DE2042251A1 - Molding compound made from films or sheets - Google Patents

Description

Molding compound made from films or sheets

The invention relates to a molding compound made of foils or plates for compression molding, the eire calendered foil or plate a vinyl-rich butadiene polymer of high viscosity which contains a peroxide curing agent. It also affects one calendered sheet per se made of a thermosetting resin. It also relates to a composite of two or more such films or sheets with a glass fiber layer between each pair of sheets or sheets.

There are various molding compounds made of foils or in the industry Sheets known that generally contain glass-reinforced polyester resins The polyester resin is chemically thickened with MgO, to form a fairly flexible thermoplastic sheet or sheet. Such are in Modern Plastics, page 36, February 1969 mentioned. A monomer such as styrene is generally incorporated into the polyester resin in order to act during the molding process copolymerize to produce a thermosetting resin. The plate must protect against evaporation and loss of the styrene and the panel is generally protected on both sides by a sheet of polyethylene. The polyethylene foils must be removed in compression molding before using the SMG (sheet molding compound). Besides, even lies in the case of applied polyethylene foils, the shelf life of the mass in the range from 3 weeks to 3 months.

It was found that a vinyl-based / ie butadiene polymer mixture high viscosity, which is a peroxide curing agent and a

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contains fibrous reinforcement, can be calendered to form a film or plate which is suitable as a molding composition from films or plates. The sheet or sheet molding compound may contain one or more such sheets, a layer of fiberglass may or may not be provided between adjacent sheets, and the fiberglass may or may not be impregnated with a resin binder of the type currently used for similar purposes or is used in the calendered sheet preferably of the type ^S ". The peroxide curing agent has the formula E ₂ (CH ₃ ) Goog (GH ₃ ) R ₂ , where R is an alkyl or aryl group of 1-10 carbon atoms. The amount of peroxide is equivalent to 0.5-8% by weight of dicumyl peroxide.

The calendered sheet of the invention has the advantage that it can be free of monomeric compound which can evaporate since the crosslinking for heat curing of the polymer used according to the invention by the vinyl groups in the polymer selbsi can be effected. Consequently, there is no need for protective films or sheets, which are made of films or in the known molding compositions Plates are used. In addition, the calendered sheet of the invention is comparatively non-tacky and has uncured properties Condition is strong enough that it does not need an outer protective layer.

The type of vinyl-rich butadiene polymer of high viscosity and compositions containing the type of peroxide mentioned here, are in the pending application of S.B. Boutsicaris and R. A. Hayes, Serial No. 818,971 filed April 24, 1969 and claimed.

In the butadiene polymer there is at least 40%, preferably at least 70% by weight, butadiene and at least 60%, preferably at least 80% by weight of the butadiene therein in the repeating structure Vinyl type butadiene units. The average molecular weight (determined by measuring the intrinsic viscosity) is at least 12,500 and the molecular weight distribution is such that at least 50% and preferably 90% of the polymer

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a molecular weight above 10,000 and at least 95 / "a molecular weight have over 2,000. It was found that the presence higher proportions of polymers with a lower molecular weight than allowed by these limits are slow curing rates and cause poor physical properties in the cured product.

The amount of peroxide used is approximately equivalent to 0.5-3 parts by weight of dicumyl peroxide per 100 parts by weight of polymer, and an oxide is used which gives radicals of the structure R ₂ (GH ₅ ) CO *, where R is a hydrocarbon radical. designated with 1-20 carbon atoms. The 3utadiene polymer should also have a viscosity in dilute solution of 0.19-1.2, preferably 0.6-1.0. The peroxy compound used in the curing process of the invention is considerably higher than that normally used for rubber vulcanization.

The curing temperature is advantageously at least 250 ⁰ F (120 ⁰ G), preferably about 300-35O ⁰ F (150-177 ⁰ C). There is generally no benefit in the process or the product if a temperature of + 20 ° 1 ^: (215 ° 0) is exceeded. Obviously, the higher the temperature, the shorter the curing time required. In general, at 35O ⁰ F

G) a satisfactory curing is achieved in less than 4 minutes, -ois curing times of less than 4 minutes usually do not bring any additional benefit. It is advisable to use a Λ filler where rapid hardening is desired in order to avoid the formation of cracks. A filler, including the asbestos fibers, glass fibers or other fibrous reinforcement, is advantageously used in the ratio of 35-70, preferably 40-60% by weight, based on the total resin filler class.

Although butadiene homopolymers are included in the scope of the invention are preferred, butadiene copolymers can also be used where the comonomers impart desirable properties and do not affect the polymer properties. The comonomers are preferably vinylaryl or isopropenyl

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BATH ORIGINAL

aryl compounds or derivatives thereof which are alkyl, aralkyl, cycloalkyl or chlorine bound to the aromatic learning and preferably have no more than 20 carbon atoms.

Typical of these aromatic comonomers are styrene, ds.-methylstyrene, Vinyl toluene, isopropenyl toluene, ethyl styrene, p-cyclohexyl styrene, o-, m- and p-Cl-styrene, vinyl naphthalene, vinyl methyl naphthalene, Vinyl but7 / lnaphthalene, vinylcyclohexylnaphthalene, Isopropenylnaphthalene, isopropenylisopropylnaphthalene, 1-vinyl-4-chloronaphthalene, i-isopropenyl-5-chloronaphthalene, vinyldiphenyl, Vinyldiphenylmethane, isopropenyldiphenyl, isopropenyldiphenylmethane, Vinyldiphenylethane, 4 ~ vinyl-4'-methyl-diphenyl, 4-vinyl-4'-chlorodiphenyl and the like Where such comonomers should be used, should generally at least 1%, preferably at least 5% by weight, can be used, and it can up to 60; a ver?; be ended.

The viscosity of the polymer, the molecular weight distribution and the percentage of recurring vinyl units are very important Elements in the invention. The properties vary for a particular molecular weight depending on the ivlo Ie kul ar weight distribution. For example, an average molecular weight of 100,000 in one case has a broad molecular weight distribution having molecular weights from 1,000 to 1,000,000 and in another case a narrow molecular weight distribution ranging from 90,000 to 110,000. The properties these two can vary considerably, even if the two are should have the same average molecular weight.

Polymers with high viscosity and high molecular weight have poor fluids and are much more difficult to shape and to use in deformation processes. However, polymers have a low viscosity and low molecular weight, slow curing and fail to develop suitable physical properties. Suitable polybutadienes with vinyl contents of at least $ 60 have a dilute solution viscosity in the broad range of 0.19

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BATH ORIGINAL

_ ₅ _ 20422hl

1.2 and preferably in the range from 0.6 to 1.0, ranges the molecular weight ranges from 12,500 to 120,000 and preferably from 65,000 to 100,000. The viscosity in dilute solution is defined as the inherent viscosity, determined at 25 C on an Oj ^ ä-dgen solution of the polymer in toluene, bie is calculated by taking the natural logarithm of the relative Viscosity divided by the percentage concentration of the solution, i.e. it is the inherent viscosity, measured at a concentration of 0.4%.

A very important factor in the invention is the fact that the molecular weight distribution of the polymer is at least 50> i above a molecular weight of 10,000, preferably 90 / -S above I. 10,000, and at least 95? <? above a molecular weight of 2 should have. Preferably at least 50% of the polymer should have a molecular weight above 50,000. Larger proportions of polymers with low molecular weight than indicated lead to slow cure rates and loss of properties described for the invention. That Average molecular weight (determined by the intrinsic viscosity) should not be less than 12,500, preferably not be less than 65,000.

With respect to the molecular weight distribution are Molekularge weights not critical except in the way _Λ view of supply and machinability of the material on the high side. However, expansion into the low molecular weight regions is very undesirable, since the curing rate is very slow and the desired properties are not achieved.

It is known in the art that anionic polymerization catalysts which are soluble in the particular polymerization system produce polymers with comparatively narrow molecular weight distributions. Examples of these are the alkyl and aryl lithium catalysts and aryl sodium catalysts in ether solution and sodium and lithium complexes with naphthalene or Biphenyl in. Ither solution. Metallic lithium and sodium and Alkyl sodium compounds that are insoluble give polymer

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- 6 sate with an undesirably broad molecular weight.

Butadiene polymers with an appropriate molecular weight can be used Distributed by making a soluble Lithium catalyst, such as 3utyllithium, is used to facilitate the polymerization to effect. Sodium-catalyzed polymerizations can be used can be used to obtain narrow molecular weight distributions when tetrahydrofuran and naphthalene are used as solvents, although the vinyl content in such solvents Cases is generally too low. It is also possible to use a polymer by extraction separation process for the purpose to produce molecular weight distribution appropriate to the invention. It has been found that polymers that are desirable Properties in the cured product produce in the approach given below within a canoe at 175 C to one Cure Rockwell E hardness of 70 or above.

Even if the DSV of the butadiene polymer is advantageously at least 0.19, it is generally preferable to work with polymers which have a DSV of 0.6 or above. It is advantageous to work with polymers which have such high viscosities as can be permitted in the various process stages for mixing the peroxide and then for manufacturing the product. Obviously, the more viscous polymers offer greater difficulty in uniformly distributing the peroxide in the polymer.

The method of the invention is very simple, and convenient apply to liquid compounding, the butadiene polymer being mixed into solvent for the purpose of compounding and the solvent can be removed before the polymer-peroxide mixture is processed and cured. When solving a the polymer is compounded in hexane, heptane, toluene or other solvent as is used in the preparation of the polymer used, dissolved or suspended. The solution is mixed with both the peroxide and a filler, as well as any other modifying agents.

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agent removed, e.g. evaporated, and then the Polymerisatkompositioii processed according to common methods. If desired the components can be mixed by L. Use of double arm mixers or other types of internal mixers especially if there are no fibers that be broken by grinding.

The peroxide-gelled products of the invention have comparatively good color, are generally opaque, and have excellent resistance to heat. These products have excellent chemical resistance and are essentially impervious to swelling in hydrocarbon solvents, including berisol. Ä

Cured products with a flexural modulus of 21,100 to 14-1,000 kg / cm ² (3,000,000 to 2 million psi) can easily be obtained, Rockwell LI hardnesses of 80-120 and Rockwell E hardnesses of 70-110 ;; iit .7är :: standardization temperatures above 40O ⁰ F (200 ⁰ C) and in many cases above 50O ⁰ P (260 ⁰ C).

The peroxides used are advantageously those which have a reasonable rate of decomposition at the temperatures used. In some cases it is desirable to ver.ven.ien a mixture of peroxides, wherein the a decomposes faster when the temperature gradually increased to the desired iereich v / ill and the other peroxide slower% in the lower -emperatarbei 'Decomposed, but reached a rapid decomposition rate later in the heating-up period.

The peroxides that can be used in the practice of the invention suitable can through the formula

CH ₅ C (R) ₂ O-OG (R) ₂ CH ₅

in which R ^ ryl or alkyl, including cycloalkyl, aralkyl, alkaryl, etc., denotes 1-20 carbon atoms. The relevant R groups in the particular compounds can be identical or different.

Typical R groups include methyl, ethyl, propyl, butyl, hexyl,

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- ο -

Heptyl, decyl, dodecyl, octadecyl, phenyl, tolyl, xylyl, benzyl, Phenethyl, ITaphthyl, methylnaphthyl, ITaphthylethyl, diphenyl, Benzylphenyl, Butylphenyl, Cyclohexyl, Cycloheptyl, Cyclohexylmetliyl, Cyclolieptyläthyl, Metliylcycloheptyl, etc.

Typical peroxy compounds of the above formula which decompose to form the desired free hadical, namely CEUCCR ^ O *, include various diperoxides and mixed peroxides. Particular examples of these are dicutyl peroxide, di-tert-butyl peroxide, tert-butyl-cumyl peroxide, di-tert-amyl peroxide, tert-butyl-tert-amyl peroxide, tert-unyl-cumyl peroxide, di-tert. octylperoxid until (i, 1-Diphnenyl-ethyl) peroxide, _Up (1,1-dicyclohexyl-ethyl) peroxide, bis ^{(l-y-1-methyl-Gyclohexyl} ätliyl) peroxide, bis (1-phenyl- 1-Ät-iyl-ethyl) peroxide, etc. The symmetrical peroxides, which have identical groups on each side of the peroxy oxygen atom, are more readily available and; preferable to all. Jo jedoc.i mixed peroxides, ie peroxides with ZV / ei different, which OR-J ^ {3) Jd 'Hao.ikalen erhältlic ^ are., They can be very satisfactory ./eise verv / grounds.

The peroxy catalyst is vortellhafterweir-e in a Len _c e ver applies that 0.5-8 weight steep Dicui-iylpcrojq / d per 100 weight parts polymer is equivalent .. Since the Lioleloilargewicnte the various peroxy compounds will vary the eriorderlichen ^ nteile to Bildun ;: same Ivlen. .'e Peroxypruppea or free radicals determined by the equivalent weight. Furthermore, the proportions of peroxygen bond required to give the desired cure or curing rate are defined as the narrow range equivalent to 0.5-8 parts by weight of dicumyl peroxide. I.-Ianchiial v / earth peroxides commercially sold in diluted form, such as "Dicup 40". These can be used by calculating the length used according to the actual peroxide content.

The optimal percentage of peroxide depends on the percentage of recurring Vinyl units contained in the polymer are, the vinyl-richer polymers require less catalyst within the specified range and the polymer

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_9_ 2ö422b1

Sates with a lower vinyl content within the stated range require more of the peroxy compound. Preferably
0.5-3 parts of dicumyl peroxide or an equivalent other peroxide compound are used for polymers which have a content of 80 or more of recurring vinyl units, and 3-8 parts of dicumyl peroxide or an equivalent!
Another peroxy compound is preferred for polymers with a vinyl content of 60-80 ^. Vinvl contents of less than 60%
do not deliver the desired results of the invention even with larger amounts of peroxide.

The polymers are treated with a
loaded with high volumes of fillers. Advantageously, f 25-70 -., Ό used fillers, and preferably 40-60 wt .- / S. Smaller amounts of filler usually result in products
inferior physical properties and a strong tendency to crack during molding. Suitable fillers include glass fibers, asbestos fibers, silicon dioxide, aluminum oxide, mica, feldspar, talc, clay, powdered metal, such as aluminum, iron, escing, tin: etc., wood flour, cellulose fibers,
Carbon black, graphite, etc. Various fibrous materials such as glass fibers, asbestos fibers, cellulose fibers and the like are preferred over the mineral powders. The other inorganic fillers. fabrics follow in the order given. The particle size
g of the filler only by practical considerations of the mixing and compounding limited.

In order to develop the desired properties as much as possible, it is advisable to add a Liit!; el to civilian domes to effect the filler and the polymer, 3s are for Organosilane compounds such as particularly suitable for this purpose

ii- (trimethoxysilypropyl) ~ ethylenediamine.

n- (Dimethoxymethylsilylisobutyl) -ethylenediamine:

(CH, 0), SiCH ₀ CHCH ₀ IiH (GH ₀ ) _O WH _O
^ ^ CH * -ΟΗ ^d * -

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2 ü 4 2 2 b 1

- ίο -

a -Hethacryloxypropyltrimethoxysilane: CHp = GCOO (OH ₀ ) ^ Si (OOH _x ) _χ

* - · ax * - *) '2 ί?
GH ₃

IT-glycidoxypropyltrimethoxysilane:

Vinyl trichlorosilane:
GH ₀ = GHSiCl _x

Me thylvinyldichl or sil au. ι
GH _x (OHp = OH) SiGl-,

Vinyl triacetoxysilane:

CH ₂ = GHSi (OCCGH ₅ ),

Y-GYiI orpropyl tr ime thoxysil an:
ClGH ₂ GH ₂ GH ₂ Si (OCH ^) ₇

The polymer according to the invention is defined by the specific restrictions described above with regard to the percentage of repeating units with attached vinyl groups, Average molecular weight (M), wt .- ^ over 10 Molecular weight, w / o over 2,000 molecular weight and viscosity in dilute solution. In addition to the various Applications of the polymer of the -cirfindiuig, as they are here for fast-hardening masses are written in which to avoid If a high percentage of filler is used for cracking, it can also be used in thin films that are not thicker

1 1

than / 32 "and preferably not thicker than / 64" be where the Y / arms quickly and evenly in the curing process is distributed, as well as in molding compounds, which at lower temperature and lower curing rate are hardened to avoid cracks. Molded products, made from this material have improved flexural strength, hardness and chemical resistance even without filler and ability and can be used for various purposes

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be where masses with superior flexural strength, hardness and resilience against. Chemicals and V / poor are beneficial.

The butadiene polymer also has at least such purposes 60; ύ and preferably more than 80: ό of the repeating butadiene unit with a vinyl group attached, has an average molecular weight, determined by viscosity measurement, between 12,500 and 100,000, have at least 50; j and preferably at least 90% by weight of the polymer one molecule arge v / i cht larger than 10,000, have at least 95 Ge, ν.-ίέ of the polymer Molecular weight greater than 2,000.

In different hardening processes, with or without filler, advantageous properties are obtained if at least 50; » and preferably at least 70; j of the total unsaturation of the polymer are consumed in the curing process. The amount of unsaturation remaining can be slightly can be determined by infrared analysis.

In order to achieve the in :: Ige mixer: Ier polymers with the large required!.! Narrow FvI .. "toif, it is most practical to effect the mixing by Plüssiglceits- or solution compounding. For such purposes it is generally desirable The preferred solvent is a mixture of tetrahydrofuran and hexane, the proportions of the two varying depending on the microstructure desired in the polymer and the molecular weight. In the case of polymers with a higher molecular weight or polymers with a higher DSV in In the stated range, more dilution is required to obtain a miscible viscosity, and then the use of larger amounts of solvent again degrades the economics of the process by removing and recovering the solvent.

The compounding of the filler and polymer can be done in one conical, vertical drum mixer, which gives a good Ki3c! effect, -as is used for large batches

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Baker-Perkins-IJischer is preferred, and it can be used for this purpose a Bramley mixer and other types of double arm mixers can also be used. In some cases, comparatively Small amounts of filler stirring by hand or with a laboratory propeller stirrer may be sufficient.

After mixing the components in solution, the solvent is removed to prevent gas or bubble formation at elevated curing temperatures to avoid. This is done for filler masks moderately by vacuum drying at ambient temperature or temperatures up to 50 ° C. This hatred is used to the calendered To make panels used in the practice of the invention.

In contrast to the current technical way of working, as To use a viscous liquid resin, to which an I.iii schmitt el, such as magnesium oxide, is added to the resin According to the invention, bringing a high viscosity becomes a solid one Resin used in the form of a calendered sheet. In addition, a Lionmeres such as styrene, used with the resin to bind the glass fibers, so that copolymerization in the curing or molding process produces a thermosetting resin. Jas solid resin of the invention is as a result its attached vinyl groups pex * se capable of networking, to produce the thermosetting resin after curing. Thus, the invention enables a ve. .damp fb ar es Lioiiomeres to omit, where it is desired. In addition, the Kalcoidrierte Polien or Sheets are permanently placed in a certain position and are therefore protective even where a copolymerizable monomer is used shall be. Consequently, the calendered films or sheets of the invention are more practical, easier to handle, and have better ones La erability and deliver products with better properties while still having the flexibility required for 'deep drawing' applications is necessary to allow.

As set out above, the invention can be in various modifications can be applied. The shape dimensions from plates can be a single calendered sheet made of vinyl-rich polybutadiene is

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hold, if desired, additional fibers, such as glass fibers or other fibers, such as asbestos fibers, in the composition of the calendered sheet. In another embodiment can use two calendered sheets with fibrous reinforcement, either fiberglass or other, such as asbestos, with or without fillers, like talc, can be used with a glass fiber layer between the two plates. The fiberglass layer can be used per se or may be mixed with a binder which is either a resin of the type previously used industrially or of the vinyl-rich butadiene polymer type. When a copolymerizable monomer is used, it is advantageous a less readily vaporizable one, such as tert-butyl styrene. A vinyl-rich butadiene polymer mixed with the glass fibers in the inner part preferably has a lower one Viscosity in comparison with the viscosity of the butadiene polymer in the calendered plate. For example, one draws a viscosity in dilute solution of about 0.95 'for the calendered panel and a DSV of 0.37 is for the resin binder advantageous in the fiberglass layer. In yet another variation, an even larger number of calendered Sheets with fiberglass layers between adjacent sheets are used, with the number of layers on the type and thickness the desired end product.

The molding material of the plates can be prepared by reacting in μ a Baker-Perkins mixer or other suitable mixer type, a hexane solution with 50-60 / 0 butadiene polymer, vorteilhaffcerweise about 0.95 dilute solution viscosity, the Peroxydkatalysator, talc powder or other mineral filler , Vinylsilane or other material to improve adhesion and a base of asbestos or glass fiber mixes. Allowing the resulting soft, rubber-like pieces to dry overnight in air or 15 minutes in an oven at 105 ⁰ O, and then they become thin, calendered flat plates of the desired size. Then the molding compound is formed from sheets by adding a predetermined!.! Narrow glass filler, woven layer or fibers, preferably using a butadiene poly-

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2Ö42251

merisats of the type described here, ^w ith a low viscosity for wetting of the glass is stacked up. This structure is then pressed by both riders to achieve an even distribution of the low viscosity polymer in the glass fiber layer for the purpose of more effective adhesion.

If blue asbestos is included in the composition, the result is somewhat stronger products than can be obtained with V / ei3asbestos, ialk improves processing and flexibility. An increase the glass content increases the impact strength considerably. Blue asbestos should be calendered because of its dark color Plates are limited to being used as inner layers in SMC construction be used, while plates made of "./e eat asbestos - bright in the color and possibly paintable - are recommended as outer layers.

A molding compound made of foils or sheets can, depending on the type of used fiberglass reinforcement in various shapes will »The basic construction method is to put the glass fibers or fabric between calendered sheets brings, using an impregnating resin to moisten the glass, preferably one that contains a vinyl-rich butadiene polymer, that has low viscosity, with or without a diluent, such as hexane, which is evaporated, or tert-butyl styrene, which is copolymerized. The composite is then pressed from both sides to bind the overall dressing together. This arrangement can provide a mold mass of plates, in which a single layer of glass divides two calendered Sheets are "sandwiched", as is a multilayer system with several layers of glass, with calendered sheets alternate, ^ he sandwich type is simpler and much more practical, while the teaching layer arrangement greater strength as a result the higher glass content can offer, - ^ m general leave both Kinds of the J-order so that the glass fibers are freely impregnated with the resin and during the processing (or pressing) stage flow more evenly between the two outer plates.

The individual calendered panels can be of any desired thickness

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ORIGINAL INSPECTED

2 O A 2 2 b 1

have, but for practical Z.veclie i /. dea - range of 0.051 mm to 25.4- mn (2mils to 1 inc ^ i). : .. it a plurality of Plates or with inlaid between two or menr sheets Glass, the composite generally has a thickness of at least 0.254 mm "(10 mils) to any thickness.

The calendered plates advantageously have 25-70; j glass fibers, .!. sbest fibers or other fiber reinforcement on and between the calendered plates 0.35 ^ glass fibers, based on the total weight of the sandwich or composite. Preferably the calendered panels have 25-4-5 / ^ glass or J ^ sbestfibers on and the interposed glass fibers are preferably 10-20 / j of the total weight of the composite off it. Consequently is the total of the glass fibers in deir. Composite material advantageously 10-70, j and preferably at least 10) j are glass fibers in the cauldroned plates.

^ s are various embodiments of the invention by the The following ideas are explained in more detail. Jiese -eisoiele these only the - ^ rIUi-carurg and sol .en the practical implementation of the invention in none .. 'eise besc-irän.id ... Zie specified here The haste and percentages relate to the weight, when it is is not otherwise specifically noted.

3eisoiel 1

A series of approaches is prepared by putting the various lomponeiites listed in Table I below in a sker-rerkins dictionary for 15 minutes at -iaua.tei.iperatur be mixed. In each verse ca 200 parts resin binders are used, the 50; - ^ exan and 50; "J> of a pole, butadiene with a D £ V of 0.95, a Vin-lgehait of 90; / ei at least 95.J. of the polymer have a loleiul ar weight of over 10,000. The glass is a mixture of fibers of 12.7 mm and 50.8 mm (/ 2 "and 2") in length. The tested robes ⁺ are calendered, but not ground plates removed and cured at 33O ⁰ F (165 ° C) and a pressure of 7> 0 kg / cm (100 psi) for 8 minutes. have they also vo.:-zeich..et in Table I below.

⁺ After the hexane has evaporated in an evaporation dish.

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BAD iG ^MAL

Table I.
Approach and evaluation of calendered boards

approach

III

IV

ivomposition:
Resin binder
Dicup-40 (40; έ

200

200

200

200

Dicumyl peroxide) example 12th 1 10 , 4-3 90 10 10 10 Calcium stearate 3 92 3 16 500 3 3 3 Vinyl triacetoxy 000 1160 SiI on 4th 703 3 1,350 3 3 3 Blue asbestos 105 000 87.5 94-, 9 - - - V / ice asbestos - 70 - , 90 2.0 100 100 - Glass - 0 117 117 133 Talk - 2 12.5 67 - - Characteristics: density Hardness "E" 77 82 79 3 level, psi 10 17,000 18 JOO 20 800 . kg / czn 1195 1286 1462 Flexural modulus 10 ⁵ psi 1 1,500 1 440 1 009 _. " . 10 ⁵ kg / cm ²
Izod-nerb- 92 101 71 impact strength 3.6 6th , 0 10.0

The following batch is stirred in a Baker-Perkins glass for 15 minutes at rtaurate temperature. - ^ aE Polybutadiene (PBD) has a viscosity in dilute solution of 0.95, a content of
Recurring butadiene units with attached vinyl of 90>i> and 95 / <> with a molecular weight of over 10,000:

Hexane solution from PBD (50 #) Dicumyl peroxide (40ro)

Calcium stearate

Vinyl triaceto ^^ a ^ ^

800 g. (400 g. Solids

40 g. (16 g. Dicumyl peroxide)

12 g. 12 g.

2Ö422b1

Asbestos fibers (crocidolite) 350 g.

Talcum powder 50 g.

Glass fibers -1/4 "200 g.

Glass fibers -2 "100 g.

The asbestos fibers and 1/4 "glass fibers are treated with the silane just prior to mixing. The product formed is in A large evaporation dish is transferred and left to air dry for 2 hours and then dried in an oven at 105 ° C. The resulting thick, rubbery lumps have roughly the following weight composition resin (PBD, peroxide and stearate) 38? ό

Glass 26%

Asbestos 3O7O

Talk 6%

The material is then calendered to give films about 0.018 "thick. A compression-molded sample (8 minutes at 168 ^° C

and 7 »0 kg / cm) shows the following properties:

density Flexural modulus, psi 1 1.58 Hardness E. kg / cm 85 Flexural Strength, psi Notched Izod impact strength, ft.lbs 16 500 kg / cm 1160 180,000 82 954 ./in 1.0

The molding compound from sheets or foils (SMG) is formed by a sheet of double-glazed mat is placed between two sets of sheets, each of which has 4 x of the above calendered films having. It becomes an impregnation varnish from 65/35 parts low viscous (DSV 0.35) resin tert-butylstyrene and 5 parts of Dicup R (1005έ dicumyl peroxide) poured over the glass mat before the second set of plates is placed on the mat. The complete composite is then pressed under a heavy plate in order to to promote the distribution of the impregnating varnish in the outer glass mat. the

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the approximate composition of the SMG in weight-70 amounts to this Point:

ilalanded plates

Glass mats (Killstoff)

added impregnating varnish "5»

The properties of a sample that is stored at 168 ° C and 70 kg / cm (100 psi) has hardened for 10 minutes are as follows: Hardness E 75

Flexural Strength, psi 13 500

kg / cm ² 949

Flexural modulus, psi 980 000

kg / cm ² 68 894

Izod impact strength (notched). 7.0

The examination of the material in application to the 5Orsi exercise of a Deep-drawn pressed part that takes the form of a membrane for air brakes makes a nearly perfect article.

" Example 3

The procedure of example 2 is repeated with the difference, that silicon dioxide dust is used instead of the talc and the glass fibers to 1/4 "thick on one surface of a thin calendered sheet made as in Example 2 is to be sprinkled. Then the glass layer is covered with the same calendered sheet that is on the underside is coated with an impregnating varnish "containing 65 parts of polybutadiene with a DSV of 0.375, 35 parts of tert-butyl styrene and 3 parts Dicup R contains. Then another layer of fiberglass is put on the upper surface of the upper calendered plate sprinkled and this covered with another coated plate and this Repeat the procedure until a composite of 5 glass-lacquer layers alternating with 6 calendered panels is built up. After curing as in Example 2, the deep-drawn article has a good, smooth surface, an E hardness of 91 and an Izod notched bar toughness from 5 * 3

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Example 4

There will be about 95 S / 2 "glass fibers between two calendered ones Plates of the insert II of the Jabelle I are stacked, each Layer is approximately 0.070 "thick and weighs 575 S. The glass fibers are moistened with 160 g of the impregnating lacquer used in Example 3 and the arrangement becomes a very flexible one 0.160 "thick composite when pressed. This provides a good but thin deep drawn cured product with an E Hardness of 83 and a notched Izod impact strength of 4.0.

Example 5

It becomes a solid deep-drawn product using the Working method of example 4 made with buckets of composite material, taking three dry Glasgewece with the impregnating varnish of the example 3 are impregnated, between zv / egg calcined foils can be used, each of which is 0.070 "thick and the neck III of Table I. The product has an S hardness of 84,

a flexural strength ν, f-72 kg / cm (6700 psi), a flexural modulus of 49 355 kg / c: o ~ "(/ 02,000 psi) and an Izod impact strength from 27.8.

3example 6

Four plates are pre-impregnated by dipping glass fabric (Hess, Go_äsmith üan ^ els class · # 181) into an impregnating varnish containing a 25% hexane solution of rolybutadiene with a DSV of 0.35 »the 3 part dicumyl peroxide (Dicup ' R) contains only 100. The four plates are dried by evaporation of the hexane and sandwiched between two sets of calendered plates, each set comprising a pair of thin calendered plates of batch III of table I. The Gesantstär.ie the uncured Verbundstofies or i'ornnasse of plates is about 0.2 ". It is obtained a very good deep-drawn hardened iTodukt, dac a 3 hardness of 68, a

Flexural strength of 1069 kg / cn (I5 200 psi), one flexural modulus

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2 ΰ 4 2 2 b 1

of 49,214 kg / cm (700,000 psi) and a notched Izod impact strength of 9) owns 0.

Example 7

A double layer glass mat (-tiandelstyp Amm-1) is covered with a Impregnating varnish of the type used in Example 3 is impregnated and sandwiched between two sets of calendered plates, wherein each ^ atz 4 individual calendered plates of approach III of the Table I. The total thickness of the arrangement is 0.150 "and the glass content about 45 Ge-.v .-%. Deep-drawing as in ^ eisjjiel 2 provides a good product with an E hardness of 81, a flexural strength of 1055 kg / cm (15,000 psi), a flexural modulus of

87,880 kg / cm (1,250,000 psi) and an Izod impact strength of 8.0.

Example 8

It is a single calendered sheet of the batch III of Table I between 0.18 "and 0.20" thickness 37.5 ^-; Containing glass fibers, formed into buckets of deep-drawn article at 155 ° C for 15 minutes at 14 kg / cm (200 psi). An excellent fitting is obtained that is 0.075 "thick,

2 an S hardness of 89, a flexural strength of 1237 kg / cm

(17,600 psi), a flexural modulus of 85,977 kg / cm ² (1,223,000 psi), and an Izod - ^ - impact strength of 2.5.

Example 9

Similar results are obtained by following the working methods of Examples 2-7 follows, with a solution as -'ränklack of 20 parts of polybutadiene with a viscosity in dilute solution of 0.9, 80 parts of hexane and 0.6 parts of dicumyl peroxide is used. The uen .e impregnating varnish used is sufficient to give the same length of the previously used low viscosity resin.

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- 21 Example 10

A molding compound is produced from plates, using calendered plates of the invention as the outer bearings of a sandwich plate and a molding compound made of polyester-styrene-glass fiber plates, which is available in the market, as the inner part. This composite is made by mixing 400 g of a polybutadiene resin (with a BSV of 0. c8, a vinyl content of about 90% and over 95; ^ of an IV molecular weight of over 10,000) in 300 g of hexane in a Baker-Perkins Liischer with 16 g of dicumyl peroxide, 12 g of calcium stearate, 12 g of mixed vinylacetoxysilane, 400 g short chrysotile asbestos fibers, glass fibers, 200 g of 2 "and 100 g talc powder After i'rocknen in an oven at 100 ⁰ O during |. 15 minutes, the resultant is dry rags are calendered into thin, flat sheets (0.50 ^{! l} to 0.075 ") that are after

When cured, have a flexural strength of 900 kg / cm "(12,800 psi). The sheet molding compound is built up by using two of these calendered sheets (total weight 381 g) as the outer layers of a sandwich sheet between which one is commercially available üinzelplatte of polyester-styrene-glass fiber, which weighs 152 g, is arranged ;. the arrangement (533 g) at 149 ⁰ C for 20 minutes at 14 kg / cm to a perfectly shaped Luftbremsmembr: ai cured.

The new molding compound made of sheets (SLvC) of the invention has a λ calendered sheet made of a vinyl-rich butadiene polymer of high viscosity which contains a peroxide compound that is 0.5-0 wt .-% equivalent to dicumyl peroxide calendered x ^; have slats containing glass fibers or other fibrous reinforcement, preferably two or more such plates with a rail of glass fibers or other fibrous reinforcement between each pair of such x ^J slats, these glass fibers being placed between the plates with or without a hardy binder. The binder is either of the type normally used, such as. Polyester, or a resin such as that used in the calendering plates. The calendered sheet made of a thermosetting resin

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i ö 4 2 no.3 1

is new per se. Such quarries are different. Ξ-slats or composite materials are molded in a single-component system with improved results in handling and handling in comparison with current dimensions of leaves used. . ■

10 9 8 Ii / 18/8

Claims (12)

2 O 4 2 2 claims 1. Improved molding compound made of foils or plates containing at least one squared plate which contains an intimate mixture the end a) 100 parts by weight of a butadiene polymer in which at least 40 wt .- / l are butadiene and which has an intrinsic viscosity average molecular weight of 12,500 to 120,000, where at least 50 wt .-; *? of the polymer has a LoieKular weight of at least 10,000 and at least 95 wt .-;.? of the polymer have a molecular weight of at least 2,000 and at least 60 ο of the recurring 3utadiene units in it have the structure with attached yinyl, b) a peroxy compound with a structure represented by the following formula CH-, C (H) _o 0-0C (H) _o CH ₂ , in which 2 denotes an alkyl or aryl radical with 1-20 carbon atoms, the i- ex>-; e of this xeroxy compound c 0.5-8 Ge; vichtsteiien dicunyl peroxide is equivalent , c, ~) a filler "-. r is substantially inert ge ^ * s, the polymer and the ^j It roxyverbindung, in such a narrow that the filler is 25-70 wt .- ;. · the mixture!.! with at least 10 wt .-;.? glass fibers in the calendered sheet or sheets, especially based on the total weight of the molding compound from sheets, and at least 0-35 Gev /.-> j glass fibers are inserted between adjacent calendered sheets. 2. Weight according to claim 1, characterized in that the filler from the pale glass fibers,. ^ sbest fibers, cellulose fibers, Aluminum oxide, mica, feldspar, JaIk, clay, metal powder, carbon black and graphite is selected. 3. Composition according to claim 1 or 2, characterized in that at least two of the calendered plates are present and that at least 10 wt .-, j of the glass fibers, besoden are inserted on the total weight of the molding compound from plates between adjacent calendered plates. 10 9 8 12/1678 4. Hasse according to claims 1-3 »characterized in that the interposed glass fibers impregnated with a thermosetting resin are. 5. pale according 'to claim 4, characterized in that the thermosetting resin is a butadiene polymer, -. Containing at least 40 wt contains -70 butadiene and butadiene least 60yi> having its repeating units of the structure with an attached vinyl. 6. mass according to ^ nspruch 3 »characterized in that at least 90% by weight of the butadiene polymer has a molecular weight of at least 10,000. 7. Mass according to. ^ Nspruch 3 »characterized in that at least 90% by weight of the butadiene polymer has a molecular weight of at least 50,000. 8. Iviasse nach .mspruch 7 »characterized in that the butadiene polymer contains at least JOjo butadiene therein. 9. Cash desk according to claim 7 »characterized in that the Bu tadiene polymer is polybutadiene. 10., mass according to claim 1, characterized in that the Butc diene polymer is polybutadiene. 11. Composition according to claim 10, characterized in that the polybutadiene 90 wt .- ^ with an ilolel: ular weight over 10,000 having. 12. Composition according to claim 10, characterized in that the polybutadiene 90 wt .-% with a molecular weight above 50,000 having. 109812/1678