CN1927941A - Preparation method of nano particle-polyurethane complex particle for macromolecule material - Google Patents
Preparation method of nano particle-polyurethane complex particle for macromolecule material Download PDFInfo
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- CN1927941A CN1927941A CN 200610029225 CN200610029225A CN1927941A CN 1927941 A CN1927941 A CN 1927941A CN 200610029225 CN200610029225 CN 200610029225 CN 200610029225 A CN200610029225 A CN 200610029225A CN 1927941 A CN1927941 A CN 1927941A
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Abstract
The present invention is preparation process of nanometer polyurethane composite particle for use in polymer material, and belongs to the field of polymer material modifier preparing technology. Nanometer silica particle, polytetramethylene ether glycol-toluene diisocyanate as the prepolymer of polyurethane, n-butyl acetate solvent are mixed homogeneously under nitrogen protection and through magnetically stirring and heating to 60-90 deg.c to react for 1-4 hr, before suction filtering and washing the filtered solid phase product for several times to obtain the nanometer polyurethane composite particle. The nanometer polyurethane composite particle of the present invention is suitable for being added into polymer material base to raise its physical and chemical performances.
Description
Technical field
The present invention relates to a kind of preparation method who is applied to the nano particle-polyurethane complex particle in the macromolecular material, belong to the fabricating technology field of macromolecular material enhancing modified additive material.
Background technology
As the nanoparticle of macromolecular material reinforcing filler, its particle diameter is more little, with the free volume of macromolecular material match good more.Simultaneously, particle diameter is more little, and specific surface area is big more, and surface effects is strong more, and the ability and the load-carrying efficiency of the motion of restriction macromolecular material macromole are also high more.The nanoparticle surface active centre is many, and size is little, and consistency is good, adding in the macromolecular material makes it become very fine and close, when being subjected to external force to do the time spent, particle is difficult for breaking away from matrix, produces a lot of distortion microcells in matrix, absorb lot of energy, make it transmit the external stress of being born preferably, and because the interaction of stress field can cause the matrix surrender again, consume a large amount of striking energys, thereby reach toughness reinforcing and enhanced effect simultaneously.
Because silicon-dioxide polarity is big, poor with general non-polar polymer consistency, the bonding force that produces between them very a little less than.And silicon dioxide microparticle is tending towards interconnecting owing to the effect of hydrogen bond, form a kind of filler aggregate network structure, in macromolecular material, be difficult for further disperseing, thereby influence the processing characteristics of macromolecular material, in order to overcome the shortcoming of silicon-dioxide itself, improve its dispersiveness in polymkeric substance, improve and improve processing characteristics, at present the most frequently used effective means is that silicon-dioxide is carried out surface modification.In a large amount of patent documentations, once reported and carried out surface modification treatment with coupling agent.One end of coupling agent molecule and silicon-dioxide connect, and chemistry " coupling " takes place between the other end and the rubber, and the result between filler and rubber bonding takes place.Silicon-dioxide has reduced the formation and the interaction of filler aggregation network with after coupling agent modified, has improved processing characteristics.
The modification of silica sphere graftomer can effectively improve dispersiveness and the wettability of mineral filler in macromolecule matrix.Because silica sphere has-the OH base exists, the silanol groups activity is bigger, can with multiple organism functional groups, be grafted with organic polymer at silica sphere at last.
My research group links at nano-silica surface and has done some research work aspect the graftomer of isocyanate functional group-NCO, and the preparation nano particle-polyurethane complex particle is as the filler in the macromolecular material, to improve its performance.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is applied to the nano particle-polyurethane complex particle in the macromolecular material.
The objective of the invention is and to finish by the following technical programs.
A kind of preparation method who is used for the nano particle-polyurethane complex particle of macromolecular material of the present invention is characterized in that having following preparation process and step:
In advance with nanometer silicon dioxide particle 120 ℃ of following vacuum-dryings 2 hours; In round-bottomed flask, base polyurethane prepolymer for use as polytetramethylene ether diol-tolylene diisocyanate (PTMEG-TDI) is dissolved in the positive butyl ester of solvent acetic acid then, add above-mentioned exsiccant nanometer silicon dioxide particle subsequently, under nitrogen protection, carry out magnetic agitation, and use the oil bath reacting by heating; Heating temperature is 60～90 ℃, and the reaction times is 1～4 hour; Reaction finishes to carry out suction filtration, and the suction filtration solid phase is repeatedly washed with a large amount of acetone, finally obtains nano particle-polyurethane complex particle.
Contain isocyanate terminated base-NCO functional group in the described base polyurethane prepolymer for use as, its content is 4～9%; The consumption of base polyurethane prepolymer for use as is 10～50wt% of n-butyl acetate consumption.
Described nano silicon particle diameter is 20～300nm.
The characteristics and the advantage of the inventive method are as follows:
(1) uses nontoxic substantially n-butyl acetate to make solvent in the inventive method, avoided problem of environmental pollution.
(2) can effectively improve dispersity and the wettability of filler in macromolecular material, strengthen the bonding strength between nano particle and macromolecular material.
(3) the inventive method technology is simple, the reaction conditions gentleness, and cost is lower, is easy to large-scale production.
Embodiment
After now embodiments of the invention specifically being described in.
Embodiment 1
The technological process and the step of present embodiment are as follows:
In advance with silicon-dioxide 120 ℃ of following vacuum-dryings 2 hours; Then in round-bottomed flask with base polyurethane prepolymer for use as polytetramethylene ether diol-tolylene diisocyanate (PTMEG-TDI, the content of isocyanato-NCO is 4.32%) 14.23ml is dissolved in the positive butyl ester of 40ml solvent acetic acid, add above-mentioned exsiccant nano silicon 0.5g subsequently, the median size of silica dioxide granule is 25nm; Carry out magnetic agitation under nitrogen protection, and use the oil bath reacting by heating, be heated to 88 ℃ of temperature of reaction, the reaction times is 4 hours; Reaction finishes to carry out suction filtration, and the suction filtration solid phase with a large amount of washing with acetones 3 times, is finally obtained nano particle-polyurethane complex particle.
Embodiment 2
The processing step of present embodiment and the foregoing description 1 is identical.
In advance with silicon-dioxide 120 ℃ of following vacuum-dryings 2 hours; Then in the circular cone flask with base polyurethane prepolymer for use as polytetramethylene ether diol-tolylene diisocyanate (PTMEG-TDI, the content of isocyanato-NCO is 4.32%) 14.23ml is dissolved in the positive butyl ester of 60ml solvent acetic acid, add above-mentioned exsiccant nano silicon 4g subsequently, the median size of silica dioxide granule is 25nm; Carry out magnetic agitation under nitrogen protection, and use the oil bath reacting by heating, be heated to 85 ℃ of temperature of reaction, the reaction times is 2 hours; Reaction finishes to carry out suction filtration, and the suction filtration solid phase with a large amount of washing with acetones 3 times, is finally obtained nano particle-polyurethane complex particle.
Embodiment 3
The processing step of present embodiment and the foregoing description 1 is identical.
In advance with silicon-dioxide 120 ℃ of following vacuum-dryings 2 hours; Then in the circular cone flask with base polyurethane prepolymer for use as polytetramethylene ether diol-tolylene diisocyanate (PTMEG-TDI, the content of isocyanato-NCO is 4.32%) 33.2ml is dissolved in the positive butyl ester of 40ml solvent acetic acid, add above-mentioned exsiccant nano silicon 0.3g subsequently, the median size of silica dioxide granule is 25nm; Carry out magnetic agitation under nitrogen protection, and use the oil bath reacting by heating, be heated to 80 ℃ of temperature of reaction, the reaction times is 4 hours; Reaction finishes to carry out suction filtration, and the suction filtration solid phase with a large amount of washing with acetones 3 times, is finally obtained nano particle-polyurethane complex particle.
Embodiment 4
The processing step of present embodiment and the foregoing description 1 is identical.
In advance with silicon-dioxide 120 ℃ of following vacuum-dryings 2 hours; Then in the circular cone flask with base polyurethane prepolymer for use as polytetramethylene ether diol-tolylene diisocyanate (PTMEG-TDI, the content of isocyanato-NCO is 8.88%) 14.23ml is dissolved in the positive butyl ester of 40ml solvent acetic acid, add above-mentioned exsiccant nano silicon 0.25g subsequently, the median size of silica dioxide granule is 25nm; Carry out magnetic agitation under nitrogen protection, and use the oil bath reacting by heating, be heated to 87 ℃ of temperature of reaction, the reaction times is 1.5 hours; Reaction finishes to carry out suction filtration, and the suction filtration solid phase with a large amount of washing with acetones 3 times, is finally obtained nano particle-polyurethane complex particle.
The prepared nanometer silicon dioxide particle of the foregoing description-urethane composite particles detects through KBr compressing tablet infrared spectra, at 2925cm
-1, 2858cm
-1About have-CH
2-the stretching vibration absorption peak, 1730cm
-1About 1540cm is arranged-carbonylic stretching vibration absorption peak among the O-CO-NH-
-1About and 2271cm is arranged-NH formation vibration absorption peak
-1The place does not have-the NCO absorption peak, and it is composite particles that the expression silica particles connects by chemical bond and base polyurethane prepolymer for use as.
The silica dioxide granule that the inventive method makes-urethane composite particles joins in the rubber as filler, can improve the physicals and the processing characteristics of rubber.
Claims (3)
1. preparation method who is used for the nano particle-polyurethane complex particle of macromolecular material is characterized in that having following preparation process and step:
In advance with nanometer silicon dioxide particle 120 ℃ of following vacuum-dryings 2 hours; In round-bottomed flask, base polyurethane prepolymer for use as polytetramethylene ether diol-tolylene diisocyanate (PTMEG-TDI) is dissolved in the positive butyl ester of solvent acetic acid then, add above-mentioned exsiccant nanometer silicon dioxide particle subsequently, under nitrogen protection, carry out magnetic agitation, and use the oil bath reacting by heating; Heating temperature is 60～90 ℃, and the reaction times is 1～4 hour; Reaction finishes to carry out suction filtration, and the suction filtration solid phase is repeatedly washed with a large amount of acetone, finally obtains nano particle-polyurethane complex particle.
2. a kind of preparation method who is used for the nano particle-polyurethane complex particle of macromolecular material as claimed in claim 1 is characterized in that containing in the described base polyurethane prepolymer for use as isocyanate terminated base-NCO functional group, and its content is 4～9%; The consumption of base polyurethane prepolymer for use as is 10～50wt% of n-butyl acetate consumption.
3. a kind of preparation method who is used for the nano particle-polyurethane complex particle of macromolecular material as claimed in claim 1 is characterized in that described nanometer silicon dioxide particle particle diameter is 20～300nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610029225A CN100577705C (en) | 2006-07-21 | 2006-07-21 | Preparation method of nano particle-polyurethane complex particle for macromolecule material |
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| CN200610029225A CN100577705C (en) | 2006-07-21 | 2006-07-21 | Preparation method of nano particle-polyurethane complex particle for macromolecule material |
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| CN1927941A true CN1927941A (en) | 2007-03-14 |
| CN100577705C CN100577705C (en) | 2010-01-06 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250338B (en) * | 2008-04-01 | 2010-11-10 | 中国科学院化学研究所 | Modified inorganic nano-particle as well as preparation method and use thereof |
| CN102910914A (en) * | 2011-08-05 | 2013-02-06 | 中国科学院上海硅酸盐研究所 | Method for coating modified superfine ceramic powder by polyurethane |
| CN104448784A (en) * | 2013-11-15 | 2015-03-25 | 江苏吉星管业科技有限公司 | Nano composite system modified polyurethane steel plastic composite tube and preparation method thereof |
| CN107602796A (en) * | 2017-09-26 | 2018-01-19 | 苏州米颜生物科技有限公司 | A kind of preparation method of compounded rubber for solid tyre |
| CN110105693A (en) * | 2019-05-29 | 2019-08-09 | 山东金潮新型建材股份有限公司 | A kind of modified calcium carbonate filler material improves the preparation method of PVC mechanical property |
-
2006
- 2006-07-21 CN CN200610029225A patent/CN100577705C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250338B (en) * | 2008-04-01 | 2010-11-10 | 中国科学院化学研究所 | Modified inorganic nano-particle as well as preparation method and use thereof |
| CN102910914A (en) * | 2011-08-05 | 2013-02-06 | 中国科学院上海硅酸盐研究所 | Method for coating modified superfine ceramic powder by polyurethane |
| CN102910914B (en) * | 2011-08-05 | 2017-03-15 | 中国科学院上海硅酸盐研究所 | The method that polyurethane wraps up modified superfine ceramic powder |
| CN104448784A (en) * | 2013-11-15 | 2015-03-25 | 江苏吉星管业科技有限公司 | Nano composite system modified polyurethane steel plastic composite tube and preparation method thereof |
| CN107602796A (en) * | 2017-09-26 | 2018-01-19 | 苏州米颜生物科技有限公司 | A kind of preparation method of compounded rubber for solid tyre |
| CN110105693A (en) * | 2019-05-29 | 2019-08-09 | 山东金潮新型建材股份有限公司 | A kind of modified calcium carbonate filler material improves the preparation method of PVC mechanical property |
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| Publication number | Publication date |
|---|---|
| CN100577705C (en) | 2010-01-06 |
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