CN106117954B - A kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials - Google Patents
A kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials Download PDFInfo
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- CN106117954B CN106117954B CN201610604523.6A CN201610604523A CN106117954B CN 106117954 B CN106117954 B CN 106117954B CN 201610604523 A CN201610604523 A CN 201610604523A CN 106117954 B CN106117954 B CN 106117954B
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The present invention provides a kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials, by mass percentage, including following component：ABS reworked materials 48% ~ 78%, PBT reworked materials 10% ~ 40%, compatilizer 2% ~ 5%, EMA toughener 2% ~ 3%, MBS toughener 5% ~ 12%, antioxidant 0.3% ~ 0.6%, lubricant 0.3% ~ 0.6% and Nano filling 1-2%.Completely using regeneration ABS, PBT resin material, ABS, PBT virgin material need not be added, significantly improve the utilization rate of regeneration ABS, PBT, and it is modified by the characteristics of ABS and PBT reworked materials, obtain a kind of oil resistant, low temperature resistant, the regeneration ABS/PBT alloy materials that impact strength is good, processability is good are made that contribution outstanding for the utilization of ABS, PBT reworked material.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials
Material.
Background technology
Acrylonitrile-butadiene-styrene (ABS)（ABS）Because of its excellent mechanical property, dimensional stability, easy to process, coloring,
The features such as post-processing facilitates and be widely used in each field of social life, be current production rate maximum, most widely used polymerization
One of object.ABS has higher melt strength, the good advantage of extrusion performance simultaneously.But there is also thermal deformations for ABS plastic simultaneously
Temperature is relatively low, chemical resistance especially oil resistivity, the shortcomings of weatherability is poor, limits its application.
Polybutylene terephthalate（PBT）Being a kind of crystalline thermoplastic polyester has nontoxic, against weather, anti-chemistry
The advantages that stability of drug products is good, high mechanical strength and oil resistant solvent resistance outstanding, but since the crystallization rate of PBT is very high,
Viscosity is very low, and melt strength is not high, it is difficult to extrusion molding.
ABS and PBT are carried out the performances such as the weatherability, oil resistivity, solvent resistance that can be effectively improved ABS material are blended,
The application space for greatly improving material, can be widely applied to the social life every field such as pipeline, architectural shape and plank.
ABS and PBT is common material, whether ABS or PBT material, will produce a large amount of defective material or substandard products,
Different degrees of aging has occurred since recovery article is after prolonged use in recovery article, again processing performance, tough
Property etc. deteriorates, therefore mainly has following manner for the processing of ABS, PBT defective material, substandard products or recovery article at present.
（1）It burns or land-fill method easily causes ring due to will produce the pernicious gases such as sulfur dioxide during the burning process
Border is polluted, and takes land-fill method, and the refractory organics of ABS and PBT can also cause environment prodigious harm, current this mode
Gradually it is eliminated.
（2）Defective material, substandard products or recovery article are simply recycled without any modification, common modeling is downgraded to
Material uses, although solving problem of environmental pollution, fails the economic value for making full use of these defective materials, application range is narrow.
（3）It is composite modified by ABS the or PBT reworked materials and the progress of corresponding ABS, PBT virgin material that add part, it obtains again
Obtain the accordingly ABS of preferable performance, PBT material.As disclosed in Chinese patent CN 201110188049.0 a kind of makrolon/
ABS alloy and preparation method and application use PC virgin materials, PC reworked materials and ABS reworked materials to be modified for main component, carry
Its high forming property, obtains a kind of modified PC/ABS alloy materials.But not having can adopt in the prior art completely
The scheme being improved with ingredient based on ABS, PBT reworked material.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials, resins
Material selects ABS, PBT reworked material completely, by technical solution toughener, compatilizer preferably and collocation, obtain
A kind of regeneration ABS/PBT alloy materials that performance is excellent.
In order to realize that the technical purpose of the present invention, the present invention adopt the following technical scheme that.
A kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials, by mass percentage, including following component：ABS is again
Raw material 48% ~ 78%, PBT reworked materials 10% ~ 40%, compatilizer 2% ~ 5%, EMA toughener 2% ~ 3%, MBS（Methyl methacrylate-fourth
Diene-styrene copolymer）Toughener 5% ~ 12%, antioxidant 0.3% ~ 0.6%, lubricant 0.3% ~ 0.6% and Nano filling 1-2%.
Preferably, the EMA toughener is preferentially from the product of 1125 AC models of DuPont Corporation.
Preferably, by mass percentage, PC/ABS alloy contents are no more than 10% in the ABS reworked materials.
Preferably, the compatilizer is SAG（Styrene-acrylonitrile-glycidyl methacrylate copolymer）, Malaysia
At least two in acid anhydrides grafted propylene nitrile-butadiene-styrene, styrene-maleic anhydride copolymer, and one such be
SAG。
Compatilizer SAG is especially selected in the present invention（Styrene-acrylonitrile-glycidyl methacrylate copolymerization
Object）, by the chain extension graft reactions between SAG and ABS, PBT, ABS, PBT reworked material processing fluidity are significantly improved, regeneration is made
ABS/PBT alloy materials have good strength character, overcome part use of having in existing ABS/PBT alloy materials
ABS, PBT virgin material improve the defect of its shaping strength.
Preferably, the compatilizer is SAG.
Preferably, it is 1 that the antioxidant, which is mass ratio,:2 antioxidant 1076 and irgasfos 168 compounds.
Preferably, the lubricant is calcium stearate, magnesium stearate, stearic amide, methylene bis stearic amide or second
At least one of double stearic amides of support.
Preferably, the Nano filling is one kind in nanomete talc powder, nano-titanium dioxide, nano zine oxide.
It is further preferred that the grain size of the Nano filling is 20-120nm.
The invention has the advantages that：The present invention provides a kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials
Material, compared with prior art, has the following advantages that：
Regeneration ABS/PBT alloy materials provided by the invention need not add completely using regeneration ABS, PBT resin material
Add ABS, PBT virgin material, significantly improve the utilization rate of regeneration ABS, PBT, and is carried out by the characteristics of ABS and PBT reworked materials
It is modified, a kind of oil resistant, low temperature resistant is obtained, the regeneration ABS/PBT alloy materials that impact strength is good, processability is good are
The utilization of ABS, PBT reworked material is made that contribution outstanding.
Composite toughening is carried out using EMA toughener and MBS toughener, by the optimum option to toughener, to regeneration
ABS/PBT alloy materials are modified, and are significantly improved the impact strength of regeneration ABS/PBT alloy materials, are met
The regeneration ABS/PBT alloy materials of performance requirement.
Using compatilizer SAG（Styrene-acrylonitrile-glycidyl methacrylate copolymer）, by SAG and ABS,
Chain extension graft reaction between PBT significantly improves ABS, PBT reworked material processing fluidity, and regeneration ABS/PBT alloy materials is made to have
There is good shaping strength, overcome part of having in existing ABS/PBT alloy materials improves it using ABS, PBT virgin material
The defect of shaping strength has the performance for not being weaker than ABS, PBT virgin material completely, realizes the environmental protection to ABS, PBT reworked material, warp
Ji utilizes, and has great economic value and social value.
By using Nano filling to ABS/PBT composite modifications, in nano-particle and ABS reworked materials, PBT reworked materials
Between under the Filamentous connection that is formed and molecular force, so that the microcrack in ABS/PBT composite materials is become micro-crack, prevent oils
Substance further corrodes, and improves the oil resistivity of ABS/PBT composite materials.
Specific implementation mode
In order to better understand the present invention, invention is described in detail with reference to specific embodiment.
Embodiment 1
A kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials, by mass percentage, including following component：ABS is again
Raw material 48%, PBT reworked materials 39.2%, SAG compatilizers 2%, EMA toughener 3%, MBS toughener 5%, antioxidant 0.5%, stearic acid
The nano-titanium dioxide of calcium 0.3% and 2%（Average grain diameter is 50nm）, the antioxidant is that mass ratio is 1:2 antioxidant 1076
It is compounded with irgasfos 168.Finished product is made after batch mixing, extrusion, pelletizing as required in said components.
Embodiment 2
A kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials, by mass percentage, including following component：ABS is again
The mixing compatilizer of raw material 59.1%, PBT reworked materials 25%, SAG and maleic anhydride grafted propylene nitrile-butadiene-styrene composition
5%, the nanomete talc powder of EMA toughener 2%, MBS toughener 7%, antioxidant 0.3%, magnesium stearate 0.6% and 1%（Average grain diameter is
100nm）, the antioxidant is that mass ratio is 1:2 antioxidant 1076 and irgasfos 168 compounds.By said components by wanting
It asks and finished product is made after batch mixing, extrusion, pelletizing.
Embodiment 3
A kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials, by mass percentage, including following component：ABS is again
Mixing compatilizer 3%, the EMA toughener of raw material 65.2%, PBT reworked materials 15%, SAG and styrene-maleic anhydride copolymer composition
2%, the nano zine oxide of MBS toughener 12%, antioxidant 0.3%, stearic amide 0.5% and 2%（Average grain diameter is 120nm）, institute
It is 1 that state antioxidant, which be mass ratio,:2 antioxidant 1076 and irgasfos 168 compounds.By said components as required through batch mixing,
It squeezes out, finished product is made after pelletizing.
Embodiment 4
A kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials, by mass percentage, including following component：ABS is again
Raw material 78%, PBT reworked materials 10%, SAG compatilizers 2%, EMA toughener 2%, MBS toughener 5%, antioxidant 0.6%, methylene bis are hard
The nano-titanium dioxide of resin acid amide 0.4% and 2%（Average grain diameter is 20nm）, the antioxidant is that mass ratio is 1:2 antioxygen
Agent 1076 and irgasfos 168 compound.Finished product is made after batch mixing, extrusion, pelletizing as required in said components.
Embodiment 5
A kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials, by mass percentage, including following component：ABS is again
Raw material 48%, PBT reworked materials 40%, SAG compatilizers 2%, EMA toughener 2%, MBS toughener 5%, antioxidant 0.5%, ethylene are double hard
The nano zine oxide of resin acid amide 0.5% and 2%（Average grain diameter is 120nm）, the antioxidant is that mass ratio is 1:2 antioxidant
1076 and irgasfos 168 compound.Finished product is made after batch mixing, extrusion, pelletizing as required in said components.
Comparative example 1（Without MBS toughener）
A kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials, by mass percentage, including following component：ABS is again
Raw material 53%, PBT reworked materials 40%, SAG compatilizers 2%, EMA toughener 2%, antioxidant 0.5%, ethylene bis stearic acid amide 0.5%
With 2% nano zine oxide（Average grain diameter is 120nm）, the antioxidant is that mass ratio is 1:2 antioxidant 1076 and antioxidant
168 compound.Finished product is made after batch mixing, extrusion, pelletizing as required in said components.
Comparative example 2（Without EMA toughener）
A kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials, by mass percentage, including following component：ABS is again
Raw material 50%, PBT reworked materials 40%, SAG compatilizers 2%, MBS toughener 5%, antioxidant 0.5%, ethylene bis stearic acid amide 0.5%
With 2% nano zine oxide（Average grain diameter is 120nm）, the antioxidant is that mass ratio is 1:2 antioxidant 1076 and antioxidant
168 compound.Finished product is made after batch mixing, extrusion, pelletizing as required in said components.
Comparative example 3（Without containing SAG）
A kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials, by mass percentage, including following component：ABS is again
Raw material 50%, PBT reworked materials 40%, EMA toughener 2%, MBS toughener 5%, antioxidant 0.5%, ethylene bis stearic acid amide 0.5%
With 2% nano zine oxide（Average grain diameter is 120nm）, the antioxidant is that mass ratio is 1:2 antioxidant 1076 and antioxidant
168 compound.Finished product is made after batch mixing, extrusion, pelletizing as required in said components.
Comparative example 4（Without containing Nano filling）
A kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials, by mass percentage, including following component：ABS is again
Raw material 50%, PBT reworked materials 40%, SAG compatilizers 2%, EMA toughener 2%, MBS toughener 5%, antioxidant 0.5% and ethylene are double hard
Resin acid amide 0.5%, the antioxidant are that mass ratio is 1:2 antioxidant 1076 and irgasfos 168 compounds.By above-mentioned group
Divide and finished product is made after batch mixing, extrusion, pelletizing as required.
To the regeneration ABS/PBT alloy materials that embodiment 1-5 and comparative example 1-4 are obtained, performance detection is carried out, as a result such as
Shown in table 1.
The regeneration ABS/PBT alloy material performance tests of table 1 embodiment 1-5 and comparative example 1-4 obtained
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Tensile strength, MPa | 40.2 | 39.5 | 38.9 | 44.2 | 45.7 | 45 | 43.6 | 30.5 | 37.9 |
| Bending strength, MPa | 56.2 | 47 | 47.6 | 49.5 | 54.9 | 55.2 | 54 | 34.2 | 45.6 |
| Bending modulus/MPa | 1930 | 1545 | 1560 | 1655 | 1860 | 1380 | 1400 | 1260 | 1550 |
| Notch impact strength, kJ/m2 | 55.1 | 48.3 | 49.2 | 47.2 | 54.2 | 35.2 | 36.5 | 33.1 | 46.2 |
| Elongation at break, % | 30.1 | 24 | 20 | 15 | 30 | 10 | 8 | 12 | 22 |
| Low temperature ball falling impact | It does not crack | It does not crack | It does not crack | It does not crack | It does not crack | Cracking | Cracking | Cracking | It does not crack |
| Oil resistance | It does not crack | It does not crack | It does not crack | It does not crack | It does not crack | It does not crack | It does not crack | It does not crack | Cracking |
Embodiment 1-5 shows in technical scheme of the present invention compared with comparative example 1, comparative example 2 by selecting toughener
EMA and MBS is composite modified to regeneration ABS/PBT alloy materials progress, significantly improves its notch impact strength and fracture toughness,
And it is also significantly increased with oil resistance to its low temperature impact properties.
Embodiment 1-5 is compared with comparative example 3, due to, as compatilizer, passing through the chain extension between SAG and ABS, PBT using SAG
Graft reaction significantly improves ABS, PBT reworked material processing fluidity, so that regeneration ABS/PBT alloy materials is had curved well
Qu Qiangdu, tensile strength, overcome part of having in existing ABS/PBT alloy materials improves it using ABS, PBT virgin material
The insufficient defect of intensity has the performance of the ABS/PBT alloy materials for the preparation for not being weaker than ABS, PBT virgin material completely, realizes
Environmental protection, economic utilization to ABS, PBT reworked material have great economic value and social value.
Embodiment 1-5 is compared with comparative example 4, due to using Nano filling to ABS/PBT composite modifications, in nanoparticle
Under the Filamentous connection formed between son and ABS reworked materials, PBT reworked materials and molecular force, make micro- in ABS/PBT composite materials
Crack becomes micro-crack, and oily substance is prevented further to corrode, and improves the oil resistivity of ABS/PBT composite materials, improves
The fuel tolerance capability of ABS/PBT composite materials.
According to upper table data, it is apparent that a kind of oil resistant provided by the invention, low temperature resistant regeneration ABS/PBT alloy materials
Material uses regeneration ABS, PBT for raw material completely with good intensity, low temperature resistant, oil resistance, the regeneration obtained
ABS/PBT alloy materials performance is not weaker than the ABS/PBT alloy materials using virgin material ABS, PBT material preparation completely, realizes
The environmental protection of ABS and PBT reworked materials is utilized.
The basic principles, main features and advantages of the invention have been shown and described above.The technical staff of the industry should
Understand, the invention is not limited in any way above-described embodiment, all to be obtained by the way of equivalent substitution or equivalent transformation
Technical solution is all fallen in protection scope of the present invention.
Claims (5)
1. a kind of oil resistant, low temperature resistant regeneration ABS/PBT alloy materials, which is characterized in that by mass percentage, including such as the following group
Point：ABS reworked materials 48%~78%, PBT reworked materials 10%~40%, compatilizer 2%~5%, EMA toughener 2%~3%,
MBS toughener 5%~12%, antioxidant 0.3%~0.6%, lubricant 0.3%~0.6% and Nano filling 1-2%；
The compatilizer is SAG or SAG, maleic anhydride grafted propylene nitrile-butadiene-styrene, phenylethylene-maleic anhydride
At least two in copolymer, and one such is SAG.
2. a kind of oil resistant according to claim 1, low temperature resistant regeneration ABS/PBT alloy materials, it is characterised in that：By quality
Percentage meter, PC/ABS alloy contents are no more than 10% in the ABS reworked materials.
3. a kind of oil resistant according to claim 1, low temperature resistant regeneration ABS/PBT alloy materials, it is characterised in that：It is described anti-
Oxygen agent is that mass ratio is 1:2 antioxidant 1076 and irgasfos 168 compounds.
4. a kind of oil resistant according to claim 1, low temperature resistant regeneration ABS/PBT alloy materials, it is characterised in that：The profit
Lubrication prescription be calcium stearate, magnesium stearate, stearic amide, methylene bis stearic amide or ethylene bis stearic acid amide at least
It is a kind of.
5. a kind of oil resistant according to claim 1, low temperature resistant regeneration ABS/PBT alloy materials, it is characterised in that：It is described to receive
Rice filler is one kind in nanomete talc powder, nano-titanium dioxide, nano zine oxide.
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| CN106633603A (en) * | 2016-12-25 | 2017-05-10 | 合肥会通新材料有限公司 | ABS (Acrylonitrile Butadiene Styrene)/PET (Polyethylene Terephthalate) alloy material and preparation method thereof |
| CN109721940B (en) * | 2018-12-06 | 2021-03-30 | 华南理工大学 | rABS/PBT/ASG composite material and preparation method thereof |
| CN110527260B (en) * | 2019-09-05 | 2021-11-26 | 天津市亚泰富通金属制品有限公司 | High-toughness regenerated environment-friendly plastic and processing technology thereof |
| CN117487306A (en) * | 2020-07-03 | 2024-02-02 | 宁波恒拓高分子材料有限公司 | Oil-resistant ABS modified material |
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| CN104559110A (en) * | 2014-12-29 | 2015-04-29 | 浙江俊尔新材料股份有限公司 | PC/PET (polycarbonate/polyethylene terephthalate) alloy material and preparation method thereof |
| CN105199303A (en) * | 2015-09-16 | 2015-12-30 | 广东天保新材料有限责任公司 | High-impact greasy-dirt-resistant modified regenerated ABS material and preparation method thereof |
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| CN105802117A (en) * | 2016-04-29 | 2016-07-27 | 江苏昇和新材料科技股份有限公司 | Special material for modified ABS new-energy battery jar and preparation method thereof |
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| CN104559110A (en) * | 2014-12-29 | 2015-04-29 | 浙江俊尔新材料股份有限公司 | PC/PET (polycarbonate/polyethylene terephthalate) alloy material and preparation method thereof |
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