CN100358944C - Composition of cinnamene resin with good light sensation and plasticity - Google Patents
Composition of cinnamene resin with good light sensation and plasticity Download PDFInfo
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- CN100358944C CN100358944C CNB2005100733959A CN200510073395A CN100358944C CN 100358944 C CN100358944 C CN 100358944C CN B2005100733959 A CNB2005100733959 A CN B2005100733959A CN 200510073395 A CN200510073395 A CN 200510073395A CN 100358944 C CN100358944 C CN 100358944C
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Abstract
The present invention relates to a cinnamene resin composition with good light sensation and plasticity, which comprises (1) 18 to 70% of graft copolymer (A) of a styrene series and an ethylene cyanide series or the styrene series, the ethylene cyanide series and other copolymerizable monomers on a diene series rubber base, (2) 30 to 72% of copolymer (B) of an aromatic ethene monomer and an ethylene cyanide monomer, (3) 0 to 10% of one and/or two kinds of elastomer (C), (4) 0 to 5% of binary or ternary copolymer (D) formed by polymerizing monomers of classes of acrylic acid and acrylate or the acrylic acid, the acrylate and styrene monomer in an emulsion way, (5) 0.2 to 10.0% of necessary components (E) of additive and assistant. The composition is particularly suitable for extrusion processing, thermoforming and vacuum forming, compared with the known extrusion grade resin, the present invention generates the cinnamene resin composition with easy forming and good light sensation by introducing an ACR (acrylate copolymer) modifying agent, so the present invention has a result that the present invention obviously has the advantages of higher toughness and hardness, uniform appearance and good gloss on the basis of suitable extrusion forming and vacuum plastic suction.
Description
(1) technical field:
The present invention relates to the preparation method of the extrusion grade styrene resin composite that a kind of gloss improved, or rather, said composition is particularly suitable for extruding processing, thermoforming and vacuum forming, it is compared with known extrusion molding grade resins, generate a kind of " easily being shaped the composition of styrene resin that light sensation is good " by " introducing ACR (acrylate copolymer) properties-correcting agent ".Preparation method, performance, particularly composition constituted major tuneup, the result obviously has the outward appearance of high toughness, hardness and homogeneous, good gloss on the basis that is fit to extrusion moulding and vacuum forming.
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 occasions such as the shell that is used for tame electrical article, liner, must satisfy characteristics such as shock-resistant and light sensation is good.
Generally speaking, for the resin of extrusion moulding, compare with other forming method, require moulding product surface luster homogeneous, and should have excellent vacuum formability and chemical resistance, the technology in relevant this field is in the exploitation constantly always.For example No. the 5041498th, U.S.'s patent of invention, the rubber like graft copolymer that three kinds of different-grain diameters distribute is provided in a kind of resin combination that provides, the difference of particle diameter has different effects, big particle diameter has improved shock strength and chemicals-resistant corrosive ability, small particle size is in order to improving the outward appearance of composition, but this method is limited to the castering action of homogeneous outward appearance.Point out in the composition patent that Japanese kokai publication sho 60-20916 provides: the weight ratio of vinylbenzene and vinyl cyanide is between 1.7-2.6 in the acetone soluble part of composition, and acetone insoluble matter rubber components storage spring rate is when 0.9 * 109-4 * 109 dyne/cm3 (cubic centimetre) scope, the vacuum formability of resin is good, yet it improves effect and not obvious to vacuum formability.
Prior art and present technique further contrast are as follows:
Patent JP8041286A2 discloses a kind of composition processed that is fit to extrude: be the graft copolymer that rubber size 0.4-0.6 μ m (micron) polymkeric substance by the vinylbenzene of the vinyl cyanide of (1) 20-40%, 80-60%, 20-80% obtains; (2) graft copolymer that obtains of particle diameter 0.05-0.2 μ m (micron) rubber of the vinylbenzene of the vinyl cyanide of 30-45%, 70-55%, 40-80%; (3) intrinsic viscosity that obtains of the vinylbenzene of the vinyl cyanide of 35-45%, 65-55% is that multipolymer three parts of 0.6-0.9 constitute.Compare with present technique, difference mainly shows as obviously difference of the used grafting of composition basis, grafted monomer composition, composite formula formation.
US5409774 has disclosed ABS (acrylonitrile-butadiene-styrene copolymer) matrix material in a kind of anti-fluorine Lyons, and it is to be made of the ABS (acrylonitrile-butadiene-styrene copolymer) of the ABS of high mist degree high impact (acrylonitrile-butadiene-styrene copolymer), low haze and fluid insulation.Composition and the present invention of matrix material who compares this patent with present technique is different resolutely, and the recovery difficulty of material.
EP0629498 discloses a kind of multilayer ABS (acrylonitrile-butadiene-styrene copolymer) sheet material of being made up of low rubber content (5-30%) and high rubber content (35-70) ABS (acrylonitrile-butadiene-styrene copolymer) resin, solved traditional low, in or the use defective of ABS (acrylonitrile-butadiene-styrene copolymer) the individual layer liner plate of high rubber content.The prescription of this patent is formed with present technique obvious difference.
The ABS that US5605963 provides (acrylonitrile-butadiene-styrene copolymer) resin combination has the outward appearance of homogeneous after the moulding.It consists of: (A) ABS (acrylonitrile-butadiene-styrene copolymer) of the glue content 1-20% that is obtained by body or solution polymerization of 5-80%; (B) ABS (acrylonitrile-butadiene-styrene copolymer) of the glue content 20-80% that obtains of the letex polymerization of 1-50%; (C) 0-70% styrene-acrylonitrile copolymer; (D) at least a letex polymerization polyhutadiene of 0.5-10%, the glue amount is 10-95%.It forms obviously different with this patent.
Extrusion-grade ABS (acrylonitrile-butadiene-styrene copolymer) resin that US4150009 proposes, with vinylbenzene and vinyl cyanide or alkyl acrylate in conjunction with and be grafted to poly-butadiene, by adding the Fatty Alcohol(C12-C14 and C12-C18) of at least four hydroxyls, extrude the back material and still keep good shock-resistance.Also distinguish to some extent with present technique.
The publication number of Taiwan Qi Mei company application is the pointed composition of patent document of CN1152006A, comprises a kind of graft copolymer (C)---it is mixed by rubber graft copolymer (A) and propenyl based copolymer (B) and all monomers of the present invention and forms through body or solution polymerization; A kind of graft copolymer of big particle diameter (D) and a kind of and similar graft copolymer (E) the three parts composition of the present composition (A).The thinking obvious and present composition differs widely.
Publication number is that ABS (acrylonitrile-butadiene-styrene copolymer) the composition essentially consist that Bayer AG's patent application case of CN1188119A is pointed out comprises 1) polyhutadiene and the bimodal latex of polyhutadiene of a kind of big particle diameter and gel 〉=70% and the grafts of monomer copolymerization of the present invention of a kind of small particle size and gel≤70%; 2) graftomer of a kind of rubber mass≤50% does not have fundamental difference with industrialized manufacture method; 3) at least a SAN (styrene-acrylonitrile copolymer).Its grafting basis, composition are formed also different with the present invention.
Therefore I introduce special modifier A CR (acrylate copolymer) in the composition blending stage, thereby institute's inventive composition its surface luster when keeping known performance is stabilized and increased.
(3) summary of the invention
In view of this, the inventor is at above deficiency, developed a kind of processing that is suitable for extruding, the styrene resin composite that hot formability is good, main purpose is to improve the vacuum formability of composition (with indulging of composition sheet material, the cross direction elongation numerical values recited characterizes, the big vacuum formability that heals is better), improving it is used under the refrigerator plate situation, the two-way even attenuate of material during for special complicated shape inflation, make it have high toughness simultaneously, the outward appearance of hardness and homogeneous, and by " introducing ACR properties-correcting agent " generation a kind of " easily being shaped the styrene resin composite that light sensation is good " in the blend stage.
The well easy plasticity styrene resin composite of light sensation of the present invention comprises:
The described percentage ratio of following summary of the invention is weight percentage.
(1) graft copolymer (A) of a kind of glue amount 18-70% (in A+B=100%), this graft copolymer (A) is to be the diene series rubber (a) of the 40-80% (in a+b+c=100%) of 0.05-1.0 μ m by median size, the aromatic vinyl monomer that comprises 60-90% (in b+c=100%) (b) with 20-60% (in a+b+c=100%), the vinyl cyanide base monomer (c) of 10-40% (in b+c=100%), and the monomer mixture of other monomer of Gong polymeric (d) of 0-10% (in b+c=100%) carries out emulsion or mass polymerization and the modified resin that obtains;
(2) multipolymer (B) of at least a 30-82% (in A+B=100%), this multipolymer (B) are the resin-oatmeals that is obtained by vinyl cyanide base monomer (d) copolymerization of the aromatic vinyl monomer (b) of 60-90% (in b+c=100%) and 10-40% (in b+c=100%); Polymerization can be adopted methods such as body, suspension or emulsion;
(3) one or both rubber elastomers (C) of 0-10% (in A+B=100%), this elastomerics (C) can be block, granular or powdery, powdered preferably, it is by divinyl and vinyl cyanide or a small amount of acrylonitrile monemer of polybutadiene rubber grafting, the copolymer latex that gets through the emulsion reaction, then with spraying drying or chemical coagulation, active isolated method is produced the mealy elastomer material, 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, vinyl cyanide etc., condense and the rubber powder of acquisition through breakdown of emulsion then, its result of use is suitable.
(4) multipolymer (D) of 0-5% (in A+B=100%), this multipolymer (D) are the ACR resins that methyl methacrylate, acrylate and three kinds of monomers of vinylbenzene obtain through emulsion polymerization.
(5) additive of necessity of 0.2-10.0% (in A+B=100%) and adjuvant component (E): E is selected from thermal stabilizer, lubricant, oxidation inhibitor, weighting agent, pigment, static inhibitor, dispersion agent;
According to above-mentioned composition, can make a kind of be fit to extrude processing, vacuum forming is good and have all quality isostatic styrene resin composites such as toughness, hardness, outward appearance homogeneous, ductility and surface luster concurrently.
Rubber graft copolymer of the present invention (A) is to be monomer by 40-80% (in a+b+c=100%) diene series rubber and 20-60% (in a+b+c=100%) styrenic monomers and vinyl cyanide, and other copolymerizable monomer of 0-10% (in b+c=100%) is carried out emulsion graft polymerization and the emulsion of the rubber graft copolymer (A) of the weight average particle diameter 0.05-1.0 μ m that obtains, through cohesion, dehydration, drying, finally make powdery graft copolymer (A) again.
Butadiene-styrene copolymer emulsion that diene series rubber emulsion of the present invention can be a suitability for industrialized production or perbutan emulsion or divinyl-methylmethacrylate copolymer emulsion or polyhutadiene emulsion etc.; Polyhutadiene emulsion preferably.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, with polystyrene, vinyl cyanide system or polystyrene, vinyl cyanide system, the mixture that (methyl) acrylic ester monomer is formed utilizes the combination of chemical or grafting that at least a polymkeric substance is connected on the rubber phase molecular chain, ratio and polymerizing condition according to monomer and butadiene-based rubber, can obtain the polymkeric substance of desirable grafting degree, polymerizing condition in the common graft polymerization reaction, the chemical property of rubbery polymer, size of particles, the speed that monomer adds, mode, chain-transfer agent, factors such as the consumption of emulsifying agent and kind all can influence its grafted degree.
The employed initiator of aforementioned polyreaction, preferred 0.1-2.0% (in polymerization single polymerization monomer 100 weight parts), 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 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 method of the continuous or increment of monomer mixture, and adding initiator, the conditioning agent of preferably continuous simultaneously or increment.Its applied initiator can be water miscible, and is also oil-soluble, and this also is that the professional person is known.
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.; Vinylbenzene preferably.
Vinyl cyanide used in the present invention is that monomer 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; Wherein be preferably methyl methacrylate.
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. recommend to use alkaline earth salt, as sal epsom, calcium chloride 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).
Graft copolymer (A) is an emphasis part of the present invention, it gives the low-temperature flexibility of asking required for the present invention, composition is not broken when standing low-temperature impact, and rubber substrate has bigger deformability when whipping agent corrodes simultaneously, has to a certain degree improved the resistance to chemical attack ability of material.
Multipolymer of the present invention (B) specifically, is a styrene-acrylonitrile copolymer, and its polymeric method can adopt modes such as solution, body, emulsion, suspension and get.The preparation of polymkeric substance (B) also is that the insider is known, no longer describes in detail here.This multipolymer (B) is the resin-oatmeal that is obtained by the vinyl cyanide base monomer copolymerizable of the aromatic vinyl monomer of 60-90% and 10-40%; Wherein, vinyl cyanide is preferably 25-35% of monomer.
Multipolymer (B) is given rigidity of the presently claimed invention, chemical resistance corrosive ability.
Rubber elastomer of the present invention (C) is polybutadiene latex, the butadiene-acrylonitrile polymer latex of graft modification, 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, vinyl cyanide etc., condense and the rubber powder of acquisition through breakdown of emulsion then, its result of use is suitable.The present invention is with the patented product of Lanzhou Petrochemical Company---and the mixture C 2 of the poly-butadiene rubber powder of powdered nitrile rubber (rubber powder that butadiene-acrylonitrile half cross-linked polymer is made) C1, powdered nitrile rubber (ditto) and low grafting powder, the poly-butadiene rubber powder C3 of low grafting powder are respectively as component (C); The result shows that the result of use of C2 is best, and its optimum amount is 1-3%.
Rubber elastomer (C) has improved the ability of vacuum forming in order to improve the extension performance of the present composition.
Multipolymer of the present invention (D), mean vinylformic acid (ester) and methyl methacrylate (butyl ester) or vinylformic acid (ester) and methyl methacrylate (butyl ester) and vinylbenzene through emulsion polymerization and polymkeric substance.Such as ACR (acrylate copolymer, the as follows)-201{ vinylformic acid (ester) of merchandise sales and the multipolymer of methyl methacrylate (butyl ester) }, ACR-401{ vinylformic acid (ester) and methyl methacrylate (butyl ester) and cinnamic multipolymer etc. all can be used as multipolymer of the present invention (D).
Multipolymer (D) has bigger contribution at aspects such as the even attenuate of sheet material, surface lusters, and can improve the tolerance of composition to R-141b and R-123.
(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.
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 18-70% (in A+B=100%), and when its content was lower than 18% (in A+B=100%), resin can't obtain needed toughness and superior vacuum formability; If during greater than 70% (in A+B=100%), then tensile strength descends, and hardness does not reach hardness of the present invention, and rigidity of the present invention has not existed yet; The homogeneity and the vacuum formability variation of while outward appearance.Generally speaking, percentage of grafting (A) is between 10-75%, and grafted rigid polymer weight average molecular weight is 40, and 000-120 in the time of between 000, can make preferable vacuum formability resin combination.The bound acrylonitrile of the multipolymer in the invention (B) is generally at 20-40%, scope is 25-35% preferably, its weight average molecular weight is generally 40,000-200,000 is good, its content should be between 30-82% (in A+B=100%), otherwise also can't obtain needed styrene resin composite with excellent vacuum formability and homogeneous outward appearance, rigid balancing; Simultaneously, (B) during less than 30% (in A+B=100%), the rigidity of composition is relatively poor, when surpassing 82% (in A+B=100%), and the toughness deterioration of composition.(C) in the composition (D) component rubbery polymer can improve the tolerance of composition to R-141b and R-123 greatly, makes composition benefited a great deal when being used as such as fields such as refrigerator linings.(C) introducing of component also can improve the shock strength of composition, improves the processing characteristics of composition, makes composition add vertical, horizontal extension in man-hour performance at plastic uptake and improves.(D) component has improved the surface luster of material.With (A) (B) (C) (D) (E) mix with suitable proportion, admix with general mixing facilities, use single screw rod or twin screw extruder granulation, can obtain the styrene resin composite that the present invention is suitable for extruding processing.
(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).
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 thing for a moment) analyze.
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 (existing most of this chromatography system of water that uses).
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.
The determination and analysis step
Requirement or the preferred concentration sample dissolution of oneself test by separator column in the instrument;
Start instrument, and with filtering good fresh solvent displacement stable system.Usually, Ci Shi flow velocity is set at 0.10.2ml/min for well;
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 generally all is 1.0ml/min, and column temperature is 30 ℃;
Sample introduction is gathered coherent signal;
The data that processing collects 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/T 1157-1997) by the chemical nitriding of classics
1.5 physical and mechanical properties test relevant criterion
* tensile property: testing standard is GB1040-92
* Izod shock strength: testing standard is GB1843-89
* melt index: testing standard is GB3682-89
* Vicat softening point: testing standard is GB1633-89
* static bending intensity: testing standard is GB9341-88
* vertical, horizontal elongation: with reference to the GB100009-88 relevant regulations
* outward appearance homogeneity evaluation method: 1.0 ± 0.2mm sheet material is with visual detection, and the smooth person of outward appearance homogeneous is with zero expression, and " zero " is The more the better; Outward appearance has granular projection or striped, flake person with * expression, and " * " many more persons are poor more.
* vacuum formability evaluation method: 1.0 ± 0.2mm sheet material in length and breadth to elongation change, vertical and horizontal elongation is big more, vacuum formability is good more, otherwise poor more.
* glossiness: ASTM D523 (untextured) 600.
2. preparation example, embodiment and comparative example
[preparation example]
For further describing the present invention in detail, below preparation example, embodiment and comparative example will support to the present invention, unless specifically stated otherwise, the composition of following composition all refers to weight: unit is gram.
The preparation of [preparation example 1] rubber graft copolymer (A1):
The composition weight part
Polyhutadiene (particle diameter 〉=300nm, gel 72.5%) 900
Vinylbenzene 770
Vinyl cyanide 330
Sodium dodecylbenzene sulfonate 12
Uncle-lauryl mercaptan 2.0
Glucose 6.0
Trisodium phosphate 6.0
Ferrous sulfate 0.12
De-salted water 2800
Di-isopropylbenzene hydroperoxide 6.0
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, use again 10% Adlerika (in an amount equivalent to the graft latex dry matter content 4%) cohesion, centrifugal, dehydration, the dry polymer A 1 that obtains.
The physical property of polymer A 1 is as follows:
Rubber content 70% (in polyhutadiene, formula calculation result), weight average particle diameter are 0.37 μ m (particle-size analyzer is directly measured), (A1) glue content is 45%, weight average particle diameter is 0.37 μ m, and percentage of grafting is 48.9% (fractionation analysis, general analytical procedure).The molecular weight of grafted styrene-acrylonitrile copolymer is 67,000 (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, and 000-120 is between 000.
The preparation of [preparation example 2] rubber graft copolymer (A2):
Polyhutadiene in the preparation example 1 (particle diameter 〉=300nm, gel 72.5%), vinylbenzene, vinyl cyanide are become 800 grams, 840 grams, 360 grams respectively, and other conditions remain unchanged.
Above-mentioned prescription obtains the emulsus polymkeric substance (A2) of transformation efficiency＞96.0% 70 ℃ of reactions 5.0 hours.
Preparation process reference rubber graft copolymer (A1).
The method cohesion that is provided with preparation 1 then, obtain graft copolymer (A2), (A2) glue content is 40% (fractionation analysis, general analytical procedure), weight average particle diameter is 0.35 μ m (particle-size analyzer is directly measured), and percentage of grafting is 52% (fractionation analysis, general analytical procedure), the molecular weight of styrene-acrylonitrile copolymer is 63,000 (gel chromatography is a benchmark with the polystyrene).
The preparation of [preparation example 3] rubber graft copolymer (A3):
Polyhutadiene in the preparation example 1 (particle diameter 〉=300nm, gel 72.5%), vinylbenzene, vinyl cyanide are become 1350 grams, 490 grams, 210 grams respectively, and other conditions remain unchanged.
Above-mentioned prescription obtains the emulsus polymkeric substance (A3) of transformation efficiency＞96.7% 70 ℃ of reactions 5.0 hours.
Preparation process reference rubber graft copolymer (A1).
The method cohesion that is provided with preparation 1 then, obtain graft copolymer (A3), (A3) glue content is 65% (fractionation analysis, general analytical procedure), weight average particle diameter is 0.34 μ m (particle-size analyzer is directly measured), and percentage of grafting is 41.5% (fractionation analysis, general analytical procedure), the molecular weight of styrene-acrylonitrile copolymer is 61,000 (gel chromatography is a benchmark with the polystyrene).
The preparation of [preparation example 4] rubber graft copolymer (A4):
Polyhutadiene in the preparation example 1 (particle diameter 〉=300nm, gel 72.5%), vinylbenzene, vinyl cyanide are become 1400 grams, 420 grams, 180 grams respectively, and add 60 gram methyl methacrylates in addition in monomer, other conditions remain unchanged.
Above-mentioned prescription obtains the emulsus polymkeric substance (A4) of transformation efficiency＞97.3% 70 ℃ of reactions 5.0 hours.
Preparation process reference rubber graft copolymer (A1).
The method cohesion that is provided with preparation 1 then, obtain graft copolymer (A4), (A4) glue content is 70% (fractionation analysis, general analytical procedure), weight average particle diameter is 0.387 μ m (particle-size analyzer is directly measured), and percentage of grafting is 30% (fractionation analysis, general analytical procedure), the molecular weight of styrene-acrylonitrile copolymer is 57,000 (gel chromatography is a benchmark with the polystyrene).
The preparation of [preparation example 5] rubber graft copolymer (A5):
Different with preparation example 4 is not contain methyl methacrylate in the prescription, and all the other conditions are identical.
The preparation of [preparation example 6] rubber graft copolymer (A6):
Compare with preparation example 4, except that not containing the methyl methacrylate, 420 gram vinylbenzene are all substituted with alpha-methyl styrene in the prescription again, other parts are constant.
The preparation of [preparation example 7] rubber graft copolymer (A7):
Different with preparation example 4 is in the prescription except that not containing the methyl methacrylate, and 180 gram vinyl cyanide substitute with the Alpha-Methyl vinyl cyanide of equal parts, and all the other conditions are identical.
The preparation of [preparation example 8] rubber graft copolymer (A8):
Different with preparation example 4 is in the prescription except that not containing the methyl methacrylate, and 60 gram methyl methacrylates substitute with the N-phenylmaleimides of equal parts, and all the other conditions are identical.
The preparation of [preparation example 9-12] styrene-acrylonitrile copolymer (B1-B4), (unit: 10-2 gram):
Prescription is formed preparation example 9 preparation examples 10 preparation examples 11 preparation examples 12
Vinylbenzene 80 75 70 65
Vinyl cyanide 20 25 30 35
H2O 120 120 120 120
Active calcium phosphate 0.8 0.8 0.8 0.8
Sodium dodecylbenzene sulfonate 0.006 0.006 0.006 0.006
Tert-dodecyl mercaptan 0.45 0.4 5 0.45 0.45
Diisopropyl azodicarboxylate 0.18 0.18 0.18 0.18
Multipolymer B1 B2 B3 B4
The preparation preparation process of styrene-acrylonitrile copolymer (B1-B4):
Above-mentioned material is added in the 5 liter stainless steel jacketed type reactors, stir the three leaf sweepback turbines slurry formula form of using, paddle width 12mm, diameter 140mm, rotating speed is stepless adjustable.Material earlier at normal temperatures under the 200rpm rotating speed stirring suspension disperse 30min, check the dispersion effect (get after 10 milliliters of suspension levels leave standstill 10 minutes, observe the oil reservoir segment thickness and be not more than 15% of whole fluid column, be suspended dispersed qualified) of suspension.The intensification polymerization of the qualified back of affirmation system suspended dispersed was raised to 75 ℃-77 ℃ in 1.5-2.0 hour, and 75 ℃ of-77 ℃ of isothermal reactions 6.0 hours, and analysis list transformation rate＞90% o'clock is warmed up to that slaking 30min finishes reaction more than 90 ℃.
Cool to about 40 ℃, material after filtration, washing removes water, divides at the dry sealings of 80 ℃ of convection oven to get final product less than 1%.
The preparation of [preparation example 13] rubber elastomer (C):
(1) C1: Lanzhou Petrochemical Company chemical research institute half cross-linked powdery butyronitrile commodity.
(2) C3: 10 parts of vinyl cyanide are after the emulsion graft polymerization reaction together with 90 parts of polyhutadiene, and cohesion and partition method that using patent CN1083827A is again provided are made the powder Butadiene Rubber;
(3) C2: with C1, C3 with 2: 1 mixed C2 component as the present composition.
Composition is 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 1-13] composition scheme sees Table 1, and result of implementation sees Table 2:
Table 1: composition scheme
| Embodiment | Composite formula | ||||
| Component | A1 A2 A3 A4 A5 A6 A7 A8 | B1 B2 B3 B4 | C 1 C 3 | C 2 | D * |
| Implement 1 | 37 - - - - - - - | 63 - - - | - - | - | - 2 |
| Implement 2 | - 42 - - - - - - | - 58 - - | - - | - | - 2 |
| Implement 3 | - - 26 - - - - - | - - 74 - | - - | - | - 2 |
| Implement 4 | - - - 24 - - - - | - - - 76 | - - | - | - 2 |
| Implement 5 | - - - 24 - - - - | - 20 30 26 | - - | 1.0 | 1.0 2 |
| Implement 6 | - - - 24 - - - - | - 20 30 26 | - - | 2.0 | 1.0 2 |
| Implement 7 | - - - 24 - - - - | - 20 30 26 | - - | 3.0 | 1.0 2 |
| Implement 8 | - - - - 24 - - - | - 20 30 26 | - - | 3.0 | 1.0 2 |
| Implement 9 | - - - - - 24 - - | - 20 30 26 | - - | 3.0 | 1.0 2 |
| Implement 10 | - - - - - - 24 - | - 20 30 26 | - - | 3.0 | 1.0 2 |
| Implement 11 | - - - - - - - 24 | - 20 30 26 | - - | 3.0 | 1.0 2 |
| Implement 12 | - - - 24 - - - - | - 20 30 26 | 3.0 - | - | - - |
| Implement 13 | - - - 24 - - - - | - 20 30 26 | - 3.0 | - | - - |
The commodity ACR-401 that Amway chemical plant, D* Suzhou produces
By above-mentioned prescription various raw materials are carried out normal temperature in super mixer and mix, through the twin screw extruder granulation, by the indicated standard method test performance of patent.
The results are shown in Table 2:
The result of table 2 embodiment 1-13
| Embodiment | Surface luster (600) | Izod shock strength (J/m) | Melt index (g/10min) | Tensile strength (Mpa) | Rockwell hardness (R) | 1mm thick sheet elongation (%) | The outward appearance homogeneity | |
| Vertical | Horizontal | |||||||
| Real-1 | 90 | 307.3 | 1.4 | 39.2 | 98.0 | 47 | 32 | ○ |
| Real-2 | 91 | 297.8 | 0.7 | 40.3 | 98.2 | 42 | 28 | ○ |
| Real-3 | 90 | 388.5 | 0.8 | 41.2 | 98.7 | 39 | 20 | ○ |
| Real-4 | 90 | 306.5 | 0.6 | 44.4 | 106.0 | 46 | 33 | ○○ |
| Real-5 | 94 | 410.5 | 0.9 | 43.7 | 105.8 | 118 | 74 | ○○ ○ |
| Real-6 | 93 | 430.7 | 0.94 | 42.8 | 105.0 | 128 | 82 | ○○ ○ |
| Real-7 | 93 | 431.7 | 0.92 | 42.3 | 103.0 | 134 | 88 | ○○ ○ |
| Real-8 | 93 | 413.2 | 1.2 | 40.1 | 98.0 | 128 | 90 | ○○ ○ |
| Real-9 | 93 | 342.4 | 0.7 | 47.0 | 112.0 | 105 | 81 | ○○ |
| Real-10 | 93 | 406.6 | 1.1 | 45.0 | 107.0 | 123 | 87 | ○○ |
| Real-11 | 93 | 428.0 | 0.89 | 43.0 | 110.0 | 106 | 83 | ○○ ○ |
| Real-12 | 87 | 397.2 | 0.7 | 39.8 | 96.7 | 93 | 76 | ○○ ○ |
| Real-13 | 81 | 457.6 | 0.9 | 39.4 | 96.0 | 118 | 96 | ○○ |
Vertical and horizontal extensibility improved after embodiment showed the resin-oatmeal plate squeezing of (A4) structure, demonstrate good attenuate, during vacuum suction moulding, increase with stress can be by uniform inflation, thickness is even everywhere for goods behind the plastic uptake, this deep processing for large-size box and the part with complicated structure is very favourable, so (A4) resin-oatmeal of structure is the resin-oatmeal of optimum structure of the present invention, possible reason perhaps will be owing to the special contribution of methyl methacrylate to the grafting phase structure.(C) adding of component has not only improved the shock strength of material, improved processing characteristics, the vacuum formability of what is more important material tends to be reasonable, it acts on similar softening agent, it should be noted that the effect when C2 component net effect is better than C1, C3 and uses separately, concrete reason remains further research.(D) joining not only of component offset (C) component to the consumption of ABS glossy, the more important thing is the surface luster of having improved resin.This is because it has little particle diameter on the one hand, and its optical characteristics shows as transparently on the other hand, so the refractive index of material is had regulating effect, effectively raises the surface luster of ABS resin.(B) component contrivance when it uses with polynary array mode obtains the equilibrated physical and mechanical properties easily, and its reason is obvious.
[comparative example]
Table 3 comparative example scheme
| Comparative example | Composite formula | ||||||
| Component | A1 | A2 | A4 | B3 | C2 | D* | E |
| Compare-1 | - | 18 | - | 82 | - | - | 2 |
| Compare-2 | - | 18 | - | 82 | - | 1 | 2 |
| Compare-3 | - | 70 | - | 30 | 2 | - | 2 |
| Compare-4 | - | 70 | - | 30 | 2 | 1 | 2 |
| Compare-5 | - | - | 18 | 82 | 2 | 1 | 2 |
| Compare-6 | - | - | 70 | 30 | 2 | 1 | 2 |
| Compare-7 | 100 | - | - | - | - | - | 2 |
The commodity ACR-401 that Amway chemical plant, D* Suzhou produces
Table 4 comparative example result of implementation
| Comparative example | Glossiness 600 | Izod shock strength (J/m) | Melt index (g/10min) | Tensile strength (Mpa) | Rockwell hardness (R) | Static bending intensity (Mpa) | 1mm thick sheet elongation (%) | The outward appearance homogeneity | |
| Vertical | Horizontal | ||||||||
| Compare-1 | 90 | 89.0 | 2.7 | 53.0 | 114.0 | 72.0 | 8.9 | 7.8 | ○ |
| Compare-2 | 94 | 121.0 | 2.5 | 52.0 | 112.0 | 71.3 | 9.2 | 8.7 | ○ |
| Compare-3 | 88 | 383.9 | 0.43 | 31.0 | 87.0 | 53.0 | 18.0 | 14.7 | × |
| Compare-4 | 92 | 375.4 | 0.41 | 30.2 | 86.3 | 51.0 | 32.0 | 29.7 | × |
| Compare-5 | 93 | 243.0 | 1.9 | 49.0 | 95.0 | 67.0 | 21.0 | 17.6 | ○ |
| Compare-6 | 92 | 340.2 | 0.32 | 27.0 | 71.0 | 49.0 | 46.3 | 37.2 | × × |
| Compare-7 | 86 | 358.0 | 0.29 | 24.0 | 71.3 | 43.0 | 24.0 | 18.2 | × × |
By comparative example 1,2,5 test-results as can be known, in the composition at the bottom of the content of (A) when 18% (weight), resin can't obtain the said toughness of the present invention, simultaneously vacuum formability is bad; And the consumption of working as (A) reaches 70% when above (relatively-6,7), although toughness is all right, and the homogeneity variation of rigidity deterioration required for the present invention, particularly outward appearance, processibility variation, vacuum formability are also undesirable.Comparative example 2,4,5,6 is because (D) glossiness that exists of component also is higher than comparative example 1,3,7.
By comparative example 3,4,5,6 test-results (elongation) as can be known, in the composition (C) (D) two components the vacuum formability to the present composition is useful really, particularly because (C) adding of component, obviously the improving to elongation in length and breadth of sheet material.
Relatively-7 show, if when lacking multipolymer (B) in the composition, also can't obtain the alleged toughness of the present invention, hardness and vacuum formability, the unified styrene resin composite of outward appearance homogeneity.
Take a broad view of embodiment 1-7, the present invention is through aforementioned each component and use quantitative limitation, has improved the vacuum formability and the outward appearance homogeneity of styrene resin composite really, makes hardness and toughness obtain balance preferably.And make that this resin combination can be for industry utilizations such as large-scale sheet material processing, tubing processing, modifying plastics, automobiles.
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 (14)
1. well easy plasticity styrene resin composite of a light sensation, it contains
The A graft copolymer, wherein comprise in (a)+(b)+(c)=100%, median size is 40～80% the diene series rubber (a) of 0.05～1.0um, 20～60% comprise 60～90% aromatic vinyl monomer (b) in (b)+(c)=100%, and carry out emulsion or mass polymerization and the modified resin that obtains in 10～40% vinyl cyanide base monomer (c) of (b)+(c)=100% and in the mixture of other monomer of Gong polymeric (d) of 0～10% of (b)+(c)=100%;
The B multipolymer wherein comprises the aromatic vinyl monomer (b) in (b)+(c)=100%, 60～90%, the resin-oatmeal that obtains by body, suspension or letex polymerization with the mixture of 10～40% vinyl cyanide base monomer (c);
The C rubber elastomer, it is the copolymer latex that is obtained through the emulsion reaction by divinyl and vinyl cyanide or a small amount of acrylonitrile monemer of polybutadiene rubber grafting, condenses bulk, granular or coccoid that isolation or freezing and pulverizing or spraying drying form then;
D multipolymer, this multipolymer are the ACR resins that methyl methacrylate, acrylate and three kinds of monomers of vinylbenzene obtain through emulsion polymerization;
The E component is selected from thermal stabilizer, lubricant, oxidation inhibitor, weighting agent, pigment, static inhibitor, dispersion agent;
It is characterized in that:
Various components are A=18～70% in the above-mentioned composition; B=30～82%; C=0.5～10%; D=0.2～5.0%; E=0.2～10.0%, it calculates C, D, E radix and adds multipolymer B=100% in polymer A, more than all percentage ratios be weight percentage.
2. according to the composition of claim 1, it is characterized in that described diene series rubber emulsion can be butadiene-styrene copolymer emulsion or perbutan emulsion or divinyl-methylmethacrylate copolymer emulsion or polyhutadiene emulsion.
3. according to the composition of claim 2, it is characterized in that described diene series rubber emulsion is the polyhutadiene emulsion.
4. according to any composition of claim 1, it is characterized in that described aromatic vinyl monomer is a styrenic monomers.
5. according to the composition of claim 4, it is characterized in that described styrenic monomers is vinylbenzene, alpha-methyl styrene, α-chloro-styrene or P-vinyl toluene.
6. according to any composition of claim 5, it is characterized in that described styrenic monomers is a styrene monomer.
7. according to any composition of claim 1, it is characterized in that described vinyl cyanide base monomer is acrylonitrile monemer or Alpha-Methyl acrylonitrile monemer.
8. according to the composition of claim 7, it is characterized in that described vinyl cyanide base monomer is an acrylonitrile monemer.
9. according to claim 1 composition, but it is characterized in that other monomer of copolymerization is that (methyl) acrylic ester, maleimide are monomer.
10. according to the composition of claim 9, it is characterized in that described monomer is methyl methacrylate or N-phenylmaleimide.
11., it is characterized in that described monomer is a methyl methacrylate according to the composition of claim 10.
12., it is characterized in that described B multipolymer is a styrene-acrylonitrile copolymer according to the composition of claim 1.
13., it is characterized in that the C rubber elastomer is a rubber powder according to the composition of claim 1.
14., it is characterized in that the D multipolymer is a commodity ACR-401 resin according to the composition of claim 1.
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| CN101885894B (en) * | 2009-05-13 | 2012-05-30 | 中国石油化工股份有限公司 | Modified abs resin and preparation method thereof |
| CN107001747B (en) * | 2015-08-31 | 2019-10-01 | 株式会社Lg化学 | Thermoplastic resin and thermoplastic resin composition comprising the thermoplastic resin |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106827A (en) * | 1993-12-10 | 1995-08-16 | 通用电气公司 | Grafting, phase-inversion and cross-linking controlled multi-stage bulk process for making abs graft copolymers |
| CN1121938A (en) * | 1994-08-15 | 1996-05-08 | 奇美实业股份有限公司 | High luster impact-resistance excellent processing fluidity styrene series resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106827A (en) * | 1993-12-10 | 1995-08-16 | 通用电气公司 | Grafting, phase-inversion and cross-linking controlled multi-stage bulk process for making abs graft copolymers |
| CN1121938A (en) * | 1994-08-15 | 1996-05-08 | 奇美实业股份有限公司 | High luster impact-resistance excellent processing fluidity styrene series resin composition |
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