CN110964133B - Low-impurity-content ABS rubber powder, preparation method thereof and ABS resin - Google Patents
Low-impurity-content ABS rubber powder, preparation method thereof and ABS resin Download PDFInfo
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Abstract
The invention discloses low-impurity-content ABS rubber powder, a preparation method thereof and ABS resin, wherein the ABS rubber powder is treated by the following steps: washing the ABS rubber powder with a washing liquid I, and monitoring the content of soluble organic carbon in the ABS rubber powder until the content of the soluble organic carbon in the ABS rubber powder is less than or equal to 9000ppm, thereby obtaining the low-impurity-content ABS rubber powder. The invention obtains the ABS resin with low yellow index less than or equal to 18 by controlling the content of soluble organic carbon or soluble organic carbon and iron ions in the ABS rubber powder.
Description
Technical Field
The invention belongs to the technical field of engineering plastic ABS resin production, and particularly relates to a preparation method of low-yellow-index ABS resin.
Background
ABS resin is one of five synthetic resins, is obtained by ternary polymerization of butadiene, styrene and acrylonitrile, is widely applied to the fields of machinery, automobiles, electronic and electrical appliances, instruments and meters, textiles, buildings and the like, and is thermoplastic engineering plastic with extremely wide application.
At present, two methods, namely a continuous bulk method and an emulsion grafting-bulk SAN blending method, are widely adopted for preparing ABS resin. The emulsion grafting-bulk SAN blending method at the present stage has the advantages of advanced technology, wide product range, large output of a single set of device and small pollution, and becomes a mainstream method for producing ABS resin.
The preparation method of the emulsion graft-bulk SAN blending method comprises the following steps: firstly, butadiene is polymerized to produce polybutadiene latex (PBL), then the polybutadiene latex, styrene and acrylonitrile are graft polymerized, ABS graft powder is obtained after coagulation and drying, and the ABS graft powder is mixed with SAN resin produced by a bulk method for granulation to obtain the ABS resin.
In some application fields, such as automobiles, household appliances and the like, the requirement on the appearance is high, and the ABS resin is required to have a low yellow index.
Patent CN109608782A discloses a preparation method of anti-yellowing ABS resin, which introduces a functional monomer with epoxy group into the shell part of the grafted powder, and utilizes the action of epoxy group and cyano group to slow down the cyclization reaction between acrylonitrile groups in ABS resin during heating process, thereby reducing the yellow index of ABS resin. The method can reduce the yellow index of the ABS resin in the processing process, but the yellow index of the ABS resin is not greatly improved, and the reaction process of the introduced epoxy group functional monomer and the acrylonitrile is uncontrollable, so that more side reactions are caused.
Patent CN201711360467X discloses a high-performance long-acting anti-yellowing ABS material and a preparation method thereof, which utilizes a method of adding an anti-yellowing agent into ABS resin to reduce the yellow index of ABS. Patent CN103819802B discloses a high density polyethylene composite additive and a preparation method thereof, wherein the antioxidant 330, the antioxidant 168 and the antioxidant 1076 are added to prepare the composite antioxidant, and the composite antioxidant is compounded with other additives to improve the oxidation induction period, thereby reducing the yellow index. In both of the above patents, the yellow index of the product is improved by adding an auxiliary agent later, so that the product cost is increased.
Compared with the continuous bulk preparation process, the emulsion graft-bulk SAN blending method is used for preparing the yellowish ABS resin, which is caused by the fact that a large amount of additives are used in the unit for producing ABS powder by emulsion grafting.
Therefore, it is urgently needed to develop a production method for producing ABS resin by using emulsion grafting-bulk SAN blending process with low yellow index.
Disclosure of Invention
In view of this, the invention provides low-impurity content ABS rubber powder, a preparation method thereof and an ABS resin prepared from the low-impurity content ABS rubber powder, and the content of soluble organic carbon or the content of soluble organic carbon and iron ions in the ABS rubber powder is controlled to obtain the ABS resin with a low yellow index.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the first aspect of the invention provides a preparation method of low-impurity-content ABS rubber powder, which is used for treating the ABS rubber powder, and the treatment comprises the following steps:
washing the ABS rubber powder with a first washing liquid, monitoring the content of soluble organic carbon in the ABS rubber powder, and washing with the first washing liquid until the content of the soluble organic carbon in the ABS rubber powder is less than or equal to 9000ppm, such as 8600ppm, 4500ppm, 4377ppm and 3700ppm, so as to obtain the low-impurity-content ABS rubber powder.
In some preferred embodiments, the ABS rubber powder is subjected to a treatment comprising the steps of:
washing the ABS rubber powder with a first washing liquid, monitoring the content of soluble organic carbon in the ABS rubber powder, and washing with the first washing liquid until the content of the soluble organic carbon in the ABS rubber powder is less than or equal to 5000ppm, for example, the content of the soluble organic carbon is 4500ppm, 4377ppm and 3700ppm, so that the low-impurity-content ABS rubber powder is obtained.
In some specific embodiments, after washing until the content M of soluble organic carbon in the ABS rubber powder is no more than 9000ppm, for example, the content of soluble organic carbon is 8600ppm, 4500ppm, 4377ppm, 3700ppm, the washed ABS rubber powder is filtered, and dried at 40-80 ℃ until the water content is about 1%, thus obtaining the low impurity content ABS rubber powder.
In the above-mentioned production process, the content of soluble organic carbon in the washed ABS rubber powder is controlled to 9000ppm or less, such as 8600ppm, 4500ppm, 4377ppm, 3700ppm, and preferably, the content of soluble organic carbon in the washed ABS rubber powder is controlled to 5000ppm or less, such as 4500ppm, 4377ppm, 3700 ppm. In the above-mentioned production method, the content range of the soluble organic carbon in the polymer rubber powder is controlled by the above-mentioned treatment so that the lower the mass concentration of the soluble portion (i.e., soluble organic carbon) in the TOC (total organic carbon) remaining in the system, the lower the impurities which contribute to the polymer rubber powder, and the lower the yellow index of the resin produced therefrom. The "soluble organic carbon" referred to in the present invention means the organic carbon portion of the ABS rubber powder which can be dissolved in water or alkali solution.
In the present invention, the content unit "ppm" of soluble organic carbon in said polymer rubber powder is based on the mass of said ABS rubber powder.
The researchers of the invention find in the research process that most of the soluble organic carbon is introduced in the polymerization process of the ABS rubber powder, and the residual unreacted acrylonitrile monomer, emulsifier and oligomer generated in the reaction process are generated in the polymerization process, wherein the acrylonitrile monomer and oligomer can generate cross-linking reaction when meeting high temperature, the longer acrylonitrile chain segment generates conjugation due to cyclization, and the conjugated double bond can absorb blue spectral band in visible light to enable the product to present earthy yellow; in addition, double bonds in the emulsifier are easily oxidized by oxygen to darken, so that the yellow index of the final ABS resin product is increased; in the preparation method, the ABS rubber powder is washed by the first washing liquid, and the content of the soluble organic carbon in the ABS rubber powder is monitored until the content of the soluble organic carbon is reduced to the range, so that the content of the organic matters causing yellowing in the ABS rubber powder is effectively reduced.
Meanwhile, the researchers of the present invention found that iron ions are introduced during the preparation of ABS rubber powder, as described in the following conditions but not limited to the conditions described in the present invention. Such as: in the emulsion polymerization process, when ferrous sulfate is used as a reducing component in an initiator, iron ions enter a reaction system; such as: when polybutadiene agglomerated latex is prepared by acetic acid agglomeration and/or graft latex is agglomerated with sulfuric acid or other acidic substance as an agglomerating agent, corrosion of the metal container by acid causes iron in the metal container to enter the reaction system in the form of an acidic salt of trivalent iron. Ferrous ions in the system are oxidized to form ferric sulfate soluble in water and ferric hydroxide insoluble in water, and the peculiar yellow color of ferric ions can cause the yellow index of the product to be increased. In addition, ferrous ions as valence-variable metal ions can play a role in catalyzing residual double bonds in the ABS rubber powder at high temperature, so that the generation of conjugated group-containing byproducts is aggravated, and the products are yellowed. In the present invention, the iron ions mentioned comprise ferrous divalent ions and/or ferric trivalent ions.
In some specific embodiments, washing the low-impurity-content ABS rubber powder obtained in the previous step with a second washing liquid is continued, the content of iron ions in the ABS rubber powder is monitored, and the second washing liquid is used for washing until the content of the iron ions in the low-impurity-content ABS rubber powder is less than or equal to 50ppm, such as 46ppm, 17.3ppm, 17ppm, 9ppm, 8.2ppm, 8ppm and 7 ppm.
In some specific embodiments, after washing until the content of iron ions in the ABS rubber powder is less than or equal to 50ppm, filtering the washed ABS rubber powder, and drying at 40-80 ℃ until the water content is about 1%, thereby obtaining the low-impurity-content ABS rubber powder.
In other specific embodiments, the low impurity content ABS rubber powder obtained by the present invention is washed with washing liquid two until the content of iron ions in the low impurity content ABS rubber powder is less than or equal to 10ppm, such as 9ppm, 8.2ppm, 8ppm and 7 ppm.
In the invention, the first washing liquid is selected from water or alkali liquor, and the alkali liquor is an aqueous solution with the mass percentage of 0.1-3%; in some preferred embodiments, the lye is selected from the group consisting of aqueous ammonia, aqueous potassium hydroxide or aqueous sodium hydroxide.
The second washing liquid is selected from water or acid liquor; when the first washing liquid is selected from water, the second washing liquid is selected from water or acid liquor; when the first washing liquid is selected from alkali liquor, the second washing liquid is selected from acid liquor; the acid solution is preferably selected from aqueous acetic acid, aqueous hydrochloric acid or aqueous sulfuric acid.
The ABS rubber powder can adopt a commercially available ABS rubber powder product; for example, Korea brocade lake ERMA151B, HR-150F, HR-181, HR-183, HR-85; ningbo Taiwan BP-828; basic innovative plastics (us): 338. 360; japanese Sanyo S-3811; shandong Wanda WD-132 and WD-133; new lake (changzhou) petrochemical DP 60; the polymerization method of the ABS rubber powder in the invention can also be selected from the existing polymerization methods, but is not limited to a specific polymerization mode, for example, the ABS rubber powder before the treatment is prepared by adopting the method comprising the following steps:
(1) carrying out emulsion polymerization on butadiene and an optional second monomer to obtain polybutadiene latex;
(2) carrying out emulsion polymerization on the polybutadiene latex, styrene, acrylonitrile and an optional third monomer to obtain a grafted ABS latex;
(3) after the graft ABS latex is subjected to coagulation-curing treatment, filtering and drying are carried out to obtain the ABS rubber powder;
preferably, the coagulation-maturation process in the step (3) is to add a coagulant to the graft ABS latex to coagulate it, and then to mature it for 0.5 to 2 hours.
In some embodiments, in step (1) of the present invention, the emulsion polymerization comprises the following steps: mixing the butadiene, the optional second monomer, an emulsifier, an optional buffering agent, a chain transfer agent, an initiator and water, and carrying out the emulsion polymerization at 60-90 ℃ to obtain the polybutadiene latex, wherein the emulsion polymerization is preferably carried out until the particle size of the polybutadiene latex is 200-400 nm;
in the step (1), by weight, 90-100 parts of butadiene, 0-10 parts of second monomer, 1-5 parts of emulsifier, 0-1 part of buffering agent, 0.2-0.7 part of chain transfer agent, 0.1-0.5 part of initiator and 150 parts of water;
preferably, in the step (1), 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 by weight.
In some specific embodiments, in step (2) of the present invention, the emulsion polymerization comprises the steps of: mixing the polybutadiene latex, the styrene, the acrylonitrile, the optional third monomer, an emulsifier, an initiator, a chain transfer agent, an optional buffering agent and optional water, carrying out emulsion polymerization at 60-90 ℃, carrying out reduced pressure steam removal when the conversion rate of the butadiene is more than or equal to 95%, removing residual low-boiling-point substances, and obtaining the polybutadiene latex when the residual monomer of the butadiene is less than or equal to 1000 ppm;
in the step (2), by weight, 55-70 parts of polybutadiene latex, 20-35 parts of styrene, 5-20 parts of acrylonitrile, 0-5 parts of a third monomer, 0.2-1 part of an emulsifier, 0.1-0.5 part of an initiator, 0.1-1 part of a chain transfer agent, 0-0.01 part of a buffering agent and 0-20 parts of water are added;
preferably, in the step (2), the polybutadiene latex is 60 to 65 parts, the styrene is 25 to 30 parts, the acrylonitrile is 10 to 15 parts, the third monomer is 1 to 3 parts, the emulsifier is 0.4 to 0.8 part, the initiator is 0.2 to 0.4 part, the chain transfer agent is 0.3 to 0.7 part, the buffer is 0.006 to 0.008 part, and the water is 5 to 15 parts by weight.
In some specific embodiments, in step (1) of the present invention, the second monomer is selected from one or more of styrene, acrylonitrile or methyl methacrylate;
in step (2) of the present invention, the third monomer is selected from butadiene and/or methyl methacrylate.
In some specific embodiments, in steps (1) and (2) of the present invention, the emulsifier is selected from anionic emulsifiers, preferably selected from one or more of potassium oleate, sodium lauryl sulfate or potassium disproportionate rosinate;
the buffer is selected from one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate and sodium pyrophosphate;
the chain transfer agent is selected from one or more of tert-dodecyl mercaptan, n-dodecyl mercaptan, alpha-methyl styrene dimer or isooctyl 3-mercaptopropionate;
in step (1) of the present invention, the initiator is selected from one or more of potassium persulfate, sodium persulfate or ammonium persulfate;
in step (2) of the present invention, the initiator is selected from oxidation-reduction initiators, 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; the reducing agent component in the oxidation-reduction initiator is selected from one or more of sodium formaldehyde sulfoxylate, sodium hydrosulfite, ascorbic acid, isoascorbic acid, sodium hydrosulfite, sodium metabisulfite, lactose, glucose, sorbose, fructose, maltose or ferrous sulfate. In some embodiments, the mass ratio of the oxidant component to the reductant component in the initiator is from 1 to 30:1, e.g., 10:1, 20:1, 25: 1.
In some specific embodiments, in step (2) of the present invention, the coagulant is selected from one or more of calcium chloride, magnesium sulfate, sulfuric acid, or acetic acid;
the coagulant is preferably a coagulant aqueous solution with a mass percentage concentration of 2-10%, and the addition amount of the coagulant is 4-6 wt% of the solid content (solid mass) in the grafted ABS latex.
The second aspect of the invention provides an ABS resin, which is prepared by blending the ABS rubber powder prepared by the preparation method and SAN resin, wherein the yellow index of the ABS resin is less than or equal to 18.
As is well known to those skilled in the art, SAN resins are copolymers of styrene acrylonitrile, engineering plastics with higher mechanical strength; the ABS resin is acrylonitrile-butadiene-styrene copolymer, and is prepared through mechanical mixing of SAN resin and ABS rubber powder, smelting, pelletizing and drying.
In some specific embodiments, the mechanically blended feedstock comprises, by weight, 20 to 40 parts of the ABS rubber powder, 60 to 80 parts of the SAN resin, 0.1 to 0.8 parts of an antioxidant and a lubricant; wherein, the antioxidant is preferably selected from one or more of 2, 2' -methylenebis (4-methyl-6-tert-butylphenol), n-octadecyl beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionate, pentaerythritol tetra- [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite and dilauryl thiodipropionate; for example, the antioxidant may be used as commercially available B900 from Pasfu Germany; the lubricant may be selected from magnesium stearate and N, N-ethylene bis stearamide.
As is well known to those skilled in the art, SAN resins have a very low yellowness index, which has a negligible effect on the yellowness index of ABS resins. Commercially available, for example, from the ELIX Polymers company SAN 230G, 250G, 260G, 280G; SAN 327, 325, 350 of medium petroleum daqing corporation; SAN 168 by national henry; qimei PN118L150, etc.
By adopting the technical scheme, the method has the following technical effects:
according to the preparation method of the low-impurity-content ABS rubber powder, the content of soluble organic carbon in the ABS rubber powder is controlled to be less than or equal to 9000ppm on the basis of the prior art, so that the impurity content in the ABS rubber powder is reduced; preferably, the content of iron ions in the ABS rubber powder is controlled to be less than or equal to 50ppm simultaneously, so that the impurity content in the rubber powder is further reduced.
The obtained ABS rubber powder is used for preparing the ABS resin, so that the yellow index of the obtained resin is less than or equal to 18, and the application field of the ABS resin is widened.
Detailed Description
The technical solution and the effects of the present invention are further described by the following specific examples. It should be understood that the following examples are only illustrative of the present invention and are not intended to limit the scope of the present invention. Simple modifications of the invention applying the inventive concept are within the scope of the invention as claimed.
The following test methods were used in the examples of the invention:
(1) yellow index: standard ASTM D6166, using a BYK Gardner instrument, usa;
(2) soluble organic carbon content:
taking 10g of ABS rubber powder, fully dissolving the ABS rubber powder in 100g of KOH aqueous solution with the mass percentage of 1%, filtering insoluble substances, and detecting the content of soluble organic carbon in the residual filtrate; the content of soluble organic carbon in the filtrate was determined using HJ 501-
3000 series TOC analyzers;
the content of soluble organic carbon in ABS rubber powder is 10, and the content of soluble organic carbon in filtrate is 10;
(3) content of metal ions: standard SL 394.1-2007, using an Agilent 720 ICP-OES spectrometer;
(4) detection of latex particle size: the prepared sample was diluted with deionized water to a mass concentration of 0.05% and then tested using a malvern-Nano-ZS 90 type particle sizer.
In the following examples, the raw material information used is as follows:
SAN resin: zhenjiangqimei, PN118L 150;
antioxidant: basf, germany, B900;
panhua chemical (Shanghai) Co., Ltd., 618;
1 part of ABS rubber powder: changzhou (new lake) petrochemical, DP 60;
ABS rubber powder 2: the preparation method is as follows.
In the examples of the present invention, other raw materials and other reagents used were reagents conventional in the art, and the purity specification thereof was analytical grade.
In the preparation example of the ABS rubber powder, all the parts are parts by weight;
(1) preparation of the polybutadiene latex: adding 1.5 parts of potassium oleate, 1.5 parts of disproportionated potassium rosinate, 95 parts of butadiene, 5 parts of styrene, 0.05 part of potassium carbonate, 0.05 part of potassium hydroxide, 0.45 part of tert-dodecyl mercaptan (TDM), 0.3 part of potassium persulfate and 130 parts of deionized water into a reaction kettle, heating to 70 ℃ for polymerization reaction, performing reduced pressure steam removal when the butadiene conversion rate is more than or equal to 95 percent, removing residual low-boiling-point substances, and obtaining polybutadiene latex when the residual monomer of butadiene is less than or equal to 1000 ppm;
slowly adding an acetic acid solution with the mass concentration of 5% into the polybutadiene latex, starting stirring, slowly adding a KOH solution with the mass concentration of 5% when the particle size reaches 300nm, and adjusting the pH to 10 to obtain agglomerated polybutadiene latex, wherein the particle size of the polybutadiene latex is 300 nm;
(2) adding 63 parts of agglomerated polybutadiene latex into a grafting kettle, heating to 80 ℃, adding 0.25 part of cumene hydroperoxide, 0.01 part of lactose, 0.00015 part of ferrous sulfate, 28 parts of styrene, 12 parts of acrylonitrile, 0.45 part of tert-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 for polymerization reaction, and obtaining grafted ABS latex when the conversion rate of acrylonitrile is 97%;
(3) 100 parts of the obtained graft ABS latex is taken, 4 parts of 10% magnesium sulfate aqueous solution and 1 part of 5% acetic acid aqueous solution are added into the graft ABS latex, and after aging is carried out for 2 hours, the graft ABS latex is filtered and dried at 80 ℃ until the water content is 1%, so that ABS rubber powder 1 is obtained.
The ABS rubber powder 1 prepared in an equal weight part is taken for content test of soluble organic carbon and iron ions, and the content of the soluble organic carbon is 12000ppm and the content of the iron ions is 94.2 ppm.
The content of soluble organic carbon and iron ions in DP60 ABS rubber powder which is sold in the market in equal weight parts is tested, and the content of soluble organic carbon is 10000ppm and the content of iron ions is 17.8 ppm.
Example 1
1kg of ABS rubber powder 1 obtained by the preparation method is washed by 5kg of sodium hydroxide aqueous solution with the mass percentage content of 0.5 percent, the content of soluble organic carbon in the ABS rubber powder 1 is monitored to be 8600ppm, the content of iron ions is monitored to be 94ppm, and the ABS rubber powder 1 with low impurity content is obtained by filtering and drying until the water content is 1 percent.
Example 2
1kg of the ABS rubber powder 1 with low impurity content prepared in the example 1 is taken, 1kg of sodium hydroxide aqueous solution with the mass percentage of 1% is continuously added into the ABS rubber powder 1 for washing, the content of soluble organic carbon in the ABS rubber powder 1 is monitored to be 4377ppm, the content of iron ions is monitored to be 94ppm, and the ABS rubber powder 2 with low impurity content is obtained after filtration and drying until the water content is 1%.
Example 3
1kg of the ABS rubber powder 1 obtained by the preparation is washed by 1kg of deionized water, the content of soluble organic carbon in the ABS rubber powder 1 is monitored to be 8900ppm, the content of iron ions is monitored to be 83 ppm, and the ABS rubber powder 3 with low impurity content is obtained by filtering and drying until the water content is 1%.
Example 4
1kg of the ABS rubber powder 3 with low impurity content prepared in the example 3 is taken, 3kg of deionized water by weight is continuously added into the ABS rubber powder for washing, the content of soluble organic carbon in the ABS rubber powder is monitored to be 4500ppm, the content of iron ions is 57ppm, and the ABS rubber powder is filtered and dried until the water content is 1 percent to obtain the ABS rubber powder 4 with low impurity content.
Example 5
1kg of the low-impurity ABS rubber powder 1 obtained in the embodiment 1 is taken, 1kg of acetic acid aqueous solution with the mass percentage content of 1% is added into the ABS rubber powder for washing, the iron ion content in the ABS rubber powder is monitored to be 46ppm, and the ABS rubber powder is filtered and dried until the water content is 1% to obtain the low-impurity ABS rubber powder 1-1;
1-1 kg of low-impurity-content ABS rubber powder is continuously added with 2kg of 3 mass percent acetic acid aqueous solution for washing, the iron ion content in the ABS rubber powder is monitored to be 8ppm, and the ABS rubber powder is filtered and dried until the water content is 1 percent to obtain the low-impurity-content ABS rubber powder 1-2.
Example 6
Taking 1kg of the low-impurity-content ABS rubber powder 2 obtained in the embodiment 2, adding 1.5 kg of 2% by mass acetic acid aqueous solution into the rubber powder for washing, monitoring the iron ion content in the ABS rubber powder to be 44ppm, filtering, and drying until the water content is 1% to obtain the low-impurity-content ABS rubber powder 2-1;
and (2) continuously adding 2kg of acetic acid aqueous solution with the mass percentage of 3% into 1kg of low-impurity-content ABS rubber powder 2-1, washing, monitoring the iron ion content in the ABS rubber powder to be 8.2ppm, filtering, and drying until the water content is 1% to obtain the low-impurity-content ABS rubber powder 2-2.
Example 7
Taking 1kg of the low-impurity-content ABS rubber powder 3 obtained in the embodiment 3, adding 3kg of water into the rubber powder for washing, monitoring the iron ion content in the ABS rubber powder to 47ppm, filtering, and drying until the water content is 1% to obtain 3-1 parts of the low-impurity-content ABS rubber powder;
and continuously adding 7kg of water into 1kg of low-impurity-content ABS rubber powder 3-1 for washing, monitoring the iron ion content in the ABS rubber powder to be 9ppm, filtering, and drying until the water content is 1% to obtain the low-impurity-content ABS rubber powder 3-2.
Example 8
1kg of the low-impurity-content ABS rubber powder 4 obtained in the embodiment 4 is taken, 1kg of water is added into the ABS rubber powder for washing, the iron ion content in the ABS rubber powder is monitored to be 46ppm, and the ABS rubber powder is filtered and dried until the water content is 1 percent to obtain the low-impurity-content ABS rubber powder 4-1;
and continuously adding 7kg of water into 1kg of low-impurity-content ABS rubber powder 4-1 for washing, monitoring the iron ion content in the ABS rubber powder to be 8ppm, filtering, and drying until the water content is 1% to obtain the low-impurity-content ABS rubber powder 4-2.
Example 9
1kg of the commercially available DP60 ABS rubber powder prepared in the above way is washed by 0.5kg of 0.5% by mass sodium hydroxide aqueous solution, the content of soluble organic carbon in the DP60 ABS rubber powder is monitored to be 7300ppm, the content of iron ions is monitored to be 17.3ppm, and the ABS rubber powder is filtered and dried until the water content is 1% to obtain the low-impurity-content ABS rubber powder 5;
and then, continuously adding 1kg of 0.5 mass percent sodium hydroxide aqueous solution into the ABS rubber powder for washing, monitoring the content of soluble organic carbon in the ABS rubber powder 5 to be 3700ppm and the content of iron ions to be 17ppm, filtering and drying until the water content is 1 percent to obtain the ABS rubber powder 6 with low impurity content.
Example 10
1kg of the ABS rubber powder 5 with low impurity content prepared in the example 9 is taken, 2kg of acetic acid aqueous solution with the mass percentage content of 3% is added into the ABS rubber powder for washing, the iron ion content in the ABS rubber powder is monitored to be 7ppm, and the ABS rubber powder is filtered and dried until the water content is 1% to obtain the ABS rubber powder 5-1 with low impurity content.
Example 11
Taking 1kg of the low-impurity-content ABS rubber powder 6 prepared in example 9, adding 2kg of 3 mass percent acetic acid aqueous solution into the rubber powder for washing, monitoring the iron ion content in the ABS rubber powder to be 7ppm, filtering, and drying until the water content is 1% to obtain the low-impurity-content ABS rubber powder 6-1.
Comparative example 1
The ABS rubber powder 1 obtained by the above preparation.
Comparative example 2
Commercially available DP60 ABS rubber powder.
The ABS rubber powder obtained in the above examples 1-11 and comparative examples 1-2 is respectively mixed with SAN resin to prepare ABS resin, and the following method can be specifically adopted:
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 are kneaded in a high-speed kneader for 5min, and then the mixed materials are subjected to melt granulation blending and granulation in a double-screw extruder to respectively obtain the following ABS resin. The ABS resin was dried in an oven at 80 ℃ for 2 hours and tested for yellowness index, the results of which are shown in Table 1.
TABLE 1
| Rubber powder | Resin composition | Yellow index |
| ABS rubber powder 1 with low impurity content | ABS resin 1 | 17.9 |
| ABS rubber powder 2 with low impurity content | ABS resin 2 | 15.1 |
| ABS rubber powder 3 with low impurity content | ABS resin 3 | 16.3 |
| ABS rubber powder 4 with low impurity content | ABS resin 4 | 12 |
| 1-1 parts of low-impurity-content ABS rubber powder | ABS resin 1-1 | 15.4 |
| 1-2 parts of low-impurity ABS rubber powder | ABS resin 1-2 | 11.3 |
| 2-1 parts of low-impurity-content ABS rubber powder | ABS resin 2-1 | 11.7 |
| 2-2 parts of low-impurity-content ABS rubber powder | ABS resin 2-2 | 8.2 |
| 3-1 parts of low-impurity-content ABS rubber powder | ABS resin 3-1 | 11.2 |
| 3-2 parts of low-impurity-content ABS rubber powder | ABS resin 3-2 | 6.1 |
| 4-1 of low-impurity-content ABS rubber powder | ABS resin 4-1 | 10.9 |
| 4-2 parts of low-impurity-content ABS rubber powder | ABS resin 4-2 | 5.7 |
| ABS rubber powder 5 with low impurity content | ABS resin 5 | 14.8 |
| ABS rubber powder 6 with low impurity content | ABS resin 6 | 10.3 |
| 5-1 parts of low-impurity-content ABS rubber powder | ABS resin 5-1 | 12.4 |
| 6-1 parts of low-impurity-content ABS rubber powder | ABS resin 6-1 | 8.1 |
| ABS rubber powder 1 | ABS resin 8 | 29.2 |
| DP60 ABS rubber powder | ABS resin 9 | 27.7 |
Claims (19)
1. A preparation method of low-impurity-content ABS rubber powder is characterized in that the ABS rubber powder is treated, and the treatment comprises the following steps:
washing the ABS rubber powder with a first washing liquid, monitoring the content of soluble organic carbon in the ABS rubber powder, and washing with the first washing liquid until the content of the soluble organic carbon in the ABS rubber powder is less than or equal to 9000ppm to obtain the low-impurity-content ABS rubber powder;
wherein the washing liquid I is selected from water or alkali liquor, and the alkali liquor is an aqueous solution with the mass percentage of 0.1-3%;
the soluble organic carbon refers to the organic carbon part which can be dissolved in water or alkali liquor in the ABS rubber powder;
the ABS rubber powder is prepared by adopting a method comprising the following steps:
(1) carrying out emulsion polymerization on butadiene and an optional second monomer to obtain polybutadiene latex;
(2) carrying out emulsion polymerization on the polybutadiene latex, styrene, acrylonitrile and an optional third monomer to obtain a grafted ABS latex;
(3) and after the graft ABS latex is subjected to coagulation-curing treatment, filtering and drying to obtain the ABS rubber powder.
2. The preparation method according to claim 1, wherein the ABS rubber powder is subjected to a treatment comprising the steps of:
washing the ABS rubber powder with a first washing liquid, monitoring the content of soluble organic carbon in the ABS rubber powder, and washing with the first washing liquid until the content of the soluble organic carbon in the ABS rubber powder is less than or equal to 5000ppm, thus obtaining the low-impurity-content ABS rubber powder.
3. The method of claim 1, wherein the treating further comprises the steps of: washing the low-impurity-content ABS rubber powder by using a second washing liquid, monitoring the content of iron ions in the ABS rubber powder, and washing by using the second washing liquid until the content of the iron ions in the low-impurity-content ABS rubber powder is less than or equal to 50 ppm.
4. The preparation method of claim 3, wherein the washing liquid II is used for washing until the content of iron ions in the low-impurity-content ABS rubber powder is less than or equal to 10 ppm.
5. The method of claim 1, wherein the alkali solution is selected from an aqueous ammonia solution, an aqueous potassium hydroxide solution, or an aqueous sodium hydroxide solution.
6. The preparation method according to claim 1, wherein the second washing solution is selected from water or an acid solution, and the acid solution is an aqueous solution with a mass percentage of 0.1-3%;
when the first washing liquid is selected from water, the second washing liquid is selected from water or acid liquor; when the first washing liquid is selected from alkali liquor, the second washing liquid is selected from acid liquor.
7. The method according to claim 6, wherein the acid solution is selected from an aqueous acetic acid solution, an aqueous hydrochloric acid solution, and an aqueous sulfuric acid solution.
8. The production method according to any one of claims 1 to 7, wherein the coagulation-maturation treatment in the step (3) is to add a coagulant to the graft ABS latex to perform coagulation, followed by maturation over 0.5 to 2 hours.
9. The production method according to claim 1, wherein in the step (1), the emulsion polymerization comprises the steps of: mixing said butadiene, optionally said second monomer, an emulsifier, optionally a buffer, a chain transfer agent, an initiator and water, and performing said emulsion polymerization at 60-90 ℃ to obtain said polybutadiene latex;
in the step (1), by weight, the butadiene accounts for 90-100 parts, the second monomer accounts for 0-10 parts, the emulsifier accounts for 1-5 parts, the buffering agent accounts for 0-1 part, the chain transfer agent accounts for 0.2-0.7 part, the initiator accounts for 0.1-0.5 part, and the water accounts for 100-150 parts.
10. The method as claimed in claim 9, wherein the polybutadiene latex in the step (1) has a particle size of 200-400 nm.
11. The production method as claimed in claim 9, wherein in the step (1), the butadiene is 93 to 98 parts, the second monomer is 2 to 7 parts, the emulsifier is 2 to 4 parts, the buffer is 0.3 to 0.7 part, the chain transfer agent is 0.3 to 0.6 part, the initiator is 0.2 to 0.4 part and the water is 110-140 parts by weight.
12. The production method according to claim 9, wherein in the step (2), the emulsion polymerization comprises the steps of: mixing said polybutadiene latex, said styrene, said acrylonitrile, optionally said third monomer, with an emulsifier, an initiator, a chain transfer agent, optionally a buffer, and optionally water, and performing said emulsion polymerization at 60-90 ℃;
in the step (2), 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 buffering agent is 0-0.01 part, and the water is 0-20 parts.
13. The method according to claim 12, wherein in the step (2), the polybutadiene latex is 60 to 65 parts, the styrene is 25 to 30 parts, the acrylonitrile is 10 to 15 parts, the third monomer is 1 to 3 parts, the emulsifier is 0.4 to 0.8 part, the initiator is 0.2 to 0.4 part, the chain transfer agent is 0.3 to 0.7 part, the buffer is 0.006 to 0.008 part, and the water is 5 to 15 parts by weight.
14. The production method according to any one of claims 9 to 13, 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.
15. The method according to claim 14, wherein in the steps (1) and (2), the emulsifier is selected from an anionic emulsifier;
the buffer is selected from one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate and sodium pyrophosphate;
the chain transfer agent is selected from one or more of tert-dodecyl mercaptan, n-dodecyl mercaptan, alpha-methyl styrene 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 oxidation-reduction initiators, 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; the reducing agent component in the oxidation-reduction initiator is selected from one or more of sodium formaldehyde sulfoxylate, sodium hydrosulfite, ascorbic acid, isoascorbic acid, sodium hydrosulfite, sodium metabisulfite, lactose, glucose, sorbose, fructose, maltose or ferrous sulfate.
16. The method according to claim 15, wherein in the steps (1) and (2), the emulsifier is selected from one or more of potassium oleate, sodium lauryl sulfate or potassium disproportionate abietate.
17. The method according to claim 15, wherein in the step (3), the coagulant is one or more selected from calcium chloride, magnesium sulfate, sulfuric acid, and acetic acid;
the coagulant is added in an amount of 4 to 6 wt% based on the solid content of the graft ABS latex.
18. The method according to claim 17, wherein the coagulant is an aqueous coagulant solution having a concentration of 2 to 10% by mass.
19. ABS resin, characterized in that, the ABS rubber powder with low impurity content prepared by the preparation method of any one of the claims 1 to 18 is blended with SAN resin to prepare the ABS resin, and the yellow index of the ABS resin is less than or equal to 18.
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| CN113416267B (en) * | 2021-07-28 | 2022-09-20 | 万华化学(四川)有限公司 | ABS graft latex coagulation method for improving biodegradability of process sewage |
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