CN115246980A

CN115246980A - Essential oil resistant ABS resin and preparation method thereof

Info

Publication number: CN115246980A
Application number: CN202210857574.5A
Authority: CN
Inventors: 杨彦菊; 查超; 汪策; 高亮
Original assignee: Guangdong Kumho Sunny Polymer Material Co ltd; Shanghai Kumho Sunny Plastics Co Ltd
Current assignee: Guangdong Kumho Sunny Polymer Material Co ltd; Shanghai Kumho Sunny Plastics Co Ltd
Priority date: 2022-07-20
Filing date: 2022-07-20
Publication date: 2022-10-28
Anticipated expiration: 2042-07-20
Also published as: CN115246980B

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. In the system, the PBT is a semi-crystalline material, the molecular chain arrangement is relatively compact, most organic small molecules can be effectively prevented from diffusing into the material, and the service life of the material is prolonged; by adding the weak-acid quaternary ammonium salt, the compound can react with esters in the 9-wormwood essential oil to carry out acidolysis on the esters, so that the damage of the essential oil to materials is weakened, and the mechanical property of the product is not influenced; by increasing the dosage of the lubricant and adding the fluorine-containing lubricant, another dense protective layer is slowly formed on the surface of the material, and the entry of organic molecules is further prevented.

Description

Essential oil resistant ABS resin and preparation method thereof

Technical Field

The invention belongs to the technical field of resin, relates to an ABS resin, and particularly relates to an essential oil resistant ABS resin and a preparation method thereof.

Background

The components of the wormwood essential oil are Ai Caosu, 4-hydroxy-8-acetoxy-1 (2), 9 (10) -guaiadiene-6, 12-lactone, elaeislactone, elaeisetin, erianin, 11-epielaeiscin, isovaleric acid, nerol ester, 13-dihydrodehydrocostuslactone, nerol isovalerate, 4-dehydrosaussurea, elaeisenin, chamomile essence, artesunolide and the like, so the wormwood essential oil is generally acidic and also has numerous esters.

ABS refers to acrylonitrile-butadiene-styrene copolymer, integrates the advantages of the acrylonitrile-butadiene-styrene copolymer, and has excellent mechanical properties with balanced toughness and rigidity, good formability and dimensional stability; in addition, it is required to have good surface gloss and coloring ability, and thus it is widely used in home appliances, electronic devices, and automobile industries. The ABS resin contains acrylonitrile components, has good chemical resistance, and generally does not have obvious defects with dilute acid, edible oil, metal salt solution, laundry detergent, liquid detergent, edible vinegar and the like (ABS resin production practice and application, soyan Shuang, chinese petrochemical press, 2015.4, page 150-151), but because the essential oil contains esters, the molecular structure of the resin can be damaged, the resin can crack in the use process of the massager, and the use temperature of the massager is about 40-50 ℃.

In general, although most of the problems of resistance of ABS can be solved by adding crystalline or semicrystalline materials, they do not have a great preventive effect on substances such as essential oils.

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 purpose of the invention is realized by 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 has butadiene content of 10-15% and acrylonitrile content of 25-35%.

The PBT resin is polybutylene terephthalate with the 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 a fluorine-containing lubricant, and also comprises one or more of ethylene-based bisstearamide, 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 (bisdecyl dimethyl ammonium chloride, laurylamine dipropylidene diamine and the like) and composite quaternary ammonium salt. The compound quaternary ammonium salt belongs to a 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) Preparing the following components in parts by weight:

(2) And (2) mixing the components in the step (1) at a high speed, putting the mixture into a screw machine, performing melt extrusion at the extrusion temperature of 160-220 ℃ and the screw rotating speed of 200-500 rpm, and cooling and granulating to obtain the essential oil resistant ABS resin composition. And then, injection molding is carried out to obtain a test sample strip and a screw column, and physical property and chemical property tests are carried out.

Compared with the prior art, the invention has the following beneficial effects:

1) The PBT is a semi-crystalline material, the molecular chain arrangement is relatively compact, most organic small molecules can be effectively prevented from diffusing into the material, and the service life of the material is prolonged;

2) According to the invention, the weak acidic quaternary ammonium salt can be added to carry out acidolysis reaction with esters in the 9 wormwood essential oil, so that the damage of the essential oil to materials is weakened, and the mechanical property of the product is not influenced;

3) According to the invention, by increasing the using amount of the lubricant and adding the fluorine-containing lubricant, another dense protective layer is slowly formed on the surface of the material, so that the organic molecules are further prevented from entering.

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 invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.

Examples 1 to 6

Embodiments 1 to 6 relate to a method for preparing an essential oil resistant ABS resin, the method comprising the steps of:

according to the weight percentage of the components in the formula in the table 1, the raw materials are added into a high-speed mixer to be fully mixed, then the mixture is placed into a screw machine to be subjected to melt extrusion at the extrusion temperature of 160-200 ℃ and the screw rotating speed of 350 r/min, and the product is obtained after cooling granulation.

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:

Wherein, the materials of table 1 are as follows:

ABS: ABS8391, high bridge petrochemical;

PBT: the weight average molecular weight is 2W;

a compatilizer: SMA218, day liter fine chemicals;

lubricant 1: PFPE, huge conversion in Zhejiang;

and 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 parts by weight of formulations of examples 1-6 and comparative examples 1-6

Performance evaluation method and implementation standard thereof

And (3) testing mechanical properties:

the ABS resin compositions prepared in examples 1-7 and comparative examples 1-5 were injection molded to obtain test specimens and screw studs, and the performance evaluation was performed, the results are shown in Table 2:

IZOD notched impact strength (1/8): testing according to ASTM D256-10 standard, with a test temperature of 23 ℃;

tensile strength: the test temperature was 23 ℃ according to ASTM D638-10.

Testing essential oil resistance: the height of the screw post is 9mm, the inner diameter is 2.8mm, the outer diameter is 5.0mm, the screw post is coated with wormwood essential oil and then placed in a 70 ℃ oven for 48 hours to observe the surface cracking condition of the screw post, and the screw post is divided into four grades, namely excellent (no surface change), good (slight surface flaw and even micro crack), medium (small amount of crack) and low (more crack).

TABLE 2 comparison of comparative and example Properties

The comparison of the performances shows that the essential oil resistance of the unmodified ABS resin (comparative example 1) is poor, and the essential oil resistance of the ABS composite material is improved after the PBT is added (comparative example 2), but cracking still occurs. Comparing examples 2 to 3 and comparative example 6, it can be seen that the combination of the two lubricants is most effective in improving the chemical resistance of ABS, since the fluorine-based lubricant synergistically acts with the internal lubricant to improve the chemical resistance of the material; the improvement effect of the fluorine lubricant is better than that of the internal lubricant because the internal lubricant is relatively free from external lubricant and can be better attached to the surface of a material, and the fluorine lubricant has better hydrophobic and oleophobic properties and can isolate chemical substances; comparing examples 2 and 6 with comparative example 5, it can be seen that quaternary ammonium salt 3 with too long carbon chain has poor effect on essential oil resistance of the material, the too long carbon chain results in larger molecular weight, and the number of effective groups is small in the same part. Comparative example 3, compared with example 1, the essential oil resistance of the ABS material is poor without adding the quaternary ammonium salt, which shows that the addition of the quaternary ammonium salt can better improve the essential oil resistance of the ABS material, and does not affect the physical properties of the ABS material.

The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims

1. An essential oil resistant ABS resin composition comprises the following components in parts by weight:

2. the essential oil resistant ABS resin composition of claim 1, wherein the ABS resin has a butadiene content of 10-15% and an acrylonitrile content of 25-35%.

3. The essential oil resistant ABS resin composition of claim 1 wherein the PBT resin is polybutylene terephthalate with a weight average molecular weight of 1-6W.

4. The essential oil resistant ABS resin composition of 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. Essential oil resistant ABS resin composition according to claim 1, wherein the lubricant comprises at least a fluorine-containing lubricant and may further comprise one or more of ethylene bis stearamide, zinc stearate, magnesium stearate, ethylene vinyl acetate copolymer.

6. The essential oil resistant ABS resin composition of claim 5 wherein the fluorine-containing lubricant is a perfluoropolyether oil.

7. The essential oil resistant ABS resin composition of claim 1, wherein the quaternary ammonium salt is an acidic quaternary ammonium salt, comprising one or more of a double-chain quaternary ammonium salt and a complex quaternary ammonium salt.

8. The essential oil resistant ABS resin composition of claim 7 wherein the double-chain quaternary ammonium salt comprises one or more of bisdecyl dimethyl ammonium chloride, laurylamine dipropylenediamine.

9. A method of preparing the essential oil resistant ABS resin composition of claim 1, wherein the method comprises: and (2) mixing the ABS resin, the PBT resin, the compatilizer, the lubricant and the quaternary ammonium salt at a high speed, putting the mixture into a screw machine, performing melt extrusion at the extrusion temperature of 160-220 ℃ and the screw rotating speed of 200-500 rpm, and cooling and granulating to obtain the essential oil resistant ABS resin composition.