CN1068885C - Method for preparing polymer nanometre composite material - Google Patents

Abstract

The present invention relates to a high performance nano composite material which is prepared from aromatic nitrogen containing substance, acrylic acid, ester derivatives, oligomers, delta-manganese dioxide, kaolin, white slime, white clay magnesia, natural layered inorganic graphite solid, natural polymers and synthetic polymers as raw materials by a multi-step diffusion method, an exchanging method and a reaction method. By adjusting conditions such as adjusting ranking medium and monomers, the concentration of oligomers, flow fields, reaction time, environment temperature, etc. by controlling the structure of products, a nano composite membrane or section can be used as lithium, lithium ion secondary batteries and electrolyte membranes, traffic products with high intensity and high impact resistance, vehicle products with high intensity and high impact resistance, building products with high intensity and high impact resistance, rubber pieces with high temperature resistance and oil resistance, heat exchanger pieces with heat conduction and corrosion resistance, transparent nontoxic thermoplastic plastics with high intensity and impact resistance for the package of biologic-medical treatment, food (high temperature resistance up to 120 DEG C), etc.

Description

The preparation method of polymer nanocomposites

The present invention relates to the preparation method of polymer nanocomposites, specifically be meant fields such as being applied to agricultural, energy environment protection, information, traffic, building, chemical industry, automobile, biologic medical apparatus, food product pack, such as the preparation method of lithium or lithium ion secondary battery electrode, solid thin film electrolyte, flexible polymer electrolytic thin-membrane, high temperature resistant elastomerics, the low-cost polymer nanocomposites of the contour performance of shock resistance transparent plastics.

The negative electrode that discloses a kind of commodity lithium-ion secondary cell in the 8th the international lithium-ion secondary cell meeting on June 16th～21,1996 has the charging capacity up to 372～900Ah (ampere hour)/Kg, but the capacity of entire cell is subjected to being limited within 100～150Ah/Kg of anode specific storage.Anode material is used cobalt dioxide lithium, nickel dioxide lithium and lithium manganese dioxide always, wherein nontoxic, the easy-formation of lithium manganese dioxide, raw material sources are wide, and price is low, but the lithium manganese dioxide reactive behavior is big, and battery cycle life only could keep under low charging or discharging current density.The H.Yoneyama of Osaka, Japan university and the beautiful C.R.Martin that schemes Colorado state university cooperate, and adopt the template synthesis method to make polypyrrole coated spinel type LiMn ₂O ₄Nanotube is made anode for lithium secondary battery active material [seeing the journal J.Electrochem.Soc.Vol.144 of U.S. ECS, No6,1923～1927 (1997)], at 0.1mA/cm ²Under the charging and discharging currents density, cyclic discharge capacity is 130mAh/g for the first time, when charging and discharging currents density increases to 0.5mA/cm ²The time, electrical capacity drops to 95mAh/g; When charging and discharging currents density increases to 1.0mA/cm ²The time, electrical capacity has dropped to 70mAh/g.

What another influenced film-type high energy secondary cell key property is the ionic conductivity of solid thin film electrolyte, and they reach 4.67 * 10 by the ionic conductivity of polyacrylonitrile (PAN) composite electrolyte membrane made the sincere Lang Gongbu of the middle forest of 1994 annual report Japan in November ^-3S/cm (room temperature), [electrochemistry (day), NO11,1034～1038 (1994)], to the Pu-WeiWu of the U.S. in 1997, people such as R.B.Kaner have made silicon-dioxide (SiO from methyl silicate (TMOS) ₂) network of micropores contains LiBF4 (LiBF ₄) gel electrolyte of salt, ionic conductivity reaches 3.5 * 10 ^-3S/cm (room temperature), 10 ^-2S/cm (80 ℃) [materials chemistry Chem, Mater.V.9NO4,1004～1011, (1997)].

Big plastics variety has polystyrene (PS), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP) etc., when the shock resistance while of improving them with rubber-like toughner, rigidity (modulus), intensity, hardness, thermotolerance and obstruct liquid, gas performance have but been reduced.United States Patent (USP) " has the good impact-resistance and the PP component of transparency " [US5541260 MontellNorth Amercica Inc. such as () A.Relliconi], and it is at 70 to 98 weight part crystallization PP or propylene and ethene and/or contains ethene and/or the alpha-olefin C of 0.5 to 10 weight % ₄～C ₁₀Multipolymer in, add elastomer copolymer 2 to the 30 weight parts composition of the ethene contain 60 to 85 weight % and one or more alkene.The problem that equally also has above-mentioned degradation.

Thermoplastic elastomer such as SBS, SIS etc., processing conditions is convenient as plastics, and also as rubber, just intensity, modulus and rebound resilience were poor slightly, not anti-benzene and gasoline kind solvent when low temperature-60 ℃～80 ℃ used down.For performances such as heat-resisting, the oil resistants that improves thermoplastic elastomer, day disclosure special permission communique: flat 07-258351,1995 reports: " the acrylic elastomer class properties-correcting agent that is used for the PVC modification ", in 100 parts of PVC, add 40 parts of this acrylic elastomer class properties-correcting agent, 80 parts of dioctyl phthalate (DOP)s (DOP), 4 parts of stablizers, making tensile strength is 9.23MPa, elongation 248%, the thermoplastic elastomer of tension set 22%.Though this thermoplastic elastomer mechanical property is medium, rise significantly because of being added with 40 parts of esters of acrylic acid rubber costs.Similar U.S. Pat 5554683 (Mitsubishi Chemical product MKV company, contriver M, oshima) also propose in: the polyvinyl chloride (PVC) RESINS elastomerics is made up of following main ingredient: the polyvinyl chloride of 100 weight parts (PVC) resin, contain acrylic rubber 10～200 weight parts of linking agent component 1～50 weight part (by acrylic resin) that is insoluble to tetrahydrofuran (THF) and the fluidizer of 30～300 weight parts and form.More than two kinds of technical schemes all exist with acrylic rubber cost height, thermotolerance is subjected to the acrylic rubber use temperature to be no more than the restriction of the upper temperature limit of 150 ℃ and fluidizer vaporization at high temperature.

The objective of the invention is to, overcome the weak point of above-mentioned background technology, utilize two or more aromatic series nitrogenous compound and laminated crystalline inorganics to be raw material, by forming new structure and the synergistic effect of nanophase interfacial layer, a kind of preparation method who comprises the polymer nanocomposites of steps such as diffusion, exchange, polymerization and/or crosslinking reaction is provided, the starting material wide material sources that it adopts, price is low relatively, can utilize the existing installation of similar factory, simultaneously can avoid environmental pollution, product properties increases substantially, use range enlarges.

The objective of the invention is to realize by following measure:

A kind of is the starting material monomer with the aromatic series nitrogenous compound, serves as the preparation method of the polymer nanocomposites of row position medium with protonic acid or aprotic acid or non-proton hydrochlorate, it is characterized in that:

(1) raw material of this law also comprises:

1. aliphatics vinylformic acid and ester derivative thereof and oligomer comprise that the chemical structure skeleton symbol is:

R in the formula ₁, R ₂Can be H, CH ₃, C ₂H ₅, C ₃H ₇, C ₄H ₉, C ₅H ₁₁C ₁₈H ₃₇, R ₁Can with R ₂Similar and different, n=2～48, its concentration is 0.02～3.5 mole aliphatics vinylformic acid and ester derivative and oligomer,

2. the laminate structure inorganics comprises: kaolin, white clay (kaolin and white mica mixture), and magnesite soil natural matter and δ-Manganse Dioxide, tindioxide, graphite oxide, plumbic oxide, lithium hydroxide, Quilonum Retard, aluminium hydroxide,

3. polymkeric substance comprises: polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyester resin, polyamide resin, polydimethylacrylamiin, poly-isobutyl-acrylamide, polyacrylic ester, polycarbonate, poly-vinyl acetic monomer and multipolymer, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), natural rubber, SBS Thermoplastic Elastomer, SIS, paracril, polyacrylonitrile, polymethyl siloxane (silicon rubber) and the blend between them

4. row position medium also comprises: lithium hexafluoro phosphate (LiPF ₆), lithium-fluoroborate (LiBF ₄), trifluoroacetic acid (CF ₃COOH), trichoroacetic acid(TCA) (CCl ₃COOH), lithium perchlorate (LiClO ₄), zinc perchlorate (Zn (ClO ₄) ₂), magnesium perchlorate (Mg (ClO ₄) ₂), aluminum perchlorate (Al (ClO ₄) ₃), aluminum chloride (AlCl ₃), dimethyl sulfoxide (DMSO) (DMSO), Witco 1298 Soft Acid and sodium salt, dinaphthyl sulfonic acid and sodium salt thereof, aluminum phosphate (AlPO ₄), Tai-Ace S 150 (Al ₂(SO ₄) ₃), L-GLUTAMICACID, polytetrafluoroethylene powder, light amino acid, corn prolamin, ((carbon atom quantity 1～20 is as methylamine, ethamine for particle diameter 20～300nm), organic fat amine for conductive carbon black ...), trolamine, acetic ester (CH ₃R is ethyl, propyl group among the COOR ... octyl group and CN yl), acetate (CH ₃Me is aluminium, zinc, calcium, lead and ammonia among the COOMe), N, N ' dimethyl formamide (DMF), its concentration is 0.1～6 mole;

(2) step and the processing condition thereof of preparation polymer nanocomposites:

Step 1: multistep diffusion and exchange:

At institute's prepared material or the requirement of goods working conditions, select two or more monomer, laminate structure inorganics and row position medium and their concentration and consumption proportion, and they are put into reactor, swelling, dissolving or fusion are spread and exchange, its temperature controlling range is-10～180 ℃, time span of control 4 minutes～46 hours

Step 2: polymerization and/or crosslinking reaction

Add industrial normal starter and linking agent, reacted 0.2～40 hour down at 20 ℃～180 ℃,

Step 3: blend

According to the requirement of institute's prepared material, add one or more polymer blends, with universal industrial equipment high-speed mixing, open refining or banburying, extrude, mode such as injection or thermovacuum moulding obtains product.

At institute's prepared material or the requirement of goods working conditions, select on the basis of raw material, monomer and row position medium, by adjusting monomer, raw material and oligomer concentration and proportioning thereof, determine diffusion, exchange and reactions steps, control reaction conditions (time, temperature etc.) makes material or the goods made reach desired structure of design and performance.

The present invention compared with prior art has following outstanding advantage:

1. utilize two or more monomer, performed polymer and multiple row position medium or the synergistic effect between the blend of multiple row position medium, make the performance index of goods, material reach the suitable requirement that fields such as being used for agricultural, energy environment protection, information, traffic, building, chemical industry, automobile, biology-medicine equipment, food product pack is higher than existing goods or product innovation respectively, opened up the new wide purposes of high-performance and low-cost polymer nanocomposites and goods.

2. polymer molecular chain is embedded in the layered inorganic lattice (in ), or the inorganic nano crystal layer is dispersed in the polymeric matrix, both guaranteed the excellent specific property that new texture had of the nano-interface layer of inorganic lattice and polymer molecule chain formation, new synergy between inorganic/organic polymer interface obtains maximum performance, the formability that has kept polymeric matrix itself to have again, the energy-absorbing shock resistance that the high mechanical strength of molecular chain orientation and viscoelastic are lax, environmental corrosion resisting, characteristics such as cost is low, thus the material and the product properties thereof of making are significantly improved.

3. polyaniline embeds δ-Manganse Dioxide lattice (interlamellar spacing: make the anode of lithium or lithium-ion secondary cell 15.3 ), make the battery can be at big charging and discharging currents density l～5mA/cm ²Under the condition, still keep 170～132mAh/g respectively.When charging and discharging currents density is 0.2mA/cm ²The time reach 180mAh/g.And charging or discharging current density is 1mA/cm ²The time, be that specific storage under 20,40,60 ℃ is respectively 170,178,182mAh/g in temperature, have good temperature stability.The polypyrrole coated spinel type LiMn that cooperates to make than Osaka, Japan university and U.S. Colorodo state university ₂O ₄Nanotube is made anode for lithium secondary battery, at 1.0mA/cm ²The time charging and discharging currents density under loading capacity be the 70mAh/g height only more than one times.

4. can make flexible polyelectrolyte membrane, thickness can reach micron-scale, distortion and strong with attachment of electrodes power, ionic conductivity δ=10 ^-1S/cm (room temperature) is than δ=4.67 * 10 that polymer dielectric is the highest so far of Japanese publication ^-3High two orders of magnitude of s/cm (room temperature), the silicon-dioxide of making than the U.S. contains LiBF ₄The dielectric δ of gel=3.5 * 10 ^-3S/cm (room temperature) and δ ≌ 10 ^-2The still high order of magnitude of s/cm (under 80 ℃).And the dielectric medium that we make is a flexible membrane, can add various liquid or solid dielectric medium salt and is applicable to various electrode ion transport, and as lithium, zinc, sodium, magnesium, aluminium plasma, use temperature is wide from-40～150 ℃ of scopes.

5. make polypropylene (PP) anti-impact transparent plastics, heatproof surpasses 155 ℃, is improving anti-impact, in the time of anti tear and heatproof, gas barrier property, has kept the original intensity of PP, modulus, hardness and protection against corrosion, characteristic such as nontoxic again.This is because we do not improve the result of impact-resistance with adding great number of elastic body or multipolymer, usually in PP, add elastomerics or multipolymer amount 8 weight %, modulus, intensity, hardness, heatproof and barrier all can descend 10～20%, and descend bigger with this amount increase.This just will add than U.S. Pat 5541260 (Montell North America Inc.), and elastomerics or the elastomeric material modulus of ethylene-propylene copolymer, intensity, hardness and the resistance to heat distorsion of (to 30 weight %) want high more than 20% in a large number.

6. make polypropylene (PP), polyethylene (PE), polystyrene (PS) and polyoxyethylene (PVC) binary or the above blend of binary, both kept or improved the mechanical property of main polymer, have the characteristic of the second or the 3rd component again concurrently: the PP/PE/PVC blend, PP high strength, high fiberizability, high-modulus have been kept, the Chinese People's Anti-Japanese Military and Political College's gas that has PVC again concurrently be exposed to the sun ability and hardness, the deep drawing quality of PE and winter hardiness extend to the lower limit of shock resistance temperature range-40 ℃; The PS/PE/PVC blend had both kept high-modulus (rigidity), the high strength of PS, have the extensibility that Chinese People's Anti-Japanese Military and Political College's gas of PVC tans by the sun ability and hardness and PE again concurrently, increase substantially the resistance to impact shock of material, more can with the PS heat-drawn wire by 90 ℃ be increased to 150 ℃～more than 170 ℃.

7. make high temperature resistant SBS or SIS thermoplastic elastomer, can be with the high temp glass transition temperature of the SBS that produces now or SIS by Tg ₂Bring up to Tg for=96 ℃ ₂=156 ℃～178 ℃, low temperature glass transition temperature Tg ₁Then remain unchanged (about 75 ℃), improve simultaneously that Young's modulus is gentle, 3～5 times of the barriers of liquid (oil, benzene etc.).The raising of these a series of performances, make use temperature, modulus, rebound resilience, the barrier range expansion of SBS or SIS thermoplastic elastomer, former rubber item with chemically crosslinked can be interrupted, high temperature such as artificial mold pressing, the dress demoulding and heavy physical operating procedure reform full automatic plastics injection into and extrude slush molding (as medical health appliances such as preparation transfusion device, pipe, hot-water bottles), thereby reduce cost significantly.

8. make the high temperature resistant 175 ℃ of rubber of oil resistant, both can be made into thermoplastic elastomer, recyclable repeated multiple times processing is used, again can be through chemically crosslinked, in machine-shaping, carry out " sulfuration ", improve the high temperature resistant and resilient seal of oil resistant, satisfy the dynamic seal in the mechanical movement such as automobile, the service requirements of the anti-high temperature seepage of antidetonation transition pipeline.Owing to we have adopted the nano lamellar organic/inorganic to mix component at polymkeric substance and in system, cost is low, the oil resistant resistance to elevated temperatures is greater than 350 ℃, and having overcome in the prior art with the acrylic elastomer is the goods of main raw, and the highest oil resistant is high temperature resistant to be not more than 150 ℃ and the high problem of cost.As day disclosure special permission communique: flat 07-258351 report: add acrylic elastomer class properties-correcting agent and reach 40 weight parts/100 weight part PVC+80 weight part DOP, oil resistant is high temperature resistant to be lower than 130 ℃: U.S. Pat 555483 (Mitsubishi Chemical product MKV company): also be acrylic elastomer 10～20 weight parts (containing linking agent 1～50 weight part)/100 weight part PVC+30～300 weight part fluidizers, oil resistant is high temperature resistant equally is no more than 150 ℃.

9. make the only product of the nanometer layer composite plastic of 1.4 graphite or rubber and pipe thereof, scatterer, heat exchanger of heat conduction, protection against corrosion, proportion, have easy-formation, can use the erosion resistance of various acid such as sulfuric acid and hydrochloric acid, the thermal conductivity suitable down at 〉=110 ℃ with aluminium.When pressure falls when improving, heat exchange coefficient can increase exponentially, and because of long-time (about 8 years) wall non-scaling, has overcome after the metalwork fouling the sharply problem of decline of thermal conductivity.And can with freeze the coupling of water refrigeration plant, form the waring and cooling air conditioning system in buildings, chemical plant, hospital, warehouse etc.Do not need coating protection, the cost of unit heat transfer area only is below 1/2 of cast iron.

The contriver once had many successful tests, following 12 embodiment of existing choosing, thus further specify content of the present invention.

Embodiment one

Do the preparation of the polymer nanocomposites that lithium or lithium-ion secondary cell anode use, its step and processing condition are as follows:

Step 1: multistep diffusion and exchange

In the 150ml conical flask, add the layered manganese oxide (δ-MnO of 2 grams through diffusion embedding butylamine ₂) and contain the 100ml ethanolic soln that aniline 1 restrains, at room temperature stir 12～24 hours after-filtration.The powdery product usefulness absolute ethanol washing that leaches 2 times, 60 ℃ following dry 6 hours.

Step 2: polyreaction

The powder of putting the step 1 gained and was placed in encloses container 12～24 hours on the 1molHCl liquid level; Cause aniline by HCl steam, aggregate into polyaniline and embed δ-MnO ₂Laminated composites (ultimate analysis shows that polyaniline content is 15.86% in the mixture).

Step 3: blend

Mixture by the polyreaction gained: conductive carbon ink: the weight ratio of tetrafluoroethylene=8: 1: 1 feeds intake, this three component is mixed the back become the thick film of 0.2mm ± 0.02mm, promptly made the anonite membrane of lithium or lithium-ion secondary cell in 80 ℃ of following vacuum-dryings in 24 hours with bar film machine bar.In the loft drier that fills Ar gas, be pressed in the standard of making on the stainless (steel) wire three electrode secondary cells with the lithium sheet.Obtain the anode specific storage listed through different charging and discharging currents density measurements as following table:

Current density (mA/cm ²) 0.2 125

Specific storage (anode) 180 170 138 132

Beginning voltage (volt) 3.9 3.9 3.9 3.9

Average voltage (volt) 3.2 3.2 3.2 3.2

Embodiment two

The preparation of high temperature resistant SBS or SIS thermoplastic elastomer, its step and processing condition are as follows:

Step 1: multistep diffusion and exchange

In the 500ml bottle, add 30 grams behind the washing decon and only contain the white clay and the 100ml dimethyl sulfoxide (DMSO) (DMSO) of kaolin, white mica at 60 ℃ of following exsiccant, stir 24 hours after-filtration down at 80 ℃, products therefrom after 2 hours, adds 6ml concentrated hydrochloric acid and 6 gram L-glutamic acid [HO 50 ℃ of following vacuum-dryings ₂CCHNH ₂(OH ₂) ₂CO ₂H] and water form the mixing solutions of 100ml, adding 100ml water again stirred 12 hours down at 80 ℃, hot water with 100ml after product filters divides three washings, wash back 50 ℃ of following vacuum-dryings 2 hours, this desciccate and 13.5ml butyl acrylate, 0.1 gram benzoyl peroxide (BPO), 150ml toluene are added the 500ml there-necked flask simultaneously, stirred 2.4 hours down at 30 ℃.

Step 2: polyreaction

Place the step 1 products therefrom of there-necked flask, feed nitrogen after repeatedly being evacuated to vacuum tightness 10-2mmHg with off-gas pump, at 60 ℃, 70 ℃ each constant temperature 1 hour down, 80 ℃ of following constant temperature after 3 hours filter product respectively, and 80 ℃ of following vacuum-dryings 2 hours.Products therefrom is that white clay/butyl polyacrylate hybridized nano composite material (is called for short: CPBA ₁).

Step 3: blend

CPBA with 1.5 grams ₁With 100 gram thermoplastic elastomer SBS, add in the mill and mix, be molded into test piece under 170 ℃, this test piece is the high elastic and strength transparent film, measures test piece tensile strength at yield and tensile yield, origin adds CPBA ₁15.70MPa and 598% be increased to 23.60MPa and 846% respectively.Low temperature glass transition temperature Tg ₁Keep original-75 ℃ of left and right sides constant, high temp glass transition temperature Tg ₂But rise to about 156 ℃, barrier increases, and thermoplasticity and processibility are constant.

Embodiment three

The preparation of nano combined snappiness film, its step and processing condition are as follows:

Step 1, two: with embodiment two.

Step 3: blend

With 6 gram CPBA ₁Add among the 100 gram SBS, mixing compressing tablet under the condition identical with embodiment two, the snappiness film of making, transparency is constant, Tg ₁And Tg ₂The same with among the embodiment three, tensile strength at yield but rises to 26.76MPa, and tensile yield keeps 732%, and particularly low temperature elasticity modulus and barrier property increase 3～5 times.

Embodiment four

The preparation of polypropylene (PP) anti-impact transparent plastics, its step and processing condition are as follows:

Step 1: multistep diffusion and exchange

In the 500ml conical flask, add 30 gram kaolin and 100ml dimethyl sulfoxide (DMSO) (DMSO), stir 24 hours after-filtration down at 80 ℃, filtered product is 50 ℃ of following vacuum-dryings after 2 hours, the mixing solutions that adds 6ml concentrated hydrochloric acid and 6 gram L-glutamic acid and 100ml water, adding 100ml water again stirred 12 hours down at 80 ℃, product filters the back and washs three times with hot water 100ml, and 50 ℃ of following vacuum-dryings after 2 hours, again dried product is added the 500ml there-necked flask, add the 13.5ml butyl acrylate again, 0.1 gram benzoyl peroxide (BPO) and 150ml toluene, and under 30 ℃, stirred 24 hours.

Step 2: polyreaction

Feed nitrogen after repeatedly being evacuated to vacuum, and under 60 ℃, heated 1 hour, 70 ℃ heating is after 1 hour down, and 80 ℃ were heated 3 hours down, product is filtered the back 80 ℃ of following vacuum-dryings 2 hours, and products therefrom is that high territory/butyl polyacrylate hybridized nano composite material (is called for short: CPBA ₂).

Step 3: blend

With 3 gram CPBA ₂Add in 97 gram polypropylene (PP) powder, make the transparent PP plastic sheet on the mixing and thermocompressor of two rollers down through 170 ℃, this sheet tensile strength is by not adding CPBA ₂34.6MP bring up to 38.2～38.7MPa, the breach shock strength is by 13.9KJ/m ²Be increased to 35.5KJ/m ², heat-drawn wire has also risen more than 7 ℃.

Embodiment five

The preparation of the anticorrosion non-scaling plastics of heat conduction, its step and processing condition are as follows:

Step 1, two:

At embodiment four preparation CPBA ₂Process in, graphite oxide is substituted kaolin, and the aniline ethanolic soln among the embodiment four and butyl acrylate is added reaction simultaneously, can be made into nano lamellar graphite/PBA (abbreviation: GPBA).

Step 3: blend

8 gram GPBA are added 92 grams, and (iPP+PVC=95: 5) in the mixture, through extruding section bar products such as can be made into sheet, pipe, the heat exchange coefficient of plastics can reach 90～150w/m ²More than the K, intensity, acidproof, erosion resistance do not reduce, 8 years non-scalings of contact process water.

Embodiment six

The preparation of flexible polyelectrolyte membrane, its step and processing condition are as follows:

Step 1: multistep diffusion, exchange

0.1mol dielectric medium salt lithium perchlorate or lithium-fluoroborate 8 grams are dissolved in the 100ml propene carbonate (PC), are mixed with uniform solution; Earlier with 26 ^#Paracril is behind mastication in the mill, and it is mixing evenly to add 1.0 weight part ZnO/100 parts by weight of rubber (phr), 1.0phr sulphur, the hard ester acid of 0.1phr, tetramethyl-dithiocarbamate zinc salt 0.5phr, again with 26 ^#Paracril rubber unvulcanizate 3 grams and Orlon hair 7 grams are dissolved in N in the ratio of 4g/100ml respectively, in the N ' dimethyl formamide (DMF);

Step 2: blend and crosslinked

When three kinds of solution of step 1 gained are 28 weight % by solids content, press the butyronitrile rubber unvulcanizate: polyacrylonitrile=7: 93 (weight part) mixes, mixing solutions is poured in the tetrafluoroethylene template, after 80 ℃ of following vacuum-drying thickness only be several microns flexible polyelectrolyte membrane.It has good mechanics elasticity and electrode materials is pasted performance, and under 26 ℃, humidity 85% records ionic conductivity and reaches 10 with ZL5 type intelligence electric bridge ^-1S/cm.

Embodiment seven

The preparation of oil resistant thermoplastic elastomer, its step and processing condition are as follows:

Step 1, two: with embodiment one.

Step 3: blend

The premix and the 52 weight % styrene-butadiene rubber(SBR) (SBR) that 48 weight %PVC are added three salt stabilizing agent 5phr and octyl phthalate (DOP) 50phr are added with 16phr (by SBR) CPBA ₁Mix material, when mill mixing, add sulphur 0.8phr, zinc oxide 1.0phr, hard ester acid 0.5phr, altax 0.4phr, mixing evenly after, 140 ℃ of compressing tablets on thermocompressor, recording the thermoplastic elastomer tensile strength reaches more than the 18MPa, elongation is 380～560%, and tension set can be regulated in 8～16% scopes, and anti-gasoline, benzene resistance can be good.

Embodiment eight

The rubber preparation that oil resistant is high temperature resistant (175 ℃), its step and processing condition are as follows:

Step 1, two: with embodiment two or four.

Step 3: blend

Ratio in 26g/100ml is dissolved in N with polyacrylonitrile (lanital) waste silk, among N ' the dimethyl formamide DMF, goes into CPAB at the polydimethyl silicon rubber central roll of 100 weight parts ₁8 weight parts or CPBA ₂6 weight parts through in the mill mixing evenly after, adding di-isopropylbenzene hydroperoxide (DCP) 0.3phr again is mixed, account for 17 weight % by polydimethyl silicon rubber, polyacrylonitrile accounts for the mixing even back of 83 weight % slice, thermal treatment is 1.5 hours in 160 ℃ of hot oxygen baking ovens, promptly make the rubber of oil resistant high temperature resistant (175 ℃), oil-proofness surpasses paracril (this glue only ability 120 ℃) and acrylic elastomer (this glue only can worked below 150 ℃), cost has only the sixth of silicon rubber, is lower than polyacrylic rubber.

Embodiment nine

The preparation of low temperature resistant, atmosphere engineering plastics, its step and processing condition are as follows:

Step 1, two: with embodiment two and embodiment four.

Step 3: blend

Polyvinyl chloride (PVC) 15 weight % with in add 6 weight part CPBA ₁Or 7 weight part CPBA ₂The uniform polystyrene-poly divinyl of pre-mixing-polyacrylonitrile multipolymer (ABS) 85 weight %, even in the twin screw extruder blend, can directly extrude the blow pressure vacuum forming and become automobile top shell, this product can overcome existing ABS shell and down the tiny crack problem take place at-40 ℃, makes its atmospheric exposure life-span prolong 4～6 times.

Embodiment ten

The preparation of high-impact PS engineering plastics, its step and processing condition are as follows:

Step 1, two: with embodiment two or four.

Step 3: blend

With polystyrene (PS is unformed) 75 weight %, SBS 5 weight % and 20 weight %CPBA ₁Or CPAB ₂Drop into cold mix in the high-speed mixer together, be mixed under the reheat to 100 ℃, again this compound is added 180 ℃ of lower sheeting moulding in hot-die, or extrude or the injection molding sample, the tensile strength of gained material is 45MPa, and elongation at break is 20%, than not adding CPBA ₁Or CPBA ₂PS, resistance to impact shock has improved 8～18 times.

Embodiment 11

The preparation of weather-proof (photoaging) PP, its step and processing condition are as follows:

Step 1, two: with embodiment two or four.

Step 3: blend

With 2 gram CPBA ₁Or CPBA ₂Adding 98 grams is furnished with in the PVC powder of 4 gram stablizers, this mixture is told 5 grams to mix with PP powder 95 grams, add new LDPE (film grade) (LDPE or LLDPE) powder 5 gram again, after mixing, section bars such as extrudate piece, plate, pipe easily in forcing machine.The intensity of extrusion plastic products, shock resistance, modulus, hardness, the particularly Chinese People's Anti-Japanese Military and Political College's gas performance of being exposed to the sun all increases considerably than PP.Melt-flow index can be adjusted with PP and the original melt-flow index of LDPE.When being used for injection molding, can also adjust transparency.

Embodiment 12

The preparation of phase change cold-storage micelle, its step and processing condition are as follows:

Step 1, two: with embodiment five.

Step 3: blend

45 gram GPBA are added in the poly-vinyl acetic monomer latex of the melamino-formaldehyde be furnished with 3 weight parts/100 weight part glue, by the dried glue composition latex of totally 100 grams.After mixing, pour in the 1000ml water that is added with 0.2 weight % Sodium dodecylbenzene sulfonate, and under 40 ℃, fully stir diameter less than the bag glue grain of micron, the micelle thermal conductivity reaches 20～34w/mK, is the energy-saving material of phase change cold-storage.

Claims (1)

1, a kind of is starting monomer with the aromatic series nitrogenous compound, serves as the preparation method of the polymer nanocomposites of row position medium with protonic acid or aprotic acid or non-proton hydrochlorate, it is characterized in that:

(1) raw material of this law also comprises:

1. aliphatics vinylformic acid and ester derivative thereof and oligomer comprise that the chemical structure skeleton symbol is:

R in the formula ₁, R ₂Can be H, CH ₃, C ₂H ₅, C ₃H ₇, C ₄H ₉, C ₅H ₁₁Until C ₁₈H ₃₇Alkyl, R ₁Can with R ₂Similar and different, n=2～48,

2. the laminate structure inorganics comprises: kaolin, white clay, magnesite soil natural matter and δ-Manganse Dioxide, tindioxide, graphite oxide, plumbic oxide, lithium hydroxide, Quilonum Retard, aluminium hydroxide,

3. polymkeric substance comprises: polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyester resin, polyamide resin, polydimethylacrylamiin, poly-isobutyl-acrylamide, polyacrylic ester, polycarbonate, poly-vinyl acetic monomer and multipolymer, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), natural rubber, SBS Thermoplastic Elastomer, SIS, paracril, polyacrylonitrile, polymethyl siloxane and the blend between them

4. row position medium also comprises: lithium hexafluoro phosphate, lithium-fluoroborate, trifluoroacetic acid, trichoroacetic acid(TCA), lithium perchlorate, zinc perchlorate, magnesium perchlorate, aluminum perchlorate, aluminum chloride, dimethyl sulfoxide (DMSO), Witco 1298 Soft Acid and sodium salt thereof, dinaphthyl sulfonic acid and sodium salt thereof, aluminum phosphate, Tai-Ace S 150, L-glutamic acid, polytetrafluoroethylene powder, light propylhomoserin, corn prolamin, conductive carbon black, organic fat amine, trolamine, acetic ester, acetate, N, N ' dimethyl formamide;

(2) step and the processing condition thereof of preparation polymer nanocomposites:

Step 1: multistep diffusion and exchange:

At institute's prepared material or the requirement of goods working conditions, select two or more monomer, laminate structure inorganics and row position medium and their concentration and consumption proportion, and they are put into reactor, swelling, dissolving or fusion are spread and exchange, its temperature controlling range is-10～180 ℃, time span of control 4 minutes～46 hours

Step 2: polymerization and/or crosslinking reaction

Add industrial normal starter and linking agent, reacted 0.2～40 hour down at 20 ℃～180 ℃,

Step 3: blend

According to the requirement of institute's prepared material, add one or more polymer blends, with universal industrial equipment high-speed mixing, open refining or banburying, extrude, mode such as injection or thermovacuum moulding obtains product.