ABS RUBBER POWDER WITH LOW IMPURITY CONTENT, PREPARATION METHOD THEREFOR, AND ABS RESIN

Abstract

Disclosed in the present invention are ABS rubber powder with a low impurity content, a preparation method therefor, and an ABS resin. The ABS rubber powder is treated by using the following steps: washing the ABS rubber powder with a washing solution I, and monitoring the content of soluble organic carbon in the ABS rubber powder until the content of soluble organic carbon in the ABS rubber powder is less than or equal to 9000 ppm, so as to obtain the ABS rubber powder with the low impurity content. In the present invention, by controlling the content of soluble organic carbon or the contents of soluble organic carbon and iron ions in the ABS powder, the ABS resin with a low yellow index of less than or equal to 18 is obtained.

Claims

1. A preparation method for ABS rubber powder with a low impurity content, wherein the ABS rubber powder is treated by using the following steps: washing the ABS rubber powder with a washing solution I, and monitoring the content of soluble organic carbon in the ABS rubber powder until the content of soluble organic carbon in the ABS rubber powder is less than or equal to 9000 ppm, so as to obtain the ABS rubber powder with the low impurity content.

2. The preparation method according to claim 1, wherein the ABS rubber powder is treated by using the following steps: washing the ABS rubber powder with a washing solution I, and monitoring the content of soluble organic carbon in the ABS rubber powder until the content of soluble organic carbon in the ABS rubber powder is less than or equal to 5000 ppm, so as to obtain the ABS rubber powder with the low impurity content.

3. The preparation method according to claim 1, wherein the treatment further comprises the following steps: washing the ABS rubber powder with the low impurity content with a washing solution II, and monitoring the content of iron ions in the ABS rubber powder until the content of iron ions in the ABS rubber powder with the low impurity content is less than or equal to 50 ppm; preferably, the ABS rubber powder with the low impurity content is washed with the washing solution II until the content of iron ions in the ABS rubber powder with the low impurity content is less than or equal to 10 ppm.

4. The preparation method according to claim 3, wherein the washing solution I is selected from water or an alkaline solution, and the alkaline solution is an aqueous solution with a mass percentage of 0.1%-3%; the alkaline solution is preferably selected from an aqueous ammonia solution, an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution.

5. The preparation method according to claim 4, wherein the washing solution II is selected from water or an acidic solution, and the acidic solution is an aqueous solution with a mass percentage of 0.1%-3%; when the washing solution I is selected from water, the washing solution II is selected from water or an acid solution; and when the washing solution I is selected from an alkaline solution, the washing solution II is selected from an acidic solution; the acid solution is preferably selected from an aqueous acetic acid solution, an aqueous hydrochloric acid solution or an aqueous sulfuric acid solution.

6. The preparation method according to claim 1, wherein the ABS rubber powder before the treatment is prepared by a method comprising the following steps: (1) subjecting butadiene and an optional second monomer to emulsion polymerization to obtain polybutadiene latex; (2) subjecting the polybutadiene latex, styrene, acrylonitrile and an optional third monomer to emulsion polymerization to obtain grafted ABS latex; (3) subjecting the grafted ABS latex to a coagulation-curing treatment, and then filtering and drying same to obtain the ABS rubber powder; preferably, the coagulation-curing treatment in step (3) is: adding a coagulant to the grafted ABS latex for coagulation, and curing the grafted ABS latex for 0.5-2 hours.

7. The preparation method according to claim 6, wherein in step (1), the emulsion polymerization comprises the following steps: mixing the butadiene, the optional second monomer, an emulsifier, an optional buffer, a chain transfer agent, an initiator and water, and carrying out the emulsion polymerization at 60° C.-90° C. to obtain the polybutadiene latex, wherein the particle size of the polybutadiene latex is preferably 200-400 nm; in step (1), in parts by weight, the butadiene is 90-100 parts, the second monomer is 0-10 parts, the emulsifier is 1-5 parts, the buffer is 0-1 part, the chain transfer agent is 0.2-0.7 part, the initiator is 0.1-0.5 part, and the water is 100-150 parts; preferably, in step (1), in parts by weight, the butadiene is 93-98 parts, the second monomer is 2-7 parts, the emulsifier is 2-4 parts, the buffer is 0.3-0.7 part, the chain transfer agent is 0.3-0.6 part, the initiator is 0.2-0.4 part, and the water is 110-140 parts.

8. The preparation method according to claim 7, wherein in step (2), the emulsion polymerization comprises the following steps: mixing the polybutadiene latex, the styrene, the acrylonitrile, the optional third monomer, an emulsifier, an initiator, a chain transfer agent, an optional buffer and optional water, and carrying out the emulsion polymerization at 60° C.-90° C.; in step (2), in parts by weight, the polybutadiene latex is 55-70 parts, the styrene is 20-35 parts, the acrylonitrile is 5-20 parts, the third monomer is 0-5 parts, the emulsifier is 0.2-1 part, the initiator is 0.1-0.5 part, the chain transfer agent is 0.1-1 part, the buffer is 0-0.01 part, and the water is 0-20 parts; preferably, in step (2), in parts by weight, the polybutadiene latex is 60-65 parts, the styrene is 25-30 parts, the acrylonitrile is 10-15 parts, the third monomer is 1-3 parts, the emulsifier is 0.4-0.8 part, the initiator is 0.2-0.4 part, the chain transfer agent is 0.3-0.7 part, the buffer is 0.006-0.008 part, and the water is 5-15 parts.

9. The preparation method according to claim 6, wherein in step (1), the second monomer is selected from one or more of styrene, acrylonitrile or methyl methacrylate; in step (2), the third monomer is selected from butadiene and/or methyl methacrylate.

10. The preparation method according to claim 9, wherein in steps (1) and (2), the emulsifier is selected from an anionic emulsifier and preferably is selected from one or more of potassium oleate, sodium dodecyl sulfate or potassium disproportionated rosin acid; the buffer is selected from one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, disodium ethylenediaminetetraacetic acid, tetrasodium ethylenediaminetetraacetic acid or sodium pyrophosphate; the chain transfer agent is selected from one or more of t-dodecyl mercaptan, n-dodecyl mercaptan, α-methylstyrene dimer or isooctyl 3-mercaptopropionate; in step (1), the initiator is selected from one or more of potassium persulfate, sodium persulfate or ammonium persulfate; in step (2), the initiator is selected from an oxidation-reduction initiator, wherein the oxidant component in the oxidation-reduction initiator is selected from one or more of potassium persulfate, sodium persulfate, ammonium persulfate, tert-butyl hydroperoxide, tert-amyl hydroperoxide or cumene hydroperoxide; and the reductant component in the oxidation-reduction initiator is selected from one or more of sodium formaldehyde sulfoxylate, sodium dithionite, ascorbic acid, erythorbic acid, sodium bisulfate, sodium metabisulfite, lactose, glucose, sorbose, fructose, maltose or ferrous sulfate.

11. The preparation method according to claim 10, wherein in step (3), the coagulant is selected from one or more of calcium chloride, magnesium sulfate, sulfuric acid or acetic acid; the coagulant is preferably an aqueous coagulant solution with a mass percentage concentration of 2%-10%, and the addition amount of the coagulant is 4-6 wt % of the solid content in the grafted ABS latex.

12. An ABS resin, wherein the ABS resin is prepared by blending the ABS rubber powder with a low impurity content prepared by the preparation method according to claim 1 and a SAN resin, and the yellowness index of the ABS resin is less than or equal to 18.

Description

DETAILED DESCRIPTION

[0052] The technical solutions and effects thereof of the present disclosure will be further described hereinafter through the specific examples. It is to be understood that the examples described below are intended to illustrate the present disclosure but are not construed to limit the scope thereof. The simple modifications made to the present disclosure in accordance with the concept of the present disclosure are within the scope of the present disclosure. The test manners used in the examples of the present disclosure are as follows:

[0053] (1) Yellowness index: standard ASTM D6166, using BYK Gardner instrument, USA;

[0054] (2) Content of soluble organic carbon:

[0055] 10 g of ABS rubber powder was dissolved in 100 g of KOH aqueous solution with a mass percentage of 1%, the insoluble matter was filtered out, and the content of soluble organic carbon in the remaining filtrate was detected; and the content of soluble organic carbon in the filtrate was detected in accordance with standard HJ 501-2009 using multi N/C® 3000 series TOC analyzer from JENA, Germany.

[0056] Content of soluble organic carbon in ABS rubber powder=10*content of soluble organic carbon in the filtrate;

[0057] (3) Content of metal ions: standard SL 394.1-2007, using Agilent 720 ICP-OES spectrometer, USA;

[0058] (4) Measurement of latex particle size: the prepared sample was diluted with deionized water until the mass concentration was 0.05% and then tested using a Malvern-Nano-ZS90 particle size analyzer.

[0059] In the following examples, the information of raw materials used is as follows:

[0060] SAN resin: PN118L150, ZHENJIANG CHIMEI;

[0061] antioxidant: B900, BASF, Germany; and [0062] 618, PWF Chemical (Shanghai) Co., Ltd.;

[0063] ABS rubber powder 1: DP60, SHINHO (Changzhou) PETROCHEMICAL;

[0064] ABS rubber powder 2: self-made using the following preparation method.

[0065] In the examples of the present disclosure, other raw materials and other reagents used herein are conventional reagents in the art, and the purity specification is analytical grade.

[0066] In the preparation examples of the ABS rubber powder, each part is part by weight.

[0067] (1) Preparation of polybutadiene latex: according to the weight parts of each component, 1.5 parts of potassium oleate, 1.5 parts of potassium disproportionated rosin acid, 95 parts of butadiene, 5 parts of styrene, 0.05 part of potassium carbonate, 0.05 part of potassium hydroxide, 0.45 part of t-dodecyl mercaptan (TDM), 0.3 part of potassium persulfate and 130 parts of deionized water were added to a reaction kettle, heated up to 70° C., and subjected to polymerization reaction, depressurization and steam desorption were carried out when the conversion rate of butadiene was greater than or equal to 95%, and residual low-boiling substances were removed, so as to obtain polybutadiene latex when the residual monomer of butadiene was less than or equal to 1000 ppm.

[0068] An acetic acid solution with a mass concentration of 5% was slowly added to the polybutadiene latex and stirred, a KOH solution with a mass concentration of 5% was slowly added when the particle size reached 300 nm, and pH was adjusted to 10, so as to obtain the agglomerated polybutadiene latex, where the particle size of the polybutadiene latex was 300 nm.

[0069] (2) According to the weight parts of each component, 63 parts of the agglomerated polybutadiene latex were added to a grafting kettle and heated up to 80° C., 0.25 part of cumene hydrogen peroxide, 0.01 part of lactose, 0.00015 part of ferrous sulfate, 28 parts of styrene, 12 parts of acrylonitrile, 0.45 parts of t-dodecyl mercaptan (TDM), 5 parts of butadiene, 0.007 part of sodium pyrophosphate, 0.6 part of potassium oleate and 10 parts of deionized water were added for polymerization reaction, so as to obtain the grafted ABS latex when the conversion rate of acrylonitrile was 97%.

[0070] (3) 4 parts of 10% aqueous magnesium sulfate solution and 1 part of 5% aqueous acetic acid solution were added to 100 parts of the grafted ABS latex, aged for 2 hours, filtered and dried at 80° C. until the content of water content was 1%, so as to obtain the ABS rubber powder 1.

[0071] The contents of soluble organic carbon and iron ions in equal weight parts of the ABS rubber powder 1 prepared above were detected. The content of soluble organic carbon was 12000 ppm, and the content of iron ions was 94.2 ppm.

[0072] The contents of soluble organic carbon and iron ions in equal weight parts of the commercially available DP60 ABS powder were detected. The content of soluble organic carbon was 10000 ppm, and the content of iron ions was 17.8 ppm.

Example 1

[0073] 1 kg of ABS rubber powder 1 prepared above was washed with 5 kg of an aqueous sodium hydroxide solution with a percentage by mass of 0.5%, and the contents of soluble organic carbon and iron ions in the ABS rubber powder 1 were monitored to be 8600 ppm and 94 ppm respectively. The ABS rubber powder 1 was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 1 with a low impurity content.

Example 2

[0074] 1 kg of the ABS rubber powder 1 with a low impurity content prepared in Example 1 was washed with 1 kg of an aqueous sodium hydroxide solution with a percentage by mass of 1%, and the contents of soluble organic carbon and iron ions in the ABS rubber powder 1 were monitored to be 4377 ppm and 94 ppm respectively. The ABS rubber powder 1 was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 2 with a low impurity content.

Example 3

[0075] 1 kg of ABS rubber powder 1 prepared above was washed with 1 kg of deionized water, and the contents of soluble organic carbon and iron ions in the ABS rubber powder 1 were monitored to be 8900 ppm and 83 ppm respectively. The ABS rubber powder 1 was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 3 with a low impurity content.

Example 4

[0076] 1 kg of the ABS rubber powder 3 with a low impurity content prepared in Example 3 was washed with 3 kg of deionized water, and the contents of soluble organic carbon and iron ions in the ABS rubber powder were monitored to be 4500 ppm and 57 ppm respectively. The ABS rubber powder was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 4 with a low impurity content.

Example 5

[0077] 1 kg of the ABS rubber powder 1 with a low impurity content prepared in Example 1 was washed with 1 kg of an aqueous acetic acid solution with a percentage by mass of 1%, and the content of iron ions in the ABS rubber powder was monitored to be 46 ppm. The ABS rubber powder was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 1-1 with a low impurity content.

[0078] 1 kg of the ABS rubber powder 1-1 with a low impurity content was washed with 2 kg of an aqueous acetic acid solution with a percentage by mass of 3%, and the content of iron ions in the ABS rubber powder was monitored to be 8 ppm. The ABS rubber powder was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 1-2 with a low impurity content.

Example 6

[0079] 1 kg of the ABS rubber powder 2 with a low impurity content prepared in Example 2 was washed with 1.5 kg of an aqueous acetic acid solution with a percentage by mass of 2%, and the content of iron ions in the ABS rubber powder was monitored to be 44 ppm. The ABS rubber powder was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 2-1 with a low impurity content.

[0080] 1 kg of the ABS rubber powder 2-1 with a low impurity content was washed with 2 kg of an aqueous acetic acid solution with a percentage by mass of 3%, and the content of iron ions in the ABS rubber powder was monitored to be 8.2 ppm. The ABS rubber powder was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 2-2 with a low impurity content.

Example 7

[0081] 1 kg of the ABS rubber powder 3 with a low impurity content prepared in Example 3 was washed with 3 kg of water, and the content of iron ions in the ABS rubber powder was monitored to be 47 ppm. The ABS rubber powder was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 3-1 with a low impurity content.

[0082] 1 kg of the ABS rubber powder 3-1 with a low impurity content was washed with 7 kg of water, and the content of iron ions in the ABS rubber powder was monitored to be 9 ppm. The ABS rubber powder was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 3-2 with a low impurity content.

Example 8

[0083] 1 kg of the ABS rubber powder 4 with a low impurity content prepared in Example 4 was washed with 1 kg of water, and the content of iron ions in the ABS rubber powder was monitored to be 46 ppm. The ABS rubber powder was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 4-1 with a low impurity content.

[0084] 1 kg of the ABS rubber powder 4-1 with a low impurity content was washed with 7 kg of water, and the content of iron ions in the ABS rubber powder was monitored to be 8 ppm. The

[0085] ABS rubber powder was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 4-2 with a low impurity content.

Example 9

[0086] 1 kg of commercially available DP60 ABS powder prepared above was washed with 0.5 kg of an aqueous sodium hydroxide solution with a percentage by mass of 0.5%, and the contents of soluble organic carbon and iron ions in the DP60 ABS powder were monitored to be 7300 ppm and 17.3 ppm respectively. The DP60 ABS powder was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 5 with a low impurity content.

[0087] The ABS rubber powder 5 with a low impurity content was washed with 1 kg of an aqueous sodium hydroxide solution with a percentage by mass of 0.5%, and the contents of soluble organic carbon and iron ions in the ABS rubber powder 5 were monitored to be 3700 ppm and 17 ppm respectively. The ABS rubber powder 5 was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 6 with a low impurity content.

Example 10

[0088] 1 kg of the ABS rubber powder 5 with a low impurity content prepared in Example 9 was washed with 2 kg of an aqueous acetic acid solution with a percentage by mass of 3%, and the content of iron ions in the ABS rubber powder was monitored to be 7 ppm. The ABS rubber powder was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 5-1 with a low impurity content.

Example 11

[0089] 1 kg of the ABS rubber powder 6 with a low impurity content prepared in Example 9 was washed with 2 kg of an aqueous acetic acid solution with a percentage by mass of 3%, and the content of iron ions in the ABS rubber powder was monitored to be 7 ppm. The ABS rubber powder was filtered and dried until the content of water was 1%, so as to obtain the ABS rubber powder 6-1 with a low impurity content.

Comparative Example 1

[0090] The ABS rubber powder 1 prepared above.

Comparative Example 2

[0091] The commercially available DP60 ABS powder.

[0092] The ABS rubber powder obtained in Examples 1 to 11 and Comparative Examples 1 to 2 was respectively mixed with a SAN resin to prepare an ABS resin specifically using the following method.

[0093] 24 parts by weight of ABS rubber powder, 76 parts by weight of PN118L150 SAN resin, 0.1 part by weight of antioxidant B900, 0.2 part by weight of magnesium stearate and 2 parts by weight of N,N-ethylene bis stearamide were kneaded in a high-speed kneader for 5 minutes, and then the mixed material was subjected to melt pelletizing and blending in a twin-screw extruder and pelletized to obtain the following ABS resins respectively. The ABS resins obtained above were dried in an oven at 80° C. for 2 hours, and the yellowness index was tested. The test results are shown in Table 1.

TABLE-US-00001 TABLE 1 Rubber powder Resin Yellowness index ABS rubber powder 1 with a low impurity content ABS resin 1 17.9 ABS rubber powder 2 with a low impurity content ABS resin 2 15.1 ABS rubber powder 3 with a low impurity content ABS resin 3 16.3 ABS rubber powder 4 with a low impurity content ABS resin 4 12 ABS rubber powder 1-1 with a low impurity content ABS resin 1-1 15.4 ABS rubber powder 1-2 with a low impurity content ABS resin 1-2 11.3 ABS rubber powder 2-1 with a low impurity content ABS resin 2-1 11.7 ABS rubber powder 2-2 with a low impurity content ABS resin 2-2 8.2 ABS rubber powder 3-1 with a low impurity content ABS resin 3-1 11.2 ABS rubber powder 3-2 with a low impurity content ABS resin 3-2 6.1 ABS rubber powder 4-1 with a low impurity content ABS resin 4-1 10.9 ABS rubber powder 4-2 with a low impurity content ABS resin 4-2 5.7 ABS rubber powder 5 with a low impurity content ABS resin 5 14.8 ABS rubber powder 6 with a low impurity content ABS resin 6 10.3 ABS rubber powder 5-1 with a low impurity content ABS resin 5-1 12.4 ABS rubber powder 6-1 with a low impurity content ABS resin 6-1 8.1 ABS rubber powder 1 ABS resin 8 29.2 DP60 ABS rubber powder ABS resin 9 27.7