1~249~:~0 This invention relates to silicate filled resin composites made with additives which comprise chlorinated aliphatic compounds. Inclusion of these additives can enhance mechanical properties of the composites.
Coupling additives for certain inorganic filled resin composites are known. For example, silane compounds are employed in various silicate filled resin composites for improving resin reinforcement by the silicate. Moreover, certain chlorinated aliphatic compounds have been utilized in resin systems to aid in fire retardancy.
It has been now discovered that certain chlorinated aliphatic compounds act to improve silicate and polyolefin resin adhesion especially when select melt times and temperatures are used during processing.
Briefly, this invention concerns composites made by a method which comprises melting a blend comprising silane-free silicate filler, polyolefin resin and a minor amount by weight of the combined weight of the silicate filler and resin of an additive which comprises one or more chlorinated aliphatic compounds with a molecular weight in the range of about 250 to 10,000 and containing from about 5 to 80~ chlorine by weight and maintaining the blend as a melt for a time and at a temperature sufficient to improve the strength of the composite.
A level of 1 to 36 parts by weight silicate filler for each 9 parts by weight polyolefin resin provides com-posites of particularly useful properties, whereas a weight ratio of the filler to resin of about 2:5 - 5:2 normally provides an optimum balance for silicates as mica flakes and a weight ratio of about 1:10 - 4:10 being advantageous for silicate as glass fibers. Preferred silicate is mica, especially mica flakes.
112~30 Polyolefin resins suitable for this invention include well known, commercially available materials designed for use in moulding (as by injection, compression, etc.) and other melt forming processes (as extrusion, stamping, etc.~. Of these commercial resins, those made from monomers comprising olefinic hydrocarbons such as ethylene, propylene and butene-l can provide composites with excellent properties as well as economic advantage.
Particularly suitable in this regard are resins comprising polyethylene or polypropylene or copolymers of ethylene and/or propylene as well as blends of any of these. As used herein, polyolefin resin means any of the above identified resins that are typically melt formed and are made from monomers comprising olefinic monomers, particularly monomers that are alphatic hydro-carbon monomers and preferably predominantly by weight l-olefins hydrocarbons such as ethylene, propylene, butene-l and 4-methyl-pentene-l. Such polyolefin resins preferably comprise a major portion of the resins in the composite (e.g., 60% by weight or more).
Upon melting, the polyolefin resin wets the surfaces of the silicate filler in the blends. Through some as yet undefined mechanism it is believed that the wetting and bonding is enhanced when the additives of this invention are included in the blends.
Propylene resins are especially benefited by this invention, particularly those with intrinsic viscosities of above 1.5 and preferably about 2.0 - 2.6 for processing expedience, although those with higher intrinsic viscosities may also be suitably employed. The propylene resins may comprise propylene homopolymer or propylene copolymer or mixtures thereof, such copolymers normally comprising at least about 75 mole percent propylene and up to 25 mole percent of other monomers such as ethylene and butene-l. The preferred propylene resins ~12~3~
comprise propylene homopolymer or copolymer normally made with stereospecific catalysts. Desirably, these propylene resins are in flake or powder form and pass through a 20 mesh screen, more preferably a 60 mesh screen, and, although currently available propylene resins are substantially re-tained on a 325 mesh screen, even smaller sizes may be used in this invention. Ethylene resins such as polyethylene homopolymer or ethylene copolymers made with other aliphatic olefin hydrocarbons as propylene, butene-l and hexene-l are also particularly desirable.
Silicate fillers are commercially available. Among the commonly used silicate fillers, especially suitable here-in, are synthetic glass fibers and natural mica as well as other naturally occurring minerals as talc. These silicate fillers generally comprise silicon, oxygen and one or more metals, e.g., Mg, Al, Na. Fillers having certain shapes as glass flakes, fibers and mica flakes offer advantage in providing increased structural integrity to polyolefin resin composites and such composites can receive particular benefits in accordance with this invention. For example, glass fibers with high length to diameter ratios, e.g. 30:1 or higher as well as flakes with at least such aspect ratios are desirable for highest strength composites. Other silicate fillers include magnesium silicate, calcium silicates, wollastonite, attapulgite, silicate clays as well as others as are disclosed in U.S. patent 3,951,680. Silicate fillers are preferred which do not contain forms of asbestos.
It is advantageous that the silicate filler as mica may be free of substantial chemical surface treatment for use in this invention. For one reason, the additives of this invention ~l~4s~a typically have low cost and can eliminate or reduce the need for more expensive surface treatments as with silane compounds.
Moreover, it is desirable that there is minimum interference with the operation of the additive on the silicate surface and the polyolefin resin.
Mica fillers can be generally characterized as being derived from aluminum silicate minerals which can be cleaved into thin sheets. Commercially available fillers which comprise principally muscovite, biotite and/or phlogopite micas (e.g., Suzorite Mica marketed by Marietta Resources International) are preferred with mica fillers comprising principally phlogopite mica being currently more preferred. Mixtures of micas as wel~l as with other silicate fillers can also be employed.
Mica flakes, especially those comprising principally phlogopite mica, having an aspect ratio (mean diameter to thick-ness) of at least about 30 (more preferably at least about 60 so as to minimize breakage effects during processing) and up to 200 or higher are preferably employed. Mica flakes which are retained on a 100 mesh screen, more preferably on a 60 mesh screen, are normally more desirable, but mica which passes through a 325 mesh can also be employed. Mica flakes which substantially pass through a 20 mesh screen are advantageous for processing expedience. Generally, glass flakes and fibers of such dimensions are especially useful herein. Although various means of preparing highly delaminated mica flakes are employed in the mineral industry, those not employing wet grinding are preferred. Especially preferred are those dry delamination processes in which ore containing in part the various forms of mica is excavated and crushed into lumps for transportation ease.
These lumps are further reduced in size by hammer milling in order to free the boxes (or single crystals of mica) from other mineral impurities.
11;i~4930 In such preferred dry processes, the crystals are typically delaminated between counter rotating drums which exert high shearing forces. The degree of delamination, hence the aspect ratio of the resulting mica flakes, is dependent upon the clearances set between the counter rotating drums. The delaminated flakes are then separated from other mineral impurities by vibration and/or air classification techniques with the purified mica still further classified according to particle size via conventional screening processes.
When prepared in this manner the mica surfaces are r~latively free from large amounts of adsorbed species (such as moisture from water grinding) which may cause interference to the additives described in this invention.
The additive which strengthens the silicate filler as mica and polyolefin resin adhesion is employed in minor amounts (e.g., 0.05 - 10%, but preferably between about 0.5-5%) by weight of the combined weight of silicate filler and polyolefin resin, sufficient to strengthen the composite. Often a sufficient amount of the additive also is less than the amount of silicate filler as measured by weight. For example, resinous chlorinated waxes are normally used at less than about 3% by weight of the total weight of silicate filler and polyolefin resin. ASTM (D-790) Flexural-Yield Strength is a convenient measure of the strengthening of the composite. Other evidence of the strengthening may be seen in, for example, enhanced tensile strength, fluxural modulus and heat deflection temperature as well as reduction of mold shrinkage.
The chlorinated aliphatic compounds preferred in this invention have a molecular weight (number average) in a range of about 500 - 10,000 (more preferably about 800 - 5,000) and a chlorine content of from about 5 - 80% by weight.
High levels (e.g., about 60 - 80%~ be weight chlorine are desirable for chlorinated saturated hydrocarbons such as chlorinated paraffin waxes. Lower levels (e.g., about 5 - 50~) of chlorine by weight are especially suitable, if there is additional polarity (e.g., carboxyl groups) or unsaturation in the chlorinated aliphatic compounds. Lower molecular weight e.g. 250 can be used especially when there is a high level of chlorine by weight.
Examples of additives comprising chlorinated aliphatic compounds include chlorinated hydrocarbons such as resinous chlorinated paraffin waxes (e.g. those marketed as Chlorowax Diamond Shamrock , Kloro-chek [Keil Chemical, a division of Ferro Chemical3 and Chlorez [Dover Chemical, a division of ICC]).
Resinous chlorinated waxes with molecular weights of about 800 -1200 are preferred, as, for example, Chlorowax 70.
In one preferred method of making composites of thisinvention, particulate tpowder, flake) polyolefin resin, silicate flakes (e.g. mica) or fibers and a powdered additive comprising chlorinated aliphatic compounds are admixed by tumbling (preferably non-intensive) followed by extrusion compounding of the blend with vacuum venting. The extrusion compounder is fitted at the end with a heated pipe which lengthens the time the passing melt is exposed to a high temperature. For propylene resin, silicate filler comprising, for example, phlogopite mica, and resinous chlorinated paraffin waxes, a total time elapsed after melting (i.e., melt residence time) of about 5 - 10 minutes at about 190 - 210C is preferred before melt is cooled. Subsequent heating, as by annealing and drying may also be used to contribute to this residence time. The melt can be shaped thereafter by molding but other fabrication techniques can be employed.
1124~930 In another preferred method of making, the silicate (e.g., mica) itself is first blended with the additive comprising one or more chlorinated aliphatic compounds to preferably provide a coating on the silicate particles (e.g. flakes as mica flakes or fibers). Resinous chlorinated aliphatic hydrocarbons as, for example, chlorinated paraffin wax is desirably melted (at up to about 15% by weight, more preferably up to about 2% by weight of the silicate) onto the silicate preferably at high temperature (e.g. 150C) but desirably below that temperature which would cause severe decomposition and deterioration of the strengthening effect attributed to the additive. This melt coating is normally conducted during gentle mixing of the silicate particles and the additive to achieve uniformity of the coating and minimize breakage of shaped particles. Preferably, the silicate filler as mica is dried prior to melt coating with additive. Advantageously, the melt coating can be accomplished in less than one hour, normally less than 15 minutes depending on such factors as equipment mixing, conditions and temperature. The coating of the silicate has the advantage of providing potentially greater uniformity for the blends as compared to mixing the ingredients separately.
The coated silicate is further compounded preferably by admixture with the polyolefin resin to form a dry powder blend for furthe~
processing.
Temperatures between about 170-300C are typically suitable during such above described preferred compoundings with the polyolefin resin. Higher temperatures with this range, e.g, 220C or higher, usually require shorter times for optimum development of properties while lower temperature require longer periods. Advantageously, the additives of this invention provide stable subsequently produced mechanical properties at usual melt ~i24930 temperatures for long periods, e.g., 30 minutes or longer.
Normally it is desirable to allow a period between about one (1) and 30 minutes at melt temperature, more desirably between about 5-15 minutes. Subsequent operations as shaping at melt conditions can contribute to this melt residence time.
After compounding, the melt, preferably having resided for an extended period at melt temperature, can be passed to a cooling zone and thereafter cut (e.g., diced) into particles suitable for shaping processes. Alternatively, the melt may be passed directly into a shaping operation. Shaping, if done by injection molding, is preferably preformed at about 3,000 - 9,000 psi at temperatures of about 190 - 210C into molds held at about 30 - 70C.
Other shaping operations such as extrusion, compression or blow molding or stamping and the like may be employed. Further, shaping operations can be used to maintain a time and temperature sufficient to strengthen the composite. Moreover, rods, sheets, tubes and films also can be fabricated and receive the benefits of this invention.
It is to be understood that blends of this invention may include combinations of fillers such as mica with glass fibers or talc as well as minor amounts of additives (e.g., stabil ze_s, pigments, lubricants and the like) which are conventionaliy in-cluded during processing of composites. For example, alkaline earth oxides (e.g., MgO, CaO) may be included at up to about 5~
by weight of the composite weight and are advantageous to absorb gases resulting from entrapped moisture or decomposition of the additive generated during high temperature compounding or melt forming processes.
The following examples are intended to illustrate this invention and are not intended as limitingthereof as those skilled in the art will appreciate that many modifications of these examples can be made within the scope of this invention.
All parts are parts by weight, all temperatures are in degrees centigrade and all tests are ASTM standards as noted, unless specifically indicated otherwise.
Example 1 In this example, composites are formed into standard ASTM specimens from formulations having varying levels and types of polyolefin resin, silicate fillers, and chlorinated aliphatic compounds.
The composites are prepared by dry blending (non-intensive mixing) the resin (powder form), silicate filler and additives comprising the chlorinated aliphatic compounds. There-after, the powdery mixture is added to a reciprocating screw injec-tion molding machine (Arburg 200U, 42 ton, 2 oz.), held at 200C
for times indicated by Talbe 2 and injected into the mold having a temperature of 30C. Shot size setting is at 6.3.
The formulation of the composites prepared appear in Table l.
Properties that are obtained from a first set of com-posites appear in Table 2. The composites for ASTM testing in this first set are made after first purging the molding machine with lO shots of the individual formulations spaced one minute apart followed by shots ta~en at intervals spaced by the time as indicated in Table 2.
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1~243;~0 In Table 3, the effect of the additive is seen by comparison of properties of composites made with and without the additive of this invention. The formulation used in making composites A and B in Table 3, below, corresponds to formula-tion 4 of Table 1, except that the formulation of B does notinclude the additive of this invention. Chlorowax(R)70-LP is used as the additive in A. The ASTM specimens having properties as set forth in Table 3 are made as those above except that the molding cycle is set for 10 minutes and the first ten specimens are discarded to approximate a steady state condition. Sufficient specimens are thereafter collected to perform the ASTM tests in Table 3.
Composite A B
- With Without 15 Physical Property UnitsAdditive Additive TENSILE STRENGTH psi 5,600 4,100 FLEXURAL STRENGTH psi 10,250 7,200 FLEXURAL MODULUS psi1,127,000 850,000 IZOD IMPACT ft-lbs1.25 1.30 20 HEAT DEFL. TEMP F
ASTM-D648 @66 psi301 266 @264 psi272 210 MOLD SHRINKAGE in/in ASTM-D955 length.002 .010 width.010 .007 thickness .020 .023 Example 2 In this example, composites are made from formulations containing 30 parts by weight Hercules Pro-Fax 6523-PM propylene '''b~
~124930 resin and 70 parts by weight muscovite mica flakes (K-100 English Mica Co.) with and without 1 part by weight Chlorowax 70-LP
powder. The procedure of Example 1 is followed and ASTM speci-mens are obtained at the time intervals indicated by Table 2.
The composites made with the additive of this invention show an ASTM-D790 Flexural Yield Strength that is higher than composites made without the additive.
Example 3 In this example, the formulations 3-8 of Example 1 are modified by the inclusion of 1 additional part by weight of the individual chlorinated aliphatic compounds. Composites are made and tested by a method similar to that described in Example 1 and likewise show the desirable strengths attained by inclus-ion of the additive of this invention as compared to composites without the additive.
Example 4 The formulation of number 4, Table 1 is compounded in an extrusion compounder (2 inch Transfermix, manufactured by Sterling Extruder Corp.) having a heated pipe extension (length 50 inches, inner diameter 2.25 inches) fitted at the end. The compounder is operated so that the passing melt has a residenoe of about 9 minutes at 200C during extrusion and passage through the heated pipe. The melt is cooled and then diced into pellets. The pellets are fed into an injection molder and molded into ASTM
specimens. These specimens are tested and show advantageous properties as compared to ones which do not have the additive of this invention and which are made in the same manner.
_xample 5 The formulation of number 4, Table 1 is modified by the addition of 5 parts by weight of commercial glass fiber (Owens-Corning, Fiberglass 885, 1/4 inch chopped strand, aspect ratio of about 500 to 1). Processing is done as in Example 1 above. Higher Yield Strength values (ASTM D-790) are seen in these composites which are molded into ASTM specimens as compared to composites made in the same manner for like periods but with-out the additive of this invention. At 20 minutes as in Table 2, the composite of this invention has a Flexural Yield Strength of 11,000 whereas the one without additive has a value of 8,000.
Example 6 Two parts by weight of a resinous chlorinated paraffin (Chlore 700 of Dover Chemical) is combined 98 parts by weight Suzorite GPA mica (Marietta Resources) by gently mixing in a V-shaped blender at room temperature for about 3 minutes. There after, this admixture is heated up to about 150 with gentle mixing continued whereupon a coating of the surface of the mica occurs and the brassy color of the mica begins to turn to a dark red gold. Small portions of the mica mixture are taken to see if the coating is complete by seeing if the surface is still wetted with water.
Mica coated in this manner with additive is used in place of the mica and additive of Example 4 and compared with a formulation containing no additive using the conditions of Example 4. Improved properties are seen in composites made in accordance with this invention.
Example 7 One part by weight of Chlorowax 70 (Diamond Shamrock) is used to coat 40 parts by weight of mica (Suzorite GPA, Marietta ~12~193~
Resources) in two ways. In Sample (A), the mica is preheated to 200C for several minutes prior to addition of the Chlorowax at that temperature. In Sample (B), the Chlorowax 70 is added at room temperature prior to heating at 200C. The coated mica samples are each allowed to cool, then separately blended with 60 parts by weight of Hercules Profax 6501 PM polypropylene and injected molded at 200C with an extended molding cycle. The following properties are obtained with ASTM testing.
A B
Flexural 8500 psi (mean of 5) 7778 (mean of 5) Strength 280 psi (std. deviation) 395 (std. deviation) Flexural 1,013,346 psi (mean of 5) 1,087,952 (mean of 5) Modulus 61,612 psi (std. devia- 57,271 (std. devia-tion 57,271) tion) Example 8 The procedure of example 6 is followed using glass flakes (aspect ratio greater than 30) rather than mica. Composites formed show desirable properties.
_ ample 9 The procedure of example l is repeated using specially prepared "nascent" glass fibers having no surface treatment with silane coupling agents. Composites are made according to pro-cedure and ormula 11 of example l. Composites made with the additive show improvement in mechanical strength over similar composites made without the additive of this invention.
As previously mentioned, a preferred compounding technique in accordance with this invention utilizes an extruder that prov-ides extended periods at melt temperatures for development of optimum mechanical properties of the composites. Basically, this may be accomplished, if desired, by including a melt holding chamber 11~4930 between the gate and the die (or nozzle~ of an extruder or the extruder portion of a more complex (i.e. injection, blow molding, foam, sheet, etc.) system. Inclusion of this melt holding chamber enables desired production rates to be maintained. The actual dimensions, of course, of the chamber will be determined by the relative output rate desired as well as physical space available.
In certain specialized instances, however, usual equipment such as large shot size injection molding devices may be used to mold small parts whereby the melt exists for longer than usual times so that optimum properties develop.
Example 10 The procedure of example 6 is repeated using talc (Beaver White 200 - United Sierra) in place of mica. The coated talc, however, does not exhibit the color changes as does mica unless the coating process is conducted at temperatures exceeding the onset of thermal decomposition of the chlorinated hydrocarbon coupling agent.
Increased Heat Deflection Temperature (ASTM-D648) is noted in composites containing 40 parts of the above described coated talc and 60 parts polypropylene homopolymer when the composite is prepared with the compounding techniques in accordance with example 4.
Example 11 Fiberized blast furnace slag (Mineral Fibers - Jim Walter Corporation), a silicate fiber filler typically containing over 40% SiO2, is washed with xylene to remove the noramally present antidusting oils and is subsequently dried. Dry powdery blends are formed of a composition of 40 parts mineral fiber, 60 parts polypropylene resin (Profax 6523-PM - Mercules, Inc.) and
2 parts of chlorinated hydrocarbon additive (Chlorez 700 - Dover Chemical).
9~0 When these powdery blends are directly injection molded in accordance with example 1 as to increase the melt residence time to 10 minutes, the resultant molded parts exhibit improved flexural strength at yield when tested in accordance wi~h ASTM-D790 (Flexural Properties of Plastics).
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