CN1295260C - Prepn process of emulsive interpenetrating thermoplastic elastomer - Google Patents
Prepn process of emulsive interpenetrating thermoplastic elastomer Download PDFInfo
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Abstract
The present invention relates to a preparation process of an emulsion interpenetrating network thermoplastic elastomer, which comprises the synthesis of a slightly crosslinked rubber elastomer seed emulsion, the synthesis of an interpenetrating network emulsion, agglomeration, drying and mixing granulation. The synthesis of the rubber elastomer seed emulsion comprises two steps: firstly, mixing seed emulsion monomers with a certain amount of crosslinking vinyl monomers with bifunctionality or multi-functionality, and controlling the use level range of a crosslinking agent to obtain the controlled rubber elastomer seed emulsion with low degree of crosslinking; dripping ethene thermoplastic polymer monomers (hard monomers) mixed with acrylonitrile in the slightly crosslinked seed emulsion, and adding a certain amount of emulsifying agents in the process of dripping the monomers. The emulsion interpenetrating network polymer with appropriate crosslinking density is obtained through the procedures of swelling, initiating polymerization, etc. Mother particles of the emulsion interpenetrating network thermoplastic elastomer are obtained through agglomeration, drying and granulation.
Description
Technical field
The present invention relates to process for preparation of thermoplastic elastomer, particularly relate to the method for the synthetic intercrossed network type thermoplastic elastomer of a kind of emulsion polymerization.
Background technology
Thermoplastic elastomer (TPE) is the class elastomer material that can realize thermoplasticity processing, because this particular performances, this elastomer material can utilize the equipment of processing plastic and method to realize highly-efficient processing, improved the processing efficient of elastomer material greatly, simultaneously can repeat processing and utilization easily again, belong to environment-friendly material.
At present, the main synthetic method of thermoplastic elastic material has anionic polymerization and dynamic blending sulfuration method.As SBS, SIS is the block polymer thermoplastic elastomer that adopts the method preparation of active anionic polymerization, the thermoplastic elastomer excellent performance of this material, the method of anionoid polymerization needs organic solvent, and the purity of monomer and solvent will reach the PPM level, also need expensive lithium alkylide as catalyzer, therefore production cost is higher, and the monomer system of adaptation is less, nonpolar monomer such as vinylbenzene, divinyl etc. more commonly used at present.With the dynamic vulcanization process is the blend polymer type thermoplastic elastomer of representative preparation, be meant and when rubber plastic blend, make the vulcanization of rubber, obtain thermoplastic elastomer, but the structure of this material and performance all are not easy control, the elasticity and the contradiction between the intensity of material are big, and tension set mostly is the problem that solves well of always failing.
Utilize method of emulsion polymerization synthetic thermoplastic elastomerics, method that can be by Multi-stage seed emulsion polymerization is at tens polymer complexes that obtain controllable structure to the submicroscopic yardstick of hundreds of nanometer, but present research field mainly concentrates in the scope of emulsion graft polymerization.Patent US4473679 discloses a kind of method of utilizing the method synthesis of acrylic ester thermoplastic elastomer of Multi-stage seed emulsion polymerization, this method is nuclear that contains the unitary hard polymer of reactive monomer (thermoplastics) of preparation earlier, these reactive groups provide further reactive activity point, be seed with this nuclear then, at its outside polymerization one deck transition layer, the component of polymer of transition layer is the monomer of nuclear and the monomeric multipolymer of shell.This transition layer will provide from a parents' that examine shell articulamentum, in the polymerization of the outside of transition layer a shell that contains the acrylic ester elastomer of function monomer, the function monomer in the shell be can with the mono-vinyl class monomer of function monomer in stratum nucleare reaction.In the course of processing, in the functional monomer unit in shell and the nuclear between the active group crosslinking reaction takes place, make between elastomerics and the hard polymer crosslinked together.This patent provides a kind of method that improves grafting efficiency, and the structure of synthetic thermoplastic elastomer belongs to graft copolymer, and its intensity is very low.
People such as Narkis are in document [Polym.Mater.Sci.Eng., 1991; 65:130-131.] and N.N.Michael, S.Silverstein, M.Narkis.In:S.C.Kim, L.H.Sperling (Edt.), IPNsAround the World:Science and Engineering, New York:John Wiley ﹠amp; Sons, Inc. in the document of 1997.pp.103-122., but proposes the elastomeric notion of emulsion intercrossed network type that thermoplasticity is processed.They are linking agent with the divinyl, and polymerization obtains crosslinked acrylic ester elastomer, are seed with this crosslinked emulsion again, add styrene monomer, the intercrossed network type thermoplastic elastomer of synthesis of acrylic ester polymkeric substance and polystyrene.It is linking agent acrylic acid synthesizing ester elastomer seed emulsion that this method is selected 5% divinyl for use, because the radical polymerization of divinyl has 1,2 polymerizations and 1,4 polymeric difference, and have only 1, just have under the 2 polymeric situations and realize crosslinked possibility, therefore the efficient of this linking agent is very low, because efficient is low, therefore in elastomerics synthetic process, the necessary excessive use of linking agent so just make that the cross-linking density of seed polymer is out of hand, and the mechanical property of cross-linking density and material has direct relation.
Summary of the invention
The technical problem to be solved in the present invention: when Multi-stage seed emulsion polymerization, control the cross-linking density of seed emulsion by the use of linking agent, regulate the polarity of hard monomer by composite hard monomer, thereby network structure between design and the control multiphase polymer makes material have the good thermoplasticity processing characteristics and the balance of strength and extension property.Provide a kind of seeded emulsion polymerization that can make polar monomer to be stablized the processing method of the high-intensity emulsion polymer intercrossed network type of the preparation of carrying out thermoplastic elastomer.
Main technical schemes: main points of the present invention are: the degree of crosslinking of control seed emulsion, monomer addition mode and order, and the polarity of control hard monomer, come the structure of controlling polymers network, the final mechanical property that realizes control material, present method comprises: synthetic rubber seed emulsion in the polymerization system that contains the monomer of seed emulsion (soft monomer), emulsifying agent, initiator; On the hevea seed emulsion after the monomeric swelling of vinyl thermoplastic polymer, further polymerization prepares interpenetrating network polymer emulsion; And cohesion, washing, dry, mixing granulator process, wherein during the synthetic rubber seed emulsion, in monomer, mix a certain amount of difunctionality or the vinyl-based cross-linking monomer of polyfunctionality, the amount ranges of control linking agent is at 0.1%～1.0% (to monomer mole ratio), make little crosslinked rubber latex cross-linking set spacing at 20 more than the structural unit, the number-average molecular weight of elastomer emulsions polymkeric substance obtains the rubber elastomer seed emulsion of controlled low crosslinking degree in 1,000,000 to 5,000,000 scope; Among little crosslinked seed emulsion, dropping is mixed with the vinyl thermoplastic polymer monomer (hard monomer) of vinyl cyanide, wherein, the ratio of vinyl cyanide is between 5%～95% (weight ratio), drip in the monomeric process and add emulsifying agent, and make the total emulsifiers consumption between 0.2～0.8% (with respect to total solid content, weight ratio), after 10～60 minutes the swelling process, utilize the radical initiator initiated polymerization, when transformation efficiency reaches 50～90% scope, add the emulsifying agent consumption and reach 1.0%, descend with the additional stability of emulsion that causes owing to the adding of polar monomer, keep the stable of letex polymerization to carry out.Under 45～80 ℃, be incubated 1～3 hour after, stop polyreaction, obtain the pellet of emulsion intercrossed network type thermoplastic elastomer then through breakdown of emulsion, drying, mixing granulator.
Above-mentioned rubber elastomer seed emulsion is acrylic elastomer emulsion, acrylonitrile-butadiene rubber latex, SBR emulsion, chloroprene rubber, silicon rubber emulsion, viton emulsion, aqueous polyvinyl acetate emulsion, polyaminoester emulsion.
Difunctionality that above-mentioned seeded emulsion polymerization uses or the vinyl-based cross-linking monomer of polyfunctionality are difunctionality or polyfunctionality (methyl) acrylate, Vinylstyrene, as: triethylene Glycol double methacrylate (TEGDA), tripropylene glycol double methacrylate (TPGDA) etc.
Above-mentioned vinyl thermoplastic polymer hard monomer is: vinylbenzene, methyl methacrylate, vinyl cyanide, (methyl) isobornyl acrylate, (methyl) vinylformic acid benzyl ester, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate or the like, and their mixture.
Contain the Vinylstyrene (DVB) of 0～0.3% (mol ratio) or polyfunctional acrylic ester etc. in the hard monomer of above-mentioned dropping.Its objective is that the degree of crosslinking with second polymkeric substance is controlled in the suitable scope.So that the segment of second polymkeric substance can have an opportunity to move in the network of first polymkeric substance, still can not from network, deviate from again, thus the mutual relationship between two kinds of polymkeric substance is defined as the relation of interpenetrating(polymer)networks.
The emulsifying agent of adding during above-mentioned dropping monomer is and the identical emulsifying agent of the used emulsifying agent of former seed letex polymerization, perhaps with the emulsifying agent of the composite use of original emulsifying agent.
Effect of the present invention: the present invention is the cross-linking efficiency height in the seeded emulsion polymerization process, can realize effective control to degree of crosslinking, the cross-linking set spacing that makes little crosslinked rubber latex is at 20 more than the structural unit, and the number-average molecular weight of elastomer emulsions polymkeric substance is in 100～5,000,000 scope.Thereby obtain the seed emulsion of controlled low cross-linking, help forming the polymer network of suitable degree of crosslinking.
The comprehensive polarity that the use polar acrylonitrile monemer that the present invention proposes is regulated the vinyl hard monomer is controlled geometrical dimension, form and the distribution in seed breast grain of microfacies effectively by the polarity of adjusting hard monomer.Prepare styrenic/Achievement of acrylate type thermo plastic elastomers as present method, styrenic polymer is that the form with the polymkeric substance microfacies of 20～120nm exists among the seed of acrylic ester polymer, the result of dsc analysis shows, is the relation of interpenetrating polymer networks between the polymkeric substance of hard monomer and the seed polymer.
The order of addition(of ingredients) that the present invention proposes, be fully on the basis of the little crosslinked seed emulsion of polymeric, drip hard monomer, make hard monomer in seed emulsion, fully permeate and swelling, in the swollen process, constantly in system, add emulsifying agent, to remedy owing to the new emulsifier concentration decline that monomer causes, the stability of maintenance emulsion of adding.
The present invention proposes adds linking agent in hard monomer, make second polymkeric substance lightly crosslinked, help forming firm interpenetrating(polymer)networks, make material in the course of processing, keep structural stability, therefore correspondingly stablize the strength and extension property of material, satisfied the needs that material repeats to process.
The polymerization technique of the synthetic rubber seed emulsion proceed step by step of the present invention's proposition by the control emulsifying agent, is stablized seeded emulsion polymerization and is carried out in addition, obtains particle diameter big (250nm), and the narrower seed emulsion of size distribution.
The abovementioned technology that the present invention taked, final effect are the emulsion interpenetrating net polymers (seeing shown in Figure 1) that forms suitable cross-linking density, thereby have improved the mechanical property of emulsion intercrossed network type thermoplastic elastomer greatly.Zhi Bei Achievement of acrylate type thermo plastic elastomers like this, tensile yield can reach more than 400%, and tensile strength at yield 12MPa is the foreign latest report with (2MPa) of analog thermoplastic elastomer 5～6 times, and tensile set is smaller or equal to 35%.
Description of drawings
Fig. 1 is little crosslinked poly-(vinylbenzene-CO-vinyl cyanide)/little crosslinked polypropylene acetoacetic ester (TEM photo of the single emulsion particle of xP (St-AN)/xPEA) system interpenetrating(polymer)networks emulsion;
Fig. 2 is little crosslinked poly-(vinylbenzene-CO-vinyl cyanide)/little crosslinked polypropylene acetoacetic ester (TEM photo of xP (St-AN)/xPEA) system intercrossed network type thermoplastic elastomer shaped material ultrathin section(ing).
Specific implementation method
Comprise following concrete steps
(1) preparation of elastomerics seed emulsion:
Required little crosslinked acrylic elastomer emulsion, acrylonitrile-butadiene rubber latex; SBR emulsion; chloroprene rubber; silicon rubber emulsion; viton emulsion; the preparation of elastomer emulsions such as aqueous polyvinyl acetate emulsion is the monomer from these emulsion polymers; in these monomers, add (methyl) acrylate of difunctionality or polyfunctionality; Vinylstyrene is as linking agent; obtain the emulsion of certain cross-linking density; for SBR emulsion; neoprene latex; in the polymerization process of viton emulsion, and employed linking agent is Vinylstyrene (DVB); double methacrylate etc.; Employed linking agent is generally polyfunctionality (methyl) acrylate in the building-up process for acrylic elastomer, as: triethylene Glycol double methacrylate (TEGDA), tripropylene glycol double methacrylate (TPGDA) triethylene Glycol double methyl methacrylate, two (methyl) acrylate of tirethylene glycol, ethylene glycol bis (methyl) acrylate, two (methyl) acrylate of propylene glycol, 1, two (methyl) acrylate of 4-butyleneglycol, the dihydroxyphenyl propane double methacrylate, two (methyl) acrylate of polymer with bis phenol A ethylene oxide ether, three vinylformic acid glyceryl ester, three (2-hydroxyethyl) isocyanuric acid triacrylate etc.Other elastomerics is selected corresponding cross-linking monomer for use according to particular case.According to the needs of different systems, the consumption of linking agent obtains the elastomer emulsions of the controlled low crosslinking degree of degree of crosslinking between 0.1%～1.0% (mol ratio).Crosslinking degree is the controlling factor of this elastomer performance, and generally more than 20 structural units, optimum value is in 500～1000 scope for its cross-linking set spacing, and the number-average molecular weight of elastomeric polymkeric substance is in 100～5,000,000 scope.In the seeded emulsion polymerization process, in order to obtain the seed emulsion of the narrow distribution of particle diameter, can be divided into two steps carries out, at first using in the presence of the 2.0%wt emulsifying agent sodium alkyl sulfate (SDS), water-soluble radical initiator causes the seed emulsion monomer polymerization, 50 ℃ of following polymerizations of polymerization temperature 2 hours, form small particle size seed emulsion I, the seed I of (weight ratio according to solid content is calculated) based on 2～15% then, continue to drip monomer, and additional emulsifying agent, the emulsifier concentration that keeps polymerization system continues the seed emulsion II that initiated polymerization obtained narrow size distribution in 2 hours 0.5～0.6%.These emulsifying agents comprise: anion surfactants such as alkyl-sulphate, alkylsulfonate, soap, nilox resin hydrochlorate, quaternary ammonium salts cats product.Dosage of surfactant is in the scope of 0.1～1.0% (weight ratio), because the consumption of tensio-active agent is very little, therefore, at aqueous phase, free emulsifying agent molecule is considerably less, and the hard monomer that newly adds system can not form the new micella of oneself, can only be penetrated among the seed breast grain.
(2) building-up process of emulsion interpenetrating net polymer
In the resulting little crosslinked seed emulsion of step (1), drip the monomer of vinyl thermoplastic material and the mixture of vinyl cyanide, purpose is the comprehensive polarity of regulating hard monomer with the polar acrylonitrile monemer, with the control swelling of hard monomer in seed emulsion and the process and the degree of IPN.For different systems, have only appropriate polar monomer just to have higher strength and extension property in the interpenetrating net polymer that seed polymer forms.Wherein the ratio of vinyl cyanide is between 5～95% (weight ratios), and for different seed emulsion, the ratio of vinyl cyanide changes to some extent, to reach the purpose of regulating polar intensity.In dripping the monomer process, to replenish and drip emulsifier solution to system, to keep the total emulsifiers consumption about 0.2%～0.8% (with respect to total solid content), after 10～60 minutes the swelling process, utilize the radical initiator initiated polymerization, initiator can be a redox initiation system, also can be the thermolysis initiator system, as: superoxide, persulphate or the like.In the time of between transformation efficiency reaches 50～90%, the emulsifying agent consumption is brought up to 1.0%,, remedy because the stability of emulsion that the adding of polar vinyl cyanide causes descends to increase the stability of emulsion.Stop polyreaction in insulation under 45～80 ℃ after 1～3 hour.Under 40～80 ℃, at 2%CaCl
2, dry under 30～100 ℃ of conditions in the solution with emulsion coagulation, obtain emulsion polymer.In the hard monomer that adds, contain cross-linking monomers such as Vinylstyrene, polyfunctional acrylic ester, to realize the lightly crosslinked of second polymkeric substance, crosslinked result makes to form more stable network relation between hard polymer and the elastomerics seed polymer, increases the stability of material in repeating the course of processing.The consumption of this linking agent is in the scope of 0～0.3% (mol ratio), and is unsuitable too high, to guarantee the strength and extension property of material.
(3) process of mixing granulator
With emulsion polymer granulation after under 100～200 ℃ of conditions mixing 5～30 minutes, obtain the pellet of emulsion intercrossed network type thermoplastic elastomer.
Embodiment 1: add emulsifying agent sodium alkyl sulfate (SDS) 5.0g in three mouthfuls of reactors of 1000ml, deionized water 325ml, get the acrylate monomer 250g that contains triethylene Glycol double methacrylate (TEGDA) linking agent, wherein the consumption of linking agent is 0.15% (mol ratio), splash among the reactor, logical nitrogen is after 20 minutes, under 50 ℃, slowly in reactor, drip 0.175g ammonium persulphate and 0.175g sodium sulfite solution simultaneously, drip off in 1 hour, then 60 ℃ of insulations 2 hours, transformation efficiency stops polymerization after 98%, behind the mensuration solid content, discharging is standby.In 1000 milliliters of three mouthfuls of reactors, adding seed I 12.5g (calculates according to solid content, about 38ml) adds deionized water 200ml, under uniform stirring velocity, get and last reacting phase monomer 237g together, splash among the reactor, dripping the monomeric while, in reactor, drip 1.0% solution of 1.25gSDS, drip off simultaneously with monomer.Under 50 ℃, utilize redox initiation system ammonium persulfate-sodium bisulfite initiated polymerization, about initiator amount 0.015% (mol ratio).After 1～3 hour, add the once initiator of above-mentioned equivalent in reaction under 60 ℃ again,, obtain little crosslinked acrylic elastomer seed emulsion (seed II) so that the residual monomers polymerization is complete.Get above-mentioned seed II emulsion 100g (calculating) according to solid content, after being diluted to solid content and being 15% (weight ratio) with deionized water, under stirring uniformly, drip second monomer (hard monomer) 33g at leisure to system, second monomer is the mixture of vinylbenzene and vinyl cyanide, and wherein vinyl cyanide and cinnamic ratio are about 1: 1 (weight ratio).Contain the divinyl benzene crosslinked agent of trace in second monomer, dosage of crosslinking agent is between 0.07% (mol ratio).The second monomeric consumption is 25% (pressing the final product weight ratio), is dripping for the second monomeric while, drips the 0.2gSDS aqueous solution in reactor, drips off synchronously with monomer; After dropwising, under 50 ℃, utilize redox initiation system: the ammonium persulfate-sodium bisulfite initiated polymerization, cause the back 60 ℃ of insulations down, when transformation efficiency reaches after 90%, in system, add 1.5gSDS.Stop polymerization after 3 hours.Shown in Fig. 1 electromicroscopic photograph, (using RuO4 dyeing in the photo, wherein the little xP of black part (St-AN) phase), in xPEA seed breast grain, xP (St-AN) is that the form with microfacies is dispersed among the seed breast grain mutually.The mean sizes of microfacies is about 90nm.Under 60 ℃, the CaCl 2%
2Condense emulsion in the solution, at 40～100 ℃ of following dry polymers, in 120～200 ℃ of following granulations and moulding.Zhi Bei Achievement of acrylate type thermo plastic elastomers like this, its mechanical property is: tensile yield 400%, tensile strength at yield 12MPa, tensile set 35%.The shaped material ultrathin section(ing) the TEM photo as shown in Figure 2, (use RuO4 dyeing, wherein black part is divided into xP (St-AN) phase) emulsion polymer constituted a tight integral material, and the microfacies of hard polymer has developed into the new microfacies of 175～200nm, and this explanation has taken place to reconfigure between the microfacies in the emulsion polymer in the forming process of material.The present invention is that the reorganization by microfacies forms the physical crosslinking between different elastomericss breast grains or the breast grain fragment.
Embodiment 2: add deionized water 350ml in 1000ml three mouth pressure reactors, in reactor, add nilox resin acid potassium 5.0g, diffusion agent N F 3.0g, get divinyl and cinnamic mixture 250g, wherein butylbenzene is than between 70/30 to 95/5, Vinylstyrene (DVB) linking agent that in mix monomer, contains 0.2% (mol ratio), splash among the reactor, under uniform stirring velocity, under about 5 ℃, utilize isopropyl benzene hydroperoxide 0.3 gram, ferrous sulfate 0.04 gram, sodium ethylene diamine tetracetate 0.1 gram, rongalite 0.2 gram initiator system initiated polymerization obtains little crosslinked styrene-butadiene rubber(SBR) seed I emulsion.
In the 1000ml pressurized vessel, taking by weighing above-mentioned seed I emulsion 18.8g (calculates according to solid content, about 63ml), add the 250ml deionized water, under agitation progressively drip the 170g monomer, the rapid used monomer of monomer and previous step is identical, drips the solution (1.0% of 1.12g emulsifying agent synchronously with monomer, about 112ml), drip off in one hour.Under about 5 ℃, utilize isopropyl benzene hydroperoxide 0.15 gram, ferrous sulfate 0.02 gram, sodium ethylene diamine tetracetate 0.05 gram, rongalite 0.1 gram initiator system initiated polymerization, obtain little crosslinked styrene-butadiene rubber(SBR) seed II emulsion.
In 1000ml four-hole reactor, add above-mentioned seed II emulsion 100g (calculating) according to solid content, after being diluted to solid content and being 25% with deionized water, under stirring uniformly, drip second monomer (hard monomer) at leisure to system, second monomer is the mixture of vinylbenzene and vinyl cyanide, and wherein the ratio of vinyl cyanide is in 5% (weight ratio).The Vinylstyrene (DVB) that contains trace in second monomer is made linking agent, and dosage of crosslinking agent is about 0.2% (mol ratio).After dropwising, under 5 ℃, utilize above-mentioned initiator system initiated polymerization.60 ℃ of insulations,, in reactor, add 1.2gSDS after one hour, stop polymerization after 3 hours when transformation efficiency reaches after 90.
Under 60 ℃, in 2% CaCl2 solution, condense emulsion, at 40～100 ℃ of following dry polymers, obtain the intercrossed network type thermoplastic elastomer in 120～200 ℃ of following granulations and shaping.Material pull apart tensile strength 18MPa, tensile yield 450%.
Embodiment 3: add deionized water 500g in 1000 milliliters of three mouthfuls of high-pressure reactors, in reactor, add emulsifying agent, these emulsifying agents are potassium stearate 2.5g, get the mixture 125g of divinyl and vinyl cyanide, wherein the ratio of divinyl and vinyl cyanide is in 75/25 (weight ratio), Vinylstyrene (DVB) linking agent that wherein contains 0.2% (mol ratio) in the mix monomer, splash among the reactor, under uniform stirring velocity, under about 5 ℃, utilize isopropyl benzene hydroperoxide-ferrous sulfate-EDTA-rongalite redox initiation system initiated polymerization, obtain little crosslinked paracril seed I emulsion.
Adding above-mentioned seed I emulsion 6.25g in the 1000ml high-pressure reactor (calculates according to solid content, about 37.5ml), adds the 500ml deionized water, get the rapid identical mix monomer 118.75g of previous step, be added drop-wise in the reactor, drip the potassium stearate aqueous solution of 0.875g synchronously with monomer.Under uniform stirring velocity, under about 5 ℃, utilize isopropyl benzene hydroperoxide-ferrous sulfate-EDTA-rongalite redox initiation system initiated polymerization, obtain little crosslinked paracril seed II emulsion.
Get above-mentioned emulsion 100g (calculating) according to solid content, after being diluted to solid content and being 15% with deionized water, under stirring uniformly, drip second monomer (hard monomer) 25g at leisure to system, second monomer is the mixture of vinylbenzene and vinyl cyanide, and wherein vinyl cyanide and cinnamic ratio were 1: 2 (weight ratio).Contain the divinyl benzene crosslinked agent of trace in second monomer, dosage of crosslinking agent is about 0.2% (mol ratio).After dropwising, under 5 ℃, utilize above-mentioned initiator system initiated polymerization.React after one hour, temperature is raised to 60 ℃, reach after 90%, in reactor, add potassium stearate 1.5g, after making the emulsifying agent consumption reach 2.0% (to the total solid content weight ratio) and being incubated a few hours, stop polymerization at transformation efficiency.Under 60 ℃, in 2% CaCl2 solution, condense emulsion, at 40～100 ℃ of following dry polymers, in 120～200 ℃ of following granulations and shaping.
Embodiment 4 (intermittent type is added emulsifying agent)
Add arbitrary seed I emulsion 20g in the foregoing description (calculating according to solid content) in the 1000ml reactor, drip the 180g monomer in reactor, the monomer that uses when this monomer and seed I prepare is identical; When the monomer add-on reaches 113g, add the emulsifying agent that all need add, and residual monomers is all splashed into.Initiated polymerization then.Add the suitable equally next step of mode of emulsifying agent like this, promptly add the step of second monomer (hard monomer) synthetic emulsion interpenetrating polymer networks.
Embodiment 5
In 1000 milliliters of three mouthfuls of reactors, add deionized water 160g, add alkyl-sulphate to system, consumption is about 0.6% (weight ratio), get the acrylate monomer 100g that contains triethylene Glycol double methacrylate (TEGDA) linking agent, the consumption of linking agent is between 0.15% (mol ratio), splash among the system, under uniform stirring velocity, under about 50 ℃ of conditions, utilize redox initiation system ammonium persulfate-sodium bisulfite initiated polymerization, about initiator amount 0.015% (mol ratio).After 1～3 hour, add the once initiator of above-mentioned equivalent in reaction under 60 ℃ again,, obtain little crosslinked acrylic elastomer seed emulsion so that the residual monomers polymerization is complete.Step according to embodiment 1 adds second monomer (hard monomer), and polymerization obtains the intercrossed network type thermoplastic elastomer.
Embodiment 6
In 1000 milliliters of three mouthfuls of reactors, add deionized water 150～200g, in reactor, add nilox resin acid potassium 0.8 gram, diffusion agent N F 0.5 gram, get divinyl and cinnamic mixture 100g, wherein butylbenzene is than between 70/30 to 95/5, Vinylstyrene (DVB) linking agent that in mix monomer, contains 0.2% (mol ratio), splash among the system, under uniform stirring velocity, under about 5 ℃, utilize isopropyl benzene hydroperoxide 0.3 gram, ferrous sulfate 0.04 gram, sodium ethylene diamine tetracetate 0.1 gram, rongalite 0.2 gram initiator system initiated polymerization obtains little crosslinked SBR emulsion.Add second monomer (hard monomer) according to embodiment 2 described steps, synthetic intercrossed network type thermoplastic elastomer.
Embodiment 7
In 1000 milliliters of three mouthfuls of high-pressure reactors, add deionized water 150～200g, in reactor, add emulsifying agent, these emulsifying agents are potassium stearate 0.8 grams, get the mixture 100g of divinyl and vinyl cyanide, wherein the ratio of divinyl and vinyl cyanide is in 80/20 (weight ratio), Vinylstyrene (DVB) linking agent that wherein contains 0.2% (mol ratio) in the mix monomer, splash among the system, under uniform stirring velocity, under about 5 ℃, utilize isopropyl benzene hydroperoxide-ferrous sulfate-EDTA-rongalite redox initiation system initiated polymerization, obtain little crosslinked acrylonitrile-butadiene rubber latex.Then, the step according to embodiment 3 prepares the intercrossed network type thermoplastic elastomer.
Claims (8)
1, a kind of emulsion intercrossed network type process for preparation of thermoplastic elastomer comprises: at the monomer that contains seed emulsion is synthetic rubber seed emulsion in the polymerization system of soft monomer, emulsifying agent, initiator; On the hevea seed emulsion after the monomeric swelling of vinyl thermoplastic polymer, further polymerization prepares interpenetrating network polymer emulsion; And cohesion, washing, dry, mixing granulator process, it is characterized in that: when A, seed emulsion are synthetic, in the monomer of seed emulsion, mix difunctionality or the vinyl-based cross-linking monomer of polyfunctionality as linking agent, make little crosslinked rubber latex cross-linking set spacing at 20 more than the structural unit, the consumption of control linking agent accounts for the monomer mole ratio scope 0.1%～1.0%, the number-average molecular weight of polymkeric substance obtains crosslinked rubber elastomer seed emulsion in 1,000,000 to 5,000,000 scope; B, among little crosslinked seed emulsion, drip the vinyl thermoplastic polymer monomer that is mixed with vinyl cyanide, that is: hard monomer, wherein, the weight ratio of vinyl cyanide is between 5%～95%, drip in the monomeric process and add emulsifying agent, and make the total emulsifiers consumption with respect to the total solid content weight ratio between 0.2～0.8%, after swelling process, utilize the radical initiator initiated polymerization, when transformation efficiency reaches 50～90% scope, add the emulsifying agent consumption and reach 1.0%, under 45～80 ℃, after being incubated 1～3 hour, stop polyreaction, then through breakdown of emulsion, dry, mixing granulator obtains the pellet of emulsion intercrossed network type thermoplastic elastomer.
2, preparation method according to claim 1 is characterized in that: the rubber elastomer seed emulsion is acrylic elastomer emulsion, acrylonitrile-butadiene rubber latex, SBR emulsion, chloroprene rubber, silicon rubber emulsion, viton emulsion, aqueous polyvinyl acetate emulsion, polyaminoester emulsion.
3, preparation method according to claim 1 is characterized in that: employed difunctionality of seeded emulsion polymerization or the vinyl-based cross-linking monomer of polyfunctionality are difunctionality or polyfunctionality (methyl) acrylate, Vinylstyrene.
4, preparation method according to claim 3, it is characterized in that: (methyl) acrylate of difunctionality or polyfunctionality is the triethylene Glycol double methacrylate, the tripropylene glycol double methacrylate, the triethylene Glycol double methyl methacrylate, two (methyl) acrylate of tirethylene glycol, ethylene glycol bis (methyl) acrylate, two (methyl) acrylate of propylene glycol, 1, two (methyl) acrylate of 4-butyleneglycol, the dihydroxyphenyl propane double methacrylate, two (methyl) acrylate of polymer with bis phenol A ethylene oxide ether, three vinylformic acid glyceryl ester, three (2-hydroxyethyl) isocyanuric acid triacrylate.
5, preparation method according to claim 1 is characterized in that: vinyl thermoplastic polymer hard monomer is: vinylbenzene, methyl methacrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid benzyl ester, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate and their mixture.
6, preparation method according to claim 1 is characterized in that: the Vinylstyrene or the polyfunctional acrylic ester that contain 0～0.3% mol ratio in the hard monomer of dropping.
7, preparation method according to claim 1 is characterized in that: the emulsifying agent of adding when dripping monomer is and the identical emulsifying agent of the used emulsifying agent of former seed letex polymerization, perhaps with the emulsifying agent of the composite use of original emulsifying agent.
8, preparation method according to claim 1, it is characterized in that: synthetic rubber seed emulsion proceed step by step, at first accounting in the presence of the emulsifying agent sodium alkyl sulfate of monomer weight 2.0%, water soluble starter causes the seed emulsion monomer polymerization, 50 ℃ of following polyreactions of polymerization temperature 2 hours, form small particle size seed emulsion I; Calculate 2～15% seed I based on the weight ratio of solid content then, continue to drip monomer, and additional emulsifying agent, the emulsifier concentration that keeps polymerization system is 0.5～0.6%, continue initiated polymerization and obtained seed emulsion II, i.e. rubber elastomer seed emulsion in 2 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110041855A (en) * | 2019-04-22 | 2019-07-23 | 成都新柯力化工科技有限公司 | A kind of environment-friendly building materials special bonding glue and preparation method |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161726B (en) * | 2010-12-23 | 2012-11-07 | 中国地质大学（北京） | Styrene-acrylate IPN/MMT nanocomposite damping material and preparation method thereof |
| CN102942720B (en) * | 2012-10-11 | 2015-11-18 | 黄山华兰科技有限公司 | The production method of the micro-cross-linked Powdered acrylonitrile-butadiene rubber of a kind of middle nitrile |
| CN103819762A (en) * | 2012-11-16 | 2014-05-28 | 中国石油天然气股份有限公司 | High-strength and high-oil-resistant butyronitrile rubber composition and preparing method thereof |
| CN103819773A (en) * | 2014-02-28 | 2014-05-28 | 苏州瑞邦塑胶有限公司 | Improved TPV formula |
| CN105085773B (en) * | 2015-08-14 | 2017-10-24 | 武汉理工大学 | A kind of inierpeneirating network structure polyacrylate multiple copolymer and preparation method thereof |
| CN108467463A (en) * | 2018-04-03 | 2018-08-31 | 长春工业大学 | A kind of water proof type aqueous coating polyurethane-polyacrylate composite emulsion and preparation method thereof |
| CN111621107B (en) * | 2020-05-29 | 2021-12-17 | 中国工程物理研究院化工材料研究所 | Fluororubber/polyhydroxy fluororubber-based polyurethane interpenetrating network reinforcing material and preparation method thereof |
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| CN110041855A (en) * | 2019-04-22 | 2019-07-23 | 成都新柯力化工科技有限公司 | A kind of environment-friendly building materials special bonding glue and preparation method |
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