DE2440580A1 - CHEMICALLY RESISTANT WARM-CURING RESINS, PROCESS FOR MANUFACTURING THE SAME AND MOLDED BODIES - Google Patents

Description

PATENT AGENCY BUBO TlEDTKE - BüHLING "KlN

TEL. (089) 53 96 53-56. TELEX: 524 845 tlpat CABLE ADDRESS: Germaniapatent Munich

8000 Munich 2

Bavarlaring 4

Postlach 202403, 23 August 1974

B 6182

Uniroyal, Ltd. Don Mills, Canada

Chemically resistant thermosetting resins, methods for making the same and formed therefrom

Moldings

The invention relates to chemically resistant, thermosetting resins based on polymerizable Vi äthy-? lenically unsaturated resin-like esterification products of polyol components and acid components, which are particularly used in Mixture with copolymerizable vinyl monomers and processes for the preparation of the same and those under Hardening of the material formed products or moldings.

In some respects, the invention is aimed at development respectively·. Providing an improved alternative to the manufac-

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conventional unsaturated polyester resin systems. Conventional unsaturated polyester resins are based on polycondensation products of dibasic carboxylic acids with dihydric alcohols. In the process, essentially linear polymer chains are formed, which have numerous ester groups from Maleate or fumarate types that contain unsaturated groups for crosslinking, as well as other ester groups such as phthalate and adipate, which do not participate in the crosslinking take part. Such polymers are polymerizable with liquid Monomers mixed for the production of resins, which by the action of heat, light, more energetic Radiation, free radical generators or compounds that generate free radicals and others in patents and the literature means that are extensively described are curable to hard, insoluble, infusible solids.

However, such cured resin products usually do not show any resistance to reactive ones Chemicals, especially aqueous solutions of strong acids and bases. Attempts to improve the chemical Resistance of these resins are mainly due to a reduction in the number of ester groups, introduction of water-repellent Groups and ether groups or formation of steric hindrance around the ester groups in the linear Polymer chain directed. For example, resins made from isophthalic acid instead of ortho-phthalic acid

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and / or hydroxyalkylated bisphenol instead of simple aliphatic glycols produced unsaturated Contain polyester, a noticeably improved chemical resistance. However, such resins contain still linear polymer chains with ester bridges, which are susceptible to splitting by chemical attack are. The breakage of any such ester group ruptures the polymer chain, drastically diminishing it Molecular weight and causes deterioration in physical properties.

The present invention therefore relates to the formation of a "polymer backbone" which consists merely of alternating aromatic and aliphatic carbon or Hydrocarbon units is made up of with appending Side chains that contain polymerizable vinyl groups in the form of acrylic acid (including © (-substituted acrylic acid -) - carry ester linkages. A breakage of the same thus does not lead to the polymer backbone chain tearing open. The polymers of the invention are also compatible with vinyl monomers compatible with styrene and methyl methacrylate and copolymerizable to form clear hard ones

solid thermoset materials that are similar to conventional cured linear polyester resins. The invention However, due to their new polymer structure, products show excellent resistance to

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chemical attack and are therefore surprisingly superior to the known products.

Monoesters of acrylic acid and methacrylic acid have long been known. Methyl methacrylate is one of the most useful monomers in the polymer industry. Other acrylates and methacrylates are also very important monomers and the number and uses of these compounds are steadily increasing. (LS Luskin and RJMeyers "Acrylic ester polymers" in Encyclopedia of Polymer Science and Technology, Vol.1, S _e ith 246-328, Interscience, NY 1964).

Diacrylate and dimethacrylate esters are also found to be important monomers as crosslinking agents. They are made smooth from the diol precursors and are usually more stable at room temperature than the conventional bifunctional crosslinking monomers such as divinylbenzene.

The range of polyacrylate and polymethacrylate esters is because of the special difficulty in the Isolation of these products has not been researched equally well. Acrylates and methacrylates are opposite one another heat-induced polymerization very susceptible. For this reason, the low-boiling points can be distilled

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Diacrylates and triacrylates and the corresponding methacrylates have been studied intensively, while only relatively little work done in the field of poly (meth) acrylates became.

According to the invention resinous esterification product of hydroxyl components (A) and acid components (B) is now a new and surprisingly useful polymerisi erbares ethylenically un-r saturated provided, which is characterized in that component A is a polyol, the reaction product through a R _€ the end

(i) an alkylene oxide and (ii) a novolak resin

is formed, the amount of (i) being at least 1 mole but not more than 1.2 moles per phenolic nucleus in (ii) and

component B is a fully monocarboxylic acid material selected from the group consisting of

(a) a <Xjß-ethylenically unsaturated monocarboxylic acid and

(b) a mixture of (a) with up to 10 % - based on the weight of (a) - of a saturated or aromatic monocarboxylic acid

is selected.

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The invention further includes addition homopolymers of the esterification product described.

According to other aspects the invention relates to a liquid mixture that contains residues addition product dissolved in a copolymerizable vinyl monomer that described polymerizable ethylenically unsaturated V _e and also addition copolymers of such a liquid mixture, as well as shaped articles such as castings, laminates, impregnations and resin-impregnated moldings or coatings, such addition copolymers include.

The invention also includes a method of making an unsaturated resinous product by mixing the polyol (A) and the acid (B) in an inert organic solvent, heating the a mixture containing a strong acid as an esterification catalyst and a polymerization inhibitor to their boiling point to bring about esterification, removal of (esterification) water and solvents of the mixture, dissolving the residue in a vinyl monomer, adding sufficient anhydrous Potassium carbonate to neutralize the acid catalyst with the formation of an insoluble potassium salt in the Mixing and separating the insoluble material from the mixture to obtain the preferred mixture of Esterification product and monomer.

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Another embodiment of the invention comprises a method in which the esterified or esterification mixture cooled after removal of the esterification water to a temperature 10 to 30 ° below its boiling point, the Potassium carbonate was added, the insoluble material separated off and the solvent removed under reduced pressure so as to obtain the esterification product itself.

According to yet another aspect, in the process according to the invention, a Excess (e.g. a 10 to 20% stoichiometric Excess) of unsaturated acid is used in order to increase the rate of esterification and the rate of esterification An alkylene oxide is added to the reaction mixture in sufficient quantity to neutralize the ester formation stage remaining free unsaturated acid (B) added. The excess acid (B) is so by the effect of the alkylene oxides converted into a hydroxyalkyl ester. This ester remains in the final mixture and acts as a monomer in subsequent curing operations. That way it becomes a waste of no spent acid avoided.

The present invention thus relates to acrylic acid esters (including oC-substituted Acrylates) from certain novolak resins derived

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Polyhydroxy compounds and processes for their production, isolation and subsequent hardening-if necessary. in the presence of vinyl monomers-to usable thermoset materials for castings, laminates, moldings, Coatings or coatings and other uses of unsaturated polyester resins are suitable.

The resins of the invention are very similar in their reactivity and physical properties to the conventional unsaturated polyester resins. Both are stable liquids of low viscosity in the uncured state and can be cured in any one of a number of the person skilled in known ways (for example by use of radical formers, either at elevated temperatures or at ambient temperatures through the use of accelerators) hard to clear virtually infusible three-dimensionally crosslinked copolymer resins. Furthermore, the resins according to the invention can be used to form castings, laminates, coverings or the like, with or without mixing with non-reactive fillers, pigments, viscosity modifiers and the like in the manner of conventional unsaturated polyester resins

are processed.

However, the chernj ff-tif ¹ character of these reactive resins according to the Er ir.iiunn differs in consideration

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their own chemical structure and significantly improved resistance to strong acids and Alkalis substantially different from that of unsaturated polyester resins currently known to those skilled in the art. So based conventional linear unsaturated polyester resins based on cx_, ß_unsaturated dicarboxylic acids such as fumaric acid and Malienic acid, which can be smoothly esterified with suitable diols in a melt reaction without the risk of There is homopolymerization of the fumarate or maleate groups. In contrast, the new resins described here are based on α, β-unsaturated monocarboxylic acids such as acrylic acid (and in particular, σί-substituted acrylic acids), which homopolymerize at elevated temperatures without the addition of catalysts, if special precautions are not taken is and thus usually not esterified at such elevated temperatures or without a solvent can be.

The o (, ß-unsaturated monocarboxylic acids are mixed with

Resin-like polyols implemented by treating. Novolak resins with 1 to 1.2 moles of an alkylene oxide per equivalent of phenolic hydroxyl in the presence of strong

Base can be produced. The final structure of this

Resins are not fully known, but it is believed that they include bodies of the following composition:

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where R and R ^{1 are the} same or different and are hydrogen or alkyl (e.g. methyl, ethyl, propyl etc.), R ″ represents hydrogen or aryl (e.g. phenyl, tolyl etc.), X is an alkyl group with no more than 3 carbon atoms ato - ien (methyl, ethyl, propyl, isopropyl) or halogen (e.g. chlorine, bromine etc.) and η ranges from 1 to 10 (inclusive) and m from 0 to 2 (inclusive). The formula represents a 100 Sig esterified body which is believed to be present in a certain amount even in products where the mean degree of esterification is less than 100 % .

The ethylene bridges are assumed to be in the ortho and para positions of the aromatic nuclei

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sit and possibly with some cores all three positions with branching of the "novolak backbone" be used.

The novolak resin used is a conventional material and can be described as a permanently meltable and soluble product obtained by reacting less than 6 moles of formaldehyde per 7 moles of phenol in an acidic medium (High polymers, Vol. VII, Phenoplasts, Carswell, p .29, Interscience Publishers, 19 ^ 7). The ratio of phenol to formaldehyde is usually 1.2 to 1.6, preferably 1.21 to 1.3. The melting point range of the novolak resin often ranges from 90 to 120 °. In many cases the average molecular weight is 500 to 1000 (according to the osmometrically determined solution vapor pressure). Modified novolaks, such as those obtained from halogenophenols such as p-bromophenol and certain alkylphenols such as p-cresol, can also be used, provided that the alkyl group (X in the structural formula above) is no longer used . coals than 3 *: · U "Mn having tome (otherwise a novolak of the invention -ut erforderiichen according to Art is not obtained) Other aldehydes such as benzaldehyde W Rinon also instead of ^Formaldehy; are rwendet ν..

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BATH ORIGINAL

£ 440 580

The reactions of phenols and polyphenols with alkylene oxides of the type

CH ₀ -CR ¹

■ \ V

where R ^{1 is} hydrogen or alkyl for producing β-hydroxyalkyl derivatives of the type

Ar t

0 1

CH ₂

R'- CH

OH

are known. Such reactions usually require a strongly basic catalyst such as an alkali metal hydroxide or tetrasubstituted ammonium hydroxide and can under atmospheric pressure, but preferably under self-generated pressure when volatile alkylene oxides such as ethylene oxide or propylene oxide be used. Propylene oxide is the preferred compound in the context of the invention. For the purpose of In the invention it is important that all of the phenolic hydroxyl groups are reacted because of the presence such groups in the final resin would cause an inhibition of the curing processes. The hydroxyalkylation

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the novolak can be used in conventional manner using at least 1 mole of alkylene oxide per mole of phenolic hydroxyl groups (to ensure the conversion of all the phenolic hydroxyl groups of the novolak in alcoholic hydroxyl groups) but not more than 1.2 moles of alkylene oxide (for V _e rmeidung the formation of hydrophilic properties in Product). Suitable alkylene oxides include ethylene oxide, propylene oxide (preferred), 1,2-butylene oxide, etc. The polyhydroxy resins obtained as products of this reaction are known to interact with and with carboxylic acids including certain unsaturated fatty acids and maleic acid which are not susceptible to homopolymerization Mixtures of acrylic acids and dicarboxylic acids can be esterified. The complete or exclusive esterification of these resins with acrylic or ot-substituted acrylic acids is associated with difficulties in view of the gelling of the reaction mixture as a result of premature polymerization of the acrylic acid esters or acrylic acids under the esterification and isolation conditions.

To esterify and isolate the esters of acrylic acids without polymerization by the vinyl groups To achieve this, it was previously necessary to use a high concentration of radical inhibitors such as hydroquinone

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use, which must be removed again in a later stage in order to allow the polymerization of the unsaturated ester. Removal of inhibitors is usually difficult if premature gelation is to be avoided. While the mono-, di-, and tri-esters of acrylic acids can be distilled, this is not the case with the present polyester product. In the present process, therefore, the volatile materials are separated and the product is left behind. To prevent premature gelation, three important variables need to be controlled: (i) The solvent, with which the reactive components are diluted, (ii) the temperature at which the R _e is performed action, and (iii) the applied amount of inhibitor. The solvent is used to dilute the reaction mixture and allows temperature control by reflux. It also serves as a component for an azeotropic separation of water of esterification. In the process according to the invention, a solvent is used which keeps all components in solution with one another (to carry out the esterification), forms an azeotropic mixture with water (preferably a two-phase azeotrope) and has a boiling point

Range from 80 ° to 130 °. By studying the effects of the variables on the chemical resistance of the In the final resins, benzene and toluene were found to be preferred solvents in the process of the present invention

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are, albeit in addition to these hydrocarbon solvents such chlorinated solvents as 1,2-dichloroethane and 1,1,2-trichloroethane are also used can be. These are generally used in amounts from about 100 or less to 100 or more ml used per g-mole of hydroxyalkyl novolak. It has been found that the optimum value is about 350 ml / g-mol. However, for the sake of ease of handling and removal, there are no solvents after the reaction has ended about 15C ml / g-Hol a suitable amount. The esterification reaction is conveniently carried out at the reflux temperature of the mixture. The during the The inhibitor present in esterification is suitably a radical polymerization inhibitor of the phenolic type such as tert-butylpyrocatechol, hydroquinone monomethyl ether etc. and hydroquinone. Generally one is small amount of inhibitor is sufficient for the present purpose, provided that the other two variables are suitably matched and the inhibitor does not have to be removed at the end of the reaction. Usually lies the amount of inhibitor used (preferably hydroquinone) at about 100 to 6CO ppm - based on the weight of the final resin - the optimum concentration is around 500 ppm.

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The preparative method usually involves dissolving the polyhydroxy compound and alkenoic acid (usually either acrylic acid or methacrylic acid) in the solvent (usually benzene or, more preferably, toluene). The acid is usually used in excess of the amount stoichiometrically required to produce the desired degree of esterification, ie 1.1 to 1.2 equivalents of acid per hydroxyl group of the polyhydroxy compound to be consumed in the esterification. The inhibitor (usually hydroquinone) is added and then a small catalytic amount of an esterification catalyst, usually formed by either p-toluenesulfonic acid or sulfuric acid. A slow stream of nitrogen is bubbled through the solution, which is brought to reflux. The water evolved during the esterification is removed from the esterification reaction mixture, conveniently in the conventional manner by separation from the condensed liquid reflux stream by gravity or density before the stream returns to the reaction vessel. The degree of esterification can be conveniently adjusted to any desired level, for example 20 to 100 %, typically 60 to 100 %. After the desired degree of esterification has been achieved by separating off an appropriate amount of water of esterification, the reaction mixture is reduced to 10 to 30 ° below its

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Cooled the reflux point temperature, enough potassium carbonate to neutralize the acid catalyst added, the resulting insoluble material removed (e.g. by decanting or pouring off, filtering or Centrifugation) and then the solvent is separated off under reduced pressure. The esterification product is usually a viscous liquid. This unsaturated ester can then, if desired, in a suitable amount of unsaturated monomers such as styrene etc. are dissolved to give the final resin, or the ester itself is homopolymerized will. .

Alternatively, the resin composition can be obtained by slightly modifying the above procedure. So will the solvent is separated off under reduced pressure after the esterification has ended in order to obtain the unsaturated one Esters with an acid catalyst still present in them, It has been found that the strongly acidic catalyst such as sulfuric acid acts as a polymerization inhibitor, presumably destroys any potential radical formers. In this way you can get harsher conditions for removing residual solvents from the ester

use. The ester is then together with the acid catalyst in such an amount of an unsaturated Monomers dissolved so that good flowability is achieved and the acid catalyst is at elevated temperature

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neutralized to form an insoluble potassium salt in the mixture. After removing the insoluble matter, the resin can be further diluted with an appropriate amount of the monomer as desired. In many cases it is noticed that the styrene ionomer has a stabilizing effect.

As indicated, the use of a slight excess of unsaturated acid in accordance with the preferred practice described has the advantage of increasing the rate of esterification in accordance with the law of mass action. Thus, for a degree of esterification of X %, about 1.1 X to 1.2 X % of the acid is generally used. This significantly increases the rate of the reaction compared to using a stoichiometric amount of acid. Especially for degrees of esterification of 20 to 100 % , a 10% excess of acid would be achieved by using 0.22 to 1.1 equivalents of acid per hydroxyl group to be esterified, while a 20 % excess would be achieved by using 0.24 to 1.2 equivalent acid would be achieved. In accordance with the invention it has been found that the excess acid can be exploited by conversion (in situ) to its hydroxyalkyl ester which serves as a monomer in the final resin composition. So will the excess

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from 0.1 X to 0.2 X % of unreacted acid after advancing esterification to the desired level, preferably by exposure to an alkylene oxide (e.g., ethylene oxide, propylene oxide, 1,2-butylene oxide, etc.) converted to the hydroxyalkyl ester. This ester then serves as a monomer. In this way, the unreacted excess of acid can be used more expediently than that it is lost by neutralization with potassium carbonate in a later stage.

The acrylic acid used in the context of the invention for the esterification of the modified novolak resin is preferably an ot-substituted acrylic acid, of which methacrylic acid and ethacrylic acid are examples. It appears that οι substitution gives the ester better chemical resistance, probably by introducing some steric hindrance around the ester groups.

According to a modification of the invention, the acid component of the esterification mixture can be a mixture of the unsaturated Monocarboxylic acid with a saturated or

aromatic monocarboxylic acid. It has been found that a necessary condition for such to be saturated or aromatic acid together with the alkenoic acid on the

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Esterification takes part, is that the saturated or aromatic acid has a boiling point which is approximately equal to or higher than that of alkenoic acid. To suitable saturated or aromatic Monocarboxylic acids include, for example, propionic acid, butyric acid, isobutyric acid, valeric acid and higher Homologues as well as benzoic acid (preferred), o-, m- and p-toluic acid and higher homologues. The monocarboxylic acid can form up to 10% by weight of the two types of acid. The purpose for using a saturated monocarboxylic acid is twofold: you can increase the crosslink density of the resin by replacing part of the unsaturated Press down acid and thus, if so desired, result in a flexible product, at the same time as an elimination of free hydroxyl groups. So you can in turn by suitable selection of the saturated acid Introduce hydrophobic properties into the resin structure while achieving better chemical resistance.

The use of solid anhydrous potassium carbonate as described has been found to be a preferred one Proven means for neutralizing the esterification mixture.

After suitable or thorough neutralization of the esterification product with potassium carbonate as

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wrote, the acid number is very low. Its hydroxyl content depends on the degree of esterification. The experimentally determined hydroxyl number of the product is satisfactory with the value calculated or estimated from the degree of esterification.

The esterified products are compatible in all proportions with vinyl monomers commonly used together with conventional polyester resins. The present esters can be mixed with monomers such as styrene or substituted styrenes (e.g. vinyl toluene, chlorostyrene), alkyl (e.g. methyl, ethyl, butyl etc.) esters of alkenoic acids such as acrylic acid, methacrylic acid and ethacrylic acid ( e.g. methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate etc.) or with the alkenoic acids themselves (e.g. acrylic acid, methacrylic acid), or nitriles of the same (such as acrylonitrile, methacrylonitrile), vinyl acetate, diallyl phthalate, vinyl pyridine, triallyl cyanurate, diethyl fumarate, ethyl acrylate or the like, ethyl acrylate or diacrylate copolymerizable monomers as described, for example, in GB-PS 9,11067 of the United States Rubber Company of November 6, 1963, page 3, line 5 ^ to page 4, line h9 . More than one such vinyl monomer can be mixed with the esterification product of the present invention, if desired. The amount of the copolymerizable mono-

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meren is often in the range from 10 to 70%, preferably 20 to 60 %, in particular 25 to 50 % (based on the weight of the mixture).

The usual radical polymerization initiators can be used to convert - either the esterification product or the mixture of the esterification product with copolymerizable vinyl monomer material to form an addition homopolymer or copolymers can be used. In this way, these resins can become three-dimensional, infusible, chemically resistant, thermoset products are hardened. Useful moldings of all kinds including castings, coatings or coatings and the like can be produced in this way. Any of those for hardening more conventional Common catalysts used in polyester resins can be used in the present resins. Examples include the peroxides (e.g. benzoyl peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, hydrogen peroxide, Potassium persulfate, cumene hydroperoxide, tert-butyl perbenzoate, Azo compounds (e.g., 2,2-azobisisobutyronitrile), ultraviolet radiation, and equivalents conventional sources of free radicals. The hardening can at room temperature (e.g. with a combination of methyl ethyl ketone peroxide and cobalt naphthenate as Accelerator or a combination of cumene hydroperoxide and manganese octoate) or at an elevated temperature.

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Fillers or other reinforcing agents such as fibers can be used or combined together with the resinous composition before curing to increase the strength of the product, such as in particular glass fibers, either as chopped fibers or in form. a mat or fabric. The castings or glass fiber laminates produced in this way from these resins have good physical properties. The new resins are much more resistant than conventional polyester resins to aqueous sodium hydroxide, aqueous nitric acid or tetrachlorethylene at ICO ⁰ . Table I shows a comparison of the chemical resistance of the resin according to the invention with that of the conventional polyester resins. In Table I, resin (a) is a commercially available polyester resin based on hydrogenated bisphenol-A, resin (b) is a commercially available polyester resin based on propoxylated bisphenol-A and resin (c) is a commercially available polyester resin based on epoxy acrylates 'while the resin (d) is a resin according to the invention (according to Example 2, resin C-> see below). All of these resin compositions contain hC % by weight styrene. The reagents HCl, HNO ^ "and NaOH used for the test were used as 10% strength aqueous solutions. The reagent TCE is tetrachlorethylene. The figures given give the percentage retention of the flexural strength of the cured resin after immersion

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same in the reagent for 9 weeks at 100 again. When testing the heart (a) in tetrachlorethylene was the sample destroyed in 5 weeks *. It can be seen from Table I that the resin (d) according to the invention is superior Shows retention of flexural strength when exposed to different corrosive media.

TABLE I.

Resin chemical resistance: (a) (b) (c) (d)

Reagent:

The following examples are provided to more specifically illustrate the practice of the invention. All temperatures are given in ⁰ C, unless stated otherwise.

example 1

In a 12 l resin kettle with a high-performance mechanical stirrer, a, thermometer and two powerful reflux condensers was a mixture of phenol

70 65 82 73 6k 56 72 80 36 h6 12th 68 0 86 77 86

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(3020 g; 32.1 M) 37% strength aqueous formaldehyde (2075 g; 25.6 M) and oxalic acid dihydrate (30 g) were added. The entire mass was heated to 80 °, at which temperature the heating was interrupted. An exothermic reaction and the solution began to reflux. After about 2 hours, the heat dissipation subsided and the supply of heat was resumed to continue the reflux treatment for a further 2 to 3 hours. The reaction mixture was left to stand overnight and the upper aqueous layer was siphoned off or removed with the aid of a siphon. The lower resinous mass was heated with stirring. Water and unreacted phenol were separated under reduced pressure until the final pot temperature reached 200 °.

The resulting novolak resin was diluted to about 160

cooled and with 35% methanolic benzyltrimethyl-

i ammonium hydroxide (30 g) was added and mixed carefully. Propylene oxide was maintained at between 140 ° and 160 ° The mass was added dropwise at a rate such that a gentle reflux was obtained. About 2400 ml of propylene oxide (about 35 M) was approximately

10 hours added. After the addition, the volatile methanol and other materials were over at 170 ° / 25 torr Separated over 15 minutes to give a product with a hydroxyl number of 310.

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The resulting propoxylated novolak was mixed into toluene (45OC ml). A solution of concentrated sulfuric acid (46 ml) in methacrylic acid (2750 g; 32 mol) was quickly added, followed by hydroquinone (5 g). The homogeneous solution obtained by heating was brought to the boil under reflux (about 115 °), while it was kept under a nitrogen atmosphere, and the esterification was followed or carried out by azeotropic separation of water. The refluxing was stopped after A _u fsammelung of about 400 ml of water (about 90% esterification). The solution was allowed to cool to 90 ° and anhydrous potassium carbonate (225 g) was slowly added. The entire mass was stirred for 1 hour and then allowed to settle. The insoluble materials settled to the bottom and the clear upper solution was poured off or decanted. Alternatively, the insoluble materials can be separated by filtration or centrifugation. The removal of solvent at 60 ° / 15 torr gave 7500 g of unsaturated ester with a hydroxyl number of 50 and an acid number of 20.

Example 2

The polyester resin of Example 1 was dissolved in various amounts of styrene, as shown in Table II are indicated in which S is the percentage of styrene (based on the weight of polyester + styrene) in each of the

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Resin Compositions A to E represent. V denotes the Brookfield viscosity of the resins measured at 25 ° (in poise). The compositions were cured with 1% benzoyl peroxide at 82.2 ⁰ C (18O ⁰ F) and the gel time (GT), the curing time (CT) and the Exothermpeak (PE; ⁰ C ⁽⁰ F)) were prepared by the standard methods of Society of Plastics Industry determined for recording exothermic curves (SSOleesky and JGMohr in · SPI Handbook of Reinforced Plastics, New York, 1964, page 51, Appendix HI.1); the results obtained are shown in Table II. ^l

TABLE II Cure of Polyester-Styrene Blends

Resin: A B C D E

P. 33 37 41 46 51

V 2.22 0.90 C, 70 -

GT 6'21 "5'44"5'5I ^- 4'48 "5'31"

CT 11'48 "10'59 ^M 10'18"9'46"10'5O"

PE 95.6 ° 102.2 ° 108.3 ° 110.6 ° 112.2 ° (20AO) (2160) (227 °) (231 °) (234 °)

Example 3

Har ^ o A, B, C and * D, as described in Example 2, were hardened between glass plates to achieve 3.2 mm O / P ") thick castings in the usual way. You can m-n with 2 % benzoyl peroxide ( 50% paste)

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70 ° C for 5 to 6 hours and then post-cured for another 10 hours at 100 °. To cure the castings at room temperature, a combination of 2.5 % cumene hydroperoxide and 0.5% manganese octoate (based on volume) was preferred. This room temperature curing generally gives a gel time of 3 to 5 hours. The hard castings obtained by curing at room temperature were then post-cured at 100 ° for 5 to 10 hours. Table IH summarizes the physical properties of the castings after post-curing at 100, namely BH the Barcol hardness, FS the flexural strength at room temperature

2 2

in kg / cm χ 10 ~ and (according to ASTM D648-61).

2-2

in kg / cm χ 10 ~ and HDT is the heat deformation temperature

TABEL III D. properties of Castings 35-40 Resin: AWAY C. - bra 30-35 30-35 35-40 100 ° FS 6.7 - HDT 114-120 ° 110-117 ° 117-118 ° Example i > «

Resins A, B and C as described in Example 2 were used to make glass mat laminates with 25 % glass according to ASTM C-581-68. A mix of

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2.5% cumene hydroperoxide and 0.5% manganese octoate used for curing at room temperature overnight with subsequent post-curing for 6 hours at 100 °. The laminates had a flexural strength between

2 2
8.4 and 9.9 x 10 kg / cm. The Barcol hardness of the laminates

varied between 45 and 50.

Example 5

The chemical resistance of those produced according to Example 4 Laminates were made by immersing them in different media at 100 ° for different Times determined using the method specified in ASTM C-581-68. The results are in the following Table IV reproduced for resin compositions A, B and C according to Example 2. The bending

2-2

strength at room temperature in kg / cm χ 10 ~ as well as after immersion in the various reagents for the specified times (for the test were. 10% sodium hydroxide solution, IC? 4 nitric acid and tetrachlorethylene (TCE) used).

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Resin: TABLE IV of glass-resin laminates C. Chemical untreated resistance B. 10.1 NAOH A. 8.6 3 weeks 8.9 8.2 5 weeks 8.2 7.5 9 weeks 8.5 7.0 6.8 ENT ₃ 7 ,? 6, c 5 weeks 6.5 8, 4 9 ^w ochen 7.7 7.2 TCE 8.6 7, A 5 weeks 7.7 9.1 9 weeks 7.5 7.9 8.5 7.8 7.0

Example 6

Propoxylated novolak according to Example 1 was mixed into 4500 ml of toluene. A solution of more concentrated Sulfuric acid (46 ml) in methacrylic acid (2750 g; 32 M) was added quickly followed by hydroquinone (5 g). The homogeneous solution thus obtained was brought to the boil Heated to reflux while keeping it under a nitrogen atmosphere and the esterification was azeotropic Separation of water followed or carried out. The reflux treatment was started after collecting approximately 460 ml of water

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canceled. Propylene oxide (300 ml) was then added to the solution to esterify excess methacrylic acid to hydroxypropyl methacrylate added. Toluene was separated under reduced pressure at 90 °. Then became styrene (1000 g) are added and the solution is treated with anhydrous potassium carbonate (50 g) at 100 and 30 minutes long stirred. Additional styrene (400 g) was added and mixed thoroughly. After allowing the solid to settle Materials on the floor the resin was poured or decanted. About 125CO g of resin were obtained. Esterification and mixing took 6 to 8 hours to complete. the Hydroxyl number 1-j / t at about 5C, the acid number at 20.

Example 7

Phenol (26CC g; 27.7 M), paraformaldehyde (91%; 730 g; 22.3 M) and toluene (3C0 ml) were placed in a 12 liter resin kettle with the equipment described in Example 1 above. The mixture was warmed to RO ⁰ and a solution of p-toluenesulfonic acid (300 mg; V / water 2 ml) was added. An exotherm occurred and the temperature of the reaction mixture was maintained at about 60-65. In about 1 hour the exotherm subsided and the resin mixture was slowly heated to reflux conditions and the water formed during the reaction was removed azeotropically with toluene. About U6C ml of water was obtained in about 5 hours. Toluene was through

B09810 / 0833

Separated distillation. The novolak resin obtained as the residue was propoxylated and esterified in the manner of Example 6. The novolak resin obtained in this example was almost identical to the material obtained in Example 1. The final resin obtained also had properties equivalent to Resin C of Examples 2 and 3; For example, castings obtained from this resin with 40 % styrene and hardened with a combination of cumene hydroperoxide and manganese octoate had a Barcol hardness of and a heat deformation temperature of 120.

Example 8

p-Bromophenol was reacted with paraformaldehyde in the same manner as in Example 1 except that the amount of p-toluenesulfonic acid was increased. p-Bromophenol (930 g; 5.4 M) paraformaldehyde (162 g; 4.9 M) and toluene (2CO ml) were thus placed in a 3 l resin kettle and a solution of p-toluenesulfonic acid (3 g) in water ( 3 ml) added. In this case, no heat generation was observed. The R _P action mixture was heated to boiling under reflux and the water evolved azeotropically with it

Toluene removed. Toluene was removed by distillation and the novolak resin that remained was propoxylated and esterified as in Example 6. The resin (with 40 % styrene)

509810/0833

was similar to Resin C of Example 2 and cured rapidly with cumene hydroperoxide and manganese octoate.

The value of the "oxygen index" (a measure of the Flammability) was determined for the cured resin (according to ASTM-D-2863); the obtained value of 24 speaks for a slight improvement over the oxygen index for Resin C of Example 2, which was found to be 22.

Example 9

Different novolak resins with varying proportions of original phenol to formaldehyde were prepared according to Example 1. The molar ratios were between 1.2 and 1.6. Ratios in the vicinity of 1.2 produce higher-melting novolaks and the propoxylation of the higher-melting novolaks is carried out at temperatures close to 20.0 °. The novolaks were propoxylated and esterified as in Example 6. A statistical analysis of e _r gebnissc indicates that a ratio of 1.25 is optimal for the best chemical resistance.

Example 10

Novolak resin was prepared as in Example 7. The novolak (488 g; 4.0 M) was in a 3 1 reaction kettle with a mechanical stirrer, reflux condenser, Thermometer and gas inlet tube heated to 170 ° and

5 09810/0833

touched. 35% methanolic benzyltriethylammonium hydroxide (7 ml) was added dropwise so that the methanol was slowly removed and the temperature at 170 ° was held. Ethylene oxide was slowly added through the gas inlet tube and with the novolak reacted at 140 to 170 ° until the theoretical weight (205 g; 4.5 M) was consumed.

The product was treated with methacrylic acid (345 g; 4.0 M), as described in Example 6, esterified using 500 ml of toluene. When the temperature drops at 80 ° propylene oxide (50 ml) and then styrene (200 g) were added. Potassium carbonate (8.5 g) added and the temperature increased to 100 ° and held there for 30 minutes. More styrene (550 g) was (s) then mixed in and precipitated solids removed by decanting.

Example 11

Novolak resin was prepared and propoxylated as described in Examples 7 and 1, respectively. The propoxylated Novolak was then esterified with acrylic acid (2300 g; 32 M) as described in Example 6, but using from 7000 ml of toluene.

509810/0833

Example 12

The procedure of Example 10 was followed, but using acrylic acid (290 g; 4.0 M) instead of methacrylic acid, and 1200 ml of toluene were used for the esterification reaction.

The resins of Examples 10, 11 and 12 with a content of 40 % styrene were cured in the form of cast bodies and as glass laminates with 25 % glass mats using a room temperature curing system with subsequent post-curing at 100 ° for 5 hours; Physical properties were tested and the results are given in Table V, in which HDT stands for the heat distortion temperature, BH the Barcol hardness and FS the flexural strength in kg / cm 10 ~ '~.

properties TABLE V Resins 10 of hardened 13th Example: 11 Cast body 116 ° 80 ° HDT 38 90 ° 37 bra '35 Laminates 10.97 11.74 FS 45 10.34 45 bra 46

50981 0/0833

Example 13

The unsaturated polyester resin (600 g) of Example 1 was separately dissolved in each of the following monomers (AOO g) to give different resins as shown in Table VI, where the monomers are represented by the following symbols: N = acrylonitrile, MA = Methyl acrylate; MMA = methyl methacrylate, IMA = isobutyl methacrylate; LMA = lauryl methacrylate, TAC = triallyl cyanurate and CS = chlorostyrene. The following properties are given: V = Brookfield viscosity; expressed in cps; measured at 25 °; HDT = heat distortion temperature; GT = gel time after the SPI test; PE = exotherm peak at ⁰ C; CT = curing temperature; TS = tensile strength of castings in kg / cm 10 ""; M = module in kg / cm χ 10 "and E = elongation at break in %.

509810/0833

Monomer V HDT N 70 110 ° MA 50 112 ° cn MMA 70 112 ° ο • co
CD IMA 140 95 ° O LMA 420 70 ° O 00
O3 TAC 3000 130 ° CO CS 130 115 °

TABLE VI Properties of Hearts and Castings

GT PE CT TS ME

4Ί7 "173.9 ° 8'45" 5.13

4Ό3 "187 ° 730" 3.02

4 « ₁₃ n 175.6 ° 9'38" 1.62

7'54 "153.3 ° 140" 1.83 1.76 1.3 ι

8'25 "141, r 16'15" 0.98 4'45 "105.0 ° 10-5" 1.05 10'56 "171.1 ° 15'21" 1.83

2.39 3.2 1.69 2.5 2.04 1.0 1.76 1.3 0.91 1.7 1.41 1.1 2.18 1.0

- 38 - 2AAObB

Bei p iel 14

The preparation was carried out as indicated in Example 10, except that 1,2-butylene oxide (345 g; 4.5M) was added instead of ethylene oxide (205 g). The final resin (40% styrene) had a Brookfield viscosity ve η 260 cps, a heat distortion temperature of 90 ° and the cured castings had a tensile strength of 4.5 χ

OO / O

10 kg / cm ", an elongation module of 1.83 x 10 * kg / cm and an elongation of 3.7 %.

Example 15

p-Cresol novolak was prepared according to the procedure of Example 7 using p-cresol (250 g; 2.3 M), paraformaldehyde (62 g; 1.9 M) and toluene (ICG ml) in the presence of p-toluenesulfonic acid catalyst .tor (150 mg) produced. The final resin (with 40 % styrene) with a Brookfield viscosity of 90 cps was then prepared according to Example 6. The thermal deformation temperature of the castings was 90 and the Barcol hardness 35.

Example 16

A novolak resin was prepared using phenol (260 g; 2.8 M), benzaldehyde (236 g; 2.2 M) and toluene (150 ml) in the presence of p-toluenesulfonic acid (2 g)

509810/0833

the procedure of B _e ispiel 7 prepared following. Propoxylation and esterification were carried out according to the procedure described in Example 6. The final resin with ^ + 0 % styrene had a Brookfield viscosity of 1200 cps. The molded body had a ^w ärmedeformationstemperatur of the 95th

BeisDiel 17

The procedure of Example 6 was repeated except that the toluene was replaced with an equal volume of benzene became. The esterification time was about three times that long. The properties of the mixture of the resulting Polyesters with styrene were those of the resin according to Example 6 in terms of viscosity, reactivity, Hardening character statistics etc very similar. The cured resin had very similar properties.

509810/0833

Claims (24)

Claims 1. Chemically resistant thermosetting resin based on polymerizable, ethylenically unsaturated, resinous esterification products of H _v dr'oxy components (A) and acid components (B), characterized in that component (A) is a polyol which is produced by a reaction product of (i) an alkylene oxide and (ii) a novolak resin is formed in which the amount of (i) is at least 1 mole but not more than 1.2 moles per phenolic nucleus lies in (ii) and component (B) is formed entirely by monocarboxylic acid material consisting of the group the end (a) a «, ß-ethylenically unsaturated monocarboxylic acid and (b) a mixture of (a) with up to 10 % - based on the weight of (a) - of a saturated or aromatic monocarboxylic acid having a boiling point which is at least as high as the boiling point of (a). 5098 1 0/0833 -Al- 2. Resin according to claim 1, characterized by polyol components (A) of the structure O
I. 0 0
I. I.
CH ₀
I * ■ CH ₂ CH
Ί R'-CH
I. R'-CH
I. R'-CH
1 I.
OH I.
OH I.
OH where R 'denotes hydrogen or alkyl and R ¹ ' denotes hydrogen or aryl, X denotes alkyl with not more than 3 carbon atoms or halogen and η ranges from 1 to 10 and m from 0 to 2 (inclusive) and acid components in which ( a) by an alkenoic acid of the formula COOH R_C _{2 is} formed, where R is hydrogen or alkyl. 3. Resin according to claim 2, characterized in that R is alkyl. 4. Resin according to claim 3, characterized in that 509810/0833 - A2 - 2 4 k Ü 5 8 that R is methyl. 5. Resin according to claim 3, characterized in that R ^{1 is} methyl. 6. Resin according to claim 3, characterized in that R ″ means hydrogen. 7. Resin according to claim 3, characterized in that m is equal to 0. 8. Resin according to claim 2, characterized in that R 'is methyl, R ¹ ' is hydrogen and m is C and (B)
is formed by methacrylic acid. 9. Resin according to claim 1, characterized in that the esterification product in a copolymerizable
Vinyl monomers is dissolved. 10. Resin according to claim 2 or 8, characterized in that the esterification product in a vinyl monomer and in particular is dissolved in styrene. 11. Moldings based on resin according to claim 1 and in particular according to claims 9 and 10, preferred 509810/0833 wise in the form of castings, laminates, impregnation or resin-impregnated bodies or coatings. 12. Shaped body according to claim 11, characterized by a glass fiber reinforcement and a hardened one Mixture of styrene and esterification product according to claim 8. 13. A method for the production of resin according to claim 1 or in particular 2, characterized in that that a solution of the polyol component (A) and the acid component (B) in an inert organic solvent for (A) and (B) which forms an azeotropic mixture with water and has a boiling point in the range from bO to 130 °, which has a strong acid as an esterification catalyst and a radical polymerization inhibitor of the phenolic type, the amount of which is formed in particular by toluene or benzene Solvent at .100 to 400 ml per g-mol (A) and the Amount of the inhibitor at 100 to 6CC ppm (based on the weight of the Frcduktes) is selected and that the Solution heated to its boiling point to induce esterification and either a) Vf = resterungsv / ater removed from it, then 509810/083 3 neutralizes the esterification catalyst and separates the solvent from the reaction mixture or b) esterification water and solvent removed from the solution, the remainder in a copolymerizable vinyl monomer dissolves, adding enough anhydrous potassium carbonate to neutralize the catalyst at an elevated temperature, creating an insoluble potassium salt in the reaction mixture is formed, which is removed from the reaction device. 14. The method according to claim 13 ^a for the production of resin according to claim 2, characterized in that the solvent used is toluene or benzene and the ratio of phenol to aldehyde in the novolak resin is between 1.2 and 1.6. 15. The method according to claim 13b, characterized in that that a polyol component is used which comprises the structure I and the acid component by an unsaturated one Monocarboxylic acid of formula II is formed. 16. The method according to claim 15, characterized in that that the unsaturated monocarboxylic acid in a 10 to 20? iigen "stoichiometric" excess over the amount included with the polyol component (A) reacts is used. 509810/0833 17. The method according to claim 13b or 15 »thereby characterized in that the amount of unsaturated monocarboxylic acid (a) in a 10 to 20% "stoichiometric" Excess over the amount which reacts with the polyol (A) is chosen and that, after the water of esterification has been separated off, an alkylene oxide is used to neutralize the excess of (a) and converting it to a hydroxyalkyl ester serving as a copolymerizable monomer remains in the resulting mixture. 18. The method according to claim 15 »characterized in that an alkacrylic acid as the acid component is used. 19. The method according to claim 15, characterized in that methacrylic acid is used as the acid component and a material of structure (I) is used as the polyol component, in which R ^{1 is} methyl, R '' is hydrogen and m is zero. 20. The method according to claim 15, characterized in that that styrene is used as the copolymerizable vinyl monomer. 21. The method according to claim 15, characterized in that that as a polymerization inhibitor hydroquinone is used. 509810/0833 2440530 22. The method according to claim 13 »characterized in that (A) a hydroxyethoxylated phenol-formaldehyde novolak resin, in which the molar ratio of phenol to formaldehyde is between 1.21 and 1.3 and that The ratio of ethylene oxide to the hydroxyl groups in the novolak is between 1 and 1.2 and (B) methacrylic acid in toluene together with a strongly acidic esterification catalyst in sufficient amount for catalysis the esterification reaction between (A) and (B) and hydroquinone as a polymerization inhibitor in ICO up to 4GC ml Toluene per g-riol (A) dissolves the mixture to induce the esterification is brought to the boil under reflux, the esterification water and toluene are removed from the mixture, dissolves the residue in styrene and neutralizes the polymerization catalyst. 23. The method according to claim 22, characterized in that the methacrylic acid in a 10 to 20% "stoichiometric" Excess over the amount consumed in the esterification of (A) is used. 24. The method according to claim 22, characterized in that after the separation of the esterification water or ethylene Propylene oxide to neutralize the excess methacrylic acid and in situ formation of hydroxyethyl or hydroxypropyl methacrylate is added to serve as a copolymerizable monomer in the final blend. 509810/0833