CN101851308A - In-situ suspension polymerization preparation method of nanocomposite material consisting of polyvinyl chloride and silicon dioxide and product thereof - Google Patents
In-situ suspension polymerization preparation method of nanocomposite material consisting of polyvinyl chloride and silicon dioxide and product thereof Download PDFInfo
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Abstract
The invention belongs to the field of a nanocomposite material of polyvinyl chloride and silicon dioxide, in particular to an in-situ suspension polymerization preparation method of the nanocomposite material consisting of the polyvinyl chloride and the silicon dioxide and a product thereof, as well as a modification technology of nano-silicon dioxide used for the nanocomposite material. The preparation method prepares the nanocomposite material consisting of the polyvinyl chloride and the silicon dioxide through the in-situ suspension polymerization method, which comprises the steps of uniformly dispersing the modified nano-silicon dioxide in vinyl chloride monomers and carrying out in-situ suspension polymerization by regulating the parameters of the polymerization process, thereby realizing the control of particle size of polyvinyl chloride particles and effectively preventing sticking a kettle. Various properties of polymerized resin are greatly improved in comparison with the pure polyvinyl chloride resin, and the method is simple and easy to operate, thereby conveniently controlling the composition, the structure and the properties of the composite material and being characterized by stable structure and uniform dispersion of inorganic nano-particles.
Description
Technical field
The invention belongs to polyvinyl chloride and silicon dioxide nano composite material field, be particularly related to in-situ suspension polymerization preparation method of the nano composite material that a kind of polyvinyl chloride and silicon-dioxide forms and products thereof, and the modification technology that is used for the nano silicon of this nano composite material.
Background technology
Polyvinyl chloride, usually be called for short polyvinyl chloride resin, it is a kind of general thermoplastics, its wear resistance, resistance to chemical corrosion, comprehensive mechanical performance, electrical insulating property, thermal insulation etc. are more excellent, be widely used in each field such as material of construction, packing, insulating material, but drawbacks limit such as its thermal stability is poor, shock resistance is poor, processing is difficult its application.
In the PVC polymkeric substance, add inorganic particulate and prepare the over-all properties that the PVC matrix material can effectively improve material, comprise hardness, modulus and thermotolerance etc., operable inorganic particulate comprises lime carbonate, barium sulfate, potter's clay, talcum powder, glass microballon and silicon-dioxide etc.Compare with micro-size particles, because the scale effect of nanoparticle and big specific surface area, nanoparticle nano level dispersion in polymeric matrix that particle is littler, two-phase strong interface effect under nanoscale is compound, makes the adding of small number of inorganic nanoparticles promptly have significant improved performance effect to polymer materials.But for the inorganic particulate of nano-scale, simple mechanical blending is difficult to overcome interparticle interface interaction, and particle is often reunited to micron-scale, can not give full play to the effect unique of nanoparticle.
The home position polymerization reaction technology is the advanced at present method for preparing polymer nanocomposites.The home position polymerization reaction technology is that nanoparticle is distributed in the polymerization single polymerization monomer, then under action of evocating, monomer is initiated polymerization under the situation that nanoparticle exists, because the interaction energy of the local heat effect of monomer polymerization and shearing force destroys the nanoparticle coacervate, improve the dispersiveness of nanoparticle in polymeric matrix effectively, increase the interfacial interaction between the two-phase, reach the purpose of strongthener over-all properties.Therefore, home position polymerization reaction provides a kind of new method and approach for the polymer nanocomposites of processability excellence.In recent years, the PVC nano composite material has been subjected to paying close attention to widely, some investigators have obtained the polyvinyl chloride nano matrix material by situ aggregation method, the mechanical property of the polyvinyl chloride nano matrix material that obtains obtained improving to a certain degree (CN1566202A, CN1631920A).And polyvinyl chloride in-situ suspension polymerization reaction because the existence of inorganic nano-particle makes vinyl chloride monomer hanging drop instability, tends to make polymerization process be difficult to control and causes the generation of sticking still phenomenon.The key of eliminating sticking still phenomenon is among nanoparticle before the initiated polymerization can be scattered in polymerization single polymerization monomer preferably, improve the stability of monomer droplet, therefore, nanoparticle is carried out effective organic modification, the nanoparticle hydrophobicity is strengthened, can eliminate the phenomenon of sticking still effectively.
Summary of the invention
The object of the present invention is to provide the in-situ suspension polymerization preparation method of the nano composite material of a kind of polyvinyl chloride and silicon-dioxide composition.
A further object of the present invention is to provide a kind of preparation method of modified manometer silicon dioxide, the modified manometer silicon dioxide that obtains with this method is used for the preparation of the nano composite material that polyvinyl chloride and silicon-dioxide forms, modified manometer silicon dioxide and vinyl chloride monomer and polyvinyl chloride (PVC) RESINS consistency are good, can effectively overcome the agglomeration of nanoparticle.
The nano composite material that another purpose of the present invention is to provide polyvinyl chloride that the in-situ suspension polymerization preparation method of the nano composite material of being made up of polyvinyl chloride and silicon-dioxide obtains and silicon-dioxide to form.
The present invention adopts modified manometer silicon dioxide (SiO
2), at low temperatures it is joined in the vinyl chloride monomer then, elder generation is evenly dispersed in the vinyl chloride monomer modified manometer silicon dioxide through stirring at a slow speed, and by stirring fast, the intensification polymerization obtains the nano composite material of polyvinyl chloride and silicon-dioxide composition then.Adopt modified manometer silicon dioxide to improve interfacial interaction power between vinyl chloride monomer and the modified manometer silicon dioxide, monomer suspension is dripped stablely during in-situ polymerization, and the controllability of polyreaction is greatly improved.Silicon-dioxide in the nano composite material that polyvinyl chloride that obtains like this and silicon-dioxide are formed is to disperse with nano level in the polyvinyl chloride matrix, and the interface is in conjunction with good, and all purer polyvinyl chloride of every performance has raising by a relatively large margin.
The in-situ suspension polymerization preparation method of the nano composite material that polyvinyl chloride of the present invention and silicon-dioxide are formed comprises that step comprises:
(1) under rare gas element (as nitrogen) protection, in the suspension polymerization still, adds modified manometer silicon dioxide, deionized water, initiator and dispersion agent in advance, introduce vinyl chloride monomer then and obtain reaction system; Temperature of reaction when temperature is lower than polymerization of vinyl choride monomer, and stir at a slow speed under the stir speed (S.S.) when not being higher than the vinyl chloride monomer home position polymerization reaction, modified manometer silicon dioxide is dispersed in the reaction system, stirring makes vinyl chloride monomer form hanging drop in reaction system fast then, obtains suspension;
(2) suspension that step (1) is obtained heats up, and control reaction temperature is 50～70 ℃, carries out the home position polymerization reaction of vinylchlorid under 700～800 rev/mins agitation condition; After polyreaction finishes, reaction paste after filtration, drying, promptly obtain the nano composite material that polyvinyl chloride and silicon-dioxide are formed.
Described reaction system is under the benchmark at the weight part with vinyl chloride monomer, and each component concentration in the reaction system is:
Vinyl chloride monomer: 100 weight parts;
Modified manometer silicon dioxide: 0.01～15 weight part;
Deionized water: 100～250 weight parts;
Initiator: 0.01～0.1 weight part;
Dispersion agent: 0.01～0.1 weight part.
The nano composite material that the described polyvinyl chloride that obtains and silicon-dioxide are formed is that component and content under the benchmark is at the weight part with vinyl chloride monomer:
Polyvinyl chloride: 100 weight parts;
Modified manometer silicon dioxide: 0.01～15 weight part.
Temperature during stirring at a slow speed in the step (1) is the temperature of reaction when being lower than polymerization of vinyl choride monomer, and preferred temperature is 0 ℃～20 ℃; The described purpose that stirs at a slow speed is for stirring under the prerequisite of not destroying the vinyl chloride monomer phase continuity, make modified manometer silicon dioxide be scattered in as much as possible vinyl chloride monomer mutually in, stir speed (S.S.) is the stir speed (S.S.) when not being higher than the vinyl chloride monomer home position polymerization reaction, the preferred stir speed (S.S.) that stirs at a slow speed is 100～400 rev/mins, and churning time is 20～40 minutes; Stir speed (S.S.) when the stir speed (S.S.) of described quick stirring is the vinyl chloride monomer home position polymerization reaction, churning time is 20～40 minutes, purpose is to be dispersed into vinyl chloride monomer as far as possible little and is dispersed in aqueous phase to form hanging drop, so that vinyl chloride monomer is caused home position polymerization reaction.
Initiator purpose used in the present invention is carried out in-situ polymerization for causing vinyl chloride monomer, can use azo-initiator, peroxide initiator or their mixture.
Described azo-initiator comprises 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate or their mixture.
Described peroxide initiator comprises at least a in the group that dibenzoyl peroxide, di-isopropyl peroxydicarbonate, peroxy dicarbonate two (2-ethylhexyl) etc. are formed.
The dispersion agent that dispersion agent used in the present invention is used during for suspension polymerization of VC, optional at least a in the group that gelatin, polyvinyl alcohol, methylcellulose gum, Vltra tears etc. are formed.
Described modified manometer silicon dioxide is the nano silicon through the organic compound surface modification, and its particle diameter is 5～200 nanometers.
Re-initiation polymerization of vinyl choride monomer after the method that the present invention adopts in-situ polymerization is dispersed in modified manometer silicon dioxide in the vinyl chloride monomer, modified manometer silicon dioxide is present in the vinylchlorid suspension monomer droplet or the drop surface, the part emits during chloroethylene polymerization, and big calorimetric drawn game portion shearing action can promote dissociating of modified nano silicon dioxide particles coacervate, increased the consistency between nano particle and the polymkeric substance, hinder the coalescence between the polyvinyl chloride primary particle, made the purer polyvinyl chloride suspension polymerization of the particle size particle of the nano composite material that polyvinyl chloride and silicon-dioxide are formed reduce to some extent; Nano silicon is homodisperse in matrix material, does not have or have only seldom to reunite.
Nano silicon is because particle diameter is less, has bigger surface free energy, ion surface contains a large amount of active hydroxys, in position in polymerization single polymerization monomer during polymerization or the final polymkeric substance, often be agglomerated into bigger particle easily, influence the stability of polyreaction and the performance of end article, can not give full play to the effect unique of nanoparticle.Therefore, the present invention adopts the nano silicon of organic compound surface modification.The surface tissue of modified manometer silicon dioxide is become the hydrophobicity (lipophilicity) on modified manometer silicon dioxide surface by the wetting ability (oleophobic property) of former nano-silica surface, improved the consistency of nanoparticle and monomer and polymkeric substance, helping nanoparticle is dispersed in vinyl chloride monomer and the final polyvinyl chloride (PVC) RESINS matrix, also solve simultaneously the hanging drop stability and the uniform problem of conducting heat in the polymerization process, reduced the possibility that sticking still phenomenon takes place.Of the present invention method is simple, can effectively control the reunion of modified manometer silicon dioxide in the polyvinyl chloride particles and prevent the sticking still of product.
Because the properties-correcting agent that commercially available modified manometer silicon dioxide is used and the difference of content thereof, the ion surface active hydroxy is still more, is not fine being applied to when of the present invention often.Therefore, for can the better polyvinyl chloride of processability and the nano composite material formed of silicon-dioxide, the present invention also provides a kind of preparation method of modified manometer silicon dioxide, and the preparation method of this modified manometer silicon dioxide is:
Weight part with nano silicon is a benchmark, raw material nano silica 1 0～100 weight part is dispersed in the organic solvent of 100～500 weight parts, under whipped state, be heated to 70～130 ℃, add organic modifiers 10～100 weight parts, under said temperature, kept stirring reaction 6～24 hours; Filtering reaction product, solid leach the thing solvent wash; Leach thing after the dry washing, obtain modified manometer silicon dioxide.
The modified manometer silicon dioxide that preparation method by the modified manometer silicon dioxide among the present invention obtains, its particle size keeps the particle size of raw material substantially.Though the removing of drying stage solvent in preparation can cause the particulate reunion, as long as the modified manometer silicon dioxide product does not lump, do not influence it and is dissociated into one nanometer silicon dioxide particle in polymerization process in position.If the modified manometer silicon dioxide product that obtains caking, the dispersion when in-situ suspension polymerization that is unfavorable for the nano composite material that it is formed at polyvinyl chloride and silicon-dioxide prepares and the formation of hanging drop, can carry out fragmentation to the modified manometer silicon dioxide that obtains in case of necessity, obtain to cross the modified manometer silicon dioxide powder of 200 order sub-sieves.The breaking method that can adopt comprises grinding, Mechanical Crushing and comminution by gas stream etc.
Described drying temperature is preferably 60 ℃～130 ℃.
Described raw material can be that particle diameter is the unmodified nano silicons of 5～200 nanometers, also can be that particle diameter is the nano silicon of 5～200 nano modifications.
Described organic solvent can be selected from least a in the group that toluene, dimethylbenzene, dimethyl sulfoxide (DMSO), acetone, methyl alcohol, ethanol, Virahol etc. are formed.
Optional at least a in the group that organic silane compound, titante coupling agent, aluminium esters of gallic acid coupling agent, stearic acid, stearate, stearate etc. are formed of described organic modifiers.Preferred organic silane compound.
Described organosilane compounds is selected from least a in the group that silane coupling agent, chlorosilane, hexamethyldisilazane etc. are formed.
Described silane coupling agent can be selected from least a in the group that aminosilane, methoxy silane, Ethoxysilane, propoxy-silane, allyl group organoalkoxysilane, epoxy group(ing) organoalkoxysilane etc. are formed.
Described chlorosilane can be selected from least a in the group that methyl chlorosilane, dimethyl-3-chloropropyl chlorosilane, phenyl methyl chloro silicomethane etc. are formed.
Described titante coupling agent can be selected from least a in the group that three Unimac 5680 isopropyl titanates, isopropyl tri (dioctylpyrophosphato)titanate, tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanic acid ester, titanium isopropylate etc. are formed.
Described aluminium esters of gallic acid coupling agent can be selected from distearyl oxygen aluminum isopropoxide acid esters, at least a in the group that phosphoric acid ester acyloxy isooctyl alcohol aluminate coupling agent etc. is formed.
Described stearate can be selected from least a in the group that sodium stearate, Magnesium Stearate, calcium stearate, lead stearate, aluminum stearate, cadmium stearate, iron stearate, potassium stearate, Zinic stearas etc. are formed.
Described stearate can be selected from least a in the group that n-butyl stearate, isobutyl stearate, the different monooctyl ester of stearic acid, pentaerythritol stearate etc. are formed.
Describedly be used to wash the aqueous solution that solvent that solid leaches thing is selected from organic solvent and water arbitrary volume ratio, described organic solvent can be selected from least a in the group that methyl alcohol, ethanol, acetone, Virahol etc. are formed, the preferred aqueous ethanolic solution of selecting, the volume ratio of preferred organic solvent and water is 1: 1.
Described drying can be selected methods such as constant pressure and dry, vacuum-drying, spraying drying or expansion drying for use.
The preparation method of the modified manometer silicon dioxide that relates among the present invention, organic modifiers is grafted on nano-silica surface, eliminated the active hydroxy of part on the raw material nano silicon-dioxide, the modified manometer silicon dioxide that obtains has been avoided the disadvantageous effect of the adding of existing nano silicon to polyreaction and product properties when being used to prepare the nano composite material of polyvinyl chloride and silicon-dioxide composition.
The in-situ suspension polymerization preparation method of the nano composite material that polyvinyl chloride provided by the invention and silicon-dioxide are formed, adopt modified manometer silicon dioxide, the consistency of this modified manometer silicon dioxide and vinyl chloride monomer and polyvinyl chloride (PVC) RESINS is good, can effectively overcome the agglomeration of nano silicon, avoid the sticking still phenomenon of product.This method needn't be carried out bigger change to suspension polymerization equipment and processing parameter, just can obtain the nano composite material that polyvinyl chloride and silicon-dioxide are formed, and has simple and easy to do characteristics.
The nano composite material that polyvinyl chloride provided by the invention and silicon-dioxide are formed, because modified manometer silicon dioxide good dispersiveness and interface compatibility in the polyvinyl chloride matrix, improved the over-all properties of material, the thermostability, mechanical property and the shock resistance that comprise pvc material have obtained the new variety of polyvinyl chloride nano matrix material.In addition, because the product particle size reduces to some extent, help absorption, absorb multiple polyvinyl chloride processing and modified additive, thereby further improve the performance of goods.The nano composite material that polyvinyl chloride that the inventive method obtains and silicon-dioxide are formed can be widely used in each field such as insulating material, material of construction, wrapping material.
Description of drawings
Figure 1A. the stereoscan photograph of the nano composite material resin particle that the polyvinyl chloride of the embodiment of the invention 1 in-situ polymerization and silicon-dioxide are formed.
Figure 1B. the stereoscan photograph of the nano composite material resin particle that the polyvinyl chloride of the embodiment of the invention 2 in-situ polymerizations and silicon-dioxide are formed.
Embodiment
The purpose of following specific embodiment is in order to further specify technical characterictic of the present invention, to need to prove, the present invention is not limited to following specific embodiment.
1. preparation modified manometer silicon dioxide: with the 10g median size is that the nano silicon of 12 nanometers is dispersed in the 400ml toluene, under whipped state, be heated to 120 ℃, add the 10g dimethylchlorosilane, under said temperature, keep 12 hours after-filtration of stirring reaction, with the mixed solvent washing several of filtrate with ethanol and water 1: 1 (volume ratio), the silicon-dioxide after the washing is dry under 110 ℃ in vacuum drying oven, cross 200 order sub-sieves after grinding and obtain modified manometer silicon dioxide.
2. prepare the nano composite material that polyvinyl chloride and silicon-dioxide are formed: under nitrogen protection; modified manometer silicon dioxide 1.10g (modified manometer silicon dioxide and vinyl chloride monomer mass percent are 0.1%), deionized water 1800ml, initiator dibenzoyl peroxide 0.5g, dispersion agent Vltra tears 0.5g are joined in the suspension polymerization still, inject vinyl chloride monomer 1100g then.Stir speed (S.S.) with 350 rev/mins under 20 ℃ stirred at a slow speed 20 minutes; Stir speed (S.S.) during again with 700 rev/mins polymerization of vinyl choride monomer stirred 30 minutes fast; Being warmed up to temperature of reaction at last is 50～70 ℃, carries out in-situ polymerization under 700 rev/mins stir speed (S.S.), and (reaction is finished) cooling removes residual monomer when system reaches certain pressure and falls; With reaction gained slurry after filtration, aftertreatment such as drying promptly obtains the polyvinyl chloride of in-situ polymerization and the nano composite material resin that silicon-dioxide is formed.Polyreaction is stable, basically eliminate sticking still phenomenon.The stereoscan photograph of the nano composite material resin particle that the polyvinyl chloride of gained in-situ polymerization and silicon-dioxide are formed shown in Figure 1A, gained PVC composite resin uniform particle diameter; The transmission electron microscope observation in-situ polymerization resin finds that silicon-dioxide disperses with nano-scale in polymkeric substance; The all purer polyvinyl chloride product of PVC composite materials property and thermostability has a more substantial increase, the gel gas chromatographic analysis, and its molecular weight and molecular weight distribution are as shown in table 1.
Embodiment 2
1. preparation modified manometer silicon dioxide: with the 10g median size is that the nano silicon of 25 nanometers is dispersed in the 200ml dimethyl sulfoxide (DMSO), under whipped state, be heated to 120 ℃, add 25g octadecyl Trimethoxy silane, under said temperature, keep 12 hours after-filtration of stirring reaction, with the mixed solvent washing several of filtrate with ethanol and water 1: 1 (volume ratio), with the silicon-dioxide after the washing in vacuum drying oven 110 ℃ of dryings, grind the back and cross 200 order sub-sieves and obtain modified manometer silicon dioxide.
2. prepare the nano composite material that polyvinyl chloride and silicon-dioxide are formed: under nitrogen protection; modified manometer silicon dioxide 11.0g (modified manometer silicon dioxide and vinyl chloride monomer mass percent are 1%), deionized water 2000ml, initiator 2,2'-Azobis(2,4-dimethylvaleronitrile) 0.6g, dispersion agent methylcellulose gum 0.5g are joined in the suspension polymerization still, inject vinyl chloride monomer 1100g then.Stir speed (S.S.) with 350 rev/mins under 10 ℃ stirred at a slow speed 20 minutes; Stir speed (S.S.) during again with 700 rev/mins polymerization of vinyl choride monomer stirred 30 minutes fast; Being warmed up to temperature of reaction at last is 50～70 ℃, carries out in-situ polymerization under 700 rev/mins stir speed (S.S.), and (reaction is finished) cooling removes residual monomer when system reaches certain pressure and falls; With reaction gained slurry after filtration, aftertreatment such as drying promptly obtains the polyvinyl chloride nano composite resin of in-situ polymerization.Polyreaction is stable, basically eliminate sticking still phenomenon.The stereoscan photograph of the nano composite material resin particle that the polyvinyl chloride of gained in-situ polymerization and silicon-dioxide are formed shown in Figure 1B, gained PVC composite resin uniform particle diameter; The transmission electron microscope observation in-situ polymerization resin finds that silicon-dioxide disperses with nano-scale in polymkeric substance; The all purer polyvinyl chloride product of PVC composite materials property and thermostability has a more substantial increase, and through the gel gas chromatographic analysis, its molecular weight and molecular weight distribution are as shown in table 1.
Embodiment 3
1. preparation modified manometer silicon dioxide: with the 10g median size is that the nano silicon of 50 nanometers is dispersed in the 300ml acetone, under whipped state, be heated to 130 ℃, add the 30g hexamethyldisilazane, under said temperature, keep 6 hours after-filtration of stirring reaction, with filtrate for several times with the mixed solvent washing of ethanol and water 1: 1 (volume ratio), with the silicon-dioxide after the washing in vacuum drying oven 110 ℃ of dryings, grind the back 200 order sub-sieves obtain modified manometer silicon dioxide.
2. prepare the nano composite material that polyvinyl chloride and silicon-dioxide are formed: under nitrogen protection; modified manometer silicon dioxide 50.0g (modified manometer silicon dioxide and vinyl chloride monomer mass percent are 5%), deionized water 2500ml, initiator peroxy dicarbonate two (2-ethylhexyl) 0.8g, dispersion agent gelatin 0.3g and methylcellulose gum 0.5g are joined in the suspension polymerization still, inject vinyl chloride monomer 1000g then.Stir speed (S.S.) with 100 rev/mins under 35 ℃ stirred at a slow speed 30 minutes; Stir speed (S.S.) during again with 700 rev/mins polymerization of vinyl choride monomer stirred 30 minutes fast; Being warmed up to temperature of reaction at last is 50～70 ℃, carries out in-situ polymerization under 700 rev/mins stir speed (S.S.), and (reaction is finished) cooling removes residual monomer when system reaches certain pressure and falls; With reaction gained slurry after filtration, aftertreatment such as drying promptly obtains the polyvinyl chloride of in-situ polymerization and the nano composite material resin that silicon-dioxide is formed.Polyreaction is stable, basically eliminate sticking still phenomenon.Gained PVC composite resin uniform particle diameter; The transmission electron microscope observation in-situ polymerization resin finds that silicon-dioxide disperses with nano-scale in polymkeric substance; The all purer polyvinyl chloride product of PVC composite materials property and thermostability has a more substantial increase, and the polyvinyl chloride nano composite resin of gained in-situ polymerization is through the gel gas chromatographic analysis, and its molecular weight and molecular weight distribution are as shown in table 1.
Embodiment 4
1. preparation modified manometer silicon dioxide: with the 150g median size is that the nano silicon of 25 nanometers is dispersed in the 1500ml Virahol, under whipped state, be heated to 70 ℃, add the 300g hexamethyldisilazane, under said temperature, keep 24 hours after-filtration of stirring reaction, with filtrate for several times with the mixed solvent washing of ethanol and water 1: 1 (volume ratio), with the silicon-dioxide after the washing in vacuum drying oven 110 ℃ of dryings, grind the back 200 order sub-sieves obtain modified manometer silicon dioxide.
2. prepare the nano composite material that polyvinyl chloride and silicon-dioxide are formed: under nitrogen protection; modified manometer silicon dioxide 150g (improved silica and vinyl chloride monomer mass percent are 15%), deionized water 2500ml, initiator Diisopropyl azodicarboxylate 1.0g, dispersion agent methylcellulose gum 0.8g are joined in the suspension polymerization still, inject vinylchlorid (VC) monomer 1000g then.Stir speed (S.S.) with 400 rev/mins under 5 ℃ stirred at a slow speed 40 minutes; Stir speed (S.S.) during again with 800 rev/mins polymerization of vinyl choride monomer stirred 20 minutes fast; Being warmed up to temperature of reaction at last is 50～70 ℃, carries out in-situ polymerization under 700 rev/mins stir speed (S.S.), and (reaction is finished) cooling removes residual monomer when system reaches certain pressure and falls; With reaction gained slurry after filtration, aftertreatment such as drying promptly obtains the polyvinyl chloride of in-situ polymerization and the nano composite material resin that silicon-dioxide is formed.Polymerization process is stable, does not have sticking still phenomenon and takes place; The transmission electron microscope observation in-situ polymerization resin finds that silicon-dioxide disperses with nano-scale in polymkeric substance; The all purer polyvinyl chloride product of PVC composite materials property and thermostability has a more substantial increase.
Comparative Examples 1
Prepare pure pvc material: under nitrogen protection, deionized water 1800ml, initiator Diisopropyl azodicarboxylate 1.0g, dispersion agent Vltra tears 0.8g are joined in the suspension polymerization still, inject vinylchlorid (VC) monomer 1200g then.Stir speed (S.S.) with 350 rev/mins under 10 ℃ stirred at a slow speed 20 minutes; Stir speed (S.S.) during again with 700 rev/mins polymerization of vinyl choride monomer stirred 30 minutes fast; Being warmed up to temperature of reaction at last is 50～70 ℃, carries out in-situ suspension polymerization under 700 rev/mins stir speed (S.S.), and (reaction is finished) cooling removes residual monomer when system reaches certain pressure and falls; With reaction gained slurry after filtration, aftertreatment such as drying promptly obtains pure polyvinyl chloride (PVC) RESINS.Polyreaction is stable, does not have sticking still phenomenon, gained polyvinyl chloride resin uniform particle diameter.Through the gel gas chromatographic analysis, its molecular weight and molecular weight distribution are as shown in table 1.
Comparative Examples 2
The nano composite material that preparation polyvinyl chloride and silicon-dioxide are formed: under nitrogen protection; with the particle diameter of non-modified is that nano silicon 1.1g (silicon-dioxide and vinyl chloride monomer mass percent are 0.1%), deionized water 1800ml, initiator dibenzoyl peroxide 0.5g, the dispersion agent Vltra tears 0.8g of 12 nanometers joins in the suspension polymerization still, injects vinyl chloride monomer 1100g then.Stir speed (S.S.) with 350 rev/mins under 10 ℃ stirred at a slow speed 20 minutes; Stir speed (S.S.) during again with 700 rev/mins polymerization of vinyl choride monomer stirred 30 minutes fast; Being warmed up to temperature of reaction at last is 50～70 ℃, carries out in-situ suspension polymerization under 700 rev/mins stir speed (S.S.), and (reaction is finished) cooling removes residual monomer when system reaches certain pressure and falls; Implode takes place in discovery polyreaction instability, and sticking still phenomenon is serious.
By above embodiment and Comparative Examples as can be seen, compare with pure PVC, the silica nanometer that adds modification carries out polyvinyl chloride/silicon dioxide nano composite material molecular weight that in-situ suspension polymerization obtains and changes not quite with molecular weight distribution, polyreaction is stable, do not have sticking still phenomenon and take place, the every performance of material all has a more substantial increase; And the silica nanometer of adding non-modified, polyreaction is difficult to control, even the implode phenomenon takes place, and sticking still phenomenon is serious.
The molecular weight and the molecular weight distribution of table 1. Comparative Examples 1 and embodiment 1,2 and 3 gained materials
Claims (10)
1. the in-situ suspension polymerization preparation method of the nano composite material formed of polyvinyl chloride and silicon-dioxide is characterized in that this method may further comprise the steps:
(1) under protection of inert gas, in the suspension polymerization still, add modified manometer silicon dioxide, deionized water, initiator and dispersion agent in advance, introduce vinyl chloride monomer then and obtain reaction system; Temperature of reaction when temperature is lower than polymerization of vinyl choride monomer, and stir at a slow speed under the stir speed (S.S.) when not being higher than the vinyl chloride monomer home position polymerization reaction, modified manometer silicon dioxide is dispersed in the reaction system, stirring makes vinyl chloride monomer form hanging drop in reaction system fast then, obtains suspension;
(2) suspension that step (1) is obtained heats up, and control reaction temperature is 50～70 ℃, carries out the home position polymerization reaction of vinylchlorid under 700～800 rev/mins agitation condition; After polyreaction finishes, reaction paste after filtration, drying, obtain the nano composite material that polyvinyl chloride and silicon-dioxide are formed;
Described reaction system is under the benchmark at the weight part with vinyl chloride monomer, and each component concentration in the reaction system is:
Vinyl chloride monomer: 100 weight parts;
Modified manometer silicon dioxide: 0.01～15 weight part;
Deionized water: 100～250 weight parts;
Initiator: 0.01～0.1 weight part;
Dispersion agent: 0.01～0.1 weight part.
2. method according to claim 1 is characterized in that: the stir speed (S.S.) the when stir speed (S.S.) of described quick stirring is the vinyl chloride monomer home position polymerization reaction.
3. method according to claim 1 is characterized in that: described initiator is azo-initiator, peroxide initiator or their mixture;
Described dispersion agent is to be selected from least a in the group that gelatin, polyvinyl alcohol, methylcellulose gum, Vltra tears form.
4. method according to claim 3 is characterized in that: described azo-initiator is 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate or their mixture;
Described peroxide initiator is selected from least a in the group that dibenzoyl peroxide, di-isopropyl peroxydicarbonate, peroxy dicarbonate two (2-ethylhexyl) formed.
5. method according to claim 1 is characterized in that: the particle diameter of described modified manometer silicon dioxide is 5～200 nanometers.
6. method according to claim 1 or 5, it is characterized in that: described modified manometer silicon dioxide is prepared by following method:
Weight part with nano silicon is a benchmark, raw material nano silica 1 0～100 weight part is dispersed in the organic solvent of 100～500 weight parts, under whipped state, be heated to 70～130 ℃, add organic modifiers 10～100 weight parts, under said temperature, kept stirring reaction 6～24 hours; Filtering reaction product, solid leach the thing solvent wash; Leach thing after the dry washing, obtaining particle diameter is 5～200 nano modification nano silicons.
7. method according to claim 6 is characterized in that: described raw material nano silicon-dioxide is that particle diameter is the unmodified nano silicons of 5～200 nanometers, or particle diameter is the nano silicon of 5～200 nano modifications.
8. method according to claim 6 is characterized in that: described organic solvent is selected from least a in the group that toluene, dimethylbenzene, dimethyl sulfoxide (DMSO), acetone, methyl alcohol, ethanol, Virahol forms;
Described organic modifiers is selected from least a in the group that organosilane compounds, titante coupling agent, aluminium esters of gallic acid coupling agent, stearic acid, stearate, stearate form.
9. method according to claim 8 is characterized in that: described organosilane compounds is selected from least a in the group that aminosilane, methoxy silane, Ethoxysilane, propoxy-silane, allyl group organoalkoxysilane, epoxy group(ing) organoalkoxysilane, methyl chlorosilane, dimethyl-3-chloropropyl chlorosilane, phenyl methyl chloro silicomethane, hexamethyldisilazane form;
Described titante coupling agent is selected from least a in the group that three Unimac 5680 isopropyl titanates, isopropyl tri (dioctylpyrophosphato)titanate, tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanic acid ester, titanium isopropylate form;
Described aluminium esters of gallic acid coupling agent is selected from distearyl acyl-oxygen aluminum isopropoxide acid esters, at least a in the group that phosphoric acid ester acyloxy isooctyl alcohol aluminate coupling agent is formed;
Described stearate is selected from least a in the group that sodium stearate, Magnesium Stearate, calcium stearate, lead stearate, aluminum stearate, cadmium stearate, iron stearate, potassium stearate, Zinic stearas form;
Described stearate is selected from least a in the group that n-butyl stearate, isobutyl stearate, the different monooctyl ester of stearic acid, pentaerythritol stearate form.
10. the nano composite material formed of polyvinyl chloride that is prepared by any described method of claim 1～5 and silicon-dioxide is characterized in that: at the weight part with vinyl chloride monomer is that component and content under the benchmark is:
Polyvinyl chloride: 100 weight parts;
Modified manometer silicon dioxide: 0.01～15 weight part.
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