CN108003549A - One kind regeneration ABS/PP alloy materials and preparation method thereof - Google Patents
One kind regeneration ABS/PP alloy materials and preparation method thereof Download PDFInfo
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- CN108003549A CN108003549A CN201711126300.4A CN201711126300A CN108003549A CN 108003549 A CN108003549 A CN 108003549A CN 201711126300 A CN201711126300 A CN 201711126300A CN 108003549 A CN108003549 A CN 108003549A
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- alloy materials
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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
- 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
Abstract
The invention discloses one kind to regenerate ABS/PP alloy materials, is mainly made of the component of following proportion by weight：Useless ABS：60~90, give up PP：10~40, ABS bases macromolecular chain extender：2~8, PP bases macromolecular chain extender：1~5, chain extension accelerating agent：0.1~0.5.The ABS/PP alloy materials utilize chain extension in situ, In Situ Compatibilization and the toughening effect of macromolecular chain extender, molecular chain structure has been repaired, boundary has been improved, adds compatibility, improves glue content, the regenerated plastics alloy material of high comprehensive performance has been made, and waste utilization has fully been carried out, realize energy-saving and emission-reduction.The invention also discloses the preparation method of above-mentioned regeneration ABS/PP alloy materials.
Description
Technical field
The invention belongs to useless PP and useless ABS technical field of regeneration, and in particular to one kind regeneration ABS/PP alloy materials and its
Preparation method.
Background technology
Polypropylene (PP) and acrylonitrile-butadiene-styrene copolymer (ABS) they are two kinds of very common plastics, the two
In contrast：PP has the advantages such as low-density, nontoxic, price is low, easy processing, while there is low rigidity, poor dimensional stability, lacks
The deficiencies of mouthful when low temperature (especially) is sensitive；Then comprehensive mechanical property is good, hardness is high, dimensionally stable by ABS, for its price is compared with PP
It is more slightly higher.The performance and price of the two have certain complementarity.
The usage amount of both plastics of PP and ABS is very huge, its discarded amount is also very considerable.For the place of waste plastics
Reason, is a kind of efficient and rational mode by its recycling.Learnt by structure after analyzing ABS and PP agings respectively, the two
The influence of light, heat, oxygen in use, occurs molecular structure fracture or resets, generate the group such as hydroxyl and carboxyl, directly
Connecing causes：1) maintain the main chain of main macroscopic mechanical performance to be broken in useless PP and useless ABS, cause penalty；2) give up ABS
Middle rubber phase is impacted larger, and the interface binding power of one side rubber phase and matrix phase, which reduces, causes comprehensive mechanical performance to decline,
On the other hand, glue content, which significantly reduces, causes toughness deterioration more notable.
In view of the above-mentioned problems, if useless PP and useless ABS can directly be prepared alloy, and make full use of useless PP and useless ABS agings
Afterwards, the hydroxyl and carboxyl isoreactivity group generated, useless PP and useless ABS strands to degradation with aging carry out chain extension, improve and give up
ABS rubber phases and matrix phase boundary, lifting glue content, the useless ABS of increase and useless PP compatibilities, will obtain a kind of performance and carry comprehensively
The secondary alloy material risen.On the other hand, due to belonging to waste material, the price differential given up between PP and useless ABS, compared with virgin material PP and virgin material
Smaller for price differential between ABS so that regeneration ABS/PP has more superiority of effectiveness, its application prospect is extensive.
The content of the invention
It is an object of the invention to provide one kind to regenerate ABS/PP alloy materials, and regeneration ABS/PP alloy materials are using greatly
Chain extension in situ, In Situ Compatibilization and the toughening effect of molecule chain extender, have repaired molecular chain structure, have improved boundary, add
Compatibility, improve glue content, and the regenerated plastics alloy material of high comprehensive performance has been made, and has fully carried out waste profit
With realizing energy-saving and emission-reduction.
The present invention also aims to provide the preparation method of above-mentioned regeneration ABS/PP alloy materials.
Above-mentioned first technical problem of the present invention is achieved by the following technical solution：One kind regeneration ABS/PP alloys
Material, is mainly made of the component of following proportion by weight：
Useless ABS：60~90
Useless PP：10~40
ABS base macromolecular chain extenders：2~8
PP base macromolecular chain extenders：1~5
Chain extension accelerating agent：0.1~0.5.
In each component of above-mentioned regeneration ABS/PP alloy materials：
The ABS base macromolecular chain extenders are preferably acrylonitrile-butadiene-styrene copolymer grafted maleic anhydride
(ABS-g-MAH)。
The PP base macromoleculars chain extender is polypropylene grafted glycidyl methacrylate (PP-g-GMA).
The chain extension accelerating agent is 2-ethyl-4-methylimidazole, benzyl dimethylamine, 2,4,6- tri- (dimethylamino methyl)
One kind in phenol.
The useless ABS is that useless ABS obtains sheet material after broken homogenizing；The useless PP is useless PP by broken equal
Sheet material is obtained after change.
Above-mentioned second purpose of the present invention is achieved through the following technical solutions：Above-mentioned regeneration ABS/PP alloy materials
The preparation method of material, comprises the following steps：Useless ABS, useless PP, ABS base macromolecular chain extender, chain extension accelerating agent are pressed into above-mentioned dosage
Relation mixes, and obtains mixed material, and mixed material fusing, screw speed control are added from the main feeding device of double screw extruder
For 30~45rpm, PP base macromolecular chain extenders are added with melting with magnitude relation from the 4th area of processing of double screw extruder by above-mentioned
The mixed material blending of change, extruded, traction, cooling, pelletizing, that is, be made regeneration ABS/PP alloy materials.
In the preparation method of regeneration ABS/PP alloy materials：
The processing warm area of the double screw extruder is preferably 195~225 DEG C.
Further, six area's temperature of processing of the double screw extruder is preferably successively：195 DEG C, 205 DEG C, 215
DEG C, 225 DEG C, 225 DEG C, 215 DEG C.
The ABS base macromoleculars chain extender added in the present invention can play following three key effects at the same time：
(1) the activity anhydride group on strand can extrude bar with the hydroxyl generated on useless ABS and useless PP agings chain
Chain extending reaction in situ occurs under part, while realizing that useless ABS and useless PP chain ruptures increase and repair, both base materials is realized and are reacted
Type increase-volume；
(2) the ABS main chains of ABS bases macromolecular chain extender, it is substantially similar to useless ABS backbone structures, it is advantageous to improve
The problem of interfacial force weakens after useless ABS agings, realizes that interface is repaired；
(3) ABS bases macromolecular chain extender is also a kind of functionalization ABS high glue powders, adds ABS base macromoleculars chain extender also phase
When in the overall glue content for improving secondary alloy material, playing toughening effect.
The PP base macromolecular chain extenders added in the present invention, contain active epoxy group on main chain, except can be with useless ABS
And hydroxyl on useless PP and carboxyl react realization chain extension in situ and response type increase-volume, improve useless PP agings interface, these
, can also be in the presence of chain extension accelerating agent, with the ABS bases added before outside similar to the effect of ABS base macromolecular chain extenders
Anhydride reaction on macromolecular chain extender, generates (PP-g-ABS) containing polypropylene grafted acrylonitrile-butadiene-styrene copolymer
The product of structure, plays physics compatibilization in the mixture.Response type increase-volume and physics increase-volume act at the same time so that intercrescence again
The compatibility of golden material greatly improves, its comprehensive mechanical performance is substantially improved.
In addition, above two chain extender is added by the way of substep, be in order to avoid and meanwhile add both chain extenders
When, it may directly react, and largely consume activity anhydride and epoxide group on itself main chain, influence it to useless PP and give up
The main chain chain extension repairing effect of ABS.
The present invention uses the main chain macromolecular chain extender identical with substrate modified structure, and substrate modified is free of with application
The small molecule chain extender of backbone structure is compared, difference lies in：If adding small molecule chain extender, easily make system middle-molecular-weihydroxyethyl smaller
The intermolecular generation chain extension of aging, even if using polyfunctional group small molecule chain extender, since it reacts steric hindrance, in addition aging
Active group is limited on molecular breakdown chain, it is also difficult to further reaction occurs with other aging molecules, it is a large amount of to ultimately result in generation
The low molecular weight chain extension product of too big help is had no to macro property.And it is chain extending reaction using the advantage of macromolecular chain extender
Occurring between macromolecular chain extender and aging chain rupture molecule, the product of generation also belongs to macromolecular, therefore with excellent
Macro-mechanical performance, this with using small molecule chain extender, it is completely different.
On the other hand, temperature and screw speed have a great influence the comprehensive performance of secondary alloy.Longer extrusion retention time
The generation of original position chain extending reaction when higher temperature may advantageously facilitate extrusion, but too long of process time and too high temperature are again
It may cause the decomposition of regrown material.By controlling 30~45rpm of screw speed, processing warm area, can be or not 195~225 DEG C
On the premise of influencing chain extension effect in situ, regrown material is avoided to decompose.
Compared with prior art, the present invention has the following advantages：
(1) present invention directly carries out original with the use of two class difference macromolecular chain extenders to useless ABS and useless PP at the same time first
Position chain extension reparation prepares secondary alloy, and macromolecular chain extender plays chain extension in situ, original position at the same time in secondary alloy preparation process
Increase-volume and toughening effect, so as to obtain a kind of extensive regrown material of application prospect；
(2) whole process of the present invention uses conventional device of plastic processing, by preferable technique, carries out anti-
Answer type to extrude, therefore can easily be promoted and applied；
(3) present invention provides a kind of brand-new solution to mix the higher value application of waste plastics, has also driven regeneration
The development of plastic industry, while Related product has the very strong market competitiveness, and meet national energy-saving emission reduction policy, have
Good Social benefit and economic benefit.
Embodiment
Embodiment 1
Regeneration ABS/PP alloy materials provided in this embodiment based on chain extension reparation in situ, are mainly matched somebody with somebody by following mass parts
The component composition of ratio：
Useless ABS：60
Useless PP：40
ABS base macromolecular chain extenders：4
PP base macromolecular chain extenders：3
Chain extension accelerating agent：0.3
Wherein ABS bases macromolecular chain extender is acrylonitrile-butadiene-styrene copolymer grafted maleic anhydride (ABS-g-
MAH).PP base macromoleculars chain extender is polypropylene grafted glycidyl methacrylate (PP-g-GMA).
Chain extension accelerating agent is 2-ethyl-4-methylimidazole.
Useless ABS is that useless ABS obtains sheet material after broken homogenizing.
Useless PP is that useless PP obtains sheet material after broken homogenizing.
The preparation method of regeneration ABS/PP alloy materials, comprises the following steps：By useless ABS, useless PP, ABS base macromolecular
Chain extender, chain extension accelerating agent are mixed as above-mentioned with magnitude relation, obtain mixed material, are added from the main feeding device of double screw extruder
Enter mixed material fusing, screw speed control is 30rpm, and machine the 4th area from twin-screw extrusion is added as above-mentioned with magnitude relation
PP base macromolecular chain extenders and the mixed material of fusing are blended, extruded, traction, cooling, pelletizing, that is, regeneration ABS/PP is made and closes
Golden material.
Twin-screw extrusion machines six area's temperature and is set as successively：195 DEG C, 205 DEG C, 215 DEG C, 225 DEG C, 225 DEG C, 215
℃。
Embodiment 2
Regeneration ABS/PP alloy materials provided in this embodiment based on chain extension reparation in situ, are mainly matched somebody with somebody by following mass parts
The component composition of ratio：
Useless ABS：60
Useless PP：40
ABS base macromolecular chain extenders：6
PP base macromolecular chain extenders：5
Chain extension accelerating agent：0.5.
Useless ABS, useless PP, ABS base macromolecular chain extender, PP base macromolecular chain extenders are the same as embodiment 1.
Chain extension accelerating agent is benzyl dimethylamine.
The preparation method of regeneration ABS/PP alloy materials, comprises the following steps：By useless ABS, useless PP, ABS base macromolecular
Chain extender, chain extension accelerating agent are mixed as above-mentioned with magnitude relation, obtain mixed material, are added from the main feeding device of double screw extruder
Enter mixed material fusing, screw speed control is 45rpm, and machine the 4th area from twin-screw extrusion is added as above-mentioned with magnitude relation
PP base macromolecular chain extenders and the mixed material of fusing are blended, extruded, traction, cooling, pelletizing, that is, regeneration ABS/PP is made and closes
Golden material.
Twin-screw extrusion machines six area's temperature and is set as successively：195 DEG C, 205 DEG C, 215 DEG C, 225 DEG C, 225 DEG C, 215
℃。
Embodiment 3
Regeneration ABS/PP alloy materials provided in this embodiment based on chain extension reparation in situ, are mainly matched somebody with somebody by following mass parts
The component composition of ratio：
Useless ABS：70
Useless PP：30
ABS base macromolecular chain extenders：7
PP base macromolecular chain extenders：5
Chain extension accelerating agent：0.5
Useless ABS, useless PP, ABS base macromolecular chain extender, PP base macromolecular chain extenders are the same as embodiment 1.
Chain extension accelerating agent is 2,4,6- tri- (dimethylamino methyl) phenol.
The preparation method of regeneration ABS/PP alloy materials, comprises the following steps：By useless ABS, useless PP, ABS base macromolecular
Chain extender, chain extension accelerating agent are mixed as above-mentioned with magnitude relation, obtain mixed material, are added from the main feeding device of double screw extruder
Enter mixed material fusing, screw speed control is 36rpm, and machine the 4th area from twin-screw extrusion is added as above-mentioned with magnitude relation
PP base macromolecular chain extenders and the mixed material of fusing are blended, extruded, traction, cooling, pelletizing, that is, regeneration ABS/PP is made and closes
Golden material.
Twin-screw extrusion machines six area's temperature and is set as successively：195 DEG C, 205 DEG C, 215 DEG C, 225 DEG C, 225 DEG C, 215
℃。
The mechanical performance of regeneration ABS/HIPS alloy materials prepared by embodiment 1-3 is summarized as follows table 1.
The mechanical performance of regeneration ABS/HIPS alloy materials prepared by 1 embodiment 1-3 of table collects
In above-mentioned table 1：
1. preparation method and step are with embodiment 1, without ABS base macromoleculars chain extender, PP base macromoleculars in material proportion
Chain extender and chain extension accelerating agent.
The regeneration ABS/PP alloys prepared it can be seen from above specific experiment data by the present invention, General Promotion
The mechanical performance of waste material, particularly to the more sensitive impact strength of backbone molecule amount, molecular chain structure, phase interface effect significantly
Improve 2.6~3.8 times.Secondary alloy product with this comprehensive mechanical performance, good market prospect.
Above-described embodiment is the preferable embodiment of the present invention, the ABS base macromolecular chain extenders ABS- selected in embodiment
G-MAH, PP base macromolecular chain extender PP-g-GMA, chain extension accelerating agent for 2-ethyl-4-methylimidazole, benzyl dimethylamine, 2,4,
(dimethylamino methyl) phenol of 6- tri- is obtained by commercially available off-the-shelf.
But embodiments of the present invention are simultaneously not restricted to the described embodiments, selected useless ABS in the above embodiment,
The off-the-shelf of commercially available similar performance also can be selected in the raw materials such as useless PP, real without other any spirit without departing from the present invention
Matter with made under principle change, modification, replacement, combine, simplification, should be equivalent substitute mode, be included in the present invention
Protection domain.
Claims (8)
1. one kind regeneration ABS/PP alloy materials, it is characterized in that being mainly made of the component of following proportion by weight：
Useless ABS：60~90
Useless PP：10~40
ABS base macromolecular chain extenders：2~8
PP base macromolecular chain extenders：1~5
Chain extension accelerating agent：0.1~0.5.
2. regeneration ABS/PP alloy materials according to claim 1, it is characterized in that：The ABS base macromolecular chain extenders
For acrylonitrile-butadiene-styrene copolymer grafted maleic anhydride.
3. regeneration ABS/PP alloy materials according to claim 1, it is characterized in that：The PP base macromolecular chain extenders are
Polypropylene grafted glycidyl methacrylate.
4. regeneration ABS/PP alloy materials according to claim 1, it is characterized in that：The chain extension accelerating agent is 2- second
One kind in base -4-methylimidazole, benzyl dimethylamine, 2,4,6- tri- (dimethylamino methyl) phenol.
5. regeneration ABS/PP alloy materials according to claim 1, it is characterized in that：The useless ABS is useless ABS by broken
Sheet material is obtained after broken homogenizing；The useless PP is that useless PP obtains sheet material after broken homogenizing.
6. claim 1-5 any one of them regenerates the preparation method of ABS/PP alloy materials, it is characterized in that including following step
Suddenly：Useless ABS, useless PP, ABS base macromolecular chain extender, chain extension accelerating agent are mixed as above-mentioned with magnitude relation, obtain mixed material,
Mixed material fusing is added from the main feeding device of double screw extruder, screw speed control is 30~45rpm, is squeezed from twin-screw
The 4th area of processing for going out machine adds PP base macromolecular chain extenders and the mixed material blending of fusing by above-mentioned with magnitude relation, through squeezing
Go out, draw, cooling down, pelletizing, that is, regeneration ABS/PP alloy materials are made.
7. the preparation method of regeneration ABS/PP alloy materials according to claim 6, it is characterized in that：The twin-screw squeezes
The processing warm area for going out machine is 195~225 DEG C.
8. the preparation method of regeneration ABS/PP alloy materials according to claim 7, it is characterized in that：The twin-screw squeezes
The six area's temperature of processing for going out machine is followed successively by：195 DEG C, 205 DEG C, 215 DEG C, 225 DEG C, 225 DEG C, 215 DEG C.
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