CN101560271A - Method for preparing polymer/houghite nano composite material - Google Patents
Method for preparing polymer/houghite nano composite material Download PDFInfo
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- CN101560271A CN101560271A CNA200910099147XA CN200910099147A CN101560271A CN 101560271 A CN101560271 A CN 101560271A CN A200910099147X A CNA200910099147X A CN A200910099147XA CN 200910099147 A CN200910099147 A CN 200910099147A CN 101560271 A CN101560271 A CN 101560271A
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Abstract
The invention provides a method for preparing a polymer/houghite nano composite material, and the method comprises the following steps: 1) houghite is added to de-ionized water, and houghite suspension is obtained under the conditions of stirring and ultrasound; 2) a monomer, an anionic surfactant, an initiator and the de-ionized water are added into a polymer reactor, polymerization reaction is executed after the mixture is stirred uniformly, and polymer emulsion is obtained after cooling; and 3) the houghite suspension and the polymer emulsion are mixed and stirred to ensure houghite lamella and emulsion particles to form composite particles by electrostatic adherence, then the stirring is stopped, the composite particle suspension is filtered, washed and dried, and the polymer/houghite nano composite material is obtained. The method can realize organic modification of the houghite and the nano composition with the polymer in one step and has the advantages of low cost, simple operation and the like. In the prepared nano composite material, the houghite has good stripping dispersivity, and the interaction between the lamella and the polymer matrix can be regulated.
Description
(1) technical field
The present invention relates to a kind of preparation method of polymer/houghite nano composite material.
(2) background technology
For many years, polymer materials is widely used in the every field of national economy, becomes one of material closely bound up, indispensable in people's material life.But, polymer materials exists rigidity insufficient strength, poor heat resistance, poor dimensional stability, easy shortcoming such as aging, inflammable, limited its Application Areas greatly, inorganic materials has preferably advantages such as intensity, rigidity, heat-resisting, ageing-resistant and dimensional stabilizing, therefore, particularly having the inorganic nano-particle of nano-scale and polymer materials inorganic materials compound is the main means that improve polymer materials, when nanoparticle in polymkeric substance during homodisperse, the rigidity of matrix material, heat-resisting, fire-retardant and barrier property can be significantly improved.
Hydrotalcite is the anion type laminated compound of a quasi-representative, and its molecular composition is [M
2+ 1-xM
3+ x(OH
-)
2]
X+(A
N- X/n) mH
2O, wherein M
2+Be main body laminate divalent cation, M
3+Be main body laminate Tricationic, A
N-Be interlayer anion.Its structure is made of the laminate that is parallel to each other, and laminate has permanent positive charge, and interlayer has tradable negatively charged ion to keep charge balance.Because unique texture and character that hydrotalcite had, quilt are used as the properties-correcting agent of chemical reaction catalyst, sorbing material and macromolecular material widely.Utilize the anionic interchangeability of hydrotalcite layers, can adopt the inorganic anion between machine anionic compound substitutable layer, realization is organically-modified to hydrotalcite, has both increased the spacing between layer and the layer, makes sheet surfaces have lipophilicity again.Can obtain the hydrotalcite of miscellaneous organic anion intercalation modifying by ion-exchange, as the shuttle acid group, alkyl sulfate, benzene sulfonamide acid group, nuclear former times acid and amino acid etc.
Adopt hydrotalcite-modified polymkeric substance, more existing patent reports both at home and abroad.US6790895 discloses calcined hydrotalcite and the organic anion modified hydrotalcite preparation method as the matrix material of polymer materials filler.CN1563179 reported the hydrotalcite with lipid acid or anion surfactant modification join vinylchlorid the suspension polymerization process of preparing polyvinyl chloride/hydrotalcite composite resin, by the in-situ inserted dispersion of peeling off that has realized the hydrotalcite lamella, prepared compound resin has static state and the dynamic thermal stability that obviously is better than pure polyvinyl chloride (PVC) RESINS.
From present disclosed patent and document as can be known, the main method of preparation polymer/houghite nano composite material is to be the realization intercalation and to peel off by fusion intercalation and in-situ polymerization, it is organically-modified often to need elder generation that hydrotalcite is realized by ion-exchange, prepares nano composite material with polymer melt blend or in-situ polymerization again.These methods belong to two step complex methods, and operational path is long, and the existence of hydrotalcite impacts character such as the molecular weight and the molecular weight distribution etc. of polymkeric substance in the situ aggregation method.
(3) summary of the invention
The object of the invention provide that a kind of cost simple to operate is low, a step is realized the organically-modified of hydrotalcite and with the preparation method of the nano combined polymer/houghite nano composite material of polymkeric substance.
The technical solution used in the present invention is:
A kind of preparation method of polymer/houghite nano composite material, described method comprises: (1) joins the hydrotalcite of 0.1～5 mass parts in the water of 100 mass parts, is stirring and ultrasonic (power 200～800W) makes hydrotalcite suspension under acting on; (2) polymer monomer of 10～50 mass parts, the anion surfactant of 0.5～3 mass parts and the initiator of 0.05～0.3 mass parts are added in the water of 100 mass parts, carry out polyreaction after fully stirring, obtain polymer emulsion; Described polymer monomer is one of following or wherein two or more mixing: methyl methacrylate, vinylbenzene, divinyl, butyl methacrylate, propylene are fine, methacrylic acid, acrylamide; Described anion surfactant and initiator are for routine and be applicable to that described polymer monomer carries out the anion surfactant and the initiator of polyreaction, and initiator is selected oil-soluble initiator or water soluble starter for use; (3) with volume ratio 1～10: 1～10 hydrotalcite suspension and polymer emulsion mix, room temperature～70 ℃ following the stirring 1～3 hour, make hydrotalcite lamella and latex particle form composite particles through the electrostatic adhesion assembling, obtaining mixed solution filters, get filter cake washing, drying, obtain described polymer/houghite nano composite material.
Described hydrotalcite structure formula is [M
2+ 1-xM
3+ x(OH
-)
2]
X+(A
N- X/n) mH
2O, wherein M
2+Be M
2+For main body laminate divalent cation, be Fe
2+, Mg
2+, Ni
2+, Zn
2+, Co
2+In a kind of; M
3+For main body laminate Tricationic, be Al
3+, Fe
3+, Co
3+, Ti
3+, V
3+In a kind of, 1-x and x are respectively M in the main body laminate
2+And M
3+Molar fraction, 0.2≤x≤0.33, A
N-Be SO
4 2-, CO
3 2-, NO
3 -, Cl
-In a kind of, m is the number of middle water molecule, 0.1≤m≤0.6.The hydrotalcite crystal is a hexagonal system, constitutes because its main component generally is a oxyhydroxide by two kinds of metals, therefore is called double-metal hydroxide (Layered Double Hydroxide is abbreviated as LDH) again.
Preferably, described M
2+Be Mg
2+Or Zn
2+, M
3+Be Al
3+
Described anion surfactant and initiator can be selected according to the polymer monomer kind, preferably, described anion surfactant is one of following or wherein two or more mixing: sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, acrylate, methacrylate, methacrylic hydroxyl sulfoacid sodium.Described initiator is selected oil-soluble initiator or water soluble starter for use, and oil-soluble initiator comprises Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide etc., and the adding mode is that initiator is dissolved in the monomer; Water soluble starter comprises Potassium Persulphate, ammonium persulphate etc., and the adding mode is that initiator is dissolved in the deionized water.As required, also can select two or more similar or non-similar initiator to carry out composite use.
Described polymer polymerizing reaction is carried out according to conventional polymeric reaction condition, and preferred, described polyreaction is carried out under 50～80 ℃, 5～10 hours reaction times.
Concrete, described method is as follows:
(1) hydrotalcite with 0.1～5 mass parts joins in the water of 100 mass parts, makes hydrotalcite suspension under stirring and ultrasonication;
(2) polymer monomer of 10～50 mass parts, the anion surfactant of 0.5～3 mass parts and the initiator of 0.05～0.3 mass parts are added in the water of 100 mass parts, stirring at room 10～30min, be warming up to 50～80 ℃ and carried out polyreaction 5～10 hours, reaction finishes postcooling to room temperature and obtains polymer emulsion; Described polymer monomer is one of following or wherein two or more mixing: methyl methacrylate, vinylbenzene, propylene are fine; Described anion surfactant is one of following or wherein two or more mixing: sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, methacrylic hydroxyl sulfoacid sodium; Described initiator is one of following or wherein two or more mixing: Diisopropyl azodicarboxylate, Potassium Persulphate, ammonium persulphate;
(3) with volume ratio 1～10: 1～10 hydrotalcite suspension and polymer emulsion mix, room temperature～70 ℃ following the stirring 1～3 hour, and mixed solution filters, and gets filter cake washing, drying, obtains described polymer/houghite nano composite material.
Advantage of the present invention is as follows:
1) compound by electrostatic interaction by having the positively charged hydrotalcite lamella in lift-off structure and surface in the hydrotalcite suspension with the latex particle that the surface has anion surfactant, one side realizes nano combined, realizes the organic modification of surface of hydrotalcite on the other hand.Realized organically-modified and nano combined one the step finish.
2) to be that emulsion that polymerization is good and hydrotalcite carry out compound in the present invention, avoided the influence of in-situ polymerization to character such as the molecular weight and the molecular weight distribution of polymeric matrix.
4) in recombination process, because hydrotalcite lamella and emulsion particle subband xenogenesis electric charge according to the principle that same sex electric charge repels each other, the charges of different polarity are inhaled mutually, are difficult between the hydrotalcite lamella coalescence takes place, this method can effectively realize fully peeling off of hydrotalcite lamella.
3) in emulsion polymerization process, be emulsifying agent by selecting different tensio-active agents, particularly select to participate in the polymeric tensio-active agent, can realize the strong interaction between hydrotalcite lamella and the polymeric matrix.
The dispersion state of hydrotalcite can adopt X-ray diffraction, scanning electronic microscope and transmission electron microscope observation (Fig. 1) in the prepared polymer/houghite nano composite material of the present invention.Prepared nano composite material has good resistance toheat and flame retardant properties (Fig. 2), can be used for the preparation of various polymeric articles.
The inventive method can one the step realize the organically-modified of hydrotalcite and nano combined with polymkeric substance thereof, have low, the simple operation and other advantages of cost.Hydrotalcite has good stripping dispersivity in the prepared nano composite material of the present invention, and the interaction of lamella and polymeric matrix also can be regulated and control.
(4) description of drawings
Fig. 1 is the electron scanning micrograph of composite emulsion among the embodiment 11;
Fig. 2 be embodiment 1 with embodiment 11 in the thermal weight loss of prepared matrix material and straight polymer contrast.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
With 0.5g magnesium/aluminum ratio 2/1 hydrotalcite ([Mg
2+ 0.67M
3+ 0.33(OH
-)
2]
0.33+(CO
3 2- 0.165) 0.33H
2O, Huzhou City water chestnut lake newly hopes chemical industry company limited produce) join in the 100g water, stirring 1h under the room temperature, ultrasonic wave (power 500w) disperses 10min to obtain hydrotalcite suspension then.
30g vinylbenzene, 2.0g sodium lauryl sulphate, 0.2g Potassium Persulphate and 100g deionized water are joined in the reactor, stir 10min under the room temperature, be warming up to 70 ℃ of beginning polymerizations, polymerization reaction time is 8 hours, after polymerization finished, cooling made emulsion naturally cool to room temperature.
Adopt the mode that drips to join in the 50g polymer emulsion 100g hydrotalcite suspension, the dropping time is 1h, dropwise back 50 ℃ and stirred 1 hour down, composite particles suspension after filtration, washing, drying obtain polystyrene/houghite nano composite material that hydrotalcite content is 4.7wt%.
Embodiment 2:
The preparation of hydrotalcite suspension and polymer emulsion is with embodiment 1.
Join in the 100g emulsion 100g hydrotalcite suspension is disposable, be warming up to 40 ℃ then and stirred 3 hours down, composite particles suspension after filtration, washing, drying obtain polystyrene/houghite nano composite material that hydrotalcite content is 2.4wt%.
Embodiment 3:
The preparation of hydrotalcite suspension and emulsion is with embodiment 1.
Adopt the mode that drips to join in the 100g emulsion 50g hydrotalcite suspension, the dropping time is 30min, be warming up to 70 ℃ after dropwising then and stirred 3 hours down, composite particles suspension after filtration, to obtain hydrotalcite content be 1.2wt% polystyrene/houghite nano composite material for washing, drying.
Embodiment 4:
With 0.1g magnesium/aluminum ratio is that 2/1 hydrotalcite joins in the 100g water, stirs 1h under the room temperature, and ultrasonic dispersing 10min obtains hydrotalcite suspension then.
The preparation of emulsion is with embodiment 1.
Adopt the mode that drips to join in the 10g emulsion 100g hydrotalcite suspension, the dropping time is 1h, dropwise under the room temperature of back and stirred 1 hour, composite particles suspension after filtration, to obtain hydrotalcite content be 4.7wt% polystyrene/houghite nano composite material for washing, drying.
Embodiment 5:
With 5.0g magnesium/aluminum ratio is that 2/1 hydrotalcite joins in the 100g water, stirs 1h under the room temperature, and ultrasonic dispersing 20min obtains hydrotalcite suspension then.
The preparation of emulsion is with embodiment 1.
Join in the 20g emulsion 10g hydrotalcite suspension is disposable, stirred 1 hour under the room temperature then, composite particles suspension after filtration, to obtain hydrotalcite content be 4.7wt% polystyrene/houghite nano composite material for washing, drying.
Embodiment 6:
The preparation that hydrotalcite suspends is with embodiment 1.
The 0.3g Diisopropyl azodicarboxylate is dissolved in the 30g vinylbenzene, the vinylbenzene, 2.0g sodium laurylsulfonate and the 100g deionized water that have dissolved initiator are joined in the reactor, stir 10min under the room temperature, be warming up to 60 ℃ of beginning polymerizations, polymerization reaction time is 8 hours, after polymerization finished, cooling made emulsion naturally cool to room temperature.
Adopt the mode that drips to join in the 50g emulsion 100g hydrotalcite suspension, the dropping time is 1h, dropwise under the room temperature of back and stirred 1 hour, composite particles suspension after filtration, to obtain hydrotalcite content be 4.5wt% polystyrene/houghite nano composite material for washing, drying.
Embodiment 7:
The preparation that hydrotalcite suspends is with embodiment 1.
The 0.1g Diisopropyl azodicarboxylate is dissolved in the 30g vinylbenzene, the vinylbenzene, 2.0g sodium laurylsulfonate, 0.1g ammonium persulphate and the 100g deionized water that have dissolved initiator are joined in the reactor, stir 10min under the room temperature, be warming up to 60 ℃ of beginning polymerizations, polymerization reaction time is 8 hours, after polymerization finished, cooling made emulsion naturally cool to room temperature.
Adopt the mode that drips to join in the 50g emulsion 100g hydrotalcite suspension, the dropping time is 1h, dropwise under the room temperature of back and stirred 1 hour, composite particles suspension after filtration, to obtain hydrotalcite content be 4.5wt% polystyrene/houghite nano composite material for washing, drying.
Embodiment 8:
The preparation that hydrotalcite suspends is with embodiment 1.
50g methyl methacrylate, 3.0g Sodium dodecylbenzene sulfonate, 0.3g Potassium Persulphate 100g deionized water are joined in the reactor, stir 10min under the room temperature, be warming up to 80 ℃ of beginning polymerizations, polymerization reaction time is 5 hours, after polymerization finished, cooling made emulsion naturally cool to room temperature.
Adopt the mode that drips to join in the 50g emulsion 100g hydrotalcite suspension, the dropping time is 1h, dropwise under the room temperature of back and stirred 1 hour, composite particles suspension after filtration, to obtain hydrotalcite content be 3.2wt% polymethylmethacrylate/houghite nano composite material for washing, drying.
Embodiment 9:
The preparation that hydrotalcite suspends is with embodiment 1.
21g vinylbenzene, 9.0g vinyl cyanide, 1.0g sodium lauryl sulphate, 0.3g Potassium Persulphate and 100g deionized water are joined in the reactor, stir 30min under the room temperature, be warming up to 50 ℃ of beginning polymerizations, polymerization reaction time is 8 hours, after polymerization finished, cooling made emulsion naturally cool to room temperature.
Adopt the mode that drips to join in the 50g emulsion 100g hydrotalcite suspension, the dropping time is 1h, dropwise under the room temperature of back and stirred 1 hour, composite particles suspension after filtration, to obtain hydrotalcite content be poly-(the styrene-acrylonitrile)/houghite nano composite material of 4.5wt% for washing, drying.
Embodiment 10:
The preparation that hydrotalcite suspends is with embodiment 1.
10g vinylbenzene, 3.0g methacrylic hydroxyl sulfoacid sodium (can vinylbenzene polymerization reaction take place), 0.3g Potassium Persulphate and 100g deionized water be joined in the reactor, stir 30min under the room temperature, be warming up to 70 ℃ of beginning polymerizations, polymerization reaction time is 10 hours, after polymerization finished, cooling made emulsion naturally cool to room temperature.
Adopt the mode that drips to join in the 50g emulsion 100g hydrotalcite suspension, the dropping time is 1h, dropwise under the room temperature of back and stirred 1 hour, composite particles suspension after filtration, to obtain hydrotalcite content be 15wt% polystyrene/houghite nano composite material for washing, drying.
Embodiment 11:
The preparation that hydrotalcite suspends is with embodiment 1.
30g vinylbenzene, 0.5g Sodium dodecylbenzene sulfonate, 3g methacrylic hydroxyl sulfoacid sodium (can vinylbenzene polymerization reaction take place), 0.3g Potassium Persulphate and 100g deionized water be joined in the reactor, stir 30min under the room temperature, be warming up to 70 ℃ of beginning polymerizations, polymerization reaction time is 10 hours, after polymerization finished, cooling made emulsion naturally cool to room temperature.
Adopt the mode that drips to join in the 50g emulsion 50g hydrotalcite suspension, the dropping time is 1h, dropwise under the room temperature of back and stir 1 hour (electron scanning micrograph of composite emulsion is seen Fig. 1), as seen from the figure, the many forms with single lamella of hydrotalcite are dispersed between the latex particle uniformly, illustrate that it has good dispersiveness.Composite particles suspension after filtration, to obtain hydrotalcite content be 3.7wt% polystyrene/houghite nano composite material for washing, drying.
The thermal weight loss of prepared matrix material and straight polymer contrasts and sees Fig. 2 among embodiment 1 and the embodiment 11, as can be seen from the figure, the prepared matrix material of the present invention is compared with corresponding straight polymer, no matter be temperature of initial decomposition, still maximum rate of decomposition temperature all is significantly improved, and illustrates that matrix material has good heat-resistant.
Embodiment 12:
With 0.5g magnesium/aluminum ratio 3/1 hydrotalcite ([Mg
2+ 0.75M
3+ 0.25(OH
-)
2]
0.25+(NO
3 - 0.25) 0.5H
2O) join in the 100g water, stir 1h under the room temperature, ultrasonic dispersing 10min obtains hydrotalcite suspension then.
Emulsion preparation is with embodiment 1.
Adopt the mode that drips to join in the 50g emulsion 100g hydrotalcite suspension, the dropping time is 1h, be warming up to 50 ℃ after dropwising and stirred 1 hour, composite particles suspension after filtration, to obtain hydrotalcite content be 4.7wt% polystyrene/houghite nano composite material for washing, drying.
Embodiment 13:
With 0.5g magnesium/aluminum ratio 4/1 hydrotalcite ([Mg
2+ 0.8M
3+ 0.2(OH
-)
2]
0.2+(NO
3 - 0.2) 0.53H
2O) join in the 100g water, stir 1h under the room temperature, ultrasonic dispersing 10min obtains hydrotalcite suspension then.
Emulsion preparation is with embodiment 1.
Adopt the mode that drips to join in the 50g emulsion 100g hydrotalcite suspension, the dropping time is 1h, be warming up to 50 ℃ after dropwising and stirred 1 hour, composite particles suspension after filtration, to obtain hydrotalcite content be 4.7wt% polystyrene/houghite nano composite material for washing, drying.
Embodiment 14:
With 0.5g zinc/aluminum ratio 2/1 hydrotalcite ([Zn
2+ 0.67M
3+ 0.33(OH
-)
2]
0.33+(CO
3 2- 0.165) 0.33H
2O) join in the 100g water, stir 1h under the room temperature, ultrasonic dispersing 10min obtains hydrotalcite suspension then.
Emulsion preparation is with embodiment 1.
Adopt the mode that drips to join in the 50g emulsion 100g hydrotalcite suspension, the dropping time is 1h, dropwise under the room temperature of back and stirred 1 hour, composite particles suspension after filtration, to obtain hydrotalcite content be 4.7wt% polystyrene/houghite nano composite material for washing, drying.
Claims (7)
1. the preparation method of a polymer/houghite nano composite material, described method comprises: (1) joins the hydrotalcite of 0.1～5 mass parts in the water of 100 mass parts, stir and ultrasonication under make hydrotalcite suspension; (2) polymer monomer of 10～50 mass parts, the anion surfactant of 0.5～3 mass parts and the initiator of 0.05～0.3 mass parts are added in the water of 100 mass parts, carry out polyreaction after fully stirring, obtain polymer emulsion; Described polymer monomer is one of following or wherein two or more mixing: methyl methacrylate, vinylbenzene, divinyl, butyl methacrylate, propylene are fine, methacrylic acid, acrylamide; (3) with volume ratio 1～10: 1～10 hydrotalcite suspension and polymer emulsion mix, room temperature～70 ℃ following the stirring 1～3 hour, and mixed solution filters, and gets filter cake washing, drying, obtains described polymer/houghite nano composite material.
2. the method for claim 1 is characterized in that described hydrotalcite structure formula is [M
2+ 1-xM
3+ x(OH
-)
2]
X+(A
N- X/n) mH
2O, wherein M
2+Be Fe
2+, Mg
2+, Ni
2+, Zn
2+, Co
2+In a kind of; M
3+Be Al
3+, Fe
3+, Co
3+, Ti
3+, V
3+In a kind of, 1-x and x are respectively M
2+And M
3+Molar fraction, 0.2≤x≤0.33, A
N-Be SO
4 2-, CO
3 2-, NO
3 -, Cl
-In a kind of, 0.1≤m≤0.6.
3. method as claimed in claim 2 is characterized in that described M
2+Be Mg
2+Or Zn
2+, M
3+Be Al
3+
4. the method for claim 1 is characterized in that described anion surfactant is one of following or wherein two or more mixing: sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, acrylate, methacrylate, methacrylic hydroxyl sulfoacid sodium.
5. the method for claim 1 is characterized in that described initiator is one of following or wherein two or more mixing: Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, Potassium Persulphate, ammonium persulphate.
6. the method for claim 1 is characterized in that described polyreaction carries out 5～10 hours reaction times under 50～80 ℃.
7. the method for claim 1 is characterized in that described method is as follows:
(1) hydrotalcite with 0.1～5 mass parts joins in the water of 100 mass parts, makes hydrotalcite suspension under stirring and ultrasonication;
(2) polymer monomer of 10～50 mass parts, the anion surfactant of 0.5～3 mass parts and the initiator of 0.05～0.3 mass parts are added in the water of 100 mass parts, stirring at room 10～30min, be warming up to 50～80 ℃ and carried out polyreaction 5～10 hours, reaction finishes postcooling to room temperature and obtains polymer emulsion; Described polymer monomer is one of following or wherein two or more mixing: methyl methacrylate, vinylbenzene, propylene are fine; Described anion surfactant is one of following or wherein two or more mixing: sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, methacrylic hydroxyl sulfoacid sodium; Described initiator is one of following or wherein two or more mixing: Diisopropyl azodicarboxylate, Potassium Persulphate, ammonium persulphate;
(3) with volume ratio 1～10: 1～10 hydrotalcite suspension and polymer emulsion mix, room temperature～70 ℃ following the stirring 1～3 hour, and mixed solution filters, and gets filter cake washing, drying, obtains described polymer/houghite nano composite material.
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