted into more complex shapes by applying heat and pressure, for example by using conventional devices for vacuum deformation. This final shaping can take place at temperatures of approximately 140 to 220 ^° C. or even higher temperatures, temperatures of 150 to 180 ^° C. being preferred. The pressure can be 0.35 to 1.40 kg / cm ² (5-20 psi) or 20 to 30 mm Hg for vacuum deformation. The period of time is comparable to the one just given above for the deformation cycle.

Cured, the polymers according to the invention have a glass transition temperature of at least 75 ⁰ C in its fully excluded g cured state and, in contrast to the known crosslinkable polymer formable and have a uniform distribution of the epoxide (reacted or unreacted) completely or partially in the Product. This uniform distribution is an essential and advantageous feature of the present invention, since it has not been possible with the known products to achieve such a uniform distribution. Another advantage of the invention is that it is possible to select the monomers and the diepoxld in their relative proportions so that a deformable and / or thermoformable polymeric mass is obtained, which can be in the form of granules, tablets or in the form of Plates or similar

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Union structures can exist, these products at normal room temperatures and under normal cold conditions resistant to being considered for periods of 3 to 4 months at room temperature or practical Can be stored in the coming cold or refrigerated conditions while still having the ability to "keep them easily." deformed or otherwise shaped or reshaped can.

In all the above embodiments, the polymers may according to the invention after deformation into the desired shape further crosslinked, ie cured by being heated to temperatures of 140 to 22O ⁰ C or higher for periods of time of about 1/4 hour to 24 Heated hours, temperatures of about 150 to 180 ⁰ G are preferred. It is often advantageous to add catalytic amounts of organic bases, such as ditertiary amines, or inorganic bases, such as sodium hydroxide, to the initial polymerizable materials in order to achieve better crosslinkability through the reaction of the epoxy groups with the carboxy groups in shorter times. Flat plates can be hung vertically in an oven or placed horizontally on felt-covered compartments in an oven to achieve complete curing. Parts of more complex shapes can be cured immediately in the mold in which they were molded when the mold is hot. Such parts can, however, also be placed in an oven and slowly heated to elevated temperatures there in order to prevent disruptive distortion of the parts. The molding compositions according to the present invention are particularly suitable for the production of lenses, refractive elements and other optical parts, or for the production of decorative inserts in areas of application where high temperature resistance is desired. The flat plates can be subjected to blow molding. Such panels are of interest in glazing military aircraft

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witness. The flat plates can also be molded into other objects in the heat, e.g. in Fresnel lenses, Refractive bodies and diffusers for fittings of lights. When the new crosslinked acrylic plastics after of the present invention are fully cured, they make durable and long-lasting plastic products which corresponds to the thermoplastic poly (methyl methacrylate) in a number of properties, such as hardness, solvent resistance, Resistance to the occurrence of stress cracks under the influence of solvents, Resistance to thermal expansion and contraction, dimensional stability in heat under load, Stiffness, fire resistance, abrasion resistance, Heat resistance and creep resistance superior to Bind.

The polymers according to the present invention are also the products known from the patent mentioned at the beginning strongly consider what is obviously due to the even distribution of the crosslinking material or the crosslinking points in the polymeric product. Ea is of particular advantage that the polymeric products according to this invention are characterized by excellent transparency and excellent optical properties. In this context, it is particularly important to ensure that the products are free from optical distortion if the Processing products in a professional manner from the unpigmented Product according to the invention without the use of volatile solvents, which are known to cause difficulties Can give rise to be produced. It is well known that the residues of solvents pose a particular problem to be removed and in the present invention it is of particular advantage that lenses or other objects that should be transparent or translucent without the hazards associated with the use of solvents can be created.

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The invention will be further elucidated in the following examples explained. The data on parts and percentages are weight data.

example 1

A mixture of 49 parts of methyl methacrylate, 21 parts of methacrylic acid and 29.4 parts of 3,4-epoxycyclohexylcarbinyl-3,4-epoxycyclohexanecarboxylate, 0.1 part of 2 (2'-hydroxy-5'-methylphenyl) benzotriazole (ultraviolet absorber), 0, 4 parts of sodium hydroxide, 0.20 part of a 75 # solution of t-butyl peroxypivalate in mineral spirits and 2 parts of n-dodecyl mercaptan are stirred until the solids have dissolved. The solution is then degassed at 30 mm Hg and melted in a glass tube under a nitrogen atmosphere. The contents of the tube are hard after 40 hours. The clear, colorless product is removed from the tube and granulated; it is soluble in methanol, softened at 50 to 60 ⁰ O and flows at 100 to HO ⁰ C. · For the polymeric powder is pre-pressing in a metal mold at 180 ⁰ C and about 42 kg / cm ² (600 psi) for 15 Minutes made a flat plate. The plate is colorless and transparent and is not attacked by methanol, methylene chloride, toluene or hot water.

Example 2

A mixture of the starting materials of Example 1 with the Exception that p-Methoxybenzylidenmalonsäuredimethylester used in place of benzotriazole, stir until homogeneous. The mixture is then placed in a cell, which is formed by two brass plates and there will be a rod-shaped, flexible spacer 3.2 mm (1/8 ") in diameter between the flats and arranged around their edges. The inner surfaces of the brass plates are coated with a mold release agent.

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layers and the air-free cell formed thereby has a thickness of about 3.0 mm (120 mila). The cell is then placed in an oven with circulating air at a temperature of about 40 ^° C. for 17 hours, a hard plate made of a polymeric product being formed. A test piece is cut out of this plate and heated ^{to about 150 ° C. in an oven for about 3 minutes.} Then this piece is given a convex curvature by air pressure. It follows from this that this plate consists of a material which is deformable under heat under blowing pressure.

Example 3

There is a similar plate as that of Example 2 in a flat condition for 16 hours at 150 ⁰ C cured. This results in a sheet made of a crosslinked acrylic polymer with the physical values given in Table I. This table also shows the properties of a sheet made of a conventional thermoplastic poly (methyl methacrylate) for comparison.

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Table I. 3.9; 1.22 Plate off 1.19 Plate made of Poly (methyl- mesh acrylic 0.1; 91 inethacrylate 92 characteristic polymers 1.7; 2 1 specific weight 1.3; 696 738 fa light through 2.7; 900) 500) nonchalance % Haze 000 600 Tensile strength kg / cm 000) (10 000) (psi) (9 modulus of elasticity 18.9 31 52.7 kg / cm ² 43 141 (450 96 (psi) (613 Abrasion resistance according to Taber (1) ; less themselves FWUB ⁰ C, (2) attack Chemical resistance no change themselves against (3) no change solves no change acetone no change no change no change solves no change toluene 0.4; water 0.3; 10% hydrochloric acid 0.4; l ^ ige sodium lye Commercially available

wax

1.5; no change attack

(1) The Taber abrasion resistance is determined by rotating a cylindrical weight of 1000 g on the plate and the percentage of haze after 100
Measures revolutions.

(2) PWUB is the dimensional stability under heat under load in degrees Celsius, with a load of 18.5
kg / cm ² (264 psi) is applied.

(3) The term "chemical resistance", both the increase in weight in percentage and given the appearance of the sample after complete fiintaiichen in the corresponding solvent for 7 days at 77 ⁰ C.

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Example 4

A solution prepared by compression molding as in Example 1 plate is situated in the vicinity of a 400 watt mercury vapor lamp at an ambient temperature of about 15O ⁰ O. As a control, a plate made of poly (methyl methacrylate) is treated in the same way. After a week, the sheet made of poly (methyl methacrylate) is very warped, whereas the sheet made of cross-linked acrylic resin has retained its original dimensions.

Example 5

a) A thin sheet-like casting is produced according to the invention as follows:

A mixture of methyl methacrylate (47 parts), methacrylic acid (20 parts), 3,4-epo: xycyclohexylcarbinyl-3 _f 4-epoxycyclohexane carboxylate (33 parts), mercaptoethanol (0.67 parts) and sodium hydroxide (0.33 parts) is stirred until it is homogeneous. Then 1/2 part of a 75% solution of t-butyl peroxypivalate in white spirit is added with stirring and carefully distributed in the mixture. The mixture is placed in a thin, airtight cell. Then, the micro is μ research for 17 hours at 45 ⁰ C cured. The thin plate obtained is removed from the cell and ^{finally cured at 150 °} C. for 16 hours.

b) For comparison purposes, an acidic emulsion copolymer is used manufactured in the following way:

236 parts of deionized water, 1.0 part of sodium lauryl sulfate and 0.5 part of potassium persulfate are placed in a stainless steel reaction vessel. The solution obtained is stirred mechanically and ^{heated to 80 °} C. with the aid of a water bath. A mixture of 70 parts of methyl methacrylate, 30 parts of methacrylic acid and 1.0 part of mercaptoethanol is then added over the course of 2 hours, the temperature of the aqueous emulsion being kept at 80 to 86.degree. After this

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the addition "is complete, the emulsion is stirred ^{at 70 to 85 0 O for 1.5 hours".} The pesticide content of the emulsion is $ 29.3. Then 0.5 part of sodium hydroxide (as a l ^ ige aqueous solution) per 100 parts of pesticides are added to the emulsion of the polymer formed. The partially neutralized emulsion is spray-dried and the polymer is isolated and dried at 100 to 110 ^° C. in a vacuum oven in order to remove the residual volatile constituents. Then the acidic copolymer is molded or cast with the same diepoxide, so that a crosslinked or hardened polymer is produced as follows:

1) The dry copolymer (100 parts) and 3,4-Epoxycyclohexylcarbinyl-3,4-epoxycyclohexane carboxylate (49 parts) are thoroughly mixed in a mechanical mixer and a thick, transparent Piim at 180 ⁰ C compression molded. The Piim is post-cured for 16 hours at 15O ⁰ C.

2) The partially neutralized, dried methyl methacrylate / methacrylic acid copolymer from part b) of this example (67 parts) is dissolved in 500 parts of methanol and then 33 parts of 3,4-epoxycyclohexyloarbinyl-3 _f 4-epoxycyclohexane carboxylate are added. The solution is spread out on an inert surface and the methanol is removed ^{at 85 ° C. in a vacuum oven.} Foaming occurs as the methanol evaporates. The rigid obtained transparent Piim is post-cured for 16 hours at 15O ⁰ C.

c) The two networked pilms according to part b) 1) and b) 2) are with the networked PiIm from part a) of this example compared. All pilme have essentially the same composition with regard to the components methyl methacrylate, Methacrylic acid, 3f4-epoxyoyolohexyloarbinyl-3,4-epoxycyclohexanecarboxylate, Mercaptoethanol and sodium hydroxide.

The cross-linked appear under the optical microscope Products according to parts b) 2) and a) completely homogeneous. The cross-linked material of part b) 1) ereoheint

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as a collection of circular areas 10 to 30 microns in diameter \ This heterogeneity can be seen with the naked eye as a grainy, orange peel-like distortion.

Samples of each of the three crosslinked films are placed overnight in a Soxhlet apparatus with methanol and then over Extracted overnight with methylene chloride. Afterwards, all soluble material is evaporated from each sample of the solvent determined by both extracts. The results are shown in Table IX. From the f want the dry, non-extractable plastic, the density of the plastic (1.2 g / oom), the weight of the The degree of swelling (volume of swollen polymer / volume of dry, non-extractable polymer). These results too are shown in Table II. The table shows that the crosslinked plastic according to the invention has the lowest Degree of swelling, i.e. the greatest resistance to solvents.

The distribution of crosslinks in the crosslinked three similar polymers to show the following experiment is performed. A test solution is prepared from known amounts of three different alkylphenoxypolyethoxyethanols of different molecular weights and sizes, in a known amount of methylene chloride. In the Grelpermeation-Chromatographle three different and recognizable maxima (peaks) are observed for the three different alkylphenoxypolyethoxyethanols. The retention volumes corresponded to r (root of the mean angle half-axis "root mean square radius") "1 ^" 19 and 30 1 due to the calibration of the chromatograph! See column. Weighed samples of each of the three extracted crosslinked polymers, which were still swollen with methylene chloride, with known amounts of the test-

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solution allowed to stand within 3 days for equilibrium to be established. Gel permeation chromatography the methylene chloride solution shows decreases in after equilibrium has been established with the crosslinked polymers the height of a few maxima, so that on this basis the amount of each of the three alkylphenoxypolyethoxyethanols, diffused into the swollen polymer could be calculated. These results are also shown in Table II as Percentage of the volume of any plastic accessible to methylene chloride but the alkylphenoxypolyethoxyethanols is not accessible. The usual interpretation of these values shows that the swollen cross-linked Polymer film from part b) 2) of this example to 100% "pores" in the polymer which are accessible to methylene chloride and which are smaller than 30 A (r). 97 $ of the pores are smaller than 19 A and 56 $ are less than 14 A and the like. The table also shows that the crosslinked polymer of this invention has an extremely narrow distribution of pore sizes: 83 $ of the pores have an apparent size between 14 and

19 A, i.e. that the distribution of the crosslinks is very uniform. The crosslinked polymer films of parts b) 1) and b) 2) have a much larger span in the distribution of pore sizes, with about half the pores being smaller than 14 A. It follows from this that these polymer films have areas in which the crosslinks form a single area have a greater distance than such with networks at a smaller distance, (although the first mentioned predominate) versus the improved polymer films of this invention.

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Table II Extractable Fractions
Weight # Film off ve met zt em plastic Swelling ratio
in methylene chloride 5a 5b) 1) 5b) 2) Percent included
Alkylphenoxy polyethoxy
ethanol 1.7 2.4 1.1 F = 14 Χ 1.4 1.6 1.8 r = 19 i F = 30 1 17th 50 56 Example 6 100 87 97 100 100 100

The procedure of Example 1 is repeated with each of the following mixtures:

a) 40 parts of methyl methacrylate, 30 parts of styrene and 30 parts Acrylic acid with the addition of 50 parts of 3,4-epoxy-1-methylcyclohexylcarbinyl-3,4-epoxy-1-methylcyclohexanecarboxylate;

b) 75 parts of styrene, 1 part of ethylthioethyl methacrylate and 24 parts of itaconic acid with the addition of 40 parts of 3,4-epoxy-6-methylcyclohexylcarbinyl-3,4-epoxy-6-methylcyclohexanecarboxylate;

c) 55 parts of methyl methaorylate, 5 parts of acrylonitrile, 25 parts Vinyl toluene, 10 parts acrylic acid and 5 parts methaoryloxypropionic acid with the addition of 20 parts of 3f4-epoxy-2-ethylcyclohexyloarbinyl-3 ^ -epoxy - ^ - ethyloyclohexanoarboxylate;

d) 20 parts of ethyl methacrylate, 70 parts of styrene, 2 parts of vinyl acetate and 8 parts of methacrylic acid with the addition of 10 parts of 3,4-epoxy-1-chloro-2-methylcyclohexyloarbinyl-3 _t 4- «poxy-1-chloro-2-methylcyclohexane carboxylate |

e) 65 parts of methyl methaorylate, 20 parts of butyl ethaorylate, 5 parts of methyl acrylate and 10 parts of methacrylic acid with the addition of 15 parts of 3,4-epoxy-1,6-dimethylcyolethylcarbinyl-3> 4-epoxy-1,4-methylcyclohexyloarboxylate and

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f) 55 parts of cyolohexyl methacrylate, 30 parts of styrene and 15 parts of methacrylic acid with the addition of 15 parts of 3,4-epoxycyclohexylcarblnyl-3,4-epoxycyclohexanecarbonic acid

Each of the solid polymers obtained is in the deformable and / or in the thermoformable phase, in which it is after the removal from the tube, in which the polymerization and the partial conversion between epoxy groups and carboxyl groups takes place, is stable and storable for several weeks to several months at normal room temperature still deformable or heat-deformable even after such storage.

Example 7

Example 1 is repeated using 58 parts of diepoxides, and a liquid viscous polymer having a viscosity of about 10 poise at room temperature is obtained. This liquid polymer is poured between a pair of glass plates with a spacer 2 mm thick on the edge of the plates. The mold is ^{heated to 170 °} C. for 15 hours, resulting in a hardened plate that is resistant to solvents.

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Claims (10)

A polymerizable preparation which, after the addition of a free radical initiator, is able to form a deformable and / or thermally malleable, viscous to solid polymer at 20 to 800C, characterized in that it is a mixture of a) a monomeric material 1) 40 to 95 wt. # _{Of a (G 1} -C ₄ ) alkyl methacrylate, a Cyoloalkylmethaorylats, a styrene, a substituted styrene or a mixture of these and 2) 5 to 60% by weight of an alpha, beta-ethylenic unsaturated acid b) a 3,4-epoxycyclohexylcarbinyl - 3 _f 4-epoxycyclohexanecarboxylate, component b) being present in such amounts that 0.1 to 2.0 epoxy groups per carboxylic acid group are present in component 2) of a). 2. Preparation according to claim 1, characterized in that the diepoxide b) is present in an amount such \ 0 _F that about 5 to 0.9 epoxy groups per Carboxonsäuregruppen according to a) are available 2) · 3. Preparation according to claim 1, characterized in that the monomeric material contains 50 to 85 wt. # Of one or more monomers according to a) 1) and 15 to 50 wt. # Of one or more acidic monomers according to 2). 4 · Preparation according to claim 2, characterized in that the monomeric material a) contains 60 to 80 wt. ^ Methyl methacrylate and 20 to 40 wt. % Methacrylic acid and the diepoxide contains 3,4-epoxyoyolohexylcarbinyl-3 _? 4-epoxycyclohexanoarboxylic acid is 109885/1693 5. Process for the production of a deformable and / or thermally formable viacose (viscosity of at least about 10 poise at room temperature) or solid polymer, characterized in that a mixture according to claim 1 with a free radical initiator at a temperature of about 20 to 80 ⁰ G is polymerized. 6. The method according to claim 5 _f, characterized in that a solid deformable and / or thermally formable polymer is produced which has a glazing temperature of at least about 75 ⁰ G after complete curing. 7. The method according to claim 5 »characterized in that the acidic monomer methacrylic acid, acrylic acid or itaoonic acid is. 8. The method according to claim 7, characterized in that the acidic monomer is methacrylic acid. 9. A malleable and / or thermally malleable viscous or solid polymeric product according to claim 5, characterized in that this product has a viscosity of at least 10 poise at normal room temperature or a solid at normal room temperature iet, 10. A solid polymeric product according to Claim 9 »thereby It is marked that there is 0.5 and 7 G- © w "# Oiirana oxygen contains. 11 "A deformable and / or similar product that is malleable in the heat, that from the mixture of Anapmoh 1 by fr®! radical! » see copolymerization of monomers 1) and 2) of these Mixture was stopped® and at d®m about 10 to 50 $ the 109885/1893 Epoiygruppen of Diepoxidee with the acidic groups of the monomers 2) have reacted and / or the CopolymermolekUle formed therefrom, wherein said product NaOH complete curing under heating a glass transition temperature about clay has at least 75 ⁰ C. 109885/1693