CN107674411A - A kind of thermoplastic polyurethane Masterbatch and preparation method thereof - Google Patents
A kind of thermoplastic polyurethane Masterbatch and preparation method thereof Download PDFInfo
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- CN107674411A CN107674411A CN201711138295.9A CN201711138295A CN107674411A CN 107674411 A CN107674411 A CN 107674411A CN 201711138295 A CN201711138295 A CN 201711138295A CN 107674411 A CN107674411 A CN 107674411A
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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Abstract
The invention discloses a kind of thermoplastic polyurethane Masterbatch and preparation method thereof, the ratio that each raw material components account for gross weight is：Thermoplastic polyurethane 40~50%, pigment 40~55%, dispersant 0.5~2%, antistatic additive 1~3%, antioxidant 1~3%, the preparation method of thermoplastic polyurethane Masterbatch is disposably to add all raw materials in banbury to be well mixed, and pressurization mixing is into bulk at 130~150 DEG C, and discharge cooling, lump material is broken into small granular, then dual-screw-stem machine is added, the extruding pelletization under 220~240 DEG C, 140~150r/min, finally dry thermoplastic polyurethane Masterbatch.The preparation method of the present invention is simple and practical, has a extensive future, and thermoplastic polyurethane Masterbatch is made and is applied to have color stable, antistatic oxidation resistant advantage when the extrusion of polyurethane, injection.
Description
Technical field
The present invention relates to plastic color master grain and its preparation technology field, is a kind of thermoplastic polyurethane color masterbatch specifically
Grain and preparation method thereof.
Background technology
Masterbatch, also known as condensed pigment, it is the proprietary material colouring agent to be arisen at the historic moment with high polymer material development, i.e.,
The pigment of super quantity is processed and a kind of aggregation of pigment obtained from being equably attached among vector resin as being blended.
Therefore pigment, vector resin, dispersant constitute three underlying dimensions of Masterbatch.While in order to obtain some properties
Or improving some performances, some Masterbatch can also add a small amount of additive, surfactant or coupling agent.Masterbatch is made
For a kind of plastic products colouring agent, oneself is through being widely used in each industrial circle.There is following advantage using Masterbatch：Masterbatch is
By pigment pre-dispersion among vector resin, pigment on the one hand can be made to have more preferable dispersiveness in the plastic, on the other hand also
Pigment can be made to keep chemical stability, the holding phase of master batch is longer.Meanwhile plastic products are coloured compared to biography using Masterbatch
System color method, biggest advantage will not exactly cause environmental pollution, and coloring process is simple, due to there is the mistake of pigment pre-dispersion
Journey so that dispersiveness of the pigment in product is more preferable, not only saves the time and also saves raw material, is convenient to clean.
With the continuous development of plastics industry, the raw material of plastic processing and constantly bringing forth new ideas for filler so that plastics are used
Increasing field, or even some traditional materials can have been substituted, such as metal material, timber, leather etc..It is and right
In the continuous demand of product color, Masterbatch almost has become one of essential material of plastics chemical industry, for system
While product increasing colour, moreover it is possible to improve some performances of material.Significantly carried with the yield, kind and quality of plastic products
Height, there is higher requirement to the performance of Masterbatch therewith, in addition to tinctorial property, other Functional Requirements there has also been and carry
It is high.Thus research and development of the people to Masterbatch are also more and more extensive now, including special color master batch, multifunctional color master batch and filler exist
Study on the modification in Masterbatch.
Thermoplasticity polyurethane (TPU) is by two different chloric acid vinegar, polymeric dihydric alcohol and chain extender these three basic raw materials
Elastomeric material of a kind of performance obtained by polymerisation between rubber and plastics, is a kind of excellent combination property
Thermoplastic elastomer (TPE).The high resiliency of its existing rubber has a high rigidity and high-strength characteristic of plastics again, also with excellent wear-resisting
Property, lower temperature resistance, chemical proofing and flexible resistance etc., while it can also replace PVC (polyvinyl chloride), be to reclaim
The high strength elastic body of recycling, advantageously accounts for pollution problem.TPU can use extrusion, injection, blown film, calendering, spinning etc.
Production method, various industrial products are can be made into, its application almost penetrates into each industrial circle, and application prospect is very wide.Such as
Modern color is the indispensable pith of plastic products, because TPU premium properties and the structure of itself are extremely complex, institute
It is function modified to TPU as anti-quiet in addition to requiring higher for the retention of color of TPU products with Masterbatch technology
Electrically and inoxidizability is also more aobvious important.
The content of the invention
For problems of the prior art and deficiency, it is an object of the invention to provide a kind of thermoplastic polyurethane color
Master batch and preparation method thereof, mainly solution thermoplastic polyurethane Masterbatch feature is single, meets plastic industry for thermoplasticity
Requirement of the polyurethane Masterbatch in terms of retention of color, antistatic and antioxygenic property.
Technical problem solved by the invention can be realized using following technical scheme：A kind of thermoplastic polyurethane color masterbatch
Grain, is mixed, on the basis of the gross weight of all raw materials, the ratio that each raw material components account for gross weight is by following raw material：
40wt%~50wt% thermoplastic polyurethanes, 40wt%~55wt% pigment, 0.5wt%~2wt% dispersants, 1wt%~
3wt% antistatic additive, 1wt%~3wt% antioxidants.
Soft segment is the chief component in TPU, is mainly made up of polyalcohol, can be divided into polyether-type and polyester-type, due to
The difference of oligomer dihydric alcohol, cause polyether-type TPU and polyester-type the TPU difference difference in performance.The present invention have chosen
The resin carrier of polyether-type and the two kinds of thermoplastic polyurethane of polyester-type as Masterbatch, it is intended to illustrate the present invention for heat
The versatility of plastic polyurethane.
The present invention have chosen the metal oxide in the azo commonly used in organic pigment, phthalein green grass or young crops class and inorganic pigment, color
Coloured silk is abundant, can prepare the master batch of multicolour, and the particle diameter for limiting pigment is not more than 500nm, and nanoscale can carry
High pigment vector resin compatibility and dispersiveness, so as to compared to stock size pigment so that plastic products have it is more steady
Fixed colored state.
Dispersant part critically important in being prepared as Masterbatch, its main function is that pigment is soaked, and is made
Pigment can be evenly dispersed in resin, and is no longer reunited in process, so the Selective artery embolization of dispersant is and resin
Compatibility it is good.In order that obtaining thermoplastic polyurethane Masterbatch can use in high temperature environments, dispersant of the invention is kept away
Exempt from using the combustible material such as solid paraffin, Tissuemat E or mineral oil, but have selected the chlorinated paraffin with ignition-proof element, hard
Resin acid acid amides, zinc stearate, magnesium stearate or N, N- ethylenebisstearamide.
Untreated polyurethane elastomer has a good electrical insulating property, thus it is rubbed during use when it is easy
Electrostatic is produced, and static discharge and Electromagnetic Interference will cause a series of disasters.According to composition characteristic, polyurethane elastomer material
The antistatic additive species of material is broadly divided into compound and blending type, wherein compound antistatic urethane elastomer material be with
Low molecule conductive materials are modifying agent, and blending type then contains electroconductive polymer.The antistatic additive of the present invention includes multiple
Mould assembly and the class of blending type two, in parts by weight meter include 5~10 parts of conductive black, 2~5 parts of iron chloride, polypyrrole 5~15
Part, 5~10 parts of polyaniline, 8~10 parts of neopelex, 2~5 parts of glycerine, 40~50 parts of water.
The antioxidant of the present invention is counted including 15~20 parts of diatomite, 15~20 parts of magnesium hydroxide, 2,4- in parts by weight
5~10 parts of dihydroxy-benzophenone, 7~10 parts of silane coupler, 10~15 parts of ethanol, 40~50 parts of water, it is inorganic and organic anti-
Oxidant is used in combination, and Inorganic antioxidant can also improve the mechanical property of Masterbatch, and the use of silane coupler then improves antioxygen
Compatibility of the agent in vector resin.
Raw material composition based on above-mentioned thermoplastic polyurethane Masterbatch, present invention also offers a kind of thermoplastic polyurethane color
The preparation method of master batch, step are as follows：
According to formula ratio, all raw materials are disposably added in banbury and are well mixed, being pressurizeed at 130~150 DEG C is kneaded
Into bulk, lump material is broken into small granular by discharging cooling, then adds dual-screw-stem machine, 220~240 DEG C, 140~
Extruding pelletization under 150r/min, finally dry thermoplastic polyurethane Masterbatch.
The preparation method of the antistatic additive is：By the conductive black counted in parts by weight, iron chloride, polypyrrole, polyphenyl
Amine, neopelex, glycerine, water, which sequentially add, to be heated to 40~50 DEG C and is uniformly mixed in mixer, be made anti-
Electrostatic agent.
The preparation method of the antioxidant is：By the diatomite counted in parts by weight, magnesium hydroxide, 2,4- dihydroxy-
Benzophenone, silane coupler, ethanol, water, which sequentially add, to be heated to 40~50 DEG C and is uniformly mixed in mixer, be made anti-
Oxidant.
The present invention compared with prior art, has advantages below and beneficial effect：
1st, the present invention adds antistatic additive and antioxidant in thermoplastic polyurethane Masterbatch, and antistatic additive is using compound
Type and the class of blending type two, antioxidant is used in combination using inorganic and organic oxidation-resistant agent, and uses silane coupler so that resisting
Oxidant is preferably scattered in vector resin, and obtained thermoplastic polyurethane Masterbatch has good colour coloring power and steady
It is qualitative, and there is good antistatic behaviour and inoxidizability.
2nd, the pigment that uses of the present invention is in nanoscale scope, can improve pigment in the compatibility of vector resin and scattered
Property, so as to the pigment compared to stock size so that plastic products have more stable colored state.
3rd, dispersant of the invention is avoided using combustible materials such as solid paraffin, Tissuemat E or mineral oil, but is selected
There is chlorinated paraffin, stearic amide, zinc stearate, magnesium stearate or N, the N- ethylenebisstearamide of ignition-proof element,
Improve the anti-flammability of plastic products.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.
A kind of thermoplastic polyurethane Masterbatch of the present invention, is mixed by following raw material, with the gross weight of all raw materials
On the basis of, the ratio that each raw material components account for gross weight is：40wt%~50wt% thermoplastic polyurethanes, 40wt%~55wt% face
Material, 0.5wt%~2wt% dispersants, 1wt%~3wt% antistatic additive, 1wt%~3wt% antioxidants.
The antistatic additive is counted including 5~10 parts of conductive black, 2~5 parts of iron chloride, polypyrrole 5~15 in parts by weight
Part, 5~10 parts of polyaniline, 8~10 parts of neopelex, 2~5 parts of glycerine, 40~50 parts of water.
The antioxidant is counted including 15~20 parts of diatomite, 15~20 parts of magnesium hydroxide, 2,4- dihydroxies in parts by weight
5~10 parts of base-benzophenone, 7~10 parts of silane coupler, 10~15 parts of ethanol, 40~50 parts of water.
The method that the present invention prepares thermoplastic polyurethane Masterbatch is, according to formula ratio, all raw materials disposably to be added
Be well mixed in banbury, at 130~150 DEG C pressurization be kneaded into bulk, discharging cooling, lump material is broken into it is small granular,
Then dual-screw-stem machine is added, the extruding pelletization under 220~240 DEG C, 140~150r/min, finally dry thermoplastic polyurethane
Masterbatch.
The preparation method of the antistatic additive is：By the conductive black counted in parts by weight, iron chloride, polypyrrole, polyphenyl
Amine, neopelex, glycerine, water, which sequentially add, to be heated to 40~50 DEG C and is uniformly mixed in mixer, be made anti-
Electrostatic agent.
The preparation method of the antioxidant is：By the diatomite counted in parts by weight, magnesium hydroxide, 2,4- dihydroxy-
Benzophenone, silane coupler, ethanol, water, which sequentially add, to be heated to 40~50 DEG C and is uniformly mixed in mixer, be made anti-
Oxidant.
Embodiment 1：
A kind of thermoplastic polyurethane Masterbatch of the present embodiment, is mixed by following raw material, with the gross weight of all raw materials
On the basis of amount, the ratio that each raw material components account for gross weight is：Polyether thermoplastic polyurethane 40wt%, organic blue pigment (phthalocyanine
Indigo plant 15:3) 55wt%, dispersant chlorinated paraffin 2wt%, antistatic additive 1wt%, antioxidant 2wt%；
The wherein composition of antistatic additive is 5 parts of conductive black, 2 parts of iron chloride, 5 parts of polypyrrole, 5 parts of polyaniline, dodecane
8 parts of base benzene sulfonic acid sodium salt, 2 parts of glycerine, 40 parts of water；
The composition of antioxidant is 15 parts of diatomite, 15 parts of magnesium hydroxide, 2,4- dihydroxy -5 parts of benzophenone, silane idol
Join 7 parts of agent, 10 parts of ethanol, 40 parts of water.
Embodiment 2：
A kind of thermoplastic polyurethane Masterbatch of the present embodiment, is mixed by following raw material, with the gross weight of all raw materials
On the basis of amount, the ratio that each raw material components account for gross weight is：Polyester-type thermoplastic polyurethane 45wt%, organic red pigment (pigment
Red 144) 50wt%, dispersant stearic amide 0.5wt%, antistatic additive 2wt%, antioxidant 1wt%；
The wherein composition of antistatic additive is 10 parts of conductive black, 5 parts of iron chloride, 15 parts of polypyrrole, 10 parts of polyaniline, 12
10 parts of sodium alkyl benzene sulfonate, 5 parts of glycerine, 50 parts of water；
The composition of antioxidant is 20 parts of diatomite, 20 parts of magnesium hydroxide, 2,4- dihydroxy -10 parts of benzophenone, silane
10 parts of coupling agent, 15 parts of ethanol, 50 parts of water.
Embodiment 3：
A kind of thermoplastic polyurethane Masterbatch of the present embodiment, is mixed by following raw material, with the gross weight of all raw materials
On the basis of amount, the ratio that each raw material components account for gross weight is：Polyether thermoplastic polyurethane 47wt%, organic red pigment (pigment
Red 122) 50wt%, dispersant zinc stearate 0.5wt%, antistatic additive 1.5wt%, antioxidant 1wt%；
The wherein composition of antistatic additive is 7 parts of conductive black, 3 parts of iron chloride, 10 parts of polypyrrole, 8 parts of polyaniline, dodecane
9 parts of base benzene sulfonic acid sodium salt, 3 parts of glycerine, 40 parts of water；
The composition of antioxidant is 16 parts of diatomite, 16 parts of magnesium hydroxide, 2,4- dihydroxy -7 parts of benzophenone, silane idol
Join 8 parts of agent, 12 parts of ethanol, 40 parts of water.
Embodiment 4：
A kind of thermoplastic polyurethane Masterbatch of the present embodiment, is mixed by following raw material, with the gross weight of all raw materials
On the basis of amount, the ratio that each raw material components account for gross weight is：Polyester-type thermoplastic polyurethane 40wt%, inorganic red (oxidation
Iron oxide red) 55wt%, dispersant magnesium stearate 2wt%, antistatic additive 2wt%, antioxidant 1wt%；
The wherein composition of antistatic additive is 8 parts of conductive black, 4 parts of iron chloride, 10 parts of polypyrrole, 5 parts of polyaniline, dodecane
8 parts of base benzene sulfonic acid sodium salt, 5 parts of glycerine, 45 parts of water；
The composition of antioxidant is 17 parts of diatomite, 17 parts of magnesium hydroxide, 2,4- dihydroxy -6 parts of benzophenone, silane idol
Join 7 parts of agent, 12 parts of ethanol, 45 parts of water.
Embodiment 5：
A kind of thermoplastic polyurethane Masterbatch of the present embodiment, is mixed by following raw material, with the gross weight of all raw materials
On the basis of amount, the ratio that each raw material components account for gross weight is：Polyether thermoplastic polyurethane 50wt%, inorganic yellow pigment (oxidation
Iron oxide yellow) 45wt%, dispersant N, N- ethylenebisstearamide 2wt%, antistatic additive 1wt%, antioxidant 2wt%；
The wherein composition of antistatic additive is 6 parts of conductive black, 4 parts of iron chloride, 12 parts of polypyrrole, 7 parts of polyaniline, dodecane
9 parts of base benzene sulfonic acid sodium salt, 4 parts of glycerine, 45 parts of water；
The composition of antioxidant is 17 parts of diatomite, 17 parts of magnesium hydroxide, 2,4- dihydroxy -6 parts of benzophenone, silane idol
Join 7 parts of agent, 12 parts of ethanol, 50 parts of water.
Embodiment 6：
A kind of thermoplastic polyurethane Masterbatch of the present embodiment, is mixed by following raw material, with the gross weight of all raw materials
On the basis of amount, the ratio that each raw material components account for gross weight is：Polyester-type thermoplastic polyurethane 40wt%, organic yellow pigment (pigment
Yellow 151) 55wt%, dispersant magnesium stearate 2wt%, antistatic additive 2wt%, antioxidant 1wt%；
The wherein composition of antistatic additive is 8 parts of conductive black, 4 parts of iron chloride, 10 parts of polypyrrole, 5 parts of polyaniline, dodecane
8 parts of base benzene sulfonic acid sodium salt, 5 parts of glycerine, 45 parts of water；
The composition of antioxidant is 18 parts of diatomite, 18 parts of magnesium hydroxide, 2,4- dihydroxy -6 parts of benzophenone, silane idol
Join 7 parts of agent, 12 parts of ethanol, 45 parts of water.
Performance test：
After thermoplasticity Masterbatch is prepared, it is mixed with thermoplastic polyurethane and carries out being molded obtained batten, Ran Houyong
Colour photometer carries out colouristic properties test to batten.
It is that 10cm is irradiated with ultraviolet light and spline surfaces distance height, the color change of batten is observed in timing.
The surface resistivity of material is determined by GB/T-1410-2006, characterizes the antistatic property of material, as a result such as following table
It is shown：
The test result of table 1
As can be seen from the above table, the aberration of embodiment 1~6 is less than commercially available Masterbatch, illustrates thermoplasticity produced by the present invention
The colour coloring power and color stability of polyurethane are better than common Masterbatch, and the unchanged explanation inoxidizability of color is preferable, surface
Small five orders of magnitude of the commercially available Masterbatch of resistivity ratio, antistatic property are good.
Finally illustrate, have been shown and described above the present invention general principle and principal character and the present invention it is excellent
Point.It will be understood by a person skilled in the art that the present invention is not limited to the above embodiments, described in above-described embodiment and specification
The simply present invention principle, without departing from the spirit and scope of the present invention, the present invention, which also has, various change and to be changed
Enter, these changes and improvements all fall within the protetion scope of the claimed invention.
Claims (9)
1. a kind of thermoplastic polyurethane Masterbatch, it is characterised in that the Masterbatch is mixed by following original by following raw material
Material mixes,：40wt%~50wt% thermoplastic polyurethanes, 40wt%~55wt% pigment, 0.5wt%~2wt% dispersants, 1wt%
~3wt% antistatic additive, 1wt%~3wt% antioxidants.
A kind of 2. thermoplastic polyurethane Masterbatch according to claim 1, it is characterised in that：The thermoplastic polyurethane is
Polyether thermoplastic polyurethane or polyester-type thermoplastic polyurethane.
A kind of 3. thermoplastic polyurethane Masterbatch according to claim 1, it is characterised in that：The pigment is azo, phthalein
One kind in blue or green organic pigment or metal oxides inorganic pigment, particle diameter≤500nm.
A kind of 4. thermoplastic polyurethane Masterbatch according to claim 1, it is characterised in that：The dispersant is chlorination stone
One or more in wax, stearic amide, zinc stearate, magnesium stearate or N, N- ethylenebisstearamide are in any proportion
The mixture of mixing.
5. a kind of thermoplastic polyurethane Masterbatch according to claim 1, it is characterised in that the antistatic additive is by weight
Number meter includes 5~10 parts of conductive black, 2~5 parts of iron chloride, 5~15 parts of polypyrrole, 5~10 parts of polyaniline, detergent alkylate
8~10 parts of sodium sulfonate, 2~5 parts of glycerine, 40~50 parts of water.
A kind of 6. thermoplastic polyurethane Masterbatch according to claim 1, it is characterised in that：The antioxidant is by weight
Number meter includes 15~20 parts of diatomite, 15~20 parts of magnesium hydroxide, 2,4- dihydroxy -5~10 parts of benzophenone, silane coupled
7~10 parts of agent, 10~15 parts of ethanol, 40~50 parts of water.
7. prepare a kind of method of thermoplastic polyurethane Masterbatch described in claim 1, it is characterised in that：According to formula ratio,
All raw materials are disposably added in banbury and are well mixed, pressurization mixing is into bulk at 130~150 DEG C, and discharging cools down, by block
Shape material is broken into small granular, then adds dual-screw-stem machine, the extruding pelletization under 220~240 DEG C, 140~150r/min, finally
Dry thermoplastic polyurethane Masterbatch.
8. the preparation method of a kind of thermoplastic polyurethane Masterbatch according to claim 7, it is characterised in that described anti-quiet
The preparation method of electric agent is：By the conductive black counted in parts by weight, iron chloride, polypyrrole, polyaniline, DBSA
Sodium, glycerine, water, which sequentially add, to be heated to 40~50 DEG C and is uniformly mixed in mixer, antistatic additive is made.
A kind of 9. preparation method of thermoplastic polyurethane Masterbatch according to claim 7, it is characterised in that the antioxygen
The preparation method of agent is：By the diatomite counted in parts by weight, magnesium hydroxide, 2,4- dihydroxy-benzophenone, silane coupled
Agent, ethanol, water, which sequentially add, to be heated to 40~50 DEG C and is uniformly mixed in mixer, antioxidant is made.
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| CN113621249A (en) * | 2021-08-24 | 2021-11-09 | 浙江鼎富橡塑科技有限公司 | Abnormal sound prevention TPE dustproof sleeve and production process thereof |
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| CN108410159A (en) * | 2018-03-23 | 2018-08-17 | 广州市聚丽颜料塑胶工业有限公司 | A kind of TPU Masterbatch and preparation method thereof |
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| CN109664530A (en) * | 2018-12-19 | 2019-04-23 | 南京九思高科技有限公司 | A kind of improved antistatic flow-guiding screen and its preparation method and application |
| CN111019328A (en) * | 2019-12-24 | 2020-04-17 | 海隆石油产品技术服务（上海）有限公司 | Thermoplastic polyurethane filling master batch and preparation method thereof |
| CN113621249A (en) * | 2021-08-24 | 2021-11-09 | 浙江鼎富橡塑科技有限公司 | Abnormal sound prevention TPE dustproof sleeve and production process thereof |
| CN113621249B (en) * | 2021-08-24 | 2022-07-26 | 浙江鼎富橡塑科技有限公司 | Abnormal sound prevention TPE dustproof sleeve and production process thereof |
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