CN109467871A - A method of plating ABS resin is prepared using continuous bulk - Google Patents
A method of plating ABS resin is prepared using continuous bulk Download PDFInfo
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- CN109467871A CN109467871A CN201811269323.5A CN201811269323A CN109467871A CN 109467871 A CN109467871 A CN 109467871A CN 201811269323 A CN201811269323 A CN 201811269323A CN 109467871 A CN109467871 A CN 109467871A
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- abs resin
- continuous bulk
- rubber
- plating abs
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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
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention belongs to technical field of polymer materials, and in particular to a method of plating ABS resin is prepared using continuous bulk.This method is that butadiene-based rubber (or mixed with butylbenzene block rubber) is dissolved in styrene, in acrylonitrile and solvent ethylbenzene, at a certain temperature by the rubber solutions system dissolved, control amount, which is continuously sent, carries out polymerization reaction into four concatenated plug flow reaction kettles, demonomerization is removed by two-stage devolatilization, it send under cement-based powder material pump molten condition to pelletizing unit again, it is pure that plating ABS resin is made in pelletizing after being blended with the fusant after high glue powder and heat-resistant agent mixture through Bitruder, gel content is low, the big partial size and small particle high glue powder for possessing 0.5 μm or more are blended, increase plating area, form the latex structures and plating roughening phase of different shape, improve electroplated layer binding force.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of using continuous bulk preparation plating ABS tree
The method of rouge.
Background technique
ABS resin is a kind of superior thermoplastic macromolecule material of comprehensive performance, is that current production rate is larger, application is more wide
General engineering material.As constantly high performance was wanted for electronic apparatus, light industrial goods, utensil and automobile product etc. in recent years
It asks, so that ABS resin develops towards the proprietary material direction of high performance, alloying, multifunction.In recent years, China's automobile
Market becomes the important consumer field of ABS downstream industry, but with automotive light weight technology and luxurious beautyization demand for development, master
It increasingly to play a significant role using plastic electroplating, plastic electroplating overcomes many defects existing for plastics itself, has gold
Belong to appearance, corrosion-resistant resistance to light is good, and abrasion resistance, heat resistance and mechanical strength have been greatly improved.Styrene, fourth two
Alkene and acrylonitrile copolymer ABS resin since molecular structure and the phase composition of itself are easy to be electroplated, existing market 90% with
On plated item be using ABS or Acrylonitrile Butadiene-Styrene copolymer as plating substrate, Vehicles Collected from Market electroplating ABS mainly pass through blending and modifying carry out
Preparation.
Summary of the invention
It is an object of the present invention to provide a kind of methods for preparing plating ABS resin using continuous bulk.This method is fourth two
Alkene system rubber (or mixed with butylbenzene block rubber) is dissolved in styrene, acrylonitrile and solvent ethylbenzene, the rubber that will have been dissolved
At a certain temperature, control amount is continuously sent carries out polymerization reaction into four concatenated plug flow reaction kettles to solution system, passes through
Two-stage devolatilization goes under demonomerization, then cement-based powder material pump molten condition to send to pelletizing unit, after high glue powder and heat-resistant agent mixture
Plating ABS resin is made in fusant pelletizing after Bitruder is blended.
Specific technical solution is as follows；
A method of plating ABS resin is prepared using continuous bulk, is included the following steps:
(1) mixed dissolution in colloidal sol kettle according to a certain percentage by the toughening rubber of chopping, solvent, acrylonitrile and styrene
To the original gelatin of uniform no blob of viscose；
(2) successively give the original gelatin dissolved, initiator, chain-transferring agent by conveying equipment to first, second, third,
Continuous bulk polymerization reaction is carried out in 4th piston flow reactor；
(3) material after polymerizeing removes demonomerization by two-stage devolatilization, then is pumped and send the polymer under molten condition to making
Grain unit is blended with the fusant after high glue powder and heat-resistant agent mixture through Bitruder, and then plating ABS tree is made in pelletizing
Rouge.
Wherein, toughening rubber is polybutadiene rubber and block butadiene-styrene rubber mixture, and weight accounts for glue total amount after dissolution
8-15%, styrene account for glue total amount 50-70%, and acrylonitrile accounts for glue total amount 15-20%, and ethylbenzene accounts for glue total amount 10-20%,
1,1- cyclohexane di-tert-butyl peroxide is initiator, is added in the inlet of the first piston flow reactor, dosage 0.04-
0.1%, n-dodecyl mercaptan is chain-transferring agent, is added, uses in the entrance of the first, second, third piston flow reactor respectively
Amount is 0.15-0.25%.
Pelletizing unit is wherein blended 45-60% glue content and 0.03-0.5 μm of partial size of high glue powder and heat-resistant agent by super
After grade mixer mixing, it is squeezed into squeeze out after double screw extruder is blended with device molten polymer by feeder plasticizing and makes
Grain.In order to guarantee that the melt index of polymer and the stabilization of physical property, high glue powder and heat-resistant agent amount of mixture are polymer total amount
5-10%, in order to increase material intermiscibility heat-resistant agent select N- maleic anhydride (SMA).
Wherein, at 100-115 DEG C, reactor mixing speed is the control of three area's temperature of the first piston flow reactor upper, middle and lower
20-30rpm,；For the control of second piston flow reactor upper, middle and lower, three area's temperature at 115-130 DEG C, reactor mixing speed is 20-
30rpm；For the control of three area's temperature of third piston flow reactor upper, middle and lower at 120-150 DEG C, reactor mixing speed is 5-10rpm；
4th piston flow reactor upper, middle and lower, three area's temperature is controlled at 145-170 DEG C, and reactor mixing speed is 0.5-5rpm.
Beneficial effects of the present invention
1, it produces that ABS resin product is pure, and gel content is low by continuous bulk, there is higher rubber component, improve
Electroplated layer binding force and reduce bad frequency.Substance law produces the big partial size and granule that ABS resin product possesses 0.5 μm or more
Diameter high glue powder is blended, and increases plating area, forms the latex structures and plating roughening phase of different shape, improves electroplated layer knot
With joint efforts.
2, the plating ABS product that this technology is produced possesses 0.03-1.0 μm of volume different size rubber size, is in bimodal point
Cloth improves the physical property of product and mechanical performance, excellent combination property.
3, the plating ABS product that this technology is produced, low VOC, low smell, environmental-protecting performance are excellent.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1
By 9.0% butadiene rubber, be added to 55% styrene, 17% acrylonitrile and 19% ethyl benzene solvent in stir
To uniform original gelatin (A1).Configured virgin rubber hydraulic control amount is delivered to the first, second, third and fourth piston flow reactor, first is anti-
Answer 3rd area of upper, middle and lower of device reaction temperature be 101 DEG C, 103 DEG C, 109 DEG C, 3rd area of upper, middle and lower of second reactor it is anti-
Answering temperature is 110 DEG C, 117 DEG C, 120 DEG C, the reaction temperature in 3rd area of upper, middle and lower of third reactor is 122.0 DEG C, 126 DEG C,
135 DEG C, the reaction temperature in 3rd area of upper, middle and lower of the 4th reactor is 150 DEG C, 159 DEG C, 165 DEG C.In the course of the polymerization process, it is added
0.04% initiator and 0.2% chain-transferring agent.Material enters devolatilization system from the outlet of the 4th piston flow reactor, and removing is not
After the monomer and solvent that participate in reaction, pelletizing unit is pumped to by polymer.Pelletizing unit is 8% high glue powder B (butadiene
55%, styrene 33%, acrylonitrile 12%) and 2% heat-resistant agent F (n- maleic anhydride) after the mixing of super mixer, pass through
Feeder plasticizing is squeezed into extruding pelletization after double screw extruder is blended with device molten polymer, obtains electroplating ABS resin
Product.Properties of product test is as shown in table 1.
The plating ABS resin performance obtained is blended in table 1:A1 formula and B, F
Embodiment 2
After 4.0% butadiene rubber and 9.0% butylbenzene block rubber are crushed, it is added to 60% styrene, the third of 16%
Alkene nitrile and 15% ethyl benzene solvent in stirring to uniform original gelatin (A2).Configured virgin rubber hydraulic control amount is delivered to first,
Two, three, four piston flow reactor, the reaction temperature in 3rd area of upper, middle and lower of first reactor are 105 DEG C, 108 DEG C, 110 DEG C, the
The reaction temperature in 3rd area of upper, middle and lower of two reactors is 112 DEG C, 115 DEG C, 118 DEG C, 3rd area of upper, middle and lower of third reactor
Reaction temperature be 125.0 DEG C, 126 DEG C, 138 DEG C, the reaction temperature in 3rd area of upper, middle and lower of the 4th reactor is 154 DEG C, 168
℃,155℃.In the course of the polymerization process, 0.05% initiator and 0.24% chain-transferring agent is added.Other units are as more than later
Embodiment 1.
The plating ABS resin performance obtained is blended in table 2:A2 formula and B, F
Embodiment 3
After 5.0% butadiene rubber and 6.0% butylbenzene block rubber are crushed, it is added to 58% styrene, the third of 20%
Alkene nitrile and 15% ethyl benzene solvent in stirring to uniform original gelatin (A3).Configured virgin rubber hydraulic control amount is delivered to first,
Two, three, four piston flow reactor, the reaction temperature in 3rd area of upper, middle and lower of first reactor are 105 DEG C, 109 DEG C, 111 DEG C, the
The reaction temperature in 3rd area of upper, middle and lower of two reactors is 115 DEG C, 122 DEG C, 126 DEG C, 3rd area of upper, middle and lower of third reactor
Reaction temperature be 130.0 DEG C, 136 DEG C, 145 DEG C, the reaction temperature in 3rd area of upper, middle and lower of the 4th reactor is 150 DEG C, 160
℃,170℃.In the course of the polymerization process, 0.06% initiator and 0.26% chain-transferring agent is added.Other units are as more than later
Embodiment 1.
The plating ABS resin performance obtained is blended in table 3:A3 formula and B, F
By three above example performance test, continuous bulk is being made using the basic trade mark product of different formulations production
Addition high glue powder and heat-resistant agent during grain, notch impact strength and heat resistance, which have, to be greatly improved, and melt flowability omits
There is decline, the product comprehensive performance of the product of comprehensive three example trades mark, A2, A3 formula production is better than A1, the A3 that compares formula
To melt index higher, VOC index will be well below using emulsion method (TVOC > 800) in A2, three examples for good product mobility
The ABS resin of production, the present invention select formula to tend to A3.
Claims (8)
1. a kind of method for preparing plating ABS resin using continuous bulk, which comprises the steps of:
(1) by the toughening rubber of chopping, solvent, acrylonitrile and styrene according to a certain percentage in colloidal sol kettle mixed dissolution to equal
One original gelatin without blob of viscose；
(2) original gelatin dissolved, initiator, chain-transferring agent are successively sent by conveying equipment to first, second, third, fourth
Continuous bulk polymerization reaction is carried out in piston flow reactor；
(3) material after polymerizeing removes demonomerization by two-stage devolatilization, then is pumped and send the polymer under molten condition to granulation list
Member is blended with the fusant after high glue powder and heat-resistant agent mixture through Bitruder, and then plating ABS resin is made in pelletizing.
2. the method according to claim 1 for preparing plating ABS resin using continuous bulk, which is characterized in that step
(1) certain proportion described in refers to each component mass fraction are as follows: toughening rubber 8-15%；Styrene 50-70%, acrylonitrile 15-
20%, solvent 10-20%.
3. the method according to claim 1 or 2 for preparing plating ABS resin using continuous bulk, which is characterized in that institute
The toughening rubber stated is polybutadiene rubber or polybutadiene rubber and block butadiene-styrene rubber mixture, and the solvent is second
Benzene.
4. the method according to claim 1 for preparing plating ABS resin using continuous bulk, which is characterized in that step
(2) initiator of 0.04%-0.10wt% is added in the inlet of the first piston flow reactor；It is reacted in the first plug flow
Device, the second piston flow reactor, third piston flow reactor inlet be added chain-transferring agent, dosage 0.15%-
0.25wt%.
5. the method according to claim 4 for preparing plating ABS resin using continuous bulk, which is characterized in that described
Initiator be 1,1- cyclohexane di-tert-butyl peroxide.
6. the method according to claim 4 for preparing plating ABS resin using continuous bulk, which is characterized in that step
(2) chain-transferring agent described in is n-dodecyl mercaptan.
7. the method according to claim 1 for preparing plating ABS resin using continuous bulk, which is characterized in that step
For the control of three area's temperature of (2) first piston flow reactor upper, middle and lower at 100-115 DEG C, reactor mixing speed is 20-30rpm；The
For the control of two piston flow reactor upper, middle and lowers, three area's temperature at 115-130 DEG C, reactor mixing speed is 20-30rpm；Third is flat-pushing
For the control of three area's temperature of flow reactor upper, middle and lower at 120-150 DEG C, reactor mixing speed is 5-10rpm；The reaction of 4th plug flow
For the control of three area's temperature of device upper, middle and lower at 145-170 DEG C, reactor mixing speed is 0.5-5rpm.
8. the method according to claim 1 for preparing plating ABS resin using continuous bulk, which is characterized in that step
(3) high glue powder and heat-resistant agent amount of mixture are the 5-10wt% of polymer total amount, and the partial size of the high glue powder is 0.03-0.5 μ
M, the heat-resistant agent are N- maleic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811269323.5A CN109467871A (en) | 2018-10-29 | 2018-10-29 | A method of plating ABS resin is prepared using continuous bulk |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811269323.5A CN109467871A (en) | 2018-10-29 | 2018-10-29 | A method of plating ABS resin is prepared using continuous bulk |
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| Publication Number | Publication Date |
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| CN109467871A true CN109467871A (en) | 2019-03-15 |
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| CN201811269323.5A Pending CN109467871A (en) | 2018-10-29 | 2018-10-29 | A method of plating ABS resin is prepared using continuous bulk |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057190A (en) * | 2019-12-11 | 2020-04-24 | 北方华锦化学工业股份有限公司 | Preparation method of high-gloss bulk ABS resin |
| CN115894808A (en) * | 2022-11-17 | 2023-04-04 | 北方华锦化学工业股份有限公司 | Low-crystal-point plate-grade ABS material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06116344A (en) * | 1992-10-05 | 1994-04-26 | Asahi Chem Ind Co Ltd | Production of abs resin |
| CN101768320A (en) * | 2008-12-31 | 2010-07-07 | 深圳市科聚新材料有限公司 | Heat-resisting ABS modified material and preparation method thereof for plating |
| KR20110042713A (en) * | 2009-10-20 | 2011-04-27 | 주식회사 엘지화학 | A method for preparing heat resistant thermoplastic resin having high impact strength and good color properties |
| CN105482045A (en) * | 2015-12-14 | 2016-04-13 | 北方华锦化学工业集团有限公司 | Method for preparing heat-resistant bulk ABS resin |
| KR20160069116A (en) * | 2014-12-08 | 2016-06-16 | 주식회사 엘지화학 | Method of preparing abs resin having good heat resistance and abs resin having good heat resistance therefrom |
| CN108299601A (en) * | 2017-12-12 | 2018-07-20 | 北方华锦化学工业股份有限公司 | A kind of continuous bulk prepares high flowing, high-impact ABS resin |
-
2018
- 2018-10-29 CN CN201811269323.5A patent/CN109467871A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06116344A (en) * | 1992-10-05 | 1994-04-26 | Asahi Chem Ind Co Ltd | Production of abs resin |
| CN101768320A (en) * | 2008-12-31 | 2010-07-07 | 深圳市科聚新材料有限公司 | Heat-resisting ABS modified material and preparation method thereof for plating |
| KR20110042713A (en) * | 2009-10-20 | 2011-04-27 | 주식회사 엘지화학 | A method for preparing heat resistant thermoplastic resin having high impact strength and good color properties |
| KR20160069116A (en) * | 2014-12-08 | 2016-06-16 | 주식회사 엘지화학 | Method of preparing abs resin having good heat resistance and abs resin having good heat resistance therefrom |
| CN105482045A (en) * | 2015-12-14 | 2016-04-13 | 北方华锦化学工业集团有限公司 | Method for preparing heat-resistant bulk ABS resin |
| CN108299601A (en) * | 2017-12-12 | 2018-07-20 | 北方华锦化学工业股份有限公司 | A kind of continuous bulk prepares high flowing, high-impact ABS resin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057190A (en) * | 2019-12-11 | 2020-04-24 | 北方华锦化学工业股份有限公司 | Preparation method of high-gloss bulk ABS resin |
| CN115894808A (en) * | 2022-11-17 | 2023-04-04 | 北方华锦化学工业股份有限公司 | Low-crystal-point plate-grade ABS material and preparation method thereof |
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Application publication date: 20190315 |
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