CN1375524A - Nanometer montmorillonoid-containing composite material and its prepn. - Google Patents
Nanometer montmorillonoid-containing composite material and its prepn. Download PDFInfo
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- CN1375524A CN1375524A CN 01109844 CN01109844A CN1375524A CN 1375524 A CN1375524 A CN 1375524A CN 01109844 CN01109844 CN 01109844 CN 01109844 A CN01109844 A CN 01109844A CN 1375524 A CN1375524 A CN 1375524A
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Abstract
The organic montmorillonoid prepared by making natural montmorillonoid undergo the process of cation exchange reaction is uniformly dispersed in polyether polyol, and their dispersion system is reacted with diisocyanate, proper quantity of chain-extender and catalyst so as to obtain a nano composite-material containing montmorillonoid. Its mechanical properties are completely raised, and its preparation process is simple.
Description
The present invention relates to a kind of nanometer montmorillonoid-containing composite material and preparation method thereof.
Urethane is the widely used polymer materials of a class, and its high performance research is included in progressively and regulates its molecular chain structure and add the organic-inorganic filler in the polymerization process.Usually introduce filler and can not strengthen simultaneously with toughness reinforcing in urethane, its elongation at break can descend when intensity improves.USP5,779,775 disclose and have prepared rigid foamed by polyurethane and the clay of renting combustion agent, solvent swelling.USP 5,693, and 696 disclose urethane and mica, clay, silicon-dioxide prepare matrix material.CN 1138593A, CN 1163288A, CN 1242392A disclose nylon, polyester, polystyrene and polynite respectively and have prepared nano composite material.
The object of the present invention is to provide a kind of nanometer montmorillonoid-containing composite material, mechanical properties such as its tensile strength and elongation at break can be improved simultaneously.
The present invention also aims to provide a kind of preparation method of nanometer montmorillonoid-containing composite material, promptly after cationite is handled, utilized the method preparation of intercalation polymeric by a kind of natural Meng Tuotuo soil.
A kind of nanometer montmorillonoid-containing composite material of the present invention by weight, comprises following component and consumption,
Urethane 100
Polynite 0.5～40
Cationite 0.5～15
Protonating agent 0.01～1.0
Dispersion medium 100～1100
" polyurethane handbook " (in September, 1992 that the urethane that the present invention was suitable for can be write with reference to [moral] G. strategic point Dare, 290 pages, Sinopec technology press), by polyether glycol, diisocyanate (as toluene diisocyanate, ditolyl methane diisocyanate), an amount of chainextender (as 1,4-butyleneglycol, ethylene glycol, quadrol etc.) and little amount of catalyst (as prepared in reaction such as two butylbenzene, two lauric acid tin, stannous octoate, tetramethyl butane diamines.
The used polynite of the present invention is a kind of nonmetal stratiform silicate minerals, and its unit cell is formed by carrying the layer of aluminum oxygen octahedra secretly in the middle of the two-layer silicon-oxy tetrahedron, connects by shared Sauerstoffatom between the two.The lamella internal surface has negative charge in the polynite, interlayer cation Na
2+, Ca
2+, Mg
2+Deng being the interchangeability positively charged ion, after cationic exchange, can make polysiloxane macromonomer be inserted into interlayer.Polynite should have cationic exchange total volume (CEC) 50～200meq/100g, is preferably 70～110meq/100g.When exchange capacity CEC greater than 200meq/100g, higher interlayer Coulomb's force makes polynite be difficult for being dispersed in the polymeric matrix; When exchange capacity is lower than 50meq/100g, polynite can not interact with polysiloxane macromonomer effectively, thereby is not enough to guarantee the consistency of polynite and polymeric matrix, makes polynite be difficult for being dispersed in the polymeric matrix equally.
The used polynite of the present invention should be crushed to suitable particle diameter with preceding, with ball mill, vibration mill jet mill etc. polynite is ground into desirable particle size then.General particle diameter should be at 40～100 μ m.
The polynite consumption is 0.5～40 part (weight part is with respect to 100 parts of urethane) in the present invention.When consumption is lower than 0.5 part, polynite is not enough to produce enough enhancements; When consumption surpasses 40 parts, polynite can not be in urethane homodisperse.In the present invention, the optimum amount scope of polynite is 2.5～20 parts.
Cationite of the present invention is a quaternary ammonium salt, comprises quaternary ammonium salts such as containing hexadecyl, octadecyl, allyl group, acrylamido, propylene ester group, as: cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride etc.
The protonating agent that the present invention was suitable for can be sulfuric acid, hydrochloric acid, sulfonic acid, acetic acid, Tricholroacetic Acid, phosphoric acid, m-phthalic acid or phthalic acid etc.
The effect of the dispersion medium that the present invention is used is to promote the dispersion of montmorillonite particle and the carrying out of cation exchange reaction, can be water, ethanol, methyl alcohol, Virahol, N, dinethylformamide etc.
Nanometer montmorillonoid-containing composite material of the present invention is an intercalation type nano composite material, disperses to be about about 4.5～4.7nm by the montmorillonite-based nano sheet interlayer spacing.
The preparation method of a kind of nanometer montmorillonoid-containing composite material of the present invention, in weight part, undertaken by following step:
It at first is the cation exchange reaction of polynite.With the cationic exchange total volume is that 50～200meq/100g, particle diameter are 0.5～40 part of the polynite of 40～100 μ m, and high-speed stirring in the presence of 80～1000 parts dispersion medium forms stable montmorillonite suspension liquid.0.5～15 part of cationite is dissolved in 20～100 parts of dispersion medium, adds 0.01～1.0 part of protonating agent, form solution.This drips of solution is added on is heated in 70～90 ℃ of polynite aaerosol solutions, will make polynite colloidal sol, this colloidal sol suction filtration, washing are not had white precipitate for extremely to dripping silver nitrate solution through 0.5～2 hour.Then through vacuum-drying, with ball mill, vibration mill or injection rub pulverize particle diameter 20～100 μ m.
Above-mentioned polynite powder through cation exchange reaction is scattered in 70～90 parts of polyether glycols for 0.5～40 part, in whipping process in 100-110 ℃ of following vacuum (＜2mmHg) dehydration degassing back after 1～2 hour with an amount of 5～20 parts of diisocyanates, 1～10 part of chainextender 60-110 ℃ of reaction 2～3 hours down, through the dehydration degassing once more, add 0.5～2 part of catalyzer and pour under 60-110 ℃ of condition, to place in the mould and made its curing molding in 12～24 hours.
Nanometer montmorillonoid-containing composite material of the present invention makes polynite have very big interfacial area, and inorganic disperse phase and polyurethane-base body interface have the ideal adhesiveproperties, can eliminate inorganics and polymeric matrix two material thermal expansivity mismatch problems.
Nanometer montmorillonoid-containing composite material of the present invention enters in the middle of the montmorillonite layer part polyurethane molecular chain, has strengthened inorganics and polymeric matrix interphase interaction, and the mechanical property of matrix material is greatly improved.The sheet polynite has iris action and the urethane interphase interaction increases the physical crosslinking of matrix material, chemically crosslinked point, and higher cross-linking density can make and impel composite property to be improved largely.
The polynite of sheet has iris action can make heat-resisting, the flame retardant resistance of material that further raising is arranged to gas in the nanometer montmorillonoid-containing composite material of the present invention.The adding of polynite has also improved the solvent resistance of matrix material simultaneously.
Simple, the easy row of the preparation manipulation of nanometer montmorillonoid-containing composite material of the present invention utilizes the production unit of conventional polyurethanes to prepare.
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1
With the cationic exchange total volume is the polynite 5g that 100meq/100g, particle diameter are about 50 μ m, adds water 100ml, and after waiting to be uniformly dispersed, high-speed stirring 20min obtains stable montmorillonite suspension liquid.The drips of solution that the 3.2g cetyl trimethylammonium bromide is formed in 30ml water adds heat to 80 ℃ montmorillonite suspension liquid, temperature maintenance is at 80 ℃, be incubated 1 hour, naturally cool to 25 ℃, suction filtration, and wash with water repeatedly, filtrate detected to there not being bromide anion with 0.2% silver nitrate solution, be dried to constant weight in the vacuum, be milled to the powder of particle diameter 50 μ m.Above-mentioned polynite powder through cation exchange reaction is scattered in the 80g dihydroxyl polyoxytrimethylene ether, in whipping process in 100 ℃ of following vacuum (＜2mmHg) the dehydration degassing after back 1.5 hours with diisocyanate, the 4g 1 of 15g, the 4-butyleneglycol reacted 2.5 hours down at 85 ℃, through the dehydration degassing once more, adding 1g two butylbenzene dilaurate tin are poured into to place under 85 ℃ of conditions in the mould and were made its curing molding in 18 hours.Promptly get matrix material.Its performance sees Table 1.
Embodiment 2
With the cationic exchange total volume is the polynite 5g that 90meq/100g, particle diameter are about 40 μ m, adds ethanol 100ml, and after waiting to be uniformly dispersed, high-speed stirring 20min obtains stable montmorillonite suspension liquid.The drips of solution that the 3.2g palmityl trimethyl ammonium chloride is formed in 30ml water adds heat to 80 ℃ montmorillonite suspension liquid, temperature maintenance is at 80 ℃, be incubated 1 hour, naturally cool to 20 ℃, suction filtration, and wash with water repeatedly, filtrate detected to there not being chlorion with 0.2% silver nitrate solution, be dried to constant weight in the vacuum, be milled to the powder that particle diameter is 40 μ m.Above-mentioned polynite powder through cation exchange reaction is scattered in the 80g trihydroxy-polyoxytrimethylene ether, in whipping process in 100 ℃ of following vacuum (＜2mmHg) the dehydration degassing after 1.5 hours with diisocyanate, the 4g 1 of 15g, the 4-butyleneglycol reacted 2.5 hours down at 85 ℃, through the dehydration degassing once more, adding 1g stannous octoate is poured into to place under 85 ℃ of conditions in the mould and was made its curing in 18 hours.Promptly get matrix material.Its performance sees Table 1.
Embodiment 3
With the cationic exchange total volume is the polynite 8g that 85meq/100g, particle diameter are about 70 μ m, adds methyl alcohol 100ml, and after waiting to be uniformly dispersed, high-speed stirring 20min obtains stable montmorillonite suspension liquid.The drips of solution that 5g octadecyl trimethylammonium bromide is formed in 30ml water adds heat to 80 ℃ montmorillonite suspension liquid, temperature maintenance is at 80 ℃, be incubated 1 hour, naturally cool to 20 ℃, suction filtration, and wash with water repeatedly, filtrate detected to there not being bromide anion with 0.2% silver nitrate solution, be dried to constant weight in the vacuum, be milled to the powder of particle diameter 60 μ m.Above-mentioned polynite powder through cation exchange reaction is scattered in the 80g trihydroxy-polyoxytrimethylene ether, in whipping process in 100 ℃ of following vacuum (＜2mmHg) the dehydration degassing after 1.5 hours with 15g diisocyanate, 4g butyleneglycol 85 ℃ of reactions 2.5 hours down, through the dehydration degassing once more, adding 1g tetramethyl butane diamine is poured into to place under 85 ℃ of conditions in the mould and was made its curing in 18 hours.Promptly get matrix material.Its performance sees Table 1.
Embodiment 4
With the cationic exchange total volume is the polynite 12.5g that 80meq/100g, particle diameter are about 60 μ m, adds Virahol 100ml, and after waiting to be uniformly dispersed, high-speed stirring 20min obtains stable montmorillonite suspension liquid.The drips of solution that the 8g octadecyl trimethyl ammonium chloride is formed in 30ml water adds heat to 80 ℃ montmorillonite suspension liquid, temperature maintenance is at 80 ℃, be incubated 1 hour, naturally cool to 25 ℃, suction filtration, and wash with water repeatedly, filtrate detected to there not being bromide anion with 0.2% silver nitrate solution, be dried to constant weight in the vacuum, be milled to particle diameter 50 μ m powder.Above-mentioned polynite powder through cation exchange reaction is scattered in the 80g trihydroxy-polyoxytrimethylene ether, in whipping process in 100 ℃ of following vacuum (＜2mmHg) the dehydration degassing after 1.5 hours with the diisocyanate of 15g, 4g diethylamine 85 ℃ of reactions 2.5 hours down, through the dehydration degassing once more, adding 1g two butylbenzene dilaurate tin are poured into to place under 85 ℃ of conditions in the mould and were made its curing molding in 18 hours.Promptly get matrix material.Its performance sees Table 1.
Embodiment 5
With the cationic exchange total volume is the polynite 2.5g that 100meq/100g, particle diameter are about 60 μ m, adds water 100ml, and after waiting to be uniformly dispersed, high-speed stirring 20min obtains stable montmorillonite suspension liquid.The drips of solution that the 1.6g cetyl trimethylammonium bromide is formed in 30ml water adds heat to 80 ℃ montmorillonite suspension liquid, temperature maintenance is at 80 ℃, be incubated 1 hour, naturally cool to 20 ℃, suction filtration, and wash with water repeatedly, filtrate detected to there not being bromide anion with 0.2% silver nitrate solution, be dried to constant weight in the vacuum, being milled to particle diameter is 40 μ m powder.Above-mentioned polynite powder through cation exchange reaction is scattered in the 80g trihydroxy-polyoxytrimethylene ether, in whipping process in 100 ℃ of following vacuum (＜2mmHg) the dehydration degassing after 1.5 hours with the 15g diisocyanate, the 4g chainextender reacted 2.5 hours down at 85 ℃, through the dehydration degassing once more, adding 1g two butylbenzene dilaurate tin go into to place under 85 ℃ of conditions in the mould made its curing molding in 18 hours.Promptly get matrix material.Its performance sees Table 1.
Comparative Examples
With 80g trihydroxy-polyoxytrimethylene ether, in whipping process in 100 ℃ of following vacuum (＜2mmHg) the dehydration degassing after 1.5 hours with diisocyanate, the 4g 1 of 15g, the 4-butyleneglycol reacted 2.5 hours down at 85 ℃, through the dehydration degassing once more, adding 1g two butylbenzene dilaurate tin are poured into to place under 85 ℃ of conditions in the mould and were made its curing in 18 hours.Promptly get pure polyurethane material.Its performance sees Table 1.
Table 1
| Embodiment | Polynite content (g) | Polyurethane content (g) | ??D 001Interplanar distance () | Tensile strength (MPa) | Elongation at break (%) | Heat decomposition temperature (℃) |
| ????1 | ????5.0 | ????100 | ????40 | ??1.00 | ????130 | ????379 |
| ????2 | ????5.0 | ????100 | ????46 | ??1.30 | ????200 | ????384 |
| ????3 | ????8.0 | ????100 | ????47 | ??1.50 | ????360 | ????385 |
| ????4 | ???12.5 | ????100 | ????45 | ??1.35 | ????220 | ????385 |
| ????5 | ????2.5 | ????100 | ????46 | ??0.98 | ????180 | ????381 |
| Comparative Examples | ?????0 | ????100 | ?????- | ??0.64 | ?????70 | ????377 |
Claims (7)
1. a nanometer montmorillonoid-containing composite material by weight, comprises following component and consumption,
Urethane 100
Polynite 0.5～40
Cationite 0.5～15
Protonating agent 0.01～1.0
Dispersion medium 100～1100
Described montmorillonite layer internal surface has negative charge, and interlayer has Na
2+, Ca
2+, Mg
2+Etc. the interchangeability positively charged ion, its cationic exchange total volume (CEC) 50～200meq/100g, described polynite with before should to be crushed to particle diameter be 40～100 μ m;
Described cationite is hexadecyl, octadecyl, allyl group, acrylamido, propylene ester based quaternary ammonium salt;
Described protonating agent is sulfuric acid, hydrochloric acid, sulfonic acid, acetic acid, Tricholroacetic Acid, phosphoric acid, m-phthalic acid or phthalic acid;
Described dispersion medium is water, ethanol, methyl alcohol, Virahol, N, dinethylformamide;
Described composite material nanometer sheet interlayer spacing is 4.5～4.7nm.
2. according to a kind of nanometer montmorillonoid-containing composite material of claim 1, it is characterized in that described polynite cationic exchange total volume (CEC) is 70～110meq/100g.
3. according to a kind of nanometer montmorillonoid-containing composite material of claim 1, it is characterized in that described polynite consumption is 2.5～20 parts.
4. according to a kind of nanometer montmorillonoid-containing composite material of claim 1, it is characterized in that described cationite is cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride.
5. the preparation method of a nanometer montmorillonoid-containing composite material, in weight part, undertaken by following step:
With the cationic exchange total volume is that 50～200meq/100g, particle diameter are 0.5～40 part of the polynite of 40～100 μ m, and high-speed stirring in the presence of 80～1000 parts dispersion medium forms stable montmorillonite suspension liquid; 0.5～15 part of cationite is dissolved in 20～100 parts of dispersion medium, adds 0.01～1.0 part of protonating agent, form solution; This drips of solution is added on is heated in 70～90 ℃ of polynite aaerosol solutions, will make polynite colloidal sol, this colloidal sol suction filtration, washing are not had white precipitate for extremely to dripping silver nitrate solution through 0.5～2 hour; Then through vacuum-drying, with ball mill, vibration mill or injection rub pulverize particle diameter 20～100 μ m;
Above-mentioned polynite powder through cation exchange reaction is scattered in 70～90 parts of polyether glycols for 0.5～40 part, in whipping process, reacted 2～3 hours down at 60-110 ℃ with 5～20 parts of an amount of diisocyanates, 1～10 part of chainextender after 1～2 hour in 100-110 ℃ of following vacuum hydro-extraction degassing back, through the dehydration degassing once more, add 0.5～2 part of catalyzer and pour under 60-110 ℃ of condition, to place in the mould and made its curing molding in 12～24 hours;
Described montmorillonite layer internal surface has negative charge, and interlayer has Na
2+, Ca
2+, Mg
2+Etc. the interchangeability positively charged ion, its cationic exchange total volume (CEC) 50～200meq/100g, described polynite with before should to be crushed to particle diameter be 40～100 μ m;
Described cationite is hexadecyl, octadecyl, allyl group, acrylamido, propylene ester based quaternary ammonium salt;
Described protonating agent is sulfuric acid, hydrochloric acid, sulfonic acid, acetic acid, Tricholroacetic Acid, phosphoric acid, m-phthalic acid or phthalic acid;
Described dispersion medium is water, ethanol, methyl alcohol, Virahol, N, dinethylformamide.
6. according to the preparation method of a kind of nanometer montmorillonoid-containing composite material of claim 5, it is characterized in that described polyether glycol is dibasic alcohol or trivalent alcohol; Described chainextender is 1,4-butyleneglycol, ethylene glycol, quadrol; Described catalyzer is two butylbenzene, two lauric acid tin, stannous octoate, tetramethyl butane diamine.
7. according to the preparation method of a kind of nanometer montmorillonoid-containing composite material of claim 5, it is characterized in that described polyether glycol is dihydroxyl polyoxytrimethylene ether, trihydroxy-polyoxytrimethylene ether.
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| CN100338149C (en) * | 2004-12-10 | 2007-09-19 | 南京大学 | Imvite, polyurethane/imvite nanometer composite material with surface modification and production thereof |
| CN100374524C (en) * | 2005-08-19 | 2008-03-12 | 上海工程技术大学 | Liquid rubber based adhesive containing Nano montmorillonite and preparation method |
| CN100376632C (en) * | 2004-08-24 | 2008-03-26 | 邱连生 | Nanometer montmorillonite-soft polyurethane foam plastic and its prepn process |
| CN100400607C (en) * | 2004-09-20 | 2008-07-09 | 中国科学院化学研究所 | Preparation method of heat stability reinforced nano-montmorillonite |
| CN100465093C (en) * | 2005-05-31 | 2009-03-04 | 华东理工大学 | Organic modification method for phyllosilicate |
| CN102277120A (en) * | 2011-08-03 | 2011-12-14 | 天津大学 | Organic-montmorillonite modified double-component polyurethane adhesive and preparation method thereof |
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| CN103360760A (en) * | 2012-03-27 | 2013-10-23 | 上海杰事杰新材料(集团)股份有限公司 | Semiaromatic polyamide/organic montmorillonite nanocomposite and preparation method thereof |
| CN103360761A (en) * | 2012-03-27 | 2013-10-23 | 上海杰事杰新材料(集团)股份有限公司 | Semiaromatic polyamide salt /organic montmorillonite nanocomposite and preparation method thereof |
| CN102617375B (en) * | 2009-07-20 | 2014-01-22 | 北京化工大学 | Photo-initiation/halogen-free flame retardant and preparation method and application thereof |
| CN103865469A (en) * | 2014-03-28 | 2014-06-18 | 哈尔滨理工大学 | Method for preparing montmorillonite modified alcohol-soluble polyurethane (PU) adhesive |
| CN106084178A (en) * | 2015-05-01 | 2016-11-09 | 郑国樑 | crosslinking agent |
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2001
- 2001-03-21 CN CNB011098449A patent/CN1162470C/en not_active Expired - Fee Related
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| CN100376632C (en) * | 2004-08-24 | 2008-03-26 | 邱连生 | Nanometer montmorillonite-soft polyurethane foam plastic and its prepn process |
| CN100400607C (en) * | 2004-09-20 | 2008-07-09 | 中国科学院化学研究所 | Preparation method of heat stability reinforced nano-montmorillonite |
| CN100338149C (en) * | 2004-12-10 | 2007-09-19 | 南京大学 | Imvite, polyurethane/imvite nanometer composite material with surface modification and production thereof |
| CN1880388B (en) * | 2005-05-25 | 2013-03-13 | 三星Sdi株式会社 | Proton conducting inorganic material, polymer nano-composite membrane including the same, and fuel cell adopting the polymer nano-composite membrane |
| CN100465093C (en) * | 2005-05-31 | 2009-03-04 | 华东理工大学 | Organic modification method for phyllosilicate |
| CN100374524C (en) * | 2005-08-19 | 2008-03-12 | 上海工程技术大学 | Liquid rubber based adhesive containing Nano montmorillonite and preparation method |
| CN102617375B (en) * | 2009-07-20 | 2014-01-22 | 北京化工大学 | Photo-initiation/halogen-free flame retardant and preparation method and application thereof |
| CN101602682B (en) * | 2009-07-20 | 2013-05-01 | 北京化工大学 | Photoinitiator/halogen-free fire retardant, preparation method and application thereof |
| CN102277120A (en) * | 2011-08-03 | 2011-12-14 | 天津大学 | Organic-montmorillonite modified double-component polyurethane adhesive and preparation method thereof |
| CN103360760A (en) * | 2012-03-27 | 2013-10-23 | 上海杰事杰新材料(集团)股份有限公司 | Semiaromatic polyamide/organic montmorillonite nanocomposite and preparation method thereof |
| CN103360761A (en) * | 2012-03-27 | 2013-10-23 | 上海杰事杰新材料(集团)股份有限公司 | Semiaromatic polyamide salt /organic montmorillonite nanocomposite and preparation method thereof |
| CN103360760B (en) * | 2012-03-27 | 2018-02-23 | 上海杰事杰新材料(集团)股份有限公司 | A kind of Semiaromatic polyamide/organic montmorillonite nanocomposite and preparation method thereof |
| CN103865469A (en) * | 2014-03-28 | 2014-06-18 | 哈尔滨理工大学 | Method for preparing montmorillonite modified alcohol-soluble polyurethane (PU) adhesive |
| CN106084173A (en) * | 2015-04-29 | 2016-11-09 | 郑国樑 | Clay-polyurethane composite material and preparation method thereof |
| CN106084178A (en) * | 2015-05-01 | 2016-11-09 | 郑国樑 | crosslinking agent |
| CN110409181A (en) * | 2019-08-31 | 2019-11-05 | 三赢家居用品(河源)有限公司 | A kind of water-proof aagent and its preparation method and application method |
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