CN112759915B - PC/ABS alloy material and preparation method and application thereof - Google Patents
PC/ABS alloy material and preparation method and application thereof Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/108—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond in a heterocyclic ring containing at least one carbon atom
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
- C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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Abstract
The invention relates to a PC/ABS alloy material and a preparation method and application thereof. The PC/ABS alloy material comprises polycarbonate resin, ABS resin, a compound auxiliary agent, a foaming agent and an antioxidant. The PC/ABS alloy material provided by the invention has the advantages of good rigidity and toughness, good foaming effect, good apparent mass and wide application prospect, and is particularly applied to thick-wall household appliances with requirements on strength.
Description
Technical Field
The invention belongs to the technical field of engineering plastics, and particularly relates to a PC/ABS alloy material and a preparation method and application thereof.
Background
ABS and PC are mixed, on one hand, a high-strength and high-toughness alloy material can be prepared, and on the other hand, performance complementation can be realized. ABS can improve the processability of PC, reduce the sensitivity of products to stress, improve the solvent resistance and reduce certain cost. PC/ABS is widely used in the household appliance industry due to its excellent performance and good appearance.
At present, the requirements of products and customers on materials are continuously improved, and the concept of reducing weight and lowering cost is gradually deepened. The polymer foam material forms a certain number of cells in the polymer matrix, so that the purposes of reducing weight and cost can be achieved, and the polymer foam material has the advantages of light weight, less strength reduction, high specific strength, less material consumption and the like, so that the polymer foam material is widely concerned by researchers.
Patent CN201810273211.0A provides a method for preparing a matte foaming PCABS material, wherein the foaming agent adopts one or more of azodicarbonamide and azodimethyldiethylallyl, the decomposition temperature of the foaming agent is only about 200 ℃ at most, the temperature is not suitable for PCABS alloy with high PC content, the foaming effect is unstable, the phenomena of foam collapse and rupture are easy to occur, and further, the surface has defects; patent No. cn201210366225.xa also uses azodicarbonamide blowing agents to prepare foamed PCABS materials, with similar problems.
Patent CN201711346175.8A provides a method of chemically foaming PCABS material, which can significantly increase the mechanical strength and hydrolysis resistance of PC/ABS microfoamed composites by adding molecular sieves.
The PCABS material has the characteristics of high gloss effect, high strength, high toughness and the like, so that the PCABS material is widely applied to television products. In addition, the blow molding plastic is also applied to bases, the weight of materials is reduced through blow molding, the problem of shrinkage and the like caused by too thick products is solved, but the blow molding has higher requirements on equipment and later processing, and the expansion of the application is limited.
Therefore, the development of the PCABS foamed light high-strength material with high strength and high apparent mass has important research significance and economic value.
Disclosure of Invention
The invention aims to solve the problems that the foaming effect of the foaming PCABS material is poor and the surface is easy to have defects in the prior art, and provides a PC/ABS alloy material. According to the PC/ABS alloy material provided by the invention, the toughness and rigidity of the material are increased by selecting the compound auxiliary agent, meanwhile, the viscosity of a resin system is regulated and controlled to facilitate foaming, and then, the PC/ABS alloy material has a good foaming effect under the action of a specific foaming agent; the PC/ABS alloy material provided by the invention has the advantages of good rigidity and toughness, good foaming effect and good apparent mass, and can be widely applied to products (such as household appliances) with high requirements on strength, apparent mass and weight.
The invention also aims to provide a preparation method of the PC/ABS alloy material.
The invention also aims to provide the application of the PC/ABS alloy material in the preparation of household appliances.
In order to achieve the purpose, the invention adopts the following technical scheme:
a PC/ABS alloy material comprises the following components in parts by weight:
the compound auxiliary agent consists of a toughening agent containing a reactive functional group and a vinyl ionic polymer in a weight ratio of 2: 1-3: 1;
the decomposition temperature of the foaming agent is not lower than 235 ℃.
The inventor of the invention finds that the viscosity of a resin system and the decomposition temperature of a foaming agent are main factors influencing the foaming injection molding effect of the PC/ABS alloy material. Through repeated exploration, the viscosity of a resin system can be adjusted to a proper range when a compound auxiliary agent with a specific composition and a specific ratio is selected; the selection of the foaming agent with higher decomposition temperature can prevent the foaming agent from decomposing under the foaming condition, thereby obtaining better foaming effect and improving the apparent quality. The toughening agent containing the reactive functional group enables the system to be more uniform, the vinyl ionic polymer increases the viscosity of the system, and the mixture achieves a relatively stable high-viscosity system through the synergistic cooperation effect of the vinyl ionic polymer and the vinyl ionic polymer. If the content of the high-molecular toughening agent containing the reactive functional group is too low, the uniformity of the material is poor, and the viscosity distribution is not uniform; if the content of the high-molecular toughening agent containing the reactive functional group is too high, the rigidity of the system is greatly reduced, and the strength is insufficient; if the content of the vinyl ionic polymer is too low, the viscosity of the system is too low, and cells are easy to break; if the content of the vinyl ionic polymer is too high, the viscosity of the system is too high, and a higher foaming ratio is not easily obtained.
In addition, the toughening agent can be dispersed to a better size through the tackifying effect of the vinyl ionic polymer, so that the toughening efficiency is improved, the rigidity loss is small, and the rigidity and the toughness are balanced.
The PC/ABS alloy material provided by the invention has the advantages of good rigidity and toughness, good foaming effect, good apparent mass and wide application prospect.
Preferably, the PC/ABS alloy material comprises the following components in parts by weight:
preferably, the polycarbonate resin is an aromatic polycarbonate; the melt index of the polycarbonate resin is 10-20 g/10min at 300 ℃ under the test condition of 1.2 kg.
Preferably, the ABS resin is prepared by a bulk method, and the melt index of the ABS resin at 220 ℃ under the test condition of 10kg is 10-20 g/10 min.
Preferably, the toughening agent containing the reactive functional group is a toughening agent containing an epoxy functional group (such as POE grafted GMA, toughening agents such as PTW and the like); the vinyl ionomer is an ethylene- (meth) acrylic acid metal salt ionomer (e.g., ethylene-methacrylic acid sodium salt in surlyn resin, etc.).
Preferably, the decomposition temperature of the foaming agent is 235-270 ℃, and more preferably hydrazinyltriazine (THT) is the name of Trihydrazinotriazine.
Preferably, the antioxidant is one or more of a phenolic compound or a phosphite ester compound.
Other functional adjuvants conventional in the art may also be added to the present invention to enhance their corresponding properties.
Preferably, the PC/ABS alloy material also comprises other functional auxiliary agents.
Specifically, the other functional auxiliary agent can be an antibacterial agent (for example, silver 350, 1-1.5 parts by weight); and (3) color masterbatch (such as black masterbatch, wherein the weight part of the black masterbatch is 0.5-1 part).
The preparation method of the PC/ABS alloy material comprises the following steps:
s1: mixing polycarbonate resin, ABS resin, a compound auxiliary agent, an antioxidant and a foaming agent (such as PC/ABS alloy material added with other functional auxiliary agents, and other functional auxiliary agents are also included in the PC/ABS alloy material), melting, extruding and granulating to obtain colloidal particles;
s2: and (3) carrying out steam injection molding on the colloidal particles by using a mirror surface appearance mold to obtain the foamed PC/ABS alloy product.
The application of the PC/ABS alloy material in the preparation of household appliances is also within the protection scope of the invention.
Preferably, the PC/ABS alloy material is applied to the preparation of televisions or bases.
Compared with the prior art, the invention has the following beneficial effects:
according to the PC/ABS alloy material provided by the invention, the toughness and rigidity of the material are increased by selecting the compound auxiliary agent, meanwhile, the viscosity of a resin system is regulated and controlled to facilitate foaming, and then, the PC/ABS alloy material has a good foaming effect under the action of a specific foaming agent; the PC/ABS alloy material provided by the invention has the advantages of good rigidity and toughness, good foaming effect, good apparent mass and wide application prospect (especially in thick-wall household appliances with requirements on strength).
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Some of the reagents selected in the examples and comparative examples of the present invention are described below:
polycarbonate resin # 1, PC A2200 (bisphenol A type resin), available from photochemical company, having a melt index of 13g/10min at 300 ℃ under 1.2kg test conditions;
polycarbonate resin 2#, PC AF1900 bisphenol a type resin), available from mitsui chemists, having a melt index of 25g/10min at 300 ℃ under 1.2kg test conditions;
ABS resin No. 1, ABS 8434, Shanghai Gaoqiao Branch of China petrochemical industry, is synthesized by a continuous bulk method, and has a melt index of 16g/10min at 220 ℃ under the test condition of 10 kg;
ABS resin No. 2 and ABS 3504, which are synthesized by continuous bulk method and have melt index of 6g/10min at 220 deg.C under 10kg test condition;
the compound additive 1#, a mixture of a high molecular toughening agent (AKEMA AX8900) containing epoxy functional groups and an ethylene- (methyl) acrylic acid ionic polymer (sarin resin 8920) according to the weight ratio of 5: 2;
a compound additive 2#, a mixture of a high molecular toughening agent (AKEMA AX8900) containing epoxy functional groups and an ethylene- (methyl) acrylic acid ionic polymer (sarin resin 8920) according to a weight ratio of 4: 2;
a compound additive 3#, a mixture of a high molecular toughening agent (AKEMAX 8900) containing an epoxy functional group and an ethylene- (methyl) acrylic acid ionic polymer (sarin resin 8920) according to a weight ratio of 4: 1;
compounding assistant 4#, POE-g-GMA (containing epoxy functional group) (SOG-02, Ningbo easy) and ethylene- (methyl) acrylic acid ion polymer (sarin resin 9520, DuPont) according to the weight ratio of 5: 2;
foaming agent 1#, hydrazinotriazine and THT, wherein the decomposition temperature is 250-270 ℃;
foaming agent 2#, azodicarbonamide and foaming agent ADC, the decomposition temperature is 180-200 ℃;
antioxidant: primary antioxidant, 1010, Ciba, switzerland; secondary antioxidant, 168, Irgafos 168, BASF;
other functional additives, black masterbatch, EG3807 and American cabot; antimicrobial silver 350, japan oasis corporation.
The PC/ABS alloy material of each embodiment and the comparative example is prepared by the following steps:
weighing raw materials (polycarbonate resin, ABS resin, a compound auxiliary agent, an antioxidant, a foaming agent and other functional auxiliary agents (if any)) and putting the raw materials into a high-speed mixer for mixing for 3-5 min, adding the mixture into a double-screw extruder after uniformly mixing, and carrying out melt blending and extrusion granulation, wherein the temperature of each section of the extruder is as follows: the first zone is 210-220 ℃, the second zone is 230-240 ℃, the third zone is 235-245 ℃, the fourth zone is 235-245 ℃, the fifth zone is 235-245 ℃, the sixth zone is 235-245 ℃, the seventh zone is 235-245 ℃, the head temperature is 230-240 ℃, the materials stay in the extruder for 0.5-1 min to obtain colloidal particles;
putting the colloidal particles into a ventilating oven at 90 ℃ for drying for 3-5 hours, adding into an injection molding machine (selecting a mirror surface appearance mold), and carrying out microcellular injection molding foaming herringbone support by adopting an RHCM (steam injection molding) technology, wherein the temperature of each section of the injection molding machine is as follows: the temperature of the first zone is 200-210 ℃, the temperature of the second zone is 240-250 ℃, the temperature of the third zone is 240-250 ℃, the temperature of the fourth zone is 240-250 ℃, and the temperature of the fifth zone is 265-275 ℃. The temperature of the front end of the injection molding machine is increased, which is beneficial to material foaming.
The performance test method and standard of the PC/ABS alloy material of each embodiment and the comparative example are as follows:
(1) impact properties: testing according to enterprise standards, injection-molding the material into a finished product of the herringbone bracket, mounting a load of 5kg at the upper end, performing an integral drop test, and recording the height of the bracket when the bracket is broken;
(2) density: testing the overall density of the herringbone bracket by adopting the GB/T4472 and 2011 standards;
(3) bending property: and (3) injection molding the sample into a mechanical sample strip, GB/T9341-2008, Plastic bending property test method.
(4) Apparent conditions are as follows: visually observing the appearance condition of the surface, and marking as 'good' when the surface has uniform luster and no obvious defects; when the surface has a small amount of heterochromatic defects (the total area of the defects is not more than 1 cm)2) In the case of water bloom, it is marked as "general"; when more heterochromatic defects exist (the total area of the defects is higher than 1 cm)2) When it is used, it is recorded as "poor".
Examples 1 to 10
This example provides a series of PC/ABS alloy materials having the formulation shown in Table 1.
TABLE 1 formulations (parts) of examples 1 to 10
Comparative examples 1 to 5
This comparative example provides a series of PC/ABS alloy materials having the formulation given in Table 2.
TABLE 2 formulations (parts) of comparative examples 1 to 5
| Comparative example | 1 | 2 | 3 | 4 | 5 |
| Polycarbonate resin 1# | 70 | 70 | 70 | 70 | 70 |
| ABS resin 1# | 20 | 20 | 20 | 20 | 20 |
| Compound auxiliary agent 1# | / | / | 7 | / | / |
| Compound auxiliary agent 3# | / | 7 | / | / | / |
| Sarin resin 8920 | / | / | / | 7 | / |
| AKEMA AX8900 | / | / | / | / | 7 |
| Foaming agent 1# | 0.3 | 0.3 | / | 0.3 | 0.3 |
| Foaming agent 2# | / | / | 0.3 | / | / |
| Primary antioxidant | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Secondary antioxidant | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Antibacterial agent | 1 | 1 | 1 | 1 | 1 |
| Black masterbatch | 1 | 1 | 1 | 1 | 1 |
The properties of the PC/ABS alloy materials of the examples and comparative examples were measured in accordance with the above-mentioned methods, and the results are shown in Table 3.
TABLE 3 results of Performance test of each example and comparative example
As can be seen from Table 3, the PC/ABS alloy material provided by the embodiments of the present invention has the properties of rigidity and toughness balance and low density, and has good apparent mass. The PC/ABS alloy material without the addition of the compound auxiliary agent (such as the comparative example 1) has insufficient toughness and inappropriate system viscosity, influences the foaming effect, and has higher density and poor apparent mass; the PC/ABS alloy material with improper mixture ratio of the added compound auxiliary agent (such as comparative example 2) has better toughness, but has lower rigidity, certain influence on foaming effect and general surface quality; the PC/ABS alloy material with lower decomposition temperature of the added foaming agent (such as comparative example 3) has poor foaming effect, poor surface quality and poor toughness; only the PC/ABS alloy material containing the ethylene- (methyl) acrylic acid ionic polymer (such as the comparative example 4) is selected, the toughness of the product is very low, the foaming effect is slightly influenced, and the surface quality is general; and only the PC/ABS alloy material of the toughening agent with the epoxy functional group (such as comparative example 5) is selected, so that the product has low rigidity, certain influence on the foaming effect, high density and general surface quality.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (9)
1. The PC/ABS alloy material is characterized by comprising the following components in parts by weight:
60-85 parts of polycarbonate resin;
10-30 parts of ABS resin;
5-8 parts of a compound auxiliary agent;
0.2-1 part of foaming agent;
0.1-1 part of antioxidant;
the compound auxiliary agent consists of a toughening agent containing a reactive functional group and a vinyl ionic polymer in a weight ratio of 2: 1-3: 1;
the reactive functional group contained in the toughening agent is an epoxy functional group;
the vinyl ionomer is an ethylene- (meth) acrylate metal salt ionomer;
the decomposition temperature of the foaming agent is not lower than 235 ℃.
2. The PC/ABS alloy material as recited in claim 1, wherein the PC/ABS alloy material comprises the following components in parts by weight:
65-80 parts of polycarbonate resin;
15-25 parts of ABS resin;
5-8 parts of a compound auxiliary agent;
0.3-0.6 part of foaming agent;
0.1-1 part of antioxidant.
3. The PC/ABS alloy material according to claim 1, wherein the polycarbonate resin is aromatic polycarbonate, and the polycarbonate resin has a melt index of 10-20 g/10min at 300 ℃ under a test condition of 1.2 kg.
4. The PC/ABS alloy material of claim 1, wherein the ABS resin is prepared by a bulk method, and the melt index of the ABS resin is 10-20 g/10min at 220 ℃ under a test condition of 10 kg.
5. The PC/ABS alloy material as recited in claim 1, wherein the decomposition temperature of the foaming agent is 235-270 ℃.
6. The PC/ABS alloy material as recited in claim 1, wherein the antioxidant is one or more of phenolic compounds or phosphite compounds.
7. The PC/ABS alloy material according to claim 1, wherein the PC/ABS alloy material further comprises other functional additives.
8. The method for preparing the PC/ABS alloy material as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps: and mixing the components, melting, extruding and granulating to obtain the PC/ABS alloy material.
9. Use of the PC/ABS alloy material of any one of claims 1 to 7 in the preparation of household electrical appliances.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE2400086A1 (en) * | 1973-01-02 | 1974-07-04 | Gen Electric | FOAMABLE POLYCARBONATE RESIN |
| CA1017500A (en) * | 1973-01-02 | 1977-09-13 | General Electric Company | Foamable polycarbonate composition |
| CN101787196B (en) * | 2009-12-17 | 2012-05-30 | 上海锦湖日丽塑料有限公司 | Flame-retarding PC (polycarbonate)/ABS composition and preparation method thereof |
| CN106674963A (en) * | 2016-12-26 | 2017-05-17 | 上海普利特化工新材料有限公司 | Microporous foamed PC (polycarbonate)-ABS (acrylonitrile butadiene styrene) alloy material and preparation method thereof |
| CN109504059A (en) * | 2018-11-20 | 2019-03-22 | 江苏科技大学 | A kind of polycarbonate fretting map product and preparation method thereof |
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