CN112226009A - Blow molding ABS material with high melt strength and high toughness and preparation method thereof - Google Patents
Blow molding ABS material with high melt strength and high toughness and preparation method thereof Download PDFInfo
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- CN112226009A CN112226009A CN202010942016.XA CN202010942016A CN112226009A CN 112226009 A CN112226009 A CN 112226009A CN 202010942016 A CN202010942016 A CN 202010942016A CN 112226009 A CN112226009 A CN 112226009A
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Abstract
The invention provides a blow molding ABS material with high melt strength and high toughness and a preparation method thereof, wherein the blow molding ABS material comprises the following components in percentage by mass: ABS high rubber powder: 25% -50%, SAN resin: 45% -70%, antioxidant: 0.1% -1%, lubricant: 0.1% -1%, cross-linking agent: 0.1% -3%, initiator: 0.1 to 1 percent; the cross-linking agent is triallyl isocyanuric acidAn acid ester; the initiator is 2, 3-dimethyl-2, 3-diphenylbutane. The blow-molded ABS obtained by the invention has high melt strength and high toughness, the melt index can reach 0.9g/10min, the tensile strength can be kept above 42MPa, and the low-temperature notch impact strength can be kept at 16KJ/m2The blow molding surface effect is good.
Description
Technical Field
The invention belongs to the technical field of ABS composite materials, and particularly relates to a blow molding ABS material with high melt strength and high toughness and a preparation method thereof.
Background
ABS resin (acrylonitrile-butadiene-styrene copolymer) is a thermoplastic high polymer material with high strength, good toughness and easy processing and forming, has excellent comprehensive performance, can be formed by various methods such as injection molding, extrusion, blow molding, rolling and the like, and is widely applied to the fields of electronic appliances, building materials, automobile interior and exterior decorations and the like.
In the blow molding process of ABS resin, when a polymer passes through a narrow neck mold, the polymer is acted by high shearing force, the parison is easy to melt and sag, excessive sag can cause uneven wall thickness of a workpiece, and even the workpiece cannot be molded in serious conditions. Therefore, the melt strength of the resin is required to be sufficiently high for the ABS resin for blow molding. For some large automobile parts, such as spoilers, seat backs, bumpers and the like, the products are required to bear load force with certain strength, and the products generally have low-temperature impact test requirements of-30 ℃ or-40 ℃, and are required not to have poor appearance such as cracks and fissures. Therefore, the ABS resin for blow molding is required to have high strength, rigidity and low-temperature toughness at the same time.
Chinese patent CN103013025 discloses an ABS resin with excellent combination properties for blow molding, which improves toughness by increasing the rubber phase content in the ABS resin, but reduces material rigidity while increasing impact strength and decreasing melt index. The prior literature discloses the improvement of impact resistance of materials by blending polymers prepared by different polymerization modes. As in patents US4430478, US5605963, US5696204, the impact properties of the material are improved by mixing the polymer produced by the emulsion polymerization process with the polymer produced by the bulk polymerization process, however the material obtained by this method has low melt strength and poor blow moulding properties; the normal temperature toughness and the low temperature toughness of the material are not in a corresponding relation, and when the normal temperature toughness is improved, the improvement of the low temperature toughness is limited.
Disclosure of Invention
The invention aims to provide a blow molding ABS material with high melt strength and high toughness and a preparation method thereof, wherein the material has the characteristics of high toughness, high melt strength and the like, so as to solve the problem that the blow molding ABS material in the prior art cannot simultaneously obtain high strength, high rigidity and high and low temperature toughness.
The invention is realized by the following technical scheme:
the invention relates to a blow molding ABS material with high melt strength and high toughness, which is characterized by comprising the following components in percentage by mass:
the crosslinker is triallyl isocyanurate (TAIC); the initiator is 2, 3-dimethyl-2, 3-diphenylbutane (DMDPB).
The ABS high-rubber powder is core-shell polymer rubber which takes styrene-acrylonitrile-butadiene with the weight-average relative molecular mass of 100,000-500,000 g/mol as a main structure, wherein the content of the butadiene rubber is 60-75 percent, and the number-average particle size of the rubber is 0.1-1.0 mu m, such as B338 of SABIC company;
the SAN resin is a styrene-acrylonitrile copolymer with the weight-average relative molecular mass of 200,000-600,000 g/mol, and the melt flow rate is 1-10 g/10min, such as PN138-H of Zhenjiang Qimei;
the antioxidant is one or a mixture of more than two of phosphite antioxidant (such as antioxidant 168 and antioxidant 618) and propionate antioxidant (such as antioxidant 1010 and antioxidant 245);
the lubricant is one or a mixture of more than two of fatty acid amide, barium stearate, magnesium stearate and pentaerythritol stearate.
The invention relates to a preparation method of a high melt strength and high toughness blow molding ABS material, which is characterized by comprising the following steps:
(1) mixing the raw material ABS high-rubber powder, SAN resin, an antioxidant, a lubricant, a cross-linking agent and an initiator for 2-30 min at a rotating speed of 20-50 rpm to obtain a mixed material;
(2) feeding the mixed material into a double-screw extruder for extrusion granulation, wherein the rotating speed of a screw is 400-600 rpm, and the processing temperature is 180-240 ℃;
(3) the extruded material is cooled, granulated and dried to obtain the high melt strength and high toughness blow molding ABS material.
Preferably, in the step (1), the raw materials are mixed for 2-10 min at a rotating speed of 20-50 rpm.
Preferably, in the step (2), the rotation speed of the screw is 400-500 rpm, and the processing temperature is 200-240 ℃.
The invention adopts DMDPB as an initiator to initiate the double bond activity of ABS high rubber powder, adopts TAIC as a cross-linking agent to carry out cross-linking, and obtains the blow-molded ABS which has high melt strength and high toughness, the melt index can reach 0.9g/10min, the tensile strength can be kept above 42MPa, and the low-temperature notch impact strength can be kept at 16KJ/m2The blow molding surface effect is good.
Detailed Description
It should be understood by those skilled in the art that the present embodiment is only for illustrating the present invention and is not to be used as a limitation of the present invention, and changes and modifications of the embodiment can be made within the scope of the claims of the present invention.
The raw materials used in this example are all commercially available.
Examples 1 to 5 and comparative examples 1 to 2
Weighing ABS high-rubber powder, SAN resin, an antioxidant, a lubricant, a cross-linking agent and an initiator according to the weight parts of the raw materials of the examples 1-7 and the comparative examples 1-2 listed in the table 1, and mixing for 2-10 min at the rotating speed of 20-50 rpm to respectively obtain mixed materials of the examples 1-7 and the comparative examples 1-2;
TABLE 1 raw material mass fractions of examples 1 to 5 and comparative examples 1 to 2
Respectively adding the mixed materials of the examples 1-7 and the comparative examples 1-2 into a main feeder of a double-screw extruder, adjusting the rotating speed of the main feeder and the rotating speed of a main machine, and finally, feeding the materials into the double-screw extruder for extrusion granulation; the double-screw extruder is 11 barrels, and vacuum ports of the double-screw extruder are positioned in the 6 th barrel and the 9 th barrel; the twin-screw extruder had the following temperature profile: from the feeding section to the machine head are respectively: 200 ℃, 210 ℃, 220 ℃, 225 ℃, 220 ℃, 225 ℃ and the screw rotating speed is 400 rpm; and (3) granulating the extruded material after water cooling, and drying the granules in a blast drying oven at 95 ℃ for 4 hours to obtain the blow molding ABS materials of examples 1-7 and comparative examples 1-2.
Experimental example 1
The blow molding ABS materials of examples 1-7 and comparative examples 1-2 were used to prepare various test specimens for physical property tests. The tensile strength was measured according to the method specified in ISO527, with a tensile speed of 50 mm/min; the notched impact strength was tested according to the method specified in ISO179-1eA simple beam, wherein: the normal temperature is 23+/-2 ℃, the low temperature is-30 +/-2 ℃, the mixture is stored for more than 24 hours at-30 ℃, and the mixture is tested in the environment of-30 ℃; the melt index is according to ISO1133, the test conditions are 260 ℃ and 5 kg; the blow molding surface is represented by 0 to 3, 0 being no good, and 3 being best.
TABLE 2 Performance test results of examples 1 to 7 and comparative examples 1 to 2
As can be seen from the comparison between examples 1 to 3 and comparative examples 1 to 2, the initiator and the crosslinking agent selected in the present invention are indispensable. With the increase of the content of the cross-linking agent, the cross-linking effect is enhanced, the tensile strength is increased, the melt index is reduced to be within a proper range of blow molding, the blow molding surface is improved, but the notch impact strength is reduced to some extent; from the comparison between the examples 2 and 4 to 6, the increase of the ABS high rubber powder content increases the impact strength and the notch impact strength of the blow-molded ABS material, and the melt index also decreases, but the increase of the ABS high rubber powder content has adverse effects on the tensile strength and the blow-molded surface, which means that the content of the high rubber powder is not too large, and a proper content range must be selected.
Claims (10)
1. A blow molding ABS material with high melt strength and high toughness is characterized by comprising the following components in percentage by mass:
ABS high rubber powder: 25 to 50 percent of the total weight of the mixture,
SAN resin: 45 to 70 percent of the total weight of the mixture,
antioxidant: 0.1 to 1 percent of the total weight of the mixture,
lubricant: 0.1 to 1 percent of the total weight of the mixture,
a crosslinking agent: 0.1 to 3 percent of the total weight of the mixture,
initiator: 0.1 to 1 percent;
the cross-linking agent is triallyl isocyanurate; the initiator is 2, 3-dimethyl-2, 3-diphenylbutane.
2. The blow molding ABS material with high melt strength and high toughness as claimed in claim 1, wherein the ABS high rubber powder is core-shell polymer rubber with a main structure of styrene-acrylonitrile-butadiene with a weight average relative molecular mass of 100,000-500,000 g/mol, wherein the butadiene rubber content is 60% -75%, and the number average particle diameter of the rubber is 0.1-1.0 μm.
3. A blow molded ABS material with high melt strength and high toughness as claimed in claim 1, wherein the SAN resin is styrene-acrylonitrile copolymer with weight average relative molecular mass of 200,000-600,000 g/mol, and the melt flow rate is 1-10 g/10 min.
4. The blow molding ABS material with high melt strength and high toughness of claim 1, wherein the antioxidant is one or a mixture of more than two of phosphite antioxidant and propionate antioxidant.
5. The blow molding ABS material with high melt strength and high toughness of claim 4, wherein the antioxidant is one or a mixture of more than two of antioxidant 168, antioxidant 618, antioxidant 1010 and antioxidant 245.
6. A blow molded ABS material with high melt strength and high toughness as claimed in claim 1, wherein the lubricant is one or a mixture of more than two of fatty acid amide, barium stearate, magnesium stearate and pentaerythritol stearate.
7. The preparation method of the blow molding ABS material with high melt strength and high toughness as claimed in any of claims 1-6, characterized by comprising the following steps:
(1) mixing the raw material ABS high-rubber powder, SAN resin, an antioxidant, a lubricant, a cross-linking agent and an initiator for 2-30 min at a rotating speed of 20-50 rpm to obtain a mixed material;
(2) feeding the mixed material into a double-screw extruder for extrusion granulation, wherein the rotating speed of a screw is 400-600 rpm, and the processing temperature is 180-240 ℃;
(3) the extruded material is cooled, granulated and dried to obtain the high melt strength and high toughness blow molding ABS material.
8. The method according to claim 7, wherein in the step (1), the raw materials are mixed at a rotation speed of 20 to 50rpm for 2 to 5 min.
9. The method according to claim 7, wherein in the step (2), the screw rotation speed is 400 to 500rpm, and the processing temperature is 200 to 240 ℃.
10. The method of claim 7, wherein the twin screw extruder comprises 11 barrels and the vacuum ports are located in 6 th and 9 th barrels.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010942016.XA CN112226009A (en) | 2020-09-09 | 2020-09-09 | Blow molding ABS material with high melt strength and high toughness and preparation method thereof |
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| CN202010942016.XA CN112226009A (en) | 2020-09-09 | 2020-09-09 | Blow molding ABS material with high melt strength and high toughness and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114085468A (en) * | 2021-12-06 | 2022-02-25 | 安徽江淮汽车集团股份有限公司 | Solvent-resistant ABS composite material suitable for blow molding and preparation method thereof |
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