CN114874515B - Modified nitrile rubber and preparation method and application thereof - Google Patents
Modified nitrile rubber and preparation method and application thereof Download PDFInfo
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- CN114874515B CN114874515B CN202210742322.8A CN202210742322A CN114874515B CN 114874515 B CN114874515 B CN 114874515B CN 202210742322 A CN202210742322 A CN 202210742322A CN 114874515 B CN114874515 B CN 114874515B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses modified nitrile rubber, a preparation method and application thereof, wherein the modified nitrile rubber comprises the following raw materials in parts by weight: acrylic acid: styrene: divinylbenzene: and (3) an initiator: nitrile rubber: the weight ratio of the organic solvent is 5-10: 5-10: 1 to 4:0.05 to 0.1: 10-20: 30 to 60 percent. According to the invention, the PC/ABS alloy material is negatively charged by introducing the carboxylic acid group, so that the hydrophilicity of the alloy material is improved, the contact area between the plating layer and the alloy material is increased, and further, the surface is easier to infiltrate by the roughening liquid during electroplating roughening, so that roughening is easier, and the electroplating effect of the PC/ABS alloy material is improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to modified nitrile rubber and a preparation method and application thereof.
Background
PC/ABS alloy materials are widely applied to automobile interior and exterior parts, such as inner and outer door handles, automobile nameplates, wheel covers, grids, decorative strips and the like, due to excellent heat resistance, toughness, fatigue resistance and electroplating performance. With the advent of plastic and full plastic automobiles in the automobile industry, the electroplating plastic has been increasingly widely used, wherein ABS electroplating has the most widely used, and the electroplating effect is the best, so that the electroplating plastic is widely used in the aspects of automobiles, radios, commercial machines, nameplates, bathrooms and the like. The electroplating PC/ABS alloy material can adopt the same electroplating process as ABS, and has good PC heat resistance and long-term use at 120 ℃, so that the heat resistance of the electroplating PC/ABS alloy material is improved compared with that of the common ABS for electroplating.
The existing electroplating-grade PC/ABS alloy products in the market depend on adding a large amount of ABS and high rubber powder to increase rubber phase or adding inorganic filler to increase etching points, so that the performances such as material strength and the like are damaged, and the problems of low yield, defects on the surface after electroplating and the like are generated in the electroplating process.
The publication number is: the patent CN103602053B discloses an electroplated PC/ABS alloy material easy to electroplate and a preparation method thereof, and specifically discloses the electroplated PC/ABS alloy material which comprises the following components in parts by weight: the preparation method comprises the steps of mixing 30-70 parts of PC resin, 15-65 parts of ABS resin, 5-10 parts of PEO resin, 0.1-1 part of antioxidant and 0.1-1 part of lubricant, granulating by a double screw extruder to prepare the PC/ABS alloy material easy to plate, wherein the PEO resin contains a large amount of hydroxyl groups to make the surface of the PC/ABS hydrophilic, so that coarsening is easier, but the PEO resin can be completely dissolved in water, coarsening liquid needs to be heated to 60-72 ℃ in the actual coarsening process, the dissolution of the PEO resin in the product is accelerated at the temperature, and the electroplated surface has defects, so that the performance of the product is affected.
At present, a technical scheme for preparing a PC/ABS alloy material by introducing an end-group-based nitrile rubber is also provided, and the technical scheme is as follows: the patent CN108250660B discloses an electroplating-grade PC/ABS alloy material and a preparation method thereof, and specifically discloses that the electroplating-grade PC/ABS alloy material comprises: the preparation method comprises the steps of mixing PC resin, ABS resin, end-group nitrile rubber and optional additives, extruding and granulating to obtain an electroplating-grade PC/ABS alloy material, wherein the PC/ABS alloy material is introduced into the end-group nitrile rubber to improve the hydrophilicity of the material, and is favorable for coarsening, however, in the actual production process, the end-group nitrile rubber is a viscous liquid, the addition amount is up to 20-35 parts by weight, the addition difficulty in the actual granulation process is relatively high, and the material is basically added with high rubber content material (similar to high rubber powder), so that the performance of the product is influenced.
At present, a technical scheme is also disclosed, for example, the publication number is: the patent CN106633776B discloses an electroplated PC/ABS alloy material suitable for door handles and a preparation method thereof, and specifically discloses the electroplated PC/ABS alloy material which comprises the following components in parts by weight: the preparation method comprises the steps of mixing the PC resin, the ABS resin, the expanded graphite, the antioxidant and the lubricant, extruding and granulating to obtain the electroplated PC/ABS alloy material suitable for the door handle, and adding inorganic materials to increase the roughened etching points, wherein the performances such as strength and the like of the alloy material are destroyed.
In summary, the existing electroplated PC/ABS alloy material has the problems of low electroplating binding force, low yield, surface defects and the like, and as shown in figure 1, the alloy product has cracks.
Disclosure of Invention
The invention aims to solve the defects of the technology, and relates to modified nitrile rubber, a preparation method and application thereof, wherein the modified nitrile rubber is used for preparing an easily electroplated PC/ABS alloy material, so that the modified nitrile rubber has the advantages of higher electroplating binding force, high electroplating yield and reduced surface defects.
The invention relates to modified nitrile rubber, which comprises the following components in parts by weight:
acrylic acid: styrene: divinylbenzene: and (3) an initiator: nitrile rubber: the weight ratio of the organic solvent is 5-10: 5-10: 1 to 4:0.05 to 0.1: 10-20: 30 to 60 percent.
In the technical scheme, the PC/ABS alloy material is negatively charged through the carboxylic acid group, so that the hydrophilicity of the alloy material is improved, the contact area between a plating layer and the alloy material is increased, and further, the surface is easier to infiltrate by roughening liquid during electroplating roughening, so that roughening is easier, and the electroplating effect of the PC/ABS alloy material is improved; the carboxylic acid groups are distributed relatively uniformly, which is beneficial to shortening the roughening time of the PC/ABS alloy material product; the carboxylic acid group can react with hydroxyl in the PC resin, and the carboxylic acid group mainly occurs in the modified nitrile rubber or the ABS resin in the roughening process, so that the etching of the PC resin in the roughening process is reduced, the strength of the PC resin is maintained, the bonding strength of a coating and a matrix material is ensured, the surface defects are reduced, and the yield is improved.
Further, the acrylonitrile mass percentage content in the nitrile rubber is 30-45%
Further, the initiator is dicumyl peroxide, benzoyl peroxide or azobisisobutyronitrile; the organic solvent is N, N-dimethylformamide.
The invention also provides a preparation method of the modified nitrile rubber, which comprises the following steps:
(1) Dissolving 5-10 g of acrylic acid, 5-10 g of styrene and 1-4 g of divinylbenzene in 30-60 g of organic solvent, and uniformly stirring and mixing;
(2) Adding 0.5-2 g of nitrile rubber into the uniformly stirred solution, and stirring and dissolving to form transparent solution;
(3) Adding 0.05-0.1 g of initiator into the transparent solution, stirring and dissolving, and raising the temperature to perform solution polymerization reaction;
(4) And removing the organic solvent after polymerization, and drying to obtain the modified nitrile rubber.
Further, the polymerization temperature is 80-90 ℃ and the polymerization time is 8-16 h.
The invention also provides application of the modified nitrile rubber, wherein the modified nitrile rubber is used for preparing PC/ABS alloy materials, and the PC/ABS alloy materials comprise the following components in parts by weight: 20 to 60 parts of PC resin, 20 to 60 parts of ABS resin, 10 to 20 parts of modified nitrile rubber, 0.5 to 1 part of antioxidant and 0.5 to 1 part of lubricant.
Further, the PC resin, the ABS resin, the modified nitrile rubber, the antioxidant and the lubricant are mixed and then are subjected to twin-screw extrusion granulation to prepare the electroplated PC/ABS alloy material.
In the technical scheme, the cross-linked gel type acrylic modified nitrile rubber with an interpenetrating network structure is prepared through polymerization reaction, and carboxylic acid groups in the modified nitrile rubber structure are utilized to provide hydrophilic groups for PC/ABS alloy material products, so that the products are negatively charged, and coarsening of the PC/ABS alloy material products is facilitated; introducing acrylic acid-styrene-divinylbenzene copolymer into nitrile rubber, and producing ABS resin by a blending method, wherein the modified nitrile rubber has a structure similar to ABS resin; acrylic acid is partially grafted onto the molecular chain of nitrile rubber, making the nitrile rubber hydrophilic as well.
Drawings
FIG. 1 is a diagram of a defective product referred to in the background of the present disclosure, which has been electroplated to create an electroplated crack that affects aesthetics;
FIG. 2 is a graph of the test effect of alloy 2 of the present invention;
FIG. 3 is a graph of the test effect of alloy 3 of the present invention;
FIG. 4 is a graph of the test effect of alloy 4 of the present invention;
FIG. 5 is a graph of the test effect of alloy 5 of the present invention;
FIG. 6 is a graph of the test effect of alloy 8 of the present invention;
FIG. 7 is a graph showing the effect of the alloy 1 according to the present invention.
Detailed Description
The invention will be described in detail below with respect to certain specific embodiments thereof in order to better understand the invention and thereby to more clearly define the scope of the invention as claimed. It should be noted that the following description is only some specific embodiments of the inventive concept, but is only a part of examples of the present invention, where the specific direct description of the related structures is only for convenience in understanding the present invention, and the specific features do not naturally and directly limit the implementation scope of the present invention. Conventional selections and substitutions made by those skilled in the art under the guidance of the inventive concept should be considered as being within the scope of the claimed invention.
The modified nitrile rubber is prepared by the following steps:
(1) Adding an organic solvent into a three-neck flask, and then adding acrylic acid, styrene and divinylbenzene for stirring and mixing;
(2) Raising the temperature of the mixed solution to 60-65 ℃, adding nitrile rubber into the mixed solution, stirring and dissolving the mixed solution, and forming transparent solution after the mixed solution is completely dissolved;
(3) Adding an initiator into the transparent solution for stirring and dissolving, and raising the temperature to 80-90 ℃ for solution polymerization for 8-16 h;
(4) After the polymerization is finished, extruding the polymer solution into strips, soaking the strips in water, removing the organic solvent, cutting the strips, and drying to obtain the modified nitrile rubber.
Comparative example 1, examples 2-5:
examples 2-5 were used to examine the effect of acrylic starting materials in modified nitrile rubber, which was prepared in the same manner as in the previous step.
Table 1 modified nitrile rubber of different Components
The modified nitrile rubber prepared in examples 2-5 was used to prepare PC/ABS alloy materials, respectively, numbered alloy 2-5. The normal PC/ABS alloy without modified nitrile rubber was taken as alloy 1 and used as comparative example 1.
The preparation method of the alloy 2-5 comprises the following steps: 45 parts of PC resin, 40 parts of ABS resin, 13 parts of modified nitrile rubber, 1 part of antioxidant and 1 part of lubricant are mixed, and then are extruded and granulated by double screws to obtain the PC/ABS alloy material easy to electroplate, and after being fully dried at 75 ℃, PC/ABS alloy material products are formed by injection molding, wherein the temperatures of different positions of a gun barrel in injection molding are respectively 240, 230, 220, 200 and 85 ℃, and the injection pressure is 12MPa. Alloy 1 was prepared in the same manner but without the addition of modified nitrile rubber.
Wherein, the coarsening time, electroplating binding force, electroplating qualification rate and ABS alloy tensile strength of each PC/ABS alloy material are tested, and the specific results are shown in Table 2.
Table 2 table of test results for alloys 1-5
As shown in Table 2, the alloy 2-5 has excellent electroplating binding force and electroplating qualification rate, because the addition amount of acrylic acid in the modified nitrile rubber is in the range of the application, the hydrophilicity of the material is improved, and further, the surface is easier to be infiltrated by the roughening liquid during electroplating roughening, so that the roughening is easier, and the electroplating effect of the PC/ABS alloy material is improved.
Examples 6 to 10:
examples 6 to 10 were used to examine the effect of the acrylonitrile content in nitrile rubber. Wherein, the components and weight of the modified nitrile rubber in examples 6-10 are respectively: 8g of acrylic acid, 8g of styrene, 2.8g of divinylbenzene, 0.08g of initiator, 15g of nitrile rubber and 50g of organic solvent, wherein the preparation method of the modified nitrile rubber is the same as the previous step.
TABLE 3 modified nitrile rubbers prepared from acrylonitrile in different contents
The acrylonitrile-butadiene rubber of example 9 had an acrylonitrile content of 40% and was the same as in examples 1 to 5.
The modified nitrile rubber prepared in the examples 6-10 is used for preparing PC/ABS alloy materials respectively, the serial numbers are alloy 6-10, and the preparation method comprises the following steps: 45 parts of PC resin, 40 parts of ABS resin, 13 parts of modified nitrile rubber, 1 part of antioxidant and 1 part of lubricant are mixed, and then are extruded and granulated by double screws to obtain the PC/ABS alloy material easy to electroplate, and after being fully dried at 75 ℃, PC/ABS alloy material products are formed by injection molding, wherein the temperatures of different positions of a gun barrel in injection molding are respectively 240, 230, 220, 200 and 85 ℃, and the injection pressure is 12MPa.
Wherein, the coarsening time, electroplating binding force, electroplating qualification rate and ABS alloy tensile strength of each PC/ABS alloy material are tested, and the specific results are shown in Table 4.
Table 4 table of test results for alloys 6-10
As can be seen from Table 4, the higher the acrylonitrile content, the better the electroplating performance and the worse the mechanical properties of the alloy, and the alloy 7-9 has excellent electroplating binding force and electroplating qualification rate, because the acrylonitrile content in the modified nitrile rubber is 30-45% in the range of the application.
In order to evaluate the actual electroplating effect of the alloy of the invention, the electroplating strength of the corresponding alloy is tested by adopting a cross glue tearing method.
And respectively taking the electroplated component products of the alloy 2-5 and the alloy 8, firstly, marking a crossed cross-shaped flower knife on the surface of the electroplated component products by using a cutter to form an X-shaped damaged surface, then adopting the same 3M glue to press and cover the damaged surface, and finally tearing the 3M glue from the surface of the component to check the damage condition of the 3M glue to the electroplated surface.
Alloy 2 is shown in FIG. 2 after being tested as described above, alloy 3 is shown in FIG. 3 after being tested as described above, alloy 4 is shown in FIG. 4 after being tested as described above, alloy 5 is shown in FIG. 5 after being tested as described above, and alloy 8 is shown in FIG. 6 after being tested as described above. In addition, a comparative test was performed using a general PC/ABS alloy under the same plating conditions, and the results are shown in FIG. 7.
As can be seen from FIGS. 2-7, the PC/ABS alloy modified by the method has obvious improvement on electroplating performance compared with unmodified PC/ABS alloy, and the damaged surface is not damaged by tearing off the 3M adhesive by external force, which indicates that the electroplated layer has strong adhesion with the alloy surface.
Claims (6)
1. The modified nitrile rubber is characterized by comprising the following raw materials in parts by weight:
acrylic acid: styrene: divinylbenzene: and (3) an initiator: nitrile rubber: the weight ratio of the organic solvent is 5-10: 5-10: 1-4: 0.05-0.1: 10-20: 30-60 parts; the acrylonitrile-butadiene rubber comprises 30-45% of acrylonitrile by mass; the initiator is one of dicumyl peroxide, benzoyl peroxide or azodiisobutyronitrile; the organic solvent is N, N-dimethylformamide.
2. The preparation method of the modified nitrile rubber is characterized by comprising the following steps of:
(1) Dissolving 5-10 g of acrylic acid, 5-10 g of styrene and 1-4 g of divinylbenzene in 30-60 g of organic solvent, and uniformly stirring and mixing;
(2) Adding 0.5-2 g of nitrile rubber into the uniformly stirred solution, and stirring and dissolving to form a transparent solution;
(3) Adding 0.05-0.1 g of initiator into the transparent solution, stirring and dissolving, and raising the temperature to perform solution polymerization reaction;
(4) And removing the organic solvent after polymerization, and drying to obtain the modified nitrile rubber.
3. The method for preparing modified nitrile rubber according to claim 2, wherein the polymerization reaction temperature is 80-90 ℃ and the polymerization time is 8-16 h.
4. The use of a modified nitrile rubber comprising a modified nitrile rubber according to claim 1 for the preparation of an electroplating grade PC/ABS alloy material.
5. The electroplating-grade PC/ABS alloy material is characterized by comprising the following components in parts by weight: 20-60 parts of PC resin, 20-40 parts of ABS resin, 10-20 parts of modified nitrile rubber according to claim 1, 0.5-1 part of antioxidant and 0.5-1 part of lubricant.
6. The electroplating grade PC/ABS alloy material according to claim 5, wherein the PC resin, the ABS resin, the modified nitrile rubber according to claim 1, the antioxidant and the lubricant are mixed and then pelletized by twin screw extrusion, so as to obtain the electroplating grade PC/ABS alloy material.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103602053A (en) * | 2013-11-05 | 2014-02-26 | 上海锦湖日丽塑料有限公司 | Easily-electroplated electroplating PC (polycarbonate)/ABS (acrylonitrile butadiene styrene) alloy material and preparation method thereof |
| CN104610596A (en) * | 2015-01-15 | 2015-05-13 | 无为县茂林电缆材料有限公司 | Liquid rubber modified nitrile rubber cable material |
| CN104788769A (en) * | 2014-05-29 | 2015-07-22 | 天长市远洋船舶设备有限公司 | Modified butadiene-acrylonitrile rubber material for ship |
| CN108250660A (en) * | 2017-12-22 | 2018-07-06 | 万华化学集团股份有限公司 | A kind of plating grade PC/ABS alloy materials and preparation method thereof |
| CN109735081A (en) * | 2018-12-25 | 2019-05-10 | 浙江普利特新材料有限公司 | A kind of plating grade PC/ABS alloy material of high fluidity and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602053A (en) * | 2013-11-05 | 2014-02-26 | 上海锦湖日丽塑料有限公司 | Easily-electroplated electroplating PC (polycarbonate)/ABS (acrylonitrile butadiene styrene) alloy material and preparation method thereof |
| CN104788769A (en) * | 2014-05-29 | 2015-07-22 | 天长市远洋船舶设备有限公司 | Modified butadiene-acrylonitrile rubber material for ship |
| CN104610596A (en) * | 2015-01-15 | 2015-05-13 | 无为县茂林电缆材料有限公司 | Liquid rubber modified nitrile rubber cable material |
| CN108250660A (en) * | 2017-12-22 | 2018-07-06 | 万华化学集团股份有限公司 | A kind of plating grade PC/ABS alloy materials and preparation method thereof |
| CN109735081A (en) * | 2018-12-25 | 2019-05-10 | 浙江普利特新材料有限公司 | A kind of plating grade PC/ABS alloy material of high fluidity and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 合成橡胶工业;中国石化文摘(07);全文 * |
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