CN108164911A - A kind of heat-resisting dumb light ABS resin composition and preparation method thereof - Google Patents
A kind of heat-resisting dumb light ABS resin composition and preparation method thereof Download PDFInfo
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- CN108164911A CN108164911A CN201711323704.2A CN201711323704A CN108164911A CN 108164911 A CN108164911 A CN 108164911A CN 201711323704 A CN201711323704 A CN 201711323704A CN 108164911 A CN108164911 A CN 108164911A
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- abs resin
- dumb light
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a kind of heat-resisting dumb light ABS resin compositions and preparation method thereof.Including 60~99wt% of heat-resisting ABS resin, 1~40wt% of delustering agent BMAT, 0.1~0.4wt% of antioxidant.The heat-resisting ABS resin is the ontology heat-resisting ABS resin prepared using laminar flow continuous bulk device, above-mentioned raw material is premixed 3~10 minutes in high-speed mixer, then premix obtains heat-resisting dumb light ABS resin through double screw extruder extruding pelletization.Compared with prior art, the present invention directly prepares the ABS resin mixture of heat-resisting dumb light using one-step method, and preparation process is simple, suitable for industrial production.Delustering agent uses SAN cross-linked polymers, does not need to additional lubrication agent and compatilizer, machinery, Effect of Thermal Performance very little to material maintain the original properties of polymer.
Description
Technical field
The invention belongs to synthesis of polymer materials and preparation field, and in particular to a kind of heat-resisting dumb light ABS resin composition
And preparation method thereof.
Background technology
Acrylnitrile-Butadiene-Styrene (ABS) is a kind of engineering plastics of high comprehensive performance, has bloom
Damp degree, the comprehensive performances such as resistant to chemical etching, high heat-resisting, easy processing, superior dimensional stability.In electronic apparatus, automobile, household electric
The fields such as device, office have a wide range of applications.ABS resin is on many electronic apparatus and automotive interior part in application, past
Toward needing to realize have the surface of extinction effect, such as computer casing, keyboard, mouse, instrument board in automotive trim, is led at sunshading board
Navigate instrument frame etc..Especially in automotive trim field, vision interference and mitigation are generated to driver for sunlight is avoided to reflect
The visual fatigue of driver so as to reach the driving purpose of safety and comfort, generally all carries out delustring or matte management, as much as possible
Reduce the lustrous surface of inside gadget.Further, since the heat resisting temperature of general ABS resin is relatively low, the heat distortion temperature one of 0.45MPA
As only 90 DEG C or so, it is heat-resisting having for car center panel, air-conditioner air outlet, steering wheel upper and lower covers and sunshading board etc.
It just cannot meet requirement during the automotive interior part of (heat distortion temperature >=100 DEG C of 0.45MPA).
In general, the method for reducing ABS article surface glossiness is mainly the following.First, die surface dermatoglyphization is handled.
I.e. by the surface treatment of mold, make the surface of Injection moulded part there is rough texture structure, so as to effectively reduce light
Pool.2nd, the rubber size of ABS resin is improved.The glossiness of ABS resin is mainly what is determined by the grain size of butadiene rubber,
Rubber size is bigger, and glossiness is lower.The rubber size of emulsion polymerization ABS resin is usually within 0.5 μm, so its surface light
Damp degree is higher, and the rubber size of bulk polymerization of ABS resin is typically larger than 0.6 μm, so its surface gloss is relatively low.It is such as beautiful
By using bulk polymerization, the ABS resin containing larger rubber grain reaches state patent US4677162 and US4526926
Reduce the purpose of ABS material gloss.3rd, incompatible polymers or filler are added.SEBS, nitrile rubber are added in ABS systems
The SAN (CN 102108176, US5580924) of (CN 1128776A), gelation, (methyl) acrylic acid of three dimensional network structure
The incompatible polymers such as Arrcostab (CN101724129) can reduce the gloss of ABS.Add silicate, aluminate, titanium dioxide
The inorganic fillers such as silicon can also reduce resin surface gloss.4th, reaction resin is added.Such as add PS-g-GMA, SAN-g-GMA
Resin with reactivity is crosslinked instead by hydroxyl, the carboxyl isoreactivity group in epoxy group therein and system
It should be so as to achieve the purpose that delustring.Patent CN 101851430, CN101787192, US4596851, US4742104 are disclosed
Resin of the addition containing glycidyl methacrylate (GMA) functional group can reduce its glossiness in PC and its alloy.Patent
US6395828 discloses a kind of side that ASA resin glossiness is reduced by epoxy-functional and amido functional group cross-linking reaction
Method.CN104403061A discloses a kind of by the use of peroxide as initiator, the completion crosslinking during ABS resin extruding pelletization
Macromolecular radical cross-linking reaction occurs for agent and ABS molecules interchain, realizes one-step method and directly prepares the ABS with matte effect
Resin group.
However, said program all there are it is certain the defects of.Only reach reduction light by changing interior trim surface texture structure
The method of damp degree cannot still meet the requirement of glossiness well in some cases, itself have high glaze spy as PC
The resin and its alloy of property, and certain limitation is also brought to interior trim surface design freedom.In addition, once due to resin
The loss of inside gadget dermatoglyph construction that scratch-resistant problem is brought, the significant difference of glossiness will occurs, cause visual color immediately
Difference leads to the failure.So the low gloss of thermoplastic resin is very important, to interior can mitigated to a certain degree
The dependence of die surface so as to widen the application range of resin, extends its service life.Using increase this side of rubber phase grain size
Method is limited for the reducing effect of gloss but the size of rubber size can influence the mechanical property of ABS resin, especially to firm
The influence of property is especially pronounced.Rubber size increases, and the tensile strength and stretch modulus of ABS resin can be greatly lowered.Except this it
Outside, rubber size is bigger, deformability also bigger, so being also easier to generate local hair when injection molding is processed and is coloured
In vain, the defects of current mark, weld bond.In order to balance other performances, have very much to reduce the gloss of ABS by increasing rubber size
Limit.Addition Incompatible Substance realizes that dumb light can lead to the physical mechanical property severe exacerbation of final material, it is impossible to meet mechanical property
It can require high occasion.The resin of gelation as delustering agent in use, since it is partial cross-linked, so product surface is deposited
Excessively coarse, and the non-uniform problem of glossiness, especially when the dermatoglyph structure of product surface is fine and smooth design, the problem
It is particularly evidently exposed.Realize that cross-linking reaction reaches matte effect using reactive extrursion, cross-linking reaction often makes extruder mouth
Melt item at mould occurs apparent melt and swells phenomenon, and then subsequent pelletizing and the dispersion in resin is made to become tired
It is difficult.And the stability of cross-linking reaction is difficult often control, easily causes product surface degree of roughness uneven and different batches
Between product matte degree fluctuation it is big.But the method preparation process needs two steps, is unfavorable for efficiently producing；Reaction system is complicated, equally
The problem of cross-linking reaction stability not enough causes the matte degree of batch inconsistent can be faced.
The matte effect of automotive interior material is mainly by article surface coated matte paint or in raw material at present
It adds delustering agent and is modified realization.But coated matte paint can increase substantially inside gadget processing cost and cause environmental pollution；
Although large-sized inorganic filler is added in material can significantly reduce the glossiness of material, can cause material impact intensity with
Mobility declines to a great extent；And although the rubber particles for adding precrosslink in the material can be good mute in article surface acquirement
Light effect has but seriously affected the mobility and heat resistance of material.
Invention content
The present invention seeks in view of the problems of the existing technology, it is proposed that and a kind of at low cost and environmentally friendly, heat resistance is high,
Shock resistance is good, does not need to additional compatilizer and lubricant, changes with regard to the heat-resisting dumb light ABS that can prepare matte effect homogeneous soft
Property material.
In order to achieve the object of the present invention, the technical solution that provides of the present invention is：
A kind of heat-resisting dumb light ABS resin composition includes each component of following weight fraction：Heat-resisting ABS resin 60~
99wt ﹪；Delustering agent 1~40wt of BMAT ﹪；0.1~0.4wt of antioxidant ﹪.
Heat-resistant monomer is N-phenylmaleimide, N- isopropylmaleimides, N- rings in the heat-resisting ABS resin
It is one or more in hexyl maleimide, maleic anhydride graft phenylethene.
The delustering agent BMAT is SAN cross-linked polymers, and glass transition temperature is 122 DEG C, and grain size (20 mesh filter screens, maximum) is
5 ﹪, volatilization are divided into 2.0 ﹪.
The antioxidant is selected from aromatic amine antioxidant, Hinered phenols antioxidant, phosphite ester kind antioxidant, monothioester
One or more of kind antioxidant, aromatic phosphate acid ester, pentaerythritol ester, auxiliary antioxidant.
The present invention also provides a kind of preparation methods of heat-resisting dumb light ABS resin composition, and described method includes following steps：
S1, the heat-resisting ABS resin, delustering agent, antioxidant are premixed 3~10 minutes in high-speed mixer；
S2, premix are through double screw extruder extruding pelletization to get the heat-resisting dumb light ABS resin mixture.
The extrusion temperature of the double screw extruder is 170~240 DEG C, and screw slenderness ratio is 32~45, and screw speed is
150~600 revs/min.
The cardinal principle of the present invention is the processing temperature section using ABS, and BMAT delustering agents can carry out beneficial with heat-proof ABS
It is crosslinked the dumb light to realize heat-resisting ABS resin.The dumb light of material can be adjusted by the additive amount and particle size range that control BMAT
Effect, matte degree uniform and smooth, lot stability are high.SAN cross-linked polymers carry out postsearch screening, molecular weight is higher, with it is resistance to
During hot ABS premixs, there is no phenomenons incompatible or hard to tolerate, do not need to compatilizer and lubricant.It can be mixed with heat-proof ABS
It is even, in melting extrusion, beneficial crosslinking occurs, so as to prepare heat-resisting dumb light ABS.And by screening delustering agent BMAT, in height
When adding score, the plasticizing capacity and physical property of polymeric substrate, such as erosion-resisting characteristics, heat resistance etc. will not be influenced.
Compared with prior art, the present invention has following advantage：
1st, the present invention realizes the matte degree of heat-resisting ABS resin, matte degree uniform and smooth using delustering agent BMAT.Pass through control
The additive amount and particle size range of delustering agent processed can adjust the matte effect of material, and after screening conditions, reaction multiplicity is good, batch
Stability is high.
2nd, the present invention does not need to compatilizer and lubricant using the SAN cross-linked polymers of continuous phase in ABS resin.With it
He compares delustering agent, does not influence the performance of base material heat-resisting ABS resin, such as impact resistance, heat resistance.
3rd, preparation process of the invention is simple, convenient for implementing in the industrial production.
Specific embodiment
It is further illustrated the present invention with reference to embodiment, but the not range of limitation the claims in the present invention protection.
The Izod notched impact strength of ABS resin product tests its impact property according to ASTM D256-1990B.Melting
Index is measured according to ASTMD 1228-1994B, and the solid content of mixture is measured using the method for electric drier drying.
Embodiment 1
Raw material is weighed as following weight percent：Heat-resisting ABS resin 60wt ﹪, delustering agent 40wt ﹪, antioxidant
0.1wt ﹪.
The heat-proof ABS is the substance law heat-resisting ABS resin prepared in the piston flow reactor of series connection；
The delustering agent BMAT is SAN cross-linked polymers, chooses the sample of 10 mesh filter screens；
The antioxidant is 1076.
The heat-resisting ABS resin weighed, delustering agent, antioxidant are carried out in high-speed mixer to be sufficiently stirred premix, then
By premix by double screw extruder, the temperature of feed zone is 170~190 DEG C, and compression section is 200~220 DEG C, and fluxing zone is
210~220 DEG C, homogenizing zone is 220~240 DEG C, and die temperature is 200~210 DEG C, and screw speed is 200~600 revs/min
Under the conditions of carry out melting extrusion, cooling granulation obtains the ABS resin composition with heat-resisting matte effect.
Embodiment 2
Raw material is weighed as following weight percent：Heat-resisting ABS resin 75wt ﹪, delustering agent 25wt ﹪, antioxidant
0.1wt ﹪.
The heat-proof ABS is the substance law heat-resisting ABS resin prepared in the piston flow reactor of series connection；
The delustering agent BMAT is SAN cross-linked polymers, chooses the sample of 20 mesh filter screens；
The antioxidant is 1076.
The heat-resisting ABS resin weighed, delustering agent, antioxidant are carried out in high-speed mixer to be sufficiently stirred premix, then
By premix by double screw extruder, the temperature of feed zone is 170~190 DEG C, and compression section is 200~220 DEG C, and fluxing zone is
210~220 DEG C, homogenizing zone is 220~240 DEG C, and die temperature is 200~210 DEG C, and screw speed is 200~600 revs/min
Under the conditions of carry out melting extrusion, cooling granulation.
Embodiment 3
Raw material is weighed as following weight percent：Heat-resisting ABS resin 90wt ﹪, delustering agent 10wt ﹪, antioxidant
0.1wt ﹪.
The heat-proof ABS is the substance law heat-resisting ABS resin prepared in the piston flow reactor of series connection；
The delustering agent BMAT is SAN cross-linked polymers, chooses the sample of 20 mesh filter screens；
The antioxidant is 1076.
The heat-resisting ABS resin weighed, delustering agent, antioxidant are carried out in high-speed mixer to be sufficiently stirred premix, then
By premix by double screw extruder, the temperature of feed zone is 170~190 DEG C, and compression section is 200~220 DEG C, and fluxing zone is
210~220 DEG C, homogenizing zone is 220~240 DEG C, and die temperature is 200~210 DEG C, and screw speed is 200~600 revs/min
Under the conditions of carry out melting extrusion, cooling granulation.
Embodiment 4
Raw material is weighed as following weight percent:Heat-resisting ABS resin 97wt ﹪, delustering agent 3wt ﹪, antioxidant 0.1wt ﹪.
The heat-proof ABS is the substance law heat-resisting ABS resin prepared in the piston flow reactor of series connection；
The delustering agent BMAT is SAN cross-linked polymers, chooses the sample of 20 mesh filter screens；
The antioxidant is 1076.
The heat-resisting ABS resin weighed, delustering agent, antioxidant are carried out in high-speed mixer to be sufficiently stirred premix, then
By premix by double screw extruder, the temperature of feed zone is 170~190 DEG C, and compression section is 200~220 DEG C, and fluxing zone is
210~220 DEG C, homogenizing zone is 220~240 DEG C, and die temperature is 200~210 DEG C, and screw speed is 200~600 revs/min
Under the conditions of carry out melting extrusion, cooling granulation.
Comparative example 1
With differing only in for embodiment 1, only containing ABS resin 99.9wt ﹪, antioxidant 0.1wt ﹪ in the comparative example,
Delustering agent BMAT is not contained, other are same as Example 1, are not repeated herein.
The performance comparison table of 1 embodiment 1 of table and comparative example 1
Comparative example 1 and comparative example 1, can as seen through the table, will not be to mechanical property after adding in delustering agent BMAT
It produces bigger effect.It after adding in delustering agent BMAT, can substantially change glossiness, prepare dumb light ABS resin.
Comparative example 2
With differing only in for embodiment 2, delustering agent used in the comparative example was the SAN crosslinkings obtained by 20 mesh filter screens
Polymer.Other are same as Example 2, are not repeated herein.
The performance comparison table of 2 embodiment 2 of table and comparative example 2
Comparative example 2 and comparative example 2, can as seen through the table, after delustering agent is crossed 20 mesh filter screens, extinction effect compared with
Filter screen will not got well, and impact strength also increases.
Comparative example 3
With differing only in for embodiment 3, SEBS is substituted St contents in delustering agent BMAT, SEBS in the comparative example is
30wt ﹪, weight average molecular weight are 15~20W.Other are same as Example 3, are not repeated herein.
The performance comparison table of 3 embodiment 3 of table and comparative example 3
Comparative example 3 and comparative example 3, can as seen through the table, after substituting delustering agent BMAT using SEBS, mechanical property
It can wait to have and greatly decline, matte effect is also be not as preferable as delustering agent BMAT.
Comparative example 4
With differing only in for embodiment 4, silica is substituted into delustering agent BMAT, silica grain size in the comparative example
It it is 10~25 μm, prepared by chemical precipitation method.
The performance comparison table of 4 embodiment 4 of table and comparative example 4
Comparative example 4 and comparative example 4 can substitute delustering agent BMAT using silica, can make as seen through the table
Resin impact strength declines to a great extent, and glossiness is also not ideal enough, and matte effect is uneven.
Examples 1 to 4 is compared, it is possible to find increased with the dosage of delustering agent BMAT, matte effect is better.Delustering agent
The use of BMAT will not change the tensile strength of material, bending strength etc., and impact property changes less, in range of needs.
By Comparative result it is found that the invention has the advantages that：1st, heat-resisting dumb light ABS materials are prepared using the blending of BMAT delustering agents
Material, the matte effect of material can be adjusted by the additive amount and particle size range that control delustering agent, and dumb light is fine and smooth；2nd, the present invention makes
It is compatible with basis material with BMAT delustering agents, that is, SAN cross-linked polymers, compatilizer is not needed to, the mechanical property of material is than other
Method improves significantly, and addition silica dioxide delustring agent can cause impact degradation, and adding incompatible body SEBS can cause just
The degradation of property.In addition the present invention realizes the preparation of heat-resisting dumb light ABS material using one-step method, and preparation process is simple, stablizes
Property it is high, be conducive to mass production.
Claims (6)
1. a kind of heat-resisting dumb light ABS resin composition, which is characterized in that each component includes by weight percentage：Heat-resisting ABS resin
60~99wt ﹪；Delustering agent 1~40wt of BMAT ﹪；0.1~0.4wt of antioxidant ﹪, it is additional.
2. heat-resisting dumb light ABS resin composition according to claim 1, which is characterized in that in the heat-resisting ABS resin
Heat-resistant monomer is N-phenylmaleimide, the grafting of N- isopropylmaleimides, N- N-cyclohexylmaleimides, maleic anhydride
It is one or more in styrene.
3. heat-resisting dumb light ABS resin composition according to claim 1, which is characterized in that the delustering agent BMAT is
SAN cross-linked polymers, glass transition temperature are 122 DEG C, and 20 mesh filter screen of grain size is up to 5 ﹪, and volatilization is divided into 2.0 ﹪.
4. heat-resisting dumb light ABS resin composition according to claim 1, which is characterized in that the antioxidant is selected from virtue
Fragrant amine antioxidants, Hinered phenols antioxidant, phosphite ester kind antioxidant, monothioester kind antioxidant, aromatic phosphate acid ester, Ji Wusi
One or more of alcohol ester, auxiliary antioxidant.
5. a kind of preparation method of heat-resisting dumb light ABS resin composition as described in claim 1, which is characterized in that including such as
Lower step：
S1, the heat-resisting ABS resin, delustering agent, antioxidant are premixed 3~10 minutes in high-speed mixer；
S2, by premix through double screw extruder extruding pelletization to get the heat-resisting dumb light ABS resin mixture.
6. according to the method described in claim 5, it is characterized in that, the extrusion temperature of the double screw extruder is 170~240
DEG C, screw slenderness ratio is 32~45, and screw speed is 150~600 revs/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265980A (en) * | 2018-07-26 | 2019-01-25 | 会通新材料股份有限公司 | A kind of good feel PA/ABS alloy material of super dumb light and preparation method thereof |
| CN110317427A (en) * | 2019-07-03 | 2019-10-11 | 南宁珀源能源材料有限公司 | Novel special backing plate of photovoltaic buddha's warrior attendant wire-electrode cutting |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298827A (en) * | 2017-06-29 | 2017-10-27 | 上海金山锦湖日丽塑料有限公司 | Low gloss heat-resisting ABS resin and preparation method thereof |
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2017
- 2017-12-12 CN CN201711323704.2A patent/CN108164911A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298827A (en) * | 2017-06-29 | 2017-10-27 | 上海金山锦湖日丽塑料有限公司 | Low gloss heat-resisting ABS resin and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265980A (en) * | 2018-07-26 | 2019-01-25 | 会通新材料股份有限公司 | A kind of good feel PA/ABS alloy material of super dumb light and preparation method thereof |
| CN109265980B (en) * | 2018-07-26 | 2021-07-09 | 会通新材料股份有限公司 | Super-matte PA/ABS alloy material with good hand feeling and preparation method thereof |
| CN110317427A (en) * | 2019-07-03 | 2019-10-11 | 南宁珀源能源材料有限公司 | Novel special backing plate of photovoltaic buddha's warrior attendant wire-electrode cutting |
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