CN109354653A - A kind of preparation method of the low smell ontology ABS resin of low VOC - Google Patents
A kind of preparation method of the low smell ontology ABS resin of low VOC Download PDFInfo
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- CN109354653A CN109354653A CN201811268456.0A CN201811268456A CN109354653A CN 109354653 A CN109354653 A CN 109354653A CN 201811268456 A CN201811268456 A CN 201811268456A CN 109354653 A CN109354653 A CN 109354653A
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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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention belongs to macromolecule material preparation areas, and in particular to a kind of preparation method of the low smell ontology ABS resin of low VOC.During substance law prepares ABS resin, mostly use thiol class substance as chain-transferring agent, mercaptan type chain transfer agent has special stink, and is difficult to volatilize.The present invention uses non-mercaptan type chain transfer agent, fundamentally solve the problems, such as that ABS resin oder levels are higher, cooperate the supercritical extraction technique in last handling process simultaneously, removing influences the small-molecule substance of VOC content in product, realize that product has two kinds of characteristics of low smell and low VOC content simultaneously, and the mechanical property of ABS resin is maintained, which can be applied to the fields such as automobile, small household appliances and 3D printing.
Description
Technical field
The invention belongs to macromolecule material preparation areas, and in particular to a kind of preparation of the low smell ontology ABS resin of low VOC
Method.
Background technique
Household electrical appliances and Automotive Industry Chain are in the stage of transition and upgrade at present, and the demand of household electrical appliance and automobile is increasingly
Greatly.As consumer pays more attention to own health, it will be not only concerned only with appearance and performance when buying household electrical appliance and automobile,
Whether whether material therefor odorous, harmful to people as important selection factor, so the low smell ontology ABS tree of low VOC
Rouge is urgently developed.
Only the low VOC ontology ABS resin of the low smell of auspiciousness production difficult to understand is contained in several companies such as Europe in the world, and has been realized
Industrialization.The low smell grade ABS resin of auspiciousness Austria is contained in Europe, except characteristics such as the original resin good fluidity of reservation and impact properties
Outside, due to unique preparation process, level of residual monomers control is in 50ppm hereinafter, oder levels reach 3 grades hereinafter, meeting food
The demand of touch-safe, be widely used in it is any may have on the component of contact with food, beverage, have different trade mark products
For Market Selection.
The low VOC ontology ABS resin research of domestic low smell compares less, and substantially all dependence import, Jilin Petrochemical exists
Low smell ABS resin exploitation aspect has done some previous research works, but its ABS product is turned using tert-dodecylmercaotan chain
The product that agent is produced by emulsion method technique is moved, causes single residual content in product to be higher by much compared with substance law ABS product, is reducing
Smell and VOC aspect method are limited, ineffective.
The preparation method of ABS resin is emulsion method and substance law, due to the difference of process characteristic, the ABS of substance law preparation
Resin has greater advantage compared with emulsion method product.The oder levels of emulsion method ABS product are at 4 grades or so, level of residual monomers
2000ppm, substance law will slightly be better than emulsion method in this respect, and oder levels are between 3-4 grades, and level of residual monomers is usually in 600-
Between 700ppm, for outdoor appliances, the product of such oder levels is acceptable, but length this for household appliances
Phase is placed on indoor and automobile interior decoration class articles, it is obviously desirable to the product of lower oder levels.
According to the difference of discharged odoring substance, smell encapsulation method, physisorphtion, chemical reaction method, devolatilization can be selected
A variety of methods such as oven drying method, air- extraction and devolatilization extraction process method, wherein most basic method is that physisorphtion and chemistry are anti-
Ying Fa, but both of which haves the defects that certain and effect is poor；Devolatilization oven drying method and the nearest one section of development of air- extraction are more
Rapidly, but only experimental stage, and investment and higher cost are rested on.
Summary of the invention
The present invention is in order to solve the problems, such as that above-mentioned ABS resin has bad smell, using non-mercaptan type chain transfer agent application
It is produced in ontology ABS, it is unpleasant fundamentally to solve thiol smell, while using supercritical extraction technique in last handling process,
Removing influences the small-molecule substance of VOC content in product, realizes the research and development of the low VOC ontology ABS resin of low smell.Particular technique side
Case is as follows:
A kind of preparation method of the low smell ontology ABS resin of low VOC, includes the following steps:
At a certain temperature by the toughening rubber of chopping, solvent, acrylonitrile and styrene, according to a certain percentage in colloidal sol
In kettle mixed dissolution to uniform no blob of viscose original gelatin；By the original gelatin dissolved, initiator, chain-transferring agent, silicone oil by conveying
Equipment is sent to progress continuous bulk polymerization reaction in first, second, third, fourth each piston flow reactor；Material after polymerization
Into supercritical extracting equipment, devolatilization granulation is carried out, the low VOC ontology ABS resin product of low smell is prepared.
Wherein, chain-transferring agent is non-mercaptan type chain transfer agent or mercaptan type chain transfer agent and non-mercaptan type chain transfer agent
It is used cooperatively, wherein non-mercaptan type chain transfer agent is double thioesters classes, methyl styrene, tri-thiol methyl acrylate.
The dosage of the chain-transferring agent is 0.2%-0.9%, preferably 0.4%-0.6%.
Wherein, the content of toughening rubber is 5%-15%, the content of styrene is 40%-55%, and the content of acrylonitrile is
18%-28%, the content of solvent are 15%-30%.
Wherein, the initiator and 0.10%- of 0.01%-0.15% are added in the inlet of the first piston flow reactor
0.25% chain-transferring agent；The chain-transferring agent of 0.15%-0.25% is added in the inlet of the second piston flow reactor；In third
The chain-transferring agent of 0.10%-0.15% and the silicone oil of 0.05%-0.15% is added in the inlet of piston flow reactor.
Wherein, the polymerization temperature of the first piston flow reactor is 87 DEG C -101 DEG C, the polymerization temperature of the second piston flow reactor
Degree is 98 DEG C -116 DEG C, and the polymerization temperature of third piston flow reactor is 113 DEG C -126 DEG C, the polymerization of the 4th piston flow reactor
Temperature is 118 DEG C -134 DEG C.
Wherein, supercritical extraction unit head temperature is 195 DEG C, and vacuum degree is -0.1MPa.
The single residual content of the ABS resin of preparation in 50ppm hereinafter, oder levels are between 2-3 grades, Izod notched impact
Intensity is between 210-250J/m.
Beneficial effects of the present invention
Although non-mercaptan type chain transfer agent type comparison is more, it is suitble to the seldom of continuous bulk ABS reaction.The present invention adopts
Non- mercaptan type chain transfer agent fundamentally solves the bad smell of ABS resin, will not make the phase transition mistake entirely reacted
Journey changes, and then will not influence product performance index；In addition, using supercritical extraction technique in last handling process, take off
Except the small-molecule substance for influencing VOC content in product, realize that ABS resin has the characteristic of low smell and low VOC simultaneously.
Specific embodiment
The present invention is further illustrated below with reference to embodiment.
Comparative example 1
13% toughening rubber, 43% styrene, 25% acrylonitrile and 19% solvent are added in colloidal sol kettle, at 30 DEG C
It is lower to stir to the original gelatin of uniform no blob of viscose；Configured original gelatin is successively delivered to the reaction of the first, second, third and fourth plug flow
Device, the reaction temperature in 3rd area of upper, middle and lower of first reactor are 89.3 DEG C, 93.7 DEG C, 97.8 DEG C, second reactor it is upper,
In, the reaction temperature in lower 3rd area be 95.7 DEG C, 108.5 DEG C, 112.2 DEG C, the reaction temperature in 3rd area of upper, middle and lower of third reactor
Degree is 114.0 DEG C, 120.5 DEG C, 125.6 DEG C, and the reaction temperature in 3rd area of upper, middle and lower of the 4th reactor is 119.1 DEG C, 128.3
DEG C, 133.0 DEG C, the mixing speed of four reactors is respectively 8,10,12,12.It is reacted in the course of the polymerization process in the first plug flow
0.05% initiator and 0.12% lauryl mercaptan chain-transferring agent is added in the inlet of device；In the second piston flow reactor
0.18% lauryl mercaptan chain-transferring agent is added in inlet；0.08% 12 is added in the inlet of third piston flow reactor
Alkyl hydrosulfide chain-transferring agent and 0.1% silicone oil.Material enters extrusion system from the outlet of the 4th piston flow reactor, and melt is through squeezing
Out, it is granulated and obtains ABS resin product.
Comparative example 2
13% toughening rubber, 43% styrene, 25% acrylonitrile and 19% solvent are added in colloidal sol kettle, at 30 DEG C
It is lower to stir to the original gelatin of uniform no blob of viscose；Configured original gelatin is successively delivered to the reaction of the first, second, third and fourth plug flow
Device, the reaction temperature in 3rd area of upper, middle and lower of first reactor are 89.3 DEG C, 93.7 DEG C, 97.8 DEG C, second reactor it is upper,
In, the reaction temperature in lower 3rd area be 95.7 DEG C, 108.5 DEG C, 112.2 DEG C, the reaction temperature in 3rd area of upper, middle and lower of third reactor
Degree is 114.0 DEG C, 120.5 DEG C, 125.6 DEG C, and the reaction temperature in 3rd area of upper, middle and lower of the 4th reactor is 119.1 DEG C, 128.3
DEG C, 133.0 DEG C, the mixing speed of four reaction kettles is respectively 8,10,12,12.It is reacted in the course of the polymerization process in the first plug flow
0.05% initiator and 0.12% lauryl mercaptan chain-transferring agent is added in the inlet of device；In the second piston flow reactor
0.18% lauryl mercaptan chain-transferring agent is added in inlet；0.08% 12 is added in the inlet of third piston flow reactor
Alkyl hydrosulfide chain-transferring agent and 0.1% silicone oil.Material enters supercritical extract system, each area from the outlet of the 4th piston flow reactor
Extrusion temperature is 190 DEG C, 210 DEG C, 225 DEG C, 235 DEG C, 245 DEG C, 245 DEG C, 235 DEG C, 220 DEG C, 192 DEG C, head temperature 195
DEG C, vacuum degree is -0.1MPa, and the monomer and solvent of reaction are had neither part nor lot in recovery mixture, and granulation obtains ABS resin product.
Embodiment 1
13% butadiene-styrene rubber, 43% styrene, 25% acrylonitrile and 19% ethyl benzene solvent are added in colloidal sol kettle,
It is stirred at 30 DEG C to the original gelatin of uniform no blob of viscose；Configured original gelatin is successively delivered to the first, second, third and fourth plug flow
0.05% initiator and 0.16% pair of thioesters class chain-transferring agent is added in the inlet of the first piston flow reactor in reactor；
0.12% pair of thioesters class chain-transferring agent is added in the inlet of the second piston flow reactor；In the entrance of third piston flow reactor
0.05% pair of thioesters class chain-transferring agent and 0.1% silicone oil is added in place；Ethylbenzene is added in the 4th piston flow reactor inlet；Upper
Under conditions of stating identical polymerization temperature and mixing speed, continuous bulk polymerization reaction is carried out, extruding pelletization obtains ABS resin production
Product.
Embodiment 2
13% butadiene-styrene rubber, 53% styrene, 18% acrylonitrile and 16% ethyl benzene solvent are added in colloidal sol kettle,
It is stirred at 30 DEG C to the original gelatin of uniform no blob of viscose；Configured original gelatin is successively delivered to the first, second, third and fourth plug flow
0.05% initiator and 0.12% methyl styrene chain tra nsfer is added in the inlet of the first piston flow reactor in reactor
Agent；0.18% methyl styrene chain-transferring agent is added in the inlet of the second piston flow reactor；In third piston flow reactor
Inlet 0.08% methyl styrene chain-transferring agent and 0.1% silicone oil is added；In above-mentioned identical polymerization temperature and stirring speed
Under conditions of degree, extruding pelletization carries out continuous bulk polymerization reaction, obtains ABS resin product.
Embodiment 3
13% butadiene-styrene rubber, 53% styrene, 18% acrylonitrile and 16% ethyl benzene solvent are added in colloidal sol kettle,
It is stirred at 30 DEG C to the original gelatin of uniform no blob of viscose；Configured original gelatin is successively delivered to the first, second, third and fourth plug flow
0.05% initiator and 0.12% tri-thiol methyl acrylate chain is added in the inlet of the first piston flow reactor in reactor
Transfer agent；0.18% tri-thiol methyl acrylate chain-transferring agent is added in the inlet of the second piston flow reactor；It is flat in third
0.08% tri-thiol methyl acrylate chain-transferring agent and 0.1% silicone oil is added in the inlet of plug-flow reactor；Above-mentioned identical
Under conditions of polymerization temperature and mixing speed, continuous bulk polymerization reaction is carried out, extruding pelletization obtains ABS resin product.
Embodiment 4
13% butadiene-styrene rubber, 53% styrene, 18% acrylonitrile and 16% ethyl benzene solvent are added in colloidal sol kettle,
It is stirred at 30 DEG C to the original gelatin of uniform no blob of viscose；Configured original gelatin is successively delivered to the first, second, third and fourth plug flow
0.05% initiator and 0.12% tri-thiol methyl acrylate chain is added in the inlet of the first piston flow reactor in reactor
Transfer agent；0.18% tri-thiol methyl acrylate chain-transferring agent is added in the inlet of the second piston flow reactor；It is flat in third
0.08% tri-thiol methyl acrylate chain-transferring agent and 0.1% silicone oil is added in the inlet of plug-flow reactor；Above-mentioned identical
Under conditions of polymerization temperature and mixing speed, continuous bulk polymerization reaction is carried out, overcritical extracting system, each area are entered after polymerization
Extrusion temperature is 190 DEG C, 210 DEG C, 225 DEG C, 235 DEG C, 245 DEG C, 245 DEG C, 235 DEG C, 220 DEG C, 192 DEG C, head temperature 195
DEG C, vacuum degree is -0.1MPa, and the monomer and solvent of reaction are had neither part nor lot in recovery mixture, and granulation obtains ABS resin product.
It is found that by supercritical extract system, oder levels do not change comparison example 1 and 2, can be by ABS resin product
The content of middle VOC drops to 50ppm hereinafter, not influencing the properties of product simultaneously.
Example 1,2 and 3 is it is found that by mercaptan type chain transfer agent double thioesters classes, methyl styrene, tri-thiol methyl acrylate
Instead of oder levels change significantly, but VOC content is held essentially constant.
Wherein, when methyl styrene is as chain-transferring agent, mechanical property is declined；
When double thioesters classes are as chain-transferring agent, the appearance color of product is influenced；
When tri-thiol methyl acrylate is as chain-transferring agent, product mechanical property is basically unchanged, while not influencing product
Appearance color.
By above-mentioned experiment it is found that selecting tri-thiol methyl acrylate as chain-transferring agent, and use supercritical extract system
System reduces the content of VOC in product, makes product while having the characteristic of low smell and low VOC.
Claims (8)
1. a kind of preparation method of the low VOC ontology ABS resin of low smell, which comprises the steps of:
(1) at a certain temperature by the toughening rubber of chopping, solvent, acrylonitrile and styrene, according to a certain percentage in colloidal sol
In kettle mixed dissolution to uniform no blob of viscose original gelatin；
(2) successively give the original gelatin dissolved, initiator, chain-transferring agent, silicone oil by conveying equipment to first, second, third,
Continuous bulk polymerization reaction is carried out in 4th piston flow reactor；
(3) material after polymerizeing enters supercritical extracting equipment, carries out devolatilization granulation, and the low VOC ontology ABS of low smell is prepared
Resin.
2. the preparation method of the low VOC ontology ABS resin of low smell according to claim 1, which is characterized in that step (1)
Described in certain proportion refer to each component mass fraction are as follows: toughening rubber 5%-15%, styrene 40%-55%, acrylonitrile
18%-28%, solvent 15%-30%.
3. the preparation method of the low VOC ontology ABS resin of low smell according to claim 1, which is characterized in that step (2)
Described in chain-transferring agent be non-mercaptan type chain transfer agent or mercaptan type chain transfer agent and non-mercaptan type chain transfer agent cooperates makes
With the non-mercaptan type chain transfer agent is one of double thioesters classes, methyl styrene, tri-thiol methyl acrylate.
4. the preparation method of the low VOC ontology ABS resin of low smell according to claim 3, which is characterized in that the chain turns
Move the preferred tri-thiol methyl acrylate of agent, dosage 0.2%-0.9wt%.
5. the preparation method of the low VOC ontology ABS resin of low smell according to claim 1, which is characterized in that step (2)
In the first piston flow reactor inlet be added 0.01%-0.15wt% initiator and 0.10%-0.25wt% chain
Transfer agent；The chain-transferring agent of 0.15%-0.25wt% is added in the inlet of the second piston flow reactor；It is anti-in third plug flow
Answer the inlet of device that the chain-transferring agent of 0.10%-0.15wt% and the silicone oil of 0.05%-0.15wt% is added.
6. the preparation method of the low VOC ontology ABS resin of low smell according to claim 1, which is characterized in that step (2)
The polymerization temperature of first piston flow reactor is 87 DEG C -101 DEG C, and the polymerization temperature of the second piston flow reactor is 98 DEG C -116
DEG C, the polymerization temperature of third piston flow reactor is 113 DEG C -126 DEG C, the polymerization temperature of the 4th piston flow reactor is 118 DEG C -
134℃。
7. the preparation method of the low VOC ontology ABS resin of low smell according to claim 1, which is characterized in that step (3)
The supercritical extracting equipment head temperature is 195 DEG C, and vacuum degree is -0.1MPa.
8. the preparation method of the low VOC ontology ABS resin of low smell according to claim 1, which is characterized in that be prepared
The single residual content of ABS resin in 50ppm hereinafter, 2-3 grades of oder levels, Izod notched impact strength 210-250J/m.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409839A (en) * | 2022-01-27 | 2022-04-29 | 万华化学集团股份有限公司 | SAN resin and preparation method thereof |
| CN114426624A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Low-odor vinyl acetate-ethylene copolymer emulsion and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196995A (en) * | 1996-10-25 | 1998-10-28 | 普拉塞尔技术有限公司 | Method for removing contaminants from polymers |
| CN102127192A (en) * | 2010-12-06 | 2011-07-20 | 宁波镇洋化工发展有限公司 | Continuous bulk preparation method of acrylonitrile-ethylene propylene diene monomer (EPDM)-styrene (AES) resin |
| JP2011219528A (en) * | 2010-04-05 | 2011-11-04 | Sekisui Chem Co Ltd | Method of manufacturing acrylic polymer |
| CN104311726A (en) * | 2014-10-30 | 2015-01-28 | 中国科学院化学研究所 | Method for preparing solid acrylic resin |
| CN104448763A (en) * | 2014-12-18 | 2015-03-25 | 上海锦湖日丽塑料有限公司 | Preparation method of low-diffusion PC/ABS alloy |
| CN105026437A (en) * | 2013-02-15 | 2015-11-04 | 阿科玛法国公司 | Use of methyl mercapto-esters as chain transfer agents |
| CN106699981A (en) * | 2016-12-16 | 2017-05-24 | 北方华锦化学工业集团有限公司 | Method of preparing transparent ABS resin by adopting continuous body device |
| 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 CN201811268456.0A patent/CN109354653A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196995A (en) * | 1996-10-25 | 1998-10-28 | 普拉塞尔技术有限公司 | Method for removing contaminants from polymers |
| JP2011219528A (en) * | 2010-04-05 | 2011-11-04 | Sekisui Chem Co Ltd | Method of manufacturing acrylic polymer |
| CN102127192A (en) * | 2010-12-06 | 2011-07-20 | 宁波镇洋化工发展有限公司 | Continuous bulk preparation method of acrylonitrile-ethylene propylene diene monomer (EPDM)-styrene (AES) resin |
| CN105026437A (en) * | 2013-02-15 | 2015-11-04 | 阿科玛法国公司 | Use of methyl mercapto-esters as chain transfer agents |
| CN104311726A (en) * | 2014-10-30 | 2015-01-28 | 中国科学院化学研究所 | Method for preparing solid acrylic resin |
| CN104448763A (en) * | 2014-12-18 | 2015-03-25 | 上海锦湖日丽塑料有限公司 | Preparation method of low-diffusion PC/ABS alloy |
| CN106699981A (en) * | 2016-12-16 | 2017-05-24 | 北方华锦化学工业集团有限公司 | Method of preparing transparent ABS resin by adopting continuous body device |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 岳丽英等: "双硫酯作为链转移剂的苯乙烯本体聚合研究", 《高校化学工程学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426624A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Low-odor vinyl acetate-ethylene copolymer emulsion and preparation method thereof |
| CN114409839A (en) * | 2022-01-27 | 2022-04-29 | 万华化学集团股份有限公司 | SAN resin and preparation method thereof |
| CN114409839B (en) * | 2022-01-27 | 2023-12-19 | 万华化学集团股份有限公司 | SAN resin and preparation method thereof |
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