CN100358945C - Method for preparing shockproof composition of styrene resin in high tensile strength and low lustre - Google Patents
Method for preparing shockproof composition of styrene resin in high tensile strength and low lustre Download PDFInfo
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- CN100358945C CN100358945C CNB2005100733963A CN200510073396A CN100358945C CN 100358945 C CN100358945 C CN 100358945C CN B2005100733963 A CNB2005100733963 A CN B2005100733963A CN 200510073396 A CN200510073396 A CN 200510073396A CN 100358945 C CN100358945 C CN 100358945C
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Abstract
The present invention relates to a styrene resin composition with impact resistance, high strength and low luster and a preparation method thereof. The method comprises: respectively preparing graft copolymers (A), copolymers (B), rubber elastomer (C) and powder polybutadiene rubber elastomer copolymers (D) which are emulsified and grafted by acrylonitrile, and mixing the three copolymers (A, B, D) and the rubber elastomer (C) with additive agents and auxiliary agent components (E) to form the low luster styrene resin composition (ABS). The styrene resin composition comprises various kinds of prepared components: A = 18 to 50%, B = 50 to 80%, C = 0.5 to 7.0%, D = 0.5 to 5.0%, and E = 0.2 to 10.0%. The composition ABS which is prepared with the present invention has the advantages of low luster, high impact strength, high tensile strength and convenient luster adjustment.
Description
(1) technical field:
The present invention relates to a kind of preparation method of rubber-modified styrene resin composite, or rather, the present invention is meant a kind of preparation method of composition of styrene resin of shock-resistant high tensile strength and low lustre, this group and thing add PBD (polyhutadiene), SBR (styrene butadiene) or NBR (acrylonitrile-butadiene) polymer powder is made gloss properties-correcting agent in the blending stage, can conveniently make the resin combination of characteristics such as having excellent impact strength, tensile strength and moulding product surface luster are easy to adjust.
Herein, all parts (%) number is weight part (%) number except that indicating.
(2) background technology
So far, styrene resin composite is to be scattered in a kind of impact resins composition made in the styrene based copolymer with rubber like graft copolymer.When the crust of the shell that is used for tame electrical article, leather trunk and fascia etc., must satisfy shock-resistant and characteristic such as low gloss.
Generally speaking, the common shock-resistant high phenylethylene resin series of healing, glossiness is lower, in other words, the rubber content of phenylethylene resin series is higher, rubber particles is healed, and big glossiness is just lower, EP 201,099 provides a kind of two-step approach polymerization technique to prepare the method for low gloss ABS (acrylonitrile-styrene-divinyl) resin; EP129 has described the approach that vinylbenzene and acrylonitrile grafting is prepared the ABS graft copolymer on polybutadiene rubber in 796; US 3,928, and 494, patent such as DE 2,057,935 further described the preparation technology of high-impact ABS.But improve tensile strength deterioration that the glue weight phenylethylene is a resin, increase the needed synthetic technology of particle diameter more complicated relatively again, although these two kinds of methods reduce glossy effect arranged, obtain that actual required glossiness has great difficulty under different field, occasion.
In addition, in resin combination, add matting agent, also can play extinction effect as materials such as zinc oxide, titanium dioxide, tripoli; Another kind of method commonly used is to improve processing technology.But these two kinds of methods all cause negative impact to some performance such as mechanical property, the dyeing behavior etc. of material, and have improved the cost of the finished product.
The inventor is at aforementioned disadvantages, utilizes aspects such as shrinking percentage, refractive property exist between two kinds of materials difference to prepare the preparation method of the composition of styrene resin of shock strength that a kind of gloss can conveniently adjust, have concurrently simultaneously again, tensile strength through means such as blend.During this method was also constantly developing at present, more approaching patented invention further was summarized as follows:
Patent JP 58-93711 has disclosed a kind of preparation process of low gloss ABS thermoplastic resin, and its method is that polystyrene is sneaked in the ABS latex, utilizes the difference of its consistency difference and two kinds of material contracts rates, reduces gloss.But this method effect on reduction resin surface gloss is not remarkable, and has therefore lost the shock strength of product.
Can prepare the low gloss ABS resin with a kind of specific emulsion polymerisation process, its characteristics are to add the carboxylic-acid monomer in polymerization process, and the polymer beads that utilizes polycondensation to generate reduces surface luster.But because the low productive rate of polycondensation, so it is very little to glossy reduction contribution, its production circulation ratio is bad still more.
Patent KP 93-6912 makes the low gloss ABS resin with suspending or body-suspension two-step approach polymerization technique.This ABS has limited its range of application along with the difference of injecting condition occurs some again such as problems such as serious contraction, gloss skewness, hardness reductions.
Low gloss ABS resin described in the patent WO 99/03904 is to add polymkeric substance gloss properties-correcting agent in ABS, reaches the purpose that reduces surface luster.This polymkeric substance gloss properties-correcting agent is to add in the ABS emulsion condensation stage to be no more than 25% PBD or SBR or NBR latex and to make.Though its defective is the gloss of prepared ABS composition and has obtained effectively reducing, and does not look after the balance of shock strength, tensile strength over-all properties, during practical application, when needing frequent the adjustment, gloss seems very inconvenient again especially.
Therefore, how to prepare a kind of styrene resin composite that has shock-resistance, high-tensile and low glossization simultaneously easily, be the problem that the people in the industry studies for a long time always.
(3) summary of the invention
In view of this, the inventor has proposed a kind of preparation method of shock-resistant high tensile strength and low lustre styrene resin composite, and main purpose provides the preparation method that a kind of method simply and simultaneously has the styrene resin composite of shock-resistance, high-tensile and low glossization.The method that said composition provided simultaneously has great convenience especially when gloss needs frequent the adjustment when practical application.
The preparation method of a kind of shock-resistant high tensile strength and low lustre styrene resin composite of the present invention, it comprises:
(1) step of preparation graft copolymer A, A is 40～80% diene series rubbers (a) of 0.05～1.0um by median size, with 20～60% 60～90% the styrenic monomers (b) of comprising, 0～40% vinyl cyanide base monomer (c), and the monomer mixture of other monomer of 0～10% Gong polymeric (d) carries out letex polymerization and the modified resin that obtains;
(2) step of preparation multipolymer B, B is by 60～90% styrenic monomers (b), 0～40% vinyl cyanide base monomer (c), and the monomer mixture of other monomer of 0～30% Gong polymeric (d) adopts body or one of suspension or emulsion process polymeric resin;
(3) step of preparation rubber elastomer C, C be by divinyl and vinyl cyanide and/or (methyl) methacrylate monomer through emulsion copolymerization, condense the polymkeric substance powdery body that isolation or freezing and pulverizing or spraying drying form then;
(4) preparation is a kind of is the step of the powdery polybutadiene rubber elastomer copolymer (D) of vinyl cyanide emulsification, and D adopts the emulsion graft polymerization preparation by 90～95% diene rubbers (a) and 5～10% vinyl cyanide base monomers (c);
(5) with above-mentioned A, B, C, D and component E according to the mixing step that becomes a kind of shock-resistant high tensile strength and low lustre styrene resin composite of following ratio;
It is characterized in that:
Various preparation components are A=18～50% in the above-mentioned composition (%); B=50～80%; C=0.5～7.0%; D=0.5～5.0%; E=0.2～10.0%.
According to above-mentioned composition, can make the adjustable again phenylethylene resin series of a kind of shock-resistant high-tensile gloss easily.
The preparation process of graft copolymer A is the chemical substance with formula ratio, add successively in the 3.5L polymerization reactor, in 1.5 hours, pass through the chuck water-bath, make polymer fluid slowly be warmed up to 70 ℃, constant temperature synthesis under normal pressure 5.0 hours is analyzed transformation efficiency＞96.0% o'clock, and the logical cold water of chuck cools to 40 ℃ to material then, again with the cohesion of 10% Adlerika, centrifugal, dehydration, the dry graft copolymer A that obtains.
Graft copolymer of the present invention (A) is to be monomer and acrylic monomer by 40～80 weight part diene series rubber latex and 20～60 parts by weight of styrene preferably, and other copolymerizable monomer of 0～5 weight part is carried out emulsion graft polymerization and the emulsion of the rubber graft copolymer (A) of weight average particle diameter 0.05～1.0 μ m that obtains, through cohesion, dehydration, drying, finally make powdery graft copolymer (A) again.
The butadiene-styrene copolymer that diene series rubber emulsion of the present invention is a suitability for industrialized production, perbutan, divinyl-methylmethacrylate copolymer, polyhutadiene etc.; It is the latex of 0.05～1.0 μ m that above-mentioned diene series rubber latex can the aforementioned monomer direct polymerization becomes particle diameter, also can synthesize the small grain size latex of 0.05～0.18 μ m earlier after, agglomerate into the particle of required size again with method chemistry or physics.
Graft polymerization reaction of the present invention is used for making polymkeric substance (A).Usually adopt the technology of emulsion graft polymerization, utilize the combination of chemical or grafting that at least a polymkeric substance is connected on the rubber phase molecular chain monomer mixtures such as polystyrene, acrylic, (methyl) acrylic ester, ratio and polymerizing condition according to monomer and butadiene-based rubber, can obtain the polymkeric substance of desirable grafting degree, usually factors such as the consumption of the speed of the chemical property of the polymerizing condition in the graft polymerization reaction, rubbery polymer, size of particles, monomer adding, mode, chain-transfer agent, emulsifying agent and kind all can influence its grafted degree.
The employed initiator of aforementioned polyreaction, can be water miscible, also can be oil-soluble, preferred 0.1～2.0% (in polymerization single polymerization monomer 100 weight parts) of consumption, for guaranteeing carrying out smoothly of polyreaction, it is best that initiator adds effect with continuous or method of addition.The molecular weight size of graft copolymer is controlled by the temperature of graft reaction, and/or cooperates the molecular weight regulator of suitable small quantities of usual, as: just-lauryl mercaptan, uncle-lauryl mercaptan etc.
The graft rubber content of control reaction is extremely important, can utilize the adding of the continuous or increment of monomer mixture, and adding initiator, the conditioning agent of preferably continuous simultaneously or increment, to guarantee the balance of the finished product over-all properties.
Polyreaction is carried out in stirring tank usually, normal pressure or device slightly with pressure all can, reach the monomer conversion more than 90%, polymerization time 4-8 hour just enough.
Styrenic monomers used in the present invention can be vinylbenzene, alpha-methyl styrene, α-chloro-styrene, p-vinyl toluene etc.; Recommend vinylbenzene.
Acrylic monomer used in the present invention can be vinyl cyanide, Alpha-Methyl vinyl cyanide etc.; Preferred vinyl cyanide.
The copolymerisable monomer that the present invention chooses wantonly has: (methyl) acrylic ester monomer, maleimide are monomer, vinylformic acid, Maleic Acid, Anhydrous, methacrylic acid glycol ester etc.; Preferable methyl methyl acrylate, N-phenylmaleimide.
Can make the emulsion of graft copolymer (A) through the above-mentioned emulsion polymerization, add suitable flocculation agent in the emulsion (A) and condense.The general optional acids of flocculation agent, alkaline earth salt etc.The slurries of finishing that condense are removed most of moisture through centrifuge dehydration, and drying is handled again, makes powdery graft copolymer (A).
Multipolymer of the present invention (B), specifically, can be styrene-acrylonitrile copolymer, methyl methacrylate-styrene-acrylonitrile copolymer etc., styrene-acrylonitrile copolymer preferably, industrial already these base polymer commodity all are indication polymkeric substance of the present invention (B); Its polymeric method can adopt any mode such as solution, body, emulsion or suspension and get, and the preparation method of B is that industry is known.
Rubber elastomer of the present invention (C) is the polymer latex of butadiene-acrylonitrile and/or (methyl) methyl acrylate, the rubber powder of producing with spraying drying or chemical coagulation, active isolated method, the also rubber powder that can use block glue to make through freezing and pulverizing, also can use above-mentioned emulsion polymeric latex, other monomer of grafting part: as vinylchlorid etc., through breakdown of emulsion cohesion and the rubber powder that obtains etc., its result of use is suitable then.
Rubber elastomer (C) preparation process is as follows:
With the separant calcium carbonate superfine powder nitrile rubber is carried out isolation processing, isolation agent is equivalent to the 2-3% of latex (butt), divide 3 batches (1/2 then, 1/4,1/4) add 10% salts solution continuously and condense in nitrile rubber, the flocculation agent consumption is equivalent to 4.0% of latex (butt), and the immortal steel cohesion of 400L still is used in cohesion, turbine slurry formula three leaves stir mixing speed 400rpm.By jacket of polymerization control coacervated system temperature is 40-60 ℃, kept pool time 1.5-2.0 hour, finish cohesion under the normal pressure, be warmed up to 80 ℃ of slakings then and solidified 30 minutes, after filtration, washing, dehydration, cyclone drying make powdered nitrile rubber-rubber elastomer (C).
Graft copolymer of the present invention (D) means the polymkeric substance of grafting 5-10% (weight) acrylonitrile monemer in the diene series rubber substrate.The grafted method does not have any difference with general letex polymerization, and it is identical with the described method of CN1083827A that it condenses isolated technology.90 parts of polybutadiene latexs (butt, particle diameter 〉=300nm, gel 72.5%), 10 parts of vinyl cyanide are together made powder Butadiene Rubber (D) with cohesion and partition method that patent CN1083827A is provided after the emulsion graft polymerization reaction.
The preparation process of powder Butadiene Rubber (D) is with polyhutadiene, deionized water, vinyl cyanide, glucose, trisodium phosphate, ferrous sulfate, di-isopropylbenzene hydroperoxide, sodium lauryl sulphate, uncle-lauryl mercaptan.Add successively in the 3.0L polymerization reactor, by the chuck water-bath, made polymer fluid slowly be warmed up to 65 ℃ in 1.5 hours, constant temperature synthesis under normal pressure 5.0 hours is analyzed transformation efficiency＞96.0% o'clock, and the logical cold water of chuck cools to 40 ℃ to material then.
Separant, anti-aging agent, part surface promoting agent are under agitation added the polyvinyl butadiene rubber Ruzhong, form separant-polyvinyl butadiene rubber breast dispersion, condense separant-polyvinyl butadiene rubber breast dispersion, make the poly-fourth suspension of mixed uniformly powder with ionogen.Suspension dehydration, drying are made powder Butadiene Rubber (D), and its cohesion is identical with (C) preparation process with isolated procedure and ratio control.
(E) component in the composition can comprise or not comprise various known additives, as: thermal stabilizer, lubricant, oxidation inhibitor, weighting agent, pigment, static inhibitor, dispersion agent and other necessary auxiliary agent, but do not comprise matting agent.
Specifically, the present invention be aforementioned (A) (B) (C) (D) (E) each several part or the part mixture.The content of (A) in the composition is 18～50% (weight parts), and when its content was lower than 18% (weight part), resin can't obtain needed toughness and glossy is unified; And during greater than 50% (weight part), resin can't obtain needed tensile strength again.The percentage of grafting of (A) should be between 25～60% simultaneously, and the number-average molecular weight of the rigid polymer in the grafting is 30,000～120, between 000.The bound acrylonitrile of the multipolymer in the invention (B) should be at 20～40% (weight parts), its number-average molecular weight should be 40,000～200,000 is good, its content should be between 50～80% (weight parts), less than the tensile strength deficiency of 50% o'clock composition, and not enough greater than the toughness of 85% o'clock composition.The introducing of (C2) component rubbery polymer in the composition can improve the shock strength of composition, improves the processing characteristics of composition, reduces the surface luster of resin, and its effect is better than (C1); It is to be noted that (D) component can make the gloss of composition descend significantly, but its consumption only just has best effect in the framework of the present definition, when its consumption surpasses 5.0 parts, the impact performance is produced detrimentally affect.When the consumption of (C) when 0.5～7.0 part and (D) consumption are between 0.5～5.0 part, can obtain the said best effect of the present invention.Do not use the present invention (C) and/or can't obtain the styrene resin composite of low glossization (D) time.
(4) embodiment
Further specify the present invention by following embodiment.
1. analysis test method that embodiment, comparative example adopted and standard:
1.1 ABS graft rubber content analysis:
Take by weighing sample 2 grams (accurately to 0.0002 gram) and place in the triumphant formula flask, add 100ml acetone, prolong is contained on the flask, in 65 ℃ of waters bath with thermostatic control, refluxed 2 hours along bottleneck.Do not make bath temperature be higher than 65 ℃ during this period, otherwise the bumping phenomenon easily takes place.
Stop to take off flask after the heating, be cooled to room temperature.Content in the flask is all changed in the polyethylene centrifuge tube of weighing, be positioned in the whizzer, centrifugation is 20 minutes under 15000rpm, then with in the supernatant liquid impouring 100ml triangular flask.With behind the insolubles (stirring) in the small amount of acetone washing centrifuge tube with glass stick again centrifugation once remove supernatant liquid.Centrifuge tube is put into vacuum drying oven, in 65 ℃ of following vacuum-dryings to constant weight after weighing (G1).
A. the result calculates
Graft rubber content X (wt%) is calculated as follows:
In the formula, G1=rubber weight, gram;
The G=sample weight, gram.
The mensuration of sample should be parallel be carried out two, and the result is calculated to second decimal place, and behind the average and digital revision of the convention, analysis report is got behind the decimal one.
In addition, by this test determination, also can obtain grafting efficiency by following formula:
In the formula, the shared percentage composition of vinylbenzene and vinyl cyanide in SAN total amount=sample weight * prescription.
1.2 SAN molecular weight and distributional analysis thereof among the ABS
Take by weighing sample 2 grams (accurately to 0.0002 gram) and place in the triumphant formula flask, add 100ml acetone, prolong is contained on the flask, in 65 ℃ of waters bath with thermostatic control, refluxed 2 hours along bottleneck.Do not make bath temperature be higher than 65 ℃ during this period, otherwise the bumping phenomenon easily takes place.
Stop to take off flask after the heating, be cooled to room temperature.Content in the flask is all changed in the polyethylene centrifuge tube of weighing, be positioned in the whizzer, centrifugation is 20 minutes under 15000rpm, then with in the supernatant liquid impouring 100ml triangular flask.With behind the insolubles (stirring) in the small amount of acetone washing centrifuge tube with glass stick again centrifugation once remove supernatant liquid, get its clear liquid and carry out drying and then make the SAN sample or directly use clear liquid as sample.Ready sample with tetrahydrofuran (THF) (THF) as dissolution with solvents, use then the GPC method (with size exclusion chromatography be the same thing) analyze.
A. test apparatus
Gel permeation chromatography (GPC) instrument of this 150-C GPC/ALC of U.S.'s water or other same type;
Vacuum filter (being with small-sized oilless vacuum pump);
Data processor (use water this chromatography system).
B. solvent
Specialty gpc analysis used reagent generally all is THF at normal temperatures, its feature be strong to most of polymer dissolution power, refractive index is low, and make with characteristic that water dissolves each other that directly dissolving latex is analyzed and become possibility.In addition, THF processings that will outgas before using is with the stability of assurance system etc.
C. determination and analysis step
(1) by the requirement of separator column in the instrument or the preferred concentration of oneself test
Sample dissolution;
(2) start instrument, and with filtering good fresh solvent displacement stable system.
Usually, Ci Shi flow velocity is set at 0.1～0.2ml/min for well;
(3) filter the good sample of dissolving, with special-purpose sample bottle the sample after filtering is put into instrument and be injected into specimen chamber constant temperature, Instrument working parameter is set.Mainly be the flow velocity and the column temperature of liquid-flow phase, flow velocity is 1.0ml/min, and column temperature is 30 ℃;
(4) sample introduction is gathered coherent signal;
(5) handle the data that collect, draw various molecular-weight average, and print the molecular weight distribution spectrogram.
1.3 the mensuration of graft latex total solid substance
On the aluminium dish of known weight, take by weighing 2g sample (accurately to 0.0002g), drip about 3g ethanol and in sample, make its cohesion.Put into infrared dryer and be dried to and become khaki color (about 10 minutes), cooling back weighing.(when many or total solid content is high when sampling amount, till amount of alcohol will be added to and solidify fully.
Calculate:
Total solid content X (weight %) is calculated as follows:
In the formula: G2--total solid matters weight+aluminium dish is heavy, gram
G1-aluminium dish is heavy, gram
The G-samples weighed, gram
1.4 the analysis of the acrylonitrile content of polymkeric substance can be carried out quantitative analysis preferably (can be equivalent to ISO1656:1988 with reference to SH/T1157-1997) by the chemical nitriding of classics
1.5 physical and mechanical properties test relevant criterion
GB1040-92 plastic tensile test method
GB1843-89 plastics izodtest method
GB3682-89 plastic melt index test method
The standard environment of GB2918-89 plastics testing status adjustment and testing circumstance
Glossiness: with reference to ASTM D523, JIS K7105 standard
2. preparation example, embodiment and comparative example
[preparation example]
2.1 the preparation process of polymer A, C, D and physical property:
1. earlier by following formulation rubber graft copolymer (A.):
Composition weight (g, gram)
Polyhutadiene (particle diameter 〉=300nm, gel 72.5%) 700
Vinylbenzene 210
Vinyl cyanide 90
Methyl methacrylate 0～30
Sodium dodecylbenzene sulfonate 4
Uncle-lauryl mercaptan 1.5
Glucose 3
Trisodium phosphate 3
Ferrous sulfate 0.6
De-salted water 1400
Di-isopropylbenzene hydroperoxide 3
The preparation process of polymer A:
Chemical substance with above-mentioned formula ratio, add successively in the 3.5L polymerization reactor, in 1.5 hours, pass through the chuck water-bath, make polymer fluid slowly be warmed up to 70 ℃, constant temperature synthesis under normal pressure 5.0 hours is analyzed transformation efficiency＞96.0% o'clock, and the logical cold water of chuck cools to 40 ℃ to material then, again with the cohesion of 10% Adlerika, centrifugal, dehydration, the dry polymer A that obtains.
The physical property of polymer A is as follows:
Rubber content 70% is (in polyhutadiene, formula calculation result), weight average particle diameter is 0.387 μ m (particle-size analyzer is directly measured), graft rubber content 89.6% (fractionation analysis, general analytical procedure), the molecular weight of styrene-acrylonitrile copolymer is 57,000 (gel chromatography is a benchmark with the polystyrene).
General, the percentage of grafting of (A) of the presently claimed invention should be between 25～60%, and the number-average molecular weight of the rigid polymer in the grafting is 30,000～120, between 000.
2. the method that adopts patent CN1083827A to be provided is made rubber elastomer (C) *;
(C) * because of use latex gel and Mooney viscosity difference can be divided into cross-linking type (C1: gel 80～90%, Mooney viscosity 100～130ML), half cross-linking type (C2: gel 50～70, Mooney viscosity 60～90ML) }
Rubber elastomer (C) preparation process is as follows:
With the separant calcium carbonate superfine powder nitrile rubber is carried out isolation processing, isolation agent is equivalent to the 2-3% of latex (butt), divide 3 batches (1/2 then, 1/4,1/4) add 10% salts solution continuously and condense in nitrile rubber, the flocculation agent consumption is equivalent to 4.0% of latex (butt), and the immortal steel cohesion of 400L still is used in cohesion, turbine slurry formula three leaves stir mixing speed 400rpm.By jacket of polymerization control coacervated system temperature is 40-60 ℃, kept pool time 1.5-2.0 hour, finish cohesion under the normal pressure, be warmed up to 80 ℃ of slakings then and solidified 30 minutes, after filtration, washing, dehydration, cyclone drying make powdered nitrile rubber-rubber elastomer (C).
Rubber elastomer (C) proterties:
White powder, ash be less than 5%, acrylonitrile content 27.8%, and granularity 90% is between the 40-60 order.
3. 90 parts of polybutadiene latexs (butt, particle diameter 〉=300nm, gel 72.5%), 10 parts of vinyl cyanide are together made powder Butadiene Rubber (D) with cohesion and partition method that patent CN1083827A is provided after the emulsion graft polymerization reaction.
The preparation process of powder Butadiene Rubber (D):
With 900 gram polyhutadiene, 1200 gram deionized waters, 100 gram vinyl cyanide, glucose 3 grams, trisodium phosphate 3 grams, ferrous sulfate 0.3 gram, di-isopropylbenzene hydroperoxide 3 grams, sodium lauryl sulphate 6 grams, uncle-lauryl mercaptan 1.5 grams.Add successively in the 3.0L polymerization reactor, by the chuck water-bath, made polymer fluid slowly be warmed up to 65 ℃ in 1.5 hours, constant temperature synthesis under normal pressure 5.0 hours is analyzed transformation efficiency＞96.0% o'clock, and the logical cold water of chuck cools to 40 ℃ to material then.
Separant, anti-aging agent, part surface promoting agent are under agitation added the polyvinyl butadiene rubber Ruzhong, form separant-polyvinyl butadiene rubber breast dispersion, condense separant-polyvinyl butadiene rubber breast dispersion, make the poly-fourth suspension of mixed uniformly powder with ionogen.Suspension dehydration, drying are made powder Butadiene Rubber (D), and its cohesion is identical with (C) preparation process with isolated procedure and ratio control.
Powder Butadiene Rubber (D) proterties:
The slightly lurid polymer powder of white, ash be less than 5%, acrylonitrile content 9.6%, and granularity 90% is between the 40-60 order.
**********************
Following examples, comparative example be all at 5L at a high speed in (1500rpm) mixing tank, normal temperature mixing 3-5 minute, and compound is through diameter 35mm (length-to-diameter ratio 32) twin screw extruder then, and extruding pelletization makes under 190-220 ℃ temperature.
The sample of gained was dried 2-4 hour in 80 ℃ of air dry ovens, injected according to the GB standard at last, and injection technological parameter is as follows:
Barrel zone temperature: 190-240 ℃
Injection pressure: 65-110MPa
Die temperature: 40-80 ℃
Injection speed: as far as possible slowly.
[embodiment]
[embodiment-1] is with 460 gram A, 1540 gram B (suspension method SAN, the styrene-acrylonitrile copolymer that suspension method is produced), 8 gram Magnesium Stearates, 8 gram EBS (ethylene stearic bicine diester imines), extruding pelletization after the 60 gram C2 blend, composition properties is: shock strength 371.2J/m (joules per meter, down together), tensile strength 37.5Mpa (MPa, down together), MI (melt index) 1.7g/10min (restraining/10 minutes), surface luster (60 ° of degree) 83.
And surface luster (600 degree) is 96 when not adding C2, and other performances are 336,39,1.9 successively.
[embodiment-2] with 430 gram A, 1570 restrain B (same embodiment-1), 8 gram Magnesium Stearates, 8 gram EBS, extruding pelletization after the 100 gram C2 blend, composition properties is: shock strength 355.1J/m, tensile strength 37.5Mpa, MI1.63g/10min, surface luster (60 °) 76.
And surface luster (600 degree) is 96.5 when not adding C2, and other performances are 315,40,2.1 successively.
[embodiment-3] with 630 gram A, 1370 restrain B (body SAN, styrene-acrylonitrile copolymer), 8 gram Magnesium Stearates, 8 gram EBS, extruding pelletization after the 60 gram C2 blend, composition properties is: shock strength 437.8J/m, tensile strength 38.7Mpa, MI1.3g/10min, surface luster (60 °) 74.
And surface luster (60 ° of degree) is not 93 when not adding C2, and other performances are 356,38,1.4 successively.
[embodiment-4] with 630 gram part A, 1370 restrain B (body SAN), 8 gram Magnesium Stearates, and 8 gram EBS, extruding pelletization after the 80 gram C2 blend, composition properties is: shock strength 466.8J/m, tensile strength 38.5Mpa, MI1.2g/10min, surface luster (60 °) 72.
And surface luster (60 ° of degree) is not 93 when not adding C2, and other performances are 356,38,1.4 successively.
[embodiment-5] with 630 gram A, 1370 restrain B (body SAN), 8 gram Magnesium Stearates, and 8 gram EBS, extruding pelletization after the 100 gram C2 blend, composition properties is: shock strength 487.2J/m, tensile strength 37.5Mpa, MI1.1g/10min, surface luster (60 °) 67.
And surface luster (60 ° of degree) is not 93 when not adding C2, and other performances are 356,38,1.4 successively.
[embodiment-6] with 460 gram A, 1540 restrain B (body SAN), 8 gram Magnesium Stearates, and 8 gram EBS, extruding pelletization after the 60 gram C1 blend, composition properties is: shock strength 267.8J/m, tensile strength 42.0Mpa, MI1.9g/10min, surface luster (60 °) 84.
And surface luster (60 ° of degree) is not 96 when not adding C1, and other performances are 336,39,1.9 successively.
[embodiment-7] with 440 gram A, 1560 restrain B (body SAN), 8 gram Magnesium Stearates, and 8 gram EBS, extruding pelletization after the 80 gram C1 blend, composition properties is: shock strength 278.1J/m, tensile strength 42.8Mpa, MI2.0g/10min, surface luster (60 °) 83.
And surface luster (60 ° of degree) is not 96.5 when not adding C1, and other performances are 318,43,2.0 successively.
[embodiment-8] with 420 gram A, 1580 restrain B (body SAN), 8 gram Magnesium Stearates, and 8 gram EBS, extruding pelletization after the 100 gram C1 blend, composition properties is: shock strength 289.5J/m, tensile strength 41.7Mpa, MI2.0g/10min, surface luster (60 °) 81.
And surface luster (60 ° of degree) is not 97 when not adding C1, and other performances are 286,43,2.1 successively.
[embodiment-9] with 360 gram A, 1640 restrain B (suspension method SAN), 8 gram Magnesium Stearates, and 8 gram EBS, extruding pelletization after the 100 gram C1 blend, composition properties is: shock strength 232.7J/m, tensile strength 39.7Mpa, MI2.2g/10min, surface luster (60 °) 85.
And surface luster (60 ° of degree) is not 98 when not adding C1, and other performances are 213,46,2.3 successively.
[embodiment-10] with 430 gram A, 1590 restrain B (suspension method SAN), 8 gram Magnesium Stearates, and 8 gram EBS, extruding pelletization after the 60 gram D blend, composition properties is: shock strength 228.1J/m, tensile strength 35.9Mpa, MI2.0g/10min, surface luster (60 °) 51.
And surface luster (60 ° of degree) is not 96.5 when not adding D, and other performances are 315,40,2.0 successively.
[embodiment-11] with 360 gram A, 1640 restrain B (suspension method SAN), 8 gram Magnesium Stearates, 8 gram EBS, extruding pelletization after 70 gram C2 and the 70 gram D blend, composition properties is: shock strength 221.3J/m, tensile strength 38.7Mpa, MI2.1g/10min, surface luster (60 °) 43.
And surface luster (60 ° of degree) is not 98 when not adding C2, D, and other performances are 213,46,2.3 successively.
[embodiment-12] with 360 gram A, 1640 restrain B (suspension method SAN), 8 gram Magnesium Stearates, 8 gram EBS, extruding pelletization after 100 gram C2 and the 60 gram D blend, composition properties is: shock strength 224.2J/m, tensile strength 37.9Mpa, MI2.1g/10min, surface luster (60 °) 41.
And surface luster (60 ° of degree) is not 98 when not adding C2, D, and other performances are 213,46,2.3 successively.
[embodiment-13] with 560 gram A, 1440 restrain B (suspension method SAN), 8 gram Magnesium Stearates, 8 gram EBS, extruding pelletization after 70 gram C2 and the 70 gram D blend, composition properties is: shock strength 457.2J/m, tensile strength 37.8Mpa, MI1.3g/10min, surface luster (60 °) 37.
And surface luster (60 ° of degree) is not 94 when not adding C2, D, and other performances are 386,38,1.6 successively.
[comparative example]
[comparative example-1] with 280 gram A, 1720 restrain B (suspension method SAN), 8 gram Magnesium Stearates, and 8 gram EBS, extruding pelletization after the 100 gram C1 blend, composition properties is: shock strength 157.7J/m, tensile strength 43.1Mpa, MI2.4g/10min, surface luster (60 °) 86.
Comparative example-1 explanation: A, the B amount ranges of not using the present invention to stipulate, though use C1 can to a certain degree adjust the gloss of product, shock strength is unsatisfactory.
[comparative example-2] with 372 gram A, 1628 restrain B (suspension method SAN), 8 gram Magnesium Stearates, and 8 gram EBS, extruding pelletization after the 140 gram D blend, composition properties is: shock strength 151.1J/m, tensile strength 35.4Mpa, MI1.9g/10min, surface luster (60 °) 38.
Comparative example-2 explanation: although used A, the B amount ranges of the present invention's regulation, after the consumption of D exceeded scope of the present invention, it was very effective to the gloss that reduces product, but shock strength is also undesirable.
[comparative example-3] with 320 gram A, 1680 restrain B (suspension method SAN), 8 gram Magnesium Stearates, 8 gram EBS, extruding pelletization after 60 gram C2 and the 140 gram D blend, composition properties is: shock strength 141.1J/m, tensile strength 34.2Mpa, MI2.1g/10min, surface luster (60 °) 27.
Comparative example-3 explanation: use the A amount ranges that is lower than the present invention's regulation, use the consumption of C2, D and D to exceed scope of the present invention simultaneously after, it is very effective to the gloss that reduces product, but shock strength can't reach effect of the present invention.
[comparative example-4] with 1000 gram A, 1000 restrain B (suspension method SAN), 8 gram Magnesium Stearates, 8 gram EBS, extruding pelletization after 70 gram C2 and the 70 gram D blend, composition properties is: shock strength 341.1J/m, tensile strength 29Mpa, MI0.3g/10min, surface luster (60 °) 41.
Comparative example-4 explanation: use the A amount ranges that is higher than the present invention's regulation, use the amount ranges of best C2 of the present invention, D simultaneously after, the shock strength of goods, to reduce the glossy effect very desirable, but tensile strength can't reach effect of the present invention.
[comparative example-5] with 500 gram A, 1500 restrain B (suspension method SAN), 8 gram Magnesium Stearates, and 8 gram EBS, extruding pelletization after the blend, composition properties is: shock strength 212.3J/m, tensile strength 46.2Mpa, MI1.3g/10min, surface luster (60 °) 95.
Comparative example 5 explanations: after not using gloss conditioning agent C of the present invention, D, can't obtain the goods that the said gloss of the present invention reduces.
By the foregoing description and comparative example as seen:
The content of (A) in the composition is 18～50% (weight parts), and when its content was lower than 18% (weight part), resin can't obtain needed toughness and glossy unified (comparative example-1,3); And during greater than 50% (weight part), resin can't obtain needed tensile strength (comparative example-4) again.The percentage of grafting of (A) should be between 25～60% simultaneously, and the number-average molecular weight of the rigid polymer in the grafting is 30,000～120, between 000.
The bound acrylonitrile of the multipolymer in the invention (B) should be at 20～40% (weight parts), its number-average molecular weight should be 40,000～200,000 is good, its content should be between 50～90% (weight parts), less than the tensile strength deficiency (comparative example-4) of 50% o'clock composition, and greater than the toughness of 85% o'clock composition not enough (comparative example-1).
(C) component all can reduce the surface luster of ABS in the composition, but experimental result also shows: the introducing of C2 component rubbery polymer can improve the shock strength of composition, improve the processing characteristics of composition, reduce the surface luster of resin, its effect is better than C1 (seeing embodiment 1～9);
It is to be noted that (D) component can make the gloss of composition descend significantly, but its consumption only just has best effect in the framework of the present definition, when its consumption surpasses 5.0 parts, the impact performance is produced detrimentally affect (embodiment-10, comparative example-2).(C) consumption can obtain the said best effect of the present invention (embodiment-12,11,13) when 0.5～7.0 part and (D) consumption are between 0.5～5.0 part.Do not use the present invention (C) and/or can't obtain the styrene resin composite (comparative example-5) of low glossization (D) time.
With (A) (B) (C) (D) (E) mix with suitable proportion, with general mixing facilities blending, use single screw rod or twin screw extruder granulation, just can obtain the alleged a kind of styrene resin composite that had both had shock-resistance, high-tensile and low glossization of the present invention, the more important thing is when practical application, when gloss needed frequent the adjustment, preparation thinking provided by the invention had demonstrated great convenience and operability especially.
Below only preferred example of the present invention summarized, known the professional and technical personnel in this field, all changes of doing according to individual example, modification, decomposition etc. all belong to the scope of this patent claim protection.
Claims (13)
1. the preparation method of a shock-resistant high tensile strength and low lustre styrene resin composite, it comprises
(1) step of preparation graft copolymer A, A is 40～80% diene series rubbers (a) of 0.05～1.0um by median size, with 20～60% 60～90% the styrenic monomers (b) of comprising, 0～40% vinyl cyanide base monomer (c), and the monomer mixture of other monomer of 0～10% Gong polymeric (d) carries out letex polymerization and the modified resin that obtains;
(2) step of preparation multipolymer B, B is by 60～90% styrenic monomers (b), 0～40% vinyl cyanide base monomer (c), and the monomer mixture of other monomer of 0～30% Gong polymeric (d) adopts body or one of suspension or emulsion process polymeric resin;
(3) step of preparation rubber elastomer C, C be by divinyl and vinyl cyanide and/or (methyl) methacrylate monomer through emulsion copolymerization, condense the polymkeric substance powdery body that isolation or freezing and pulverizing or spraying drying form then;
(4) preparation is a kind of is the step of the powdery polybutadiene rubber elastomer copolymer (D) of vinyl cyanide emulsification, and D adopts the emulsion graft polymerization preparation by 90～95% diene rubbers (a) and 5～10% vinyl cyanide base monomers (c);
(5) with above-mentioned A, B, C, D and component E according to the mixing step that becomes a kind of shock-resistant high tensile strength and low lustre styrene resin composite of following ratio, wherein E is selected from thermal stabilizer, lubricant, oxidation inhibitor, weighting agent, pigment, static inhibitor, dispersion agent;
It is characterized in that:
Various preparation components are A=18～50% in the above-mentioned composition (%); B=50～80%; C=0.5～7.0%; D=0.5～5.0%; E=0.2～10.0%.
2. according to the preparation method of claim 1, it is characterized in that described diene series rubber emulsion (a) is butadiene-styrene copolymer emulsion, perbutan emulsion, divinyl-methylmethacrylate copolymer emulsion or polyhutadiene emulsion.
3. according to the preparation method of claim 1, it is characterized in that described styrenic monomers is vinylbenzene, alpha-methyl styrene, α-chloro-styrene or P-vinyl toluene.
4. according to the preparation method of claim 1, it is characterized in that styrenic monomers and vinyl cyanide base monomer content are 20～40% among the graft copolymer A.
5. according to claim 3, any preparation method of 4, it is characterized in that described styrenic monomers is vinylbenzene, alpha-methyl styrene.
6. according to the preparation method of claim 5, it is characterized in that described styrenic monomers is a styrene monomer.
7. according to claim 1, any preparation method of 4, it is characterized in that described vinyl cyanide base monomer is vinyl cyanide or Alpha-Methyl acrylonitrile monemer.
8. according to the preparation method of claim 7, it is characterized in that described vinyl cyanide base monomer is an acrylonitrile monemer.
9. according to the preparation method of claim 1, but it is characterized in that other monomer (d) of copolymerization is that (methyl) acrylic ester or maleimide are monomer.
10. according to the preparation method of claim 9, it is characterized in that described monomer (d) is methyl methacrylate or N-phenylmaleimide.
11., it is characterized in that described B multipolymer is styrene-acrylonitrile or methyl methacrylate-styrene-acrylonitrile copolymer according to the preparation method of claim 1.
12. preparation method according to claim 1, it is characterized in that rubber elastomer C is the polymer latex of butadiene-acrylonitrile and/or (methyl) methyl acrylate, the rubber powder that generates with spraying drying or chemical coagulation, active isolated method or use the rubber powder that block glue makes through freezing and pulverizing or use above-mentioned latex, the grafting vinyl chloride monomer is through breakdown of emulsion, the rubber powder that obtains of cohesion.
13. a kind of shock-resistant high tensile strength and low lustre styrene resin composite according to any preparation method preparation of claim 1-12.
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| CN102203679A (en) * | 2008-10-30 | 2011-09-28 | 大日精化工业株式会社 | Process for production of pigment/resin composition, coloring agent and coloring method |
| KR20120075724A (en) * | 2010-12-29 | 2012-07-09 | 제일모직주식회사 | Flame retardant abs resin composition with low-gloss and improved impact resistance |
| CN105131307A (en) * | 2015-09-11 | 2015-12-09 | 怡维怡橡胶研究院有限公司 | Continuous preparation method for rubber masterbatch and rubber masterbatch prepared by method |
| CN107298827B (en) * | 2017-06-29 | 2020-07-03 | 上海金山锦湖日丽塑料有限公司 | Low-gloss heat-resistant ABS resin and preparation method thereof |
| CN115449163B (en) * | 2022-09-30 | 2023-10-31 | 中化国际聚合物(连云港)有限公司 | Resin composition with sub-photochemical impact resistance and high tensile strength and preparation method thereof |
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| WO1998032796A1 (en) * | 1997-01-27 | 1998-07-30 | Basf Aktiengesellschaft | High-tenacity thermoplastic moulding materials |
| CN1472249A (en) * | 2002-07-29 | 2004-02-04 | 上海普利特复合材料有限公司 | Composition of delustered styrene acrylonitrile copolymer containing gel powder acrylonitrile butadiene rubber |
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| WO1998032796A1 (en) * | 1997-01-27 | 1998-07-30 | Basf Aktiengesellschaft | High-tenacity thermoplastic moulding materials |
| CN1472249A (en) * | 2002-07-29 | 2004-02-04 | 上海普利特复合材料有限公司 | Composition of delustered styrene acrylonitrile copolymer containing gel powder acrylonitrile butadiene rubber |
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