CN108329646A - A kind of highly resistance is leapt high flowing ABS resin and preparation method thereof - Google Patents
A kind of highly resistance is leapt high flowing ABS resin and preparation method thereof Download PDFInfo
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- CN108329646A CN108329646A CN201711323967.3A CN201711323967A CN108329646A CN 108329646 A CN108329646 A CN 108329646A CN 201711323967 A CN201711323967 A CN 201711323967A CN 108329646 A CN108329646 A CN 108329646A
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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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only 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
- 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
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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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
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Abstract
The invention belongs to technical field of polymer materials, and in particular to a kind of highly resistance is leapt high the preparation method of flowing ABS resin.This method prepares the ABS resin of high impact by DOW continuous bulks first, and ontology ABS resin, SAN resins, plasticizer, lubricant, compatilizer are added in blender and are sufficiently mixed by the percentage of certain mass, obtains mixed material；Obtained mixed material is finally sent into double screw extruder, be kneaded, squeezed out, tie rod, cooling, pelletizing, obtain high-impact, high flowing ABS resin.The ABS resin that the present invention is prepared has advantageous Ground shock waves performance；Compatilizer is added during blending simultaneously, increases the compatibility of ABS resin and SAN resins, bonding force increases between being allowed to two kinds of polymer, forms more stable structure.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of highly resistance is leapt high flowing ABS resin and its preparation
Method.
Background technology
ABS resin is the high molecular material made of styrene, acrylonitrile and butadiene copolymerization, has excellent resultant force
Learn performance.It is recently as fields such as automobile and electrical appliance industries fast-developing so that ABS resin is flowed towards height and high-impact
The direction of performance is developed.
At present there are two types of the preparation methods of ABS resin, i.e. emulsion graft polymerization blending method and continuous bulk.Emulsion graft polymerization blends
Method is that ABS resin carries out industrialized method earliest.The particle size and distribution controllability of this method latex are stronger, while can give birth to
The grafting powder product of high-glue content is produced, but the technique productions are of high cost, environmental pollution is big, while remaining auxiliary agent is to product
It is affected, so seriously constraining its production；Continuous bulk applies more wide model, the life in industrialized production at present
Production. art concision and compact, pollution is small, can carry out continuous production, while using four reaction kettle laminar flow techniques material is being filled
It sets that the middle residence time is longer, can be prepared with the ABS resin compared with high impact.
Chinese patent CN105733120 disclose it is a kind of prepare high flowing, high impact ABS resin method, anti-
Preparation ABS graft latexes in kettle are answered, being dried to obtain ABS using 80-90 DEG C is grafted powder；By emulsion method SAN resins and ontology
Method SAN resins are mixed with high flowing SAN resins；It is high in proportion that above-mentioned ABS is grafted powder, high flowing SAN resins, auxiliary agent etc.
5-10min is blended in speed, and the ABS resin highest melt index finally prepared can reach 65g/10min, and impact strength is on the left sides 175J/m
The right side, and melt index, in 25-37g/10min, impact strength is in 160-200J/m or so.
Chinese patent CN103923429A disclose it is a kind of it is high flowing ABS resin preparation method, by ABS be grafted powder,
SAN resins, melt viscosity modifying agent and lubricant etc. are put into super mixer into mixing is granulated after two minutes, is obtained
The melt index of ABS resin be 27g/min or so, impact strength is between 250-262J/m；After material is mixed five minutes
It is granulated, the melt index of ABS resin can be increased to 30g/min, but impact strength decreased is to 175J/m；And it is material is first
Mixing two minutes, remixes two minutes, 350J/ can be improved in the impact strength of ABS resin product after adding a part of auxiliary agent
M, but melt index is reduced to 10g/min again.
The mechanical property of ABS resin can be reduced while improving mobile performance by preparing high flowing ABS resin with blending method,
If not influencing the mechanical property of ABS resin its mobile performance can not be greatly improved.It is above-mentioned in order to solve the problems, such as,
The present invention utilizes ABS resin prepared by continuous bulk, itself has certain mobility, while having higher impact strong
Degree can increase substantially the melt index of high ABS resin, while keeping excellent power using ontology ABS resin as blending matrix
Learn performance.
Invention content
The present invention is above-mentioned in order to solve the problems, such as, ABS resin is prepared using continuous bulk, itself has certain
Mobility, while there is higher impact strength, using ontology ABS resin as blending matrix, high ABS trees can be increased substantially
The melt index of fat, while keeping excellent mechanical property.Specific technical solution is as follows：
A kind of high-impact, high flowing ABS resin material, are grouped as by the group of following mass percent：
Wherein, the ontology ABS resin is using prepared by four reaction kettle laminar flow techniques.
Wherein, the rubber content of the ontology ABS resin is in 8%-15%, styrene-content 30%-70%, acrylonitrile
Content 20%-30%, melt index 11-20g/min, impact strength 210-280J/m.
Wherein, the styrene-content 40%-75% of the SAN resins, weight average molecular weight 1 × 106-2×106g/mol。
Wherein, the plasticizer be phthalate, citric acid ester type, phosphoric acid ester, epoxies one kind or
It is a variety of.
Wherein, the lubricant be ethylene bis stearamide, silicone oil, polyethylene wax, stearate it is one or more.
Wherein, the compatilizer is maleic anhydride analog copolymer, such as SEBS-g-MAH, EPDM-g-MAH, ST-co-MAH
Or maleic anhydride stem grafting polyolefin.
The preparation method of a kind of high-impact, high flowing ABS resin material, includes the following steps：
(a) by the rubber of chopping, ethylbenzene, acrylonitrile and styrene, in colloidal sol kettle mixed dissolution to uniform original gelatin,
The original gelatin dissolved is sent it is for use to raw material storage still, then by conveying equipment by the original gelatin in raw material storage still send successively to
First, second, third and fourth piston flow reactor carries out bulk polymerization, finally enters extruder, carries out devolatilization and is granulated to obtain ontology
ABS resin product；
(b) the ontology ABS resin that step (a) is obtained by mass percentage, SAN resins, plasticizer, lubricant, compatible
Agent, which is added in blender, to be carried out being sufficiently mixed 30, obtains mixed material；
(c) obtained mixed material in step (b) is sent into double screw extruder, is kneaded, is squeezed out, is tie rod, cold
But, pelletizing is to get the ABS resin flowed to high-impact, height.
The draw ratio of the double screw extruder be 40-48, screw speed 400-600rmp, 210 DEG C of head temperature,
Barrel temperature：200-230 DEG C of leading portion, 200-240 DEG C of stage casing, 200-230 DEG C of back segment.
A kind of melt index of high-impact, high flowing ABS resin is 30-50g/10min, impact strength 195-
265J/m。
Beneficial effects of the present invention
Compared with the existing method for preparing high flowing ABS resin, the present invention solves high flowing ABS resin impact strength
Relatively low problem.In addition, the present invention prepares ABS resin using DOW chemistry continuous bulks, can be prepared by adjusting technological parameter
The ABS resin of a variety of trades mark so that ABS resin can have certain mobile performance, while make one of reaction in preparation process
Material is divided to realize cycle inside polymerization system, and reaction mass is simultaneously filled with four reaction kettles during the reaction, makes
The residence time of reaction mass in the reactor is long, and polymerisation is complete, and the ABS resin being prepared has again to be rushed advantageously
Hit performance；Compatilizer is added during blending simultaneously, increases the compatibility of ABS resin and SAN resins, is allowed to two kinds and gathers
Bonding force increases between closing object, forms more stable structure.
Specific implementation mode
The present invention is further explained in the light of specific embodiments.
In embodiment 1-9, ontology ABS resin selects ABS8434 and ABS3504 prepared by laminar flow continuous bulk；SAN
Resin selects strange beautiful PN-107L150；Plasticizer selects phthalic acid ester；Lubricant selects silicone oil；Compatilizer selects Malaysia
Acid anhydrides graft copolymer SEBS-g-MAH.
Prepared ABS resin carries out the test of physical properties in embodiment 1-9, and each quantitative measurement standard is such as
Shown in following table
Embodiment 1-3
Ontology ABS resin 8434, SAN resins, plasticizer, lubricant and compatilizer are added to stirring in the ratio of table 1
It is sufficiently mixed in machine, obtains mixed material；Obtained mixed material is sent into double screw extruder again, be kneaded,
Extrusion, tie rod, cooling, pelletizing, wherein screw speed be 500rmp, 210 DEG C of head temperature, 200-230 DEG C of machine barrel front-end temperature,
200-240 DEG C of stage casing temperature, 200-230 DEG C of back segment temperature.
Table 1：Specifically each material composition matches embodiment 1-3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| ABS resin 8434 | 55% | 60% | 65% |
| SAN resins | 37% | 32% | 27% |
| Plasticizer | 3% | 3% | 3% |
| Lubricant | 2% | 2% | 2% |
| Compatilizer | 3% | 3% | 3% |
Table 2：The physical properties test result of ABS resin prepared by embodiment 1-3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Melt index (g/min) | 47 | 44 | 40 |
| Tensile strength (MPa) | 40 | 42 | 45 |
| Bending strength (MPa) | 81 | 83 | 85 |
| Bending modulus (MPa) | 2492 | 2526 | 2588 |
| Impact strength (J/m) | 211J/m | 221J/m | 229J/m |
Embodiment 4-6
Ontology ABS resin 3504, SAN resins, plasticizer, lubricant and compatilizer are added to stirring in the ratio of table 1
It is sufficiently mixed in machine, obtains mixed material；Obtained mixed material is sent into double screw extruder again, be kneaded,
Extrusion, tie rod, cooling, pelletizing, wherein screw speed be 500rmp, 210 DEG C of head temperature, 200-230 DEG C of machine barrel front-end temperature,
200-240 DEG C of stage casing temperature, 200-230 DEG C of back segment temperature.
Table 3：Specifically each material composition matches embodiment 4-6
| Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| ABS resin 3504 | 55% | 60% | 65% |
| SAN resins | 37% | 32% | 27% |
| Plasticizer | 3% | 3% | 3% |
| Lubricant | 2% | 2% | 2% |
| Compatilizer | 3% | 3% | 3% |
As a result table 4：The physical properties of ABS resin prepared by embodiment 4-6 are tested
| Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Melt index (g/min) | 41 | 35 | 30 |
| Tensile strength (MPa) | 44 | 45 | 47 |
| Bending strength (MPa) | 85 | 87 | 88 |
| Bending modulus (MPa) | 2587 | 2646 | 2688 |
| Impact strength (J/m) | 237/m | 254J/m | 262J/m |
Embodiment 7-9
Ontology ABS resin 8434, ontology ABS resin 3504, SAN resins, plasticizer, lubricant and compatilizer are pressed into table 1
Ratio be added in blender and be sufficiently mixed, obtain mixed material；Obtained mixed material is sent into twin-screw again
Extruder, be kneaded, squeezed out, tie rod, cooling, pelletizing, wherein screw speed be 500rmp, 210 DEG C of head temperature, before machine barrel
Duan Wendu 200-230 DEG C, 200-240 DEG C of stage casing temperature, 200-230 DEG C of back segment temperature.
Table 5：Specifically each material composition matches embodiment 7-9
| Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| ABS resin 8434 | 40% | 30% | 20% |
| ABS resin 3504 | 20% | 30% | 40% |
| SAN resins | 32% | 32% | 32% |
| Plasticizer | 3% | 3% | 3% |
| Lubricant | 2% | 2% | 2% |
| Compatilizer | 3% | 3% | 3% |
Table 6：The physical properties test result of ABS resin prepared by embodiment 7-9 and with embodiment 2,5 compare
By above-mentioned experimental result it is found that can be prepared with high fluidity using ontology ABS resin and SAN resin alloys
The ABS resin of energy, high impact property, and with the raising of ontology ABS resin content, the impact property of product increases,
But melt index is declined；Be matrix with ontology ABS resin 8343, the product melt index of preparation is larger, impact strength compared with
It is low, it is matrix with ontology ABS resin 3504, the product melt index of preparation is smaller, and impact strength is higher, so can press the two
Proportion adjustment is blended, and prepares the melt index of product in 35-45g/min, impact strength can make product in 230-250J/m
Have both processing performance and mechanical property simultaneously.
Claims (9)
- The flowing ABS resin 1. a kind of highly resistance is leapt high, which is characterized in that percentage, including following components：The rubber content of the ontology ABS resin is in 8%-15%, styrene-content 30%-70%, acrylonitrile content 20%- 30%, melt index 11-20g/min, Izod notched impact strength 210-280J/m.
- The flowing ABS resin 2. a kind of highly resistance according to claim 1 is leapt high, which is characterized in that the ontology SAN resins Styrene-content 40%-75%, weight average molecular weight 1 × 106-2×106g/mol。
- The flowing ABS resin 3. a kind of highly resistance according to claim 1 is leapt high, which is characterized in that the plasticizer is adjacent benzene Diformic ester, citric acid ester type, phosphoric acid ester, epoxies it is one or more.
- The flowing ABS resin 4. a kind of highly resistance according to claim 1 is leapt high, which is characterized in that the lubricant is ethylene Bis-stearamides, silicone oil, polyethylene wax, stearate it is one or more.
- The flowing ABS resin 5. a kind of highly resistance according to claim 1 is leapt high, which is characterized in that the compatilizer is Malaysia Acid anhydrides analog copolymer.
- The flowing ABS resin 6. a kind of highly resistance according to claim 5 is leapt high, which is characterized in that the maleic acid anhydride is total Polymers is SEBS-g-MAH, EPDM-g-MAH, ST-co-MAH or maleic anhydride stem grafting polyolefin.
- 7. a kind of highly resistance according to claim 1 leap high flowing ABS resin preparation method, which is characterized in that including with Lower step：(a) by the rubber of chopping, ethylbenzene, acrylonitrile and styrene, mixed dissolution, will be molten to uniform original gelatin in colloidal sol kettle The original gelatin solved send for use to raw material storage still, then is sent the original gelatin in raw material storage still to successively by conveying equipment One, two, three, four piston flow reactors carry out bulk polymerization, finally enter extruder, carry out devolatilization and are granulated to obtain ontology ABS resin；(b) ontology ABS resin, ontology SAN resins, plasticizer, lubricant, compatilizer are added to blender by mass percentage In be sufficiently mixed, obtain mixed material；(c) obtained mixed material in (b) step is sent into double screw extruder, is kneaded, is squeezed out, tie rod, cooling, is cut Grain to get flowing of leaping high to highly resistance ABS resin.
- The preparation method of flowing ABS resin 8. a kind of highly resistance according to claim 7 is leapt high, which is characterized in that described double The draw ratio of screw extruder is 40-48, screw speed 400-600rmp, 210 DEG C of head temperature, barrel temperature：Leading portion 200-230 DEG C, 200-240 DEG C of stage casing, 200-230 DEG C of back segment.
- The preparation method of flowing ABS resin 9. a kind of highly resistance according to claim 8 is leapt high, which is characterized in that be prepared into Melt index to ABS resin is 30-50g/10min, impact strength 195-265J/m.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467870A (en) * | 2018-10-29 | 2019-03-15 | 北方华锦化学工业股份有限公司 | A kind of low smell highly resistance, which is leapt high, flows ABS resin and preparation method thereof |
| CN113337046A (en) * | 2021-07-23 | 2021-09-03 | 浙江智英石化技术有限公司 | Preparation method of ABS resin particles |
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| JPS60248761A (en) * | 1984-05-23 | 1985-12-09 | Kanegafuchi Chem Ind Co Ltd | Heat-resistant, flame-retardant and impact-resistant resin composition |
| CN103044846A (en) * | 2012-12-25 | 2013-04-17 | 江苏金发科技新材料有限公司 | High-flow and weather-proof bulk ABS modified material and preparation method thereof |
| CN103923429A (en) * | 2013-01-11 | 2014-07-16 | 中国石油天然气股份有限公司 | High-flow ABS resin and preparation method thereof |
| CN105733120A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | High-fluidity and high-impact-resistance ABS resin and preparation method thereof |
-
2017
- 2017-12-12 CN CN201711323967.3A patent/CN108329646A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60248761A (en) * | 1984-05-23 | 1985-12-09 | Kanegafuchi Chem Ind Co Ltd | Heat-resistant, flame-retardant and impact-resistant resin composition |
| CN103044846A (en) * | 2012-12-25 | 2013-04-17 | 江苏金发科技新材料有限公司 | High-flow and weather-proof bulk ABS modified material and preparation method thereof |
| CN103923429A (en) * | 2013-01-11 | 2014-07-16 | 中国石油天然气股份有限公司 | High-flow ABS resin and preparation method thereof |
| CN105733120A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | High-fluidity and high-impact-resistance ABS resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王楠等: "连续本体法制备高流动中抗冲ABS的橡胶相筛选", 《工程塑料应用》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467870A (en) * | 2018-10-29 | 2019-03-15 | 北方华锦化学工业股份有限公司 | A kind of low smell highly resistance, which is leapt high, flows ABS resin and preparation method thereof |
| CN113337046A (en) * | 2021-07-23 | 2021-09-03 | 浙江智英石化技术有限公司 | Preparation method of ABS resin particles |
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Application publication date: 20180727 |