CN115246980B - Essential oil-resistant ABS resin and preparation method thereof - Google Patents
Essential oil-resistant ABS resin and preparation method thereof Download PDFInfo
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- CN115246980B CN115246980B CN202210857574.5A CN202210857574A CN115246980B CN 115246980 B CN115246980 B CN 115246980B CN 202210857574 A CN202210857574 A CN 202210857574A CN 115246980 B CN115246980 B CN 115246980B
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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
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Abstract
The invention discloses an essential oil-resistant ABS resin and a preparation method thereof; the composition comprises the following components in parts by weight: 60-95 parts of ABS resin, 5-60 parts of PBT resin, 2-6 parts of compatilizer, 1-4 parts of lubricant and 0.1-0.5 part of quaternary ammonium salt. The PBT in the system is a semi-crystalline material, has relatively compact molecular chain arrangement, can effectively prevent most small organic molecules from diffusing into the material, and prolongs the service life of the material; the addition of the slightly acidic quaternary ammonium salt can react with esters in the 9-mugwort essential oil to carry out acidolysis on the esters, so that the damage of the essential oil to materials is weakened, and the mechanical properties of the product are not influenced; by increasing the dosage of the lubricant and adding the fluorine-containing lubricant, another compact protective layer is slowly formed on the surface of the material, and the entry of organic molecules is further prevented.
Description
Technical Field
The invention belongs to the technical field of resins, and relates to an ABS resin, in particular to an essential oil-resistant ABS resin and a preparation method thereof.
Background
The components of the mugwort essential oil are typically mugwort extract, 4-hydroxy-8-acetoxy-1 (2), 9 (10) -guaifenesin-6, 12-lactone, chamomile Ai Nazhi, chamomile Ai Nazhi, mugwort extract, ai Caoning, 11-epinastine, isovaleric acid, nerol ester, 13-dihydro-dehydrocostuslactone, isonerol ester, 4-dehydrooxychrysin, an Yangai element, globinula, arteterpene lactone and the like, so the mugwort essential oil is typically acidic and also has numerous esters.
ABS refers to an acrylonitrile-butadiene-styrene copolymer, integrates the advantages of the acrylonitrile-butadiene-styrene copolymer, has excellent mechanical properties of balanced toughness and rigidity, and has good formability and dimensional stability; in addition, it is required to have good surface gloss and coloring ability, so that it is widely used in home appliances, electronic devices and automobile industries. The ABS resin contains acrylonitrile component, has better chemical resistance, generally does not generate obvious defects with dilute acid, edible oil, metal salt solution, liquid laundry detergent, liquid detergent, edible vinegar and the like (ABS resin production practice and application, soxhlet glow, china petrochemical Press, 2015.4, pages 150-151), but the essential oil contains esters, so that the molecular structure of the resin can be damaged, the resin can be cracked in the use process of the massager, and the use temperature of the massager is about 40-50 ℃.
The problem of the resistance of ABS is generally solved by adding crystalline or semi-crystalline materials, which can solve most of the problems, but the prevention effect on substances such as essential oils is not great.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an essential oil-resistant ABS resin and a preparation method thereof.
The invention aims at realizing the following technical scheme:
the invention relates to an essential oil-resistant ABS resin composition, which comprises the following components in parts by weight:
the ABS resin contains 10-15% of butadiene and 25-35% of acrylonitrile.
The PBT resin is polybutylene terephthalate with weight-average molecular weight of 1-6W.
The compatilizer is one or more of ethylene-methyl acrylate-glycidyl methacrylate ternary random copolymer, polyethylene grafted maleic anhydride and ethylene/butyl acrylate/carbonyl ternary copolymer.
The lubricant at least comprises fluorine-containing lubricant, and can also comprise one or more of ethylene bis stearamide, zinc stearate, magnesium stearate and ethylene-vinyl acetate copolymer.
The fluorine-containing lubricant is perfluoropolyether oil.
The quaternary ammonium salt is acidic quaternary ammonium salt, and comprises one or more of double-chain quaternary ammonium salt (bissunflower-based dimethyl ammonium chloride, laurylamine dipropylene diamine and the like) and compound quaternary ammonium salt. The compound quaternary ammonium salt belongs to the fourth-generation double-chain quaternary ammonium salt.
The invention also relates to a preparation method of the essential oil-resistant ABS resin composition, which comprises the following steps:
(1) The components are prepared according to the following weight portions:
(2) Mixing the components in the step (1) at a high speed, putting the mixture into a screw machine, carrying out melt extrusion at 160-220 ℃ and at a screw rotating speed of 200-500 rpm, and cooling and granulating to obtain the essential oil-resistant ABS resin composition. And then, preparing test sample bars and screw columns after injection molding, and testing physical properties and chemical properties.
Compared with the prior art, the invention has the following beneficial effects:
1) The PBT is a semi-crystalline material, has relatively compact molecular chain arrangement, can effectively prevent most small organic molecules from diffusing into the material, and prolongs the service life of the material;
2) According to the invention, the addition of the slightly acidic quaternary ammonium salt can perform acidolysis reaction with esters in the 9-mugwort essential oil, so that the damage of the essential oil to materials is weakened, and the mechanical properties of the product are not influenced;
3) The invention can slowly form another compact protective layer on the surface of the material by increasing the dosage of the lubricant and adding the fluorine-containing lubricant, thereby further preventing the entry of organic molecules.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Examples 1 to 6
Examples 1 to 6 relate to a method for preparing an essential oil-resistant ABS resin, comprising the steps of:
according to the weight percentage of the formula components in the table 1, the raw materials are added into a high-speed mixer for fully mixing, then are placed into a screw machine for melt extrusion at 160-200 ℃ and at a screw speed of 350 rpm, and are cooled and granulated to obtain the product.
Comparative examples 1 to 6
Comparative examples 1 to 6 relate to a method for preparing an essential oil-resistant ABS resin, comprising the steps of:
according to the weight percentage of the formula components in the table 1, the raw materials are added into a high-speed mixer for fully mixing, then are placed into a screw machine for melt extrusion at 160-200 ℃ and at a screw speed of 350 rpm, and are cooled and granulated to obtain the product.
Wherein the materials of table 1 are as follows:
ABS: ABS8391, high bridge petrochemical;
PBT: the weight average molecular weight is 2W;
and (3) a compatilizer: SMA218, daily liter fine chemical;
lubricant 1: PFPE, zhejiang macro;
lubricant 2: ethylene bis stearamide, commercially available;
quaternary ammonium salt 1:TB，Diversey；
quaternary ammonium salt 2: laurylamine dipropylene diamine;
quaternary ammonium salt 3:II 256，Diversey。
table 1 examples 1-6 and comparative examples 1-6 formulations parts by weight
Performance evaluation method and implementation standard thereof
Mechanical property test:
the ABS resin compositions prepared in examples 1 to 7 and comparative examples 1 to 5 were injection molded to prepare test bars and screw columns, and the results of performance evaluation are shown in Table 2:
IZOD notched impact strength (1/8): the test temperature is 23 ℃ according to ASTM D256-10 standard test;
tensile strength: the test temperature was 23℃according to ASTM D638-10.
Essential oil resistance test: the screw column is 9mm in height, 2.8mm in inner diameter and 5.0mm in outer diameter, is coated with the mugwort essential oil, is placed in a 70 ℃ oven for 48 hours to observe the surface cracking condition of the screw column, and is classified into four grades of excellent grade (no change of the surface), good grade (slight flaws on the surface and microcracks, few cracks) medium grade (more cracks) and lower grade (more cracks).
Table 2 comparative examples and comparative examples performance
The performance comparison shows that the unmodified ABS resin (comparative example 1) has poor essential oil resistance, and the essential oil resistance of the ABS composite material is improved after PBT is added (comparative example 2), but cracking still occurs. Comparative examples 2-3 and comparative example 6 found that the combination of the two lubricants gave the best improvement in chemical resistance of ABS, since the fluorine-based lubricant works in cooperation with the internal lubricant to improve the chemical resistance of the material; the improvement effect of the fluorine-based lubricant is better than that of the internal lubricant, because the internal lubricant is relatively free from the external lubricating ability and better adheres to the surface of the material, and the fluorine-based lubricant has better water and oil repellency and can isolate chemical substances; comparative examples 2 and 6 and comparative example 5 show that quaternary ammonium salt 3 having too long a carbon chain has poor essential oil resistance effect on the material, and that too long a carbon chain results in a larger molecular weight and a smaller number of effective groups in the same fraction. Comparative example 3 shows that the essential oil resistance is inferior to that of example 1 without adding quaternary ammonium salt, and that the addition of quaternary ammonium salt can better improve the essential oil resistance of ABS without affecting the physical properties of the material.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (7)
1. The essential oil-resistant ABS resin composition comprises the following components in parts by weight:
60-95 parts of ABS resin,
5-60 parts of PBT resin,
2-6 parts of a compatilizer,
1-4 parts of a lubricant,
0.1-0.5 part of quaternary ammonium salt;
the lubricant at least comprises a fluorine-containing lubricant; the quaternary ammonium salt is at least one of Virex TB, diversey and laurylamine dipropylene diamine.
2. The essential oil-resistant ABS resin composition according to claim 1, wherein the ABS resin has a butadiene content of 10 to 15% and an acrylonitrile content of 25 to 35%.
3. The essential oil-resistant ABS resin composition according to claim 1, wherein the PBT resin is polybutylene terephthalate having a weight average molecular weight of 1 to 6 tens of thousands.
4. The essential oil-resistant ABS resin composition according to claim 1, wherein the compatibilizer is one or more of ethylene-methyl acrylate-glycidyl methacrylate terpolymer, polyethylene grafted maleic anhydride, ethylene/butyl acrylate/carbonyl terpolymer.
5. The essential oil-resistant ABS resin composition according to claim 1, wherein the lubricant further comprises one or more of ethylene-based bis-stearamide, zinc stearate, magnesium stearate, ethylene-vinyl acetate copolymer.
6. The essential oil-resistant ABS resin composition according to claim 1, wherein the fluorine-containing lubricant is a perfluoropolyether oil.
7. A method for preparing the essential oil-resistant ABS resin composition according to claim 1, comprising: mixing the ABS resin, the PBT resin, the compatilizer, the lubricant and the quaternary ammonium salt at high speed, putting into a screw machine, carrying out melt extrusion at 160-220 ℃ and under the screw rotating speed condition of 200-500 rpm, and cooling and granulating to obtain the essential oil-resistant ABS resin composition.
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