DE2261330A1 - HEAT-RESISTANT MOLDING POWDERS USING POLYMERS WITH GLYCIDYL METHACRYLATE FUNCTION AND MONOMER ANHYDRIDE CROSS-LINKING AGENTS, AND MOLDED BODIES MANUFACTURED FROM THEM - Google Patents

Description

The invention relates to self-crosslinking, dry, thermosetting molding powder which is used for rapid hardening during the. Processing, for example by compression molding and injection molding processes, and are suitable for the production of solid or rigid, tough materials, e.g. for car body panels, housings for electrical systems, boat constructions, Storage tanks, lines, in particular those for the transfer of heated liquids and the like, can be used

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are and molded articles made from them.

The novel thermosetting resin powder of the present invention, the can be shaped with the formation of products that are characterized by relatively high elongation at break in the bending determination, Strength and high modulus and characterized by a high glass transition temperature are made from a mixture of a prepolymers consisting essentially of glycidyl methacrylate, methyl methacrylate and methacrylonitrile or acrylonitrile and an anhydride crosslinking agent.

After molding, the thermosetting materials of the invention have a glass transition temperature of over 9CPC, preferably over 12D ¹ C. These moldings give a strength in the range of about 1,100 to 2,100 kg / cm at room temperature (20 to 25 ° C) when determined for bending ² (16,000 to about 30,000 psi) or greater, a modulus in the range of about 0.084 to 0.16 10 ⁶ kg / cm ² (about 1.2 to 2.25 χ 10 ⁶ psi) or greater, and an elongation at break ranging from about 1 to about 3 % or higher.

The glass transition temperature is the temperature at which a vitreous material loses its rigidity and hardness and approaches the behavior of an elastomer. More accurate Expressed, the glass transition temperature is expressed as the temperature defined at which this material is a maximum of its mechanical damping at low frequencies, e.g. about one oscillation per second.

I. Composition of the prepolymer

The prepolymer preferably has at least three monomer components and, with the exception of the limited substitution indicated below, has the following basic composition :

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Glycidyl methacrylate 15 - 40, preferably 20 - 35% by weight Methacrylonitrile 0-30, preferably 10-25% by weight of methyl methacrylate remainder

Methacrylonitrile can be replaced in whole or in part by acrylonitrile, but methacrylonitrile is the preferred Respondents; as products made from this component containing prepolymers and the crosslinking agents used here, a higher heat distortion temperature (Glass transition temperature) than the corresponding products using acrylonitrile, all other factors being equal.

A smaller proportion of the methyl methacrylate, preferably not more than 1/3, can be replaced by styrene, α-methylstyrene, vinyl acetate or a different ester of acrylic or methacrylic acid and monohydric alcohol, preferably an alcohol with 2 to 4 carbon atoms, for example ethyl acrylate, butyl acrylate, Butyl methacrylate and the like. This replacement should not exceed about 15% of the total amount of monomers used to form the prepolymer, and preferably does not exceed 10 %. In the case of the CV substitute, this component preferably does not exceed 1/5 of the methyl methacrylate. With the exception of styrene, the substitution agents mentioned in this paragraph result in an increase in the flexibility of the polymer, ie the elongation at break, and a decrease in the softening point (glass transition temperature).

II. Properties of the prepolymer

The prepolymer has an average molecular weight in the range from about 1,500 to about 16,000, preferably about 2,000 to about 10,000, and more preferably about 3,500 to

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about 8,000 as determined by vapor phase osmometry using methyl ethyl ketone as solvent. »Less than about 5 % of the molecules should have a molecular weight below about 1,000.

The prepolymer has a softening point of over 25 ^° C., preferably in the range from about 50 to about 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. 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 obtained by evaporation however, if this embodiment is used, the product should be washed with an appropriate solvent washed to remove low molecular weight components.

A free radical initiator is used in the combined monomers Dissolved reactants and is advantageously used in an amount of about 1 to 4% by weight of the combined weight of monomers applied. Usual free radical initiators are suitable for this purpose, such as Acyl peroxides, peresters and azo compounds. For specific materials that have been used with success, include 2,2 * -azobis (2-methylpropionitrile), the following is designated as AIBN, benzoyl peroxide, tert-butyl perbenzoate and tert-butyl peroxypivalate.

As mentioned above, the reaction 1Ii takes place in an inert Solvents, for example toluene or a mixture of toluene and dioxane and the like. Appropriate the weight of the solvent is equal to or less than

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the combined weight of reactant and initiator.

In a preferred method of preparation, the monomeric reactants and the free radical initiator are used added in small portions, e.g., dropwise, to the refluxing solvent under nitrogen. After the addition is complete, the initiator is used in an amount of about 0.1% of the monomer weight in a small amount Solvent dissolved and added over a period of 20 to 60 minutes. The reflux treatment is then about Continued for 2 hours. The prepolymer is then coagulated won. This is preferably done in the manner described below. The reaction solution becomes further diluted with additional solvent until the prepolymer is about 20 to about 30% by weight of the resulting solution matters. This solution is then slowly added to a liquid which causes the prepolymer to precipitate. In this case, hexane is very suitable. A fine powder precipitates. This is filtered off, dried and broken open by rolling or grinding if necessary.

In addition to the above-described method of preparing the prepolymer, the prepolymer can be prepared according to known ones Methods of emulsion polymerization, bulk polymerization and suspension polymerization can be prepared. The suspension polymerization is preferably carried out using water as the suspending medium. Because ionic Stabilizers react with glycidyl methacrylate, only non-ionic materials can be used for stabilization the suspension can be used. Polyvinyl alcohol and a Alkylaryl polyether alcohol (Triton X. 100, Rohm & Haas Co.) turned out to be very satisfactory. To carry out the suspension polymerization, the monomer mixture is added

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A cooled (about (K) 0.1% solution of polyvinyl alcohol in water) is added. The mixture is rapidly agitated ^! ** ~ * : ~ .ν.ή the initiator is added over a period of about 30 minutes then controlled so that it remains between 55 and 6O ⁰ C for 6 to 8 hours. After cooling to room temperature, the polymer is filtered off. Since the polymerization must be carried out below 65 ⁰ C, only the initiators, the one below this temperature An effective source of free radicals can be used. Suitable initiators for the suspension polymerization include tert-butyl peroxypivalate and diisopropyl peroxycarbonate. 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 used in the invention are suitable, the anhydrides fall into the following three classifications:

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

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

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Carbon atom are separated), for example glutaric anhydride, 1,2-dimethylglutaric anhydride and 1,3-dimethylglutaric anhydride and

(3) monomeric anhydrides of cyclic di-, tri- or tetracarboxylic acids, wherein 3ecLes carbon atom of an anhydride group directly with one carbon atom of a pair of directly bonded and adjacent carbon atoms one C. Connected to C ^ Q ring structure.

(a) If the ring is aromatic, this embodiment is for example phthalic anhydride ... trimellitic anhydride, Dimellitic anhydride and naphthalenetetracarboxylic dianhydride are illustrated.

(b) If the ring is a saturated aliphatic (carbon-carbon) Ring is, this embodiment is represented by hexahydrophthalic anhydride, cyclooctane-1,2-dicarboxylic anhydride and cyclobutanedicarboxylic anhydride.

(c) If the ring is an unsaturated aliphatic (carbon -Carbon) ring, this embodiment is exemplified by Tetrahydrophthalsäu » reanhydride explained.

(d) When the ring is a heterocyclic ring, this embodiment is represented by, for example, tetrahydrofuran-2, 3 »^ _f 5-tetracarboxylic acid dianhydride, 7-0xabicyclo [2.2.1] -heptane-1,3-dicarboxylic acid anhydride and 7-heptane-2 , 3-dicarboxylic anhydride and 7-0xabicyclo [2.2.1] -hept-5-ene-2,3-dicarboxylic anhydride.

It is clear to the person skilled in the art that in the monomeric anhydrides listed above, a hydrogen atom is replaced by a Methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy or Butoxy group or can be replaced by a halogen atom. In the case of heterocyclic anhydrides, can

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a ring substitution for a carbon atom by an oxygen atom, a sulfur atom, a divalent silicon radical or a divalent phosphorus radical take place. The anhydride is used in an amount sufficient to provide about 0.5 to about 1.5, preferably 0.6 to 0.9, _{f of} hydride groups for each epoxy group in the molding powder.

V. Partial replacement of the prepolymer with epoxy compound A smaller proportion, ie about 2 to about 20 % of the epoxy groups provided by the prepolymer can be replaced by using an epoxy compound with at least two epoxy groups, preferably a diepoxide, for this portion of the prepolymer.

These diepoxides should be ^{liquid at 14O 3} C or below and have a molecular weight in the range from about 300 to about 4,000 and a viscosity at 14O ⁵ C of less than 50 poises.

The diepoxide can be an aromatic, an acyclic aliphatic or cycloaliphatic diepoxide. These diepoxides should consist essentially of carbon, hydrogen and oxygen, but may have substituents, which do not interfere with the crosslinking reactions, e.g. sulfonyl groups, nitro groups, alkylthio groups and halogens.

These diepoxides are known and many are commercially available. Typical examples include diglycidyl esters of polybasic or dibasic acids according to the US patent 2,866,767; Diglycidyl ethers of dihydric phenols disclosed in U.S. Patents 2,467,171, 2,506,486, 2,640,037 and 1,841,595i Diglycidyl ethers of diols disclosed in US Pat. Nos. 2,538,072 and 2,581,464 and diepoxides obtained by peracid epoxidation of Serve to be received. A collection of suitable diepoxides is illustrated in US Pat

is referred to here. Although the diepoxides for the invention are to be preferred, low viscosity polyepoxides can also be used with advantage.

VI. Catalysts

A catalyst is used in the molding powder mixture to facilitate the crosslinking reaction. Quaternary ammonium salts give a high degree of specificity for the epoxy-anhydride reaction. These include tetrabutylammonium amide, -chloride, -bromide, tetraethylammonium-iodide, -chloride and -bromide, tetramethylammonium bromide, -chloride and -iodide, benzyltrimethylammonium iodide, -chloride and -bromide, -benzyldimethylammoniumbromide and -benzyldimethyl-iodo-bromide chloride, benzyldimethylammonium-bromide-chloride chloride and the like. Catalysts of this type are useful in amounts of about 0.05 to about 1.0 wt.% Of the combined reactants.

Other catalysts ₅ that can be used include solid tertiary amines such as triethylenediamine, amine salts such as trimethylamine ptoluenesulfonate or imidazoles such as 2-ethyl-4-methylimidazole or metal carboxylates such as lithium benzoate. Catalysts of this type are suitable in the same concentration ranges as indicated above.

These catalysts were found to be latent catalysts for the anhydride-epoxy reactions. This means that the catalysts do not noticeably increase the reaction rate at room temperature, but are effective above certain temperatures. The catalysts which are latent up to at least 50 ³ C are preferred.

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VII. Preparation of the Molded Powder Mixture The powdered prepolymer, crosslinking agent and catalyst are dissolved in a suitable solvent, for example acetone, methylene chloride, benzene and the like, and the solution is stirred thoroughly. The solvent is evaporated in vacuo leaving a solid cake which is broken into a fine powder. The powder is further dried under vacuum so that it contains less than 1 % solvent.

It is also possible to add crosslinking agent and catalyst to the prepolymer solution obtained by polymerization. The solution is stirred until homogeneous and then slowly added to a vigorously stirred precipitant such as hexane. The precipitated powder is dried under vacuum. To ensure its homogeneity, the molding powder is passed through a roller mill at 50 to 10O ¹³ C. Instead of using the precipitant and the roller mill, it is only possible to evaporate the solvent from the prepolymer solution.

Another method of making the molding powder is to use the powdered prepolymer, crosslinking agent and mixing the catalyst together and passing it through an extruder mixer or a roller mill to homogenize.

If necessary, reinforcing fillers such as asbestos, glass fibers, clay, calcium carbonate, Calcium silicate and the like can be incorporated into the molding powder. A particularly effective filler is calcium metasilicate (CaSiO,).

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The powders produced in this way are suitable for use in injection molding, compression molding and transfer molding.

The invention is described in more detail with reference to the following illustrative examples, the flexural properties of the fittings are determined by the bending test of the American Society of Testing & Materials, D 790 - 1966. In This test uses rectangular bars 3.2 mm (1/8 inch) thick, 13 to 15 mm (0.5 mm wide) to 0.6 inch) and a length of 10.2 cm (4 inches) was used to determine flexural properties. For testing a mechanical Instron tester (table model) is used here. It is driven at a crosshead speed of 0.1 cm / min (0.04 in / min) and a recording sheet speed of 5 cm / min (2 in / min). The formulas in procedure B (ASTM - D 790-66) are used for calculation the flexural modulus, elongation at break and strength.

The prepolymers in the illustrative examples have softening points between 50 and 110 ^° C., with less than 5 % of the molecules having a molecular weight below 1,000. The molded articles of all examples have glass transition temperatures above 90 ⁰ C.

example 1

A prepolymer is prepared from the following ingredients in the following manner: Reactant Amount (g)% by weight of glycidyl methacrylate 532 31

Methyl methacrylate 870 50.5

Methacrylonitrile 318 18.5

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AIBN, ie 2.2 ^f -azobis (2-methylpropionitrile), is added to the monomer mixture in an amount of 54 g (3%). This solution is added dropwise over a period of 4 hours to 1,950 ml of toluene at 108 to 111 ^° C. under a nitrogen atmosphere. Then 2.0 g of AIBN, dissolved in 20 ml of acetone, are added over a period of 1/2 hour and the reflux treatment is continued for 3 more hours.

The polymer solution is diluted with 3,000 ml of acetone and coagulated in hexane. The white powder is dried 7O ⁰ C in a vacuum oven 35 h at. The molecular weight was ^ / M _n = 6231/3466 with a molecular weight per epoxide unit, hereinafter referred to as WPE, of 496.

This prepolymer is used in the manufacture of molding powder. In this procedure 35.0 g of the prepolymer are obtained combined with 10.7 g of tetrahydrophthalic anhydride and 0.046 g of tetrabutylammonium iodide and 16 hours in the ball mill ground. Then 28.0 g of this powder are combined with 32.0 g of calcium metasilicate (CaSiO,) and put in the ball mill for 2 hours marry. The resulting mixture is made the same with 20.0 g of staple glass fibers (average length 6.3 mm (1/4 inch)) Length is used in all later examples unless otherwise specified). After union of the molding powder with the staple glass fibers, the mixture is circulated. This will make the mixing of all the ingredients produced without damaging the fiber. A preform is then made for molding.

This powder and fiber mixture is formed into a sheet or plate (11.9 × 13 cm) by pressing the mixture at a pressure of 105 kg / cm (1,500 psi) and a temperature of 193 ^° C. (380 ^{° F) for 30 minutes} 2 0.3 cm - 4.7 x 5.2 χ 1/8 inch - all molded panels in the examples below have these dimensions.

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This molded article gives the following flexural properties Flexural strength elongation at break flexural modulus

kg / cm ² (psi) % kfl / cnn (p si)

1760 (25,000) 2.0 0.15 x 10 ^b (2.2 χ 10 ⁶ )

This molding powder was found to be processable, i.e., all in one State for carrying out the above measures after standing at room temperature for 3.5 months »

Example 2

The prepolymer of Example 1 is mixed in an amount of 35.0 g with 7.1 g of succinic anhydride and 0.058 g of tetrabutylammonium chloride. After grinding this mixture in the ball mill for 16 hours, 28.0 g of this mixture are mixed with 32.0 g of calcium metasilicate and ground 2 Stalin in the ball mill. The resulting mixture is g with 2O _5, Q stacking glass fibers mixed "Wax Federation of the mold powder with the staple fibers, the mixture is circulated _g to distribute the glass fibers, and it is a preform made for molding.

A plate made from this material is molded under identical molding conditions as those used in Example 1. shaped »It has been found that this panel has the following flexural properties:
Flexural strength elongation at break flexural modulus

kg / cm ² (psi) % kff / cm ² (psi)

1560 (22 100) 1.7 0.14x1 O ^ (2.04x10 ⁶ )

Example $

The prepolymer of Example 1 is mixed in an amount of 25.0 g with 7.5 g of phthalic anhydride and 0 ₉ 049 g of tetrabutylammonium bromide. After marrying the family for 16 hours

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components in the ball mill are 32.5 g of the molding powder with 37.0 g calcium metasilicate and 23 »2 g staple glass fibers mixed and processed using the identical procedure as in the previous examples.

A plate molded from this material molded using identical molding conditions as in Example 1 has the following flexural properties: flexural strength elongation at break flexural modulus

kg / cm (psi) % kg / cm (psi)

1690 (24,000) 1.9 0.13 x 10 ⁵ (1.85 x 10 ⁶ )

Example 4

The prepolymer from Example 1 is combined in an amount of 25.0 g with 6.6 g of glutaric anhydride and 0.32 g of tetraethylammonium bromide. After the constituents have been ground in the ball mill for 1.6 hours, 28 g of the molding powder are processed using the identical method as in Example 1 with 32 g of calcium metasilicate and 20.0 g of staple glass fibers. A plate is molded using the same molding conditions as in Example 1. This plate had the following flexural properties:
Flexural strength elongation at break flexural modulus

kg / cm (psi) % kg / cm (psi)

1580 (22 400) 1.5 0.14 χ 10 ⁵ (2.03 χ 10 ⁶ )

Example 5

The prepolymer from Example 1 is combined in an amount of 25.0 g with 7.7 g of hexahydrophthalic anhydride and 0.0033 g of tetramethylammonium iodide. After dry mixing of the ingredients by grinding in a ball mill for 15 hours, 28.0 g of this mold powder are added using the identical procedure as in Example 1 with 32.0 g of calcium metal.

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silicate and 20.0 g of StapeX glass fibers processed. It becomes a plate using the identical molding conditions shaped as in Example 1, which had the following flexural properties:

Flexural strength elongation at break flexural modulus

kg / cm ² (psi) % kg / cm ² (psi)

1720 (24 500) 1.8 0.14 χ 10 ^b (2.02 χ 10 ⁶ )

Example 6

The prepolymer of Example 1 is added in an amount of 25.0 g with 5.0 g of trimellitic anhydride and 0.030 g of benzyldimethylphenylammonium chloride united. After dry mixing of the ingredients by grinding in a ball mill for 15 hours 28.0 g of the molding powder mixture with 32.0 g of calcium metasilicate and 20.0 g of staple glass fibers using the identical procedure as in Example 1 processed. One Plate is made by compression molding using the identical conditions as in Example 1.

Example 7

The prepolymer of Example 1 is used in an amount of 25 »0 g with 8.0 g of octric anhydride, i.e. α- [2-carboxyethyl] -glutaric anhydride and 0.033 g of triethylenediamine combined. Wake up dry mixing of the ingredients by grinding for 15 hours 28.0 g of this molding powder with 32.0 g of calcium metasilicate and 20 g of staple glass fibers are placed in the ball mill Using the identical procedure as in Example 1 processed. A plate is produced by compression molding using the identical conditions as in Example ί.

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Example 8

The procedure of Example 1 is followed with the exception of the exception repeats that the tetrahydrophthalic anhydride is replaced by an equimolar amount of p-chlorophthalic anhydride will.

Example 9

The procedure of Example 1 is repeated with the exception that the tetrahydrophthalic anhydride by replaced an equimolar amount of tetrabromophthalic anhydride

Example 10

The procedure according to Example 1 is, with the exception of the calibration repeats that the tetrahydrophthalic anhydride is replaced by an equimolar amount of methylsuccinic anhydride will.

Example 11

The process of Example 1 is repeated with the exception that the tetrahydrophthalic anhydride is replaced by an equimolar amount of 4.4 ^l - (2-acetoxy-1,3-glyceryl) bisanhydrotrimellic anhydride.

Example 12

The process of Example 1 is repeated with the exception that the calcium metasilicate is replaced by 40 g of calcium carbonate is replaced.

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Example 15

The procedure of Example 1 is repeated "Chung except Atwei that the tetrahydrophthalic anhydride is replaced with tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride in an amount such that a number of anhydride groups is provided which is equal to the replaced number ₀

Example 14

The procedure of Example 1 is repeated with the exception that the tetrahydrophthalic anhydride is replaced by an equimolar amount of 7-0xabicyclo [2 _o 2 ", 1] hept-5-ene-2 _i> 3-di · - carboxylic anhydride"

Example ^ 15

The procedure of Example 1 is repeated with the exception that the tetrahydrophthalic anhydride is replaced by an equimolar amount of 7-C) xabicyclo [2.2.1] heptane = 2 ₉ 3-dicarboxylic anhydride »

Example J? J5

The procedure of Example 1 is repeated with the exception of differential _t \ that the amount of Calciummetasilicats used is g 20th

Example 17 ^ ^:

The procedure of Example 1 is that the prepolymer of 40 wt.% Glycidyl methacrylate and 60 wt.% Of methyl methacrylate formed ν ± τά and the amount of the anhydride used is adjusted so ,, that the change in the number of repeats with the exception of.-Abxfeichung, Epoxy groups in the prepolymer

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ren is compensated.

Example 18

The procedure of Example 1 is, with the exception of the deviation repeats that the prepolymer of 35 wt. $ glycidyl methacrylate, 25% by weight of methacrylonitrile and 40% by weight of methyl methacrylate is formed and the amount of amhydride is adjusted so that the change in the number of epoxy groups is compensated in the prepolymer.

Example 19

The procedure according to Example 1 is repeated with the difference, that the prepolymer consists of 30% by weight glycidyl methacrylate, 20% by weight of methacrylonitrile and 50% by weight of ethyl methacrylate formed and the amount of anhydride is adjusted so that the change in the number of epoxy groups in the prepolymer is compensated.

Example 20

The procedure of Example 1 is, with the exception of the deviation repeats that the prepolymer of 30 wt. SS glycldyl methacrylate, 20% by weight of acrylonitrile and 50% by weight of methyl methacrylate is formed and the amount of anhydride is adjusted so that the change in the number of epoxy groups in the Prepolymer is compensated.

Example 21

The procedure according to Example 1 is repeated with the difference, that the prepolymer from 20 Gew.ü5 glycidyl methacrylate, 25% by weight methacrylonitrile, 5% by weight Butyl acrylate, 5 wt.? 5 Butyl methacrylate, 5% by weight of 2-ethylhexyl acrylate and 40% by weight

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Methyl methacrylate is formed with the amount of anhydride is adjusted so that the change in the number of epoxy groups in the prepolymer is compensated ",

Example 22

The procedure of Example 1 is repeated with the difference that the prepolymer of 15 wt.% Glyeidylmethacrylat, 30 wt.% Of methacrylonitrile, and 55 wt.% Of methyl methacrylate is formed and the Aaahydridmenge Set- is such that the change in the number of epoxy groups in the prepolymer is compensated.

Example 23

The procedure of Example 1 is repeated with the difference that the prepolymer of 35 wt.% Glycidyl methacrylate, 10 wt.% Of methacrylonitrile, 10 wt.% Styrene and 45 wt.% Of methyl methacrylate formed, and the amount of anhydride is adjusted so that the Change in the number of epoxy groups in the prepolymer is compensated for.

Example 24

The process of Example 1 is repeated with the difference that the prepolymer is formed from 15 wt. $ 6 glycidyl methacrylate, 30 wt. % Methacrylonitrile and 55 wt Prepolymer is compensated.

Example 25

The procedure according to Example 1 is repeated with the difference

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derholt that the prepolymer of 20 Gew.56 glycidyl methacrylate, 30 wt.% acrylonitrile and 50 wt.% of methyl methacrylate is formed and the amount of anhydride is adjusted so that the change in the number of epoxy groups is compensated in the prepolymer.

Example 26

The procedure of Examples 1 through 10 inclusive is followed by the deviation repeats that the anhydride is used in an amount equal to 0.5 anhydride groups ^ e epoxy group in the supplies thermosetting molding powder.

Example 27

The procedure of Examples 1 to 10 inclusive is repeated except that the anhydride is in an amount is used which provides 1.5 anhydride groups per epoxy group in the thermosetting molding powder.

Example 28

The process of Example 1 is repeated with the difference that the molecular weight (M_) of the prepolymer is about 1 500 is.

Example 29

The procedure of Example 1 is repeated with the difference that the molecular weight (M _n ) of the prepolymer is about 2,000.

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Example 50

The procedure according to Example 1 is repeated with the softening, that the molecular weight (^ L) of the prepolymer is about 3,000.

Example 51

The procedure according to Example 1 is repeated with the difference, that the molecular weight (ML) of the prepolymer is about 6,000.

Example 52

The procedure of Example 1 is repeated with the difference that the molecular weight (M) of the prepolymer is about Is 10,000.

Example 55

The procedure of Example 1 is repeated with the difference that the molecular weight (H _n ) of the prepolymer is about 16,000.

Example 54

The procedure of Example 1 is, with the exception of the deviation repeats that in the preparation of the prepolymer 25% by weight of the methyl methacrylate by an equimolar Amount of styrene to be replaced.

Example 35

The procedure according to Example 1 is carried out with the exception of the

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chung repeats that in the preparation of the prepolymer 25% by weight of the methacrylonitrile by an equimolar amount
Acrylonitrile can be replaced.

Example 36

The process of Example 1 is repeated with the exception that in the preparation of the prepolymer 50% by weight of the methacrylonitrile by an equimolar amount
Acrylonitrile can be replaced.

Example 37

The process of Example 1 is repeated with the exception that in the preparation of the prepolymer 75% by weight of the methacrylonitrile by an equimolar amount
Acrylonitrile can be replaced,

Example 36 . '..

The procedure of Example 1 is repeated except for the difference that 25 wt.% Of methyl methacrylate are replaced by an equimolar amount of a-methyl styrene in the preparation of the prepolymer.

Example 39

The procedure of Example 1 is, with the exception of the deviation repeats that in the manufacture of the molding powder The amount of catalyst used is 0.05% by weight of the combined weight of the reactants.

Example 40

The procedure according to Example 1 is carried out with the exception of the

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chung repeats that in the manufacture of the molding powder Amount of catalyst used 0.25% by weight of the combined weight the respondent is.

Example 41

The procedure of Example 1 is repeated with the difference that that used in the production of the molding powder Amount of catalyst 0.5% by weight of the combined weight of the reactants amounts to.

Example 42

The procedure of Example 1 is repeated with the exception that that used in the preparation of the molding powder Amount of catalyst 1.0 wt% of the combined weight the respondent is.

Example 43

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 held at 90 to 100 ^° C. for 1 hour. The mixture or adduct is quite fluid at 100 ⁰ C. The mixture or adduct mixture is allowed to cool and solidify. It is then ground to a fine powder. The molding powder is put together by combining 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. After grinding the constituents in the ball mill for 16 hours, 28.0 g of the molding powder with 32.0 g of calcium metasilicate and 20.0 g of staple glass fibers are processed using the identical procedure as in Example 1.

The molding powder is made into a plate by compression molding

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Using the identical molding conditions as in Example 1 produced. This plate has the following bending properties:

Flexural strength Elongation at break Flexural modulus kg / cm (psi) % kg / cm (pci) 1900 (27 200) 1.7 0.158 χ 10 ⁶ (2.25 χ 10 ⁶ )

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 to 525 and average molecular weight about 900th

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

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Μ — O,

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J-O I

: —Οι

ο —ο — ο

κ— ο - κ

ι JU — ο - tr}

I SS— ϋ

I O

co TT ο

O - O -

O I

I I

Example 44

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 used in an amount to provide the same number of epoxy groups.

Example 45

The procedure of Example 43 is repeated except that a quantity of the prepolymer which provides 10% of the epoxy groups is replaced by the diepoxide of Example 43 and is applied in an amount which provides the same number of epoxy groups.

Example 46

The procedure of Example 43 is repeated with the exception that an amount of the prepolymer which provides 20% of the epoxy groups is replaced by the diepoxide of Example 43 and is used in an amount which provides the same number of epoxy groups.

Example 47

The procedure of Example 43 is repeated except that an equimolar amount of an aliphatic diepoxide is used in place of the aromatic diepoxide used in Example 43. This aliphatic diepoxide is prepared as follows: 1 mol of 2,3-butanediol (91 »12 g) and 4 mol of epichlorohydrin (370 g ) brought in. The temperature is kept at 110 ⁰ C, while 2 mol of sodium hydroxide (80.0 g)

added dropwise as a 30% aqueous solution. The rate of addition is regulated so that the reaction mixture remains neutral. After about 3 hours, the organic layer is separated, dried, distilled and concentrated Polymer is obtained. This polymer product is represented by the following structural formula:

309827/1015

do

I. U 35 I.
• 4 —Κ < ^ o C. on
35
r < -35 ■■ »-ν_ # ■ - »» JtJ χ - Ι-ι-Ι _ C —W -O X , I.
-ο-a ■ "" "'■'" '• "Li I. ι
-υ cn
X
ο— O ι I.
-O -ο 35 I.
-Γ "> ι m
35
-O I. O I.
κ— O I. I. ac
ο— -O I.
■ Ü 35— I. O I. OO ■ ο O - I. 33— ,O I. I. O 35 - <

309827/1015

Example 48

The procedure of Example 43 is followed with the exception of the exception repeats that the tetrahydrophthalic anhydride is replaced by an equimolar amount of succinic anhydride.

Example 49

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

Example 50

The procedure of Example 43 is followed with the exception of the exception repeats that the tetrahydrophthalic anhydride is replaced by an equimolar amount of phthalic anhydride «

Example 51

A prepolymer is made using the identical process, which was used to prepare the prepolymer according to Example 1, made from the following monomers, which are used in the following conditions? Glycidyl methacrylate, 30 wt.? 6 Methacrylonitrile - 18% by weight methyl methacrylate 52% by weight

AIBN 1.5% by weight

The molecular weight is obtained using about 2 wt.% _# Regulated on the combined weight of the reactants, of lauryl mercaptan.

The prepolymer obtained has a molecular weight of = 8564/4674 and a WPE ¥ ert of 474. It becomes a 309827/1015

Molding powder mixture by grinding in a ball mill for 15 hours of 100.0 g of the copolymer with 32.1 g of tetrahydrophthalic anhydride and 0.250 g of triethylenediamine produced. This mixture is used in an amount of 28.0 g with 32.0 g of calcium metasilicate and 20..0 g of staple glass fibers processed according to the identical procedure of Example 1.

From this mixture, using the identical molding conditions as in Example 1, a plate is produced by compression molding. This sheet has the following flexural properties: Flexural strength Elongation at break Flexural modulus kg / cnr (psi) % kg / cnr (psi) 1730 (24 642) 1.82 0.13 x 10 ^b (2 _t 17 x 10 ⁶ )

Example 52

The procedures of Examples 1 and 43 are used with the exception repeats that the tetrabutylammonium iodide by an equimolar amount of tetramethylammonium chloride is replaced,

Example 53 '

The procedures of Examples 1 and 43 are repeated with the difference that the tetrabutylammonium ^ odid by a equimolar amount of tetraethylammonium bromide is replaced.

Example 54

The procedures of Examples 1 and 43 are used with the exception repeats that the tetrabutylammonium iodide is replaced by an equimolar amount of tetrabutylammonium bromide,

Example 55

The procedures of Examples 1 and 43 are carried out with the deviation

3 0 9 8 2 7/1015

chung repeats that the tetrabutylammonium iodide by a equimolar amount of benzyldimethylphenylaramonium iodide is replaced.

Example 56

A heat-cured molding is produced without filler in the following "manner: The prepolymer according to Example 1 is in an amount of 100.0 g with 32.07 g of tetrahydrophthalic acid anhydride and 0.250 g of triethylenediamine mixed. After grinding the ingredients in the ball mill for 15 hours the molding powder mixture was molded under the identical conditions of the molding process used in Example 1. These shaped plate has the following flexural properties: flexural strength elongation at break flexural modulus

ί
kg / cm ' (16 (psi) % -SZ kpc / cm (psi) 1150 300) 3.1 41050 (582 835) example

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

Example 58

The procedures of Examples 1 and 43 are repeated except that the anhydride is used in an amount will, the 0.9 anhydride groups per epoxy group in the thermosetting Mold powder supplies.

Example 59

A monomer mixture with the following composition is

3 0 9827/1015

production:

Glycidyl methacrylate 15% by weight

Methyl methacrylate 57% wt.

Isobornyl methacrylate 28% by weight

The polymerization is carried out using the identical procedure of Example 1 with the exception that the concentration of AIBN catalyst used is 1 % (based on the weight of the reactants). The prepolymer obtained has a Tg (glass transition temperature) of about 11O ⁰ C and an average molecular weight of about 8 500th

This prepolymer is in an amount of 30.0 g with 2.1 g Glutaric anhydride and 0.0320 g of tetrapropylammonium iodide mixed. The mixture is dry blended by ball milling for 15 hours and using the identical Process processed 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 prepared from the following ingredients:% by weight glycidyl methacrylate 20 Methyl methacrylate 55% by weight of ethyl acrylate 25 Gev.%.

The polymerization is carried out using the identical procedure as in Example 1 with the exception that the concentration of AIBN catalyst used is 1 % (based on the weight of the reactants). The prepolymer obtained has a Tg value of 50 ^° C. and an average molecular weight of about 8,500.

309827/1015

This prepolymer is in an amount of 30 g with 2.5 g of succinic anhydride and 0.033 g of benzyldimethylphenylammonium chloride mixed. After mixing the ingredients in the ball mill for 15 hours, the powder becomes more identical using Conditions processed as in Example 1 and using the identical molding conditions of Example 1 to a plate processed by compression molding.

The above examples serve to illustrate the invention without limiting it. ·

309827/1015

Claims (40)

Claims 1. Molding powder, characterized by » that it is a particulate intimate mixture (a) a copolymer, (1) that of about 15 to about 40 Gev,% glycidyl methacrylate » 0 to about 30 weight percent acrylonitrile and one essentially The remainder consists of methyl methacrylate and (2) an average molecular weight in the range of about 1,500 to about 16,000, a softening point above 25 "C and has epoxy groups in its molecular structure, which is characterized by the inclusion of glycidyl acrylate as a component monomer thereof, and (b) a monomeric anhydride present in an amount that is about 0.5 to about 1.5 anhydride groups per epoxy group in the form of powder, contains .. 2. molding powder according to claim 1, characterized that the copolymer has an average molecular weight in the range of about 2,000 to about 10,000. 3. Form powder according to claim 1, characterized that the copolymer has an average molecular weight in the range of about 3,500 to about 8,000. 4. Molding powder according to claim 1 to 3, characterized in that less than 5 % of the molecules of the copolymer have a molecular weight below 1,000. 3 0 9 8 2 7/1015 5. molding powder according to claim 1 to 4, characterized in that. that the anhydride in an amount is used containing about 0.6 to about 0.9 anhydride groups each Epoxy group in the molding powder results in » 6. molding powder, characterized in that that it is a particulate intimate mixture (a) a copolymer ^ (1) that of about 15 to about 40% by weight glycidyl methacrylate 0 to about 30% by weight of acrylonitrile or methacrylonitrile and a radical consisting essentially of methyl methacrylate and (2) an average molecular weight in the range of about 1,500 to about 16,000, a softening point of over 25 ⁰ C and epoxy groups in its molecular structure, which result from the inclusion of the glycidyl methacrylate as a monomer component thereof and (b) contains a monomeric anhydride which is present in an amount which gives about 0.5 to 1.5 anhydride groups per epoxy group in the molding powder, the anhydride from (1) monomeric anhydrides of acyclic dicarboxylic acids in which each carbon atom in an anhydride group is directly is linked to one carbon atom of a pair of carbon atoms that are directly bonded and are adjacent to each other, (2) monomeric anhydrides of acyclic dicarboxylic acids in which each carbon atom in an anhydride group is directly is connected to one carbon atom of a pair of carbon atoms, which are represented by at least 1 Carbon atom are separated and / or (3) monomeric anhydrides of cyclic di-, tri- or tetracarboxylic acids where each carbon atom of an anhydride group directly connects to a carbon atom 309827/1015 of a pair of directly linked and adjacent carbon atoms in a ring structure of 4 to 10 carbon atoms. 7. molding powder according to claim 6, characterized that the copolymer has an average molecular weight in the range of about 2,000 to about 10,000. 8. molding powder according to claim 6, characterized in that the copolymer has an average molecular weight in the range of about 3,500 to about 8,000. 9. molding powder according to claim 6 to 8, characterized in that less than 5 % of the molecules of the copolymer have a molecular weight below 1,000. 10. The molding powder of claim 6 to 9 _f characterized in _t that is used in addition to the copolymer a different epoxy resin having at least two epoxy groups per molecule, a molecular weight in the range of about 300 to about 4000 and a viscosity at 140 ⁰ C of less than 50 poises, the variant epoxy resin being used in an amount which provides between about 2 to about 20 percent of the epoxy groups in the molding powder. 11. The molding powder of claim 6 to 10, characterized in that in addition to the copolymer a diepoxide is employed which has a molecular weight in the range of about 300 to about 4000 and a viscosity at 140 ⁰ C of less than 50 poises, wherein the diepoxide 4 · ^{η is used in} an amount which provides between about 2 and about 20 % of the epoxy groups in the molding powder. 12. Molding powder according to claim 6 to 11, characterized in that g e - 309327/1015 indicates that -particulate form reinforcing filler is intimately dispersed with the copolymer and the monomeric anhydride. 13. Molding powder according to claim 6 to 12, characterized in that that particulate CaSiO ^ and glass fibers intimately with the copolymer and the monomeric anhydride are dispersed. 14. Molding powder according to claim 6 to 13 _f dadur-ch, that the anhydride is used in ^{1 in} an amount which provides about 0.6 to about 0.9 anhydride groups per epoxy group in the molding powder. 15. Molding powder according to claim 6 to 14, characterized that it is a particulate intimate mixture (a) a copolymer ^ (1) the j from about 15 to about 40 Ge \.% Glycidyl methacrylate, about 10 to about 25 wt.% Of acrylonitrile or methacrylonitrile and a group consisting essentially of methyl methacrylate and balance being (2) an average molecular weight in the range of about 2,000 to about 10,000, a softening point of over 25 ⁰ C and epoxy groups in its molecular structure, which result from the inclusion of the glycidyl methacrylate as a monomer component thereof and (b) contains a monomeric anhydride which is present in an amount the about 0.5 to about 1.5 anhydride groups per epoxy group in the form of powder, the anhydride of (1) monomeric anhydrides of acyclic dicarboxylic acids, in which each carbon atom in an anhydride group directly with one carbon atom of a pair of Carbon atoms linked that are linked directly 30 3827/1015 and are adjacent to each other, (2) monomeric anhydrides of acyclic dicarboxylic acids in which each carbon atom in an anhydride group is directly is linked to one carbon atom of a pair of carbon atoms represented by at least 1 carbon atom are separated and / or (3) monomeric anhydrides of cyclic di- _f tri- or tetracarboxylic acids is where each carbon atom is an anhydride group directly connected to a carbon atom of a pair of directly linked and benachbarter- carbon atoms of a ring structure having 4 to 10 carbon atoms. 16. Molding powder according to claim 15 _f, characterized in that the monomeric anhydride is phthalic anhydride. 17. mold powder according to claim 15 _t characterized in that the monomeric anhydride is TetrahydrophthalsMureanhydrid. 18. Molding powder according to claim 15 _f, characterized in that the monomeric anhydride is hexahydrophthalic anhydride. 19. Molding powder according to claim 15 _t, characterized in that the monomeric anhydride is tetra 'bromophthalic anhydride. 20. Molding powder according to claim 15 _f, characterized in that the monomeric anhydride is p-chlorophthalic anhydride. 21. Molding powder according to claim 15, characterized that the monomeric anhydride succinic anhydride} $ 9% 2 7/1015 22. Molding powder according to claim 15, characterized that the monomeric anhydride is methylsuccinic anhydride. 23. Molding powder according to claim 15, characterized that the monomeric anhydride is glutaric anhydride. 24. Molding powder according to claim 15, characterized that the monomeric anhydride a- [2-carboxyethyl] glutaric anhydride is. 25. Molding powder according to claim 15, characterized that the monomeric anhydride trimel-3itic anhydride is. 26. Molding powder according to claim 15, characterized in that the monomeric anhydride 4,4 '- (2-acetoxy-1,3-glyceryl) -bis-anhydro-trimelli / acid anhydride is. 27. Molding powder according to claim 15, characterized in that the monomeric anhydride is tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride is. 28. Molding powder according to claim 15, characterized in that the monomeric anhydride 7-0xabicyclo- [2.2.1] -hept-ene-2,3-dicarboxylic anhydride is. 29. Molding powder according to claim 15, characterized that the monomeric anhydride 7-0xabicyclo- [2.2,1] -heptane-2,3-dicarboxylic anhydride is; 309827/1015 30. Molding powder according to claim 6 to 29, characterized in that that it is a particulate intimate mixture (a) a copolymer, (1) which consists of about 20 to about 35 % by weight of glycidyl methacrylate, about 10 to about 25% by weight of methacrylonitrile and a remainder consisting essentially of methyl methacrylate and (2) an average molecular weight in the iron range approximately 3500 has to about 8000, a softening point of about 25 ⁰ C and epoxy groups in its molecular structure, resulting from the inclusion of glycidyl methacrylate as a Monomerenbestandteil 'thereof, and (b) contains a monomeric anhydride which is present in an amount the about 0.5 to about 1.5 anhydride groups ^ per epoxy group in the molding powder results, the anhydride from (1) monomeric anhydrides of acyclic dicarboxylic acids in which each carbon atom in an anhydride group is directly with one carbon atom of a pair of carbon atoms connected, which are directly connected and adjacent to each other, (2) monomeric anhydrides of acyclic dicarboxylic acids, wherein each carbon atom in an anhydride group directly with one carbon atom of a pair of carbon atoms which are separated by at least 1 carbon atom and / or. (3) monomeric anhydrides of cyclic di-, tri- or tetracarboxylic acids where each carbon atom of an anhydride group directly connects to a carbon atom a pair of directly connected and adjacent carbon atoms in a ring structure of 4 to 10 carbon atoms connected is. 309827/1015 31. A molded article having a glass transition temperature greater than 90PC, a flexural strength greater than about 1,100 kg / cm (16,000 psi), a flexural modulus greater than about. 0.084 χ 10 kg / cm (1.2 10 psi) and an elongation at break of over 1 % and which is formed from a molding powder which is a particulate intimate mixture of (a) a copolymer, (1) that of about 15 to about 40 wt.% Glycidyl methacrylate, 0 to about 30% by weight of acrylonitrile and one essentially consists of a residue consisting of methyl methacrylate and (2) an average molecular weight in the range of about 1,500 to about 16,000, a softening point of over 25 ⁰ C and epoxy groups in its molecular structure, which result from the inclusion of the glycidyl methacrylate as a monomer component thereof and (b) contains a monomeric anhydride which is present in an amount the about 0.5 to about 1 * 5 anhydride groups per epoxy group in the molding powder. 32. Shaped article according to claim 31, characterized that the monomeric anhydride from (1) monomeric anhydrides of acyclic dicarboxylic acids, wherein each carbon atom in an anhydride group is directly related to one carbon atom is linked to a pair of carbon atoms that are directly linked and adjacent to each other are, (2) acyclic monomeric anhydrides. Dicarboxylic acids, wherein each carbon atom in an anhydride group directly with one carbon atom of a pair of carbon atoms which are separated by at least 1 carbon atom and / or 309827/1015 (3) monomeric anhydrides of cyclic di-, tri- or tetracarboxylic acids where each carbon atom is an anhydride group directly with one carbon atom of a pair directly connected and adjacent carbon atoms one Ring structure is connected with 4 to 10 carbon atoms, consists, 33. Shaped article according to claim 31 to 32, characterized in that the copolymer consists of about 15 to about 40 weight percent glycidyl methacrylate, about 10 to about 25 weight percent acrylonitrile or methacrylonitrile, and one essentially The remainder consists of methyl methacrylate. 34. A molded article according to claim 31 to 32, characterized in that the copolymer consists of about 20 to about 35 wt.% Glycidyl methacrylate, about 10 to about 25 Gev.% Methacrylonitrile and consisting essentially of methyl methacrylate residue. 35. Shaped article according to claim 31 to 34, d a du r c h characterized in that the monomeric anhydride is used in an amount containing from about 0.6 to about 0.9 anhydride groups per epoxy group in the molding powder. 36. Shaped article according to claims 31 to 35 »characterized in that the copolymer has an average molecular weight in the range from about 2,000 to about 10,000 and less than 5 % of the molecules of the copolymer have a molecular weight below 1,000. 37. Shaped article according to claims 31 to 35, characterized in that the copolymer has an average molecular weight in the range from about 3,500 to about 8,000 and less than 5 % of the molecules of the copolymer have a molecular weight of less than 1,000. 309827/1015 38. Shaped article according to claim 31 to 37, characterized in that, in addition to the "'" copolymers, a diepoxide is used which has a molecular weight in the range from about 300 to about. 4,000 and a viscosity t> ei 14CPC of less than BO poisen, the diepoxide being used in an amount which provides about 2 to about 20% of the epoxy groups in the molding powder. 39. molded counterpart according to claim 31 to 38, characterized in that the article contains particulate CaSiO ₃ . 40. Shaped article according to claim 31 to 39, characterized characterized in that the object is glass fibers contains. 309827/1015