CN110240778A - A kind of preparation method of ontology ABS resin - Google Patents
A kind of preparation method of ontology ABS resin Download PDFInfo
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- CN110240778A CN110240778A CN201910566726.4A CN201910566726A CN110240778A CN 110240778 A CN110240778 A CN 110240778A CN 201910566726 A CN201910566726 A CN 201910566726A CN 110240778 A CN110240778 A CN 110240778A
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- abs resin
- preparation
- reaction kettle
- resin material
- material according
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- 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
-
- 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
Abstract
The invention belongs to high molecular materials, and field is blended, and in particular to a kind of preparation method of ontology ABS resin.Mainly solve the problems, such as that existing body apparatus preparation high-glue content ABS resin gloss is poor.Process flow includes rubber solution, monomer polymerization and is granulated three processes, wherein increasing stirring intensity in sol-process and polymerization process, while a part of first reaction kettle entrance material is passed through conveying equipment to the second reaction kettle and third reaction kettle.The ABS resin rubber content of this method preparation is higher, while having the characteristics that small particle, has both good impact property and luster performance, and the product applications are larger, has good market prospects.
Description
Technical field
The invention belongs to high molecular materials, and field, in particular to a kind of preparation method of ontology ABS resin is blended.
Background technique
In recent years, the center of gravity of China's ABS resin consumption market and application gradually shifts, the ABS resin of single performance
It is difficult to meet the requirement in market, so the direction of ABS resin towards high performance, fining, functionalization is developed.
High glaze ABS resin market demand is larger at this stage, and ABS resin gloss degree is mainly the partial size by toughening rubber
It being determined, rubber size is smaller, and glossiness is higher, and the rubber size of emulsion polymerization ABS resin is usually less than 0.5 μm, so
Its surface gloss is relatively high, and the rubber size of bulk polymerization of ABS resin is typically larger than 0.6 μm, so prepared by bulk polymerization
ABS resin glossiness it is higher.
Domestic each manufacturer mostly uses emulsion polymerization or the method for blending and modifying to prepare high glaze ABS resin at present, this
There has been no any reports at present for body method.Emulsion method and blending method usually will be greatly reduced the glossiness of ABS resin, but resin
Mechanical property is decreased obviously, and makes product while there is high glaze and preferable mechanical property can not achieve, comprehensive performance and import
Also there are still very big gaps for product, so high glaze ABS material majority derives from import.
A kind of high gloss flame-retardant ABS modified resin of Chinese patent CN101463177A and preparation method thereof, by ABS resin height
Rubber powder, SAN resin, antioxidant, heat stabilizer etc. are mixed in a certain ratio, and prepare glazed flame-retardant by double screw extruder
ABS, wherein the dosage of high glue powder is 0.01%-4%, and the rubber size of prepared ABS resin is less than 1 μm.
A kind of PET/ABS alloy resin of high gloss high tenacity of Chinese patent CN201010609543.5 and its preparation side
Method, by ABS resin, PET resin, toughener, compatilizer, processing aid blending extrusion by a certain percentage.This method is keeping ABS
While basic performance, the glossiness and chemical-resistance of product are improved.
A kind of flame-retarding high-lustre pool PC/ABS composition of Chinese patent CN200810203125.9, by PC resin, ABS resin,
PMMA resin, main flame retardant, auxiliary flame retardant, toughener, antioxidant carry out blending granulation.According to above technical scheme preparation
PC/ABS composition has good glossiness, can be used for the material of the multiple electric parts product such as terminal box, connector, switch
Material.
Summary of the invention
It is an object of the present invention to provide a kind of preparation methods of ontology ABS resin material.Concrete scheme is as follows:
A kind of preparation method of ontology ABS resin material, includes the following steps:
1) it by toughening rubber, solvent, acrylonitrile and styrene at 25 DEG C, mixes stir in colloidal sol kettle according to a certain percentage
It mixes, until original gelatin is uniform and without blob of viscose；
2) original gelatin dissolved, initiator, chain-transferring agent, processing aid and silicone oil are sent to each piston flow reactor
Carry out continuous bulk polymerization reaction, wherein by a part of first reaction kettle entrance material by conveying equipment to the second reaction kettle and
In third reaction kettle；
3) polymer material is finally entered into extruder, devolatilization granulation is carried out in extruder, obtains high glue small particle ontology
ABS resin.
The toughening rubber selects one or two kinds of combinations of high viscosity low cis rubber 55AE and 50AF.
The dosage of the toughening glue rubber is 12%-21%, and wherein 15%-18% is best.
The styrene-content 32%-60%, acrylonitrile content 18%-28%, solvent content 20%-30%.
The toughening rubber stirs 3-8h in colloidal sol kettle, and wherein 4-5h is best.
Initiator and chain-transferring agent is added in the inlet in the first piston flow reactor；It is reacted in the second plug flow
Chain-transferring agent, the first reaction kettle entrance material and improving gloss agent is added in the inlet of device；In entering for third piston flow reactor
Chain-transferring agent, silicone oil, the first reaction kettle entrance material and improving gloss agent are added at mouthful；In the 4th piston flow reactor inlet
Styrene monomer is added.
It is passed through the first anti-kettle material content in second reaction kettle and is passed through first in 3%-8%, third reaction kettle
Anti- kettle material content is in 1%-5%.
The improving gloss agent be zinc stearate, ethylene bis stearic acid amide, polyethylene glycol laurate one kind or
Two kinds.
The dosage of the second reaction kettle improving gloss agent is 0.05%-0.3%, the second reaction kettle improving gloss agent
Dosage is 0.05%-0.15%.
The draw ratio of the screw extruder be 40-48, screw speed 400-600rmp, 210 DEG C of head temperature, machine
Cylinder temperature: 210-230 DEG C of leading portion, 220-240 DEG C of middle section, 220-240 DEG C of back segment.
The ABS resin impact strength of the preparation is 220-290J/m, and particle size is 0.5-0.8 μm.
Beneficial effects of the present invention
The invention firstly uses continuous bulk devices to prepare high glue small particle ABS resin.During preparing original gelatin
Increase mixing time and intensity, while small particle prepolymer is passed into the second reaction kettle and third reaction during preparation
Kettle provides the polymerization " seed " of small particle, is prepared high glue small particle ABS resin, product have good impact property and
Luster performance.
Specific embodiment
The present invention is further illustrated below with reference to embodiment, but the not range of limitation the claims in the present invention protection.
Comparative example
12% toughening rubber, 40% styrene, 28% acrylonitrile and 17% solvent are added in colloidal sol kettle, at 25 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 86.3 DEG C, 90.7 DEG C, 94.8 DEG C, second reactor it is upper,
In, the reaction temperature in lower 3rd area be 92.7 DEG C, 105.5 DEG C, 109.2 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 10,12,15,15.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
0.15% lauryl mercaptan chain-transferring agent and 0.15% improving gloss agent is added in inlet；In entering for third piston flow reactor
0.10% lauryl mercaptan chain-transferring agent, 0.1% silicone oil and 0.10% improving gloss agent are added at mouthful.Material is flat-pushing from the 4th
Flow reactor outlet enters extrusion system, and melt is squeezed out, is granulated to obtain ABS resin product.
Embodiment 1-3
15%, 18%, 21% toughening rubber 55AE, 40% styrene, 28% acrylonitrile and 17% solvent are added respectively
Enter into colloidal sol kettle, is stirred at 25 DEG C to the original gelatin of uniform no blob of viscose；Configured original gelatin is successively delivered to first,
Two, 0.05% initiator is added in three, four piston flow reactor in the inlet of the first piston flow reactor in the course of the polymerization process
With 0.12% lauryl mercaptan chain-transferring agent；0.15% lauryl mercaptan is added in the inlet of the second piston flow reactor
Chain-transferring agent and 0.15% improving gloss agent；0.10% lauryl mercaptan chain is added in the inlet of third piston flow reactor
Transfer agent, 0.1% silicone oil and 0.10% improving gloss agent.Material enters extrusion system from the outlet of the 4th piston flow reactor, melts
Body is squeezed out, is granulated to obtain ABS resin product.
Each performance of ABS resin product that comparative experiments and embodiment 1-3 are prepared is tested, test result such as table 1
It is shown.
Table 1: comparative experiments and embodiment 1-3 performance test
According to comparative experiments and embodiment 1-3, with the increase of 55AE rubber content, impact strength, bending modulus and grain
Diameter size increases simultaneously, and tensile strength and bending strength have a declining tendency, when the content of toughening rubber increases to 18%,
Rubber size amplification is smaller while impact strength significantly increases, so the dosage of toughening rubber selects 18%.
Embodiment 4-6
Respectively by 18% 50AF, 55AE:50AF 1:2,55AE:50AF be 2:1 toughening rubber, 40% styrene,
28% acrylonitrile and 17% solvent are added in colloidal sol kettle, are stirred at 25 DEG C to the original gelatin of uniform no blob of viscose；It will configure
Original gelatin be successively delivered to the first, second, third and fourth piston flow reactor, in the course of the polymerization process in the first piston flow reactor
0.05% initiator and 0.12% lauryl mercaptan chain-transferring agent is added in inlet；In the entrance of the second piston flow reactor
0.15% lauryl mercaptan chain-transferring agent and 0.15% improving gloss agent is added in place；In the inlet of third piston flow reactor
0.10% lauryl mercaptan chain-transferring agent, 0.1% silicone oil and 0.10% improving gloss agent is added.Material is anti-from the 4th plug flow
Device outlet is answered to enter extrusion system, melt is squeezed out, is granulated to obtain ABS resin product.
Each performance of ABS resin product being prepared is tested, test result such as table 2.
Table 2: embodiment 4-6 performance test
Select single toughening rubber that cannot have both HI high impact when the dosage of toughening rubber is 18% according to embodiment 4-6
Intensity and the lesser performance of partial size select 55AE and 50AF when being used in compounding in the ratio of 1:2, impact it is strong it is higher simultaneously, grain
Diameter size is also substantially reduced.
Embodiment 7-9
It is respectively that 2:1 toughening rubber, 40% styrene, 28% acrylonitrile and 17% solvent add by 18% 55AE:50AF
Enter into colloidal sol kettle, is stirred at 25 DEG C to the original gelatin of uniform no blob of viscose；Configured original gelatin is successively delivered to first,
Two, 0.05% initiator is added in three, four piston flow reactor in the inlet of the first piston flow reactor in the course of the polymerization process
With 0.12% lauryl mercaptan chain-transferring agent；0.15% lauryl mercaptan is added in the inlet of the second piston flow reactor
Chain-transferring agent, 0.15% improving gloss agent and 3%-8% the first reaction kettle entrance material；In the entrance of third piston flow reactor
0.10% lauryl mercaptan chain-transferring agent, 0.1% silicone oil and 0.10% improving gloss agent is added in place.Material is from the 4th plug flow
Reactor outlet enters extrusion system, and melt is squeezed out, is granulated to obtain ABS resin product.
Each performance of ABS resin product being prepared is tested, test result such as table 3
Table 3: embodiment 7-9 performance test
According to embodiment 7-9, the first reaction kettle entrance material is delivered in the second reaction kettle by transmission device, is passed through
The prepolymer for introducing small particle, reduces the rubber size of ABS resin, while making particle size at bimodal distribution, increases ABS
The impact strength of resin.
Embodiment 10-12
It is respectively that 2:1 toughening rubber, 40% styrene, 28% acrylonitrile and 17% solvent add by 18% 55AE:50AF
Enter into colloidal sol kettle, is stirred at 25 DEG C to the original gelatin of uniform no blob of viscose；Configured original gelatin is successively delivered to first,
Two, 0.05% initiator is added in three, four piston flow reactor in the inlet of the first piston flow reactor in the course of the polymerization process
With 0.12% lauryl mercaptan chain-transferring agent；0.15% lauryl mercaptan is added in the inlet of the second piston flow reactor
Chain-transferring agent, 0.15% improving gloss agent and the 5% the first reaction kettle entrance materials；Add in the inlet of third piston flow reactor
Enter 0.10% lauryl mercaptan chain-transferring agent, 0.1% silicone oil, 0.10% improving gloss agent and the first reaction kettle of 1%-5% to enter
Mouth material.Material enters extrusion system from the outlet of the 4th piston flow reactor, and melt is squeezed out, is granulated to obtain ABS resin product.
Each performance of ABS resin product being prepared is tested, test result such as table 4
Table 4: embodiment 10-12 performance test
According to embodiment 10-12, the first reaction kettle entrance material is delivered in third reaction kettle by equipment, when first
When reaction kettle entrance material is 2%, the toughening intensity of ABS resin can reach 260J/m or so, and rubber size size is 0.7 μm.
With the increase of first reactor materials, impact strength also decreases while particle size reduces.
Claims (10)
1. a kind of preparation method of ontology ABS resin material, which comprises the steps of:
1) it by toughening rubber, styrene, acrylonitrile and solvent at 25 DEG C, is mixed in colloidal sol kettle according to a certain percentage
The original gelatin of uniform no blob of viscose；
2) configured original gelatin, initiator, chain-transferring agent, processing aid and silicone oil are sent to carrying out in each piston flow reactor
Continuous bulk polymerization reaction, wherein by a part of first reaction kettle entrance material by conveying equipment be delivered to the second reaction kettle with
In third reaction kettle；
3) polymer material is finally entered into extruder, devolatilization granulation is carried out in extruder, obtains ontology ABS resin.
2. the preparation method of ontology ABS resin material according to claim 1, which is characterized in that the toughening rubber
Select one or both of high viscosity low cis rubber 55AE or 50AF mixing.
3. the preparation method of ontology ABS resin material according to claim 2, which is characterized in that the toughening rubber
High viscosity low cis rubber 55AE and 50AF is selected to compound by the mass ratio of 1:2.
4. the preparation method of ontology ABS resin material according to claim 1, which is characterized in that the toughening glue rubber
The dosage of glue is 12%-21%, styrene-content 32%-60%, acrylonitrile content 18%-28%, solvent content 20%-
30%.
5. the preparation method of ontology ABS resin material according to claim 1, which is characterized in that the toughening rubber
3-8h is stirred in colloidal sol kettle.
6. the preparation method of ontology ABS resin material according to claim 1, which is characterized in that second reaction
It is passed through the first reaction kettle material content in kettle and is passed through the first reaction kettle material content in 3%-8%, third reaction kettle in 1%-
5%.
7. the preparation method of ontology ABS resin material according to claim 1, which is characterized in that the improving gloss
Agent is one or more kinds of mixing of zinc stearate, ethylene bis stearic acid amide, polyethylene glycol laurate.
8. the preparation method of ontology ABS resin material according to claim 1, which is characterized in that second reaction
The dosage of kettle improving gloss agent is 0.05%-0.3%, and the dosage of third reaction kettle improving gloss agent is 0.05%-0.15%.
9. the preparation method of ontology ABS resin material according to claim 1, which is characterized in that the extruder
Draw ratio is 40-48, screw speed 400-600rmp, 210 DEG C of head temperature, barrel temperature: and 210-230 DEG C of leading portion, middle section
220-240 DEG C, 220-240 DEG C of back segment.
10. the preparation method of ontology ABS resin material according to claim 1, which is characterized in that the ABS of the preparation
Resin impact strength is 220-290J/m, and particle size is 0.5-0.8 μm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031727A (en) * | 2021-11-26 | 2022-02-11 | 北方华锦化学工业股份有限公司 | High-fluidity high-AN-content bulk ABS resin and preparation method thereof |
| 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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| CN114031727A (en) * | 2021-11-26 | 2022-02-11 | 北方华锦化学工业股份有限公司 | High-fluidity high-AN-content bulk ABS resin and preparation method thereof |
| 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: 20190917 |