CN1150232C - Making method of impact resistance resin composition - Google Patents
Making method of impact resistance resin composition Download PDFInfo
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- CN1150232C CN1150232C CNB951203487A CN95120348A CN1150232C CN 1150232 C CN1150232 C CN 1150232C CN B951203487 A CNB951203487 A CN B951203487A CN 95120348 A CN95120348 A CN 95120348A CN 1150232 C CN1150232 C CN 1150232C
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Abstract
The present invention provides a resin composition with high chrominance, high shock resistance and good rigid physical property balance, and also provides a method for manufacturing the shock resistance resin composition capable of largely reducing sewage pollution. By using a continuous mass polymerization method to manufacture resin without containing rubber components, in the later half process of a monomer removal step, the resin composition with shock resistance is manufactured by adding and mixing graft copolymers containing rubber components when resin is in a melting state. The graft copolymer is serous fluid obtained from emulsion polymerization latex or substances obtained from a water-containing filter cake after preliminary dewatering and drying.
Description
The present invention relates to the manufacture method of impact resistant resin composition, relate to the manufacture method of impact resistance resin composition good aspect tone and shock-resistance and inflexible rerum natura balance in more detail.
Having cooperated with ABS resin and high impact polystyrene is the impact resistance resin of the rubber constituent of representative, on the balance of its various rerum naturas and shaping processability is good resin, can be used on the extensive use of trolley part, electric installation parts and transaction facility parts etc.
In order to make the impact resistance resin that has cooperated these rubber constituents give full expression to its sufficient mechanical properties, the vinyl monomers such as vinylbenzene in the rubber constituent need be carried out graft polymerization, adopted emulsion grafting polymerization in the past as manufacture method.
But letex polymerization exists, and operation is many, and auxiliary material is many, the problem that cost is increased and need carry out draining processing etc.
Therefore, in order to reduce the shortcoming of these letex polymerizations, developed and make the high rubber graft copolymer that contains emulsion grafting polymerization and carry out the polymer melt blended method (" ABS " resin is compiled by polymer association) that suspension polymerization obtains by not containing rubber.And then, in recent years, develop the technology that direct continuous bulk polymerization contains the impact resistance resin of rubber again, and be applied to actual production (for example, special public clear 47-14136 communique, special public clear 49-26711 communique, chemical engineering 53 (6) 423～426 (1989) etc.).
; by containing of emulsion grafting polymerization high rubber polymer and do not conform to rubber after the polymkeric substance that chain mass polymerization or suspension polymerization obtain makes each independent polymkeric substance; using melting mixing method advantage is to be easy to successfully control its rerum natura; but because when fusion; and then be subjected to thermal process; so have tone insufficient, shock-resistance and the inadequate shortcoming of inflexible rerum natura balance.
On the other hand, the method that contains the impact resistance resin of rubber by direct continuous bulk polymerization manufactured, advantage is that operation and auxiliary material are few, do not need draining to handle, the control difficulty of the graft polymerization reaction when but shortcoming is mass polymerization and since rubber constituent often be subjected to big thermal process, so the resin tone that obtains is bad, moreover, can't satisfy the aspect requirement of impact-resistant rerum natura.In addition, rubber constituent for a long time because the deterioration thing of rubber can be trapped in the device or it strips down to bringing problem on manufacturing processed and the quality product.
Therefore, present inventors through with keen determination research, its purpose is to provide the manufacture method of the good impact resistance resin composition in tone and aspects such as shock-resistance and inflexible rerum natura balance, thereby has finished the present invention to the problems referred to above.
That is to say the manufacture method that the invention provides impact resistance resin composition, it is characterized in that to by aromatic vinyl monomer 20-100% weight, cyano group vinyl monomer 0-60% weight, in multipolymer (A) the 10-95 weight part of the molten state that (methyl) acrylic ester monomer 0-80% weight and can carrying out with the monomer mixture that other vinyl monomers 0-60% weight of these copolymerization is formed obtains in the technique of continuous bulk polymerization, add being blended in the existence of 5-80 parts by weight of rubber polymkeric substance down continuously, by aromatic vinyl monomer 10-100% weight, cyano group vinyl monomer 0-50% weight, graft copolymer (B) the 90-5 weight part that obtains after (methyl) acrylic ester monomer 0-80% weight and the monomer mixture 95-20 weight part graft polymerization that can form with other vinyl monomers 0-60% weight of these copolymerization.
And, in the aforesaid method, slurries that graft copolymer (B) is obtained by emulsion polymerization latex or moisture filter cake dehydrated in advance obtain, but preferably slurries that will obtain from emulsion polymerization latex or moisture filter cake are through giving first dehydration, and with air or nitrogen gas stream drying, dehydrate after perhaps supplying to squeezing device with ditch, hole or gap that fraction is passed through and venting hole.
Below describe the present invention in detail.
Constituting multipolymer (A) that uses among the present invention and the aromatic ethylene that connects branched copolymer (B) is that monomer is meant the aromatic substance with energy polymerisable double bond, and concrete example can be enumerated vinylbenzene, alpha-methyl styrene, p-methylstyrene, Vinyl toluene, propylstyrene, butylstyrene and phenylcyclohexane ethene etc.These aromatic ethylenes are monomer, can use the mixture more than a kind or 2 kinds.These aromatic ethylenes are preferably to use vinylbenzene and alpha-methyl styrene in the monomer.
The multipolymer (A) that uses among formation the present invention and the cyano group vinyl monomer of graft copolymer (B) are meant the compound with energy polymerisable double bond and cyano group, and concrete can enumerate vinyl cyanide and methacrylonitrile etc.These cyano group vinyl monomers can use the mixture more than a kind or 2 kinds.In these cyano group vinyl monomers, the particularly preferred vinyl cyanide that is to use.
The monomeric object lesson of (methyl) acrylic ester that constitutes the multipolymer (A) that uses among the present invention and graft copolymer (B) can be enumerated the propyl ester of methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, glycidyl methacrylate, hydroxyethyl methylacrylate, methyl acrylate, ethyl propenoate, propylene and butyl acrylate etc.These (methyl) acrylic ester monomers can use the mixture more than a kind or 2 kinds.In these (methyl) acrylic ester monomers, preferably use methyl methacrylate.
The multipolymer (A) that uses among formation the present invention and other vinyl monomers of graft copolymer (B) can be enumerated as N-phenylmaleimide, N-cyclohexyl maleimide, methyl substituted N-phenylmaleimide, maleic anhydride, vinylformic acid and methacrylic acid etc.The wherein most preferred N-phenylmaleimide that is to use.
The rubbery polymer that constitutes the graft copolymer (B) of the present invention's use can be enumerated diene series rubber, acrylic rubber, ethene is rubber etc., and concrete example can be enumerated polyhutadiene, poly-(butadiene-styrene), poly-(butadiene-acrylonitrile), polyisoprene, poly-(butadiene-acrylic acid butyl ester), poly-(butadiene-acrylic acid methyl esters), poly-(divinyl-methyl methacrylate), poly-(butadiene-acrylic acid ethyl ester), ethylene-propylene rubber, ethylene-propylene-elastoprene, poly-(ethene-isoprene), and poly-(ethylene-methyl acrylate) etc.Can use the mixture more than a kind or 2 kinds in these rubbery polymers.Particularly preferred polyhutadiene, poly-(butadiene-styrene), poly-(butadiene-acrylonitrile) and the ethylene-propylene rubber of being to use in these rubbery polymers.
Can enumerate polyethylene, styrene-acrylonitrile copolymer, vinylbenzene-N-phenylmaleimide multipolymer, styrene-acrylonitrile-phenyl maleimide multipolymer, styrene-acrylonitrile-methylmethacrylate copolymer, styrene-methylmethacrylate copolymer as the preference of the multipolymer that uses among the present invention (A), wherein particularly preferably be styrene-acrylonitrile copolymer.
The preferred example of the graft copolymer that uses among the present invention (B) can be enumerated the phenylethene grafted copolymer of polyhutadiene, the phenylethene grafted copolymer of poly-(butadiene-styrene), the styrene-acrylonitrile graft copolymer of polyhutadiene, the styrene-acrylonitrile graft copolymer of poly-(butadiene-styrene), the styrene-acrylonitrile graft copolymer of poly-(butadiene-acrylonitrile), the styrene-acrylonitrile graft copolymer of the styrene-acrylonitrile-methyl methacrylate graft copolymer of polyhutadiene and poly-(ethylene-propylene) etc.
On the other hand, each monomer usage ratio for multipolymer (A) is that needing aromatic vinyl is that monomer is that 20-100 weight %, cyano group vinyl monomer are that 0-60%, (methyl) acrylic ester monomer are 0-80 weight % and can are 0-60 weight % with other vinyl monomers of these copolymerization according to the requirement of physical strength, tone and the formability of the resin combination that obtains.Preferably, aromatic vinyl is that monomer is that 30-100 weight %, cyano group vinyl monomer are that 0-50 weight %, (methyl) acrylic ester monomer are 0-70 weight % and can are 0-50 weight % with other vinyl monomers of these copolymerization, more preferably, aromatic vinyl is that monomer is that 60-100 weight %, cyano group vinyl monomer are that 10-40 weight %, (methyl) acrylic ester monomer are 0-60 weight % and can are 0-40 weight % with other vinyl monomers of these copolymerization.
Forebody operation of the present invention, be about to by aromatic vinyl be continuous bulk polymerization process in the operation of monomer 20-100 weight %, cyano group vinyl monomer 0-60 weight %, (methyl) acrylic ester monomer 0-80 weight % and the monomer mixture continuous bulk polymerization that can form with other vinyl monomers 0-60 weight % of these copolymerization without any restriction, can adopt any continuous bulk polymerization method.For example in polymerization tank, adopt known demonomerization (degassing) method after the polymerization.Can use as polymerization tank to have the polymerization tank that various paddles are for example starched mixed types such as formula blade, turbine blade, propeller blade, two-way agitating vane (Block Le マ one ジ Application), multistage blade ground anchor type blade, maximum hybrid blade and twin screws blade, perhaps various tower reactors etc.And then, also can use pattern polymerization reactors such as multi-tubular reactor, kneading type reactor, double-shafted extruder (for example, the polymer manufacturing process is estimated 10 " evaluations of impact resistant polystyrene ": polymer association, on January 26th, 1989 etc.).These polymerization tank classes (reactor) are used 1 (groove) or 2 (groove), in case of necessity, also can use the reactor of combination more than 2 kinds.
The reaction mixture of polymeric multipolymer (A) in these polymerization tanks or reactor continues to deliver to the demonomerization operation usually, so that remove monomer and other volatile components.Method as demonomerization has following several, one or two extrusion machine having venting hole as use, in heating, normal pressure or decompression down from venting hole remove the method for volatile component, the rotating cylinder of the interior plate wing well heater that centrifugal type is housed or vaporizer, remove volatile component method, with thin-film evaporators such as centrifugal type remove volatile component method, use multi tube heat exchanger, utilize waste heat, the foaming back method that volatile component is removed in flash distillation in vacuum tank.Can use above-mentioned any a kind of method, but preferably use single shaft or double-shafted extruder with venting hole.
Can take not use the thermopolymerization of initiator during the continuous bulk polymerization of multipolymer (A), also can take to use the initiator polymerization of initiator, in addition can and with thermopolymerization and initiator polymerization.Can use superoxide or azo based compound as initiator.
Can enumerate benzoyl peroxide, cumene peroxide, dicumyl peroxide, dicumyl peroxide, tert-butyl peroxide, tertiary butyl cumyl peroxide, tert-butyl hydroperoxide acetyl, tert-butyl hydroperoxide benzoyl, tert-butyl hydroperoxide sec.-propyl carbonic ether, ditertiary butyl peroxide, the tertiary butyl as the concrete example of superoxide and cross monooctyl ester, 1, two (t-butyl peroxy) 3,3 of 1-, 5-trimethyl-cyclohexane, 1, two (t-butyl peroxy) hexanaphthenes of 1-, t-butyl peroxy-2-ethylhexanoate etc.Wherein particularly preferably be cumene peroxide and 1, two (t-butyl peroxy) 3,3 of 1-, 5-trimethyl-cyclohexane.Concrete example as the azo based compound can be enumerated, Diisopropyl azodicarboxylate, azo two (2, the 4-methyl pentane nitrile), 2-phenylazo--2,4-dimethyl-4-methoxyl group valeronitrile, 2-cyano group-2-propyl group azoformamide, 1,1 '-azo bicyclohexane-1-nitrile, azo two (4-methoxyl group-2,2,2 the 4-methyl pentane nitrile), '-azo-bis-iso-dimethyl, 1-tertiary butyl azo-1-cyanocyclohexanoic alkane, 2-tertiary butyl azo-2-cyano group butane and 2-tertiary butyl azo-2-cyano group-4-methoxyl group-4-methylpentane etc.When using these initiators, can use a kind, perhaps also with more than 2 kinds.Wherein preferably 1,1 '-azo bicyclohexane-1-nitrile.
In order to regulate the polymerization degree of the multipolymer (A) that uses among the present invention, can use the chain-transfer agent of mercaptan, terpenes etc., its concrete example can enumerate n-octyl mercaptan, uncle's lauryl mercaptan, n-dodecyl mercaptan, n-tetradecane base mercaptan, just-Stearyl mercaptan, terpinolene etc.When using these chain-transfer agents, can use more than a kind or 2 kinds and usefulness.Wherein particularly preferred n-octyl mercaptan, uncle's lauryl mercaptan, the n-dodecyl mercaptan of being to use.
The multipolymer that uses among the present invention (A) is to use the continuous bulk polymerization manufactured, but also can use the solvent of a small amount of (for example below 20%) to carry out polymerization, and this is also included within the scope of the present invention.
Another constituent graft copolymer (B) that uses among the present invention is that to make by aromatic vinyl be that monomer 10-100 weight %, cyano group vinyl monomer 0-50 weight %, (methyl) acrylic ester monomer 0-80 weight % and the monomer mixture 95-20 weight part that can form with other vinyl monomers 0-60 weight % of these copolymerization and rubbery polymer 5-80 weight part carry out graft polymerization reaction and the multipolymer that obtains, carry out grafting but there is no need full dose, use usually and the mixture that does not have the grafted multipolymer.To the percentage of grafting of graft copolymer (B) without limits, but preferably use the preferred use of 5-150% 10-100 weight %.Percentage of grafting calculates by following formula.
Percentage of grafting (weight %)=(graft weight/rubbery copolymer weight) * 100
The ratio of rubbery polymer in the graft copolymer (B) is considered from the resin combination physical strength, tone and the plasticity that obtain, is the 5-80 weight part, preferably 20-70 weight %.Each monomeric usage ratio beyond the rubbery polymer of graft copolymer (B) is that aromatic vinyl is monomer 10-100 weight %, cyano group vinyl monomer 0-50 weight %, (methyl) acrylic ester monomer 0-80 weight % and can with other vinyl monomers 0-60 weight % of these copolymerization, more preferably (1) aromatic vinyl is a monomer 60-100 weight, cyano group vinyl monomer 10-40 weight % and (methyl) acrylic ester monomer 0-60 weight %, perhaps (2) aromatic vinyl is monomer 20-60 weight %, cyano group vinyl monomer 0-30 weight % and (methyl) acrylic ester monomer 40-80 weight %.
Manufacture method to graft copolymer (B) does not have special restriction, preferably letex polymerization or bulk polymerization, more preferably emulsion polymerisation process.
Here said emulsion polymerization is meant in the presence of rubbery polymer latex, with the method for vinyl monomer or monomer mixture emulsification graft polymerization.The emulsifying agent that uses during for emulsion polymerization does not have particular restriction, can use various tensio-active agents, and for example the negatively charged ion of carboxylic acid type, sulfuric acid type, sulfonate type etc. is that tensio-active agent is preferred especially the use.The concrete example of these emulsifying agents can be enumerated octylate, caprate, lauroleate, myristate, palmitate, the octadecane hydrochlorate, oleate, octadecadienoic acid salt, punicic acid salt, rosinate, behenic acid salt, the Viscotrol C sulfuric acid, the lauryl alcohol sulfuric acid, other higher alcohol sulfate salt, dodecylbenzene sulfonate, sulfonated alkyl naphathalene, alkyl diphenyl ether disulfonate, naphthalenesulfonate condensation compound, dialkyl sulfosuccinates, the polyoxyethylene lauryl sulfate, polyethylene oxide alkyl ethers vitriol and polyoxyethylene alkyl phenyl ether sulfate etc.Here said salt is meant that the concrete example of an alkali metal salt, ammonium salt etc., an alkali metal salt can enumerate sylvite, sodium salt and lithium salts etc.These emulsifying agents can use more than a kind or 2 kinds and use.
In addition,, listed initiator and chain-transfer agent in above-mentioned multipolymer (A) manufacturing can be enumerated, also reducto oxydative system can be used as initiator as employed initiator and chain-transfer agent in these emulsion grafting polymerizations.
Behind the graft copolymer (B) with the letex polymerization manufacturing, then add peptizer, the coagulum layer reclaims graft copolymer (B).Can use acid or water-soluble salt as peptizer, its concrete example can be enumerated sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, calcium chloride, magnesium chloride, bariumchloride, aluminum chloride, sal epsom, Tai-Ace S 150, exsiccated ammonium alum, potassium aluminium sulfate and aluminium sodium sulfate etc.These peptizer can use the mixture more than a kind or 2 kinds.
The graft copolymer (B) that has been solidified gives earlier and adding in the multipolymer (A) of molten state through dehydration, drying layer.Above-mentioned dehydration, dry preferably with the graft copolymer (B) of cakey slurries or moisture filter cake shape in giving dehydration earlier and in air or nitrogen gas stream, carry out or it is supplied to extruder assembly with ditch, hole or gap that fraction is passed through and venting hole.This dehydration, exsiccant squeezing device are to be made of spiral, cylinder body, screw drives parts, and preferably cylinder body has heating, refrigerative ability.And the forebody of cylinder body (supply side) has fraction is passed through, and the intransitable ditch of most of solids component, hole or gap, latter half of go up (outlet side) has more than one venting hole, and single shaft extrusion machine or double-shafted extruder can.Supply with the graft copolymer (B) of slurries or moisture filter cake shape to this squeezing device, in the rotation of the low-temperature region (forebody) of cylinder body by spiral, material is compressed, after most water is discharged from ditch, hole or the gap of cylinder body forebody (supply side), in the heating region of cylinder body latter half of (outlet side), remaining moisture and volatile component are discharged from venting hole, supply with multipolymer (A) continuously from the top of cylinder body.Venting hole can be under the normal pressure or also can be in decompression down, and then, also can and with 2 above normal pressures and decompression exhaust hole.
In addition, graft copolymer (B) also can be used the mass polymerization manufactured.During with the mass polymerization manufactured, the graft copolymer (B) of the molten state of coming out from the demonomerization machine directly can be added to the multipolymer (A), perhaps will give earlier single from graft copolymer (B) add in the multipolymer (A), consider that from the serialization that prevents thermal degradation when and technology preferably the graft copolymer (B) of the molten state that will come out from the demonomerization machine directly adds to (A).
In the multipolymer (A) of the molten state that obtains with bulk technique of the present invention, add graft copolymer (B) continuously after, be necessary to mix, by such processing just can obtain tone, anti-in good resin combination such as hitting property.And at this moment, be necessary to add graft copolymer (B) 90-5 weight part in multipolymer (A) the 10-95 weight part in molten state continuously, more preferably in multipolymer (A) 30-95 weight part, mix behind the graft copolymer (B) of interpolation 70-5 weight part continuously.The interpolation of graft copolymer this moment (B) is after the demonomerization operation or demonomerization operation in the bulk technique of multipolymer (A), when remaining monomer is to be preferably 5% below 10% to carry out following the time, in the later like this demonomerization operation, rubber constituent can be owing to thermal process deterioration, and make the tone, shock-resistance etc. of feature of the present invention further improve.In addition, in the present invention, mix after in multipolymer (A), continuously adding graft copolymer (B), if with melting mixing owing to the rerum natura that more can fully show shock-resistant grade, so more preferred.The melting mixing of this moment can be carried out when add mixing, also can the mixture list from after, for example carry out during melt-shaping.
Continuous addition means to graft copolymer (B) does not have special restriction, can adopt addition means arbitrarily.Usually can use various charging process, for example belt-type charging, spiral charging, single shaft extrusion machine, double-shafted extruder etc.But preferably use single shaft extrusion machine and double-shafted extruder.These continuous adding sets preferably can be quantitative.In addition, preferably on the adding set heating unit is arranged continuously, when graft copolymer (B) was made semi-melting or molten state interpolation, its admixture more can be good.For reaching this purpose, can use extrusion machine that has heating unit etc.
Among the present invention, also can further cooperate the strongthener of lubricant, softening agent, tinting material, weighting agent, glass fibre, carbon fiber etc. of the weather agent, static inhibitor, ethene bis-stearamides, metal base etc. of the various antioxidants, UV light absorber, photostabilizer etc. of phenol system, phosphorus system, sulphur system etc. and fire retardant etc. as required.
[embodiment]
Below, explain the present invention with embodiment, but the invention is not restricted to these embodiment.In addition, used " % " of present embodiment reaches that " part " is represented weight % and weight part respectively.The colour-difference meter that particulate YI value is to use ス ガ trier (strain) to make is measured yellow index (YI value).Lzod impact strength is measured according to ASTM638 according to ASTMD 256 mensuration, tensile strength.
Reference example 1 (manufacture method of graft copolymer)
With polybutadiene latex (as micelle subsystem 0.3 μ m, gel content 85%) 50 parts (being converted into solid formation branch), 200 parts of pure water, 0.4 part of sodium sulfoxylate formaldehyde, 0.1 part in ethylene dinitrilotetra-acetic acid sodium, ferrous sulfate (0.01 part) and sodium phosphate join in the reaction vessel for 0.1 part, behind the nitrogen replacement, temperature adjustment to 65 ℃, under agitation, in 4 hours, splash into 35 parts of vinylbenzene continuously, the mixture that 15 parts of vinyl cyanide and n-dodecyl mercaptan are 0.3 part, simultaneously, abreast, in 5 hours, splash into 0.25 part of cumene peroxide continuously, mixture as 25 parts of 2.5 parts of the sodium laurates of emulsifying agent and pure water, drip end after, kept 1 hour, polymerization ends.
Latex with polymerization ends solidifies with 1.5% sulfuric acid, then, with the alkali neutralization, clean, centrifugal dewatering, use fluidised bed drying machine, in heating nitrogen flows, be dried to water ratio below 3%, prepare pulverous graft copolymer (B-1).With the graft copolymer powder (B-1) that obtains, with the methylethylketone extraction, the percentage of grafting of mensuration is 45%.
Reference example 2 (manufacture method of graft copolymer)
With reference example 1 in the same manner, make graft polymer latex, after this latex is solidified with 1.5% sulfuric acid, with the alkali neutralization, clean, with the filtration device dehydration, prepare the graftomer filter cake (B-2) of water ratio 60-80%.
Reference example 3-9 (manufacture method of graft copolymer)
Identical with reference example 1, in the presence of various rubbery polymers, the mixture of polymerizing styrene and other vinyl monomer, preparation is by the graft copolymer powder of forming shown in the table 3 (B-3～9).In addition, the PBD in the table 3 represents that the identical polybutadiene rubber, the SBR that use with reference example 1 represent to be represented to be represented by acrylonitrile/butadiene copolymer rubber, EPDM that vinyl cyanide 25% and divinyl 75% are formed by styrene/butadiene copolymers rubber, NBR that vinylbenzene 25%, divinyl 75% are formed the ethylene/propene/5-ethylidene-2-norbornene ter-polymer rubber (ethylene/propene=68.5/31.5 mol ratio) of iodine number 23, mooney viscosity 60.
Reference example 10 (manufacture method of graft copolymer)
Except the usage quantity of polybutadiene rubber is become 70 parts (being converted into solid formation branch), cinnamic usage quantity is become 21 parts, the usage quantity of vinyl cyanide is become 9 parts from 15 parts from 35 parts from 50 parts, other and reference example 1 carry out converging operation identically, obtain latex.Solid formation at this latex divides in 25 parts, adds 25 parts of vinylbenzene, after fully stirring, adds 0.8 part in sal epsom.With mixed solution, the polymer/monomer phase (emulsus) of an extracting waste adds 0.03 part of 29 parts of vinylbenzene, vinyl cyanide 21 minutes, 0.15 part of n-dodecyl mercaptan and cumene peroxide, makes homogeneous solution (stock liquid).Then, stock liquid is joined continuously in the polymerization tank of chuck, this polymerization tank has spiral banding pattern stirring arm, directly be provided with to coagulate condenser and standing separation device with top with connecting and water is taken out outside the paradigmatic system mutually from the following of separator, can only take out monomer and turn back to polymerization tank from last phase.The adding speed of stock liquid, when successive polymerization is stablized, the polymerization reaction mixture of the polymer concentration in the polymerization tank 75% is taken out continuously, join in the biaxial extruder with venting port, under 180～240 ℃ from the vacuum venting mouth, remove remaining monomer, obtain graft copolymer (B-10).
Reference example 11 (manufacture method of graft copolymer)
With 10 parts of diolefine NF35A (Asahi Chemical Industry's (strain) system solid shape divinyl rubber), be dissolved in 90 parts of the vinylbenzene after, carry out continuous bulk polymerization/demonomerization, obtain the graft copolymer (B-11) of rubber constituent 15%.
Reference example 12 (manufacture method of graft copolymer)
Diolefine NF35A10 part is dissolved in 90 parts of the monomer mixtures be made up of vinylbenzene 70% and vinyl cyanide 30%, carries out continuous bulk polymerization/demonomerization then, obtain the graft copolymer (B-12) of rubber constituent 10%.
Embodiment 1
Use by 2 grooves with specification shown in the table 1 and give hot device, demonomerization machine and have be serially connected in apart from demonomerization machine top 1/3 long sleeve place, extrude the continous way mass polymerization device that the type feeder is formed by two bars of heating unit, will be by 70 parts of vinylbenzene, 30 parts of vinyl cyanide and 0.15 part of monomer mixture of forming of n-octyl mercaptan, speed during with 135kg/ is supplied with the 1st polymerization tank continuously, carries out continuous bulk polymerization.The percent polymerization of the 1st polymerization tank is 58-61%, the 2nd polymerization tank come out polymkeric substance, be controlled between the 90-91% and turn round.Polymerization reaction mixture, from venting port, extrude type demonomerization machine reduction vaporization by single pole and reclaim unreacted monomer, 1/3 place, top at the demonomerization machine, as seen the percent polymerization on apparent rises to 98%, in remaining monomer is 2% styrene/acrylonitrile copolymer, under the semi-melting state, speed during with 65kg/, extrude the type feeder from two bars, during when adding is the tert-butyl hydroxytoluene 0.15kg/ of stablizer as phenol and as three (nonyl phenyl) phosphoesterase 30 .15kg/ of the stablizer of phosphorus system and the graft copolymer powder (B-1) made of reference example 1, in the demonomerization machine, after carrying out melting mixing with styrene/acrylonitrile copolymer, and then, from venting port, reduction vaporization reclaims unreacted monomer, when apparent percent polymerization is 99% when above, after the outflow of monofilament shape ground, by cutting off, obtain the styrene resin composite particle.
The YI value of the styrene resin composite that obtains is as shown in table 4.In addition, the injection forming sheet of the styrene resin composite that shaping obtains, it measures the result of rerum natura, and is as shown in table 4.Show that as table 4 with the styrene resin composite that the inventive method is made, its tone, rerum natura are all good.
Embodiment 2
Except the graft copolymer block (B-2) that reference example 2 is made, by the single shaft forcing machine with water flowing gap and 2 venting holes dewater, drying, at the semi-melting state, speed during with 65kg/ is supplied with, outside the graft copolymer powder (B-1) that replaces embodiment 1, other and embodiment 1 carry out identically, obtain the styrene resin composite particle.The physical property measurement result of the test piece that obtains behind the YI value of the styrene resin composite that obtains and the injection-molded resin composition is as shown in table 4.Show that from table 4 the tone transitivity of the styrene resin composite made from the inventive method is all good.
Embodiment 3-12
Except extruding the type feeder with warmed-up 2, the graft copolymer (B-3～12) that reference example 3-12 makes is under the semi-melting state, outside speed supply as shown in table 4, other and embodiment 1 are identically, with styrene/acrylonitrile, by continuous bulk polymerization/demonomerization machine, reduction vaporization reclaims unreacted monomer and reaches in the demonomerization machine, with styrene/acrylonitrile copolymer and graft copolymer carry out fusion, mixing after, flow out with monofilament shape ground, obtain the styrene resin composite particle.The physical property measurement result of the test piece that obtains behind the YI value of the styrene resin composite that obtains and the injection-molded resin composition, as shown in table 4.Show that as table 4 tone, the rerum natura of the styrene resin composite made from the inventive method are all good.
Embodiment 13
Use the continous way mass polymerization device identical with embodiment 1, the monomer mixture with 100 parts of vinylbenzene and 0.15 part of composition of tert-butyl mercaptan with the speed of 135kg/h, supplies to the 1st polymerization tank continuously, and carries out polymerization continuously.The percent polymerization that the 1st polymerization tank comes out is 67-70%, and the percent polymerization that the 2nd polymerization tank comes out is controlled between the 90-91% and turns round.Polymerization reaction mixture and embodiment 1 are in the same manner, extruding type with single pole gives after hot machine gives heat, extrude type demonomerization machine with two bars, with unreacted monomer, carrying out underpressure distillation from venting port reclaims, at 1/3 place, demonomerization machine top, the percent polymerization on apparent rises to 96%, in remaining monomer is 4% styrene polymer, under the semi-melting state, speed with 65kg/h, extrude the type feeder from warmed-up pair of bar, add the graft copolymer (B-5) that tert-butyl hydroxytoluene 0.15kg/h and reference example 5 are made, in the demonomerization machine, carry out melting mixing with styrene polymer, and then from venting port, reduction vaporization reclaims unreacted monomer, when apparent percent polymerization is 99% when above, after monofilament shape ground flows out,, obtain the styrene resin composite particle by cutting off.
The physical property measurement result of the test piece that obtains behind the YI value of the styrene resin composite that obtains and the injection-molded resin composition is as shown in table 4.
Embodiment 14
Use is by 1 groove with specification shown in the table 2 and give hot device, demonomerization machine and have the continuous bulk polymerization device that the two bar forcing machine feeders by heating unit that are serially connected in apart from demonomerization machine top 1/3 long sleeve place are formed, will be by 67 parts of vinylbenzene, 33 parts of vinyl cyanide, 0.18 part of n-octyl mercaptan and 0.01 part of monomer mixture of forming of tert-butyl superoxide speed with 135kg/h, supply with polymerization tank continuously, and carry out polymerization continuously.The percent polymerization that polymerization tank comes out is controlled between the 74-76%, turns round.Polymerization reaction mixture, single pole extrude type give give heat in the hot machine after, extrude type demonomerization machine by two bars, with unreacted monomer, from venting port, carrying out underpressure distillation reclaims, at 1/3 place, top of demonomerization machine, the percent polymerization on apparent rises at 98% o'clock, in remaining monomer is 2% styrene/acrylonitrile copolymer, adding is the tert-butyl hydroxytoluene 0.15kg/h of stablizer as phenol and is three (nonyl phenyl) phosphoesterase 30 .15kg/h of stablizer as phosphorus, under the semi-melting state, supply with the graft copolymer (B-7) that reference example 7 is made with the speed of 65kg/h, in the demonomerization machine simultaneously, carry out melting mixing with styrene/acrylonitrile copolymer, and then, with unreacted monomer,, carry out reduction vaporization and reclaim from venting port, apparent percent polymerization is made particle after reaching more than 99%.
The physical property measurement result of the test piece that styrene resin composite particulate YI value that obtains and injection-molded resin composition obtain, as shown in table 4.
Embodiment 15
Use the continuous bulk polymerization device identical with embodiment 14, will be by 49 parts of vinylbenzene, 21 parts of vinyl cyanide, 30 parts of N-phenylmaleimides, 10 parts of toluene and 0.18 part of n-octyl mercaptan and 0.01 part of monomer/solvent mixture of forming of tert-butyl superoxide, speed with 135kg/h, supply in the polymerization tank continuously, and carry out polymerization continuously.The percent polymerization that polymerization tank comes out is controlled between the 74-76% and turns round.Polymerization reaction mixture, single pole extrude type give give heat in the hot machine after, extrude type demonomerization machine by two bars, from venting port, unreacted monomer and toluene are carried out the underpressure distillation recovery, 1/3 place, top at the demonomerization machine, percent polymerization on apparent rises to 98%, in remaining monomer is styrene/acrylonitrile/N-phenyl maleimide amine copolymer thing of 2%, add tert-butyl hydroxytoluene 0.15kg/h and three (nonyl phenyl) phosphoesterase 30 .15kg/h and under the semi-melting state, supply with the graft copolymer (B-1) that reference example 1 is made with the speed of 65kg/h, in the demonomerization machine, carry out melting mixing with styrene/acrylonitrile/N-phenylmaleimide multipolymer, and then, from venting port, unreacted monomer is carried out reduction vaporization reclaim, apparent percent polymerization reaches after 99%, makes particle.
The physical property measurement result of the test piece that the YI value of the imide series resin particle that obtains and injection-molded resin composition obtain, as shown in table 4.
Comparative example 1
Use is by 2 of polymerization tanks with specification shown in the table 1 and give hot device and continous way mass polymerization device that the demonomerization machine is formed, will be by 70 parts of vinylbenzene, 30 parts of vinyl cyanide and 0.18 part of monomer mixture of forming of n-octyl mercaptan, with the speed of 135kg/h, join continuously in the 1st polymerization tank, and carry out polymerization continuously.The percent polymerization of the polymkeric substance that the percent polymerization that the 1st polymerization tank comes out is controlled between the 58-61%, the 2nd polymerization tank comes out is controlled between the 90-91% and turns round.Polymerization reaction mixture is extruded type demonomerization machine by two bars, from venting port, unreacted monomer is carried out underpressure distillation reclaim, and apparent percent polymerization reaches 99% when above, and the outflow of monofilament shape ground is made particle by cut-out.With the styrene/acrylonitrile copolymer particle that obtains and the graft copolymer made from reference example 1 (B-1), with the ratio shown in the table 4, carry out dry blending after, carry out melting mixing/extrude granulating again after, obtain the styrene resin composite particle.The physical property measurement result of the test piece that styrene resin composite particulate YI value that obtains and injection-molded resin composition obtain, as shown in table 4.Comparison shows that with embodiment the tone (particle YI) of the styrene resin composite made from this comparative example is poor.
Comparative example 2
The monomer mixture that will be grouped into by 70 parts of vinylbenzene, 30 parts of vinyl cyanide and uncle-lauryl mercaptan 0.18; carry out suspension polymerization; after dehydrating; with styrene/acrylonitrile copolymer bead-like body that obtains and the graft copolymer made from reference example 1 (B-1); with ratio as shown in table 4, carry out dry blending after, carry out melting mixing/extrude; after the granulating, obtain the styrene resin composite particle.The physical property measurement result of the test piece that styrene resin composite particulate YI value that obtains and injection-molded resin composition obtain, as shown in table 4.Comparison shows that with embodiment the tone (particle YI) of the styrene resin composite made from this comparative example is poor.
Comparative example 3
Use the continous way mass polymerization device identical with embodiment 1, the speed that to close anti-135kg/h by 49 parts of vinylbenzene, 21 parts of vinyl cyanide, 30 parts of N-phenylmaleimides, 10 parts of toluene and 0.18 part of n-octyl mercaptan and 0.01 part of monomer/solvent of forming of tert-butyl superoxide, join in the polymerization tank continuously, and carry out successive polymerization.The percent polymerization that polymerization tank comes out is controlled between the 74-76%, also running.Polymerization reaction mixture, in the single pole forcing machine, give heat after, from venting port, extrude type demonomerization machine with two bars, with unreacted monomer and toluene carry out that underpressure distillation is reclaimed, apparent percent polymerization reaches 99% when above, the outflow of monofilament shape ground, by cutting off, make particle.With styrene/acrylonitrile/N-phenylmaleimide copolymer pellet that obtains and the graft copolymer made from reference example 1 (B-1), with ratio as shown in table 4, carry out dry blending after, carry out melting mixing/extrude again, after the granulation, obtain imide series resin composition pellet material.The physical property measurement result of the test piece that styrene resin composite particulate YI value that obtains and injection-molded resin composition obtain, as shown in table 4.Comparison shows that with embodiment the tone (particle YI) of the imide series resin combination made from this comparative example is poor.
Comparative example 4
Except the feed rate with the graft copolymer (B-1) of embodiment 1 was taken as 5kg/h, other and embodiment 1 were identical, obtain composition of styrene resin.The physical property measurement result of the test piece that styrene resin composite particulate YI value that obtains and injection forming composition of styrene resin obtain, as shown in table 4.Comparison shows that with embodiment the impact strength of the styrene resin composite made from this comparative example is poor.
Comparative example 5
Except the feed rate with the monomer mixture of the vinylbenzene of embodiment 1 and vinyl cyanide is taken as 9kg/h.The feed rate of graft copolymer (B-1) is taken as outside the 92kg/h, and other are identical with embodiment 1, obtain styrene resin composite.The physical property measurement result of the test piece that styrene resin composite particulate YI value that obtains and injection forming composition of styrene resin obtain, as shown in table 4.Comparison shows that with embodiment the tensile strength of the styrene resin composite made from this comparative example is poor.
[table 1] poly-unit specification
| The 1st polymerization tank | The 2nd polymerization tank | |
| Stirring-type | Complete mixed type with spiral shape blade | Plug flow type with multistage orifice plate and paddle |
| Temperature (℃) | 115 | 155 bottoms 195,130 middle parts, top |
| Pressure (kg/cm 2G) | 0.9 | 1.2 |
| Refrigerating unit | The evaporation reflux exchanger that has chuck and monomer vapours | |
The specification of [table 2] poly-unit
| Stirring-type | Have the complete mixed type of spiral shape blade |
| Temperature (℃) | 135 |
| Pressure (kg/cm 2G) | 0.9 |
| Refrigerating unit | The evaporation that has chuck and monomer vapours refluxes and coagulates condenser |
[table 3]
| Reference example No. | Graft copolymer No. | Graft copolymer (weight %) | Percentage of grafting (weight %) | |||||
| Rubber polymer | Vinylbenzene | Vinyl cyanide | Methyl methacrylate | N-phenylmaleimide | ||||
| The rubber kind | Content | |||||||
| 1 | B-1 | PBD | 50 | 35 | 15 | 45 | ||
| 2 | B-2 | PBD | 50 | 35 | 15 | 45 | ||
| 3 | B-3 | PBD | 45 | 42 | 13 | 55 | ||
| 4 | B-4 | PBD | 45 | 26 | 12 | 17 | 58 | |
| 5 | B-5 | PBD | 60 | 40 | 20 | |||
| 6 | B-6 | PBD | 45 | 17 | 3 | 35 | 40 | |
| 7 | B-7 | NBR | 60 | 18 | 12 | 30 | ||
| 8 | B-8 | SBR | 50 | 37 | 13 | 40 | ||
| 9 | B-9 | EPDM | 40 | 45 | 15 | 45 | ||
| 10 | B-10 | PBD | 23 | 55 | 22 | 60 | ||
| 11 | B-11 | PBD | 10 | 90 | 80 | |||
| 12 | B-12 | PBD | 10 | 63 | 27 | 90 | ||
[table 4]
| Embodiment No. | Multipolymer zoarium (%) | Particle YI value | |||||||||
| Form (weight %) | Feed rate kg/ Time | Remaining amount of monomer (weight %) | Seed Class | Feed rate (kg/ Time) | Blending means | Dust Zuo Shi Red Finding-stuff Strong degree (kgcm/cm) | Draw intensity (kg/cm 2) | ||||
| Vinylbenzene | Vinyl cyanide | N-phenylmaleimide | |||||||||
| EXAMPLE l | 70 | 30 | 135 | 2 | B-1 | 65 | Behind multipolymer (A) demonomerization | 22 | 25 | 400 | |
| Embodiment 2 | 70 | 30 | 135 | 2 | B-2 | 65 | The same | 23 | 24 | 410 | |
| Embodiment 3 | 70 | 30 | 135 | 2 | B-3 | 65 | The same | 21 | 23 | 430 | |
| Embodiment 4 | 70 | 30 | 135 | 2 | B-4 | 65 | The same | 25 | 15 | 450 | |
| Embodiment 5 | 70 | 30 | 135 | 2 | B-5 | 65 | The same | 20 | 12 | 450 | |
| Embodiment 6 | 70 | 30 | 135 | 2 | B-6 | 65 | The same | 21 | 20 | 420 | |
| Embodiment 7 | 70 | 30 | 135 | 2 | B-7 | 65 | The same | 24 | 15 | 450 | |
| Embodiment 8 | 70 | 30 | 135 | 2 | B-8 | 65 | The same | 22 | 19 | 410 | |
| Embodiment 9 | 70 | 30 | 135 | 2 | B-9 | 65 | The same | 23 | 14 | 430 | |
| Embodiment 10 | 70 | 30 | 135 | 2 | B-10 | 65 | The same | 19 | 11 | 450 | |
| Embodiment 11 | 70 | 30 | 135 | 2 | B-11 | 65 | The same | 17 | 8 | 460 | |
| Embodiment 12 | 70 | 30 | 135 | 2 | B-12 | 65 | The same | 18 | 10 | 450 | |
| Embodiment 13 | 100 | 135 | 4 | B-5 | 65 | The same | 20 | 15 | 440 | ||
| Embodiment 14 | 76 | 33 | 135 | 2 | B-7 | 65 | The same | 21 | 20 | 410 | |
| Embodiment 15 | 49 | 21 | 33 | 135 | 2 | B-1 | 65 | The same | 28 | 17 | 440 |
| Bi More example 1 | 70 | 30 | 135 | - | B-1 | 65 | Do and mix | 32 | 25 | 400 | |
| Bi More example 2 | 70 | 30 | 135 | - | B-1 | 65 | Do and mix | 35 | 25 | 410 | |
| Bi More example 3 | 49 | 21 | 33 | 135 | - | B-1 | 65 | Do and mix | 42 | 11 | 450 |
| Bi More example 4 | 70 | 30 | 135 | - | B-1 | 5 | Behind the demonomerization of multipolymer (A) | 20 | 3 | 580 | |
| Bi More example 5 | 70 | 30 | 9 | - | B-1 | 92 | The same | 38 | 45 | 100 | |
Feature of the present invention is the resin that does not contain rubber constituent with the continuous bulk polymerization manufactured, and latter half of in the demonomerization operation when resin is in molten state, is added and mix the graft copolymer that contains rubber constituent.Therefore, as embodiment 1-15 is described, can obtain the good resin combination of color harmony physical strength.In addition, use manufacture method of the present invention, can reduce draining and handle, and then reduce manufacturing process, reduce cost.
Claims (10)
1. the manufacture method of an impact resistance resin composition is characterized in that, add the graft copolymer (B) of 90-5 weight part continuously to the molten multipolymer (A) of 10-95 weight part, and make its mixing,
Described multipolymer (A) makes
Aromatic vinyl be monomer 20-100 weight %,
Cyano group vinyl monomer 0-60 weight %,
Methacrylate ester monomer 0-80 weight % and
Can with other vinyl monomers 0-60 weight % of these monomer copolymerizations
The monomer mixture of being formed carries out the multipolymer (A) of the molten state in the technology of continuous bulk polymerization;
Described multipolymer (B) is in the presence of 5-80 parts by weight of rubber shaped polymer, and the following monomer mixture that makes the 95-20 weight part is carried out graftomer and the graft copolymer (B) that obtains, and the described monomer mixture that carries out graft polymerization is:
Aromatic vinyl be monomer 10-100 weight %,
Cyano group vinyl monomer 0-50 weight %,
Methacrylate ester monomer 0-80 weight % and
Can with other vinyl monomers 0-60 weight % of these monomer copolymerizations.
2. the manufacture method of the described impact resistance resin composition of claim 1, wherein, slurries that described graft copolymer (B) obtains emulsion polymerization latex or moisture filter cake dehydrate through in advance and obtain.
3. the manufacture method of claim 1 or 2 described impact resistance resin compositions, wherein, graft copolymer (B) dewaters, carries out dry back in advance with slurries or the moisture filter cake that is obtained by emulsion polymerization latex and obtains in air or stream of nitrogen gas.
4. the manufacture method of claim 1 or 2 described impact resistance resin compositions, wherein, graft copolymer (B) is after the slurries that will be obtained by emulsion polymerization latex or moisture filter cake supply to the squeezing device with ditch, hole or gap that liquid is passed through and venting hole, dehydrates to obtain.
5. the manufacture method of claim 1 or 2 described impact resistance resin compositions wherein, is a multipolymer (A) below the 10 weight % to remaining amount of monomer, adds graft copolymer (B) continuously.
6. the manufacture method of claim 1 or 2 described impact resistance resin compositions, wherein, in the monomer operation at the continuous bulk polymerization of multipolymer (A) or after the demonomerization operation, remaining amount of monomer is that the following multipolymer (A) of 10 weight % adds graft copolymers (B).
7. the manufacture method of claim 1 or 2 described impact resistance resin compositions wherein, is added graft copolymer (B) with semi-melting or molten state.
8. the manufacture method of claim 1 or 2 described impact resistance resin compositions, wherein, the rubbery polymer of graft copolymer (B) is a diene series rubber.
9. the manufacture method of claim 1 or 2 described impact resistance resin compositions, wherein, multipolymer (A) is a styrene-acrylonitrile copolymer, multipolymer (B) is to make styrene-acrylonitrile be grafted on graft copolymer on the rubbery polymer.
10. the manufacture method of claim 1 or 2 described impact resistance resin compositions, wherein, the demonomerization operation of the continuous bulk polymerization of multipolymer (A) is to use the single shaft that has venting hole or double-shafted extruder to carry out, and the continuous adding set of graft copolymer (B) is single shaft or the two extrusion machine that is connected on the demonomerization extrusion machine of multipolymer (A).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB951203487A CN1150232C (en) | 1995-10-27 | 1995-10-27 | Making method of impact resistance resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB951203487A CN1150232C (en) | 1995-10-27 | 1995-10-27 | Making method of impact resistance resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1149592A CN1149592A (en) | 1997-05-14 |
| CN1150232C true CN1150232C (en) | 2004-05-19 |
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|---|---|---|---|
| CNB951203487A Expired - Lifetime CN1150232C (en) | 1995-10-27 | 1995-10-27 | Making method of impact resistance resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100360987B1 (en) | 2000-07-06 | 2002-11-18 | 주식회사 엘지화학 | Process for preparing thermoplastic transparent resin |
| FR2831546B1 (en) * | 2001-10-31 | 2007-03-23 | Atofina | THERMOPLASTIC POLYMER MATERIAL FOR AUDIO AND / OR OPTICAL INFORMATION RECORDING MEDIA |
| ATE426624T1 (en) * | 2003-02-05 | 2009-04-15 | Dow Global Technologies Inc | HIGH-GLOSS RUBBER-MODIFIED MONOVINYL AROMATE POLYMERS PRODUCED BY A BULK POLYMERIZATION PROCESS |
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