CN117683319A

CN117683319A - PP-ABS compatible master batch, PP-ABS alloy and preparation method thereof

Info

Publication number: CN117683319A
Application number: CN202410146871.8A
Authority: CN
Inventors: 刘洪洋; 刘心婷
Original assignee: Foshan Shehede New Material Technology Co ltd
Current assignee: Foshan Shehede New Material Technology Co ltd
Priority date: 2024-02-02
Filing date: 2024-02-02
Publication date: 2024-03-12
Anticipated expiration: 2044-02-02
Also published as: CN117683319B

Abstract

The invention belongs to the technical field of organic polymer materials, and relates to a PP-ABS compatible master batch, a PP-ABS alloy and a preparation method thereof, wherein the compatible master batch comprises the following raw material components in parts by weight: 45-85 parts of ABS resin, 10-40 parts of PP resin, 5-15 parts of compatilizer A, 2-10 parts of compatilizer B and 0.5-3 parts of lubricant; the compatilizer A is a mixture obtained by oxidizing and hydrolyzing SAN or ABS resin; the compatilizer B is one or two of grafts of maleic anhydride grafted polypropylene or grafts of glycidyl acrylate grafted polyethylene. The compatilizer A can be well fused with the ABS base material, and the amide group of the compatilizer A can react with the compatilizer B to form a chemical bond in the process of mixing and melting, so that the compatibility of PP and ABS is improved, the compatilizer A can be applied to PP-ABS alloy, the mechanical property of alloy material can be improved, and the surface glossiness of the material is good.

Description

PP-ABS compatible master batch, PP-ABS alloy and preparation method thereof

Technical Field

The invention belongs to the technical field of organic polymer materials, and particularly relates to a PP-ABS compatible master batch, a PP-ABS alloy and a preparation method thereof.

Background

Polypropylene (PP) is a nonpolar resin with low density, good chemical stability and high cost performance, and has wide application. Because the PP resin has crystallization property, the shrinkage rate is large, the dimensional stability is poor, the mechanical property is not high, and the requirement of a specific working condition cannot be met. In order to overcome the defects of PP resins, it is generally necessary to add fillers to compensate for the defects, but this causes other problems.

Acrylonitrile-butadiene-styrene (ABS) is a polar, amorphous resin with good engineering plastic properties, good mechanical properties and dimensional stability, but poor chemical stability and poor resistance to chemical solvents.

The PP-ABS alloy synthesized by blending PP and ABS effectively reduces the shrinkage of PP resin, improves the mechanical strength of the PP resin, and has the advantages of good dimensional stability, solvent resistance, lower density and the like. However, due to the characteristic difference between the polar and nonpolar materials, the compatibility of the polar and nonpolar materials is poor, and the alloy materials after melt mixing have serious problems such as wiredrawing, layering or peeling. Therefore, the problem of compatibility of PP and ABS becomes a key problem for restricting the development and application of PP-ABS alloy materials.

In order to improve the compatibility of PP and ABS, reduce the shrinkage of PP and improve the strength of alloy materials, the field technicians have studied on the aspect of adding compatilizers and auxiliaries. As in WO 2019/100468 A1, thirty functional additives are adopted to attempt improvement in aspects of thermal stability, antistatic, antibacterial and the like, PP-ABS composite materials with excellent comprehensive properties are prepared, but large-scale production is difficult due to the large number of additives.

In the patent application document CN 108285578A, the PP-ABS micro-foaming material is prepared by adopting filler nano particles, dispersing agent PE wax and solubilizer PE-g-GMA, so that the influence on the mechanical property of the PP-ABS composite material caused by incompatibility of PP and ABS is avoided. The method has low cost and convenient processing and production.

Patent application document CN 102408633a discloses an ABS master batch using a phosphorus-containing flame retardant, which realizes uniform dispersion of the flame retardant in PP-ABS alloy under the action of a first compatibilizer maleic anhydride graft and a second compatibilizer acrylic ester graft, and besides improving the flame retardance of the material, the alloy material also maintains excellent mechanical properties, rigidity creep resistance and dimensional stability. However, the compatibility problem of PP with ABS has not been thoroughly solved.

In the patent application document CN 105462152A, an organic compatilizer and an inorganic compatilizer are adopted to compatilize PP and ABS, so that the PP-ABS alloy material with small density and good mechanical property is obtained. Wherein, the organic compatilizer comprises a graft of Maleic Anhydride (MAH) and AS, ABS, PP resin, a graft of acrylic ester and polyolefin, a graft of SBS and maleic anhydride, etc.; the inorganic compatilizer is selected from calcium carbonate, talcum powder, barium sulfate, wollastonite or mica with the particle size of 1-100 nm. The method is simple to operate and convenient to produce, but inorganic powder is difficult to disperse uniformly, so that the method becomes a fatal weakness in the production process, and the compatibility of PP and ABS still has a plurality of problems to be solved urgently.

It can be seen that the problem of compatibility of PP with ABS has also plagued the development of PP-ABS alloy materials.

Disclosure of Invention

Based on the compatibility, the PP-ABS compatible master batch provided by the invention can improve the compatibility of PP and ABS, the formed alloy material has no compatibility defect, the mechanical property is further improved, and the surface glossiness of the material is good.

The invention provides a PP-ABS compatible master batch, which comprises the following raw material components in parts by weight: 45-85 parts of ABS resin, 10-40 parts of PP resin, 5-15 parts of compatilizer A, 2-10 parts of compatilizer B and 0.5-3 parts of lubricant.

The compatilizer A is a mixture obtained by oxidizing and hydrolyzing an acrylonitrile-styrene copolymer (SAN) or an ABS resin, the hydrolysis rate is not critical, and in some embodiments, the ammonia value of the mixture is 5-15%.

The compatilizer B is one or two of a graft (PP-g-MAH) of Maleic Anhydride (MAH) grafted polypropylene or a graft (PE-g-GMA) of glycidyl acrylate (GMA) grafted polyethylene.

In the PP-ABS compatible master batch, the compatilizer A is a mixture obtained by oxidizing and hydrolyzing acrylonitrile-styrene copolymer (SAN) or ABS resin, wherein the mixture (AMS-SAN) containing most of SAN copolymer and styrene-acrylic acid Amide (AMS) can be well fused with an ABS base material, and the amide group of the compatilizer A can be compatible with the compatilizer B in the process of mixing and melting, and particularly gradually amidates and imidizes with Maleic Anhydride (MAH) groups in the compatilizer B-PP-g-MAH or ring-opening addition reaction with epoxy groups in glycidyl ether of the compatilizer PE-g-GMA and amidates with the AMS; finally, PP and ABS are compatible. Because of the formation of chemical bonds, the compatibility of PP and ABS is improved, the formed alloy material basically has no compatibility defect, the mechanical property is further improved, and the surface glossiness of the material is good.

However, PP-g-MAH is more commonly used because PE-g-GMA compatibilizers are less heat resistant than PP-g-MAH. Preferably, the compatilizer B is PP-g-MAH.

Preferably, the ABS resin is a core-shell polymer formed by styrene and acrylonitrile-butadiene rubber, wherein the content of the acrylonitrile-butadiene rubber is 55-70 wt%; the impact property of the material can be improved by adding a small amount of the rubber, wherein the molecular chain of the rubber segment can be compatible with the copolymerized PP, and the high-content rubber can toughen the PP resin. The common trade name is ABS high rubber powder, which can be related trade name produced by Korea Jinhu and Korea Basv.

Preferably, the PP resin is one or two of homo-polypropylene and co-polypropylene. Further preferred is a copolymerized PP having a melt index of 5-50g/10min.

Preferably, the lubricant is one of calcium stearate and EBS (N, N' -ethylene bis-stearamide).

Preferably, the raw material SAN or ABS resin of the compatilizer A is prepared by an emulsion method; SAN prepared by the emulsification method can be swelled or dissolved in a solvent such as DMSO, and is beneficial to the reaction.

Further preferably, the preparation method of the compatilizer A is as follows: adding SAN or ABS resin into dimethyl sulfoxide solvent under ice bath and stirring conditions, then adding 30wt% hydrogen peroxide and potassium carbonate, moderately heating to start reaction, and then keeping the reaction temperature at 25+/-3 ℃; and after the reaction is completed for 5-30 min, adding pure water, cooling, washing, filtering and collecting a product to obtain the compatilizer A. The compatilizer A contains partial SAN and has good compatibility with ABS resin, and the amino group of the molecular side chain can carry out amidation reaction with the compatilizer B under the high temperature condition, so that the aim of compatibility is finally achieved.

Further preferably, the concentration of the SAN or ABS resin in the dimethylsulfoxide solvent is 30% -40wt%.

The second aspect of the invention also provides a PP-ABS alloy which is prepared from the following raw materials in parts by weight: 50-80 parts of ABS resin, 10-30 parts of PP resin, 10-20 parts of PP-ABS compatible master batch, 0.1-1.5 parts of antioxidant and 0.5-2 parts of lubricant.

Preferably, the antioxidant is formed by mixing an antioxidant 1010 and an antioxidant 168 according to a weight ratio of 1:1.

The third aspect of the invention also provides a preparation method of the PP-ABS compatible master batch, comprising the following steps: and uniformly mixing the raw materials, and extruding the mixture through a double-screw extruder to obtain the PP-ABS compatible master batch.

Preferably, the temperature of the first region of the twin-screw extruder is 175-185 ℃, the temperature of the second region is 175-205 ℃, the temperature of the third region is 185-215 ℃, the temperature of the fourth region is 195-225 ℃, the temperature of the fifth region is 190-225 ℃, the temperature of the sixth region is 190-225 ℃, the temperature of the seventh region is 190-225 ℃, the temperature of the eighth region is 175-205 ℃, the temperature of the ninth region is 175-215 ℃, and the temperature of the machine head is 180-230 ℃; the rotation speed of the host machine is 300-500rmp.

The fourth aspect of the present invention also provides a method for preparing the PP-ABS alloy, comprising the steps of: and uniformly mixing the raw materials, and extruding the mixture through a double-screw extruder to obtain the PP-ABS alloy.

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

(1) The invention uses the principle of cyano hydrolysis and takes SAN as a raw material to prepare SAN hydrolysis product styrene-acrylamide copolymer (SAM), wherein part of the SAN is not hydrolyzed, and the formed composite (SAN-SAM) of the styrene-acrylonitrile copolymer and the styrene-acrylamide copolymer is used as a compatilizer A, and the compatilizer A has good compatibility with ABS resin, can generate amidation or imidization reaction with PP compatilizer B, and enhances the compatibility of the PP and the ABS resin.

(2) The prepared PP-ABS alloy has the advantages of small density, good mechanical property and mechanical property, reduced production risk of material defects caused by compatibility problems and improved product quality through the chemical reaction of the ABS compatilizer A and the PP compatilizer B.

(3) The invention solves the compatibility problem of PP and ABS materials, adopts mature technology, has simple operation process and is convenient for popularization and use.

Drawings

FIG. 1 is a schematic diagram of SAN amidation reaction;

FIG. 2 is a schematic diagram of the mechanism of ABS and PP compatibility;

FIG. 3 is a photograph of a sample strip of example 3-2 of the present invention;

FIG. 4 is a photograph of a sample bar of comparative examples 1-5 of the present invention.

Detailed Description

The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention.

All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

The reagents, materials and equipment used in the examples are all commercially available sources unless otherwise specified; the test methods are conventional in the art unless otherwise specified.

Material description:

ABS resin is HR-183 ABS high rubber powder (Han Guojin lake), the rubber content is 60 percent, and the tensile strength is 45MPa (23 ℃);

PP resin is purchased from Yanshan petrochemical PP K9026, and has a melt index of 15g/10min, a tensile strength of 18MPa, a notched Izod impact strength of 53 kJ/square meter (23 ℃), and a flexural modulus of 850MPa;

SAN resin is bench NX3260 (emulsion method), its melt index is 6.0g/10min, tensile strength (50 mm/min,3.2 mm) 77.45MPa, notched Izod impact strength (23 ℃,3.2 mm) 1.5 kJ/square meter, flexural modulus (23 ℃,2.0 mm/min) 3440MPa;

the compatilizer B is copolymerized PP-g-MAH, and is purchased from P353 of Dow chemical, wherein the specific gravity of the compatilizer B is 0.904g/cm, and the melt index of the compatilizer B is 22.4 g/10min (160 ℃ C., 5 kg);

the lubricant was EBS, a lubricant purchased from japan flower king;

the antioxidant is obtained by mixing an antioxidant 1010 and an antioxidant 168 according to a weight ratio of 1:1, and is purchased from Tianjin An Long;

dimethyl sulfoxide DMSO, hydrogen peroxide (30 wt%) and potassium carbonate are all commercial reagents.

The present invention will be described in detail with reference to specific 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 variations and modifications can be made by those skilled in the art without departing from the spirit of the invention, which falls within the scope of the invention.

Example 1 preparation of compatibilizer A

300ml of dimethyl sulfoxide (DMSO) was added to the three-necked flask, stirred, and SAN resin (157 g,1 eq.) was added thereto and dissolved at room temperature for 2 hours; then under ice bath condition, 30wt% hydrogen peroxide (120 ml) and potassium carbonate (50 g) are added, the reaction is started by proper heating, the reaction is violently exothermic, the reaction is maintained at room temperature for 5min-30min to complete the reaction, 5000ml pure water is added, the reaction product is cooled, filtered and collected, and dried at 85 ℃ to obtain compatilizer A (> 170 g) with an ammonia value of 10 (g/100 g).

The reaction principle is shown in figure 1.

Example 2 preparation of PP-ABS compatible masterbatch (SS)

The formulation of PP-ABS compatible master batches of each of examples 2-1, 2-2 and 2-3 in example 2 is shown in Table 1.

Table 1 formulation of PP-ABS compatible masterbatch of example 2

The preparation method comprises the following steps:

weighing the components according to the formula table of the table 1, respectively, and putting the components into a mixing bucket for uniformly mixing, wherein the compatilizer A is the compatilizer prepared in the example 1; and then extruding, cooling, drying and granulating in a double-screw extruder to obtain PP-ABS compatible master batches SS-1, SS-2 and SS-3 respectively.

The extrusion process conditions were as follows:

the extruder main machine rotation speed is 350 rpm, the extruder temperature range is 170 ℃ to 230 ℃, and the specific conditions are shown in table 2.

TABLE 2 PP temperature ranges of ABS compatible masterbatch (SS) extruder

Example 3 preparation of PP-ABS alloy

The formulation of PP-ABS alloy for each of examples 3-1, 3-2 and 3-3 in example 3 is shown in Table 3.

The preparation method comprises the following steps:

weighing ABS resin, PP-ABS compatible master batch (SS-1), antioxidant and lubricant according to the table 3, respectively adding into a mixing barrel, uniformly mixing, extruding in a double-screw extruder, cooling, drying and granulating to obtain the PP-ABS alloy.

Table 3 PP-ABS alloy examples ratio

Extrusion process conditions: the rotation speed of the host machine is 350 rpm; the extruder temperature was 170℃to 230℃and is shown in Table 4.

TABLE 4 PP-ABS alloy extruder temperature Range

For further explanation of the examples, comparative examples were developed. The technical idea and data of the comparative example are all within the protection scope of the invention.

Comparative example 1

The comparative PP-ABS alloy and the compatible master batch components thereof are shown in tables 5 and 6, respectively.

The preparation is described in example 3.

Comparative example 1-1 was compared with example 3-1, with compatibilizer B, and instead of compatibilizer A of example 1, SAN was used.

Comparative examples 1-2 are compared to examples 3-2 with compatibilizer B, without SAN and compatibilizer A.

Comparative examples 1-3 were compared to examples 3-2 with compatibilizer A and no compatibilizer B.

Comparative examples 1-4 were compared with examples 3-2, with compatibilizer B, without compatibilizer A and SAN, but with differences in the amounts of the components in the compatibilized master batch from comparative examples 1-2.

Comparative examples 1-5 were compared with examples 3-2, and no compatibilizing agent A, compatibilizing agent B and SAN were added.

TABLE 5 comparative example PP-ABS alloy composition

TABLE 6 comparative compatible masterbatch compositions

Performance testing

1. Density: testing according to the national standard ISO 1183 method; units: g/cm 3;

2. tensile strength: the stretching speed is 50mm/min measured according to the national standard ISO 527 method; units: MPa;

3. flexural strength: spline size measured according to national standard ISO 178 method: 80X 10X 4mm, bending speed: 2mm/min; units: MPa;

4. flexural modulus: spline size measured according to national standard ISO 178 method: 80X 10X 4mm, bending speed: 2mm/min; units: MPa;

5. notched Izod impact Strength: spline size measured according to national standard ISO 180 method: 80×8×4mm, pendulum energy: 2.75J; units: kJ/-square meter.

Test results

The PP-ABS alloy samples of example 3 and comparative example 1 were subjected to performance test, and the results are shown in Table 7.

Table 7 test results of examples and comparative examples

Data analysis and discussion

Analysis was performed based on the appearance of the sample and the test data, with the following results discussed:

1. appearance: the appearance of the sample of example 3 is significantly better than that of the comparative example. The appearance of the test bars of the examples was substantially free of compatibility defects, smooth in surface and good in hand. In particular, the bars of example 3-2 (FIG. 3) were relatively fine and smooth, with a flat and smooth surface. The bars of comparative examples 1-1 to 1-4 were significantly worse due to the absence of the compatibilizer, while the bars of comparative examples 1-5 (FIG. 4) had more surface defects such as foaming, stringing and skinning. Indicating that the compatible master batch plays a good role in compatibility.

2. Density: in example 3, the main factor contributing to the density is ABS (ABS density of about 1.05 g/cm. Times.), with increasing amounts of ABS, the density of the material increases. Theoretical analysis shows that the amidation and imidization reactions occur between the functional groups of the compatilizer A and the compatilizer B, the compatibility of the ABS and the PP is improved, the structure of the material is compact, the density of the material is relatively improved, and the density test result also proves that the density of the sample in the embodiment is mostly higher than that of the sample in the comparative example.

3. Mechanical properties of the material: because the compatilizer A is compatible with ABS, the compatilizer B is compatible with PP, wherein the acid anhydride group in the compatilizer B and the amino group in the compatilizer A are subjected to amidation and imidization reaction, and finally the degree of compatibility of the two is achieved. In examples 3-1 to 3-5, the mechanical properties were relatively reduced with the decrease in the amount of the compatible master batch as the amount of ABS was increased. In comparison, the mechanical properties of the sample bars of example 3-2 are best, the appearance of the sample bars is good, and further, the compatibility of example 3-2 is better. In comparative examples 1-5, only ABS was melt blended with PP, and the surface of the sample bar was defective due to the absence of the compatibilizer, and the mechanical properties were far inferior to those of example 3-1. With respect to example 3-2, only one compatibilizer in comparative examples 1-3 and comparative examples 1-4 did not produce good compatibility between ABS and PP, and their mechanical properties were inferior to those of examples 3-3 and examples 3-4.

In a word, the compatilizer A is a mixture (AMS-SAN) containing most of SAN copolymer and styrene-acrylic acid Amide (AMS), can be well fused with an ABS base material, and amide groups of the compatilizer A can gradually carry out amidation and imidization reactions with Maleic Anhydride (MAH) groups in the PP compatilizer (PP-g-MAH) in the process of mixing and melting, so that the compatibility of PP and ABS is finally achieved (see figure 2), the formed chemical bond fuses ABS and PP, the effect of mixing and dispersing is achieved, the compatibility degree of ABS and PP is improved, the physical property and mechanical property of the PP-ABS material are improved, the compatibility defect is basically not generated in the formed alloy material, the mechanical property is further improved, and the surface gloss of the material is good.

The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.

The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims

1. A PP-ABS compatible master batch is characterized in that: the composite material comprises the following raw material components in parts by weight: 45-85 parts of ABS resin, 10-40 parts of PP resin, 5-15 parts of compatilizer A, 2-10 parts of compatilizer B and 0.5-3 parts of lubricant;

the compatilizer A is a mixture obtained by oxidizing and hydrolyzing SAN or ABS resin;

the compatilizer B is one or two of grafts of maleic anhydride grafted polypropylene or grafts of glycidyl acrylate grafted polyethylene.

2. The PP-ABS compatible master batch according to claim 1, wherein the ABS resin is a core-shell polymer formed by styrene and acrylonitrile-butadiene rubber, and the acrylonitrile-butadiene rubber content is 55-70 wt%.

3. The PP-ABS compatible master batch of claim 1 wherein the PP resin is one or both of homo-polypropylene or co-polypropylene.

4. The PP-ABS compatible master batch of claim 1 wherein the lubricant is one of calcium stearate, EBS.

5. The PP-ABS compatible master batch according to claim 1, wherein the raw material SAN or ABS resin of the compatilizer A is prepared by an emulsion method.

6. The PP-ABS compatible master batch according to claim 5, wherein the preparation method of the compatilizer A is as follows: adding SAN or ABS resin into dimethyl sulfoxide solvent under ice bath and stirring conditions, then adding 30wt% hydrogen peroxide and potassium carbonate, heating to start reaction, and then keeping the reaction temperature at 25+/-3 ℃; and after the reaction is completed for 5-30 min, adding pure water, cooling, washing, filtering and collecting a product to obtain the compatilizer A.

7. A PP-ABS alloy is characterized in that: the composite material comprises the following raw material components in parts by weight: 50-80 parts of ABS resin, 10-30 parts of PP resin, 10-20 parts of PP-ABS compatible master batch according to any one of claims 1-6, 0.1-1.5 parts of antioxidant and 0.5-2 parts of lubricant.

8. The PP-ABS alloy of claim 7, wherein the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 1:1.

9. The method for preparing the PP-ABS compatible master batch according to any one of claims 1 to 6, comprising the following steps: and uniformly mixing the raw materials, and extruding the mixture through a double-screw extruder to obtain the PP-ABS compatible master batch.

10. The method for producing a PP-ABS alloy according to any one of claims 7 to 8, comprising the steps of: and uniformly mixing the raw materials, and extruding the mixture through a double-screw extruder to obtain the PP-ABS alloy.