CN101948636A - Preparation method of modified nanometer precipitated barium sulfate - Google Patents
Preparation method of modified nanometer precipitated barium sulfate Download PDFInfo
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- CN101948636A CN101948636A CN2010102688770A CN201010268877A CN101948636A CN 101948636 A CN101948636 A CN 101948636A CN 2010102688770 A CN2010102688770 A CN 2010102688770A CN 201010268877 A CN201010268877 A CN 201010268877A CN 101948636 A CN101948636 A CN 101948636A
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Abstract
The invention provides a preparation method of modified nanometer precipitated barium sulfate. The modified nanometer precipitated barium sulfate is prepared by modifying precipitated barium sulfate by using a modifier which is selected from one or several of silicate, aluminate, phosphate, polyethylene glycol, polyvinyl alcohol, stearate, laurate, silane coupling agent, titanate coupling agent and aluminate coupling agent. The modified nanometer precipitated barium sulfate prepared by the method of the invention has even particle size distribution. The technology of manufacturing chemical fiber by using the modified nanometer precipitated barium sulfate is simple, the technical index is rational and reliable, and the operation is easy; moreover, the mechanical properties, such as tensile strength, impact strength and breaking elongation of the polyethylene material, are greatly improved. The application of the modified nanometer precipitated barium sulfate can greatly reduce the product cost of the polyethylene fiber and further increase the popularization and application range of the polyethylene fiber.
Description
Technical field
The present invention relates to a kind of preparation method of modified Nano process white.
Background technology
In the prior art, barium sulfate is as a kind of material with cost advantage, and range of application progressively enlarges, but Shang Weiyou successfully is applied to barium sulfate to make the technical scheme of chemical fibre.The principal element that influences its application is the characteristics such as big, the easy reunion of surface tension of nano material.During concrete the application, cause shortcomings such as skewness easily.
The polyethylene kind chemical fibre has very widespread use at industry-by-industry, uses in industries such as fishing net, rope especially and occupies larger specific gravity.But the mechanical property of polyethylene own is compared with nylon and is had a certain distance, can't satisfy the application of some high strength aspects, causes the limitation of its application and popularization.
The polyethylene fibre of producing in the prior art and the various aspects of performance of nylon are as follows:
| Kind | Tensile strength MPa | Elongation at break % | Notched Izod impact strength kJ/m 2 |
| The level that stretches polyethylene | 24 | 500 | 15 |
| Wire drawing level nylon | 60 | 200 | 10 |
Though but polyethylene fibre of the prior art is to a certain degree possessing corresponding mechanics intensity, its mechanical strength still can't satisfy the service requirements in fishing net, rope field fully.And raw-material use causes its production cost too high, causes the application of polyethylene fibre limited, is difficult to large-scale promotion application in making fishing net, rope.
The polyethylene kind film has very widespread use at industry-by-industry, and special the application in the film of agricultural usefulness occupied larger specific gravity.But the mechanical strength of agricultural polyethylene film of the prior art and weathering resistance are not fine, can't satisfy the application of some high strength and high-weatherability aspect.Especially film for agricultural use is open-air use, it directly is exposed in the atmospheric environment, is subjected to the erosion of external environment easily, and especially sunlight is exposed to the sun, can the film after long-time sunlight is exposed to the sun keep the performance of its each side, is the important measurement index of film for agricultural use quality.
Though polyethylene film of the prior art is to a certain degree possessing corresponding mechanics intensity and weathering resistance, its mechanical strength still can't satisfy the service requirements in plastic sheeting for farm use field fully.And raw-material use causes its production cost higher, causes polyethylene film limited in the application of agriculture field.
Therefore, seeking a kind ofly can provide the mechanical strength of chemical fibre and film and the material of mechanical property, becomes to promote the important technological problems that enlarges chemical fibre and film Application Areas.
In the prior art, barium sulfate is as a kind of material with cost advantage, and range of application progressively enlarges.But Shang Weiyou successfully is applied to barium sulfate to make the technical scheme of chemical fibre and film.
Summary of the invention
The objective of the invention is provides a kind of preparation method of modified Nano process white in order to overcome deficiency of the prior art, thinks that chemical fibre and film provide one of a kind of novel raw material.
For realizing above purpose, the present invention is achieved through the following technical solutions:
The preparation method of modified Nano process white, it is characterized in that, described modified Nano process white is that process white uses modifier modification to form, and described properties-correcting agent is selected from one or more in silicate, aluminate, phosphoric acid salt, polyoxyethylene glycol, polyvinyl alcohol, stearate, lauroleate, silane coupling agent, titanate coupling agent, the aluminate coupling agent.
Available silicate includes but not limited to water glass, potassium silicate.The available aluminate includes but not limited to sodium aluminate, Potcrate.Available phosphoric acid salt includes but not limited to sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC.The available stearate includes but not limited to sodium stearate, potassium stearate.The available lauroleate includes but not limited to sodium laurate, potassium laurate.
The available silane coupling agent includes but not limited to vinyl trichloro silane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-An Bingjisanyiyangjiguiwan, γ-glycidyl ether oxygen propyl trimethyl silane, γ-(methacryloxy) propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, anilinomethyl triethoxysilane and anilinomethyl trimethoxy silane.
The available titanate coupling agent includes but not limited to isopropoxy three different capryloyl titanic acid ester, isopropoxy three isostearoyl base titanic acid ester, dioleoyl ethylene titanate, three oleoyl isopropyl titanate and tetrabutyl titanates.
Preferably, the particle diameter of described modified Nano process white is 10nm～900nm.More preferably be that the particle diameter of described modified Nano process white is 50nm～500nm.
Preferably, described preparation method comprises step: the solution that barium carbonate or hydrated barta water is made into solid content weight content 5%～30%, the catalyzer that adds solution weight 0.01%～5%, be added dropwise to the vitriol oil that makes barium carbonate or hydrated barta complete reaction in the stirring, reaction gets process white after finishing after-filtration, the modifier solution that adds properties-correcting agent or properties-correcting agent weight content 1%～25% carries out surface treatment to process white, properties-correcting agent weight is 0.2%～5% of process white weight, then dehydration, drying forms the modified Nano process white.
As properties-correcting agent is liquid, then can directly add in the process white it is carried out modification; As properties-correcting agent is solid, then is configured to the aqueous solution earlier, adds in the process white again it is carried out modification.During modification, can adopt modes such as stirring, make properties-correcting agent or modifier solution and process white uniform mixing, with to the even modification of process white.
Preferably, described catalyzer is selected from acidity and is better than the acid of barium carbonate acid group or their water-soluble salt.
Preferably, during to the barium sulfate modification, under 50 ℃～100 ℃, carry out modification.
Preferably, described catalyzer is selected from acidity and is better than the acid of carbonic acid or their water-soluble salt.The acid that acidity is better than carbonic acid includes but not limited to hydrochloric acid, nitric acid, acetic acid; Their salt includes but not limited to water-soluble sodium-chlor, Repone K; SODIUMNITRATE, saltpetre; Sodium-acetate, Potassium ethanoate.
The effect of using these catalyzer is a reaction process of accelerating process white.
Purpose to the nano barium sulfate modification is in order to improve its production operability and dispersiveness in organic polymer and avidity.To nano barium sulfate carry out advantage after the modification be can be in organic polymer homodisperse, improve its chemical fibre each side mechanical strength.
Preferably, the modifier solution joining day is 10～100 minutes.More preferably be that modifier solution at the uniform velocity adds.
Described modified Nano process white can be used for making chemical fibre, and the weight content of nano modification process white in chemical fibre is 6%～50%.
Preferably, after the nano modification process white is made master batch, be used further to make chemical fibre.
The purpose of making the barium sulfate master batch earlier is barium sulfate to be carried out pre-dispersed, improves the dispersiveness of barium sulfate powder in plastics.Dust pollution when reducing execute-in-place.Making master batch, to make the advantage of chemical fibre again be scattered, and execute-in-place is simple, and stability is high.
Preferably, described master batch comprises 1%～90% resin carrier according to weight percent, 1%～15% lubricant, and 0.01%～10% grafted monomer, 0.001%～5% initiator, surplus is the modified Nano process white.
Preferably, described master batch is used to make chemical fibre and film, and described resin carrier adopts and chemical fibre matrix or film matrix identical materials.For example, the matrix of high density polyethylene(HDPE) chemical fibre is a high density polyethylene(HDPE), and then resin carrier is preferably high density polyethylene(HDPE); The matrix of linear polyethylene chemical fibre is a linear polyethylene, and then resin carrier is preferably linear polyethylene; The matrix of linear polyethylene film is a linear polyethylene, and then resin carrier is preferably linear polyethylene.
Preferably, described resin carrier is selected from one or both the mixture in high density polyethylene(HDPE), linear polyethylene, new LDPE (film grade), polypropylene, the ethylene-vinyl acetate copolymer.
Preferably, lubricant is selected from one or more in polyethylene wax, vinyl bis-stearamides, Zinic stearas, stearic acid pentaerythritol ester, polyoxyethylene glycol, titanate coupling agent, the aluminate coupling agent.
Preferably, grafted monomer is selected from one or more in maleic anhydride, vinylformic acid, vinylbenzene, the butyl acrylate.
Preferably, described initiator is selected from dicumyl peroxide, dibenzoyl peroxide, di-t-butyl peroxide (DTBP), dilauroyl peroxide, di-cyclohexylperoxy dicarbonate, di-isopropyl peroxydicarbonate, peroxy dicarbonate two (2-ethylhexyl) ester, two (2-phenyl ethoxy) esters of peroxy dicarbonate, the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester and peroxidized t-butyl perbenzoate.
Preferably, the preparation method of described master batch is: after each raw material is stirred with high-speed mixer, extrude air-cooled granulation through twin screw extruder under 100 ℃～200 ℃.
Preferably, in the chemical fibre, described master batch weight percentage is 10%～40%.
Preferably, the manufacture method of described chemical fibre is: injection molded with injection moulding machine after 180 ℃～250 ℃ fusions after master batch and other chemical fibre raw materials are mixed, and during injection moulding, 40 ℃～110 ℃ of die temperatures, injection pressure 50～100Mpa.
Preferably, described chemical fibre is an organic fibre.
Preferably, described chemical fibre comprises terylene, acrylic fibers, polypropylene fibre, polyvinyl, polyvinyl chloride fibre, polyethylene, spandex and second spandex.More preferably be that described chemical fibre is hdpe fiber or linear polyethylene fiber.
Above-described nano modification process white also can be used to make film, especially polyethylene film.When being used to make film, also can use above-mentioned master batch.When being used to make polyethylene film, preferably described polyethylene comprises linear polyethylene and high-pressure polyethylene.More preferably be that the weight ratio of described linear polyethylene and high-pressure polyethylene is 2～5: 1.
The preparation method that a kind of modified Nano process white is provided of the present invention, the nano modification process white that uses the inventive method to prepare, even particle size distribution.Increase the new purposes of nano barium sulfate.Both widen the use range of nano barium sulfate, improved the mechanical property of polyethylene fibre again.It is simple to use the modified Nano process white to make the technology of chemical fibre, and technical indicator is rationally reliable, and easy handling has also improved the mechanical property of the aspects such as tensile strength, shock strength, elongation at break of polythene material simultaneously in a large number.Use modified Nano process white can reduce the production cost of polyethylene fibre significantly, further increases the extent of spreading amd application of polyethylene fibre.
Description of drawings
Fig. 1 is the size distribution figure of the modified nano-barium sulfate of embodiment 1 preparation.
Fig. 2 is the size distribution figure of the modified nano-barium sulfate of embodiment 2 preparations.
Fig. 3 is the modified nano-barium sulfate Electronic Speculum figure (100000 times) of embodiment 1 preparation.
Fig. 4 is the modified nano-barium sulfate Electronic Speculum figure (100000 times) of embodiment 2 preparations.
Fig. 5 is the modified nano-barium sulfate Electronic Speculum figure (30000 times) of embodiment 3 preparations.
Fig. 6 is the modified nano-barium sulfate Electronic Speculum figure (50000 times) of embodiment 4 preparations.
Fig. 7 is the modified nano-barium sulfate Electronic Speculum figure (50000 times) of embodiment 5 preparations.
Fig. 8 is the modified nano-barium sulfate Electronic Speculum figure (50000 times) of embodiment 6 preparations.
Fig. 9 is the section Electronic Speculum figure (10000 times) of the chemical fibre of embodiment 21 preparations.
Figure 10 is the section Electronic Speculum figure (14000 times) of the film of embodiment 29 preparations.
Embodiment
Below in conjunction with embodiment the present invention is described in detail:
The preparation of modified Nano process white
Embodiment 1
Add 600kg technical grade lightweight barium carbonate and 3400kg water at 5 cubical reactors, solid content is 15%.In reactor, add 25kg hydrochloric acid (concentration 31%).The reactor stirring velocity is controlled at 200r/min, at the uniform velocity added the 300kg vitriol oil (concentration 98%) to reaction again and finish in 30-40 minute.Reaction end pH is controlled at 5.5.With filter screen will react good barium sulfate slurry with the filtration of 1000 mesh filter screens after, obtain the 720Kg process white.The aqueous solution that at the uniform velocity adds sodium stearate weight content 10% in process white carries out surface treatment to process white, joining day is 30 minutes, sodium stearate weight is 20kg, temperature during modification is controlled at 80 ℃, dewater with pressure filter then, use flash dryer, the automatic packing machine packing forms modified Nano process white powder.
Get the modified Nano process white that 0.2 gram embodiment 1 produces, put into the beaker that 100 ml waters are housed, add two 10% Sodium hexametaphosphate 99.Disperseed 5 minutes with ultrasonic echography, be transferred to desired concn then, put Ma Erwen NANO-S90 particle diameter tester into and test.The particle size data test result is as shown in table 1, its distribution plan as shown in Figure 1, gained modified Nano process white particle size range is 37.8～122nm.D50 is 57nm.
Table 1:
| Particle diameter (nm) | Weight percentage (%) |
| 37.8 | 4.0 |
| 43.8 | 16.3 |
| 50.7 | 27.6 |
| 58.8 | 25.8 |
| 68.1 | 15.8 |
| 78.8 | 7.2 |
| 91.3 | 2.5 |
| 106 | 0.6 |
| 122 | 0.2 |
Embodiment 2
Add 1000kg technical grade lightweight barium carbonate at 5 cubical reactors, add 3000kg water, add 25kg hydrochloric acid (concentration 31%), the reactor stirring velocity is controlled at 250r/min, in 30-40 minute, at the uniform velocity add the 500kg vitriol oil (concentration 98%) to reaction again and finish.Reaction end pH is controlled at 5.6.With filter screen will react good barium sulfate slurry with the filtration of 1000 mesh filter screens after, obtain the 1200Kg process white.The aqueous solution that at the uniform velocity adds sodium stearate weight content 5% in process white carries out surface treatment to process white, joining day is 20 minutes, sodium stearate weight is 30kg, temperature during modification is controlled at 80 ℃, dewater with pressure filter then, use flash dryer, the automatic packing machine packing forms modified Nano process white powder.
Get the modified Nano process white that 0.2 gram embodiment 2 is produced, put into the beaker that 100 ml waters are housed, add two 10% Sodium hexametaphosphate 99.Disperseed 5 minutes with ultrasonic echography, be transferred to desired concn then, put Ma Erwen NANO-S90 particle diameter tester into and test.The particle size data test result is as shown in table 2, its distribution plan as shown in Figure 2, gained modified Nano process white particle size range is 50.7nm～142nm.D50 is 68nm.
Table 2:
| Particle diameter (nm) | Weight percentage (%) |
| 50.7 | 6.4 |
| 58.8 | 21.8 |
| 68.1 | 30.7 |
| 78.8 | 23.8 |
| 91.3 | 12.0 |
| 106 | 4.2 |
| 122 | 1.0 |
| 142 | 0.1 |
Embodiment 3
Add 200kg technical grade lightweight barium carbonate and 3800kg water at 5 cubical reactors, solid content is 5%.In reactor, add 20kg sodium-chlor.The reactor stirring velocity is controlled at 100r/min, at the uniform velocity added the 100kg vitriol oil (concentration 98%) to reaction again and finish in 50 minutes.Reaction end pH is controlled at 6.With filter screen will react good barium sulfate slurry with the filtration of 1000 mesh filter screens after, obtain the 240Kg process white.The vinyl trichloro silane properties-correcting agent that at the uniform velocity adds 10kg in process white carries out surface treatment, joining day was controlled at 40 minutes, temperature during modification is controlled at 55 ℃, dewater with pressure filter then, use flash dryer, the automatic packing machine packing forms modified Nano process white powder.Gained modified Nano process white particle diameter is 150-200nm.D50 is 175nm.
Embodiment 4
Add 400kg technical grade lightweight barium carbonate and 3600kg water at 5 cubical reactors, solid content is 10%.In reactor, add 10kg acetic acid.The reactor stirring velocity is controlled at 600r/min, adds the 200kg vitriol oil (concentration 98%) to reaction again and finishes.Reaction end pH is controlled at 5.8.With filter screen will react good barium sulfate slurry with the filtration of 1000 mesh filter screens after, obtain the 480Kg process white.The dioleoyl ethylene titanate properties-correcting agent that adds 10kg in process white carries out surface treatment; joining day was controlled at 50 minutes; temperature during modification is controlled at 60 ℃; dewater with pressure filter then; use flash dryer, the automatic packing machine packing forms modified Nano process white powder.Gained modified Nano process white particle diameter is 100-250nm.D50 is 200nm.
Embodiment 5
Add 800kg technical grade lightweight barium carbonate and 3200kg water at 5 cubical reactors, solid content is 20%.In reactor, add 50kg hydrochloric acid (31%).The reactor stirring velocity is controlled at 750r/min, adds the 400kg vitriol oil (concentration 98%) to reaction again and finishes.Reaction end pH is controlled at 5.7.With filter screen will react good barium sulfate slurry with the filtration of 1000 mesh filter screens after, obtain the 960Kg process white.The tetrabutyl titanate properties-correcting agent that adds 20kg in process white carries out surface treatment, joining day was controlled at 60 minutes, and the temperature during modification is controlled at 98 ℃, dewaters with pressure filter then, use flash dryer, the automatic packing machine packing forms modified Nano process white powder.Gained modified Nano process white particle diameter is 30-50nm.
Embodiment 6
Add 500kg technical grade lightweight barium carbonate and 3500kg water at 5 cubical reactors, solid content is 12.5%.In reactor, add 20kg acetic acid.The reactor stirring velocity is controlled at 600r/min, at the uniform velocity added the 250kg vitriol oil (concentration 98%) to reaction again and finish in 50 minutes.Reaction end pH is controlled at 5.5.With filter screen will react good barium sulfate slurry with the filtration of 1000 mesh filter screens after, obtain the 600Kg process white.The sodium silicate aqueous solution of weight content 20% in process white, water glass weight 12kg is that 10% dilute sulphuric acid accent terminal point pH is 7 with concentration then.The sodium silicate aqueous solution joining day was controlled at 90 minutes.Temperature during modification is controlled at 75 ℃, with the pressure filter dehydration, uses flash dryer then, and the automatic packing machine packing forms modified Nano process white powder.Gained modified Nano process white particle diameter is 100-250nm.
Barium carbonate among the embodiment 1-6 can adopt hydrated barta to replace.
The size distribution Electronic Speculum figure of the modified nano-barium sulfate of embodiment 1-6 preparation is shown in Fig. 3-8.
From table 1, table 2 and Fig. 1 to Fig. 8 as can be seen, the size distribution of the modified nano-barium sulfate of the present invention's preparation is even.Minimum grain size can reach 30nm, and maximum particle diameter also has only 300nm.
From Fig. 3 to Fig. 8 as can be seen, the modified nano-barium sulfate good dispersity of the present invention's preparation.Do not have obviously and reunite the particle clear-cut.
The preparation of master batch
Embodiment 7
Get the nano modification process white 400g (particle diameter D50 is 57nm) of embodiment 1 preparation, high density polyethylene(HDPE) 75g, polyethylene wax 15g, EBS (ethylene bis stearamide) 5g, maleic anhydride 1g, dicumyl peroxide (DCP) 0.2g is added to high-speed mixer in regular turn with above-mentioned materials, after stirring with high-speed mixer.150 ℃ service temperature, be that the twin screw extruder of 200r/min is extruded through rotating speed, air-cooled granulation is prepared from master batch.
Embodiment 8
Get the nano modification process white 374.5g (particle diameter D50 is 68nm) of embodiment 2 preparations, high density polyethylene(HDPE) 95g, polyethylene wax 25g, maleic anhydride 5g, di-t-butyl peroxide (DTBP) 0.5g is added to high-speed mixer in regular turn with above-mentioned materials.After stirring with high-speed mixer, be that the twin screw extruder of 200r/min is extruded 190 ℃ service temperatures, through rotating speed, air-cooled granulation is prepared from master batch.
Embodiment 9
Get embodiment 1 nano modification process white 400g (particle diameter D50 is 57nm), high density polyethylene(HDPE) 65g, EBS12.5g, maleic anhydride 10g, di-cyclohexylperoxy dicarbonate 0.25g is added to high-speed mixer in regular turn with above-mentioned materials.After stirring with high-speed mixer, be that the twin screw extruder of 300r/min is extruded 150 ℃ service temperatures, through rotating speed, air-cooled granulation is prepared from master batch.
Get embodiment 2 nano modification process white 400g (particle diameter D50 is 68nm), linear polyethylene 75g, polyethylene wax 10g, EBS (ethylene bis stearamide) 5g, Zinic stearas 5g, maleic anhydride 1g, dicumyl peroxide (DCP) 0.2g is added to high-speed mixer in regular turn with above-mentioned materials.After stirring with high-speed mixer, be that the twin screw extruder of 450r/min is extruded 145 ℃ service temperatures, through rotating speed, air-cooled granulation is prepared from master batch.
Embodiment 11
Get embodiment 5 nano modification process white 438.8g (particle diameter D50 is 42nm), linear polyethylene 50g, EBS (ethylene bis stearamide) 5g, Zinic stearas 5g, maleic anhydride 1g, dicumyl peroxide (DCP) 0.2g is added to high-speed mixer in regular turn with above-mentioned materials.After stirring with high-speed mixer, be that the twin screw extruder of 500r/min is extruded 165 ℃ service temperatures, through rotating speed, air-cooled granulation is prepared from master batch.
Embodiment 12
Get the nano modification process white 394.5g (particle diameter D50 is 57nm) of embodiment 1 preparation, linear polyethylene 85g, Zinic stearas 10g, maleic anhydride 10g, two (2-phenyl ethoxy) the ester 0.5g of peroxy dicarbonate.Above-mentioned materials is added to high-speed mixer in regular turn.After stirring with high-speed mixer, be that the twin screw extruder of 150r/min is extruded 125 ℃ service temperatures, through rotating speed, air-cooled granulation is prepared from master batch.
Embodiment 13
Get embodiment 2 nano modification process white 407.22g (particle diameter D50 is 68nm), linear polyethylene 75g, polyethylene wax 15g, maleic anhydride 2.5g, dibenzoyl peroxide 0.28g is added to high-speed mixer in regular turn with above-mentioned materials.After stirring with high-speed mixer, be that the twin screw extruder of 250r/min is extruded 180 ℃ service temperatures, through rotating speed, air-cooled granulation is prepared from master batch.
Embodiment 14
Get embodiment 2 nano modification process white 309.22g (particle diameter D50 is 68nm), linear polyethylene 125g, polyethylene wax 63g, maleic anhydride 25g, dibenzoyl peroxide 2.5g is added to high-speed mixer in regular turn with above-mentioned materials.After stirring with high-speed mixer, be that the twin screw extruder of 350r/min is extruded 160 ℃ service temperatures, through rotating speed, air-cooled granulation is prepared from master batch.
Embodiment 15
Get the nano modification process white 310g (particle diameter D50 is 57nm) of embodiment 1 preparation, linear polyethylene 100g, Zinic stearas 50g, maleic anhydride 35g, two (2-phenyl ethoxy) the ester 5g of peroxy dicarbonate.Above-mentioned materials is added to high-speed mixer in regular turn.After stirring with high-speed mixer, be that the twin screw extruder of 300r/min is extruded 170 ℃ service temperatures, through rotating speed, air-cooled granulation is prepared from master batch.
Embodiment 16
Get the nano modification process white 409.5g (particle diameter D50 is 57nm) of embodiment 1 preparation, linear polyethylene 50g, Zinic stearas 35g, maleic anhydride 5g, two (2-phenyl ethoxy) the ester 0.5g of peroxy dicarbonate.Above-mentioned materials is added to high-speed mixer in regular turn.After stirring with high-speed mixer, be that the twin screw extruder of 200r/min is extruded 120 ℃ service temperatures, through rotating speed, air-cooled granulation is prepared from master batch.
Embodiment 17
Get embodiment 5 nano modification process white 404.7g (particle diameter D50 is 42nm), linear polyethylene 80g, EBS (ethylene bis stearamide) 10g, Zinic stearas 3g, maleic anhydride 0.5g, dicumyl peroxide (DCP) 1.8g is added to high-speed mixer in regular turn with above-mentioned materials.After stirring with high-speed mixer, be that the twin screw extruder of 200r/min is extruded 195 ℃ service temperatures, through rotating speed, air-cooled granulation is prepared from master batch.
Embodiment 18
Get embodiment 5 nano modification process white 463.8g (particle diameter D50 is 42nm), linear polyethylene 25g, EBS (ethylene bis stearamide) 5g, Zinic stearas 5g, vinylformic acid 1g, dicumyl peroxide (DCP) 0.2g.Above-mentioned materials is added to high-speed mixer in regular turn.After stirring with high-speed mixer, be that the twin screw extruder of 400r/min is extruded 150 ℃ service temperatures, through rotating speed, air-cooled granulation is prepared from master batch.
Embodiment 19
Get embodiment 5 nano modification process white 338.8g (particle diameter D50 is 42nm), linear polyethylene 150g, EBS (ethylene bis stearamide) 7g, Zinic stearas 3g, butyl acrylate 1g, dibenzoyl peroxide 0.2g.Above-mentioned materials is added to high-speed mixer in regular turn.After stirring with high-speed mixer, be that the twin screw extruder of 200r/min is extruded 155 ℃ service temperatures, through rotating speed, air-cooled granulation is prepared from master batch.
Get the nano modification process white 354.5g (particle diameter D50 is 57nm) of embodiment 1 preparation, linear polyethylene 125g, polyethylene wax 10g, vinylbenzene 10g, two (2-phenyl ethoxy) the ester 0.5g of peroxy dicarbonate.Above-mentioned materials is added to high-speed mixer in regular turn.After stirring with high-speed mixer, be that the twin screw extruder of 200r/min is extruded 135 ℃ service temperatures, through rotating speed, air-cooled granulation is prepared from master batch.
Among the embodiment 7-20, the speed of high-speed mixer can be determined according to practical situation.
The preparation of chemical fibre
Embodiment 21
Get high density polyethylene(HDPE) 450g, get the prepared master batch 50g of embodiment 7, it is injection molded with injection moulding machine to mix the back.230 ℃ of injection moulding machine melt temperatures, 40 ℃ of die temperatures, the about 50MPa of injection pressure.Get injection molded Mechanics Performance Testing standard batten and carry out Mechanics Performance Testing.10000 times of chemical fibre section Electronic Speculum figure of present embodiment preparation as shown in Figure 9.As can be seen from Figure 9, the chemical fibre of the present invention's preparation has advantages such as powder is uniformly dispersed, avidity is good.
Embodiment 22
Get high density polyethylene(HDPE) 400g, get the prepared master batch 100g of embodiment 7, it is injection molded with injection moulding machine to mix the back.200 ℃ of injection moulding machine melt temperatures, 50 ℃ of die temperatures, the about 100MPa of injection pressure.Get injection molded Mechanics Performance Testing standard batten and carry out Mechanics Performance Testing.
Embodiment 23
Get high density polyethylene(HDPE) 350g, get the prepared master batch 150g of embodiment 7, it is injection molded with injection moulding machine to mix the back.185 ℃ of injection moulding machine melt temperatures, about 90 ℃ of die temperature, the about 70MPa of injection pressure.Get injection molded Mechanics Performance Testing standard batten and carry out Mechanics Performance Testing.
Embodiment 24
Get high density polyethylene(HDPE) 300g, get the prepared master batch 200g of embodiment 7, it is injection molded with injection moulding machine to mix the back.210 ℃ of injection moulding machine melt temperatures, about 105 ℃ of die temperature, the about 90MPa of injection pressure.Get injection molded Mechanics Performance Testing standard batten and carry out Mechanics Performance Testing.
Embodiment 25
Line taking property polyethylene 450g gets the prepared master batch 50g of embodiment 10, and it is injection molded with injection moulding machine to mix the back.Injection moulding machine melt temperature scope between 190 ℃, about 70 ℃ of die temperature, injection pressure 80MPa.Get injection molded Mechanics Performance Testing standard batten and carry out Mechanics Performance Testing.
Embodiment 26
Line taking property polyethylene 400g gets embodiment 10 prepared master batch 100g, mixes the back and uses injection moulding machine injection molded.195 ℃ of injection moulding machine melt temperatures, about 55 ℃ of die temperature, the about 65MPa of injection pressure.Get injection molded Mechanics Performance Testing standard batten and carry out Mechanics Performance Testing.
Embodiment 27
Line taking property polyethylene 350g gets embodiment 10 prepared master batch 150g, mixes the back and uses injection moulding machine injection molded.225 ℃ of injection moulding machine melt temperatures, 110 ℃ of die temperatures, the about 50MPa of injection pressure.Get injection molded Mechanics Performance Testing standard batten and carry out Mechanics Performance Testing.
Embodiment 28
Line taking property polyethylene 300g gets the prepared master batch 200g of embodiment 10, and it is injection molded with injection moulding machine to mix the back.200 ℃ of injection moulding machine melt temperatures, about 60 ℃ of die temperature, the about 70MPa of injection pressure.Get injection molded Mechanics Performance Testing standard batten and carry out Mechanics Performance Testing.
The The performance test results that the chemical fibre of embodiment 21 to 24 preparations reaches the chemical fibre that does not add modification sees Table 3
Table 3
| Embodiment | Master batch content | High density polyethylene(HDPE) content | Tensile strength (MPa) | Shock strength (KJ/m2) | Elongation at break % |
| 0 | 100％ | 24.1 | 17.2 | 569.00％ | |
| 21 | 10％ | 90％ | 28.3 | 18.5 | 664.00％ |
| 22 | 20％ | 80％ | 29.6 | 18.9 | 692.00％ |
| 23 | 30％ | 70％ | 31.1 | 20.3 | 545.00％ |
| 24 | 40％ | 60％ | 28.8 | 20.8 | 520.00％ |
The The performance test results that the chemical fibre of embodiment 25 to 28 preparations reaches the chemical fibre that does not add modified nano-barium sulfate sees Table 4
Table 4
| Embodiment | Master batch content | Linear polyethylene content | Tensile strength (MPa) | Disconnected shock strength (KJ/m2) | Elongation at break % |
| 0 | 100％ | 20.5 | 23.2 | 602.00％ | |
| 25 | 10％ | 90％ | 25.6 | 25.5 | 750.00％ |
| 26 | 20％ | 80％ | 26.2 | 26.7 | 782.00％ |
| 27 | 30％ | 70％ | 25..8 | 28.5 | 724.00％ |
| 28 | 40％ | 60％ | 24.5 | 28.8 | 540.00％ |
Influence the results are shown in Table 5 to the chemical fibre production cost to use master batch to produce chemical fibre.
Table 5
| Embodiment | Master batch content | High density polyethylene(HDPE) content | Linear polyethylene content | Total cost (ton/unit) |
| 0 | 100％ | 13000 | ||
| 21 | 10％ | 90％ | 12200 | |
| 22 | 20％ | 80％ | 11400 | |
| 23 | 30％ | 70％ | 10600 | |
| 24 | 40％ | 60％ | 9800 | |
| 0 | 100％ | 13000 | ||
| 25 | 10％ | 90％ | 12200 | |
| 26 | 20％ | 80％ | 11400 | |
| 27 | 30％ | 70％ | 10600 | |
| 28 | 40％ | 60％ | 9800 |
From table 1～3 as can be seen, the polyethylene that adds master batch has almost improved tensile strength and shock strength simultaneously, and addition can also improve poly elongation at break below 20%.And its cost of manufacture also can reduce significantly.Believe raising polyethylene range of application in chemical fibre that these will be a large amount of, particularly aspect the high-intensity chemical fibre use of some needs.
The preparation of film
Embodiment 29
Line taking property polyethylene (LLDPE7042) 3800g, high-pressure polyethylene (LDPE2426H) 950g gets the master batch 250g of embodiment 7, after mixing, carries out blown film with inflation film manufacturing machine, and the length-to-diameter ratio of the screw rod of the inflation film manufacturing machine of employing is 1: 28, and roller bar rotating speed is 40r/min.Barrel zone temperature: the feed section is that 170-175 ℃, metering zone are that 160-165 ℃, head temperature are: 170-175 ℃.Blow-up ratio is 2.0 during step (2) blown film, blows out the film of 5um, 10um, three kinds of thickness of 50um respectively.14000 times of Electronic Speculum figure of thin-membrane section of present embodiment preparation as shown in figure 10.As can be seen from Figure 10, the film of the present invention's preparation has advantages such as powder is uniformly dispersed, avidity is good.
Line taking property polyethylene (LLDPE7042) 3600g, high-pressure polyethylene (LDPE2426H) 900g, get the master batch 500g of embodiment 7 preparations, after mixing, carry out blown film with inflation film manufacturing machine, the length-to-diameter ratio of the screw rod of the inflation film manufacturing machine that adopts is 1: 28, and roller bar rotating speed is 40r/min, barrel zone temperature: the feed section is that 170-175 ℃, metering zone are that 160-165 ℃, head temperature are: 170-175 ℃.Blow-up ratio is 2.0 during step (2) blown film, blows out the film of 5um, 10um, three kinds of thickness of 50um respectively.
Embodiment 31
Line taking property polyethylene (LLDPE7042) 3200g, high-pressure polyethylene (LDPE2426H) 800g, get the master batch 1000g of embodiment 7 preparations, after mixing, carry out blown film with inflation film manufacturing machine, the length-to-diameter ratio of the screw rod of the inflation film manufacturing machine that adopts is 1: 28, and roller bar rotating speed is 4040r/min, barrel zone temperature: the feed section is that 170-175 ℃, metering zone are that 160-165 ℃, head temperature are: 170-175 ℃.Blow-up ratio is 2.0 during step (2) blown film, blows out the film of 5um, 10um, three kinds of thickness of 50um respectively.
Embodiment 32
Line taking property polyethylene (LLDPE7042) 2800g, high-pressure polyethylene (LDPE2426H) 700g, get the master batch 1500g of embodiment 8 preparations, after mixing, carry out blown film with inflation film manufacturing machine, the length-to-diameter ratio of the screw rod of the inflation film manufacturing machine that adopts is 1: 28, and roller bar rotating speed is 4040r/min, barrel zone temperature: the feed section is that 170-175 ℃, metering zone are that 160-165 ℃, head temperature are: 170-175 ℃.Blow-up ratio is 2.0 during step (2) blown film, blows out the film of 5um, 10um, three kinds of thickness of 50um respectively.
Embodiment 33
Line taking property polyethylene (LLDPE7042) 2400g, high-pressure polyethylene (LDPE2426H) 600g, get the master batch 2000g of embodiment 8 preparations, after mixing, carry out blown film with inflation film manufacturing machine, the length-to-diameter ratio of the screw rod of the inflation film manufacturing machine that adopts is 1: 28, and roller bar rotating speed is 4040r/min, barrel zone temperature: the feed section is that 170-175 ℃, metering zone are that 160-165 ℃, head temperature are: 170-175 ℃.Blow-up ratio is 2.0 during step (2) blown film, blows out the film of 5um, 10um, three kinds of thickness of 50um respectively.
Embodiment 34
Line taking property polyethylene (LLDPE7042) 4000g, high-pressure polyethylene (LDPE2426H) 1000g, after mixing, carry out blown film with inflation film manufacturing machine, the length-to-diameter ratio of the screw rod of the inflation film manufacturing machine that adopts is 1: 28, roller bar rotating speed is 4040r/min, barrel zone temperature: the feed section is that 170-175 ℃, metering zone are that 160-165 ℃, head temperature are: 170-175 ℃.Blow-up ratio is 2.0 during step (2) blown film, blows out the film of 5um, 10um, three kinds of thickness of 50um respectively.
Table 1 adds the film transmittance contrast behind the barium sulfate master batch
| Embodiment | 34 | 29 | 30 | 31 | 32 | 33 |
| Barium sulfate master batch content | 0 | 5％ | 10％ | 20％ | 30％ | 40％ |
| Film thickness 5um transmittance | 94 | 94 | 93 | 92 | 90 | 87 |
| Film thickness 1um transmittance | 93 | 93 | 92 | 90 | 88 | 85 |
| Film thickness 50um transmittance | 92 | 91 | 88 | 85 | 80 | 76 |
Table 2 adds the thin film mechanical performance contrast behind the barium sulfate master batch
Table 3 adds the weather resistance contrast of barium sulfate master batch rear film
Table 4 adds the cost contrast of barium sulfate master batch rear film
| Embodiment | 34 | 29 | 30 | 31 | 32 | 33 |
| Barium sulfate master batch content | 0 | 5％ | 10％ | 20％ | 30％ | 40％ |
| Cost (unit) | 11000 | 10700 | 10400 | 9800 | 9200 | 8600 |
Embodiment among the present invention only is used for that the present invention will be described, does not constitute the restriction to the claim scope, and other substituting of being equal in fact that those skilled in that art can expect are all in protection domain of the present invention.
Claims (6)
1. the preparation method of modified Nano process white, it is characterized in that, described modified Nano process white is that process white uses modifier modification to form, and described properties-correcting agent is selected from one or more in silicate, aluminate, phosphoric acid salt, polyoxyethylene glycol, polyvinyl alcohol, stearate, lauroleate, silane coupling agent, titanate coupling agent, the aluminate coupling agent.
2. the preparation method of modified Nano process white according to claim 1 is characterized in that, the particle diameter of described modified Nano process white is 10nm～900nm.
3. the preparation method of modified Nano process white according to claim 1, it is characterized in that, described preparation method comprises step: the solution that barium carbonate or hydrated barta water is made into solid content weight content 5%～30%, the catalyzer that adds solution weight 0.01%～5%, be added dropwise to the vitriol oil that can make barium carbonate or hydrated barta complete reaction, reaction gets process white after finishing after-filtration, the modifier solution that adds properties-correcting agent or properties-correcting agent weight content 1%～25% carries out surface treatment to process white, properties-correcting agent weight is 0.2%～5% of process white weight, and the back dehydration is handled in modification, drying forms the modified Nano process white.
4. the preparation method of modified Nano process white according to claim 3 is characterized in that, described catalyzer is selected from acidity and is better than the acid of carbonic acid or their water-soluble salt.
5. the preparation method of modified Nano process white according to claim 3 is characterized in that, during to the barium sulfate modification, carries out modification under 50 ℃～100 ℃.
6. the preparation method of modified Nano process white according to claim 3 is characterized in that, the modifier solution joining day is 10～100 minutes.
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| CN102874859A (en) * | 2012-10-15 | 2013-01-16 | 贵州宏凯化工有限公司 | Process for preparing modified nano barium sulfate |
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| CN109279640B (en) * | 2018-11-27 | 2020-06-23 | 清华大学 | Barium sulfate material and preparation method thereof |
| CN109279640A (en) * | 2018-11-27 | 2019-01-29 | 清华大学 | A kind of barium sulfate material and preparation method thereof |
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Application publication date: 20110119 |