CN101891901B - Method for foaming polymer microspheres with two-component or multi-component foaming agent under low pressure - Google Patents
Method for foaming polymer microspheres with two-component or multi-component foaming agent under low pressure Download PDFInfo
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Abstract
The invention relates to a method for foaming polymer microspheres with two-component or multi-component foaming agent under a low pressure and a foamed material obtained by the method. The polymer microspheres are comprised of a polymer serving as shells and foaming agent serving as a nuclear, wherein the polymer shells may be formed by the polymerization of a polymerizable monomer and a crosslinking agent; and the foaming agent consists of two or more components between which the boiling point difference is 10 to 100 DEG C, preferably 20 to 90 DEG C and more preferably 30 to 80 DEG C. When the outside pressure is less than a standard atmosphere, preferably 0.5 to 0.8 standard atmosphere, and the temperature is 100 to 180 DEG C, preferably 110 to 170 DEG C and more preferably 120 to 160 DEG C, the polymer microspheres begin to foam to form foamed material of which the foaming expansion ratio is no less than 20 times.
Description
Technical field
The present invention relates to a kind of low pressure foaming method and thus obtained foam material that contains the polymer microballoon of binary or polynary whipping agent.Two or more whipping agents can play synergy in foaming process, adopt the low pressure foaming method, reduce the blowing temperature of polymer microballoon, improve its expansion ratio and frothing percentage.
Background technology
But the polymkeric substance foam microspheres can be applicable to fields such as printing ink, explosive and paper, and can in rubber, plastics and coating, serve as the weight of weighting agent with lightening material, and improves elastic properties of materials, sound insulation and effect of heat insulation.
But the polymkeric substance foam microspheres utilizes suspension polymerization to make usually; Normally in the water system dispersion medium, make the mixture that contains polymerisable monomer and volatile foaming agent carry out suspension polymerization; Along with the carrying out of polyreaction, the polymer formation shell of generation, whipping agent is enclosed in this shell with the embedding mode; Thereby obtain polymer microballoon, it has the structure of polymer shell encapsulated blowing agent.Polymer shell has good gas barrier property usually, and the boiling point of the whipping agent that includes is not higher than the softening temperature of polymer shell.
This polymer microballoon has two kinds of use-patterns usually; The one, join the polymer microballoon that has foamed to play in other material and fill or other effects; Be to join the polymer microballoon of not foaming in the other materials in addition, in the course of processing of other materials, carry out the microballoon foaming.How this makes the polymer microballoon foaming if all relating to.The foaming mode that adopts at present usually is a type of heating, promptly heats microballoon, when reach or softening temperature near polymkeric substance before, the whipping agent of sealing in the microballoon gasifies, and drives polymer shell and expand, thereby reaches the foaming purpose.The polymer microballoon of foaming is commonly called heat-expandable macrosphere like this.
General a kind of whipping agent or several kinds of mixed foaming agents that boiling point differs greatly of adopting in the present polymer microballoon; They will try to achieve very harsh to the blowing temperature of operation; Be easy to the low microballoon of appearance temperature and can not send out, and the high microballoon of temperature just bursts situation about falling.Therefore hope that the best blowing temperature of polymer microballoon has the scope of broad; Particularly all the more so when the processing of the foaming of polymer microballoon and plastics, rubber and thermoplastic elastomer etc. is carried out simultaneously; And because the different polymer material has different processing temperatures, so polymer microballoon preferably has adjustable blowing temperature.In addition; Even polymer microballoon hopes also that filling or other application foaming already in advance before best blowing temperature decreases, this not only helps save energy; And through reducing best blowing temperature, the polymerizable material that those softening temperatures are low also can be used for the polymer shell of microballoon.
Summary of the invention
The purpose of this invention is to provide a kind of low pressure foaming method that contains the polymer microballoon of binary or polynary whipping agent, the blowing temperature that this polymer microballoon has relative broad range and is prone to regulate under low pressure can foam, and have higher expansion ratio and frothing percentage.
The inventor finds that through the further investigation back through selecting 10～100 ℃ of two or more boiling point differences, be preferably 20～90 ℃, more preferably 30～80 ℃ component constitutes.The whipping agent component is also suitably selected its content; Make them in the polymer microballoon foaming process, play synergy; This synergy produces whipping agent on its boiling point pressure following temperature variation is able to buffering; Thereby reach more easily or near the softening temperature of polymkeric substance, and reducing under the situation of ambient pressure, whipping agent can expand lower blowing temperature gasified being arranged and drive polymer shell; Expansion drive power is strengthened greatly, thereby has improved expansion ratio and frothing percentage.
Compare with the traditional method foaming, under the low pressure condition, make the polymer microballoon foaming can reduce its blowing temperature, and can be according to the variation modulation different operation temperature of processing conditions.
Therefore,, a kind of polymer microballoon that contains binary or polynary whipping agent that has than high foamability is provided, and a kind of low pressure foaming method of this polymer microballoon is provided according to the present invention; Wherein, said polymer microballoon is made up of polymer shell and whipping agent kernel, and polymer shell is polymerized by polymerisable monomer and linking agent; Whipping agent is preferably 20～90 ℃ by 10～100 ℃ of two or more boiling point differences, and more preferably 30～80 ℃ component constitutes; It is characterized in that, said polymer microballoon at ambient pressure less than a standard atmospheric pressure, under the situation of preferred 0.5～0.8 standard atmospheric pressure; Reach 100～180 ℃ in temperature, preferred 110～170 ℃, more preferably begin foaming 120～160 ℃ the time; Form expansion ratio and be not less than 20 times, preferred 25～50 times, more preferably 30～50 times foam material.
Said whipping agent is two or more in the hydro carbons such as Trimethylmethane, normal butane, iso-pentane, Skellysolve A, pentamethylene, normal hexane, hexanaphthene, normal heptane, isoheptane, octane, octane-iso and sherwood oil.
Said two or more whipping agents play synergy in the microballoon foaming process, the pressure following temperature variation that whipping agent is produced on its boiling point is able to buffering.The synergy here is meant that the approaching whipping agent of two or more boiling points interior pressure motivating force of its generation in foaming process produces comparatively gentle variation with blowing temperature; The mixed foaming agent that this point and previous a kind of whipping agent or several kinds of boiling points differ greatly is different; They require the blowing temperature of operation very harsh; Be easy to cause the low microballoon of temperature can not send out, the high microballoon of temperature just bursts.And the blowing temperature of synergy whipping agent operation of the present invention can be an interval, is prone to realize the industriallization operation, and keeps higher frothing percentage.
Said polymerisable monomer comprise vinyl cyanide and/or methacrylonitrile and with its can copolymerization vinyl monomer, the weight percentage that vinyl cyanide accounts for polymerisable monomer is not less than 70%, preferably is not less than 75%, more preferably is not less than 80%.
Said polymerisable monomer comprise vinylidene chloride and with its can copolymerization vinyl monomer, the weight percentage that vinylidene chloride accounts for polymerisable monomer is not less than 60%, preferably is not less than 65%, more preferably is not less than 70%.
Two or more components of said whipping agent are 10～90% of polymerisable monomer weight; Preferred 15～70%, more preferably 20～50%, the weight content of a certain component in the whipping agent is 5～95%; Be preferably 20～70 weight %, more preferably 40～50 weight %.
The structure of said linking agent is that single or a plurality of alkyl diols two ends connect two polymerisable carbon-carbon double bonds, and the weight percentage that linking agent accounts for polymerisable monomer is 1～5%, preferred 1.2～4%, preferred especially 1.5～3%.
In low pressure when foaming,, with 1-200 handkerchief/second speed, preferred 3-50 handkerchief/speed reduction second external pressure that foams until predetermined pressure, and was kept this low pressure 2-3 hour.
Therefore the foamable polymer microballoon of the low pressure that the present invention relates to also provides a kind of method of manufacture that has than the foamable polymer microballoon of low pressure of high foamability, particularly through the suspension polymerization manufactured; Be in containing the water system dispersion medium of dispersion stabilizer, in the presence of whipping agent, make polymerisable monomer and linking agent suspension polymerization, wherein; Whipping agent is by 10～100 ℃ of two or more boiling point differences; Be preferably 20～90 ℃, more preferably 30～80 ℃ component constitutes, and two or more components of whipping agent are 10～90% of polymerisable monomer weight; Preferred 15～70%; More preferably 20～50%, the weight content of a certain component in the whipping agent is 5～95%, is preferably 20～70 weight %; More preferably 40～50 weight % have the polymer microballoon of in by the shell that generates polymer formation, enclosing the structure that whipping agent is arranged thereby make.
Embodiment
The foamable polymer microballoon of low pressure of the present invention has encloses the structure that whipping agent is arranged in by the shell of polymer formation.The following specifically describes raw material, suspension polymerization that the present invention adopts and the polymer microballoon that obtains thus, and the low pressure foaming method of this polymer microballoon.
Polymerisable monomer
The polymerisable monomer that the present invention uses comprise vinyl cyanide and/or methacrylonitrile and with its can copolymerization vinyl monomer or comprise vinylidene chloride and with its can copolymerization vinyl monomer.
Specifically, vinyl monomer is selected from vinylidene chloride, vinyl cyanide, methacrylonitrile, vinylformic acid, methylacrylic acid, esters of acrylic acid, methyl acrylic ester, vinyl aromatic compounds class and vinyl acetate.
As esters of acrylic acid, for example can enumerate methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, vinylformic acid two cyclopentenes esters.As methyl acrylic ester, for example can enumerate out TEB 3K, Jia Jibingxisuanyizhi, NSC 20956, isobornyl methacrylate.As the vinyl aromatic compounds class, for example can enumerate out vinylbenzene, alpha-methyl styrene, halogenated styrenes.
As vinyl monomer, except above-mentioned mono-vinyl monomer, can also use the nitrile monomer class of α-Lv Bingxijing, α-ethoxy propylene nitrile, flumaronitrile etc.; Vinylchlorid; The conjugated diene of chloroprene, isoprene, divinyl etc.; The N-substituted maleimide of N-phenylmaleimide, N-naphthyl maleimide, N-cyclohexyl maleimide, methyl maleimide etc.; The various vinyl monomers of the unsaturated acids of Ba Dousuan, maleic anhydride etc. etc.
As vinylidene chloride polymer, polymerisable monomer can use separately vinylidene chloride, or use vinylidene chloride with can with the polymkeric substance that mixture obtained of the vinyl monomer of its copolymerization.As can with the monomer of vinylidene chloride copolymerization, can enumerate out for example vinyl cyanide, methacrylonitrile, methacrylic ester, propenoate, vinylbenzene, vinyl acetate etc.
When polymerisable monomer comprise vinylidene chloride and with its can copolymerization vinyl monomer the time, the weight percentage that vinylidene chloride accounts for polymerisable monomer is not less than 60%, preferably is not less than 65%, more preferably is not less than 70%.
As such vinylidene chloride polymer, the polymkeric substance that preferably uses vinylidene chloride 60～100 weight %, obtains with at least a vinyl monomer 0～40 weight % that is selected from vinyl cyanide, methacrylonitrile, propenoate, methacrylic ester, vinylbenzene and vinyl acetate as polymerisable monomer.
In addition; As vinylidene chloride polymer, preferred polymerisable monomer use vinylidene chloride 60～80 weight %, with the polymkeric substance that is selected from least a vinyl monomer 0～40 weight % in vinyl cyanide and the methacrylonitrile, obtains with at least a vinyl monomer 0～40 weight % that is selected from propenoate and the methacrylic ester.Through processing this polymkeric substance, can be convenient to design blowing temperature to a certain extent, and also be easy to reach high foamability.
As methyl) acrylonitrile polymer, polymerisable monomer can use independent (methyl) vinyl cyanide, perhaps (methyl) vinyl cyanide and the polymkeric substance that can obtain with the vinyl monomer of its copolymerization.(methyl) vinyl cyanide means vinyl cyanide and/or methacrylonitrile.In other words, so-called (methyl) vinyl cyanide means at least a nitrile monomer that is selected from vinyl cyanide and the methacrylonitrile.As can with the vinyl monomer of (methyl) acrylic acid copolymer, can enumerate vinylidene chloride, propenoate, methacrylic ester, vinylbenzene, vinyl acetate.
When polymerisable monomer comprise vinyl cyanide and/or methacrylonitrile and with its can copolymerization vinyl monomer the time, vinyl cyanide accounts for monomeric weight percentage and is not less than 70%, preferably is not less than 75%, more preferably is not less than 80%.
Linking agent
Among the present invention, but the polymer shell of low pressure foam microspheres be polymerized by polymerisable monomer and linking agent, linking agent also is called as cross-linkable monomer.Use linking agent through merging, can improve processibility, foaming character, thermotolerance, solvent resistance etc.
As linking agent, usually use to have 2 or a plurality of polymerizable carbon-to-carbon double bond (multi-functional compounds C=C-), the structure of preferred linking agent is that single or a plurality of alkyl diols two ends connect two polymerisable carbon-carbon double bonds.As the polymerizable carbon-to-carbon double bond, can enumerate for example vinyl, methylpropenyl, propenyl, allyl group.2 or a plurality of polymerizable carbon-to-carbon double bond can be identical or different.
As linking agent, can enumerate for example glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, Tri Ethyleneglycol diacrylate, Tri Ethyleneglycol dimethacrylate etc.; 1,4-butyleneglycol, 1, the diacrylate or the dimethacrylate of 9-nonanediol etc.
Use two such functional crosslinkers; Can obtain when keeping high foamability; Reduce the temperature dependency of the modulus of outer cover polymer; And in mixing processing, rolling processing, extrude in the manufacturing procedure of processing, injection molding etc., microballoon is not easy also to occur that shell destroys, the problem of interior bag gas dissipation.
The usage ratio of linking agent with respect to polymerisable monomer 100 weight parts, is generally below 5 weight parts, is preferably 1～5 weight part, and more preferably 1.2～4 weight parts are preferably 1.5～3 weight parts especially.
Whipping agent
Among the present invention, whipping agent is made up of two or more components.Whipping agent is generally two or more in the hydro carbons such as Trimethylmethane, normal butane, iso-pentane, Skellysolve A, pentamethylene, normal hexane, hexanaphthene, normal heptane, isoheptane, octane, octane-iso and sherwood oil etc.
Selecting for use of whipping agent mainly is in order to make two or more whipping agents in the microballoon foaming process, play synergy; Thereby the interior pressure (vp that whipping agent produces) effectively during the control foaming, and can the balance certain temperature and pressure under processibility and lathering property; Can make the control in blowing temperature zone become easy in addition.For this purpose, the boiling point difference of preferred two or more whipping agents that adopt is 10～100 ℃, is preferably 20～90 ℃, more preferably 30～80 ℃.
The usage ratio of two or more whipping agents with respect to polymerisable monomer 100 weight parts, is generally 10～90 weight parts, that is polymerisable monomer weight 10～90%, preferred 15～70%, more preferably 20～50%.
And with regard to two or more whipping agents itself, wherein a certain content is 5～95 weight %, is preferably 20～70 weight %, more preferably 40～50 weight %.After the kind of the whipping agent of having selected the combination use, the relative consumption between them is very important for effective performance synergy.
The method of manufacture of polymer microballoon
The foamable polymer microballoon of low pressure of the present invention; Can through in containing the water system dispersion medium system of dispersion stabilizer, the method that in the presence of whipping agent, makes polymerisable monomer and linking agent carry out suspension polymerization makes; Wherein, At least the polymerizable mixture that contains polymerisable monomer and linking agent and whipping agent is distributed in the water system dispersion medium, forms the drop of butyrous polymerizable mixture, the water system dispersion medium that will contain this polymerizable mixture fine droplet then adds in reactor drum such as the polymeric kettle; Choose wantonly in the presence of initiator, such as N
2Deng under the inert atmosphere at 40～90 ℃, preferred 50～80 ℃, more preferably stirring reaction 8～20 hours under 60～70 ℃ of temperature; Preferred 10～15 hours, most preferably 12～13 hours, the product that obtains is like this carried out aftertreatment; Like washing; Filter etc., the filter cake that obtains is air-dry, grind, and finally makes foamable polymer microballoon.
As polymerization starter; Can use the general material that uses in present technique field; But preferably dissolve in the oil-soluble polymerization initiator of polymerisable monomer; For example dialkyl, peroxo-diacyl, peroxyester, peroxy dicarbonate and azo cpd etc., object lesson can be enumerated the dialkyl of appearing oxidation methyl ethyl, di-t-butyl peroxide, dicumyl peroxide etc.; The peroxo-diacyl of peroxo-isobutyl-, Lucidol base, peroxo-2,4 dichloro benzene formyl radical etc.; T-butylperoxy pivarate, uncle's hexyl peroxo-pivalate, tert-butyl hydroperoxide neodecanoic acid ester, uncle's hexyl new decanoate ester peroxide, 1-cyclohexyl-1-methylethyl new decanoate ester peroxide, 1; 1; 3, the peroxyester of 3-tetramethyl butyl new decanoate ester peroxide, cumyl new decanoate ester peroxide etc.; The peroxy dicarbonate of two (4-tert-butylcyclohexyl) peroxy dicarbonate, di oxygen base two carbonic ethers, diisopropyl peroxydicarbonate, two (peroxo-of 2-ethyl diethyldithiocarbamate) two carbonic ethers, dimethoxy butyl peroxyization two carbonic ethers etc.; Diisopropyl azodicarboxylate, 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 1, the azo cpd of 1 '-azo two (1-hexanaphthene formonitrile HCN) etc. etc.The preferred Diisopropyl azodicarboxylate that adopts is as polymerization starter.
Polymerization starter; Be generally comprised within the polymerizable mixture; But suppress at needs under the situation of premature polymerization; Also can in the drop formation operation of polymerizable mixture or after the drop formation operation one of which partly or entirely be added in the water system dispersion medium, make in its drop of transferring to polymerizable mixture.
Polymerization starter is a benchmark with the water system dispersion medium, uses with the ratio of 0.0001～3 weight % usually.
Suspension polymerization is carried out in containing the water system dispersion medium of dispersion stabilizer usually.As dispersion stabilizer, can enumerate for example inorganic particles such as silicon-dioxide, titanium oxide, zinc oxide, Marinco H.In addition, as auxiliary stabilizer, can use condensation product, oleic acid, polyethylene oxide, various emulsifying agents of for example PVP K120, diethylolamine and aliphatic dicarboxylic acid etc.
The usage ratio of dispersion stabilizer with respect to polymerisable monomer 100 weight parts, is generally 0.1～10 weight part.
Contain the water system dispersion medium of dispersion stabilizer, normally dispersion stabilizer, auxiliary stabilizer are coupled in the deionized water and modulate.The pH value of the water during polymerization can be confirmed according to the kind of employed dispersion stabilizer, auxiliary stabilizer aptly.For example, under the situation of silicon-dioxide as dispersion stabilizer such as use colloid silica, should under sour environment, carry out polymerization.In order to make the water system dispersion medium for acid, can add acid as required, the pH value of reaction system is adjusted to below 6, preferably adjust to pH 3～4.
As one of preferably combination of dispersion stabilizer, there is the combination of colloidal titania and oleic acid to use.If add inorganic salt such as sodium-chlor, sodium sulfate, but then obtain to have the more evenly low pressure foam microspheres of particle shape easily.Inorganic salt use salt usually.
The consumption of colloidal titania changes according to its particle diameter to some extent, but with respect to polymerisable monomer 100 weight parts, is generally 1～20 weight part, is preferably the ratio of 2～15 weight parts.Oleic usage ratio with respect to polymerisable monomer 100 weight parts, is generally 0.05～2 weight part.The usage ratio of inorganic salt with respect to polymerisable monomer 100 weight parts, is generally 0～80 weight part, preferred 5～50 weight parts.
Can use the anionic surfactant according to processing requirement, for example SULPHOSUCCINIC ACID ESTER of dialkyl sulfosuccinates or polyxyethylated (allyl group) ether etc.
As reagent and additive in polymerization, at least a kind of compound from nitrite alkali metal-salt, tin protochloride, tin chloride, water-soluble xitix class and boric acid, selecting is present in the water system dispersion medium.If in the presence of these compounds, carry out suspension polymerization, then when polymerization, just can not cause the cohesion between the polymer particles, polymkeric substance can not adhere to the polymeric kettle wall, can stably make the foamable polymer microballoon of low pressure.
Preferred Sodium Nitrite and potassium nitrite in the nitrite alkali metal-salt.Their usage ratio with respect to polymerizable monomer 100 weight parts, is generally 0.001～1 weight part, is preferably 0.01～0.1 weight part.
The order of in the water system dispersion medium, adding each composition is arbitrarily, but adds entry and dispersion stabilizer usually, adds stabilization aid and reagent and additive in polymerization etc. as required, and modulation contains the water system dispersion medium of dispersion stabilizer.Whipping agent, polymerisable monomer (vinyl monomer) and linking agent; Also can add in the water system dispersion medium respectively; In the water system dispersion medium, reach integrated, form polymerizable mixture (oily mixture), but add to again in the water system dispersion medium after in advance it being mixed usually.Polymerization starter can add in the polymerisable monomer in advance and uses; But avoid at needs under the situation of premature polymerization; Also can for example polymerizable mixture be added in the water system dispersion medium, add polymerization starter, in the water system dispersion medium, reach integrated while stir.Polymerizable mixture can carry out in other container with mixing of water system dispersion medium, after mixing with stirrer, dispersion machine with high shear, added in the polymeric kettle.
Through polymerizable mixture and water system dispersion medium are mixed, in the water system dispersion medium, form the drop of polymerizable mixture.The median size of drop preferably with the median size basically identical of subject polymer microballoon, is generally 5～80 μ m, is preferably 8～60 μ m, is preferably 10～40 μ m especially.
Suspension polymerization generally is with outgasing in the reactive tank, perhaps replace with rare gas element such as nitrogen, being warming up to 40～90 ℃, preferred 50～80 ℃ temperature.In suspension polymerization, can polymerization temperature be controlled at certain temperature, polymerization also can heat up to the stage.
After the suspension polymerization, but, utilize methods such as washing, filtration, spinning or sedimentation to handle, from reaction mixture, isolate the foamable polymer microballoon of low pressure of the present invention the reaction mixture that contains the low pressure foam microspheres that generates.But isolated low pressure foam microspheres is behind washing and filtering, with the state recovery of wet cake.As required, but the low pressure foam microspheres is dry under the lower temperature that does not begin to foam.
The low pressure foaming method of polymer microballoon
But low pressure foam microspheres of the present invention has the structure that is made up of polymer shell and whipping agent kernel.Median size to polymer microballoon does not have special qualification, but is generally 3～150 μ m, is preferably 5～100 μ m, is preferably 8～60 μ m especially.Polymer shell uses polymerisable monomer (mainly being vinyl monomer) and linking agent to form through merging.The content of two or more whipping agents in the polymer microballoon with respect to polymerisable monomer 100 weight parts, is generally 10～90 weight parts, that is monomer weight 10～90%, preferred 15～70%, more preferably 20～50%.
Because the present invention adopts the whipping agent of two or more components; The pressure following temperature that utilizes the synergy of whipping agent component that whipping agent is produced on its boiling point changes and is able to buffering; Thereby the interior pressure motivating force that whipping agent produces in foaming process more leniently changes with blowing temperature; Therefore blowing temperature can be an interval, thereby when polymer microballoon low pressure foams, also is convenient to regulate blowing temperature.
In order to make the foaming of polymer microballoon low pressure, regulate ambient pressure less than a standard atmospheric pressure, preferred 0.5～0.8 standard atmospheric pressure; Make temperature reach 100～180 ℃ simultaneously, preferred 110～170 ℃, more preferably 120～160 ℃ the time; This moment, microballoon began foaming; The expansion ratio of the foam material that finally obtains is not less than 20 times, and preferred 25～50 times, more preferably 30～50 times.
The low pressure that when polymer microballoon foams, needs reaches like this, and exsiccant microballoon filter cake is joined in the rotary type baking oven to be lower than 1/80 of baking oven maximum volume, and baking oven and vacuum buffer bottle link; Prevent that with silica wool shutoff baking oven joint inlet the microballoon suck-back from going into the vacuum buffer bottle; Another interface and the vacuumometer of baking oven link, and reduce the foaming external pressure with 1-200 handkerchief/second speed, preferred 3-50 handkerchief/second speed; Until predetermined pressure, and kept this low pressure 2-3 hour.
Low pressure condition when setting foaming and through selecting and regulate the kind and the ratio of components of two or more whipping agents can make actual blowing temperature be lower than the temperature of normal pressure foaming, and have higher expansion ratio and frothing percentage.
Purposes
But low pressure foam microspheres of the present invention has multiple use as the low pressure foam material, and this low pressure foam material is lower than 1 standard atmospheric pressure at ambient pressure, and is preferred 0.5～0.8, and standard atmospheric pressure is foaming down.
But low pressure foam microspheres of the present invention can directly be used for various fields through low pressure foamable (thermal expansion) or without foaming; For example utilize its swelling property, be used to weighting agent, wallpaper, the foaming China ink (T-shirt etc. have relief style) of coating whipping agent, shrink and prevent agent etc.
But the characteristic that low pressure foam microspheres utilization of the present invention foaming increases volume is used to lightweight and porous materialization, various functional the giving (for example sliding, heat insulating ability, resiliency, sound insulation property etc.) of the polymer materials, coating, various materials etc. of synthetic resins (thermoplastic resin, heat-curing resin), rubber etc.As polymer materials, can enumerate out for example Vilaterm, Vestolen PP 7052, PS, ABS resin, SBS, SIS, Hydrogenated SBS, hydrogenation SIS, tree elastomer, various viton, thermoplastic polyurethane etc.
But low pressure foam microspheres of the present invention can be dissolved in whipping agent or the tinting material of dispersed dye etc., spices, insect-proof agent, antiseptic-germicide etc., performance function separately.But the state that the low pressure foam microspheres with such function also can keep not foaming is used.
Embodiment
Below enumerate embodiment and comparative example, the present invention more specifically is described.
Measuring method
(1) expansion ratio
But 0.7g puts into the driven type baking oven with the low pressure foam microspheres, and heating made its foaming in 2 minutes under defined temperature (blowing temperature) and selected pressure below atmospheric pressure.The foam that obtains is put into graduated cylinder, measure volume, but the volume of the low pressure foam microspheres of the volume of foam when not foaming is calculated expansion ratio.
(2) median size
Use particle size distribution measuring device (like the SALD-3000J of Shimadzu Seisakusho Ltd.'s system) to measure the size-grade distribution of heat-expandable macrosphere, represent median size (μ m) with its median particle diameter.
Embodiment 1
(1) preparation of polymer microballoon
Get colloid titanium oxide 7.5g, oleic acid 0.1g, sodium-chlor 22.5g, 1: 10 hydrochloric acid 1g, and the 75g deionized water is made into water system dispersion medium system.By vinyl cyanide 33g, methacrylonitrile 3.7g, methyl acrylate 1.0g, bifunctional crosslinking agent's Tri Ethyleneglycol dimethacrylate 1.0g, Skellysolve A 4g, hexanaphthene 6g, Diisopropyl azodicarboxylate 0.07g constitutes polymerizable mixture.
The polymerizable mixture and the water system dispersion medium that form are mixed in clarifixator, make polymerizable mixture form fine droplet and be dispersed in aqueous phase.The fine droplet diameter is 15-20 μ m, dispersion coefficient 1.3%.The water system dispersion medium that will contain this polymerizable mixture fine droplet adds and has in the polymeric kettle of stirrer, at N
2The following 70 ℃ of reactions of atmosphere 12 hours.The product repeated water washing is filtered, and the filter cake that obtains is air-dry, grind, and makes mean diameter 17 μ m, but the foam microspheres of dispersion coefficient 1.3%.
(2) low pressure of polymer microballoon foaming
Exsiccant microballoon filter cake is joined in the rotary type baking oven to account for 1/80 of baking oven maximum volume, and baking oven and vacuum buffer bottle link, and enter the mouth with silica wool shutoff baking oven joint; Another interface and the vacuumometer of baking oven link, with 20 handkerchiefs/speed reduction foaming second external pressure, until predetermined pressure 0.7 standard atmospheric pressure; And kept this low pressure 2 hours; Under 160 ℃, make this microballoon foaming, reach 50 times of maximum expansion ratios, frothing percentage is 95%.Foaming respectively under 150 ℃ and 170 ℃ under the same low pressure condition, the expansion ratio that reaches is 40 times, and the frothing percentage of this moment is 93%.
Embodiment 2
(1) preparation of polymer microballoon
Get colloid titanium oxide 5g, sodium oleate 10% aqueous solution 0.5g, sodium-chlor 30g, 1: 10 hydrochloric acid 1g, and the 80g deionized water constitutes water system dispersion medium system.In addition, by vinyl cyanide 35g, methacrylonitrile 4g, methyl acrylate 1.2g, bifunctional crosslinking agent's Tri Ethyleneglycol dimethacrylate 1.5g, normal hexane 5g, octane-iso 5g, Diisopropyl azodicarboxylate 0.1g constitutes polymerizable mixture.
This polymerizable mixture and water system dispersion medium are mixed in clarifixator, make polymerizable mixture form fine droplet and be dispersed in aqueous phase.The fine droplet diameter is 12-15 μ m, dispersion coefficient 1.7%.The water system dispersion medium that will contain this polymerizable mixture fine droplet adds and has in the polymeric kettle of stirrer, at N
2The following 70 ℃ of reactions of atmosphere 12 hours.The product repeated water washing is filtered, and the filter cake that obtains is air-dry, grind, and obtains mean diameter 13 μ m, but the foam microspheres of dispersion coefficient 1.7%.
(2) low pressure of polymer microballoon foaming
Exsiccant microballoon filter cake is joined in the rotary type baking oven to account for 1/120 of baking oven maximum volume, and baking oven and vacuum buffer bottle link, and enter the mouth with silica wool shutoff baking oven joint; Another interface and the vacuumometer of baking oven link, with 50 handkerchiefs/speed reduction foaming second external pressure, until 0.6 standard atmospheric pressure; And kept this low pressure 2 hours; Under 150 ℃, make this microballoon foaming, reach 48 times of maximum expansion ratios, frothing percentage is 93%.
Embodiment 3
(1) preparation of polymer microballoon
Get colloidal silicon dioxide 9g, diethylolamine-methylene-succinic acid polycondensate 10% aqueous solution 0.8g, sodium-chlor 20g, 1: 10 hydrochloric acid 1.5g, and the 70g deionized water constitutes water system dispersion medium system.In addition, preparation Skellysolve A content 4g, normal hexane content 5g, the polymerizable mixture that all the other monomer content and embodiment 2 are identical.
This polymerizable mixture and water system dispersion medium are mixed in clarifixator, make polymerizable mixture form fine droplet and be dispersed in aqueous phase.The fine droplet diameter is 15-20 μ m, dispersion coefficient 1.5%.The water system dispersion medium that will contain this polymerizable mixture fine droplet adds and has in the polymeric kettle of stirrer, at N
2The following 70 ℃ of reactions of atmosphere 12 hours.The product repeated water washing is filtered, and the filter cake that obtains is air-dry, grind, and obtains mean diameter 18 μ m, but the foam microspheres of dispersion coefficient 1.5%.
(2) low pressure of polymer microballoon foaming
Exsiccant microballoon filter cake is joined in the rotary type baking oven to account for 1/150 of baking oven maximum volume, and baking oven and vacuum buffer bottle link, and enter the mouth with silica wool shutoff baking oven joint; Another interface and the vacuumometer of baking oven link, with 80 handkerchiefs/speed reduction foaming second external pressure, until 0.5 standard atmospheric pressure; And kept this low pressure 3 hours; Under 145 ℃, make this microballoon foaming, reach 45 times of maximum expansion ratios, frothing percentage is 91%.
Embodiment 4
(1) preparation of polymer microballoon
Press embodiment 3 preparation water system dispersion medium systems.In addition, configuration Skellysolve A content 4g, normal hexane content 4g, isooctane content 4g, the polymerizable mixture that all the other monomer content and embodiment 1 are identical.
This polymerizable mixture and water system dispersion medium are mixed in clarifixator, make polymerizable mixture form fine droplet and be dispersed in aqueous phase.The fine droplet diameter is 17-22 μ m, dispersion coefficient 1.7%.The water system dispersion medium that will contain this polymerizable mixture fine droplet adds and has in the polymeric kettle of stirrer, at N
2The following 70 ℃ of reactions of atmosphere 12 hours.The product repeated water washing is filtered, and the filter cake that obtains is air-dry, grind, and obtains mean diameter 20 μ m, but the foam microspheres of dispersion coefficient 1.7%.
(2) low pressure of polymer microballoon foaming
Exsiccant microballoon filter cake is joined in the rotary type baking oven to account for 1/120 of baking oven maximum volume, and baking oven and vacuum buffer bottle link, and enter the mouth with silica wool shutoff baking oven joint; Another interface and the vacuumometer of baking oven link, with 40 handkerchiefs/speed reduction foaming second external pressure, until 0.7 standard atmospheric pressure; And kept this low pressure 3 hours; Under 160 ℃, make this microballoon foaming, reach 48 times of maximum expansion ratios, frothing percentage is 95%.
Embodiment 5
(1) preparation of polymer microballoon
Get Marinco H 5.0g, PVP K120 0.1g, sodium-chlor 22.5g, Sodium Nitrite 0.05g, 1: 10 hydrochloric acid 1g, and the 75g deionized water constitutes water system dispersion medium system.In addition, by vinylidene chloride 22g, vinyl cyanide 14g, TEB 3K 2.0g, bifunctional crosslinking agent's Tri Ethyleneglycol dimethacrylate 1.0g, normal hexane 4.0g, iso-pentane 6.0g, ABVN 0.20g constitutes polymerizable mixture.
This polymerizable mixture and water system dispersion medium are mixed in clarifixator, make polymerizable mixture form fine droplet and be dispersed in aqueous phase.The fine droplet diameter is 20-25 μ m, dispersion coefficient 1.7%.The water system dispersion medium that will contain this polymerizable mixture fine droplet adds and has in the polymeric kettle of stirrer, at N
2The following 52 ℃ of reactions of atmosphere 12 hours.The product repeated water washing is filtered, and the filter cake that obtains is air-dry, grind, but obtains the foam microspheres of mean diameter 23 μ m, dispersion coefficient 1.3%.
(2) low pressure of polymer microballoon foaming
Exsiccant microballoon filter cake is joined in the rotary type baking oven to account for 1/150 of baking oven maximum volume, and baking oven and vacuum buffer bottle link, and enter the mouth with silica wool shutoff baking oven joint; Another interface and the vacuumometer of baking oven link, with 150 handkerchiefs/speed reduction foaming second external pressure, until 0.7 standard atmospheric pressure; And kept this low pressure 2 hours; Under 100 ℃, make this microballoon foaming, reach 45 times of maximum expansion ratios, frothing percentage is 92%.110 ℃ of foaming down, the expansion ratio that reaches is 44 times under the same low pressure condition, and the frothing percentage of this moment is 91%.
Embodiment 6
(1) preparation of polymer microballoon
Get Marinco H 8.0g, polyethylene oxide 0.2g, salt 25g, Sodium Nitrite 0.05g, 1: 10 hydrochloric acid 1.2g, and the 80g deionized water constitutes water system dispersion medium system.In addition, by vinylidene chloride 25g, vinyl cyanide 12g, TEB 3K 2.0g, bifunctional crosslinking agent's Tri Ethyleneglycol dimethacrylate 1.2g, Skellysolve A 3.0g, normal butane 7.0g, Diisopropyl azodicarboxylate 0.20g constitutes polymerizable mixture.
This polymerizable mixture and water system dispersion medium are mixed in clarifixator, make polymerizable mixture form fine droplet and be dispersed in aqueous phase.The fine droplet diameter is 15-20 μ m, dispersion coefficient 2.0%.The water system dispersion medium that will contain this polymerizable mixture fine droplet adds and has in the polymeric kettle of stirrer, at N
2The following 70 ℃ of reactions of atmosphere 12 hours.The product repeated water washing is filtered, and the filter cake that obtains is air-dry, grind, and obtains mean diameter 18 μ m, but the foam microspheres of dispersion coefficient 2.0%.
(2) low pressure of polymer microballoon foaming
Exsiccant microballoon filter cake is joined in the rotary type baking oven to account for 1/90 of baking oven maximum volume, and baking oven and vacuum buffer bottle link, and enter the mouth with silica wool shutoff baking oven joint; Another interface and the vacuumometer of baking oven link, with 50 handkerchiefs/speed reduction foaming second external pressure, until 0.5 standard atmospheric pressure; And kept this low pressure 3 hours; Under 100 ℃, make this microballoon foaming, reach 50 times of maximum expansion ratios, frothing percentage is 95%.
Embodiment 7
(1) preparation of polymer microballoon
Water system dispersion medium system is pressed embodiment 5 preparations.By vinylidene chloride 25g, vinyl cyanide 12g, TEB 3K 2.0g, bifunctional crosslinking agent's ethylene glycol dimethacrylate 1.0g, iso-pentane 4.0g, Trimethylmethane 6.0g, ABVN 0.20g constitutes polymerizable mixture.
This polymerizable mixture and water system dispersion medium are mixed in clarifixator, make polymerizable mixture form fine droplet and be dispersed in aqueous phase.The fine droplet diameter is 17-22 μ m, dispersion coefficient 1.5%.The water system dispersion medium that will contain this polymerizable mixture fine droplet adds and has in the polymeric kettle of stirrer, at N
2The following 52 ℃ of reactions of atmosphere 12 hours.The product repeated water washing is filtered, and the filter cake that obtains is air-dry, grind, and obtains mean diameter 20 μ m, but the foam microspheres of dispersion coefficient 1.5%.
(2) low pressure of polymer microballoon foaming
Exsiccant microballoon filter cake is joined in the rotary type baking oven to account for 1/100 of baking oven maximum volume, and baking oven and vacuum buffer bottle link, and enter the mouth with silica wool shutoff baking oven joint; Another interface and the vacuumometer of baking oven link, with 40 handkerchiefs/speed reduction foaming second external pressure, until 0.6 standard atmospheric pressure; And kept this low pressure 2.5 hours; Under 100 ℃, make this microballoon foaming, reach 48 times of maximum expansion ratios, frothing percentage is 94%.110 ℃ of foaming down, the expansion ratio that reaches is 44 times under the same low pressure condition, and frothing percentage is 92%.
Comparative example 1
Use with embodiment 1 same method and carry out suspension polymerization, obtain median size mean diameter 17 μ m, but the foam microspheres of dispersion coefficient 1.3%.
Depress at standard atmosphere and to foam, 180 ℃ of blowing temperatures reach 30 times of maximum expansion ratios, and frothing percentage is 70%.
Comparative example 2
Use with embodiment 5 same methods and carry out suspension polymerization, different is that whipping agent changes normal hexane 4.0g and Trimethylmethane 6.0g into by collaborative whipping agent, obtains median size mean diameter 23 μ m, but the foam microspheres of dispersion coefficient 1.7%.
Depress at 1 standard atmosphere, make its foaming under 170 ℃, reach 20 times of maximum expansion ratios, and nextly are difficult to foaming at 110 ℃.Temperature is elevated to 150 ℃, though foaming, expansion ratio is 15 times, and frothing percentage is 65%, with embodiment 5 110 ℃ of frothing percentages 95% compare descend a lot, when this foam with microballoon interior pressure excessive burst relevant.
Claims (26)
1. low pressure foaming method that contains the polymer microballoon of binary or polynary whipping agent; Wherein, said polymer microballoon is made up of polymer shell and whipping agent kernel, and polymer shell is polymerized by polymerisable monomer and linking agent; Whipping agent is made up of the component of 20～90 ℃ of two or more boiling point differences; It is characterized in that said polymer microballoon is under the situation of 0.5～0.8 standard atmospheric pressure at ambient pressure, when temperature reaches 100～170 ℃, begin foaming; Form expansion ratio and be not less than 20 times foam material
During the low pressure foaming, with 1-200 handkerchief/speed reduction foaming second external pressure, until predetermined pressure,
Said whipping agent is two or more in Trimethylmethane, normal butane, iso-pentane, Skellysolve A, pentamethylene, normal hexane, hexanaphthene, normal heptane, isoheptane, octane and the octane-iso,
Two or more components of said whipping agent are 10～90% of polymerisable monomer weight,
The weight percentage that linking agent accounts for polymerisable monomer is 1～5%.
2. according to the low pressure foaming method of the polymer microballoon of claim 1, it is characterized in that whipping agent is made up of the component of 30～80 ℃ of two or more boiling point differences.
3. according to the low pressure foaming method of the polymer microballoon of claim 1, it is characterized in that, when temperature reaches 110～170 ℃, begin foaming.
4. according to the low pressure foaming method of the polymer microballoon of claim 1, it is characterized in that, when temperature reaches 120～160 ℃, begin foaming.
5. according to the low pressure foaming method of the polymer microballoon of claim 1, it is characterized in that, form the foam material of 25～50 times of expansion ratios.
6. according to the low pressure foaming method of the polymer microballoon of claim 1, it is characterized in that, form the foam material of 30～50 times of expansion ratios.
7. according to the low pressure foaming method of the polymer microballoon of claim 1; It is characterized in that; Said polymerisable monomer comprise vinyl cyanide and/or methacrylonitrile and with its can copolymerization vinyl monomer, the weight percentage that vinyl cyanide accounts for polymerisable monomer is not less than 70%.
8. according to the low pressure foaming method of the polymer microballoon of claim 7, it is characterized in that the weight percentage that vinyl cyanide accounts for polymerisable monomer is not less than 75%.
9. according to the low pressure foaming method of the polymer microballoon of claim 7, it is characterized in that the weight percentage that vinyl cyanide accounts for polymerisable monomer is not less than 80%.
10. according to the low pressure foaming method of the polymer microballoon of claim 1, it is characterized in that, said polymerisable monomer comprise vinylidene chloride and with its can copolymerization vinyl monomer, the weight percentage that vinylidene chloride accounts for polymerisable monomer is not less than 60%.
11. the low pressure foaming method according to the polymer microballoon of claim 10 is characterized in that the weight percentage that vinylidene chloride accounts for polymerisable monomer is not less than 65%.
12. the low pressure foaming method according to the polymer microballoon of claim 10 is characterized in that the weight percentage that vinylidene chloride accounts for polymerisable monomer is not less than 70%.
13. the low pressure foaming method according to the polymer microballoon of one of claim 1～12 is characterized in that two or more components of said whipping agent are 15～70% of polymerisable monomer weight.
14. the low pressure foaming method according to the polymer microballoon of one of claim 1～12 is characterized in that two or more components of said whipping agent are 20～50% of polymerisable monomer weight.
15. low pressure foaming method according to the polymer microballoon of one of claim 1～12; It is characterized in that; The structure of said linking agent is that single or a plurality of alkyl diols two ends connect two polymerisable carbon-carbon double bonds, and the weight percentage that linking agent accounts for polymerisable monomer is 1.2～4%.
16. the low pressure foaming method according to the polymer microballoon of one of claim 1～12 is characterized in that the weight percentage that linking agent accounts for polymerisable monomer is 1.5～3%.
17. the low pressure foaming method according to the polymer microballoon of one of claim 1～12 is characterized in that, during the low pressure foaming, reduces the external pressure that foams with 1-200 handkerchief/second speed, until predetermined pressure, and keeps this low pressure 2-3 hour.
18. the low pressure foaming method according to the polymer microballoon of claim 17 is characterized in that, during the low pressure foaming, reduces the external pressure that foams with 3-50 handkerchief/second speed.
19. foamable polymer microballoon of low pressure; Its structure is made up of polymer shell and whipping agent kernel, it is characterized in that: polymer shell is polymerized by polymerisable monomer and linking agent, and whipping agent is made up of the component of 20～90 ℃ of two or more boiling point differences; Wherein, Two or more components of whipping agent are 10～90% of polymerisable monomer weight, and the expansion ratio of said polymer microballoon is not less than 20 times
Said whipping agent is two or more in Trimethylmethane, normal butane, iso-pentane, Skellysolve A, pentamethylene, normal hexane, hexanaphthene, normal heptane, isoheptane, octane and the octane-iso,
The weight percentage that linking agent accounts for polymerisable monomer is 1～5%.
20. according to the foamable polymer microballoon of the low pressure of claim 19, its structure is made up of polymer shell and whipping agent kernel, it is characterized in that, whipping agent is made up of the component of 30～80 ℃ of two or more boiling point differences.
21. according to the foamable polymer microballoon of the low pressure of claim 19, its structure is made up of polymer shell and whipping agent kernel, it is characterized in that, two or more components of whipping agent are 15～70% of polymerisable monomer weight.
22. according to the foamable polymer microballoon of the low pressure of claim 19, its structure is made up of polymer shell and whipping agent kernel, it is characterized in that, two or more components of whipping agent are 20～50% of polymerisable monomer weight.
23. preparation method according to the foamable polymer microballoon of the described low pressure of one of claim 19～22; It is characterized in that; In containing the water system dispersion medium of dispersion stabilizer, in the presence of whipping agent, make polymerisable monomer and linking agent suspension polymerization, have the foamable polymer microballoon of low pressure of in by the shell that generates polymer formation, enclosing the structure that whipping agent is arranged thereby make; Wherein, Whipping agent is made up of the component of 20～90 ℃ of two or more boiling point differences, and two or more components of whipping agent are 10～90% of polymerisable monomer weight
Said whipping agent is two or more in Trimethylmethane, normal butane, iso-pentane, Skellysolve A, pentamethylene, normal hexane, hexanaphthene, normal heptane, isoheptane, octane and the octane-iso.
24. the preparation method of the foamable polymer microballoon of low pressure according to claim 23 is characterized in that, whipping agent is made up of the component of 30～80 ℃ of two or more boiling point differences.
25. the preparation method of the foamable polymer microballoon of low pressure according to claim 23 is characterized in that, two or more components of whipping agent are 15～70% of polymerisable monomer weight.
26. the preparation method of the foamable polymer microballoon of low pressure according to claim 23 is characterized in that, two or more components of whipping agent are 20～50% of polymerisable monomer weight.
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| CN103589411B (en) * | 2013-10-22 | 2016-02-10 | 中国石油天然气股份有限公司 | Thickened oil steam-stimulated well is material block blocking up energization and preparation method thereof and application temporarily |
| CN103665419B (en) * | 2013-12-06 | 2016-08-24 | 上海金狮化工有限公司 | The synthetic method of middle Low Temperature Thermal expandable microspheres and application process thereof |
| CN106585054A (en) * | 2016-12-01 | 2017-04-26 | 江阴万高塑业有限公司 | Formula of thermoplastic elastomer foamed synthetic leather and preparation process |
| CN108587282A (en) * | 2018-04-27 | 2018-09-28 | 江门市力昌新材料有限公司 | A kind of conduction heat-insulating powder coating and preparation method thereof |
| CN109796763A (en) * | 2018-12-05 | 2019-05-24 | 深圳市鑫昌龙新材料科技股份有限公司 | Microballoon and the composition of oil-based material and preparation method thereof |
| CN111851139B (en) * | 2019-04-30 | 2022-08-12 | 陆筱棣 | Method for preparing expandable microspheres, microspheres obtained by method and application of microspheres |
| CN110591250B (en) * | 2019-09-12 | 2021-04-13 | 宁波东胜橡胶制品有限公司 | PVC (polyvinyl chloride) foam material for sports shock pad and preparation process thereof |
| CN111961395B (en) * | 2020-08-28 | 2021-11-05 | 广东沐峰节能创新科技有限公司 | Shock-absorbing sound-insulation coating |
| CN113201194B (en) * | 2021-06-07 | 2023-02-03 | 长春联塑实业有限公司 | Low-foaming high-impact PVC product and preparation method and application thereof |
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