DE2261330B2 - Thermosetting molding powders and their use - Google Patents

Description

an anhydride

c) t ReI ^ ÄiÄU, where «a ^

a subordinate part of the methyl methane compound produced. p, fimW

acrylates replaced by other monomers. ^Dle "'^ artable Materal,", the E' ^fi nd "° g

be ta «,." d where the mixed poly · «^ rt ^ TS ^" SSTSTS
S.

ErweichunesDunkt of about 25 ⁰ C up ^{25 C> in} bending strength determination in S5 S ^{range of about 110} ° ^to 21CO kg / cm ² (16 000 to

20 about 30,000 psi) or higher, a module in area B: a monomeric anhydride an acyclic of about 0.084 to 0.16 · 10 ^e kg / cm ² (about 1.2 to dicarboxylic acid or a cyclic di-, tri- 2, 25 x 10 * psi) or higher and an elongation at break im or tetracarboxylic acid in an amount ranging from about 1 to about 3 % or higher,
is present, the 0.5 to 1.5 anhydride groups per The glass transition temperature is the temperature

Epoxy group in the copolymer A 25 in which a vitreous material its rigidity and supplies. Loses hardness and the behavior of an elastomer

2. Molding powder according to claim 1, thereby approximating to meren. More precisely, the glass is identified that the copolymer A defines the transition temperature as the temperature at Using 10 to 25 weight percent meth- this material maximizes its mechanical acrylonitrile has been produced. 30 attenuation at low frequencies, e.g. B. about one

3. molding powder according to claim 1 or 2, characterized by oscillation per second, shows
characterized in that the copolymer is,,, "...
Average molecular weight in the range of 3500 »· Composition of the prepolymer

to 8000. The prepolymer preferably has at least

4. Molding powder according to claim 1 to 3, characterized in that it has three monomer components and is marked with the fact that the anhydride is used in an amount of the limited sub-uses specified below, the 0.6 to 0.9 anhydride groups per stitution the following basic composition:
Epoxy group results in the molding powder. Glycidyl methacrylate 15 to 40, preferably 20 to

5. molding powder according to claim 1 to 4, characterized 35. percent by weight methacrylonitrile 0 to 30, preferred shows that in addition to the copolymer 40 added 10 to 25 percent by weight methyl methacrylate a different epoxy resin with at least two groups.

Epoxy groups per molecule, a molecular methacrylonitrile can be wholly or partially through

Weight in the range from 300 to 4000 and an acrylonitrile can be replaced, but methacrylonitrile viscosity at 140 ⁰ C of less than 50 poise, the preferred reactant, since products, especially a diepoxide, are made from prepolymers containing this component in an amount and Wendet, which provides between about 2 to about 20% of the epoxy groups made by the crosslinking agents used herein in the molding powder. become a higher heat distortion temperature

6. molding powder according to claim 1 to 5, characterized (glass transition temperature) have, as the denoted that particulate reinforcing products using Acrylkungsfüllstoff intimately with the copolymer and 50 nitrile, all other factors being the same,
the monomeric anhydride is dispersed. A smaller proportion of the methyl methacrylate,

7. Use of the molding powder according to claim 1, preferably not more than V3. can by styrene, <x-Mebis 6 for the production of molded articles with thylstyrene, vinyl acetate or a different ester with a glass transition temperature of over 90 ⁰ C, of acrylic or methacrylic acid and monohydric a flexural strength of over 1100 kg / cm ² , an alcohol, preferably an alcohol with 2 to 4 carbon flexural modulus of over 0.084 · 10 · kg / cm ² and material atoms, for example ethyl acrylate, butyl acrylate, an elongation at break of over 1%. Butyl methacrylate and the like. This replacement should be about 15% of the amount needed to form the prepoly-

mers used total amount of monomers

Do not exceed 60 and preferably do not exceed 10%. In the case of the C ₄ substitution agent

The invention relates to self-crosslinking, dry, this component preferably does not step Vs des Litz-curable molding powder, which is used for rapid curing methyl methacrylate. Those mentioned in this paragraph During processing, for example by means of form substitution or substitutes, result in eating out and injection molding processes are suitable and styrene would increase the flexibility of the Production of solid or rigid tough materials, in the case of polymers, d. H. the elongation at break and a For example for car body panels, housings for lowering the softening point (glass over-electric Systems, boat constructions, storage tanks, transition temperature).

II. Properties of the prepolymer

The prepolymer has an average molecular weight in the range from 1500 to 16,000, preferably 2000 to 10,000 and more preferably 3500 to 8000 as determined by vapor phase osmometry using of methyl ethyl ketone as a solvent. Less than 5% of the molecules should have a molecular weight below 1000.

The prepolymer has a softening point of over 25 ^° C., preferably in the range from 50 to 110 ^° C.

III. Preparation of the prepolymer

The prepolymer is advantageously made by solution polymerization using heat, a free radical initiator and an inert solvent! educated. The prepolymer is preferably obtained by coagulation. Hexane, a mixture of hexane and toluene and the like are suitable for this purpose. It can be vaporized but if this embodiment is used, the product should be obtained with a suitable solvents to remove low molecular weight components.

A free radical initiator is combined in the Dissolved monomeric reactants and is advantageously used in an amount of 1 to 4 percent by weight of combined monomer weight applied. Usual free radical initiators are for this Purpose suitable, such as acyl peroxides, peresters and azo compounds. To specific materials, which have been used with success include 2,2'-azobis- (2-methylpropionitrile), the following is referred to as AlBN, benzoyl peroxide, tert-butyl perbenzoate and tert-butyl peroxypivalate.

As mentioned above, the reaction takes place in an inert solvent, for example toluene or a mixture of toluene and dioxane and the like. The weight of the solvent is appropriate equal to or greater than the combined weight of the reactant and initiator.

In a preferred method of preparation, the monomeric reactants and the free radical Initiator in small proportions, e.g. B. dropwise, to which refluxed under nitrogen Solvent added. After the addition is complete, the initiator is used in an amount of about 0.1% of the Monomer weight dissolved in a small amount of solvent and over a period of 20 to Added for 60 min. The reflux treatment is then continued for about 2 hours. The prepolymer then becomes obtained by coagulation. This is preferably done in the manner described below. The reaction solution is further diluted with additional solvent) until the prepolymer is about 20 to about 30 percent by weight of the resulting solution. This solution then slowly turns into a liquid added, which causes the prepolymer to precipitate. In this case, hexane is very suitable. A fine powder precipitates. This is filtered off, dried and, if necessary, by rolling or Grinding broken.

In addition to the method of preparing the prepolymer described above, the prepolymer according to the known methods of emulsion polymerisation, polymerisation in the bulk and suspension polymerisation getting produced. Db suspension polymerization is preferably carried out using of water as the suspending medium. Since ionic stabilizers react with glycidyl methacrylate, only nonionic materials can be used to stabilize the suspension. Polyvinyl alcohol and an alkylaryl polyether alcohol were found to be very satisfactory. To carry out the. Suspension polymerization is the monomer

xo mixture is added to cooled (about 0 ⁰ C), 0.1% solution of polyvinyl alcohol in water. The mixture is stirred rapidly and the initiator added over a period of about 30 minutes. The temperature of the reaction mixture is then regulated so that

it remains between 55 and 60 ° C for 6 to 8 hours. After cooling to room temperature, the polymer is filtered off. Since the polymerization is below 65 ° C must be carried out, only the initiators that have an effective below this temperature

ao same source of free radicals are to be used. Suitable initiators for suspension polymerization include tert-butyl peroxypivalate and diisopropyl peroxycarbonate. The molecular weight of the prepolymer can be adjusted, among other things, by using 0.1 to 5 percent by weight (based on the monomer weight) a chain transfer agent such as lauryl mercaptan.

IV. Crosslinking Agents

The crosslinking agent of this thermosetting system is a monomeric anhydride. Among the anhydrides which are suitable for the invention are the anhydrides of the following three classifications:

(1) Monomeric anhydrides of acyclic dicarboxylic acids, wherein each carbon atom in one Anhydride group linked directly to one of a pair of carbon atoms which are bonded directly and adjacent to one another, for example succinic anhydride, Citraconic anhydride, methylsuccinic anhydride, 1,2-dimethylsuccinic anhydride, and dodecylsuccinic anhydride,

(2) monomeric anhydrides of acyclic dicarboxylic acids in which each carbon atom is in an anhydride group directly connected to one carbon atom of a pair of carbon atoms that are not directly and adjacent to one another are bound (i.e. by at least one carbon

s ° lenstoffatom are separated), for example glutaric anhy drid, 1,2-dimethylglutaric anhydride, 1,3-dimethylglutaric anhydride and «- [2-carboxyethyl] glutaric anhydride.

(3) monomeric anhydrides of cyclic di-, tri- or tetracarboxylic acids in which each carbon atom of an anhydride group is directly linked to one carbon atom of a pair of directly bonded and adjacent carbon atoms of a C ₄ to C ₁₀ ring structure.

(a) If the ring is aromatic, phthalic anhydride, trimellitic anhydride, Dimellitic anhydride, 4,4 '- (2-acetoxy-l.S-glyceryty-bis-anhydro-trimellitic acid- anhydride, naphthalenetetracarboxylic acid dian-

hydride can be used;

(b) when the ring is a saturated aliphatic (carbon-carbon) ring, can

Hexahydrophthalic anhydride, cyclooctane reaction. These include tetrabutylammonium iodide,

.1,2-dicarboxylic anhydride and cyclobutane chloride, bromide, tetraethylammonium iodide, chloride

dicarboxylic anhydride can be used; and bromide, tetramethylammonium bromide, chloride

(c) when the ring is an unsaturated aliphatic and iodide, benzyltrimethylammonium iodide, chloride tischer (carbon-carbon) ring is, 5 and -bromide, benzyldhnethylphenylammoniumchlokann Tetrahydrophthalic acid auride, bromide and iodide, stearyldircethylbenzylammo will; nium iodide, bromide and chloride. Catalysts this

(d) if the ring is a heterocyclic ring type in amounts of 0.05 to 1.0 weight, tetrahydrofuran-2,3,4,5-tetra percent of the combined reactants,
carboxylic acid dianhydride, 7-oxabicyclo [2,2,1] - "Other catalysts that can and may be used include solid tertiary amines such as 7-heptane-2,3-dicarboxylic anhydride and wise Triethylenediamine, amine salts, such as trimethyl-7-oxabicyclo [2,2,1] -hept-5-ene-2,3-dicarbonamine-p-toluenesulfonate or imidazoles, such as 2-ethylic acid anhydride, 4-methylimidazoi or metal carboxylates, such as Lithi-

15 umbenzoate. Catalysts of this type are in the

hi the same monomeric concentration ranges listed above as stated above

hydrideji can be a hydrogen atom suitably by a me.

ethyl, ethyl, propyl, butyl, methoxy, ethoxy, these catalysts turned out to be latent cata-propoxy or butoxy groups or a halogen analyzer for the anhydride-epoxy reactions. The atom will be replaced. Particularly suitable halogen- * ° means that the catalysts are the reaction rate-substituted anhydrides do not noticeably increase tetrabromophthalic acidity at room temperature, anhydride and chlorophthalic anhydride. In the case of the heterocyclic anhydrides which are effective above certain temperatures, however, a ring substituent can be. The catalysts which are latent up to at least 50 ^J C tion for a carbon atom through an oxygen atom are preferred,
a sulfur atom, a divalent silicon radical or ⁹ 5 ,, ",. ". _. . .
a divalent phosphorus residue take place. The arrival of the ^m manufacturing Formpulvergem.schs
hydride is used in an amount sufficient to provide the powdered prepolymer, the crosslinking to 0.5 to 1.5, preferably 0.6 to 0.9, anhydride groups and the catalyst in an appropriate one for each epoxy group in the molding powder. Solvent, for example acetone, methylene chloride., _ ... η - ι · r - ³ ° «d, benzene and the like, dissolved, and the solution is v. Partial replacement of the prepolymer with epoxy stirred thoroughly. The solvent is evaporated off under vacuum, leaving a solid cake to-A smaller proportion, ie 2 to 20% of the residue, which is crushed to a fine powder, the prepolymer-supplied epoxy groups, can- The powder is further dried under vacuum , so be set by for this portion of the prepoly 35 that it contains less than 1% solvent,
An epoxy compound having at least two can also be added to the prepolymer solution, preferably a diepoxide, that is used to add crosslinking agents and catalysts to the epoxy groups obtained by polymerization. admit lyser. The solution is stirred until Homoge-These diepoxides should at 140 ⁰ C or below nity and then be vigorously geflüssig slowly to a and a molecular weight in the range of 4 ° stirred precipitant, such as hexane, to-300 to 4000 and a viscosity at 140 ⁰ C given by we-. The precipitated powder will be less than 50 poise under vacuum. dried. To ensure its homogeneity The diepoxide can be an aromatic, an acyclic diepoxide through a wake mill for aliphatic or cycloaliphatic diepoxide. 50 to 100 ⁰ C given. Instead of the application of these diepoxides should essentially of carbon ⁴⁵ precipitant and the rolling mill can be made Iestoff, hydrogen and oxygen, the solvent may, however, have substituents which evaporate the networking diglich of the prepolymer.

Do not interfere with zing reactions, e.g. sulfonyl groups, Another method for producing the form · Nitro groups, Alkylthiognippen and Halogens. powder consists in the powdered prepolymer, typical examples include diglycidyl ester of ⁵ ° crosslinking agent and the catalyst with each other polybasic or dibasic acids according to the mixing and passing through a US-PS 28 66 767; Diglycidyl ethers from divalent extruder mixers or a roller mill to homophenols according to US Pat. No. 2,467,171, 2,506,486.

26 40 037 and 28 41 595; Diglycidyl ethers of diols If necessary, reinforcing fillers,

according to US-PS 25 38 072 and 25 81 464 and Di- 55 such as asbestos, glass fibers, clay, calcium carbonate, CaI-

epoxides, which are incorporated into the molding powder by peracid epoxidation of dienesilicate,

can be obtained. A collection of suitable diepoxides A particularly effective filler is calcium meta-

is explained in US patent application 43,895 on silicate (CaSiO ₃ ).

which is referred to here. Although the di- The powders produced in this way are suitable for

Epoxides are preferred for the invention, can be used in injection molding, compression molding and compression molding

also polyepoxides with low viscosity with advantage transfer molding.

be used. The invention is based on the following

VI Catalysts purifying examples described in more detail, the

Bending properties of the fittings by bending in the molding powder mixture is used to facilitate 65 test of the American Society of Testing & Materials, a catalyst is used in the crosslinking reaction. D 790-1966. In this test Quaternary ammonium salts give rise to be rectangular rods with a thickness of Degree of specificity in terms of epoxy anhydride 3.2 mm, a width of 13 to 15 mm and a

Length of 10.2 cm to determine the inherent _{flexural strength,} elongation at break, flexural modulus

shafts used. A mechanical Instron tester (table model) is used for testing r <> · .. *. Es kg / cm ¹ A kg / cm ¹

is carried out at a crosshead speed of 0.1 cm /

min and a recording sheet speed of 5 1760 2.0 0.15 x 10 '

5 cm / min used. The formulas in procedure B
(ASTM-D 790-66) are used to calculate the flexural modulus, elongation at break and strength. This molding powder was found to be processable, ie used. in a state for carrying out the above The prepolymers in the illustrative examples io measures after it had stood for 3.5 months at room having softening points between 50 and 110 ⁰ C, temperature, with less than 5% of the molecules being a molecular. . weigh less than 1000. The molded articles example of all examples have glass transition temperatures. The prepolymer of example 1 is in a door of over 90 ° C. 15 amount of 35.0 g with 7.1 g of succinic anhydride

and 0.058 g of tetrabutylammonium chloride mixed.

Example 1 After grinding this mixture in

A prepolymer is made from the following components - the ball mill will contain 28.0 g of this mixture

parts made in the following way: 32.0 g of calcium metasilicate mixed and 2 hours in

ao the ball mill. The resulting mixture

. is mixed with 20.0 g of staple glass fibers. To

Reactant Amount Weight Association of the molding powder with the staple glass fibers

(g) percent _w i _r s _a mixture dd circulated to the glass fibers to

and it becomes a preform for molding

35 manufactured.

A sheet of this material is molded under identical molding conditions to those used in Example 1. This plate was found to have the following flexural properties: 30

Glycidyl methacrylate 532 31 Methyl methacrylate 870 50.5 Methacrylonitrile 318 18.5

AlBN, d. H. 2,2'-azobis (2-methylpropionitrile) becomes

in an amount of 54 g (3%) to the monomer flexural strength elongation at break flexural modulus

mixture added. This solution is added dropwise kg / cm ' % kg / cm'

to 1950 ml of toluene over a period of 4 hours

108 to lire were added under a nitrogen atmosphere. 35 1560 1.7 0.14 x 10 "

Then 2.0 g of AiBN, dissolved in 20 ml of acetone,

added over a period of ¹ l ₂ hours and Example 3

the reflux treatment continued for 3 more hours.

The polymer solution is treated with 3000 ml of acetone. The prepolymer of Example 1 is used in an amount

thin and coagulated in hexane. The white powder 40 of 25.0 g with 7.5 g of phthalic anhydride and 0.049 g

35 hrs. at 70 ⁰ C is mixed getrock- tetrabutylammonium bromide in a vacuum oven. After 16 hours

net. The molecular weight was MwIM _n - 6231 / digem grinding the ingredients in the ball mill

34 (6 b; i a molecular weight per epoxide unit, 32.5 g of the form powder with 37.0 g of calcium

hereinafter referred to as WPE, of 496th metasilicate and 23.2 g of staple glass fibers mixed unc

This prepolymer is used in the production of 45 using de, ideitic processes such as ir

Molding powder used. In this procedure the previous examples are processed.

35.0 g of the prepolymer with 10.7 g of tetrahydrophthalic A plate molded from this material, the untei

Acid anhydride and 0.046 g of tetrabutylammonium iodide using identical shape conditions as in

combined and ground in a ball mill for 16 hours. Example 1 has the following flexures

Then 28.0 g of this powder are combined with 32.0 g of CaI properties: cium metasilicate (CaSiO ₃ ) and 2 hours

grind in the ball mill. The resulting mixture ~; ; ; ~~ ~

is filled with 20.0 g of staple glass fibers (average length of bending structure.t elongation at break Bmgemodul

6.3 mm, the same length will be in all later kg / cm =% kg / cm ⁸

Examples used unless otherwise stated) 55

mixed. After combining the molding powder with 1690 1.9 0.13-10

The mixture is circulated around the staple glass fibers.

This makes the mixing of all the ingredients _. . . .

produced without damaging the fiber. Then an ^{a sp}

^{Preform Manufactured for Molding 6o} The prepolymer of Example 1 is converted into a

This powder and fiber mixture is converted into an amount of 25.0 g with 6.6 g of glutaric anhydride

Pressing the mixture at a pressure of 105 kg / cm ^{2 combined} 0.32 g of tetraethylammonium bromide. Nac

and a temperature of 193 ⁰ C for 30 minutes 1.6 hours grinding of the constituents in d <

a path t ζ v. Plate (11.9 X 13.2 X 0.3 cm all ball mills 28 g of the molding powder rac \ dei

molded plates in the following examples ⁶ S identical procedure as in Example 1 mi "2

have these dimensions) molded calcium metasilicate and 20.0 g staple glasfasem ve

This shaped body results in the following bending work: A plate is made using di

properties: identical shape conditions as in the example

^w ίο

shaped. This plate possessed the following flexural phthalic anhydride by an equimolar amount shafts: methylsuccinic anhydride is replaced.

Flexural strength elongation at break flexural modulus Example 11

kg / cm ' % kg / cm' 5 The procedure of Example 1 is excepted

the deviation repeats that the tetrahydro-

¹⁵⁸⁰ ! ' ⁵ °> ¹⁴ · 10 "phthalic anhydride by an equimolar amount

Example 5 ⁴ . ⁴ '- (2-acetoxy-1,3-glyceryl) -bis-anhydrotrimellitic acid

anhydride is replaced.

The prepolymer of Example 1 is in an io

Quantity of 25.0 g with 7.7 g of hexahydrophthalic acid - Example 12

anhydride and 0.0033 g of tetramethylammonium iodide The procedure of Example 1 is with the exception

united. After dry mixing of the constituents, the deviation repeats that the calcium metal

parts are replaced by 40 g calcium carbonate by grinding in a ball mill for 15 hours,
28.0 g of this molding powder are obtained using application 15

the identical procedure as in example 1 with example 13

32.0 g calcium metasilicate and 20.0 g staple glass fibers The procedure of Example 1 is with the exception

processed. A plate is repeated using the deviation that the tetrahydro-

»Dental molding conditions as in Example 1 phthalic anhydride by tetrahydrofuran-2,3,4,5-te-

that had the following flexural properties: _{20 replaced} tracarboxylic dianhydride in an amount

so that a number of anhydride groups are supplied

Flexural strength elongation at break flexural modulus, which is equal to the number replaced.
kg / cm «% kg / cm =.
. Example 14

1720 1.8 0.14 x 10 " ^{25 The procedure of} Example 1 is repeated except

the deviation repeats that the Tttrahydro-

In game 6 phthalic anhydride by an equimolar amount

The prepolymer of Example 1 is in an amount ^ ^a ^ f ^, ^ hept-S-ene ^ S-dicarboxylic anhy of 25.0 g with 5.0 g of trimellitic anhydride and 30

0.030g benzyldimethylphenylammonium chloride based on Example 15

agree. After dry mixing the ingredients, the procedure of Example 1 is followed with the exception

by grinding in a ball mill for 1 hour, the deviation is repeated that the tetrahydro is 28 0 g of the molding powder mixture with 32.0 g of phthalic anhydride through an equimolar amount of Calcmmmetasihcat and 20.0 g of staple glass fibers under 35 7-oxabicyclo [2 2 llhentane-2 3 dicarhomic acid-nhvdrid Use of the identical procedure as in the example replaced _w f _rd ^lülAZ ' ^ljne P ^tan ^ -dicarboxylic acid-nnyüria game 1 processed. A plate is made by compression molding using the identical conditions of Example 16
produced as in example 1. _{The procedure according to example} , _χ ^ ^ _exception

If ρ ie 1 7 ⁴ ° of ^the deviation repeats that the amount of the

The prepolymer of Example 1 is used in an amount "" *** ^Calcium Meta ^ ats 20 g,

of 25.0 g with 8.0 g of octric anhydride, d. H. «- [2-carboxy example 17

ethyl-glutaric anhydride and 0 033 g of triethylene- The procedure of Example 1 is with the exception

djamin veremigt. After dry blending 45 the deviation again often that the prepolymer

the components by marrying them for 15 hours in the "" ^ "' na.puij

using the identical procedure as in HAR provides HW} ^An is processed so nydnds e nge example. 1 It is a plate DURS ₅ o EpoxyZj 'η 1 Ii ^{V% of de} _ ™ ⁿ S ^ r number of molding using the identical loading ^ P ^{Xygrup en} compensated ^{in the} prepolymer conditions prepared as in Example. 1

_B - ₁₈ Example 18

y is formed and the amount of anhydride

Example 9 s ° is set that the change in number

The procedure according to Example 1 is ^repeated with the exception of ° ^ Ερ ° ^Χ ^ ^ϋ ΡΡ ^{εη in} ^ m prepolymers compensated for the deviation that the tetrahydro-

phthalic anhydride by an equimolar amount Example 19

Tetrabromophthalic anhydride is replaced. The method according to Example 1 is carried out with the

B is ρ ie 1 10 ^{5 w} ? ^lc hung repeats that the prepolymer of 30 ge

The procedure of Example 1 is followed with the exception of H ^ SS ^^^^ ²⁰ ^ A
the deviation repeats that the tetrahydro-

11 12

is set so that the change in the number of groups per epoxy group in the thermosetting mold

Epoxy groups in the prepolymer is compensated. powder supplies.

Example 20 Example 27

The procedure of Example 1 is followed by the procedure of Examples 1 to 10 inclusive, with the exception of 5

the deviation repeats that the prepolymer is repeated with the deviation that the

30 weight percent glycidyl methacrylate, 20 weight hydride is used in an amount that 1.5 anhydride

percent acrylonitrile and 50 percent by weight methyl dride groups per epoxy group in the thermosetting

methacrylate is formed and the anhydride powder provides molding powder,

it is set that the change in the number of _l0

Epoxy groups in the prepolymer is compensated. example

. 1O ₁ The method according to Example 1 is carried out with the

Example I repeats that the molecular weight (M _n )

The method according to Example 1 is carried out with the Ab- the prepolymer is 1500,

softening repeats that the prepolymer from 20 Ge _x5

weight percent glycidyl methacrylate, 25 weight percent- Example 29
cent methacrylonitrile, 5 percent by weight butyl acrylate. The process of Example 1 is repeated with the exception that 5 percent by weight butyl methacrylate and 5 percent by weight have a molecular weight (M _n ) of 2-ethylhexyl acrylate and 40 percent by weight of prepolymer 2000.
Methyl methacrylate is formed and the anhydride 20.
amount is set so that the change in the example JU
Number of epoxy groups in the prepolymer The procedure of Example 1 is compensated for. softening repeats that the molecular weight (M _n )

If ρ ie 1 22 of ^the P ° ty ^{meren is} 3000.

The procedure according to example 1 is carried out with the ab- B e 1 s ρ 1 e 1 31
The process of Example 1 is repeated with the weight percent glycidyl methacrylate, 30 percent by weight softening that the molecular weight (Af _n ) cent methacrylonitrile and 55 percent by weight methyl of the prepolymer is 6000,
methacrylate is formed and the amount of anhydride is 30 _.
it is set that the change in the number of B e 1 s ρ 1 e I 32
Epoxy groups in the prepolymer compensated for. The process of Example 1 is repeated, except that the molecular weight (M _n ) B cis ρ ie 1 23 of ^the prepolymer is 10,000.

The procedure of Example 1 is followed by Example 33

softening repeats that the prepolymer from 35 Ge The method according to Example 1 is with the exception

percent by weight glycidyl methacrylate, 10 percent by weight repeated that the molecular weight (M _n )

cent methacrylonitrile, 10 percent by weight styrene and the prepolymer is 16,000,

and 45 weight percent methyl methacrylate formed 40

and the amount of anhydride is adjusted so that Example 34
the change in the number of epoxy groups in

the prepolymer is compensated. The procedure of Example 1 is with the exception

. ■ 1 ·) λ of the deviation repeated that in the manufacture

Example 24 45 of the prepolymer 25 percent by weight of the methyl

The method according to Example 1 is carried out with the ab- methacrylate by an equimolar amount of styrene

softening repeats that the prepolymer from 15 Ge is replaced,

weight percent glycidyl methacrylate, 30 weight percent- Example 35
cent methacrylonitrile and 55 percent by weight methyl

methacrylate is formed and the amount of anhydride is so 50 The procedure of Example 1 is with the exception

is set so that the change in the number of the deviation repeats that in the manufacture

Epoxy groups in the prepolymer compensates for the prepolymer 25 percent by weight of the methacrylic

will. nitrile replaced by an equimolar amount of acrylonitrile

Example 25 ^{will be} "

rs ΛΓΓί. .. «- ,, j ■ λ » ι. ⁵⁵ Example 36

The process of Example 1 is repeated with the difference that the prepolymer from The process of Example 1 is repeated with the exception of 20 percent by weight of glycidyl methacrylate, 30 percent by weight of the difference that in the preparation percent acrylonitrile and 50 percent by weight methyl of the prepolymer 50 percent by weight of the Methacryl · methacrylate is formed and the amount of anhydride is set so that 60 nitriles are replaced by an equimolar amount of acrylonitrile that the change in the number of.
Epoxy groups in the prepolymer compensated for Example 37

iVlifl

Example 26 ^^ Procedure according to Example 1 is with exception

65 of the deviation repeats that in the manufacturing

The procedure of Examples 1 through 10 inclusive of the prepolymer 75 percent by weight of the methacrylic is repeated with the difference that the anhyonitrile is replaced by an equimolar amount of acrylonitrile drid is used in an amount that becomes 0.5 anhydride.

Example 38 Example 43

The procedure of Example 1 is repeated with the exception of the difference that in the manufacture of the prepolymer 25 percent by weight of the methyl methacrylate by an equimolar amount of α-methylstyrene be replaced.

Example 39

The procedure of Example 1 is repeated with the exception of the difference that in the manufacture The amount of catalyst used of the molding powder is 0.05 weight percent of the combined weight of the Respondent is. .

Example 40

The procedure of Example 1 is repeated with the exception of the difference that in the manufacture of the molding powder, the amount of catalyst used is 0.25 weight percent of the combined weight of the Respondent is.

Example 41

The procedure of Example 1 is used with the exception repeats that the amount of catalyst used in the preparation of the molding powder is 0.5 percent by weight of the combined weight of the reactants.

Example 42

The procedure of Example 1 is repeated with the exception of the difference that in the manufacture The amount of catalyst used in the molding powder was 1.0 percent by weight of the combined weight of the reactants amounts to.

A solid epoxy resin in an amount of 7.0 g is melted and 11 g of tetrahydrophthalic anhydride are added with stirring. The temperature is kept at 90 to 100 ^° C. for 1 hour. The mixture or adduct mixture is quite liquid at 100 ° C. The mixture or adduct mixture is allowed to cool and solidify. It will then

ίο ground to a fine powder. The molding powder is put together by adding 17.0 g of the prepolymer according to Example 1, 11.0 g of the mixture or adduct mixture and 0.028 g of tetrabutylammonium iodide are combined. After marrying for 16 hours

If the ingredients in the ball mill are 28.0 g of the molding powder with 32.0 g calcium metasilicate and 20.0 g staple glass fibers using the identical one Process processed as in Example 1. A plate is made from the molding powder

»Ο Compression molding using the identical molding conditions produced as in example 1. This plate has the following bending properties:

Flexural Strength kg / cm ¹

Elongation at break %

Flexural modulus kg / cm ¹

1900

1.7

0.158 · 10 «

The epoxy resin used in this example is a commercially available diepoxide having the following typical properties: melting point about 64-76 ⁰ C, epoxy equivalent about 450 to 525 and average molecular weight about 900th

This diepoxide is represented by the following structural formula, in which η = 2:

H H H - <κ> CH ₃
ι 44 HHH
III -O-
η O CH ₃ HHH
I 111 H-C II
-CC-
H example V- \ III
YOCCC-
^/ \ \ \
OHH H meren that 20% of the -CZ ^ VOCC-CH
I ^v ^ IV
CH ₃ H Epoxy groups, through the

The procedure of Example 43 is repeated with the difference that an amount of the prepolymer which provides 2% of the epoxy groups is replaced by the diepoxide of Example 43, which is in a Amount is applied to provide the same number of epoxy groups.

Example 45

The procedure of Example 43 is repeated with the exception that an amount of the prepolymer, which supplies 10% of the epoxy groups, through the diepoxide of Example 43 and used in an amount containing the same number of epoxy groups supplies

Example 46

The procedure of Example 43 is repeated with the exception that a mer ^ e of the prepoly-

p p

Amount is applied which provides the same number of epoxy groups.

Example 47

The process of Example 43 is repeated with the exception that an equimolar amount of an aliphatic diepoxide is used in place of the aromatic diepoxide used in Example 4: This aliphatic diepoxide is prepared in the following manner: In a 2000 ml three-necked flask, the mi stirrer, dropping funnel, thermometer and nitrogen inlet is provided, 1 mole of 2,3-Butandio (91.12 g) and 4MoI epichlorohydrin (370 g) are introduced, the temperature is maintained at 110 ⁰ C for 2 moles of sodium hydroxide (80.0 g) are added dropwise as a 30% aqueous solution. The rate of addition is regulated so that the reaction mixture remains neutral

2 61

For 3 hours, the organic layer is separated, dried, distilled, and a polymer is recovered. This polymer product is represented by the following structural formula:

O ^H

H-C C-C-

I · I I

HHH

H CH ₃ H OH H

Il! Il

-O-C-C-O-C-C-C-C- H CH, H _n

Il I / \

_O — C — C — O — C — C — C — C — H

CH, H

HHH CH, H

H H

Example 48 Example 52

The procedure according to Example 43 is repeated with exception 15. The procedures according to Examples 1 and 43 are repeated with the difference that the tetrahydro- with the difference that the tetrabutylphthalic anhydride is repeated by an equimolar amount
Succinic anhydride is replaced.

ammonium iodide with an equimolar amount of tetramethylammonium chloride is replaced.

Example 49

The procedure of Example 43 is repeated with the exception that the tetrahydrophthalic anhydride is replaced by an equimolar amount of glutaric anhydride.

Example SO

The procedure of Example 43 is repeated with the exception that the tetrahydrophthalic anhydride is replaced by an equimolar amount of phthalic anhydride.

Example Sl

It becomes a prepolymer using the identical procedure used to make the prepolymer was applied according to Example 1, prepared from the following monomers, which are used in the following Conditions are used:

Glycidyl methacrylate ... 30 percent by weight

Methacrylonitrile 18 percent by weight

Methyl methacrylate 52 weight percent

AIBN 1.5 percent by weight

The molecular weight is using about 2 weight percent based on the combined Weight of the reactants, regulated by lauryl mercaptan.

The prepolymer obtained has a molecular weight of MwIM _n - 8564/4674 and a WPE value of 474. A molding powder mixture is prepared by grinding in a ball mill 100.0 g of the copolymer with 32.1 g of tetrahydrophthalic anhydride and 0.250 g of triethylenediamine for 15 hours. This mixture is processed in an amount of 28.0 g with 32.0 g calcium metasilicate and 20.0 g staple glass fibers according to the identical procedure of Example 1.

From this mixture, using the identical molding conditions as in Example 1, a Plate made by compression molding. This plate has the following bending properties:

. Flexural strength kg / cm »

Elongation at break

O/ /O

Flexural modulus kg / cm ¹

1.82

0.15 x 10 "

Example 53

The procedures of Examples 1 and 43 are repeated with the exception that the tetrabutylammonium iodide is replaced by an equimolar amount of tetraethylammonium bromide.

Example 54

The procedures of Examples 1 and 43 are repeated except that the tetrabutylammonium iodide is replaced by an equimolar amount of tetrabutylammonium bromide.

Example 55

The procedures of Examples 1 and 43 are repeated except that the tetrabutylammonium iodide is replaced by an equimolar amount of benzyldimethylphenylammoniurajodid.

40

Example 56

A heat-cured molding is produced without filler in the following way: The prepolymer according to Example 1, in an amount of 100.0 g with 32.07 g of tetrahydrophthalic anhydride nnd 0.250 g Triethylenediamine mixed. After grinding the ingredients in the ball mill for 15 hours, the Molding powder mixture under the identical conditions of the compression molding process used in Example 1 shaped. This shaped plate has the following bending properties:

55 Flexural strength kg / cm «

Elongation at break

Bending module kg / cm «

1150 3.1

41050

Example 57

The procedures of Examples 1 and 43 are repeated with the difference that the anhydride in an amount is used which is 0.6 anhydride groups per epoxy group in the thermosetting molding powder supplies.

Example 58

The procedures of Examples 1 and 43 are repeated except that the anhydride in

«509 526/358

10

a lot used win !, the 0.9 anhydride groups per epoxy group in the heat-hardenable molding powder supplies.

Example 59

It becomes a monomer mixture with the following Composition made:

Glycidyl methacrylate.
Methyl methacrylate ..
Isobornyl methacrylate

15 percent by weight
57 percent by weight
28 percent by weight

The polymerization is carried out using the identical procedure of Example 1 with the exception that the applied concentration of AIBN catalyst (based on the weight of the Reaktioiisteilnehmer) 1% cheating The prepolymer obtained has a Tg (glass transition temperature) of 110 ⁰ C and an average molecular weight of

This prepolymer is in an amount of 30.0 g with 2.1 g of glutaric anhydride and 0.0320 g Tetrapropyiammonium iodide mixed. The mixture is milled in a ball mill for 15 hours dry blended and processed using the identical procedure as in Example 1 and compression molded using the identical molding conditions as in Example 1.

Example 60

A monomer mixture of the following composition is made from the following components:

Glycidyl methacrylate ... 20 Weight percentage :, MeLimethacrylat .... 55 percent by weight

Ethyl acrylate. 25 percent by weight

The polymerization is carried out using the identical procedure as in Example 1 with the SSm? that the applied concentration of AKN catalyst 1% (based on weight Reaction participants) is The obtained ^ has a Tg value of 50 = G and a

SS SSSKA range of 30 _g * o mif 2 5 g of succinic anhydride and 0.033 g BenzyldTmethylphenylammoniumchlorid mixed After Issem mixing the ingredients in the KugelmüWe the powder is gen using identical Beingm processed as in Example 1 and under _aS AnwenSg the identical molding conditions of BeTptel 1 to a plate processed by compression molding.

Claims (1)

Lines, in particular those for transferring patent claims: heated liquids and the like can be used and molded articles made from them. 1. Thermosetting molding powder consisting of the novel thermosetting resin according to the invention a particulate intimate mixture of: 5 powders that are molded to form products A: a copolymer which can be obtained, which is different in the bending determination is through copolymerization of due to relatively high elongation at break, strength and a> 15 b.40Ge.Jchtspro ™, G, _y c _io "me,". ^^^ L ^ XZ