CN105462149A - Macromolecular compatilizer for ABS (acrylonitrile-butadiene-styrene)-HIPS (high impact polystyrene) alloys and preparation method of macromolecular compatilizer - Google Patents
Macromolecular compatilizer for ABS (acrylonitrile-butadiene-styrene)-HIPS (high impact polystyrene) alloys and preparation method of macromolecular compatilizer Download PDFInfo
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- CN105462149A CN105462149A CN201510907018.4A CN201510907018A CN105462149A CN 105462149 A CN105462149 A CN 105462149A CN 201510907018 A CN201510907018 A CN 201510907018A CN 105462149 A CN105462149 A CN 105462149A
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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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
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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
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
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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
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Abstract
The invention provides a macromolecular compatilizer for ABS (acrylonitrile-butadiene-styrene)-HIPS (high impact polystyrene) alloys and a preparation method of the macromolecular compatilizer. The compatilizer comprises components in percentage by weight as follows: styrene monomers, glycidyl acrylate monomers, a free radical initiator and SAM (styrene-maleic anhydride-acrylonitrile). The preparation method comprises steps as follows: the styrene monomers, the glycidyl acrylate monomers and the free radical initiator react with a polymerization method, and a copolymer is obtained; the copolymer is uniformly mixed with SAM, and the macromolecular compatilizer for the ABS-HIPS alloys is obtained with a melt blending method. The macromolecular compatilizer has the benefits as follows: the amphipathic macromolecular compatilizer is obtained through one-step reaction and melt blending, a preparation process is simple, the proportion of polystyrene chain segments to SAM chain segments in the compatilizer is better adjusted, and the macromolecular compatilizer is suitable for blending systems of ABS and HIPS in various proportions. Experiment results show that the compatilizer has a remarkable compatibilization effect.
Description
Technical field
The present invention relates to a kind of Macromolecular Compatibilizer for ABS-HIPS alloy and preparation method thereof, belong to plastic compatible agent technical field.
Background technology
The usual mechanical property of the blended products therefrom of incompatible polymer is bad, and tracing it to its cause is because interface binding power is weak between each phase mostly, caused by Dispersed Phase Size is comparatively large.The means of current modifying plastics industry universal add compatilizer.Compatilizer adds on a small quantity and can strengthen interface binding power, refinement Dispersed Phase Size thus obtain the good product of mechanical property.Current compatilizer can be block polymerization, graft polymerization or random copolymers.
Acrylonitrile-butadiene-styrene copolymer (ABS) and high-impact polystyrene (HIPS) have excellent mechanical property, and be easy to forming process, be widely used in the electric and office equipment fields such as household electrical appliance, computer and perimeter equipment, print copying device.Along with the replacement cycle of the electronics such as household electrical appliance, computer is shorter and shorter, a large amount of ABS and the HIPS plastic that need recovery will be produced.Independent ABS or HIPS reclaims not much problems, but ABS and HIPS consistency extreme difference, even if having few HIPS or polystyrene (PS) to be mixed into ABS all may produce the problems such as layering, peeling, physicals deterioration.And HIPS and ABS Application Areas is overlapping, outward appearance and similar density, even strict management and control sorting has part to be mixed into all unavoidably.This brings larger problem to the recovery of ABS and HIPS.
How to improve ABS/HIPS blend performance to have become, reclaim ABS, HIPS field problem demanding prompt solution.Dong Zhixian, Zhou Yanhao etc. have studied chlorinatedpolyethylene, (styrene/butadiene/styrene) segmented copolymer (SBS) and K resin has compatibilization and toughening modifying function in various degree to ABS/HIPS intermingling material.Styrenic mixing reclaimed materials CN102888072A, styrenic mixing reclaimed materials preparation method CN102863735A, ABS and HIPS mixture is reclaimed in two parts of patent core-shell tougheners and styrenic block polymers modification.Existing what be used as ABS/HIPS compatilizer is segmented copolymer good with PS component compatibility mostly, not good with ABS consistency, can not be dispersed in the result that two-phase interface plays good increase consistency, just by the toughness reinforcing blend of its rubber property.
Summary of the invention
Object of the present invention is providing a kind of for ABS-HIPS compatilizer preparation method.This compatilizer can solve the problem such as peeling, layering, physicals deterioration that ABS-HIPS blend compatibility difference causes.
The present invention is achieved by the following technical solutions:
First aspect, the invention provides a kind of Macromolecular Compatibilizer for ABS-HIPS alloy, and it comprises the following component counted by weight:
Glycidyl acrylate class monomer content is too high, easily forms crosslinking structure, causes plastifying, compatilizer effect declines greatly, the too low person of content and SAM react not obvious, formation have the polymkeric substance of compatilizer effect very few, compatibilized effect is also undesirable, radical initiator too high levels, speed of response is too fast, is polymerized wayward, and the too low speed of response of content is slow, reaction is incomplete, low conversion rate.It is also waste that SAM too high levels does not have enough SG to react with it, and the compatibilizer content that very few person is formed is few, promotes that com-patibilising effect is not good.
Preferably, described styrene monomer is selected from least one in vinylbenzene, vinyl toluene, vinylstyrene, tert. butylstyrene.
Preferably, described glycidyl acrylate class monomer is selected from the one in glycidyl acrylate, glycidyl methacrylate.
Preferably, in described SAM, the massfraction of maleic anhydride is 1 ~ 30%.
Second aspect, present invention also offers a kind of as the aforementioned for the preparation method of the Macromolecular Compatibilizer of ABS-HIPS alloy, it comprises the steps:
Styrene monomer, glycidyl acrylate class monomer, radical initiator are reacted by the method for polymerization at 65 ~ 95 DEG C, obtains multipolymer;
After being mixed with SAM by described multipolymer, by the method for melt blending in twin screw extruder, obtain the Macromolecular Compatibilizer for ABS-HIPS alloy.
Preferably, the method for described polymerization is mass polymerization, solution polymerization or suspension polymerization.
Preferably, the ratio of described multipolymer and SAM is 1:1 ~ 1:9.
The present invention reacts under adopting styrene-t glycidyl ester copolymer (SG) and phenylethylene-maleic anhydride-acrylonitrile copolymer (SAM) molten state, prepare the compatilizer of PS-g-SAM structural polymer as ABS-HIPS, based on the macromolecular structure of long-chain grafting, utilize SAM molecular chain compatible with AS in ABS phase, the feature that vinylbenzene epoxy copolymerized thing segment is compatible with polystyrene, makes Macromolecular Compatibilizer effectively can improve consistency between ABS, HIPS.
Beneficial outcomes of the present invention is: adopt reactive mode to obtain the polystyrene segment with reactive epoxy groups, the Macromolecular Compatibilizer of amphiphilic can be obtained by single step reaction melt blending, preparation technology is simple, and better regulate the ratio of polystyrene segment and SAM segment in compatilizer, go for the ABS/HIPS co-mixing system of multiple ratio.Show from experimental result, this compatilizer has obvious compatibilization effect.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
embodiment 1
Prepare raw material in following ratio, polymerization process is solution polymerization
Diisopropyl azodicarboxylate is dissolved in vinylbenzene, then adds glycidyl methacrylate, mix in rear importing flask, then pour the dried toluene of 45ml into, add magneton, connect spherical condensation tube, vacuumize, nitrogen protection.Controlling temperature of reaction is 90 DEG C, and pass into water of condensation, the reaction times is 12h.Get 80ml ethanol to precipitate, to be precipitated leave standstill after, remove supernatant liquid, obtain bottom sediment, add 50ml methylene dichloride and carry out secondary dissolving.Until completely dissolved, slowly instilled in 80ml methyl alcohol by solution, pour Büchner funnel into after obtaining white powder precipitation and carry out vacuum filtration, put into watch-glass after obtaining white precipitate, product is put into vacuum drying oven dry, temperature is set to 50 DEG C.
By the multipolymer that obtains and industrial SAM, be mixed in high-speed mixer machine even, be added in twin screw extruder, extruder temperature is arranged between 180 DEG C-220 DEG C, and mixture is frit reaction at this temperature.Through extruding tie rod, cooling granulation, drying obtain required compatilizer.
embodiment 2
Prepare raw material in following ratio, polymerization process is suspension polymerization
Add 1200ml de-salted water in 3000ml there-necked flask, be warming up to 85 DEG C, add 6g polyvinyl alcohol, start and stir, until polyvinyl alcohol dissolves completely.Measure vinyl toluene, glycidyl acrylate, dibenzoyl peroxide in proportion, after mixing, add there-necked flask, stopped reaction after reaction 7h.Fully wash with hot desalinized water, the dispersion agent of removing surface attachment and monomer, then drying for standby.
By the multipolymer that obtains and industrial SAM, be mixed in high-speed mixer machine even, be added in twin screw extruder, extruder temperature is arranged between 180 DEG C-220 DEG C, and mixture is frit reaction at this temperature.Through extruding tie rod, cooling granulation, drying obtain required compatilizer.
embodiment 3
Prepare raw material in following ratio, polymerization process is mass polymerization
Vinylbenzene, glycidyl methacrylate, dibenzoyl peroxide are weighed up in proportion, mixes and pour in three-necked bottle, vacuumize and pass into nitrogen protection; logical water of condensation, oil bath is heated to 80 DEG C, reaction 1h; react 12h proceeding in the water-bath of 60 DEG C, obtain polymkeric substance.
By the multipolymer that obtains and industrial SAM, be mixed in high-speed mixer machine even, be added in twin screw extruder, extruder temperature is arranged between 180 DEG C-220 DEG C, and mixture is frit reaction at this temperature.Through extruding tie rod, cooling granulation, drying obtain required compatilizer.
embodiment 4
Prepare raw material in following ratio, polymerization process is suspension polymerization
Add 1200ml de-salted water in 3000ml there-necked flask, be warming up to 75 DEG C, add 7g polyvinyl alcohol, start and stir, until polyvinyl alcohol dissolves completely.Measure ethyl styrene, glycidyl acrylate, dibenzoyl peroxide in proportion, after mixing, add there-necked flask, after reaction 6h, be warmed up to 95 DEG C of reactions 1 hour, then stopped reaction.Fully wash with hot desalinized water, the dispersion agent of removing surface attachment and monomer, then drying for standby.
By the multipolymer that obtains and industrial SAM, be mixed in high-speed mixer machine even, be added in twin screw extruder, extruder temperature is arranged between 180 DEG C-220 DEG C, and mixture is frit reaction at this temperature.Through extruding tie rod, cooling granulation, drying obtain required compatilizer.
comparative example 1
Select report for the Macromolecular Compatibilizer block copolymer SBS (C001) of ABS/HIPS alloy, and the Compatibilizer C 002 (preparing gained by embodiment 2) prepared of this patent institute extracting method and C003 (preparing gained by enforcement 4).Select the strange beautiful ABS (trade mark: PA757) in Zhenjiang and Shanghai match section HIPS (trade mark: 622P), according to the mass ratio of 7:3, add compatilizer 3wt%, at 200-220 degree Celsius of lower extruding pelletization in twin screw extruder, then according to ASTM standard injection moulding test sample.The mechanical property of beta alloy, result is as shown in the table:
| C001 | C002 | C003 | |
| Flexural strength MPa | 43 | 55 | 60 |
| Modulus in flexure MPa | 2063 | 2203 | 2221 |
| Tensile strength Mpa | 41 | 51 | 52 |
| IZOD notched Izod impact strength J/m | 90 | 131 | 143 |
ABS/HIPS compatilizer prepared by the present invention effectively can improve the consistency between ABS and HIPS, thus improves the mechanical property of alloy.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (7)
1. for a Macromolecular Compatibilizer for ABS-HIPS alloy, it is characterized in that, comprise the following component counted by weight:
2., as claimed in claim 1 for the Macromolecular Compatibilizer of ABS-HIPS alloy, it is characterized in that, described styrene monomer is selected from least one in vinylbenzene, vinyl toluene, vinylstyrene, tert. butylstyrene.
3., as claimed in claim 1 for the Macromolecular Compatibilizer of ABS-HIPS alloy, it is characterized in that, described glycidyl acrylate class monomer is selected from the one in glycidyl acrylate, glycidyl methacrylate.
4., as claimed in claim 1 for the Macromolecular Compatibilizer of ABS-HIPS alloy, it is characterized in that, in described SAM, the massfraction of maleic anhydride is 1 ~ 30%.
5., as claimed in claim 1 for a preparation method for the Macromolecular Compatibilizer of ABS-HIPS alloy, it is characterized in that, comprise the steps:
Styrene monomer, glycidyl acrylate class monomer, radical initiator are reacted by the method for polymerization at 65 ~ 95 DEG C, obtains multipolymer;
After being mixed with SAM by described multipolymer, by the method for melt blending in twin screw extruder, obtain the Macromolecular Compatibilizer for ABS-HIPS alloy.
6., as claimed in claim 5 for the preparation method of the Macromolecular Compatibilizer of ABS-HIPS alloy, it is characterized in that, the method for described polymerization is mass polymerization, solution polymerization or suspension polymerization.
7., as claimed in claim 5 for the preparation method of the Macromolecular Compatibilizer of ABS-HIPS alloy, it is characterized in that, the ratio of described multipolymer and SAM is 1:1 ~ 1:9.
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| CN201510907018.4A CN105462149A (en) | 2015-12-09 | 2015-12-09 | Macromolecular compatilizer for ABS (acrylonitrile-butadiene-styrene)-HIPS (high impact polystyrene) alloys and preparation method of macromolecular compatilizer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109294145A (en) * | 2017-07-25 | 2019-02-01 | 中国石油化工股份有限公司 | PS/ASA alloy composite and PS/ASA alloy material and its application |
| CN110615872A (en) * | 2019-09-03 | 2019-12-27 | 铨盛聚碳科技股份有限公司 | Epoxy group-containing core-shell structure compatilizer and preparation method thereof |
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| CN109294145A (en) * | 2017-07-25 | 2019-02-01 | 中国石油化工股份有限公司 | PS/ASA alloy composite and PS/ASA alloy material and its application |
| CN109294145B (en) * | 2017-07-25 | 2020-12-18 | 中国石油化工股份有限公司 | PS/ASA alloy composition, PS/ASA alloy material and application thereof |
| CN110615872A (en) * | 2019-09-03 | 2019-12-27 | 铨盛聚碳科技股份有限公司 | Epoxy group-containing core-shell structure compatilizer and preparation method thereof |
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