Polymkeric substance/silicon dioxide nano particle composite material and preparation method
Technical field
The present invention relates to a kind of nano composition and method for making, especially polymkeric substance/silicon dioxide nano particle composite material and preparation method.
Background technology
At present, people for polymeric matrix is strengthened, toughness reinforcing and increase just, and make polymkeric substance represent nano effect, often in polymkeric substance, add inorganic nano-particle, as " nano redigity impact modifying agent and preparation method thereof " that discloses among the Chinese invention patent ublic specification of application CN 1358786A that announces on July 17th, 2002.It is intended to rigid polyvinyl chloride (RPVC) is carried out modification; Properties-correcting agent is for containing the polymkeric substance of 5~95 (weight) % nano inoganic particle and 5~95 (weight) %, wherein, polymkeric substance be based on the methyl methacrylate of butyl acrylate, 10~60 (weight) % of this total polymer weight 10~70 (weight) % and (or) ethyl propenoate of 10~30 (weight) % and (or) vinylbenzene of 0~50 (weight) % and (or) acrylic acid emulsion copolymers of 0~20 (weight) %; The preparation method is in letex polymerization, and the linking agent of active modifier, 0.1~5 (weight) % of emulsifying agent, 0.01~5 (weight) % of initiator, 0.01~10 (weight) % of use 0.01~5 (weight) % makes by in-situ emulsion polymerization.But, this properties-correcting agent only can carry out modification to RPVC, and can not be helpful to the improvement of other polymer performances, and also just properties-correcting agent is a kind of for the prepared product of its preparation method, do not have versatility, and use kind, the additive of raw material all more, technology is more numerous and diverse, the time is longer.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of widely applicable, easy to prepare polymkeric substance/silicon dioxide nano particle composite material and preparation method for overcoming weak point of the prior art.
Polymkeric substance/silicon dioxide nano particle composite material comprises Nano particles of silicon dioxide, weight ratio between particularly said Nano particles of silicon dioxide and polymkeric substance is 0.1~40 to 100 and is nucleocapsid structure between the two, wherein, nuclear is polymkeric substance for Nano particles of silicon dioxide, shell, nuclear with shell between be connected with the Si-O-C chemical bond, the said polymer is a polyethylene terephthalate.
As the further improvement of polymkeric substance/silicon dioxide nano particle composite material, the particle diameter of described Nano particles of silicon dioxide is 1~100nm.
The preparation method of polymkeric substance/silicon dioxide nano particle composite material comprises that obtaining the surface with ordinary method contains the Nano particles of silicon dioxide of active Si-OH key, the monomer of polymkeric substance and the oligopolymer of polyethylene terephthalate, particularly it is finished according to the following steps: (1), Nano particles of silicon dioxide and terephthalic acid and ethylene glycol were stirred 80~100 minutes under 220~250 ℃ of temperature, pressure 0.2~0.4MPa obtains mixture; (2), in mixture, add the oligopolymer of antimony acetate or zinc acetate and polyethylene terephthalate, under 260~285 ℃ of temperature and pressure 10~50Pa, stirred 90~150 minutes, make polymkeric substance/silicon dioxide nano particle composite material.
As the preparation method's of polymkeric substance/silicon dioxide nano particle composite material further improvement, the weight ratio between described Nano particles of silicon dioxide and terephthalic acid is 0.1~40 to 100; Weight ratio between described Nano particles of silicon dioxide and ethylene glycol is 0.1~20 to 100; Weight ratio between described mixture and antimony acetate or zinc acetate is 1 to 600~800ppm; Weight ratio between the oligopolymer of described mixture and polyethylene terephthalate is 1 to 0.5~5.
Beneficial effect with respect to prior art is, one, matrix material is placed under the transmission electron microscope at the thin slice that is cut into 80~100nm under the refrigerated condition observes, the visible equal Individual existence of each Nano particles of silicon dioxide, and a shell is all arranged on the surface of particle.This matrix material is dissolved in chloroform and trifluoroacetic mixed solvent again, be made into 1% solution, as seen the solution clear has strong reactive force between this explanation Nano particles of silicon dioxide and the macromolecular chain, is dissolved in solution together in company with macromolecular chain and has suffered.At this moment, get a supernatant liquid and drop in the copper mesh that is used for transmission electron microscope observing, behind the solvent flashing, under transmission electron microscope, observe, can see Nano particles of silicon dioxide and be embedded in the film of polymkeric substance, form nucleocapsid structure preferably with polymer materials as egg yolk; Its two, by the Nano particles of silicon dioxide that contains different ratios and the matrix material of polymkeric substance are tested with the ultra-red mass spectrum instrument, by its infrared spectrogram as can be seen, at 1130cm
-1A new peak appears, and it is stronger that this peak becomes along with the increase of nanoparticle content, this peak does not occur in pure polymkeric substance, peak that neither Nano particles of silicon dioxide, calculate by analysis, this peak is in the Nano particles of silicon dioxide-in OH key and the polymkeric substance-COOH or-the Si-O-C chemical bond of COOR formation.In addition, the silicon in the matrix material, oxygen and carbon are done the photoelectron spectrum analysis, its result also illustrates the chemical bond that has generated the Si-O-C chemical bond, and this further illustrates the strong interaction power that has formed chemical bond between Nano particles of silicon dioxide and the polymkeric substance; Its three, choose and the polymeric matrix of Nano particles of silicon dioxide are selected polyester for use, and determining of proportional range between the two, have fundamentally solved the reunion and the weak difficult problem of organic and inorganic interface binding power of Nano particles of silicon dioxide.Directly set up the starting point of polyreaction on the surface of Nano particles of silicon dioxide, for carrying out the polyreaction of long-chain, formation is nuclear with the Nano particles of silicon dioxide, the polymkeric substance macromolecular chain is shell, and the matrix material that is connected with strong chemical bond between nuclear and the shell is laid a good foundation.Now illustrate the mechanism of action of itself and Nano particles of silicon dioxide: in preparation process with polyethylene terephthalate, active Si-OH and terephthalic acid (HOOC-C6H5-COOH that the Nano particles of silicon dioxide surface is a large amount of, one of monomer of polyethylene terephthalate) carboxyl in forms the bridged bond that Si-O-C connects, the carboxyl of the other end and ethylene glycol (HO-CH2CH2-OH, one of monomer of polyethylene terephthalate) carries out esterification, again with this starting point as polycondensation, under higher vacuum tightness, carry out polyreaction, finally generate a kind of polyethylene terephthalate/silicon dioxide nano particle composite material that coexists with the macromolecular chain of end capped macromolecular chain of nanoparticle and homopolymerization; They are four years old, choosing of Nano particles of silicon dioxide particle size range, make matrix material both have the good characteristic of polymer materials, the functional performance and the small-size effect that have nanoparticle again, brought into play enhancing, the toughening effect of nanoparticle to greatest extent, can also be compound in the multiple macromolecular material and go with matrix material as functional master batch, for polymkeric substance inorganic modified provides unitized method, and provide new approach for the functional materials of research and development polymkeric substance; Its five, the preparation method is simple and easy to do, no longer need use additive, as initiator, emulsifying agent, active modifier, linking agent etc., also needn't use ultrasonic equipment, the time of matrix material output is shorter; They are six years old, directly the monomer with polymkeric substance carries out polyreaction on the surface of Nano particles of silicon dioxide, do not introduce any low-molecular-weight additive, reunite, further played conclusive effect for the dispersion of Nano particles of silicon dioxide in polymeric matrix to preventing nanoparticle.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 be freezing microtome section to matrix material take the photograph after with Japanese JOEL100CX II type transmission electron microscopy observation photo, wherein, (a) figure is the matrix material photo when containing 0.2% Nano particles of silicon dioxide weight; (b) figure is the matrix material photo when containing 1% Nano particles of silicon dioxide weight; (c) figure is the matrix material photo when containing 3% Nano particles of silicon dioxide weight; (d) figure is the matrix material photo when containing 6% Nano particles of silicon dioxide weight.
Fig. 2 is that the freezing microtome section with matrix material is dissolved in chloroform and the trifluoroacetic mixed solvent, be made into 1% solution, the supernatant liquid of getting this solution drops in the copper mesh that is used for transmission electron microscope observing, behind the solvent flashing, with take the photograph behind the Japanese JOEL100CX II type transmission electron microscopy observation photo.
Fig. 3 is the infrared spectrogram that obtains after the matrix material of Nano particles of silicon dioxide that contains different ratios and polymkeric substance is tested with the ultra-red mass spectrum instrument, and wherein, ordinate zou is relative conversion value, and X-coordinate is a wave number.
Embodiment
At first make or buy the surface and contain the Nano particles of silicon dioxide of active Si-OH key and the monomer and the oligopolymer of polymkeric substance from market with ordinary method, wherein, the particle diameter of Nano particles of silicon dioxide is 1~100nm, polymkeric substance is a polyethylene terephthalate, and the oligopolymer of polymkeric substance is the oligopolymer of polyethylene terephthalate.
Embodiment 1: earlier be that the Nano particles of silicon dioxide of 2nm and terephthalic acid and ethylene glycol stirred 80 minutes under 220 ℃ of temperature, pressure 0.4MPa with particle diameter; Wherein, the weight ratio between Nano particles of silicon dioxide and terephthalic acid is 0.4 to 100, the weight ratio between Nano particles of silicon dioxide and ethylene glycol is 0.2 to 100; Obtain mixture.In mixture, add antimony acetate and oligopolymer again, under 260 ℃ of temperature and pressure 50Pa, stirred 90 minutes; Wherein, the weight ratio between mixture and antimony acetate is 1 to be 1 to 0.5 than the weight ratio between 600ppm, mixture and oligopolymer; Make as Fig. 1 (a) and be similar to Fig. 2 and polymkeric substance/silicon dioxide nano particle composite material shown in Figure 3.
Embodiment 2: earlier be that the Nano particles of silicon dioxide of 9nm and terephthalic acid and ethylene glycol stirred 85 minutes under 230 ℃ of temperature, pressure 0.35MPa with particle diameter; Wherein, the weight ratio between Nano particles of silicon dioxide and terephthalic acid is 5 to 100, the weight ratio between Nano particles of silicon dioxide and ethylene glycol is 2.5 to 100; Obtain mixture.In mixture, add antimony acetate and oligopolymer again, under 266 ℃ of temperature and pressure 40Pa, stirred 105 minutes; Wherein, the weight ratio between mixture and antimony acetate is 1 to be 1 to 1 than the weight ratio between 650ppm, mixture and oligopolymer; Make and be similar to as Fig. 1 (b) and Fig. 2 and polymkeric substance/silicon dioxide nano particle composite material shown in Figure 3.
Embodiment 3: earlier be that the Nano particles of silicon dioxide of 25nm and terephthalic acid and ethylene glycol stirred 90 minutes under 235 ℃ of temperature, pressure 0.3MPa with particle diameter; Wherein, the weight ratio between Nano particles of silicon dioxide and terephthalic acid is 20 to 100, the weight ratio between Nano particles of silicon dioxide and ethylene glycol is 10 to 100; Obtain mixture.In mixture, add antimony acetate and oligopolymer again, under 273 ℃ of temperature and pressure 30Pa, stirred 120 minutes; Wherein, the weight ratio between mixture and antimony acetate is 1 to be 1 to 2 than the weight ratio between 700ppm, mixture and oligopolymer; Make and be similar to as Fig. 1 (c) and be similar to Fig. 2 and polymkeric substance/silicon dioxide nano particle composite material shown in Figure 3.
Embodiment 4: earlier be that the Nano particles of silicon dioxide of 50nm and terephthalic acid and ethylene glycol stirred 95 minutes under 245 ℃ of temperature, pressure 0.25MPa with particle diameter; Wherein, the weight ratio between Nano particles of silicon dioxide and terephthalic acid is 30 to 100, the weight ratio between Nano particles of silicon dioxide and ethylene glycol is 15 to 100; Obtain mixture.In mixture, add antimony acetate and oligopolymer again, under 280 ℃ of temperature and pressure 20Pa, stirred 135 minutes; Wherein, the weight ratio between mixture and antimony acetate is 1 to be 1 to 3 than the weight ratio between 750ppm, mixture and oligopolymer; Make and be similar to as Fig. 1 (d) and be similar to Fig. 2 and polymkeric substance/silicon dioxide nano particle composite material shown in Figure 3.
Embodiment 5: earlier be that the Nano particles of silicon dioxide of 100nm and terephthalic acid and ethylene glycol stirred 100 minutes under 250 ℃ of temperature, pressure 0.2MPa with particle diameter; Wherein, the weight ratio between Nano particles of silicon dioxide and terephthalic acid is 40 to 100, the weight ratio between Nano particles of silicon dioxide and ethylene glycol is 20 to 100; Obtain mixture.In mixture, add antimony acetate and oligopolymer again, under 285 ℃ of temperature and pressure 10Pa, stirred 150 minutes; Wherein, the weight ratio between mixture and antimony acetate is 1 to be 1 to 5 than the weight ratio between 800ppm, mixture and oligopolymer; Make and be similar to as Fig. 1 (a) and be similar to Fig. 2 and polymkeric substance/silicon dioxide nano particle composite material shown in Figure 3.
Obviously, those skilled in the art can carry out various changes and modification to polymkeric substance/silicon dioxide nano particle composite material of the present invention and preparation method and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.