CN100489024C - Functional white color masterbatch and its preparation process and use - Google Patents
Functional white color masterbatch and its preparation process and use Download PDFInfo
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Abstract
The invention discloses a white masterbatch which consisits of skeleton inorganic powder, titanium dioxide, auxiliary agent and carrier resin, in which the said auxiliary agent consists of disperser, coupling agent and process agent. The white masterbatch prepared by this invention also has reinforcing and toughening functionalities except has the same whitening function with the common white masterbatch. Compared with the common white masterbatch which has equal whitening function, the titanium dioxide content is just 1/2-1/4 of the common white masterbatch, which largely saves the consumption of the titanium dioxide and distinctively reduces the cost of products. The comprehensive dynamic behavior of the products prepared by the white masterbatch of this invention can increase by 3-8 % compared with the products prepared by the common white masterbatch with the same steming amount.
Description
Technical field
The present invention relates to the Masterbatch that field of plastics processing uses, relate in particular to white master batch, it is used for plastics are carried out painted and modification.
Background technology
It is painted often to use Masterbatch that it is carried out in the plastics-production processing, and wherein white master batch is most important, most widely used a kind of Masterbatch.It is female that white master batch is called for short white, made by tinting material, carrier and dispersion agent at least usually, and used tinting material is generally titanium dioxide.Existing market is sold the ordinary white mother and after directly titanium dioxide and dispersion agent coupling agent, processing aid and vector resin being mixed by a certain percentage, is formed through the twin screw extruder granulation.Titanium dioxide content is more than 60% among the gained white mother, thereby because the higher cost that causes of expensive titanium dioxide content is very high; And since titanium dioxide to assemble agglomerating its dispersion effect that causes bad, make that the utilization ratio of titanium dioxide is low among the white mother.For example application number is that 02135591.6 Chinese patent application discloses the female technology of a kind of preparation high density polyolefins white, it mixes by pigment, partly plastic auxiliary agent and vector resin are added in the super mixer, add coupling agent and whiteruss mixture then and stir, it is female to extrude preparation white through twin screw extruder then.Pigment (titanium dioxide) content is 50-80wt% among the gained white mother.
Titanium dioxide is according to different anatase titanium dioxide and rutile-type two classes of dividing of preparation technology, its particle diameter is usually in the scope of 0.2-0.4 μ m, particle diameter so little inorganic powder sub-surface can be very big, be difficult to exist with the form of primary partical, but with tens or the form of a hundreds of primary partical reunion exist.In the female technology of preparation white that generally adopts at present, the titanium dioxide agglomerating particles can't be broken up, therefore titanium dioxide normally exists down with agglomerate particle form among the prepared white mother.When gained white mother is applied in the process of plastics, titanium dioxide is that the form with agglomerating particles is dispersed in the goods, can't bring into play the whitening effect of titanium dioxide fully.The chemical formula of titanium dioxide is: TiO
2, titanium is valuable rare metal, tellurian reserves are very limited.From titanium ore, refine TiO
2Need a large amount of vitriol oils, produce large amount of sewage, contaminate environment not only has higher economic interests so improve the utilization ratio of titanium dioxide, and the good social benefit is also arranged.
The ordinary white mother who produces is only brightened function at present, and addition also can reduce the intensity of plastics for a long time.
In view of the foregoing, expectation obtains and can brighten and can be female to the white of its modification plastics, and titanium dioxide utilization ratio height, good dispersity, with low cost among the white mother.
Summary of the invention
The object of the present invention is to provide the white that can brighten and can modification female, wherein titanium dioxide utilization ratio height, good dispersity, with low cost.
Another object of the present invention is to provide above-mentioned white female preparation method.
The objective of the invention is to be achieved through the following technical solutions.
White mother provided by the invention comprises skeleton inorganic powder, titanium dioxide, auxiliary agent and vector resin, particularly, preferably include following components by weight ratio: 20-65 parts of skeleton inorganic powder, 20-60 parts of titanium dioxides, 3-15 parts of the gross weights of various auxiliary agents, 10-20 parts of vector resins; More preferably comprise: 40-53 parts of skeleton inorganic powder, 26-34 parts of titanium dioxides, 5-10 parts of the gross weights of various auxiliary agents, 10-15 parts of vector resins.
Wherein 1. auxiliary agent mainly comprises dispersion agent, 2. coupling agent and 3. processing aid three classes.
The present invention also provides above-mentioned white female preparation method, this method comprises: earlier with titanium dioxide agglomerating particles high shear force grinding machine, under the dispersion agent effect, fully break up, and be coated on the surface of skeleton inorganic powder particle, add coupling agent, processing aid and vector resin more successively, in grinding machine, mix, after the twin screw extruder granulation form.
Particularly, above-mentioned preparation method comprises:
1. titanium dioxide, skeleton inorganic powder and dispersion agent being joined by weight proportion intermittent type has in the high shear force grinding machine, for example in ball mill, vibrating mill or the centrifugal vibrating grinder, ground 6-10 minutes, when treating that temperature of charge rises to 80-85 ℃, add coupling agent, continue to grind 4-6 minutes, add processing aid and vector resin again, ground 2-4 minutes, this moment, temperature of charge can reach 110-120 ℃, discharging again;
2. be 48: 1 twin screw extruder granulation with length-to-diameter ratio, make and have the functional white master batch of strengthening and toughening.
Below describe the present invention.
Titanium dioxide:
Among the present invention, used titanium dioxide (TiO
2) be the mixture of any one or two kinds in two kinds of anatase titanium dioxide and the rutile-types, its particle diameter is 0.2-0.4 μ m (a primary partical particle diameter).
Skeleton inorganic powder:
The maximum characteristics of the white master batch of the present invention's preparation have been to improve the utilization ratio of titanium dioxide.This mainly be by select particle diameter much larger than the skeleton inorganic powder of titanium dioxide particle diameter as nuclear, under the effect of dispersion agent, utilize mechanical energy, the collision that is high shear force grinding machine (for example ball mill, vibrating mill or centrifugal vibrating grinder) medium ball is ground, make the titanium dioxide agglomerating particles be broken up and be adsorbed onto the skeleton inorganic powder particle surface, thereby play the pigmentation of titanium dioxide with the form of electrostatic force or chemical bonding force.When being applied to white mother of the present invention in the plastics, the particle of the skeleton inorganic powder of coated titanium white powder is dispersed in the plastics, and what performance and titanium dioxide were same brightens colouring function.Because the agglomerating particles of titanium dioxide is broken up, titanium dioxide is attached on the skeleton inorganic powder with the dispersive primary particle, avoided the clustering phenomena of titanium dioxide, like this then greatly improved the utilization ratio of titanium dioxide, and brighten uniform coloring, and used skeleton inorganic powder all is resourceful cheap raw materials, can reduce the female production cost of white significantly.
Used skeleton inorganic powder normally has the inorganic powder of microtextures such as the porous network shape of strengthening and toughening function, fibrous or sheet structure, for example zeolite powder, calcined kaolin, wollastonite powder, talcum powder, tremolite powder, mica powder or polynite powder etc., can use in these materials one or more, in order to make skeleton inorganic powder and titanium dioxide particle diameter coupling, make titanium dioxide well to be coated on the skeleton inorganic powder, the particle diameter of skeleton inorganic powder is preferably 5-15 μ m.Because the skeleton inorganic powder that is adopted in the invention, zeolite powder for example, calcined kaolin, wollastonite powder, talcum powder, tremolite powder, mica powder and polynite powder etc., its microtexture or be the vesicular network structure, filamentary structure or sheet structure, owing to the structural performance of skeleton inorganic powder own has good ductility, physical property such as toughness and intensity, when the skeleton inorganic powder that will have above-mentioned special construction is filled in the plastics, it plays the strengthening and toughening effect, make that prepared white is female also to have a good strengthening and toughening performance, this is that common white is female not available.In order to obtain better strengthening and toughening effect, the mixture that can use above-mentioned substance is as skeleton inorganic powder, mixes when composite at multiple material, and it can any weight proportion mixes and be not particularly limited.
Auxiliary agent:
Employed auxiliary agent mainly comprises following three classes among the present invention: 1. dispersion agent: for example be selected from whiteruss, solid paraffin, macromolecule wax (preferred 2000≤molecular weight≤20000), the silicone oil one or more, its weight proportion is 0.5-2 parts, and the effect of dispersion agent is the depolymerization that promotes the titanium dioxide agglomerating particles; 2. coupling agent: for example be selected from aluminic acid ester, titanic acid ester, aluminium/titanium composite coupler, acid phosphorous acid ester, silane coupling agent and the rare-earth coupling agent one kind of multiple, its weight proportion is 1-3 parts, the effect of coupling agent is that the skeleton inorganic powder particle surface that has to the coated titanium white powder carries out activation treatment, be beneficial to it and in vector resin or plastics, disperse, and form stronger avidity; 3. processing aid: for example be selected from stearic acid and salt thereof (preferred as alkali salt), fatty acyl amide compound (the fatty amide compound that wherein preferred C12-C18 acid forms), polyethylene wax, Poly Propylene Wax and the Microcrystalline Wax one or more, its weight proportion is 0.5-10 parts, the effect of processing aid is the frictional force that reduces in the granulation process, increase Flow of Goods and Materials, cut down the consumption of energy.
Vector resin:
Generally speaking, the female used vector resin of preparation white promptly can be used for the present invention.Used vector resin is preferably the big resin of melt speed among the present invention, for example is selected from polyethylene, polypropylene, polystyrene, ethene-acetate ethylene copolymer (EVA), ethene one acrylic copolymer (EAA), K resin and the nylon-12 one or more.
The employed raw material of the invention described above all can commercially availablely be buied.
The strengthening and toughening functional white color master batch of the present invention's preparation brightens the function equally except that having with the ordinary white master batch, also has the strengthening and toughening function.Compare with the ordinary white master batch of equal whitening effect, its titanium dioxide content only is 1/2-1/4 of ordinary white master batch, has saved the consumption of titanium dioxide greatly, significantly reduces product cost.Under the situation of identical loading level, use the female comprehensive mechanical property of filling resulting product of the present invention's white can improve 3-8% than the goods that use the ordinary white master batch.
Embodiment
Further describe the present invention below in conjunction with embodiment; but what those skilled in the art should understand that is; embodiment is used to illustrate the present invention's technical scheme required for protection; claimed scope is not produced any influence, the equivalence of being done under conceiving mental condition without prejudice to the present invention is replaced or is changed and all belongs to protection scope of the present invention.
Embodiment 1
Take by weighing the 20Kg anatase thpe white powder, the 40Kg whiteness is greater than 92%, and median size is zeolite powder and the 0.4Kg white oil of 10 μ m, joins together in the 100 liter ball mills, ground 8 minutes, temperature of charge reaches 85 ℃, adds the 1.6Kg titanate coupling agent, continues to grind 5 minutes, add the 0.8Kg Magnesium Stearate again, 1.2Kg polyethylene wax and 12Kg polyethylene ground 3 minutes again, temperature of charge reaches 115 ℃ of blowings.With length-to-diameter ratio is 48: 1 twin screw extruder granulation, makes strengthening and toughening functional white color master batch.
Polyethylene is pressed 95:5 weight ratio preparation standard batten with the white mother, measures its mechanical property and whiteness, result such as following table:
| Performance | TiO in the goods 2Content/% | Whiteness/% | Tensile strength/MPa | Elongation at break/% | Notched Izod impact strength/KJ/m 2 | Flexural strength/Kg/cm 2 |
| Use ordinary white mother | 3.5 | 98 | 165 | 260 | 12.6 | 362 |
| Use embodiment 1 white female | 1.25 | 97.8 | 172 | 278 | 13.2 | 375 |
Annotate: TiO among the ordinary white mother
2Content is 70%
TiO among the present invention's white mother
2Content is 25%
Embodiment 2
Take by weighing 30Kg rutile titanium white powder, the 20Kg whiteness is greater than 90%, median size is 12.5 μ m tremolite powders, the 16Kg whiteness is greater than 92%, and median size is the talcum powder of 15 μ m, 2Kg diethyl silicone oil, join in the centrifugal vibrations grinding machine of 100 liters, ground 6 minutes, and after temperature of charge reaches 80 ℃, added 3Kg aluminium/titanium composite coupler, continue to grind 4 minutes, add the 0.8Kg stearic acid more successively, 0.8Kg polyethylene wax, 0.8Kg oleylamide, the 20Kg polypropylene, ground 2 minutes, temperature of charge reaches 120 ℃, discharging again.With length-to-diameter ratio is 48: 1 twin screw extruder granulation, makes strengthening and toughening functional white color master batch.
Polyethylene is pressed 95:5 weight ratio preparation standard batten with the white mother, measures its mechanical property and whiteness, result such as following table:
| Performance | TiO in the goods 2Content/% | Whiteness/% | Tensile strength/MPa | Elongation at break/% | Notched Izod impact strength/KJ/m 2 | Flexural strength/Kg/cm 2 |
| Use ordinary white mother | 3.5 | 97.8 | 264 | 220 | 16.5 | 340 |
| Use embodiment 2 whites female | 1.65 | 98.2 | 272 | 232 | 16.9 | 352 |
Annotate: TiO among the ordinary white mother
2Content is 70%
TiO among the present invention's white mother
2Content is 33%
Embodiment 3
Take by weighing 30Kg anatase thpe white powder and 30Kg Rutile type Titanium Dioxide, the 65Kg whiteness is greater than 92%, median size is zeolite powder and the 2Kg white oil of 10 μ m, joins together in the 100 liter ball mills, grinds 10 minutes, temperature of charge reaches 85 ℃, add 3Kg aluminic acid ester, continue to grind 5 minutes, add 8Kg calcium stearate, 2Kg Poly Propylene Wax and 5Kg ethene one acrylic copolymer (EAA) and 15Kg polyethylene again, ground 3 minutes, temperature of charge reaches 115 ℃ of blowings again.With length-to-diameter ratio is 48: 1 twin screw extruder granulation, makes strengthening and toughening functional white color master batch.
Polyethylene is pressed 95:5 weight ratio preparation standard batten with the white mother, measures its mechanical property and whiteness, result such as following table:
| Performance | TiO in the goods 2Content/% | Whiteness/% | Tensile strength/MPa | Elongation at break/% | Notched Izod impact strength/KJ/m 2 | Flexural strength/Kg/cm 2 |
| Use ordinary white mother | 3.5 | 98 | 185 | 230 | 13.6 | 342 |
| Use embodiment 3 whites female | 1.4 | 98 | 194 | 259 | 13.9 | 355 |
Annotate: TiO among the ordinary white mother
2Content is 70%
TiO among the present invention's white mother
2Content is 25%
Embodiment 4
Take by weighing the 34Kg Rutile type Titanium Dioxide, the 50Kg whiteness is greater than 90%, and median size is mica powder and the 1Kg silicone oil of 8 μ m, joins together in the 100 liter ball mills, ground 6 minutes, temperature of charge reaches 80 ℃, adds the 2Kg silane coupling agent, continues to grind 6 minutes, add the 4Kg Magnesium Stearate again, 1Kg Poly Propylene Wax and 16KgK resin ground 4 minutes again, and temperature of charge reaches 120 ℃ of blowings.With length-to-diameter ratio is 48: 1 twin screw extruder granulation, makes strengthening and toughening functional white color master batch.
Polystyrene is pressed 95:5 weight ratio preparation standard batten with the white mother, measures its mechanical property and whiteness, result such as following table:
| Performance | TiO in the goods 2Content/% | Whiteness/% | Tensile strength/MPa | Elongation at break/% | Notched Izod impact strength/KJ/m 2 | Flexural strength/Kg/cm 2 |
| Use ordinary white mother | 3.5 | 98 | 190 | 240 | 14.7 | 358 |
| Use embodiment 4 whites female | 1.35 | 97.8 | 199 | 252 | 15.2 | 370 |
Annotate: TiO among the ordinary white mother
2Content is 70%
TiO among the present invention's white mother
2Content is 25%
Claims (9)
1, a kind of white is female, comprises skeleton inorganic powder, titanium dioxide, auxiliary agent and vector resin, and the weight proportion of each composition is: 20-65 parts of skeleton inorganic powder, and 20-60 parts of titanium dioxides, 3-15 parts of the gross weights of various auxiliary agents, 10-20 parts of vector resins,
Wherein, described skeleton inorganic powder is one or more in zeolite powder, calcined kaolin, wollastonite powder, talcum powder, tremolite powder, mica powder and the polynite powder.
2, white according to claim 1 is female, it is characterized in that it comprises following components by weight ratio: skeleton inorganic powder 40-53 part, 26-34 parts of titanium dioxides, 5-10 parts of the gross weights of various auxiliary agents, 10-15 parts of vector resins.
3, white according to claim 1 is female, it is characterized in that, described titanium dioxide is the mixture of any one or two kinds in two kinds of anatase titanium dioxide and the rutile-types.
4, white according to claim 1 is female, it is characterized in that the particle diameter of described skeleton inorganic powder is 5-15 μ m.
5, white according to claim 1 is female, it is characterized in that, described auxiliary agent is by dispersion agent, coupling agent and processing aid are formed, wherein dispersion agent is for being selected from whiteruss, solid paraffin, in macromolecule wax and the silicone oil one or more, its weight proportion is 0.5-2 parts, coupling agent is for being selected from the aluminic acid ester, titanic acid ester, aluminium/titanium composite coupler, the acid phosphorous acid ester, in silane coupling agent and the rare-earth coupling agent one or more, its weight proportion is 1-3 parts, processing aid is for being selected from stearic acid and salt thereof, fatty acyl amide compound, polyethylene wax, in Poly Propylene Wax and the Microcrystalline Wax one or more, its weight proportion is 0.5-10 parts.
6, white according to claim 1 is female, it is characterized in that described vector resin is selected from one or more in polyethylene, polypropylene, polystyrene, ethene-acetate ethylene copolymer, ethene-acrylic copolymer, K resin and the nylon-12.
7, prepare the female method of each described white of claim 1-6, this method comprises: earlier with titanium dioxide agglomerating particles high shear force grinding machine, under the effect of this auxiliary agent of dispersion agent, fully break up, and be coated on the surface of skeleton inorganic powder particle, add coupling agent and processing aid this two kinds of auxiliary agents and vector resin more successively, in grinding machine, mix, after the twin screw extruder granulation form.
8, method according to claim 7, this method comprises:
1. titanium dioxide, skeleton inorganic powder and dispersion agent being joined by weight proportion intermittent type has in the high shear force grinding machine, ground 6-10 minutes, when treating that temperature of charge rises to 80-85 ℃, add coupling agent, continue to grind 4-6 minutes, add processing aid and vector resin again, ground again 2-4 minutes, this moment, temperature of charge reached 110-120 ℃, discharging;
2. be 48: 1 twin screw extruder granulation with length-to-diameter ratio, make and have the functional white master batch of strengthening and toughening.
9, method according to Claim 8 is characterized in that, described high shear force grinding machine is ball mill, vibrating mill or centrifugal vibrating grinder.
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| CN100489024C true CN100489024C (en) | 2009-05-20 |
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| CN110746721A (en) * | 2019-11-29 | 2020-02-04 | 北京友合攀宝科技发展有限公司 | Calcined zeolite powder, preparation method thereof and application thereof in plastics |
| CN111704812A (en) * | 2020-05-07 | 2020-09-25 | 阳泉灿坤工贸有限公司 | Titanium dioxide organic coating preparation process |
| CN115368659A (en) * | 2022-09-19 | 2022-11-22 | 山东诺森塑胶有限公司 | Preparation process of anti-aging special color master batch formula |
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