CN103160007A - Polyolefin breathable masterbatch, and preparation method thereof - Google Patents
Polyolefin breathable masterbatch, and preparation method thereof Download PDFInfo
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- CN103160007A CN103160007A CN2011104227576A CN201110422757A CN103160007A CN 103160007 A CN103160007 A CN 103160007A CN 2011104227576 A CN2011104227576 A CN 2011104227576A CN 201110422757 A CN201110422757 A CN 201110422757A CN 103160007 A CN103160007 A CN 103160007A
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Abstract
The invention discloses a polyolefin breathable masterbatch which comprises the following raw materials by weight ratio: 40-70 % of polyolefin resin, and 40-70 % of inorganic filling materials; and a moisture content of the polyolefin breathable masterbatch prepared from the polyolefin resin and the inorganic filling materials is less than or equal to 300 ppm. Correspondingly, the invention discloses a preparation method of the polyolefin breathable masterbatch. The polyolefin breathable masterbatch need not to be dried, and moisture of the breathable masterbatch can be removed through adjusting a temperature of cooling water, controlling a surface temperature of particles after being passed through a vibrating screen and using a delivery way with multichannel airducts. According to the invention, the polyolefin breathable masterbatch is good in physical and chemical properties, and greatly reduced in moisture content; production operation is simplified, energy consumption is minimized, subsequent requirements on film making is satisfied, quality and output of products are guaranteed, and influence of excess moisture on appearances, physical properties and pH value of the subsequently prepared films, as well as generation of broken holes and other adverse circumstances can be prevented.
Description
Technical field
The present invention relates to new material technology field, particularly ventilative master batch of a kind of polyene hydroxyl and preparation method thereof.
Background technology
Polyolefin permeable membrane is succeeded in developing by Japan the earliest, after import Korea S, Taiwan into.This technology obtains very large development in Korea S, and its equipment and technology technology also is greatly improved.Last century, this technology of the nineties began to import into China, and because the Chinese market demand is large, numerous domestic enterprises are the prospect of very good this product all, and numerous and confused investment is to this field.
Air-permeable envelope is called as " film that can breathe " because of the characteristics of a permeable watertight.This air-permeable envelope can be by polyolefin resin and a certain proportion of mineral filler granulation that is mixed, stretched operation again after casting machine or inflation film manufacturing machine moulding, form hole around making mineral filler, these apertures are very little, only have the small molecules of the free states such as air molecule or water vapour to pass through, and can not pass through because of the effect that Van der Waals force is arranged between liquid water molecules.
Air-permeable envelope is widely used because of its characteristic that " can breathe ".Be applied to personal hygiene article in daily life, as sanitary napkin, protection pad, paper diaper for infant, adult diaper etc.; Medical and medical aspect is as protective clothing, medical sheet, disposable surgical clothing etc.; Be widely used in addition the fields such as environmental protection, building, smelting.
Chinese patent application CN02116720.6 discloses a kind of preparation and method of polyolefine resin specially for permeating curtain coated film, base oneself upon domestic polyolefin resin (LDPE, LLDPE, three kinds of copolymerization PP are composite) and fine mineral filler (calcium carbonate, talcum powder etc., particle diameter 3 ~ l0 μ m) be main raw material, add Ti-Al composite coupler, POE properties-correcting agent, OPE dispersion agent, through coupling processing, increase-volume disperses, banburying and extrude the pelletizing processes and form.
Chinese patent application 200910176457.7 discloses a kind of ultra-thin, high porosity film and preparation thereof
Method.By weight percentage, formed by following material: PE (LDPE/LLDPE): 40% ~ 50%, calcium carbonate: 45% ~ 55%, modified additive (plasticity auxiliary agent and film coalescence aid): 3% ~ 5%.The manufacturing process flow of air-permeable envelope masterbatch wherein is: adding calcium carbonate after the polyolefine melting of recipe ratio, and through high-speed stirring, the twin screw extrusion molten, cooling and dicing is made after drying and dehydrating.
In follow-up numerous film manufacturer production processes, the water content of air-permeable envelope master batch can directly have influence on quality, output, pH value of product etc.Above two patent application technology all are not described in detail in ventilative master batch granulation process the drying means to ventilative master batch.General ventilative master batch manufacturer can adopt the mode of water cooling bracing pelletizing, and this mode needs more operator, inevitably causes waste material during draping, wastes very large.The water temperature of the cold rinse bank that the water cooling bracing pelletizing is adopted is uncontrollable, and the temperature in winter and summer differs widely.Pelletizing obtains just finished product of the ventilative master batch of polyene hydroxyl through water cooling bracing, then needs to adopt drying installation to dewater.Ventilative master batch is general over 200 ℃ from dual-screw pelletizer temperature out; water cooling bracing is cooled to pelletizing behind 30 ℃ of left and right; be warming up to 90 ℃ with drying machine again and remove moisture content; the temperature of ventilative master batch experience be 200 ℃ to 30 ℃ again to 90 ℃; cooling heats up again can increase unnecessary energy consumption, and purchasing of fabric dryer increased production cost simultaneously.And ventilative masterbatch generally all needs through water cooling in granulation process, and the surface can be brought moisture content into.Moisture content in follow-up film-forming process in ventilative master batch can affect outward appearance and the physicals of film, even produces holes.
In order to reduce the water content in ventilative master batch, the water-absorbing dry drying prescription that is mixed during some producers can select in the formula of master batch of breathing freely, but add the water-absorbing dry drying prescription that contains calcium oxide can cause the pH value of film solution to significantly improve, affected use range; The drying machine method such as dry again of using that has, but use drying machine again dryly can increase energy consumption, increase operation, efficient affected.
Summary of the invention
Embodiment of the present invention technical problem to be solved is, ventilative master batch of a kind of polyene hydroxyl and preparation method thereof is provided, the ventilative master batch of described polyene hydroxyl need not through drying process, by regulating the temperature of water coolant, control the surface temperature through particle after vibratory screening apparatus, the mode of using the multiple tracks airduct to carry reaches and removes ventilative master batch moisture content, make its Shui divide Han Liang＜=300ppm, physical and chemical performance is good.
For reaching above-mentioned technique effect, the embodiment of the present invention provides a kind of polyene hydroxyl master batch of breathing freely, and its main raw material formula in weight proportion is as follows:
Polyene hydroxyl resin 40 ~ 70%;
Mineral filler 40 ~ 70%;
The Shui that is the ventilative master batch of the described polyene hydroxyl that makes of main raw material by described polyolefin resin and mineral filler divides Han Liang＜=300ppm;
Wherein, described polyolefin resin is a kind of or combination in Low Density Polyethylene, high density polyethylene(HDPE), linear low density polyethylene, metallocene PE, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, homo-polypropylene;
Described mineral filler is a kind of or combination in water-ground limestone, light calcium carbonate, barium sulfate, calcium sulfate, talcum powder, wollastonite, silicon-dioxide, calcium oxide.
As the improvement of such scheme, the Shui that is the ventilative master batch of the described polyene hydroxyl that makes of main raw material by described polyolefin resin and mineral filler divides Han Liang＜=200ppm;
The density of described Low Density Polyethylene is 0.910 ~ 0.935g/cm
3
The density of described high density polyethylene(HDPE) is 0.940 ~ 0.980g/cm
3
The density of described linear low density polyethylene is 0.910-0.940 g/cm
3
The melting index of described metallocene PE is 1 ~ 6 g/10min;
The melting index of described ethylene-octene copolymer is 2 ~ 4 g/10min;
Vinyl acetate content in described ethylene-vinyl acetate copolymer is 5% ~ 40%.
As the improvement of such scheme, described mineral filler is the ultra-fine inorganic filler, and its grain size is 0. 3 microns ~ 12 microns.
As the improvement of such scheme, the main raw material formula of described ceramic membrane also comprises:
Processing aid 0.01 ~ 2%;
Oxidation inhibitor 0.01 ~ 2%;
Described processing aid is a kind of or combination in PE wax, E wax, calcium stearate, Zinic stearas, Magnesium Stearate, rare earth class lubricant;
Described oxidation inhibitor is one or both the compound in Hinered phenols antioxidant and phosphite ester kind antioxidant.
Correspondingly, the embodiment of the present invention provides the preparation method of the ventilative master batch of a kind of polyene hydroxyl, and described preparation method comprises the following steps:
To put in the parallel dual-screw tablets press through pretreated mixing raw material, and extrude pelletizing and obtain the ventilative master batch of polyene hydroxyl, wherein, described tablets press adopts the mode of underwater cutpellet, and the water temperature of described underwater cutpellet is controlled at 75 ~ 95 ℃;
Material water separator by propeller type separates the ventilative master batch of described polyene hydroxyl from water;
To carry by 2 ~ 7 road pipelines by ventilative master batch through the described polyene hydroxyl that separates, described per pass pipeline is provided with independently blower fan;
Under the condition of the Liao Wen of the ventilative master batch of described polyene hydroxyl＞=60 ℃, collects and pack, obtain described polyene hydroxyl that Shui the divides Han Liang＜=300ppm master batch of breathing freely.
As the improvement of such scheme, the length-to-diameter ratio of described tablets press is 35 ~ 50;
Wherein, the temperature distribution of described tablets press barrel is as follows: 170 ~ 180 ℃, a district, two 190 ~ 195 ℃, 180 ~ 190 ℃ three, district districts, four 180 ~ 190 ℃, districts, five 175 ~ 185 ℃, districts, six 180 ~ 190 ℃, districts, seven 190 ~ 200 ℃, districts, 200 ~ 220 ℃ of die heads.
Wherein, the vacuum tightness in described tablets press barrel the 6th district be made as-0.2 MPa ~-0.01MPa.
As the improvement of such scheme, will carry by 2 ~ 7 road pipelines by ventilative master batch through the described polyene hydroxyl that separates, described per pass pipeline is provided with in the step of blower fan independently:
Described pipeline is stainless steel pipes;
Described pipeline external parcel the foam material thermal insulation layer that is used for keeping homo(io)thermism;
Long 2 ~ 10 meters of described per pass pipeline;
The end of described per pass pipeline is provided with the opening funnel for collection material.
As the improvement of such scheme, in will putting into the parallel dual-screw tablets press through pretreated mixing raw material, extrude before pelletizing obtains the ventilative master batch step of polyene hydroxyl, also comprise:
40 ~ 70% polyolefin resines, 0.01 ~ 2% processing aid and 0.01 ~ 2% oxidation inhibitor are joined mix 5 ~ 20 minutes in high speed mixer, obtain mixture, the rotating speed of described high speed mixer is 800 ~ 1200 rev/mins;
40 ~ 70% mineral fillers are joined in homogenizer, continue to mix 10 ~ 25 minutes with described mixture, obtain through pretreated mixing raw material, the rotating speed of described high speed mixer is 800 ~ 1200 rev/mins.
As the improvement of such scheme, described polyolefin resin is a kind of or combination in Low Density Polyethylene, high density polyethylene(HDPE), linear low density polyethylene, metallocene PE, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, homo-polypropylene;
Described mineral filler is a kind of or combination in water-ground limestone, light calcium carbonate, barium sulfate, calcium sulfate, talcum powder, wollastonite, silicon-dioxide, calcium oxide, and its grain size is 0. 3 microns ~ 12 microns;
Described processing aid is a kind of or combination in PE wax, E wax, calcium stearate, Zinic stearas, Magnesium Stearate, rare earth class lubricant;
Described oxidation inhibitor is one or both the compound in Hinered phenols antioxidant and phosphite ester kind antioxidant.
As the improvement of such scheme, the Shui that is the ventilative master batch of the described polyene hydroxyl that makes of main raw material by described polyolefin resin and mineral filler divides Han Liang＜=200ppm;
The density of described Low Density Polyethylene is 0.910 ~ 0.935g/cm
3
The density of described high density polyethylene(HDPE) is 0.940 ~ 0.980g/cm
3
The density of described linear low density polyethylene is 0.910-0.940 g/cm
3
The melting index of described metallocene PE is 1 ~ 6 g/10min;
The melting index of described ethylene-octene copolymer is 2 ~ 4 g/10min;
Vinyl acetate content in described ethylene-vinyl acetate copolymer is 5% ~ 40%.
Implement the present invention and have following beneficial effect:
The present invention is about ventilative master batch of a kind of polyene hydroxyl and preparation method thereof, in the ventilative master batch preparation field of polyene hydroxyl, compared with prior art, need not through drying process first, but by regulating the temperature of water coolant, control the surface temperature of particle, the mode of using the multiple tracks airduct to carry reaches and removes ventilative master batch moisture content, makes its Shui divide Han Liang＜=300ppm, You Xuan Wei＜=200ppm, physical and chemical performance is good.The temperature that the present invention controls particle keeps constant, avoid temperature to die-off suddenly increasing be mainly by: the water temperature of 1, controlling underwater cutpellet is 75 ~ 95 ℃, thereby the temperature that guarantees the ventilative master batch of polyene hydroxyl is not less than 75 ℃; 2, adopt the multiple tracks airduct to carry, the pipeline external parcel the foam material thermal insulation layer that is used for keeping homo(io)thermism, can rapid drawdown to keep material temperature; 3, under the condition of 60 ℃ of material temperatures, collect and pack the ventilative master batch of polyene hydroxyl, to guarantee that particle does not absorb airborne moisture content and just packs, avoid again heating and the energy consumption that increases.
Adopt the present invention, simplified the production process of ventilative master batch, reduce energy consumption, the ventilative master batch moisture content Han Liang＜=300ppm that makes, You Xuan Wei＜=200ppm, compare with the moisture content Han Liang＜=600ppm of prior art, the water content of the ventilative master batch of polyene hydroxyl of the present invention obviously reduces, and avoids the outward appearance of the excessive ventilative prepared film of master batch of moisture content impact and physicals, pH value, the unfavorable condition such as holes even.In addition, other indexs of the present invention all are improved, and such as melting index, tensile strength, fracture extension rate, flexural strength, modulus in flexure etc. can be satisfied the requirement of follow-up masking, guarantee the Quality and yield of product.In addition, the present invention also utilizes the dispersing uniformity of high filler loading capacity fine mineral filler (grain size is 0. 3 microns ~ 12 microns), has improved its mechanical property and processing characteristics, satisfies requirement and the service requirements of the process for processing of follow-up preparation film.
Description of drawings
Fig. 1 is the preparation method's of the ventilative master batch of a kind of polyene hydroxyl of the present invention schema;
Fig. 2 is the preparation method's of the ventilative master batch of a kind of polyene hydroxyl of the present invention another schema;
Fig. 3 is the schematic diagram of stainless steel transport pipe of the present invention.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, the present invention is described in further detail below in conjunction with accompanying drawing.
The embodiment of the present invention provides a kind of polyene hydroxyl master batch of breathing freely, and its main raw material formula in weight proportion is as follows:
Polyene hydroxyl resin 40 ~ 70%;
Mineral filler 40 ~ 70%;
Preferably, the ventilative master batch of polyene hydroxyl is as follows in the main raw material formula of weight proportion:
Polyene hydroxyl resin 45 ~ 65%;
Mineral filler 45 ~ 65%.
The Shui that is the ventilative master batch of the described polyene hydroxyl that makes of main raw material by described polyolefin resin and mineral filler divides Han Liang＜=300ppm;
Preferably, the Shui that is the ventilative master batch of the described polyene hydroxyl that makes of main raw material by described polyolefin resin and mineral filler divides Han Liang＜=200ppm.
The water content of the ventilative master batch of polyene hydroxyl of the present invention obviously reduces, and avoids the outward appearance of the excessive ventilative prepared film of master batch of moisture content impact and physicals, pH value, the unfavorable condition such as holes even.In addition, other indexs of the present invention all are improved, and such as melting index, tensile strength, fracture extension rate, flexural strength, modulus in flexure etc. can be satisfied the requirement of follow-up masking, guarantee the Quality and yield of product.
Wherein, described polyolefin resin is a kind of or combination in Low Density Polyethylene, high density polyethylene(HDPE), linear low density polyethylene, metallocene PE, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, homo-polypropylene;
Described mineral filler is a kind of or combination in water-ground limestone, light calcium carbonate, barium sulfate, calcium sulfate, talcum powder, wollastonite, silicon-dioxide, calcium oxide.
The density of described Low Density Polyethylene is 0.910 ~ 0.935g/cm
3
Preferably, the density of described Low Density Polyethylene is 0.915 ~ 0.920g/cm
3
Further preferably, the density of described Low Density Polyethylene is 0.917g/cm
3
The density of described high density polyethylene(HDPE) is 0.940 ~ 0.980g/cm
3
Preferably, the density of described high density polyethylene(HDPE) is 0.948 ~ 0.960g/cm
3
Further preferably, the density of described high density polyethylene(HDPE) is 0.950g/cm
3
The density of described linear low density polyethylene is 0.910-0.940 g/cm
3
Preferably, the density of described linear low density polyethylene is 0.915-0.930 g/cm
3
Further preferably, the density of described linear low density polyethylene is 0.920g/cm
3
The melting index of described metallocene PE is 1 ~ 6 g/10min;
Preferably, the melting index of described metallocene PE is 2 ~ 4 g/10min;
Further preferably, the melting index of described metallocene PE is 3 g/10min.
The melting index of described ethylene-octene copolymer is 2 ~ 4 g/10min;
Preferably, the melting index of described ethylene-octene copolymer is 2.8 ~ 3.8 g/10min;
Further preferably, the melting index of described ethylene-octene copolymer is 3.5 g/10min.
Vinyl acetate content in described ethylene-vinyl acetate copolymer is 5% ~ 40%;
Preferably, the vinyl acetate content in described ethylene-vinyl acetate copolymer is 20% ~ 40%;
Further preferably, the vinyl acetate content in described ethylene-vinyl acetate copolymer is 35%.
Described mineral filler is the ultra-fine inorganic filler, and its grain size is 0. 3 microns ~ 12 microns;
Preferably, the grain size of described mineral filler is 0. 5 microns ~ 10 microns.
It is the mineral filler of 3 microns ~ 10 microns that prior art generally adopts grain size, and it is 0. 3 microns ~ 12 microns that the present invention adopts grain size, is preferably the high filler loading capacity fine mineral filler of 0. 5 microns ~ 10 microns.Compared with prior art, the present invention can utilize the dispersing uniformity of high filler loading capacity fine mineral filler better, has improved its mechanical property and processing characteristics, satisfies requirement and the service requirements of the process for processing of follow-up preparation film.
The main raw material formula of described ceramic membrane also comprises:
Processing aid 0.01 ~ 2%;
Oxidation inhibitor 0.01 ~ 2%;
Preferably, the main raw material formula of described ceramic membrane also comprises:
Processing aid 0.1 ~ 1%;
Oxidation inhibitor 0.1 ~ 1%.
Described processing aid is a kind of or combination in PE wax, E wax, calcium stearate, Zinic stearas, Magnesium Stearate, rare earth class lubricant;
Described oxidation inhibitor is one or both the compound in Hinered phenols antioxidant and phosphite ester kind antioxidant.
More preferably, a kind of polyene hydroxyl of the present invention master batch of breathing freely, its main raw material formula in weight proportion is as follows:
Polyene hydroxyl resin 45 ~ 65%;
Mineral filler 45 ~ 65%;
Processing aid 0.1 ~ 1%;
Oxidation inhibitor 0.1 ~ 1%.
As shown in Figure 1, the embodiment of the present invention also provides the preparation method of the ventilative master batch of a kind of polyene hydroxyl, comprising:
S100 will put in the parallel dual-screw tablets press through pretreated mixing raw material, extrude pelletizing and obtain the ventilative master batch of polyene hydroxyl, and wherein, described tablets press adopts the mode of underwater cutpellet, and the water temperature of described underwater cutpellet is controlled at 75 ~ 95 ℃.
The length-to-diameter ratio of described tablets press is 35 ~ 50;
Wherein, the temperature distribution of described tablets press barrel is as follows: 170 ~ 180 ℃, a district, two 190 ~ 195 ℃, 180 ~ 190 ℃ three, district districts, four 180 ~ 190 ℃, districts, five 175 ~ 185 ℃, districts, six 180 ~ 190 ℃, districts, seven 190 ~ 200 ℃, districts, 200 ~ 220 ℃ of die heads.
Wherein, the vacuum tightness in described tablets press barrel the 6th district be made as-0.2 MPa ~-0.01MPa.
Preferably, the vacuum tightness in described tablets press barrel the 6th district be made as-0.1 MPa ~-0.02MPa.
The present invention is by being provided with venting hole above tablets press barrel the 6th district, venting hole connects vacuum pump, thus realize controlling vacuum tightness be-0.2 MPa ~-purpose of 0.01MPa.
Need to prove, the draping mode of tablets press is hydraulic pressure net switching, and it has two web plate mouths alternately to use.
75 ~ 95 ℃ of the water temperature range of underwater cutpellet can by but be not limited to the accurate control that temperature regulating device is realized water temperature, thereby the temperature that guarantees the ventilative master batch of polyene hydroxyl is not less than 75 ℃.
S101, the material water separator by propeller type separates the ventilative master batch of described polyene hydroxyl from water.
The temperature that the ventilative master batch of polyene hydroxyl separates from water is controlled at 75 ~ 95 ℃.
After separating, the ventilative master batch of polyene hydroxyl can also by the screening of vibratory screening apparatus, with the ventilative master batch segregation excision of the polyene hydroxyl beyond specification, stay the ventilative master batch of polyene hydroxyl up to specification from water.
S102 will carry by 2 ~ 7 road pipelines by ventilative master batch through the described polyene hydroxyl that separates, and described per pass pipeline is provided with independently blower fan.
The per pass pipeline is provided with independently blower fan, can guarantee that the moisture of former process can not have influence on next procedure.
Preferably, will carry by 3 ~ 5 road pipelines by ventilative master batch through the described polyene hydroxyl that separates.
Wherein, described pipeline is stainless steel pipes;
Described pipeline external parcel the foam material thermal insulation layer that be used for to keep homo(io)thermism, can rapid drawdown to keep material temperature;
Long 2 ~ 10 meters of described per pass pipeline, preferably, long 3 ~ 6 meters of per pass pipeline;
The end of described per pass pipeline is provided with the opening funnel for collection material.
The opening funnel arranges the end of per pass pipeline, and its collection material is to enter next transportation section.
Need to prove, pipeline should be straight as far as possible, reduces the frictional force of pipeline mass transport, reduces the energy consumption that produces because of frictional force.
S103 under the condition of the Liao Wen of the ventilative master batch of described polyene hydroxyl＞=60 ℃, collects and packs, and obtains described polyene hydroxyl that Shui the divides Han Liang＜=300ppm master batch of breathing freely.
Preferably, preferably, the ventilative master batch of polyene hydroxyl can be collected also and pack with aluminium plastic bag under the condition of Liao Wen＞=70 ℃, obtains described polyene hydroxyl that Shui the divides Han Liang＜=200ppm master batch of breathing freely.
The packaging temp of ventilative master batch is controlled at more than 70 ℃, to guarantee that particle does not absorb airborne moisture content and just packs.The temperature of ventilative master batch experience is 200 ℃ and is down to 70 ℃, concerning ventilative particle, just ventilative particle is not heated again since machine is out rear, does not increase unnecessary energy consumption.
In conjunction with Fig. 2 and Fig. 3, the embodiment of the present invention provides the preparation method of the ventilative master batch of another kind of polyene hydroxyl, comprising:
S200 joins 40 ~ 70% polyolefin resines, 0.01 ~ 2% processing aid and 0.01 ~ 2% oxidation inhibitor and mixes 5 ~ 20 minutes in high speed mixer, obtains mixture, and the rotating speed of described high speed mixer is 800 ~ 1200 rev/mins.
Preferably, 45 ~ 65% polyolefin resines, 0.1 ~ 1% processing aid and 0. 1 ~ 1% oxidation inhibitor are joined mix 10 minutes in high speed mixer, the rotating speed of described high speed mixer is 1000 rev/mins.
S201 joins 40 ~ 70% mineral fillers in homogenizer, continues to mix 10 ~ 25 minutes with described mixture, obtains through pretreated mixing raw material, and the rotating speed of described high speed mixer is 800 ~ 1200 rev/mins.
Preferably, 45 ~ 65% mineral fillers are joined in homogenizer, continue to mix 15 minutes with described mixture, the rotating speed of described high speed mixer is 1000 rev/mins.
S202 will put in the parallel dual-screw tablets press through pretreated mixing raw material, extrude pelletizing and obtain the ventilative master batch of polyene hydroxyl, and wherein, described tablets press adopts the mode of underwater cutpellet, and the water temperature of described underwater cutpellet is controlled at 75 ~ 95 ℃.
The length-to-diameter ratio of described tablets press is 35 ~ 50;
Wherein, the temperature distribution of described tablets press barrel is as follows: 170 ~ 180 ℃, a district, two 190 ~ 195 ℃, 180 ~ 190 ℃ three, district districts, four 180 ~ 190 ℃, districts, five 175 ~ 185 ℃, districts, six 180 ~ 190 ℃, districts, seven 190 ~ 200 ℃, districts, 200 ~ 220 ℃ of die heads.
Wherein, the vacuum tightness in described tablets press barrel the 6th district be made as-0.2 MPa ~-0.01MPa.
Preferably, the vacuum tightness in described tablets press barrel the 6th district be made as-0.1 MPa ~-0.02MPa.
The present invention is by being provided with venting hole above tablets press barrel the 6th district, venting hole connects vacuum pump, thus realize controlling vacuum tightness be-0.2 MPa ~-purpose of 0.01MPa.
Need to prove, the draping mode of tablets press is hydraulic pressure net switching, and it has two web plate mouths alternately to use.
75 ~ 95 ℃ of the water temperature range of underwater cutpellet can by but be not limited to the accurate control that temperature regulating device is realized water temperature, thereby the temperature that guarantees the ventilative master batch of polyene hydroxyl is not less than 75 ℃.
S203, the material water separator by propeller type separates the ventilative master batch of described polyene hydroxyl from water.
The temperature that the ventilative master batch of polyene hydroxyl separates from water is controlled at 75 ~ 95 ℃.
S204, the ventilative master batch of polyene hydroxyl separates rear screening by vibratory screening apparatus from water.
By the screening of vibratory screening apparatus, with the ventilative master batch segregation excision of the polyene hydroxyl beyond specification, stay the ventilative master batch of polyene hydroxyl up to specification.
S205 will carry by 3 ~ 5 road pipelines by ventilative master batch through the described polyene hydroxyl that separates, and described per pass pipeline is provided with independently blower fan.
The per pass pipeline is provided with independently blower fan, can guarantee that the moisture of former process can not have influence on next procedure.
Wherein, described pipeline is stainless steel pipes;
Described pipeline external parcel the foam material thermal insulation layer that be used for to keep homo(io)thermism, can rapid drawdown to keep material temperature;
Long 3 ~ 6 meters of described per pass pipeline;
The end of described per pass pipeline is provided with the opening funnel for collection material.
The opening funnel arranges the end of per pass pipeline, and its collection material is to enter next transportation section.
Need to prove, pipeline should be straight as far as possible, reduces the frictional force of pipeline mass transport, reduces the energy consumption that produces because of frictional force.
The schematic diagram of stainless steel transport pipe as shown in Figure 3 comprises 3 road stainless steel transport pipes.Wherein, each pipeline 1 arranges in horizontal direction, and per pass pipeline 1 is provided with independently blower fan 2,3 ~ 6 meters of pipeline 1 length, the end of pipeline 1 is provided with the opening funnel 3 for collection material, and opening funnel 3 is also venting port, and pipeline 1 external parcel the foam material thermal insulation layer that is used for keeping homo(io)thermism.
Need to prove, first pipeline charging place 4 connects the feed opening of separator or vibratory screening apparatus, and last deferent way discharging device place connects holding tank.
S206 under the condition of the Liao Wen of the ventilative master batch of described polyene hydroxyl＞=60 ℃, collects in holding tank, and with finished product packing, obtains the ventilative master batch of described polyene hydroxyl that Shui divides Han Liang＜=300ppm.
Preferably, the ventilative master batch of polyene hydroxyl can be collected also and pack with aluminium plastic bag under the condition of Liao Wen＞=70 ℃, obtains described polyene hydroxyl that Shui the divides Han Liang＜=200ppm master batch of breathing freely.
The packaging temp of ventilative master batch is controlled at more than 70 ℃, to guarantee that particle does not absorb airborne moisture content and just packs.The temperature of ventilative master batch experience is 200 ℃ and is down to 70 ℃, concerning ventilative particle, just ventilative particle is not heated again since machine is out rear, does not increase unnecessary energy consumption.
The below carries out technical indicator to the ventilative master batch of polyene hydroxyl of the present invention and detects, and with industry in the versatility product index compare, testing method and detect data as shown in Table 1:
As seen from the above table, the water content of the ventilative master batch of polyene hydroxyl of the present invention is＜200ppm, and universal product index water content＜600ppm compares with prior art, and its moisture content has reduced by 400 ppm, has namely reduced by 66.7%, the obvious decrease of water content.And other indexs all are improved, wherein, compared with prior art, the ventilative master batch melting index of polyene hydroxyl of the present invention has increased that 0.6 g/10min, tensile strength have increased by 1 MPa, fracture extension rate has increased by 20%, and ash content, flexural strength, modulus in flexure, socle girder notched Izod impact strength etc. performance index approach.
Below further illustrate the present invention with specific embodiment.
Embodiment 1
(Low Density Polyethylene: linear low density polyethylene=1:5), 1% Zinic stearas and 1% Hinered phenols antioxidant (trade mark 1010) mixed 10 minutes, and rotating speed is 1000 rev/mins to add 45% polyolefin resin in high speed mixer; 45% ultra-fine inorganic filler-calcium carbonate (particle diameter is for being of a size of 0. 5 microns ~ 10 microns) is joined again and mix together 15 minutes in homogenizer, rotating speed is 1000 rev/mins; Then put in dual-screw pelletizer, the temperature of barrel: 180 °, a district C, two 185 °, district C, three 190 °, district C, four 180 °, district C, five 175 °, district C, six 185 °, district C, seven 190 °, district C, 210 ° of C of die head, the vacuum tightness of venting port is-0.07 MPa, and circulating water temperature is made as 85 ° of C, underwater cutpellet; Ventilative particle separates water through the material water separator of propeller type with ventilative master batch, enter first stainless steel transport pipe through the vibratory screening apparatus screening is laggard, then enter successively second and third, four, five road stainless steel transport pipes; Collect ventilative master batch, pack with aluminium plastic bag, the temperature during packing is 65 ° of C.
Embodiment 2
(Low Density Polyethylene: linear low density polyethylene=1:3), 0.5% Zinic stearas and 0.5% Hinered phenols antioxidant (trade mark 1010) mixed 10 minutes, and rotating speed is 1000 rev/mins to add 50% polyolefin resin in high speed mixer; 52% ultra-fine inorganic filler-calcium carbonate (particle diameter is for being of a size of 0. 5 microns ~ 10 microns) is joined again and mix together 15 minutes in homogenizer, rotating speed is 1000 rev/mins; Then put in dual-screw pelletizer the temperature of barrel: 180 °, a district C, two 185 °, district C, three 190 °, district C, four 180 °, district C, five 175 °, district C, six 185 °, district C, seven 190 °, district C, 210 ° of C of die head, the vacuum tightness of venting port is-0.0,6 MPa, circulating water temperature is made as 90 ° of C, underwater cutpellet; Ventilative particle separates water through the material water separator of propeller type with ventilative master batch, enter first stainless steel transport pipe through the vibratory screening apparatus screening is laggard, then enter successively second and third, four, five road stainless steel transport pipes; Collect ventilative master batch, pack with aluminium plastic bag, the temperature during packing is 70 ° of C.
Embodiment 3
(Low Density Polyethylene: linear low density polyethylene: ethylene-octene copolymer=1:5:2), 0.8% Zinic stearas and 0.7% Hinered phenols antioxidant (trade mark 1010) mixed 10 minutes, and rotating speed is 1000 rev/mins to add 60% polyolefin resin in high speed mixer; 48% ultra-fine inorganic filler-calcium carbonate (particle diameter is for being of a size of 0. 5 microns ~ 10 microns) is joined again and mix together 15 minutes in homogenizer, rotating speed is 1000 rev/mins; Then put in dual-screw pelletizer, the temperature of barrel: 180 °, a district C, two 185 °, district C, three 190 °, district C, four 180 °, district C, five 175 °, district C, six 185 °, district C, seven 190 °, district C, 210 ° of C of die head, the vacuum tightness of venting port is-0.08 MPa, and circulating water temperature is made as 95 ° of C, underwater cutpellet; Ventilative particle separates water through the material water separator of propeller type with ventilative master batch, enter first stainless steel transport pipe through the vibratory screening apparatus screening is laggard, then enter successively second and third, four, five road stainless steel transport pipes; Collect ventilative master batch, pack with aluminium plastic bag, the temperature during packing is 75 ° of C.
Embodiment 4
(Low Density Polyethylene: high density polyethylene(HDPE): linear low density polyethylene: ethylene-octene copolymer=1:2:5:2), 0.:3 % Zinic stearas and 0.4% Hinered phenols antioxidant (trade mark 1010) mixed 10 minutes, and rotating speed is 1000 rev/mins to add 55% polyolefin resin in high speed mixer; 55% ultra-fine inorganic filler-calcium carbonate (particle diameter is for being of a size of 0. 5 microns ~ 10 microns) is joined again and mix together 15 minutes in homogenizer, rotating speed is 1000 rev/mins; Then put in dual-screw pelletizer, the temperature of barrel: 180 °, a district C, two 185 °, district C, three 190 °, district C, four 180 °, district C, five 175 °, district C, six 185 °, district C, seven 190 °, district C, 210 ° of C of die head, the vacuum tightness of venting port is-0.1 MPa, and circulating water temperature is made as 90 ° of C, underwater cutpellet; Ventilative particle separates water through the material water separator of propeller type with ventilative master batch, enter first stainless steel transport pipe through the vibratory screening apparatus screening is laggard, then enter successively second and third, four, five road stainless steel transport pipes; Collect ventilative master batch, pack with aluminium plastic bag, the temperature during packing is 65 ° of C.
Reference example 1
(Low Density Polyethylene: linear low density polyethylene=1:5), 1% Zinic stearas and 1% Hinered phenols antioxidant (trade mark 1010) mixed 10 minutes, and rotating speed is 1000 rev/mins to add 45% polyolefin resin in high speed mixer; 45% ultra-fine inorganic filler-calcium carbonate (particle diameter is for being of a size of 0. 5 microns ~ 10 microns) is joined again and mix together 15 minutes in homogenizer, rotating speed is 1000 rev/mins; Then put in dual-screw pelletizer; adopt the mode of water cooling bracing pelletizing; obtain just finished product of the ventilative master batch of polyene hydroxyl; ventilative master batch surpasses 200 ° of C from dual-screw pelletizer temperature out; water cooling bracing is cooled to 30 ° of rear pelletizings in C left and right; be warming up to 90 ° of C with drying machine again and remove moisture content, obtain finished product.
Embodiment 1 to 4, and reference example 1, all adopts the testing method of GB12006.2 to carry out the test of water content to it, and detected result is as shown in following table two:
In sum, implement the present invention and have following beneficial effect:
The present invention is about ventilative master batch of a kind of polyene hydroxyl and preparation method thereof, in the ventilative master batch preparation field of polyene hydroxyl, compared with prior art, need not through drying process first, but by regulating the temperature of water coolant, control the surface temperature of particle, the mode of using the multiple tracks airduct to carry reaches and removes ventilative master batch moisture content, makes its Shui divide Han Liang＜=300ppm, You Xuan Wei＜=200ppm, physical and chemical performance is good.The temperature that the present invention controls particle be mainly by: the water temperature of 1, controlling underwater cutpellet is 75 ~ 95 ℃, thereby the temperature that guarantees the ventilative master batch of polyene hydroxyl is not less than 75 ℃; 2, adopt the multiple tracks airduct to carry, the pipeline external parcel the foam material thermal insulation layer that is used for keeping homo(io)thermism, can rapid drawdown to keep material temperature; 3, under the condition of 60 ℃ of material temperatures, collect and pack the ventilative master batch of polyene hydroxyl, to guarantee that particle does not absorb airborne moisture content and just packs, avoid again heating and the energy consumption that increases.
Adopt the present invention, simplified the production process of ventilative master batch, reduce energy consumption, the ventilative master batch moisture content Han Liang＜=300ppm that makes, You Xuan Wei＜=200ppm, compare with the moisture content Han Liang＜=600ppm of prior art, the water content of the ventilative master batch of polyene hydroxyl of the present invention obviously reduces, and avoids the outward appearance of the excessive ventilative prepared film of master batch of moisture content impact and physicals, pH value, the unfavorable condition such as holes even.In addition, other indexs of the present invention all are improved, and such as melting index, tensile strength, fracture extension rate, flexural strength, modulus in flexure etc. can be satisfied the requirement of follow-up masking, guarantee the Quality and yield of product.In addition, the present invention also utilizes the dispersing uniformity of high filler loading capacity fine mineral filler (grain size is 0. 3 microns ~ 12 microns), has improved its mechanical property and processing characteristics, satisfies requirement and the service requirements of the process for processing of follow-up preparation film.
The above is the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.
Claims (10)
1. the ventilative master batch of polyene hydroxyl, is characterized in that, its main raw material formula in weight proportion is as follows:
Polyene hydroxyl resin 40 ~ 70%;
Mineral filler 40 ~ 70%;
The Shui that is the ventilative master batch of the described polyene hydroxyl that makes of main raw material by described polyolefin resin and mineral filler divides Han Liang＜=300ppm;
Wherein, described polyolefin resin is a kind of or combination in Low Density Polyethylene, high density polyethylene(HDPE), linear low density polyethylene, metallocene PE, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, homo-polypropylene;
Described mineral filler is a kind of or combination in water-ground limestone, light calcium carbonate, barium sulfate, calcium sulfate, talcum powder, wollastonite, silicon-dioxide, calcium oxide.
2. the ventilative master batch of polyene hydroxyl as claimed in claim 1, is characterized in that, the Shui that is the ventilative master batch of described polyene hydroxyl that makes of main raw material by described polyolefin resin and mineral filler divides Han Liang＜=200ppm;
The density of described Low Density Polyethylene is 0.910 ~ 0.935g/cm
3
The density of described high density polyethylene(HDPE) is 0.940 ~ 0.980g/cm
3
The density of described linear low density polyethylene is 0.910-0.940 g/cm
3
The melting index of described metallocene PE is 1 ~ 6 g/10min;
The melting index of described ethylene-octene copolymer is 2 ~ 4 g/10min;
Vinyl acetate content in described ethylene-vinyl acetate copolymer is 5% ~ 40%.
3. the ventilative master batch of polyene hydroxyl as claimed in claim 2, is characterized in that, described mineral filler is the ultra-fine inorganic filler, and its grain size is 0. 3 microns ~ 12 microns.
4. the ventilative master batch of polyene hydroxyl as claimed in claim 3, is characterized in that, the main raw material formula of described ceramic membrane also comprises:
Processing aid 0.01 ~ 2%;
Oxidation inhibitor 0.01 ~ 2%;
Described processing aid is a kind of or combination in PE wax, E wax, calcium stearate, Zinic stearas, Magnesium Stearate, rare earth class lubricant;
Described oxidation inhibitor is one or both the compound in Hinered phenols antioxidant and phosphite ester kind antioxidant.
5. the preparation method of the ventilative master batch of polyene hydroxyl, is characterized in that, described preparation method comprises the following steps:
To put in the parallel dual-screw tablets press through pretreated mixing raw material, and extrude pelletizing and obtain the ventilative master batch of polyene hydroxyl, wherein, described tablets press adopts the mode of underwater cutpellet, and the water temperature of described underwater cutpellet is controlled at 75 ~ 95 ℃;
Material water separator by propeller type separates the ventilative master batch of described polyene hydroxyl from water;
To carry by 2 ~ 7 road pipelines by ventilative master batch through the described polyene hydroxyl that separates, described per pass pipeline is provided with independently blower fan;
Under the condition of the Liao Wen of the ventilative master batch of described polyene hydroxyl＞=60 ℃, collects and pack, obtain described polyene hydroxyl that Shui the divides Han Liang＜=300ppm master batch of breathing freely.
6. the preparation method of the ventilative master batch of polyene hydroxyl as claimed in claim 5, is characterized in that, the length-to-diameter ratio of described tablets press is 35 ~ 50;
Wherein, the temperature distribution of described tablets press barrel is as follows: 170 ~ 180 ℃, a district, two 190 ~ 195 ℃, 180 ~ 190 ℃ three, district districts, four 180 ~ 190 ℃, districts, five 175 ~ 185 ℃, districts, six 180 ~ 190 ℃, districts, seven 190 ~ 200 ℃, districts, 200 ~ 220 ℃ of die heads;
Wherein, the vacuum tightness in described tablets press barrel the 6th district be made as-0.2 MPa ~-0.01MPa.
7. the preparation method of the ventilative master batch of polyene hydroxyl as claimed in claim 5, is characterized in that, will be through the described polyene hydroxyl that separates ventilative master batch by 2 ~ 7 road pipelines conveyings, described per pass pipeline is provided with in the step of blower fan independently:
Described pipeline is stainless steel pipes;
Described pipeline external parcel the foam material thermal insulation layer that is used for keeping homo(io)thermism;
Long 2 ~ 10 meters of described per pass pipeline;
The end of described per pass pipeline is provided with the opening funnel for collection material.
8. the preparation method of the ventilative master batch of polyene hydroxyl as claimed in claim 5, is characterized in that, in will putting into the parallel dual-screw tablets press through pretreated mixing raw material, extrudes pelletizing and obtain the polyene hydroxyl and breathe freely before the master batch step, also comprises:
40 ~ 70% polyolefin resines, 0.01 ~ 2% processing aid and 0.01 ~ 2% oxidation inhibitor are joined mix 5 ~ 20 minutes in high speed mixer, obtain mixture, the rotating speed of described high speed mixer is 800 ~ 1200 rev/mins;
40 ~ 70% mineral fillers are joined in homogenizer, continue to mix 10 ~ 25 minutes with described mixture, obtain through pretreated mixing raw material, the rotating speed of described high speed mixer is 800 ~ 1200 rev/mins.
9. the preparation method of the ventilative master batch of polyene hydroxyl as claimed in claim 8, it is characterized in that, described polyolefin resin is a kind of or combination in Low Density Polyethylene, high density polyethylene(HDPE), linear low density polyethylene, metallocene PE, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, homo-polypropylene;
Described mineral filler is a kind of or combination in water-ground limestone, light calcium carbonate, barium sulfate, calcium sulfate, talcum powder, wollastonite, silicon-dioxide, calcium oxide, and its grain size is 0. 3 microns ~ 12 microns;
Described processing aid is a kind of or combination in PE wax, E wax, calcium stearate, Zinic stearas, Magnesium Stearate, rare earth class lubricant;
Described oxidation inhibitor is one or both the compound in Hinered phenols antioxidant and phosphite ester kind antioxidant.
10. the preparation method of the ventilative master batch of polyene hydroxyl as claimed in claim 9, is characterized in that, the Shui that is the ventilative master batch of described polyene hydroxyl that makes of main raw material by described polyolefin resin and mineral filler divides Han Liang＜=200ppm;
The density of described Low Density Polyethylene is 0.910 ~ 0.935g/cm
3
The density of described high density polyethylene(HDPE) is 0.940 ~ 0.980g/cm
3
The density of described linear low density polyethylene is 0.910-0.940 g/cm
3
The melting index of described metallocene PE is 1 ~ 6 g/10min;
The melting index of described ethylene-octene copolymer is 2 ~ 4 g/10min;
Vinyl acetate content in described ethylene-vinyl acetate copolymer is 5% ~ 40%.
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