JPS62940B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to curable compositions of ethylene copolymer blends and shaped articles formed therefrom. More specifically, the present invention describes the use of ethylene and a flexibilizing monomer.
and a third monomer containing pendant epoxy groups and carbon monoxide, and a thermosetting resin blend. The present invention relates to shaped articles, films and fibers formed from such blends. Ethylene polymers are characterized by low polarity and low reactivity. They are similar to waxes in this respect and therefore have low dielectric constants and are soluble in hot oils, hot waxes and hydrocarbons. They are also known to be very inert. For some applications, ethylene polymers can be modified to make them flexible, impart greater polarity to the ethylene polymers, and make them available for reaction with other resins. is desirable. The incorporation of unsaturated organic esters such as vinyl acetate or acrylates into the ethylene polymer can impart a lower degree of polarity and some flexibility to the ethylene polymer. However, to provide a high degree of polarity, high levels of ester are required, which adversely affects the advantages of long ethylene chains, such as low cost, good low temperature behavior, etc. Therefore, it is desirable to increase the polarity of ethylene copolymers while retaining the hydrocarbon chain as the main characteristic of ethylene copolymers. However, ethylene copolymers modified to be flexible and more polar can still be relatively unreactive. Consider now the technology related to thermosets and especially blends with other polymers. Commercially available thermosetting resins such as phenolic resins, epoxy resins, etc. have been found useful because they retain their performance at elevated temperatures. This retention of performance is related to the crosslinking or curing effect present in the structure of the thermosetting resin used. However, this retention of high temperature performance is accompanied by high stiffness and brittleness, which makes it desirable to reduce stiffness or, if some stiffness is desired, to provide higher toughness. ) makes it desirable to reduce the stiffness. To our knowledge, the obvious solution of blending flexible polymers into thermosetting resins has never been successful. Molecular compatibility is never achieved; the desirable properties of thermosets are lost. According to the invention, from 1 to 99% by weight of a solid organic thermosetting resin selected from the group consisting of phenolic resins, such as phenol formaldehyde resins; epoxy resins and melamine formaldehyde resins;
Substantially (a) 40-90% by weight of ethylene; (b) carbon monoxide
(c) unsaturated monocarboxylic or dicarboxylic acids of 3 to 20 carbon atoms, esters of such unsaturated monocarboxylic or dicarboxylic acids, the acid group having 1 to 18 carbon atoms; vinyl esters of saturated carboxylic acids with alkyl groups of 1 to 18 carbon atoms, acrylonitrile, methacrylonitrile, α-olefins of 3 to 20 carbon atoms, norbornene and vinyl aromatic compounds 5 to 40% by weight of monomers belonging to the group and capable of copolymerizing said (a) and (b) to give a flexible polymer; and (d) 4 to 21 monomers containing epoxy groups. Curable blends are provided with 1 to 99% by weight of copolymers consisting of 0.2 to 15% by weight of ethylenically unsaturated monomers of carbon atoms. The term "phenolic resin" refers to thermosetting phenolic-aldehyde resins, such as those prepared from phenols, cresols, e.g. m-p-cresol mixtures, p-cresol or cresylic acid, resorcinols and aldehydes such as formaldehyde and furfural. It is meant to include them. One-step (Resol) or two-step (Novolak) versions are useful (US Pat. No. 3,438,931). Useful are phenol-formaldehyde resins modified with alkylphenols (eg, cresol), polyhydric phenols (eg, resorcinol, hydroxynon, etc.), or polyphenols (eg, bisphenol A). Preferred blends include (a) ethylene, (b) carbon monoxide, (c) vinyl alkanoates, such as vinyl acetate,
Vinyl propionate, vinyl butyrate; alkyl is 1
alkyl acrylates and alkyl methacrylates having ~20 carbon atoms; monomers copolymerizable with (a) and (b) above; and (d) copolymerizable unsaturated organic It contains a copolymer of epoxy-containing monomers selected from the group consisting of epoxy esters of acids, epoxy ethers of vinyl ethers and allyl ethers, and mono-epoxy substituted diolefins of 4 to 12 carbon atoms. Certain preferred blends have copolymers of (a) ethylene, (b) carbon monoxide, (c) vinyl acetate, and (d) glycidyl acrylate or methacrylate. The copolymers in preferred blends contain the following weight percent of components (a) to (d): (a) 45 to 90, more preferably 50 to 70, (b) not more than 15, (c) 10-33, more preferably 20-30, (d) 0.4-9, even more preferably 1.5-6. The copolymer usually has a molecular weight of 0.1 to 3000, preferably 5 to 3000.
It has a melt index of 500. Before curing the curable blend,
It can be formed into sheets, molded blocks, or fibers. The curable blend may be in solid form that can be ground to a powder and subsequently formed into molded or shaped articles, films, coatings or fibers before curing. A cured composition of the form described above is obtained by heating the curable blend described above in an oven, mold, or the like. The poor performance of thermosetting resins such as phenolic resins is generally indicated by a high degree of brittleness. This is usually caused by brittle failure due to high-velocity impact.
failure) or brittle failure at low strains under slow speed tests such as bending. In actual use, this can occur if a molded item such as a bolt cap is dropped on the floor, if the toy is twisted, or even by slight thermal distortion. The latter often occurs with molded articles with metal inserts that may be used under the hood of a car. In order to prove the invention, it is necessary to convert the qualitative brittleness problem described above into quantitative laboratory measurements. In slow bending measurements, the inventors have found that commonly used filled phenolic and epoxy resins fail when the strain on the sample is as small as about 1%. For practical purposes, increasing the level of strain to failure by a factor of 2-3; ie, 2-3% is a major accomplishment. The notched Izot test was chosen as the impact measurement method. In this test, commonly filled phenolic molding resins, which measure the impact energy absorption capacity of molded pieces, exhibit very low values, 0.1 to 0.3 foot pounds per inch notch when the sample breaks. This value depends on the type or combination of fillers. It can be increased by modifying the structure with more expensive phenolic resins or by using long glass fibers or cotton flock. Although resins using these types of fillers are available on a commercial basis, they are not widely used because of the high blend manufacturing costs and practical difficulties of commercially available products. Therefore, there remains a need for resin modifiers that can be added to thermoset molding compounds to increase their toughness. The present invention requires, and is also based on, that the modifying resin be compatible with the thermosetting resin. There are two types of compatibility according to the present invention, in two stages: before and after curing. One type of compatibility is very common compatibility, in which the two resin blends are completely miscible in molecular affinity and give a transparent film. The present invention encompasses compatibility of the type described herein. The invention also requires and is based on a second and lower degree of compatibility, which is also important. Two-phase opacity (two-phase opacity) of a film made by blending two resins and molding them
-phase opacity) can often be found to appear to be incompatible. Nevertheless, the present invention finds that the blend is strong and tough; the two resins are functionally compatible. This functional compatibility occurs because the two phases are interdependent and are not pure phases of the starting resin. Each phase contains small amounts of the other resin. In fact, there is an equilibrium state in this type of molten two-phase blend with constant movement of molecules across the phase boundaries. One theory suggests that the cooled sample has some molecularly trapped partial passages across the boundary, thereby imparting improved mechanical performance. Most polymer/polymer blends do not exhibit this functional compatibility. Blends such as polyvinyl chloride and polystyrene do not appear to exhibit molecular interdependence in the melt, and in fact exhibit extremely friable, brittle, opaque films. This behavior is the general case. It is part of the present invention to tailor the structure of the modifying resin to match that of the fully cured thermoset to provide good melt working characterstics and functional compatibility. . It is also essential to the invention that said compatibility is not destroyed by the curing process. It is possible to devise polymer-resin blends that are completely compatible (transparent) before curing, but are two-phase (opaque) after curing. The molecular motion that occurs during the curing process allows the resin molecules to reach the best position for chemical curing and at the same time allows the modifier molecules to be rejected into a separate or second phase. do. An essential part of the present invention is to incorporate into the modifier molecule a site that co-cures with the thermosetting resin. Such sites are essential for both fully compatible blends and functionally compatible blends of the present invention. The copolymers in the blends of the present invention consist essentially of ethylene, carbon monoxide, and the monomers (c) a copolymerizable ethylenically unsaturated organic compound and (b) in the amounts described above. Monomers (c) are unsaturated monocarboxylic or dicarboxylic acids of 3 to 20 carbon atoms, esters of such unsaturated monocarboxylic or dicarboxylic acids, saturated carboxylic acids whose acid group has 1 to 18 carbon atoms. copolymerizable unsaturated hydrocarbons such as vinyl esters, vinyl alkyl ethers in which the alkyl group has 1 to 18 carbon atoms, acrylonitrile, methacrylonitrile, and α-olefins of 3 to 20 carbon atoms; and vinyl aromatic compounds. Vinyl acetate is a preferred monomer (c)
It is. Monomer (d) is an ethylenically unsaturated monomer of 4 to 21 carbon atoms containing epoxy groups. Such monomers include copolymerizable unsaturated organic acids, such as epoxy esters of acrylic acid or methacrylic acid; epoxy ethers of vinyl and allyl ethers, such as glycidyl vinyl ether, vinyl cyclohexane monoxide, etc.
or mono-epoxy substituted di-olelefins of 4 to 12 carbon atoms. Glycidyl acrylate and methacrylate are preferred monomers (d). In preparing the copolymers of the present invention, commercially available ethylene, carbon monoxide and 100% pure unsaturated monomers (c) and (d) are initially used and a continuous structure for polymerization is used. A feed stream is used to supply the The reaction vessels used are capable of withstanding high pressures and temperatures and are equipped with high speed motor driven stirrers and pressure relief valves and jacketed walls for circulating heating or cooling fluids to control temperature. The carbon monoxide and other monomers are pumped at reactor pressure into the ethylene monomer feed stream, and the monomer mixture, either together or separately, is pumped into the reactor at reactor pressure. . Catalyst is optionally pumped into the reactor through separate feed lines. The mixture of copolymer and monomer leaves the reactor and the pressure decreases as the mixture flows into the separator. The monomers leave the separator and are either separated or pumped for recycling to the reactor with the constituent monomers. The molten copolymer leaves the separator in a stream and is then cooled and further processed. For example, the copolymer can be cut into appropriately sized particles and placed in a suitable container for shipping. Ethylene, carbon monoxide, monomer (c) to reactor
and (d) and the flow of catalysts is carefully controlled so that they enter the reactor in constant continuous molar quantities and at the same continuous rate as product and unreacted monomers are removed from the reactor. The rates and molar ratios are such that the product copolymer contains 40-90% by weight of ethylene, 0-20% by weight of carbon monoxide, and 5-40% by weight of monomer (c).
and the monomer (d) is adjusted to 0.2 to 15% by weight. Effective agitation is usually provided at a rate of at least 0.25 horsepower per gallon of reactor volume to maintain the reacting monomers in intimate mixing throughout the reactor. Reactor temperature should be at least 140°C. Reactor temperature to approx. 155
-300°C, most preferably in the range of 155-225°C, and reactor pressure of 5000-60000 psi,
Preferably it is maintained within the range of about 20,000-35,000 psi. Preparing the solid copolymers of the invention by keeping the contents of the reactor homogeneous with respect to ethylene, carbon monoxide and the weight ratio of monomers (c) and (d) It is important in None of the monomers should be depleted so that no less than all the monomers are reacting. Since different monomers react at different rates, more reactive monomers will react at a greater percentage in a given time. As a result, the ratio of monomer feed rates will be different from the desired ratio of these monomers in the resulting copolymer. For example, carbon monoxide reacts about five times as fast as ethylene, so that when 10% ethylene is incorporated into the polymer, about 50% carbon monoxide is present in the polymer. The conditions required to make a particular copolymer will vary depending on the reactivity of monomers (c) and (d); for example, vinyl acetate reacts at the same rate as ethylene, whereas methyl Other monomers such as methacrylate react at about the same rate as carbon monoxide or faster. The epoxy-containing monomer (d) can react at various rates between that of ethylene and that of carbon monoxide. The free radical polymerization catalyst used in this method is:
It can be any of the catalysts commonly used in the polymerization of ethylene, such as peroxides, peresters, azo compounds, or percarbonates. Selected compounds within these groups are dilauroyl peroxide, di-t-butyl peroxide, t-butyl perisobutyrate, t-butyl peracetate,
α,α′-azobisisobutyronitrile and other compounds with corresponding free radical activity. Typically, the catalyst is dissolved in a suitable inert organic liquid solvent or mixture of solvents such as benzene, kerosene, mineral oil. Typical catalyst levels are used, ie, about 25 to 2500 ppm, preferably about 75 to 500 ppm, based on the weight of monomer fed to the reactor. For purposes of this invention, it is desirable to understand the nature of blends of two molten polymers. This is because blending is influenced by the molecular properties of the high polymer. Thermosetting resins such as phenolic resins are prepared as medium molecular weight polymers for processing into the desired form prior to the curing step. (These resins cannot be molded after curing.) When attempting to melt and blend an uncured thermoset into a molten thermoplastic, the dispersion of the thermoplastic polymer is This is accomplished by shearing the resin. In order to disperse the molten thermoplastic polymer into very small droplets, the two molten polymers must be separated so that shear forces in the molten thermosetting resin act on the molten thermoplastic resin. There must be an interaction between the two polymers at their mutual interface. This is achieved when each polymer is partially soluble in the other polymer. Otherwise, the thermoplastic resin remains in the liquid as relatively large particles. Therefore, the first requirement of the present invention is
The objective is to find a molecular structure that provides a thermoplastic resin that is partially soluble in the liquid thermoset resin. Curing of a thermosetting resin occurs when thermosetting molecules are chemically bonded through sites that are present on average at more than two sites per molecule. Once the non-reactive thermoplastic polymer is dissolved into the thermoset, these thermoset molecules rapidly move around and displace the thermoset during the curing period. The thermoplastic polymer is thereby forced out of the solidifying thermoset composition. As a result, a two-phase system is formed. One phase is a hardened brittle thermoset matrix. The second phase consists of the previously melted thermoplastic resin. Therefore, the second requirement of the present invention is to introduce into the thermoplastic copolymer reactive epoxy groups that provide sites for the thermoplastic copolymer to participate in the curing process. The thermoplastic copolymer thereby becomes tightly bonded into the cured thermoset resin matrix. In summary, it is intended that the thermoplastic resins described above serve as useful modifiers for thermoset resins. To be effective, it must be partially dispersed on a molecular scale, i.e. it must be partially dissolved in the thermoset resin before curing;
and it must remain substantially dispersed in the thermoset resin after curing. Another point that must be recognized is that there are two useful degrees of dispersion in the sense explained above. One is when the thermoplastic resin is sufficiently dispersed that the resulting blend is transparent after curing. Films molded and cured from such blends are more flexible than unmodified thermosets. It has a moderate and useful degree of elongation before the sample fails, but when the sample fails it breaks brittle without much energy absorption. However, it is well known in the art that rubbery impact modifiers for rigid thermoplastics should be finely dispersed as a separate phase that is intimately bound to the rigid phase. On the other hand, it is even more difficult to make thermosetting resins tough. The present invention adjusts the structure of the copolymers to achieve a similar effect; that is, the copolymers of the present invention are adjusted such that they are only partially soluble in the uncured thermoset resin. obtain;
This includes the discovery that In this case, therefore, after curing, the small agglomerates of the thermoplastic resin according to the invention can absorb impact energy;
In fact, they do so because they too are bonded via reactive sites to the cured thermoset matrix. The copolymers described above can be used to form curable blends with an effective amount of a solid organic thermoset resin selected from the group consisting of phenolic resins, such as phenol formaldehyde resins; epoxy resins; and melamine formaldehyde resins. can. The term "phenolic resin" refers to thermosetting phenolic-aldehyde resins, such as those prepared from phenols, cresols, such as m-p-cresol mixtures, p-cresol or cresylic acid, resorcinols and alhydetes such as formalhyde and furfural. It is meant to include. One-step (Resol) or two-step (Novolak) versions are useful (US Pat. No. 3,438,931). Also useful are phenol-formaldehyde resins modified with alkylphenols (eg, cresol), polyphenols (eg, resorcinol, hydroquinone, etc.), or polyphenols (eg, bisphenol A). These curable blends contain the copolymer 1
~99°C and may contain 1 to 99% thermosetting resin. Copolymer is 5-95% in the blend
present and thermosetting resin in the blend from 5 to 95
% is preferred. Particularly preferred ranges are 10-50% copolymer and 90-50% thermosetting resin. The curable blends described above can be filled with conventional fillers used in thermoset systems. These fillers include wood flour, asbestos, silica, glass fiber, cotton flock, mica, cloth flour and cord, rags, carbon black, or iron,
It may also be a metal such as lead, copper, etc. The curable blends can be used to make flexible, semi-rigid or rigid film coatings, fibers, molded articles, foamed articles and adhesives. The invention is further illustrated by the following examples. Percentages are by weight unless otherwise specified. Examples 1-14 Ethylene, carbon monoxide, vinyl acetate, and the fourth monomer listed in the table are mixed at the feed ratios listed, and the resulting mixture is then mixed with catalyst of the type and amount listed in the table. A copolymer of the above monomers was prepared by feeding the above monomers into a highly stirred reaction vessel of 700 c.c. Reactor pressure and temperature and conversion of monomer to polymer are also shown in the table. Reaction vessel residence time was 4.5 minutes. The melt index of the polymers reported in the table was determined according to ASTM D1238-65T Condition E.

【table】

[Table] Example 15 Novolac phenol resin (Hooker Chemi-
Durez 14000, a powdered two-step phenol formaldehyde resin containing approximately 7% hexamethylenetetramine, supplied by Durez Diυision of the oal Company, with 15% of the copolymer of Example 2.
A blend containing the following was made by dissolving both polymers in tetrahydrofuran. The blend was dried on a hot platen and then pressed into a 2 mil film. While pressing the film
Cured at 165° C. for 15 minutes at 20,000 psi pressure.
The cured film from this blend is clear, indicating good compatibility, and can be bent almost 180 degrees before breaking. This result is in contrast to the behavior of films from poorly modified cured novolac phenolic resins, which are very brittle and break under very small strains. The compatibility properties of this blend contrast with those obtained using ethylene/vinyl acetate/glycidyl methacrylate copolymers without carbon monoxide copolymerization. When this second copolymer is used, an opaque, incompatible blend is obtained, indicating that a carbon monoxide component is essential if a transparent film is desired. The comonomer ratio of this copolymer was 71/22/7. Example 16 A solution blend containing 35% of the polymer of Example 2 and the novolac phenolic resin of Example 15 was made. The blend was pressed into 3" x 3" x 1/8" bars and cured at 150°C for 10 minutes. The bars were cut to 21/2" x 1/2" x 1/8". It was made into a bar. The Izot impact strength of these bars is 0.25ft, lb./inch compared to the value of modified phenolic resin.
It was 0.39ft.lb./inch. Example 17 A 50/50 blend was made from solution using the copolymer of Example 3 and the novolak resin of Example 15. The uncured film, ie, the cast from the solution, is clear, indicating compatibility. This film was cured in an air oven at 110° C. for 20 minutes to obtain a transparent and flexible film. This film can be folded and creased without cracking. The cured film was placed in a beaker containing boiling acetone. This sample remained a film after stirring for 30 minutes, indicating complete curing. Example 18 A 50/50 blend was made on a two roll mill at a temperature of 75°C. 15 g of the polymer of Example 3 was added to Durez
Blend with 15 g of powdered one-step phenolic resin (Resol) supplied as 26164. A 10 mil film was melt pressed from this blend and found to be hazy. This indicates only partial compatibility. This blend was pressed into bars and cured. The Izot impact strength of this bar was 2.5. This is a very high value for a cured polymer. Example 19 15 g of the polymer of Example 3 was added to a powdered two-step phenolic resin (novolac) Durez 22091 15 sold by Hooker Chemical Co., containing no curing agent.
I practiced with g. The blend was pressed into a 10 mil film and then held in the press at 150°C for 1 hour to cure. This film is transparent;
This indicates compatibility and is insoluble in boiling tetrahydrofuran, indicating curing. Example 20 A 50/50 solution blend was made of the polymer of Example 3 with the novolac phenolic resin described in Example 15 containing 8% hexamethylenetetramine. Press a 10 mil film at 100℃ and adjust the temperature to
Raised to 150°C for 30 minutes. The film was transparent. The tensile properties of this film are tensile strength
2150 psi; elongation 60%; tensile modulus 18000 psi. When the broken specimen was returned to its original position, the above elongation was found to be >95% elastic (ASTM D-1708-66 [0.2″/min, crosshead speed]). Example 21 0.5 g of the polymer of Example 1 and an epoxy equivalent weight of about 190 and at 25°C.
1.5 g liquid diglycidyl ether of bisphenol A with a viscosity of 13000 psi (Epon, sold by Shell)
(828) was used to create a solution blend in tetrahydrofuran. 0.15 g of the curing agent triethylenetetramine was added. The solution was evaporated to dryness to form a film. The film was cured by heating on a steam bath for 1 hour. The film was transparent and could be folded without exhibiting brittleness. This behavior was in contrast to the brittle behavior of a similarly made control film without the addition of the Example 1 polymer. Example 22 50% of the polymer of Example 2 and 50% of a melamine-formaldehyde resin, hexamethoxymethylmelamine (Cymel 301) sold by American Cyanamid.
A solution blend was made in tetrahydrofuran of As a curing catalyst, p-toluenesulfonic acid was added at a concentration of 0.25% by weight excluding the solvent.
This solution is coated onto aluminum, dried and cured for 1 hour at 150°C. The resulting film was very slightly hazy, flexible, and could be folded without cracking. A similar film containing only melamine formalhyde resin and catalyst was coated onto aluminum and cured. In contrast, this film was very brittle and cracked when the aluminum was bent. Examples 23-30 A series of tetrapolymers were prepared according to the method of Examples 1-14. Polymer composition and reaction conditions are summarized in the table

【table】

[Table] Comparative Example 1 and Examples 31 to 33 Wood flour and two-step (novolac) phenolic resin
Created a blend of phenolic resins based on a 50/50 blend. Eight parts of hexamethylenetetramine was added during the blending process to act as a curing catalyst. All blends contain 40% wood flour for comparison purposes. An additional amount of novolak phenolic resin was used in place of the tetrapolymer of the present invention. With the exception of Control Example 1, a polymer of the invention was added to replace a portion of the phenol. Bar 1/8″×1/2
″×5″ was molded at 100°C and cured at 160°C for 10 minutes. The results shown in the table show that higher flexural strengths and higher flexural strains at failure can be obtained with only a slight reduction in the elastic modulus (Example 31); It can be found that a significant increase in the bending strain at failure, a large decrease in the modulus of elasticity, accompanied by a decrease in the bending strength can be obtained (Examples 32-33).

Table Comparative Example 2 and Examples 34-36 Blends of phenolic resin containing wood flour as in Examples 34 and 32 were molded into 1/8" black and cured as described above. The blacks were tested (Gardner Test) with a falling spear weighing 1/4 pound to determine the height at which cracks appear on the back side of the black.The results in the table include:
It has been shown that the energy to rupture can be increased by a factor of 2-3 or more depending on the structure of the added polymer.

[Table] Polymer

[Table] Polymer
36 Tetra of Example 30 25 5.5
polymer
Comparative Example 3 and Examples 37-39 A commercial grade phenolic resin is compounded with medium length glass fiber filler and various additives for electrical applications, among others. This formulation is coded Durez23570. Three types of tetrabolimers and two types of turbolimers of the present invention were added at 20% of the total composition. For comparison, 20% pure novolac resin was added to obtain a control with the same amount of fillers and additives. Samples were molded, cured, and tested for electrical properties. In the table it is shown that the electrical properties must not be impaired to a significant extent. However, the volume resistivity is improved by at least 5 times.

Table: Examples 40-42 Elastic cured products can be made when the phenolic resin is less than 50% of the blend. Examples of such behavior are shown in the table. % elongation to failure is 100-200%, and the elastic recovery of this elongation after failure is about 90%.

Table Comparative Example 4 and Examples 43-45 Commercially available epoxy resins were filled with glass fibers and pelletized for injection molding (Fiberite
E2748). Blends were made and evaluated as shown in the table.

Table: Control Example 5 and Examples 46-48 Blends were made on a two roll mill using glass fiber filled phenolic resin FM1005 manufactured by Fiberite Corporation. All examples were tested at 20%, including control example 6 such that all examples contained the same amount of glass fiber filler.
Contains % additives. Molding the bar at 100℃,
It was then cured at 160°C before testing. The results in the table indicate a combined increase in flexural strength, strain to failure, and optionally impact toughness, or a combined increase in flexural modulus and strength depending on the structure of the additive. It can be seen that a large increase in toughness can be achieved.

【table】

Claims (1)

[Claims] 1 A curable blend of an ethylene copolymer and an organic thermosetting resin, wherein the blend comprises substantially (a) 40 to 90% by weight of ethylene; (b) 20% by weight of carbon monoxide.
(c) unsaturated monocarboxylic or dicarboxylic acids of 3 to 20 carbon atoms, esters of such unsaturated monocarboxylic or dicarboxylic acids, not exceeding 1% by weight;
Vinyl esters of saturated carboxylic acids with up to 18 carbon atoms, vinyl alkyl ethers with alkyl groups of 1 to 18 carbon atoms, acrylonitrile, methacrylonitrile, α-olefins with 3 to 20 carbon atoms, norbornene and (d) epoxy groups; and 5 to 40% by weight of monomers selected from the group consisting of Copolymers 1 to 1 consisting of 0.2 to 15% by weight of ethylenically unsaturated monomers of 4 to 21 carbon atoms containing
99% by weight and 1 to 99% by weight of an organic thermosetting resin, and the copolymer is at least functionally compatible with the thermosetting resin, and the resin is a phenolic resin, an epoxy resin. and melamine formaldehyde resin.