CN1043146A - The preparation method of high-low pressure polythene and polypropylene general purpose granular packing - Google Patents

Abstract

The preparation method of a kind of high and low pressure polyethylene, polypropylene general particulate filler, this method comprises making as the carbonate powder of the periodic table of elements II family metallic element of filling material of polymers and hydro carbons lubricating substance or organic carboxyl acid and ester thereof and is mixed together stirring, this carbonate powder is carried out surface treatment, when handling or after handling, add coupling agent, after stirring, add macromolecular material again, extrude pelletizing after stirring.

Description

The preparation method of high-low pressure polythene and polypropylene general purpose granular packing

The present invention relates to a kind of preparation method of the mineral filler that high and low pressure polyethylene, polypropylene all are suitable for, particularly relate to and a kind ofly high and low pressure polyethylene, polypropylene are had good affinity and dispersiveness, the preparation method of the filler that is easy to concoct.

As everyone knows, mineral filler commonly used has metal carbonate and silicate powder, and these fillers can be widely used in fields such as plastics, rubber, coating.Reasonably select filler to improve plastics performance to greatest extent, expand its Application Areas, save the synthetic resins raw material, save energy reduces cost.But, if pulverizing such as various metal carbonates with natural generation, just add in the macromolecular material and do not add any processing, owing to the affinity between two kinds of materials is very poor, and the reasons such as secondary aggregation that produce, can occur disperseing uneven phenomenon, its purposes and effect are restricted, the effect that improves performance is also not obvious.

In addition, existing macromolecule resin material is generally granular, and when being filled in the macromolecular material with the metal carbonate powder type, because granular resin and pulverulent filler proportion are different, incomplete mixing can not carry out effective high density and fill.Thereby do not reach the purpose of improving the finished product performance yet.

In order to overcome above-mentioned shortcoming, people had once used the whole bag of tricks, as selected the powder or the particle of uniform particle diameter for use, or carried out surface treatment etc.But the former usually produces secondary aggregation because of powder and organic affinity difference, causes blending inhomogeneous, disperse bad, thereby make the macromolecular material improvement effect little; And the latter, promptly to powder, particle carries out surface treatment etc., this method is meant so-called damp process, its roughly step be in calcium hydroxide aqueous solution, to add tensio-active agent, metallic soap or lipid acid etc., feeding carbonic anhydride again makes it generate lime carbonate, again with the lime carbonate dehydration that makes, dry, pulverize then and make the good surface treatment calcium carbonate powders of surface property, perhaps, add lime carbonate and stir in the aqueous solution of organic carboxyl acid or derivatives thereofs such as stearic acid (as various stearic esters), crushed after being dried is made the good surface-treated calcium carbonate powders of surface property.That but the shortcoming of this damp process is a manufacturing process is loaded down with trivial details, efficient is low, cost is high.

In addition to the above methods, also have with various metal carbonate powder and mentioned reagent mixing and stirring under dehydration conditions, make the metal-salt particle surface form the coating layer of one deck organic carboxyl acid calcium and other salt.This method people has a long time ago just been known, but fillers dispersed and surface luster property etc. are good inadequately, have influenced the processing of plastic effect.

The present inventor is in order to overcome the shortcoming of above-mentioned various prior aries, a large amount of careful research work have been carried out, abandoned surface preparation in the past, found with metal carbonate absorption or in conjunction with hydrocarbons or organic carboxyl acid and ester thereof, stir with coupling agent again, then with the method for small amount of polymer resin restir, found to obtain excellent dispersed, surface property and other improves the new way of the impact of performance.

Or rather, 100 parts of metal carbonate powder are after carrying out the surface-treated while or handling with a spot of hydrocarbons (about 0.05～15 part) and/or organic carboxyl acid or derivatives thereof (about 0.1～12 part), the mode that adds 0.1～10 part of reagent such as coupling agent by per 100 parts of metal carbonates adds coupling agent and high-speed stirring again, make powder particle surface form a coating layer, and then add 1～15 part of macromolecular material, high-speed stirring and extrude, pelletizing.

Be to improve dispersiveness, the high density fillibility of filler, the feature of the inventive method is to make filling adsorption in advance or in conjunction with reagent such as required lubricant and coupling agents, and then stirs with a spot of macromolecular material fusion.Thereby can improve the blending of filler significantly to macromolecular material.

Used powder is meant powder particle median size 120～600 purpose periodic table of elements II family metal carbonate powder in the inventive method, and as calcium carbonate powders, its one matter or mixture all can.Containing a certain amount of water and thing, composite salt or other mineral in the composition also can.

The employed hydro carbons lubricant of the inventive method has whiteruss, native paraffin, microcrystalline wax, polyethylene wax, hydrochloric ether, hydrofluoric ether, usually add with wherein a kind of paraffin or two or more mixtures, its consumption can suitably be adjusted according to application target and condition, but for giving full play to effect of the present invention, can add 0.05～15 part in per 100 parts of metal carbonate powder, and be the best with 2～10 parts.

Employed organic carboxyl acid of the inventive method and derivative thereof have: saturated fatty acid or unsaturated fatty acids and various esters thereof such as lauric acid, tetradecanoic acid, Palmiticacid, stearic acid, linolic acid, calcium stearate, lead stearate, butyl stearate.Wherein a kind of can be used separately, also use can be severally mixed.It can be the best with 0.5～6 part with 0.1～12 part that its consumption is generally per 100 parts of metal carbonate powder.

Employed coupling agent in the inventive method: be titante coupling agent, mainly contain sec.-propyl (dioctyl is phosphate-based) titanic acid ester, sec.-propyl (dioctylphyrophosphoric acid ester group) titanic acid ester, two (dioctyl is phosphate-based) oxo acetic acid titanium, two (dioctyl is phosphate-based) ethylene titanic acid ester, tetraoctyloxy titanium di (dilauryl phosphorite base) titanic acid ester etc.Its addition be per 100 parts of metal carbonate powder with 0.1～10 part, be the best with 0.5～3 part.

Used macromolecular material has high-pressure polyethylene, polypropylene etc. in the inventive method, its consumption be per 100 parts of metal carbonate powder with 1～15 part, 2～11 parts of the bests especially.

Method of the present invention adds a small amount of macromolecular material (as high-pressure polyethylene) after being to use metal carbonate (as lime carbonate) and hydrocarbons or organic carboxyl acid class material and coupling agent to mediate again in the high speed shear heat-sealing machine, mediate and pelletizing through single screw extrusion machine or twin screw extruder then, thereby make high and low pressure polyethylene, polyacrylic conventional packing.

With the filler that method of the present invention makes, almost can't see the secondary aggregation phenomenon, when with the macromolecular material mix, show fabulous glossiness, dispersiveness and with affinity of organic polymer material etc.In addition, the preparation method of filler of the present invention is simple, and is with low cost, cheap, and has fabulous dispersiveness and affinity, can realize to macromolecular material that high density is filled and cooperate, so, see it also is a kind of fabulous filler from economic angle.

The present invention is further described with embodiment below.

Embodiment

With 100 parts of adding stirrers of 120～600 purpose light calcium carbonate powder, under 60 ℃ temperature, add 10 parts of native paraffins, 1 part of sec.-propyl (dioctylphyrophosphoric acid ester group) titanate coupling agent.15 parts of high-speed stirring add 10 parts of high-pressure polyethylenees then in said mixture, stir kneading pelletizing after 10 minutes through twin screw extruder again, just can make high and low pressure polyethylene, the polyacrylic general grain of filling out.

Application examples 1

Put into mixing roll with the filler that the foregoing descriptions of different umbers makes for 100 parts with polyethylene (1F7B type), mix at normal temperatures, with the composition that mixes at 150 ℃, die temperature is under 100 ℃ the condition, on injection machine, be shaped, make model, measure every performance by GB1039-79 every testing method such as " plastics mechanical test method general provisions " then, the results are shown in Table 1, and the reference examples in the table 1 is not for using the blank of filler of the present invention.

Table 1

As can be seen from Table 1, use filler of the present invention can improve its blending performance for polyethylene.

Application examples 2

Filler (being provided by embodiment) and 100 parts of polypropylene (2401 type) with different umbers mix, in forcing machine, resin is warmed up to 260 ℃, transfer equal resin compound, at plastics composite is 260 ℃, die temperature is under 180 ℃ of conditions, after being shaped on the injection machine, make the model bar, carry out every performance test by GB1039-79 " plastics mechanical test method general provisions " then, the results are shown in Table 2 for it, and the reference examples in the table 2 is not for adding the polypropylene of filler of the present invention.

Table 2

As can be seen from Table 2, filler of the present invention has good affinity to polypropylene, and has improved the performance of acrylic plastering.

Claims (10)

1, the preparation method of a kind of high and low pressure polyethylene, polypropylene general particulate filler, this method comprises making as the carbonate powder of the periodic table of elements II family metallic element of filling material of polymers and hydro carbons lubricating substance or organic carboxyl acid and ester thereof and is mixed together stirring, this carbonate powder is carried out surface treatment, when handling or after handling, add coupling agent, after stirring, add macromolecular material again, extrude pelletizing after stirring.

2, method according to claim 1, wherein said surface treatment adopt the high speed shear heat-sealing machine to carry out.

3, method according to claim 1, wherein per 100 parts metal carbonate powder and 0.05～15 part hydro carbons lubricating substance, 0.1～10 part coupling agent mix, and then mix with 1～15 part macromolecular material, said umber all refers to parts by weight.

4, method according to claim 1, wherein per 100 parts metal carbonate powder and 0.1～12 part organic carboxyl acid or derivatives thereof, 0.1～10 part coupling agent mix, and then mix with 5～15 parts macromolecular material, said umber all refers to parts by weight.

5, according to claim 3 or 4 said methods, wherein said metal carbonate powder is a calcium carbonate powders.

6, according to the said method of claim 3, wherein said hydro carbons lubricating substance is whiteruss, native paraffin, microcrystalline wax, polyethylene wax, hydrochloric ether and hydrofluoric ether, its preferable amount be per 100 parts of calcium carbonate powderss with 2～10 parts, said umber refers to parts by weight.

7, method according to claim 3, wherein said coupling agent is a titante coupling agent, mainly contain sec.-propyl (dioctyl is phosphate-based) titanic acid ester, sec.-propyl (dioctylphyrophosphoric acid ester group) titanic acid ester, two (dioctyl is phosphate-based) oxo acetic acid titanium, two (dioctyl is phosphate-based) ethylene titanic acid ester, tetraoctyloxy titanium di (dilauryl phosphorite base) titanic acid ester, its preferable amount is per 100 parts of calcium carbonate powderss with 0.5～3 part of weight, and said umber is parts by weight.

8, method according to claim 3, wherein said macromolecular material is high and low pressure polyethylene, polypropylene, its preferred amounts be per 100 parts of calcium carbonate powderss with 2～11 parts, said umber is parts by weight.

9, method according to claim 4, wherein said organic carboxyl acid and derivative thereof have lauric acid, tetradecanoic acid, Palmiticacid, stearic acid and linolic acid and derivative thereof, its optimum amount be per 100 parts of calcium carbonate powderss with 0.5～6 part, said umber is parts by weight.

10, method according to claim 1, wherein said high-speed stirring are extruded with twin screw extruder or single screw extrusion machine and are carried out.