DE1620999A1 - Process for the production of reinforced polymeric compositions based on styrene-acrylonitrile copolymers - Google Patents

Description

W. 12 65Ö / 66 13 / Ko

Monsanto Company _ti St * louis, Missouri (V.St.A.)

Process for the production of reinforced polymeric compositions based on styrene-aorylnitrile copolymers

The invention also relates to reinforced polymeric compositions as well as a process for their production In certain * Regard, the invention relates to rigid copolymers, the copolymers of styrene and acrylonitrile plus one bonded to the copolymer Reinforcement medium included

As used herein, "reinforcing agent" and "gain medium" ¹ denote inorganic substances} which have been treated with a coupling or binders to provide a capability for adhering bond to a polymer. This is in contrast to inorganic materials as fillers or Thinner for

828/1690

serve a polymer system and are not adhesively bonded to the polymer matrix «Since the reinforcement produced by the practice of the invention is achieved by a certain type of adhesive bond, which is explained in more detail below, the terms" reinforced polymeric mass "and refer "Reinforced polymer" refers to those compositions in which the interface between the polymer and the inorganic component is characterized by the presence of a third component, which is specified as a binding or coupling component several reactive groups, of which at least one is suitable for chemical reaction with the polymer or monomers and at least one is capable of reacting with the reinforcing agent «, The term" particulate "used hereinafter refers to granular, platelet-shaped and acicular particles mi t a ratio of length to diameter (1 / d) up to about 25: I ₉ preferably about 2Q: 1 and especially in the range of about 1: 1 to 15 * 1 "In contrast, the hierjverwendete term" fibrous "particles, de »en 1 / d ratio is greater than 25: 1 and is usually greater than 50si respected ■ ——, —- ~ _ ^ __

BATH

9323/1633

It is well known in the art that polymeric masses can be filled with non-polymeric substances, that is, with materials which do not enter the polymerisation process: but can be mixed with the monomer charge or the polymer product to form a uniform finished product Originally, various fillers were used in a polymer material to color the polymer, to change the coefficient of expansion, to improve the abrasion resistance and also to improve the modulus and strength and to dilute the polymer in order to reduce its costs. It was and is still common practice to mix a filler and a polymer in various ways in order to create a mechanical bond between the two components. According to one procedure, a liquid prepolymer and filler were mixed thoroughly and then the polymerization of the torpolymer was completed, whereby a mass was produced in which the filler is intimately dispersed in the finished product. In a different way of working, an uncured polymer and a filler are subjected to a shear force »whereby the filler is brought into a certain type of mechanical bond with the polymer during curing» Various other methods of achieving / a mechanical bond: from the filler to the Polymers are also well known in the art «-: v _s _- ~ *

009829/1690

The upper limit of the amount of filler that can be used in mechanical Mixing with polymers without adverse effects the physical properties of the product used is low · The tensile and flexural strengths decrease at relatively low concentration

particularly

in terms of filler / sharp. An exception to this general Hegel was the use of fibrous material, especially fibrous glasses; hen in polymeric masses * Di Incorporation of fibrous glass (glass fibers) into a polymer significantly increases the physical properties, however, generally one such improvement-by the Use of particulate material not achieved; became «The reason for this decrease in strength by that of with particulate! Material-filled polymers shown is based on being a particulate filler in a polymer there is no component that is associated with a fiber in terms of load distribution properties is comparable · Usually a filler effects rather a concentration of the stresses or strains

as its stranding. As a result, the polymer-filler interface is the weak bond in the composite structure. In the case of a fibrous filler, the Multiple weak bonds along the fiber structure a noticeably strong bond when stress is applied in a direction parallel to the orientation of the fibers

ÖQ8828 / 169 8 ^BAD original

'1620990

If a transverse stress is applied to the longitudinally oriented fiber particles of the filler, or if any stress is applied to particulate filler materials, this stress will not be well distributed and the composition will be weak. Therefore, "a polymeric product provided with a filler, which contains less polymer per unit volume of the product than an unfilled or filler-free product, has inferior physical properties to the filler-free polymer ^ /

Various polymer-partial-filler systems have been used for various aspects, such as cost reduction or UV resistance, developed » It has now been found that by a suitable combination a styrene / acrylonitrile copolymer and a particulate inorganic material, the inorganic Material no longer acts as a mere filler, but can be modified to "act" as a reinforcing agent. According to the invention, the physical properties increase of the polymer no longer with increasing proportions, Filler will decrease, but will rather be significant at high levels Improved proportions of reinforcing agents *

BATH ORIGINAL

9 828/1 B

The reinforcement of styrene / acrylonitrile mixed polymer masses by granular, platelet-shaped or needle-shaped particles As opposed to fibrous particles, a particularly advantageous and desirable trait is because a G-emic consists of a granular inorganic material and a monomer or prepolymer is more flowable and accordingly easier is cast or compression molded as a mixture containing an equivalent amount of a fibrous material

The object of the invention is to create a method for the production of reinforced styrene-acrylonitrile copolymers with an excellent combination of mechanical properties not previously available. Furthermore, the invention aims to create a styro-acrylonitrile! which is reinforced with a reinforcing agent or medium, wherein the inorganic Component of the reinforcing agent to the copolymer is bound by a binding or coupling agent ο The invention It is also an object to provide a method of treating inorganic particles with a coupling or binding agent so that the resulting inorganic Material-coupler addition product or adduct then adhered to a styrene / acrylonitrile copolymer · Another purpose of the invention is that Creation of reinforced iOrm objects from a styrene / Acrylonitrile! «Mixed polymer»

BATH

Ö99S2S / 1688

Me polymeric compositions according to the invention include Styrofoam 1-acrylonitrile mixed oil and a strengthening agent with a l / d ^ ratio of about 25? 1 »that to that Copolymer through, a XupplüngS'- or binding title of subsequent general formula ^

is bound ₉ in which X is a hydrolysiqrljaren Hestj T a Hydroversfeöffliest _t E an Älitylenrest with 1 to about 20 carbon & t @ m @ n.% S © ineii örgäniSGhen Eest with Ethylenischer IXnsaturated, η a g _a fi2s @: 2a | ii iron ö Ms -1 _r a is an integer from 1 to 3, 1) an integer from 0 to 2, c is an integer from 1 ^ to 3, where ν is the sum of a + b + c equal to 4. The expression ^ ^M "strengthening agent" refers to such inorganic pull-off materials which have been reacted with a coupling or binding agent. The masses can furthermore be characterized by certain sizes of mechanical properties that are known masses similar to those known up to now JS Some of these compositions according to the invention have flexural modulus values of at least about 0.56 x ^ Q at C 8 ^ O psl) in combination with strength index values of at least 2 χ

10 <"The strength index is a measure of the relationship between Sheet metal strength and notched impact strength of a material »

'BATH.

Those useful in the compositions according to the invention Styrene-acrylonitrile copolymers include such mixed polymers with a styrene-acrylonitrile weight ratio from about 95 * 5 to about 50:50. Such copolymers are preferred with ratios approaching the azeotropic 76:24 — Polymerization Mixture of Styrene and Acrylonitrile «Im generally styrene / acrylonitrile mixed polymers have styrene / acrylonitrile ratios in the range between 80 ° and 2 ° C and 70:30 most of the desirable and beneficial properties of copolymers obtained by polymerization a 76:24 azeotropic polymerization mixture of the components.

Substituted styrene and substituted acrylonitrile can also be used to produce the copolymers according to of the invention apply, examples of Breakable substituted styrenes are a-methylstyrenes, Vinyltoluenes, vinylxylenes, p-chlorostrol, p-methoxystyrene and Other Similar Materials »Suitable substituted acrylonitriles include methacrylonitrile, β-chloroacrylonitrile, and the like. The preferred range of component ratios for styrene / acrylonitrile copolymers, with one or both of the polymerizable monomers being substituted, varies somewhat from that for the unsubstituierte_styrene / acrylonitril-Misctipolymerisat specified preferred c ο *

Q9828 / 1698

As examples of a suitable selection of preferred Kompoa tenant ratios for substituted styrene-acrylonitrile-Ii Copolymers below are various substituted copolymers together with the required grain * component weight ratios for an azeotropic mixture indicated, namely, α-methylstyrene / acrylonitrile 69:31, styrene / methacrylonitrile 65:35, vinyl toluene acrylonitrile 78:22; Ct-Kethylstyrene / methacrylonitrile 57 ^ 3, Vinylxylene / Acrylni- · tril 80; 2 © and vinyl toluene / methacrylonitrile 68: 32o

According to the invention are also terpolymers of Styrene ^. · Acrylonitrile and a third polymerizable Monomers provided in which; the third polymerizes Bare monomer component up to 33% of the total polymer comprises ". Examples of polymerizable monomers which can be used for this in addition to the styrenes and acrylonitriles of the aforementioned type include acrylic acid and methacrylic acid, alkyl acrylates, and methacrylates, diethyl fumarate and monoethyl and diethyl maleate, maleic anhydride, Vinyla acetate, vinylidene chloride, Viny Imethy licet on and 2-Vi- ^ lpyridino e » Examples of suitable terpolymerisates with a preferred, but not the only preferred component weight ratio are as follows: styrene / acrylonitrile / α-methylstyrene 54 * 26:20; Styrene / acrylonitrile / methacrylonitrile

^ BATH ORIGINAL

9828/1698

73: .Ί 7 / 1CF | Styrene / AcryJhitriiyMethylmethacrylat; 65:12:25; Styrene / acrylonitrile / vinylidene chloride: 58: 37: 5; Styrene / acrylonitrile / vinyl acetate: 66:15:19; Styrene / methacrylonitrile: ethyl methacrylate: 60-24:16; ct-methylstyrene / acrylonitrile / methyl methacrylate: 60:21:19 and vinyl toluene / methacrylonitrile / methacrylic acid: 52J18: 30 »Further and other preferred copolymers can be selected by the person skilled in the art using the method described by Drs _a Robert J» Slocombe and George L "7 / esp in U.S. Patents 2,984-651, 2,984,650, 2,965,618, and 2,829,128. Thus, the term "styrene / acrylonitrile copolymer" used here includes unsubstituted styrene / unsubstituted acrylonitrile copolymer, copolymers in which either styrene or acrylonitrile or both are substituted with substituents that do not interfere with the polymerization reaction, and terpolymer salts of substituted or unsubstituted styrene , Acrylonitrile and a third polymerizable monomer, in which the third polymerizable component _{comprises up to 33% of the total Polymerisatm a} trix »

The above-described styrene / acrylonitrile mixed ' polymers can be linear or cross-linked »The cross-linking creates a certain improvement in the physical and mechanical properties, especially at the heat distortion temperature, although the linear

. BATH ORIGINAL

000026/1698

The maximum amount or the maximum extent of permissible crosslinking in the polymer depends on the intended use of the finished compound slightly lower notched flickering and flexural strength. Accordingly, the Regeluxig provides networking a Veränderliehe, dil © AfestiDpaaea one of the polymer to the production, a mass mu: the desired properties ermogliebfj »Bio suitable Jtusmäß of networking · Zung is the one Melüh &: _ a pole ^ Merisat. with ones: .effek -.-- * tlven molecular weight of about ZQ, 000 or SaPUb ^ r _3, preferably 50,000 or more. Furthermore, a linear styrene / acrylonitrile copolymer with a molecular weight of about 20,000 or more does not become crosslinked; while a polymer with a lower molecular weight, for example a polymer with a molecular weight of 5000 or less, is used in the practice of the invention It is better to use "if it is crosslinked" Suitable crosslinking agents are known in the art and can be used here in the usual way e.g. Dlvinyl—

982S / 1698

benzene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and other materials.

Modifications of the reinforced polymer systems according to the invention for providing an increased Kerbsohlag- toughness at the cost of bending properties can be obtained by mixing mkh small amounts of a rubbery polymer with the styrene / Ac / Initril-Misehpolymerisat be. The incorporation of a rubber-like polymer in a monomer sludge which already contains at least two monomers, a coupling or binding agent, an inorganic material, a polymerization catalyst and other additives with subsequent polymerization of the monomers and reinforcement of the resulting polymer can produce compounds with superior flexural properties and notched impact strengths compared with those of an unmodified styrene / acrylonitrile copolymer. In view of the known results in this field, the achievement of such an improvement is actually surprising. According to known processes, rubber materials have been incorporated into various polymer! - sate systems to improve the Kedb impact strength. . According to

ÖQ9828 / 1698

other known working methods were the flexural modulus (stiff- helt) through. Filling the polymer with an inorganic one Material such as lime or similar materials improved The filling of a polymer with an increase of the flexural modulus leads to a decrease in flexural strength and notched impact strength stiff, brittle and brittle »The application of a coupler * or Binder to turn a filled system into a reinforced one Transferring the system results in a substantial improvement ~

the flexural strength and the flexural modulus are significant with little or no loss of notched impact strength compared to the unmodified copolymer ^ improved * the additional incorporation of a katiischuk-like Polymer creates masses that are stronger, tougher, more elastic and more rigid than the unmodified polymer, what a substantial and unexpected improvement over represents the state of the art.

The rubber-like polymer used, if any is preferably used in concentrations in the range up to about 20%, and especially from about 1 to 10%, based on the weight of the styrene / acrylonitrile copolymer used « Higher rubber contents can of course be used according to the invention, in particular if the

§09828 / 1808, ■ ..- ■■ '■'. ■ / "BAD ORIGINAL

chosen rubber is a partially degraded rubber of low molecular weight and low viscosity » Reinforced styrene ^ acrylonitrile biopolymers with a Content up to about 10% of dispersed rubber, based on on the copolymer, can be used effortlessly the working methods given in the examples below are made, difficulties in handling and processing are encountered when the rubber content exceeds 15 or 16%. Other way of working such as a -iua * «c pressure fepwfeatae - squirting out into a form can of course be used and allow the polymerisation of molded forms of reinforced styrene / aeryl nitrile copolymers containing 20% or more of dispersed rubber. According to the preferred execution However, the invention is to be molded to compositions with a maximum content of about 20% by weight of dispersed rubber, based on the styrene / acrylonitrile copolymer, directed · This is due in particular to the fact that at higher rubber concentrations unsatisfactory flexural properties can be obtained. A maximum rubber concentration of 10% is particularly preferred because of the ease of use. activity of potting and molding, this area also with the very extensive and satisfactory area mechanical properties that are found in reinforced styrene / acrylonitrile copolymers with a Content of 1 to 10% of rubber dispersed therein

QQÖ32S / 16SS ...., _ Can be held. —-_

~ 15 -

For a convenient and advantageous production of the reinforced masses, preference is given to selecting a rubber-like polymer which is soluble in the styrene / acrylonitrile-Moriomerejisystem, although other, not completely soluble rubber materials with some loss of product uniformity? can be used »^ SITUATE designated rubbery polymers, the Po ^ ybutadienkautschiikmaterialieiij Polyisoprenkautschukstoffe include styrene * / butadiene rubber _r SatÜrlichen rubber ,. Acylnitrile / butadiene rubber, Bu-fca <äi © n /? Inylpyridine rubber, butadiene / styrene / vinyl pyridine rubber, polychloroprene, isobutylene / isoprene rubber, ethylene / vinyl acetate rubber and ethylene / propylene rubber, alkyl acrylate rubber / Propylene / Conjugated Diene Chewable »Specific examples of rubbery polymers which are particularly satisfactory for use in accordance with the invention include polybutadienes having from about 97 to 100 percent of the theoretical unsaturation calculated for the rubber; Styrene / butadiene mixed polymers with 1 to © twa - # 0? » liischpolymerisate butadiene polymerized styrene and acrylonitrile / β of up to about 40 wt .- # pölymerisiertem of acrylonitrile are preferably such kautsckukartigen.Polymerisate as above _s: little or no cross-linked 3-el contain, "^ =

000820/1008

~ 16 -

The rubber must be thoroughly dispersed in the reinforced material the polymer chain becomes mischpolymerlsie ^v »A simple mixture of the polymer components does not lead to a satisfactory combination of mechanical properties as is achieved by a copolymer of the rubber and the styrene-acrylonitrile copolymer * Simple, non-copolymerized mixtures of reinforced copolymer and rubber wind nevertheless useful for certain applications in which notched impact strength is not an essential characteristic. For example, 1 to 3% of a saturated acrylic rubber which is unsuitable for substantial interpolymerization is useful in the regulation of Sc lamb viscosity and gives the reinforced polymerized sheets or sheets a better surface appearance. AcySHLnitril mixed polymer, polystyrene, polymethyl methacrylate or the like can be obtained.

609828./1693 '. ^0AD

\ 162Q999

The inorganic filler materials which can be used as reinforcing agents include those which are essentially insoluble in water, ie are less than 0.15 U per 1 liter of water. Such materials can be selected from a variety of minerals, metals, metal oxides, metal salts such as metal aluminates and metal silicates, other silicon-containing materials, and mixtures thereof. Generally, such material Lieh, the surface upon treatment with a B _a se an alkaline "Surface obtain or possess is best for the reinforced poly E merisatmassen according _r-making suitable" Since metal silicates, and silicon-containing materials usually AEIA ~ he wished alkaline own or can easily obtain, a mixture is preferably used according to the invention which contains a predominant proportion, * "h" more than 50% by weight, of metal silicates or silicon-containing materials. with which they can be bound to the polymer, preferably. However, other substances, for example aluminum, which are bound to a styrene / acrylonitrile copolymer through the use of higher concentrations of coupling agents or binders, can be used as reinforcing components either alone or preferably in conjunction with other minerals that make up the Implementation with a coupler or binding

Ö09828 / 1 69Ö ■ "

. ■ '; BATH

are more accessible, and especially preferably in connection with smaller amounts, that is, in percentage amounts of less than 50% of the total inorganic material are used alumina may be mixed, is feldspar, a crystalline Urgestein mineral with a content of about 67UpSi (Xj * about 20% Al ₂ O ^ and about 13% alkali and e _r dalkalioxyden ₀ feldspar can be converted according to the invention in one of the preferred reinforcing agent, and a feldspar-aluminum oxide mixture is also useful. Other materials particularly preferred for conversion to reinforcing agents according to the invention are those having an alkaline surface such as wallastonite, a calcium metasilidate, asbestos such as chrysotile, a hydrated magnesium silicate, crocidolxt, and others Gaacium magnesium silicates. Change usable inorg Anic substances which can be converted into reinforcing agents include quartz and other forms of silica or silicon dioxide, such as silicon dioxide gel, glass powder, glass fibers, crystalite, carbon black, graphite or the like, metals such as aluminum, tin, lead, magnesium, Calcium, strontium, barium, titanium, zirconium, vanadium, chlorine, manganese, iron, cobalt, nickel, copper and zinc, metal oxides such as oxides of aluminum,

QÖ9828 / 1698

~ 19

Tin, lead, magnesium, calcium, strontium, barium, titanium, Zircon, Vanadium, Ch ^ om, Manganese, Iron, Cobalt, Nickel, Copper and zinc, heavy metal phosphates, sulfides and sulfates, and minerals and mineral salts, such as spodumehj, mullite, (M4ea) mica, mint morillonite, kaolinite, bentonite, hectorite, Beidellite, attapulgite, graphite, chrysolite, (Garnet) Garnet, Saponite and Hercynite »

If the reinforced styrene / acrylonitrile copolymers according to the EEfiaatMg are intended for such purposes, when they are subjected to high humidity, then there is a choice of certain SHills-tofj ? - ~ fen masses which give their mechanical properties to an unusually high level Maintain extent »In general, fillers from which no noticeable hydrolyzable components can be extracted by the action of boiling water are best suited for such purposes. In particular, quartz is very useful; Wollestonite and feldspar are of medium value; calcium carbonate is not recommended. Fillers that do not contain perceivable amounts of extractables »can be used to make masses with a preferred combination of mechanical. Properties can be used even after IGC hours of immersion in boiling water.

BATH

9828 / -16S8 '"' ■ .-. /." .. ■

As used herein, the term "inorganic material" normally refers to solid pulp materials such as those discussed above, for example. It should be noted that carbon black and graphite have been listed above as suitable inorganic fillers. The term "inorganic material" includes in addition to the usual inorganic materials including those carbonaceous materials which are characterized by the substantial absence of KohlenwassÄrstoffbindungen, ie _o below 1 wt .-% of hydrogen. Inorganic silicon-containing materials are particularly preferred which have an alkaline surface or can acquire them on treatment with a base and have a 3-dimensional crystal structure in contrast to a 2-dimensional or plane crystal configuration. These silicon-like materials are also due to a certain refractory nature recorded with a melting point of above about 800 ° C, a Moh's hardness of at least 4 and a water solubility of less than 0.1 g / liter. Examples of preferred silicon-containing materials include minerals such as feldspar, resin, wollastoni, mullite, kyanite, chrysolite, oristobalite, grocidolite, fibrous aluminosilicate of the formula Al ^ SiO ₁ - »sppdumene and garnet. These minerals are for a number of reasons for use with the reinforced styrene / acrylonitrile copolymers according to the Er-. finding particularly desirable »For example. lead.: them to

9828/1898

162099B

a mass with better abrasion resistance, flexural strength and modulus, tensile strength and modulus, notched impact strength durability, strength index, resistance to Thermal deformation and resistance to thermal expansion than the common clay fillers and inorganic pigments, like ζ ο Bö Weißmacher: (whiting) β Furthermore, the deliver minerals described above "higher stress

Loading
or SgywypTWgttMHg ^ values al "can be achieved with Grlasfasern what of considerable economic and technical importance _ö addition, STALER laden Nepf StyroI-Äcrylnitril-Mönomerensculämme be poured directly into a finished polymerized Forioai, which mettere Terarbeitungs- ofier Behandiungsstufen that with glass fiber reinforced masses are required, be dismantled *. ■

Metals have been suggested above as suitable reinforcing agents. In addition to producing reinforced polymeric compositions of high strength, the use of certain metals such as copper, silver, iron, and others can provide certain important additional benefits. Medium to Jp (C high concentrations of metals make kinhYme polymeric masses electrically conductive, what makes the composition suitable for an electroplating process, in which the composition with a thin coating of a metal * z _e B _o -von Ohlom, silver, gold-öd _{e dLgl a} electro- -

ÖÖ 9 8 2 8/1 S9β BADOBiQlNAL

can be plated or electroplated »Also know through the use of iron or steel as a reinforcing agent the polymer mass is given magnetic properties if the particles are oriented within the mass «

The in the production of the polymer masses ^ em ^ .ß der The amount of reinforcing agent to be used in the invention can cover a wide range with a maximum value, mainly by the ability of the polymer to make the reinforcing agent or medium adhere to one another Binding mass, being limited, will vary ^ by the following The methods described above include the production of polymer masses with a content of up to 90 or 55 GeWo-% of reinforcing agent enables »

The lower range of the reinforcing agent concentration is only limited in that the presence of a Sufficient amount of inorganic material to effect an improvement in physical and / or mechanical. Properties of the polymer mass is necessary / final * Accordingly, concentrations of inorganic substances down to 25% by weight or less can be used, especially when the finished mass is squirted out into a thread shape should be »A preferred lower limit for the reinforcing agent, especially for compression molded masses, is 30% of the total composition and is preferred 40 GeWo-%, especially if high strength indexes.

009828 / 169Ö -,

BAD ORfGINAL

values are required * Suitable values for gain ' Medium concentrations in the ready-to-use measures are in the range from about 25 "to 90%, preferably from about 4-0 to 90% and in particular from about 50 to 90% by weight «articles that should no longer be reworked afterwards ,, can with higher concentrations of reinforcing agent are produced will.

The particle shape and size of the reinforcing agent influence the mechanical properties of the finished mass. According to a preferred embodiment of the invention, the reinforcing agent is mixed with a monomer or prepolymer and then poured into a mold, in which the polymer formed and cured _o In such A _r beitsweisewird the viscosity of the monomer or prepolymer inorganic ^ r fabric Mixture at the limit of the maximum amount of reinforcing agent that can be used, ie too high a concentration of inorganic material results in mixtures that are too viscous to be poured in molds. The constraint imposed on the viscosity with respect to · the concentration of inorganic material is partly dependent on the form · of the particulate inorganic material «Example-

. so great ■

spherical ¹ parts do not result in an increase in the apparent viscosity of the monomer mixture, such as hade 1-shaped or fibrous materials. Through the -setting-

009 828/1 69 8 ■ ■ bathroom

, * 24 -

development or adaptation of the particle shape of an enhancer and thus by regulating the viscosity of the monomer mixture It is also possible to use improved cast and moldable polymers To produce masses with a very large proportion of reinforcing agent »At concentrations of inorganic Material of 80% by weight or less of the total mass the particularly preferred particle shapes are usually a mixture of granular and needle-shaped particles with a 1 / d ratio of about 3: 1 to about 20 or 25: 1.

Fillers with a 1 / d ratio can also be used.

from 2: 1 down to 1:15 or 20 »As explained above, When viewed as flattened rods, platelike fillers have 1 / d ratios less than 1: 1. The areas for the particle shapes can vary according to the invention from about 25: 1 down to 1:25 and are preferably in the range of about 15: 1 up to 1: 1.

Another factor that has an impact on the top The limit d, the concentration of inorganic material exerts, is the particle size distribution of the inorganic material. A wide distribution of particle sizes creates a mass with a smaller amount of voids or voids between the particles, thereby reducing the amount of polymer to fill these spaces and to bind the particles together '

162099t

What is required is - - Blue, a suitable combination of the two. Creates variables of particle shape and size distribution the possibility of production before aterk ¥ e3? §tä, rfetei3, masses with a t? © 3 ^ iegendeii share

Me feilotiengrößenverteiXmig- fcesltsst eiüe V / MPACT on the Ga? AAE ea-mögXioliei ¹ B © utilization qThe loading anorgani '* soaem MaterfaX "Generally iDeilclieni are the durcn a sewer? corresponding one:? Se% ^ «^ a clear size γόη about 2 ^ OfO, (60 mesfe screen) do _r suffice ^ small» in the masses according to the? DJi? Finding ': used to turn, particles with a ^ <5 ^ © ß "up to su 1ΟΌΟ μ; (ΐδ mesh) can be used with the same or almost the same Ej? Fpig and (particles" the sq small as Q _% 3 μ are, ^^ -were used successfully, whereby particles in the range from 200 to 400 mjrt suy can also be used ? d _? _ is an indication of the particle size

lin suitable range "he ά Tei.lQhengrößen, -vertellung is given below; 250 Ji or- less (60 mesh) or less 149 fi (1.00 mesh)

50% - 44 μ bdep less (325 mesh) * ν

w 5 μ or less «; _:

BATH ORIGINAL

A narrower distribution that is also suitable for use in accordance with the invention is that. the following: 100% - 62 μ or less (230 mesh) 90% - 44 u or less (325 ms eh) 50% - 11 yes or we younger 10% - 8 μ or less.

A relatively large colored mixture made according to the invention is useful, there is the following particle size distribution! .-

1QQ% -250u or less (60 mesh) 90% - 149 u or less (100 mesh) 50% - 105 ju or less (140 mesh) 10? Ό - 44 ji or less (325 mesh) A suitable finely divided mixture has the following Particle size distribution:

100% - 44 µ or less (325 mesh) 90% - 10 µ or less 50% - 2 µ or less 10% - 0.5 µ or less.

The above numerical values with regard to the particle size distribution are not to be regarded as restrictive, since both broader and narrower ranges of the distribution can also be broken down and coarser or finer materials can be used. Rather, represent this

ßAö

Numerical explanatory examples of inorganic. Crowds represents, according to the invention for use in manufacture the reinforced polymer masks, fairy / are. «As Example of the diversity of particle sizes in the reinforced polymeric masses according to the invention to the. Application can also be great; Aggregates on the order of 2.54 cm in diameter or above (in inches) of the polymer matrix for special effects, examples of which are ground Glass, roofing granules, quartz chips or pieces or the like are.

The reinforcing means serve a dual function in the finished masses. Depending on the material chosen, they can serve as an inexpensive extender to the polymer, thereby lowering the cost of the end product. The second and more important Wirkunr of these inorganic materials is when bound to the polymer by a binding or coupling agent, the production of compositions with Sige physical properties which are far 'superior to those of unreinforced _r en polymers - _t - whereby deiai using Mn Ahv / ending areas for which the unreinforced polymers were previously unsuitable, is made possible; ■ ^f - *.

• '- ■'. ". BAD OMGJNAL

9628 / 1698- / ^.

To achieve the advantages according to the invention, namely the production of easily cast or moldable, strongly reinforced polymeric masses and also one Lower costs through higher loading of reinforcing agents it is necessary that the reinforcement

medium essentially "* grainy or acicular in its Form is as fibrous. In general, the reinforcements should

up to particle a / length / diameter ratio. of / about 25: 1, preferably "up to about 20: 1 and in particular in the range of about 3: 1 to 15: 1" However, a small amount of fibrous material can be incorporated into a polymeric system if the amount of granular or needle-like material is reduced by a somewhat larger amount »Be'ismelsweise 3 or 4% by weight, based on the total weight of the reinforced mass *, of glass fibers with a length of about 1.27 cm (0.5 inch) in a Monome renbrei with a content of about 50 to 5 x 5 wt .-% of granular incorporated feldspar werden.- The resulting slurry can be about as good as · a Monomerenschlainm with a content of only 65 wt -.% ■ On the other hand, if castability is not required, larger amounts of fibrous material can be incorporated into the mass, thereby strengthening the end product to an even greater extent.

Ö09828 / 1698

The most commonly used, fibrous : ■ "- ■ are: -"-'- ^: ■ "" _ ".": ■ "'■ -. ■ ..:"; - inorganic material i "s # fibrous, silidiunuial "Inert glass particles" These fibers are most easily incorporated into the polymer masses when they are broken up into strands or strands with a length of about 0.254 to about 7 * 62: cm (φϊ to 3 in ches), whereby they are either can be added to a prepolymer — Euppler's sealant — as separate beads, or formed into a mat onto which the polymer is cast prior to polymerization. These glass fiber incorporation procedures are known in the art and are mentioned here to illustrate that "the granular-reinforced polymers according to; the invention additionally by incorporating fibrous .Materials according to procedures known in the art or according to the methods described here as being applicable to granular reinforcing agents can be reinforced,... "_;

After the optimal TeilGhengrQßenverteiliiung of Verytärkunssmittel for a special Poiymerisatsystem overall ^'w: is _keeps>% may ,, as ersichtlleh be reaches an upper limit on VersSÄrkungsmittels in which * the composition ziu viscous is "poured into a form to. "Viscosity of the monomers onC inorganic material can be developed by: overf if'Ohenaktiv © 'means"

Me reduced viscosity /> rlavutte the * formation @ 1ϊκ3 # celebrate: n \ smoothersn; ' Procurement: l, t in ä $ m

Qelegentliah / can be a figured ^

-.30 -

composition with a high content of reinforcing agents, for example above 70% »a grainy or coarse texture or texture and can even have voids or open spaces due to the inability of the

complete
have viscous mixture to / confluence prior to polymerization. The addition of a surface-active agent eliminates this problem and provides a smooth and appealing or attractive * appearance on heavily reinforced materials.

Appearance or a smooth 3-structure is required, '"then allowed a decrease in viscosity, incorporation of large amounts of reinforcing agents in the monomer feed » Aenionic, cationic and non-ionic marriage Surfactants can be used to soften the sludge • viscosity used '«earths and materials, v / ie. Zinc stearate, long-range alkyl-trimethylammonium halogen and Alkylene oxide condensates of long-chain carbon env / as scr- toff compounds were used successfully »

An essential and important material in the production of the reinforced polymer masses according to the invention is the Euf: plun ~ ₃ s - or binding agent, which binds the inorganic material to the polymer. A coupling or binding agent can be characterized by its functional groups, one of which Group aur chemical reaction with at least one of the monomers wcar

Ö08828 / 1698

the polymerization, and at least one group is suitable and capable of reacting with: the reinforcing agent. The coupling or binding agent must contain an organic group with a carbon-carbon double bond and at least one hydrolyzable group which is suitable for reaction with the surface of the inorganic reinforcing agent. polymerisiereiiden the monomers and demKuppler instead findete However, such couplers produce ^1, .the. have functional groups which, as expected, with. A polymerizing monomer can enter into a Kischpolyme-risti-tio-n, or with a polymerized. .Polymer, react. körme.n ,. Compositions with properties drawn with axis, while. Couplers which do not contain such functional groups generally give compositions with poorer properties. The inorganic material un, d the Küppier v / earth connected by being in the absence or in the presence of a solvent for the coupler, such as water, alcohol, dioxane or the like. united. It is likely that the hydrolyzable group of the coupler reacts with free hydroxyl groups attached to the alkaline surface of inorganic materials. Theoretically, hydroxyl groups are present on the surface of most lietallic substances containing silicon or can erit-

Ö09828 / 1698. - ~ *

will be wrapped, what ^ uch one for implementation with a hydrolyzable group of a coupler accessible plate is created «This theory of availability or train The possibility of hydroxyl groups on an inorganic surface can explain why many silicon-containing. Minerals are preferred reinforcing agents and why silicon-based coupling or binding agents are particularly important preferred for use with the silicon-containing minerals i.e. the silane groups of the coupler, -Si- (QR) -, react with the silanol groups of the inorganic Materials, -Si-OH with the formation of the very stable siloxane

bond -Si-O-Si- ο If the theory given above ■ - ■ r, ι ι. . . - _;

exactly applies, a chemical bond of the coupler to the inorganic material achieved in the masts according to the invention. Other theories can be suggested indicating the presence of a true covalent bond between the inorganic material and the coupler are negative. Regardless of any theoretical explanation presented here that is not to be regarded as limiting, will the coupler to the inorganic material through contact «* bring the two substances bound. The mixture is dried beforehand, but not necessarily afterwards “A bond between the inorganic material and the coupler is obtained in this way »The implementation of

- '■ ..- ■■ - ■■■■■. :. · - _. ßAo 009828 / 1-6 9 8 ','

Inorganic material and coupler can be carried out separately and the adduct of inorganic material and coupler can then subsequently: added to the monomer -ppBredenjOder the reaction can take place in the future; the monomers are executed and then the entire mixture to remove flücji ^ ^ strength EeaktiQnsprQdukten and egetesnenfalls used - ■ solvents dried »YoEzugsweise is the 4ddukt from: supplied coupler and inorganic material Warm | to increase the extent of the bond ^

As described above, grazing Silankuppliinfsmittel for Gcehrauch according to the invention heVorZUgti s inshe other _e% when an excellent Come nation of meGhanischen schnften is desirable in the fertiggestelliie.n mass "; wisely used silane coupling agent Äerdeii by the general formula

s: ellt _v in which 3C is a hydrolysierfearen beat, capable of reacting with the © herfläche, an anorgamseheji material |; _t "at ^ pieslLWeisZe halogen _% i

04er ^ _t ^ ^

contain fuel ^ a ^ firuppeii usuallyj · S or | feniger> least of fatome ^ X have one;
an alkylene radical m4t 1 to about SQ-

BADOBlQfNAL

a radical which can be copolymerized with styrene or acrylonitrile or a radical which is reactive towards a styrene / acrylonitrile copolymer, Z ₀ B _{0 is} a vinyl, allyl, acryloxy, methacryloxy, styryl, cyanoalkenyl or other similar unsaturation contains a remainder, η an integer from O to 1, a an integer from 1 to 3, b an integer from O to 2, c an integer from 1 to 3 and the sum of a + b + c ' equals 4 _o Particularly preferred coupling agents of the formula given above are those in which the number a? «3, b ** O, c« 1, n = 1, Z is an alkoxy group with up to 4 carbon atoms, Zj is a methacryloxy / f group, d, h «CHo ^ C-COQ-, and R is an alkylene radical

GH ₃

with about 3 to 18 carbon atoms represent »The effect of groups Z and X has already been explained. The alkylene group in the bevorzugslten embodiments of the coupling means according to the invention serves as a bridge between the Foiymerisatt-reactive group and the silane group of the coupler "The alkylene bridge is üblicherweise- in a coupling agent due to the additional stability which they ^ m coupling agent imparts _t Available * also acts the coupler, since the number of carbon atoms in the itlkylenkette the coupler ΊΟ or reaches 12 _t harden as a Yiskosität the degrading. Medium, creating higher levels of inorganic. Tonic enables _x. Than them.

~ 35 -

with couplers "with shorter chains of the Alk -? - lenre'ste present therein can be used. The Y group can consist of" any hydrocarbon group; The V / irkdna of the Y group can be the modification of the extent of the bond between the polymer and the 'inorganic material, which regulates the viscosity of the monomeric sludge, or it does not have any effect at all in the polymer funds. Their presence may be due to the necessity or square shape for the use of a hydrocarbon-substituted silane reaction participant in the synthesis of a silane coupler. Preferred hydrocarbon groups if they are used -because, are often short-chain alkyl radicals with up to 4-carbon atoms "examples of useful silane-copper"? _'- '· "■ ■ ^: ^ .- ■ - ■; · Λ.

Vinylmethyldichlorosilane: GH ₂ = GH-S ^

n- (2i ^ thyldifluorosilyl) -acrylate _{25 5} ;

yίilyIsthylm ^ thacrylate (CE ₅ C ¹ ) ^. SiC ^ H ^ OOGQ (GH ^) - CH,;

^ -rTrichlorosilylbutyl acrylate

(Cl) ₃ SiC ^ E ₈ CCGGH = GH ₂ 5

6 ^ -Tricy c lohexy loxy s i Iy lhexy lme rhac ry lat

_009828/1698; ... ..

H-trimethoxysilylundecyl methacrylate (CH, O), SiC _/ , _/ , HppOOC-C (OH,)

le-triethoxysilyloctadecyl acrylate

■ 18-triacetoxysilyloctadecyl acrylate
(CH ₅ COO) ₅ SiC ₁₈ H ₃₆ OOCCH-CH ₅

p- / ~ 3-trimethoxysilylpropyl7-styrene (CH ₅ O) ₅ SiC ₅ H ₆ C ₆ H ₄ CH-CH ₂ ; and

ß- / ~ 6-trichlorosilylhex7 / 1.7-acrylonitrile

Another class of coupling agents are the coupling agents based on phosphorus of the general formula:

Rf - P _ R »

RMl -

• ' to the "

in which R ^{1 is} an inorganic material reactive group corresponding to the X group of the silane compounds, R "is a polymer reactive group corresponding to the R -ZG group of the silane compounds and R" ^{1 is} either a non-reactive group corresponding to the Y group of the silane compounds or corresponding to the R ¹ or R "group of the present compounds. Specific examples of compounds which can be used here are from US patent _{specification ββββ} ·, o. (US patent application Serial Hr. 333 630 of December 26, 1963 ) visible «, 009828/1698

1620939

Other compounds useful as couplers according to the invention include complex chromium compounds which contain functional groups corresponding to the Jr »and Z groups of the silicon compounds 'rfeatoohrjaiomsäurechloridj MethacrylätOel ^ rQmsäurehydrQxyd und Oxyd

The small number of couplers with which the inorganic material is traded is comparatively small. As little as there are coupling or binding agents per 1000 g of reinforcing agent results in a polymeric compound with superior physical properties compared to those of a polymeric compound, the same untreated filler . contain, Im; general a. erwiese-ii to Mengert of the coupler in the range from 2 ^ Q to _2Q% 0 g per g 1Ό00 ferstärjfcungsmittel particularly to '^ can be satisfactorily _t although amounts above this Bereic'hs * also be used. If different masses according to the invention are known due to their superior mechanical properties compared to other known substances. Mass drawing “It is common practice to use the Xoung modulus of the elasticity of a polymer by filling it with a particle. miicen anoyganischert material he / heights * However, it is both hinsichtlicit the bending and the tensile strength · _t and the Beatän.digkeIt-to impact a iEompromdisi done, "Mr many AnwemdungszweiCik: e lsi; niichfe mm die: ¥ erbea ~

it is necessary to improve one property at the expense of another, but rather an improvement of a combination of properties »What combination of own— Shafts to be improved depends on the intended Applications for the finished product from »For such uses, like planes, furniture components, automobile ^ -

. components ,, home furnishings ,, building boards and others

-

Applicatio "Sgebiete in which the tensile and flexural strengths and moduli and impact strength are essential and important factors, a value is _f supports the elimination of suitable from unsuitable materials, the strength Indexa is sflndex The strength a jiigen- economy of a material on the basis of the relationship between flexural strength and impact strength of a material, "The higher the strength index of a mass, the more valuable this material is in general for various of the above-mentioned uses". The strength index is the product the notched Izod impact strength and the square of the flexural strength and is indicated here by the abbreviated designation SI (strength ~ _e Sskig-Schlagzäiiigkeit) Qj56 x 10- at (8 χ 1C ⁷ psi) marked

009828 / Ϊ698

The flexural strength and modulus were determined 'according to' the ASTM D-790 procedure and the IzOd notched impact strength is c: e- ■ mt ^; ß der-, preclirift ASTM-D-256j VBTfahren A, measured

As catalysts for initiating the polymerization reaction, any compounds which form free radicals under the conditions of Bealctdonsbedinguhgen can be used, with peroxy compounds being preferred. "Special" classes of compounds that can be used include peroxides,,, diacetyl peroxide, acetylbenzoyl peroxide, bipropionyl peroxide, dilauroyl peroxide , Benzoyl peroxide, dimethy Iperoxide, diethyIperoxide, DipropyIperoxyd, TeträlihperOxyd, Gyclohexanperoxid, acetone peroxide, Hydroperoxyd, like Glyköliexylhydroperoxyd, Cumolhydroperoxvä, Hydrodrazine like Hydroxdroxid like Hydrazidrozidrazid, like 'Hydroa- _{butylhydrohrazidrazid,' t} at, ■ Diberrzoylhydrazih, Biacetylhydrazine, TrimethylhydrazöniύΓύ ^ ι-οdid; - Ami-no xy -de ν '"· νχe- Pyridinoxyd, SrimpthylaniinGxyä,""imetliylar.ilincx .d, iilkali- and Ammonium—'persul-'persul perborate mid ^{-percarbcinite;} V ^; erbinduncren _$ containing the Jrurre> G = K and "derived" from Ketaldonen

em
are, άιϊϊο a / ketone or aldehyde, like die-azines "(which contains the 'group>C" = I7-K ": C <) ■'., ' z _c B _c Bena ^ lazin, Heptäldaz-iri-' and biphenylicetazine, oximes (which contain the group> C5 = IvOH), e.g. d-canchoroxime, acetone oxia ₄ a-3enzildioxiia, 3utyraldoxini,

009828/1698

α-Benzoinoxime, dimethylglyoxime, hydrazones (which contain the group> σ «Ν-Ν * Ο), z * B. Ben / Sizaldehydphenylhydrazon, phenylhydrazones of cyclohexanone, cyclopentanone, acetophenone, Methon, Eampher and benzophenone, semicarbazones (the group _XC-N-2 CHCOBH included), such as _e semicarbazones of acetone, methyl ethyl ketone, Diäthylketonbiacetyl, cyclopentanone, cyclohexanone, acetophenone, Priopiophenon, camphor and benzophenone, ship-specific bases (containing the group> C = N- included), eg Benaalanilin, benzal-p-toluidine _t benzal-o-toluidine, Benaftldehydderivate of methylamine, ethyl ^ amine unqHeptylamin, anils and analogous compounds of other amines such as acetaldehydanil, isobutyraldehydanil, heptaldehydanil od.dglo oxygen and the reaction products of organomet aiii see compounds such as boron alkylene, cadmium alkyl] p., zinc alkylene, tetraethyl lead _T aluminum alkylene or the like. with oxygen

These catalysts are generally used in quantities from about 0.001% to 0.5%, based on the weight of the total activity participants.

can
do not think it is necessary / for the production of particularly high reaction levels or for other special purposes, higher amounts of KetXalysatoren be used »For example, amounts in the range up to Λ% or even up to 5% can be used as the upper limit will"

0Q98287 1698

~ 41 ~

Preferred catalyst systems for the preparation of the reinforced polymeric compositions according to the invention are made by the rapid catalytic decomposition of per-oxygen compounds en received. Any material that is a free radical from // issuing material <^ activated ^ within ^ a

for a short time / £ ~ can be used ^ For example can be a boron derivative with three hydrocarbon residues, BR ^ used to activate a peroxygen connection to produce useful polymeric compositions «The activity the BR ^ component is due to the complex-forming effect an amino compound as well as modified by the appropriate selection of the R radicals in the 'BR ^, compound'.

Compounds which are useful as activators include borohydrides (boranes) and substituted boranes such as borane, diborane, iPriborane, tetraborane, trimethylborane, iriäthylbzforan, Tripropylb ^ oran, Trihexylborani ü? Rioctylboran, Tridecylboran, Tritridecyclohenyl, tridecylborane, tritridecylborane, Tribenzylborane, triphenethylborane, tri-monomethylbenzylborane and trl-tolylborane. A trialkylborane of the formula BR is preferably used, in which R _; means an alkyl group having 1 to about 14 carbon atoms. The boron compounds can be complexed with a basic complexing agent, the complexing agent having an ionization constant of about 10

bath

to about 10 ", preferably from 10 ' to 10. In particular, amino compounds with an ionization

-7-10
constant between 10 ' and 10 preferred, of which a notable example is pyridine. Other suitable amines which can be used include methylamine, dimethylamine, trimethylamine, dimethylbutylamine, n-o ^ tylamine, the picolines, aniline, dimethylaniline, UIe toluidines, Triethylenediamine and mixtures of several different amines »The molar ratio of amine to boron compound is within the range from 0.1: 2 to about 10; 1 and preferably within the range from 0.5: 1 to 2: 1., The catalyst system, a trialkylborane complexing agent with a peroxygen compound, allows a rapid polymerization reaction with high conversion without the dangers of a runaway-type reaction. Although the use of an amine as a complexing agent for the trialkylburane is preferred, other compounds for this are also known For the purpose of application, Z ₀ B ₀ tetrahydrofuran and tripheny! Phosphine »for determ mte ;! Applications, oxygen or air can be used instead of the peroxygen compounds »

Other ^Katalys: .torsysteme can reach the Erfindmag according to the application, although their use is generally more Polymeris-vfciontemperatur and / or longer periods of time also in the production of reinforced compositions

009828/1698 o ^ _Q

-i0 - ■■ ■■■. ■■■ ■■ ;. - γ ■■ '/. ;

require take. These systems include dime fchy! Aniline / BenzoJlperoxd, KVN-Dimetnyl-p-tbluidin / Benzoylperoxid und kpbaltnaphtkenat / Dimethylanxlin ^ eth ^ läthylketoirperpxyd ·. ·

The reinforced polymeric compositions according to the invention can be produced according to a rapid casting process. According to this procedure, a flowable mixture is which is the monomer material. Contains reinforcing agent, coupling agent and catalyst, placed in a mold, and a molded solid product comes out of the mold inside a short time away. The system is based on a rapid regulated or controlled polymerization for the production of complicated shapes at moderate temperatures and pressures applicable. Other processing techniques applicable to the reinforced masses according to the invention include Compression molding, compression molding, injection molding, rotary pressing, etc. centrifugal potting.

In general terms, the method according to the invention the implementation of a coupling or binding agent, as explained in more detail above, with an anorganic see material for forming an adduct from the inorganic material, udud coupler and then carrying out one Polymerization of a styrene and acrylonitrile in the presence of this adduct to produce a styrene-acrylonitrile * - Copolymer, which is adherent to the addict of the inorganic material and coupler * --- "The coupler can in advance with the inorganic material before the poly-

009828 / 1B98

merization of the monomer mixture; (As described in more detail in some of the examples below), or the inorganic material, the coupler and the monomer mixture can all be mixed with one another before the polymerization of the monomer or after the polymerization of the polymer. Essentially the reaction of couplers and inorganic material may be aided by supplying heat in the range of 90 his 10O ⁰ C prior to insertion. When using a styrene-acrylonitrile monomer mixture as a dispersant a satisfactory operation for obtaining comprises a good reaction between couplers and an inorganic material, the addition of the coupler to the monomers ^ the addition of the inorganic material to the mixture, stirring vigorously and heating to 100 ⁰ C to remove water and some of the monomers, cooling the resulting sludge to 25 ⁰ C, adjusting the monomers to the initial concentrations, adding the initiator and optionally the accelerator and pouring into a mold '"

The polymerization of styrene and aoryl nitrile monomers can using a wide range of polymer! οηε temperature ^, press and duration «are executed in Depending on the desired mechanical properties, the type of catalyst system used and the values, which are selected for the other polymerization conditions «

009828/1698

The temperatures can be in the range from 20 ⁰ O or below to 10O ⁰ O or above. If temperatures above 70 or 75 ⁰ C are used, the polymerization should be carried out in a closed Ge gf '& B under pressure in order to prevent volatilization of the acrylonitrile. The pressures can be in the range from 760 mm Hg or below to to several atmospheres vary ο Polymerization times from as few as Λ ο 4 or 2 minutes to several hours. can be used «-

Depending on the process technology used, the production of polymeric masses is with varying degree of crosslinking or no significant at all Degree of crosslinking possible. «The in situ reaction of Kuppler and inorganic material before their addition 'to the monomers' ren can lead to a sufficiently linear polymer, which enabled satisfactory processing by injection molding. The in situ combination of inorganic Material, couplers and monomers simultaneously with the Polymerization of the monomers leads to a sufficiently crosslinked mass for its subsequent processing in the Preventing injection molding of suitable objects;

With respect to the. Mixed with rubber Two basic procedures can be employed ,, namely a mechanical mixing and Polymerisatiorismischen For _e

00 9 8 2 8 1 1 6 98 bad original

achieving good mechanically mixed rubber / reinforced styrene / acrylonitrile copolymer mass can be a rubber-like polymer and the increased mass on a given Vorridhtung, eg _o on a heated mixer or roll mill to obtain a homogeneous mixture, mixing together, the can then be converted into the finished form according to the injection molding process or compression molding process. Polymerization mixing can be carried out by interpolymerizing styrene and acrylonitrile in the presence of the rubbery polymer. One of the main advantages of polymerization mixing is the superior dispersion of rubber in the interpolymer, which can be achieved when an unsaturated rubber is also used reached, a substantial interpolymerization of rubber-like polymer and polymerizing monomers can be obtained, whereby the mechanical properties are modified even more effectively than with a non-polymerizable rubber.

The reinforced compositions can also be prepared according to the invention Hannen by _a rz mixes the filler-free H with the inorganic material and the coupler _a; Mixing can be done in a customary manner on a mixer. * y eg a Banbury mixer with subsequent mixing rollers or on another mixing device that can produce the required degree of mixing «, The" 009828/1698 ^ ___ r

8D

Size or the extent of the misclien is conveniently referred to as the required size in order to obtain the desired shafts of one's own. The temperature, the relative speed of the mixing rollers or miso blades, pressure, time, amount of filler and composition of the resin are some of the variables that affect the finished batch. influence ... When using a roll mill - "or a rolling mill ^{3 2} B ¹¹¹ mixing a". 76: 24 Misohpolymerisats of styrene and acrylonitrile _t d _a s SSF> amount of treated with couplers quartz treated with a sufficient K " a mass with a content of 65 G.ew. -ψο yield of inorganic material, Walzenteaperaturen jAveils of 175 ° and 185 ⁰ C for the front or rear roller respectively, a mixing time \ qi Kinuten 10 is a mass having mechanical properties obtained that are roughly comparable to the cash registers, which are comparable by polymerizing the monomers in the presence of the filler *

The unusual properties of the marketed masses according to the invention make the expert noteworthy Applicable areas for these materials close to “Da with a A hard, smooth surface can be obtained with simple casting processes, support and counter bearing surfaces can be used as well as billiard and foul game table surfaces and floor and 7 / and coverings or coverings are produced. ' the

009828/169

Polymerisatlonssclilämme can be used for the production of Rotationsgießlingenj for the production of complex shapes and for the centrifugal casting of pipes and pipelines be used. The sludge ?! can also be modified be used to produce thixotropic mixtures for support press moldings (la; £ - up moldings). Compression molding or sintering powder can be produced in the potting area.

The invention is hereinafter referred to by examples ■ explained in more detail. ■

example 1

In a reaction vessel, 314 g of styrene, 99 g of acrylonitrile, 5.3 g of trimethoxysilylpropyl methacrylate, 17 »1 S nonylphenol / ethylene oxide addition product (Tergitol NP-27), 8.1 g of a 5% solution of benzyl peroxide in trikibyl phosphate and See 824 g of wollastonite in the order given. After evacuation for 5 minutes to remove air, the liquid sludge is poured into a mold preheated to 65 ° C. The temperature of 65 ° C is maintained for 20 hours, after which the mold is cooled and the polymer is removed will »The finished mass contains 65% of the inorganic material. The mechanical properties of this product are summarized in the table below.

- BAD ORIGINAL

009828/1698

' Example 2

The procedure described in Example 1 is followed with _s Amendment ₉ that the Trimet * | oxysilylpropylmetha * - methacrylate wollastonite before its incorporation into the Monomerenschlamm we added you the reaction of coupler and minerals is as follows caused The coupler is in Tl Dissolved methylol and added to the WoXlastonit. After mixing, the methanol is evaporated and the thus treated "wollastonite at 24O ⁰ C for 1 hour and 15 minutes heated W _a cfe cooling is ground · the mineral to break up aggregates formed die'während the treatment stage. The behaz punched mineral is then the Monomerenbrei added, which is then encapsulated and polymerized ₀ the. results "obtained are summarized in table I below»

- Example 3 .: -; . _

The procedure described in Example 2 is followed with the modification that instead of the 5.3 g of coupler used in Examples 1 and 2, 8.5 g are used to give a mass which is a coupler with 2% instead of. · ■ the 1,5 ^ coupler treated according to Examples 1 and 2. The results are in FIG

f ■■ .-. '■ · ■■ "■" .- ■■ -

subsequent]! Eabelle I compiled »:" ..---

Also in Table I are comparative values for three similar ones Styrene / acrylonitrile copolymers, listed Die Hasse A is a filler-free, unreinforced styrene /

Acrylonitrile-läischpolymerisät (s / ^ ANl, which according to the in ———- ^ - k

: - ΐ SADOBfGfNAi

Example 1 was prepared with the modification that no inorganic material (i) or coupling agent (C) was used. The composition B was prepared according to Example 1 except that no inorganic material was used ₀ mass B differs from dev compound A characterized in that it comprises a coupling agent ,, ^ ± e mass C was cozy eat in Example 1 prepared procedure described, wherein no coupler was used, but an inorganic pull material.

The flexural strengths and moduli are in accordance with the regulation ^ ASTM test D-790 measured. The impact strengths are measured according to ASTM regulation Test D-256.

Table I.

Mass AB C 1 2 -3

S / AN / S / AN / S / AN / Art S / AN ■ S / A.N / G S / AN / l i / C I-O! -Ο

Flexural strengthWi

kg / cin 738 702.8 464 980 1062 1120 s | ji 10500 10400 6600 14000 H600 16000

_{Flexural modulus 2} 4 4 'κ 5 51 kg / cm' ¹ 3.3x10 ^ 3.3x10 ⁴ 1.2XiO ⁵ 1.2x10 ^ 0.98x1o ^D '»

^{6 6 6}

psi 4.7x10 ⁵ 4.7x1 Q ⁵ 1.7 * K> ⁶ 1.7x10 ⁶ 1.4x1O ⁶ 1.6 x1o ⁶

Izodkerb-

impact strength

fJt-Ib s./inch, of

oy corr. for

Shaking (correck

ed for toss) 0.26 0.15 0.12 0.23 0.15 B, 23

Strength index "^

S ^ I 2.9x10 '1.6x10' 5.2x10 ^D #, 5x1O '3.2x30 ^l 5.9x1 0 ¹

009828/1698

From the values in the table above it can be seen that a real real synergistic effect through the combination of inorganic material and coupler is achieved in a styrene / Ä-CrylnitriT mixed polymer. The addition of the coupler alone leads to the copolymer only to a certain deterioration in properties (Impact strength or impact resistance). Me combination j of inorganic material in chemical association with the Kupjler with the polymer molecules, however, there was a significant improvement in the flexural properties without or with little loss of impact strength · In addition, the combination of flexural modulus and strength index values shows that the reinforcement of styrene / acrylonitrile resins according to FIG

Invention supplies masses with far superior properties ^ - Vfer- · gle ^ -ch ^ nk with the known masses. Example-5 shows that flexural properties can be improved by increasing the coupler concentration from 1.3 $ to 2 ^ ₁ based on the weight of the inorganic material.

; . ,. .- --- ■ - ■; Example 4 ^ ^: - ■, - ■ -.

The polymer produced in Example 3 is fused to a coarse powder and injection molding on a 28.3 g (Toa) Watson-Stillman injection molding machine using a cylinder temperature of 260 ° C, a molding temperature of 65 ° G and a. Molding cycle of 20 seconds subjected to ₀ The material was suitable for injection molding, the mechanical properties are ■ together in the following Table II ^

Q9 828/1 69 8 BATHROOM

posed. For comparison, the composition of Example 1 could not be made into a finished article by the injection molding process be shaped.

Table II
Dimensions
Type -

Flexural Strength kg / cm ² 1120
psi

Flexural modulus kg / cm psi

Notched impact strength

corrected uncorrected

Strength index SI

3 4th 1 poured injected
poured can not
injection molded
will 1120
16000 833
11900 0.27.10 ⁶
1.8xi06 0.105x1O ⁶
1.5X1O ⁶ 0.23
0.41 0.14
0.33

2, Ox10

Albeit the properties of the injection-molded sample have noticeably worsened, they still are those of the unreinforced polymer (A) or that with Superior to polymer (C) with filler,

Example 5

The procedure described in Example 1 was repeated with the modification that the nonionic dispersant (lergitol NP-2?) was omitted and the wollastonite content was adjusted to 60 wt .- # of the total mass ^. The mechanical properties were similar like those obtained in the compositions of Examples 1 and 3 Measurement results measured. All masses (from the examples 1,3

009828/1698

BATH

■: - 53 -

Dimensions
Art

and 5) were then placed in boiling water for 24 hours brought in and checked again afterwards, to their bimpfind— resistance to conditions of high humidity and temperature to consider". The results are in the following Table III compiled «,

Table III

3. 5

S / AN / I

Tergitol additive 3a wt .- # Wöllasto-

nit 65.3

Flexural strength before the "Ködhtua.

S / AN / 1 / σ

Yes

65.0

S / AN / I-O

65.3

before boiling 1.57x10 after boiling !, 44x10

Notched Izod

Tenacity (a;

before cooking 0.12-0.31

after this

Cooking 0.14-0.32

]? estness ~
index SI 6

before cooking 5,2x10 after the ^

Cooking "3.9X ¹ O

1.73x10 ° 1.45x1.0 ⁶

0.23-0.43

1.84x10
1.55x10

0.2 ^ 0.41
0.24-0.44

4.5x10

4.7x1

S / AN / I / C none

60.0

psi 6600 14000 16000 13400 nbh to cooking
PFi -5700 - I25OO - -
I4OÖO 13600 Be ^ .gemodul

1.47x10 ° 1.55x1O ⁶

• 0.28-0.46 0.18-0.38

5, OxiO ⁷ 3.3x1Q ⁷

(a) The initial value is based on the toss factor
corrected

BATH

If the dispersant is omitted from the approach, are the bending properties of reinforced styrene / acrylic

ι '·' ·· ■ · nitrile Mischpoüiymerisaten afteene-iTiernct unaffected by prolonged exposure to boiling water _e Such excellent retention of properties, both in the presence and in the absence of a -Dispergiermittels is completely surprising with respect to the work carried out with other reinforced polymer systems, which showed a considerably greater degradation of mechanical properties in boiling water than was observed here.

Example 6

Attempts to reduce the polymerization time for the polymer were in the below! en examples The procedure of Example 3 was followed with the modification

_n Ω

tion followed, ¹ that the cast material was only maintained at 65 G for 10 hours instead of 20 hours. .

Example 7

The procedure of Example 3 was repeated with the modification that the cast material was only at 65 ° G during Was maintained for 7 hours instead of 20 hours.

Example 8

The procedure of Example 3 was followed with the modification that the φχΐί eaten material was held in the mold at 65 C for only 4.5 hours instead of 20 hours. After removal from the mold, the polymer is post-cured for 1.5 hours at 95 G. The results obtained are summarized in Table IV below.

posed. 009828/1698.

BAD OfilQlNTAL

Example 9

This was repeated in Example 3besehriebeneVerfahren was washed with the modification that the cast material in place in the mold at 65 ° C for 4 hours, kept 20 hours "After removal from the mold ^ the polymer rde postcured for 17 hours at 0O ⁰ C" The results obtained are summarized in Table IV below set ·

Table IV

Mass 3 6 7 8 9

Hours at 65 ° e 20 10 7 4.5 4 hours at 95 ° C 0 0 0 / 1.5 (outside of the
Shape)

Flexural strength

psi 16000 5, 13900 1 T 300 16200. 17600 Bending module
(psi x 10 ^& ) 1, , 84 1.68 1.51 1.72 - 2.24 Impact _Q
Tenacity ^]
WrIIbs / in, notch) 0.20 Strength
Index s ^ i , 9x1o ⁷ 6.2x1O ⁷

Example 8 shows the significantly shortened polarization

s time caused by the hardening outside the Form at a slightly higher temperature than that of the execution the temperature applied to the polymerization is reached

009828/1698

Example 10

The procedure described in Example 1 is with the modification was followed by changing the wollastonite content to give a composition of 68.6% by weight to deliver inorganic material "

Example 11

The mass produced in Example 10 is ground in an Abbe * grinder (Abbe grinder) and 940 g of the milled. The reinforced styrene / acrylonitrile copolymer is mixed with 66 g of a rubbery acrylonitrile / butadiene polymer (Hycar 1042) on a heated mixer or roller mill. The finished composition contains 20 parts of rubber-like polymer per 100 parts of styrene / acrylonitrile mixed polymer. ^ The finished mass contains $ 64.5> inorganic material, 29.6? έ styrene / aeryl nitrile copolymer and $ 5.9 rubber. The results obtained are listed in Table V below «

Example 12

The procedure described in Example 3 was followed with the modification that 12.4 g of a stereospecific polybutadiene are dissolved in the monomeric mixture of styrene and acrylonitrile before it is polymerized. The finished mass is a polymerisation polymer mixture which contains 3 parts of rubber per 100 parts of styrene / acrylonitrile copolymer and 1,1 ^ KaUtSChUk, based on the total mass, the results obtained are listed in Table V below.

009828/1698

BATH

Table V ■

10 11 'Flexural Strength (psi) 151OQ 8100 Bending module

1.7x10 ⁶ 8.9x1O ⁵

Notched Izod Impact Strength

corrected for Schiittel

or shock factor (toss-- '.

factor) 0.22 0.42

uncorrected on shock,. ' "-

factor 0.40 _; 0.65

8300 1.1x10 *

0.61 0 * 83

A comparison of the masses 10 and 11 shows the changes or modifications in properties made by mechanically blending a chewy-type polymer can be achieved with the masses according to the invention. A "comparison of the masses 10 and 11 shows the increased improvement, those through the use of polymerization mixing techniques are available »

In the following examples, the example .2 described method of operation carried out «. It became the Influence of varying amounts of different rubbers on the reinforced masses according to the invention examined The results obtained are in the Table VI below. ·

BATH

000828/1600

Example no, Table VI

Notched impact flexural flexural strength strength modulus (ft.Ib./in, speed (psi notch) (psi) x1O ⁶ )

Strength index 2 χ 10 '

Stereospecific polybutadiene chewing t s chuk 1 phr * SAN 1.5 phr SAN 2.0 phr SAN 5.0 phr SAN 10.0

FRS-1006 styrene / butadiene rubber schuk ($ 23.6 S)

1 phr SAN

2 phr SAN 5 phr SAN

PRS-182 styrene / butadiene rubber ($ 42.6 S)

1 phr SAN

2 phr SAN 5 phr SAN

0.33-0.54 12500 1.4o 5.2 5.7 0.38-0.59 12200 1, # 6 6.1 0.48-0.67 11300 1.23 3.6 0.92-1.11 6300 0.77 1.3 1.15-1.39 3400 0.28

0.30-0.50

0.39-0.59 0.62 ~ 0.82

0.25-0.45 0.39-0.58 0.53-0.73 14,700 1.52 6.5

12600 1.41 6.2

7300 0.93 3.3

15,000 1.73 5.6

13900 1.58 7.6

9300 1.19 4.6

. * phr SAN = parts per 100 parts of styrene / acrylic acrylic copolymer

BATH

0 Q 9 8 2 8/1 6 9

Examination of the values from Examples 2 and 3 showed that large amounts of coupler were required to obtain maximum mechanical properties. Table VII below gives the results of the test used to determine the optimum concentration of 3-trimethoxysilylpropyl methacrylate in wollastonite The mineral-coupler interaction is obtained in the following way: the specified amount of coupler is added to the mineral in methanol solution, the mixture is dried, whereupon the treated Ha * ea? ± al mineral at 210 ^° G for 75 Minutes. -Obgleich diee "below"'niehi ^ is indicated, produces a heating time of 15 minutes at 105 ⁰ C apparently identical properties in the finished composition. Similar results would be obtained by dry blending the coupler with the hineral without the use of methanol or other solvent.

Table VII

Example Silankon bending bending notch strengthening

No. Centration strength module impact

in woolen aesthetics (psi ^ toughness index *

nit (^) .-- (- pbA) ·. x10 °) ftUIbs / in. S ^ I χ 1Ό ^Γ

23 2.0 15300 1.8 ~ y 0.20 4th , 7 24 1.5 15700 1. % 0.19; 4th , 7 25th 1.0. 16700 2.0 0.24 6th , 7 26th 0.5 15800 2.0 0.23 5 ,8th ϊ 27 0.25 16400. :,:. 2.0 0.2t; 5 rl 28 0.10 13200 1.9 • 0.20 ■ 3 V5 29 no 9300 1.9 0.07 0 , 6

0098 287 1698

bath

Examination of the above values shows that a change in coupler concentration from $ 0.25 "to $ 2 one moderate effect on the mechanical properties de »fer-> tied, reinforced polymer masses has · The However, removal of silane leads to completely unsuitable materials.

When performing the rubber compounding operation

* plus coupled or tied reinforcement it is possible Crowds with a large area and diversity of mechanical properties where / by using them in several different applicationsE territories is possible »

009828/1698

Claims (1)

16 2 Q 9 9-9 - et - Patent claims 1 ♦ Process for the production of reinforced polymeric compositions based on styrene / acrylonitrile mixed polymerizates, characterized in that '.''...' (a) a coupling or binding agent with an inorganic one Filling / fcoff converts and _ "~ (b) the polymerization of styrene and aeryl nitrile monomers in. Presence of the filler to form a bonded to this filler material Executes styrene / acrylonitrile Kischpolymerisata. 2, the method according to claim Ί, characterized in that one polymerizes unsubstituted styrene and acrylonitrile monomers «. : 5. The method according to claim. 1 or 2, characterized by _t ' ■■■■ - ■■ .-. ■■ "■ ■ ^ that the inorganic filler material is combined with a coupling or binding agent made from a compound aex general formula . Ib - ■ ■ -Ar ^Si - ^ _n - Ά ■ in which Σ is a hydrolyzable radical, Y is a hydrocarbon radical, H is an alkylene radical with 1 to about 20 carbon atoms, Z is an organic radical containing ethylenic unsaturation, η is an integer from 0 to T, a is an integer from 1 to 3 »B is an integer γόη Q to 2 and c is an integer from 1 to 5, with provided that the sum of a + b + c equals 4, '——-- * ^ * 0D9a28 / 169Ö - ■: BAD CWGlNAL Process according to one of Claims 1 to 3, characterized in that the filler material is treated with the coupler in the presence of the monomer system. Process according to one of Claims 1 to 3, characterized in that the filler material is treated with the coupler prior to addition treated to the monomer system. 6 β method according to one of claims 1 to 5, characterized in that the filler material is a silicon-containing inorganic material with a 3-dimensional crystal structure, a certain refractory nature with a melting point of above 800 ⁰ C, a Mohs hardness of at least 4, one solubility in water of less than 0.1 g / liter and a ratio of length to diameter of the particles up to about 25% is used indicates that "a mixture of styrenes and acrylonitrile monomers with a weight ratio of about the azeotropic mixture polymerisation of 76:24 styrene - acrylonitrile polymerizesβ 8. The method according to any one of claims 1 to 7, characterized in that a coupling or binding agent of the above formula is used _s In which X is an alkoxy radical with up to 4 carbon atoms _f Z is a methacryloxy group ,, R is an alkylene radical with about ü up to 18 carbon atoms © 09828 / t69S ~ Gz - ■■■. ' - ■. ■■ - ■■■ :. '.'^;-; ■ ^: '■ - " 9. The method according to any one of claims 1 to 8y doxlurch characterized in that the Ki.rpplunx, SL-iittei ^ -Tiiaikoxysilylpropyimevhacrylat, in which the alkoxy groups up to 4 _; Have carbon atoms, or 11-Trialkoxysilylundeeylmethaerylat, in which the alkoxy groups have up to 4 carbon atoms, used. 10. The method according to any one of claims 1 to 9, characterized in that the reinforcing agent (inorganic filler material) is sugrbt in an amount of * about .25 to 90 wt. - ^c / o of the total mass. 1! .The method of a © of claims 1 to TO, in datixreh used da3 one Victorian as Verstärkungsiaittel a Tanorga ^ filler material which is free in wesentliehen of hydrolyzable components that can be extracted carcasses äarch the ^MPACT by boiling. " 12. The method according to any one of claims 1 to 11, characterized it is known that the reinforced styrene / acrylonitrile: Mixture of brisate is a rubber-like polymer Mixes and then mixes to form a homogeneous register the mass with the formation of a finished object by pre-forming subject. "■". "; ~ -" -. ' 15 · The method of any of claims 1 to 12 _t dadurchgekennseichnet, DAJ iaan ■■ / - ■ ''. ^::; ^ "\ - (A) a coupling agent reacts with a filler and (b) the polymerisation of styrene and aoryl nitrile monomer coarse in the presence of the treated filler material rubber-like polymer with the formation of a styrene / acrylonitrile Miscnpolyinerisat s, which adheres to the reinforcing agent is bound and contains the rubber-like polymer dispersed in the finished mass, executes. t% o Method according to one of claims 12-13 »characterized in that a rubber-like polymer is used which may have ethylene unsaturation« bath Q09828 / 16P3