CN106009653A - Antibacterial nano-silica material and preparation method thereof - Google Patents
Antibacterial nano-silica material and preparation method thereof Download PDFInfo
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- CN106009653A CN106009653A CN201610636546.5A CN201610636546A CN106009653A CN 106009653 A CN106009653 A CN 106009653A CN 201610636546 A CN201610636546 A CN 201610636546A CN 106009653 A CN106009653 A CN 106009653A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses an antibacterial nano-silica material. The antibacterial nano-silica material comprises, by weight, 0.4-1 part of gamma-aminopropyltriethoxysilane, 10-13 parts of nano-silica, 70-84 parts of caprolactam, 20-23 parts of oxalic acid, 5-7 parts of tetrabutyl titanate, 0.6-1 part of didecyldimethylammonium bromide, 10-13 parts of an antibacterial emulsion, 0.06-0.1 parts of dibasic lead phosphite, 2-4 parts of polyisoprene and 0.5-1 part of polyamide wax micro-powder. Nano-silica is processed with silane to obtain nano-silica with the surface containing an amino group, a high-disperse polymerization material can be obtained through a reaction of a caprolactam ring opening product aminocaproic acid and the amino group on the surface of nano-silica in the caprolactam polymerization process, and polybenzimidazole, calcium propionate and isothiazolinone can be added in the invention to effectively improve the antibacterial performance of the above finished material.
Description
Technical field
The present invention relates to technical field of nano material, particularly relate to a kind of antimicrobial nano earth silicon material and preparation method thereof.
Background technology
Along with emerging in large numbers of new technique, research and the understanding of polymer based nanocomposites are deepened continuously by people, and preparation method and production technology to nano composite material are also evolving and enrich.In recent years, the method preparing polymer based nanocomposites material also has bigger development, mainly has blending method, graft process, sol-gel process, in-situ method, mother material etc.；
The combination property of polymer matrix composite depends not only on the specific functionality of added filler, and the compatibility and the adhesion of dispersion phase degree of scatter, size and matrix material in matrix material also have large effect to the combination property of composite.At present, the compatibility of filler and matrix material, boundary strength, interaction force are conducted in-depth research, and achieve ideal result by a lot of scholars；
Polyamide is due to its good mechanical property, barrier property, anti-wear performance, acid-proof alkaline and good processing characteristics, indispensable material is increasingly becomed as engineering plastics and non-fibre material, its application relates to the fields such as auto parts and components, cord fabric, tyre equatorial, electronic apparatus, household supplies, and consumption becomes kinds most in polyamide product.But in application process, the polar group of polyamide 6 material makes it be prone to absorb moisture, cause dry state and low temperature impact strength is low, product stability is poor, friction easily occurs the phenomenon such as plastic deformation, serious wear, additionally, use as mine engineering plastics, do not possess antistatic property, easily produce gas explosion etc., thus affect the stability of its product size, antiwear and friction reduction property and electrical property, which has limited its range of application；
Nano material refers to that the unidimensional scale of an at least phase in the duplex structure of material reaches the material of nano-grade size, and nanotechnology is the science studying material performance at molecule and atomic level.According to the structural parameters of nano material, it is generally divided into zero dimensional nanometer materials, monodimension nanometer material, two-dimension nano materials and three-dimensional nanometer material.Owing to the size of nano material is in the range of 1-100 nm, it is closely sized in electronics coherence length, due to strong relevant reason so that nano material shows the property being different from traditional material at aspects such as fusing point, magnetic, optics, heat conduction, conductions；One of material having development potentiality is compared as 21 century, in the last few years, the research of nano material is concentrated mainly on the aspects such as medical science, the energy, environmental protection, material, integrated micro-system, potential using value is shown in security system, explosive fuse, coating, Penetration weapon, stock's detection and the field such as indiffusion, in-depth weapon knowledge of regularity of nuclear weapon, at present, nano material and the development of nanosecond science and technology and application enjoy the extensive concern of people；
Along with the development of nano material theory and technology, inorganic nano-particle shows the performance of excellence as filler compared with traditional material.By suitable technology and method, inorganic nano-particle is joined in polymeric matrix material so that it is fully demonstrate the nano-meter characteristic of nano material, and then improve the combination property of nano composite material；The development of nano material and nanosecond science and technology will promote polymer based nanocomposites to become one of 21st century the most promising material.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of antimicrobial nano earth silicon material and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of antimicrobial nano earth silicon material, it is made up of the raw material of following weight parts:
Gamma-aminopropyl-triethoxy-silane 0.4-1, nano silicon 10-13, caprolactam 70-84, ethanedioic acid 20-23, butyl titanate 5-7, double decyl dimethyl ammonium bromide 0.6-1, antimicrobial emulsion 10-13, dibasic lead phosphite 0.06-0.1, polyisoprene 2-4, polyamide wax micropowder 0.5-1.
Described a kind of antimicrobial nano earth silicon material, described antimicrobial emulsion is made up of the raw material of following weight parts:
Calcium ricinoleate 1.4-2, hydrolytic polymaleic anhydride 0.2-0.3, allyl polyglycol 1-2, polybenzimidazoles 0.7-1, calcium propionate 0.1-0.3, isothiazolone 0.2-0.4, lauric acid amide of ethanol 1-2, deionized water 80-100；
(1) take the 30-40% of above-mentioned deionized water weight, add hydrolytic polymaleic anhydride, rise high-temperature and be 60-70 DEG C, add above-mentioned calcium ricinoleate, the sodium hydroxide of dropping 3-5mol/l, regulation pH is 10-13, insulated and stirred 10-14 minute, adding isothiazolone, stirring, to room temperature, obtains antibacterial liquid；
(2) by above-mentioned polybenzimidazoles, calcium propionate mixing, join in remaining deionized water, stir, add allyl polyglycol, antibacterial liquid, 100-200 rev/min is stirred 3-5 minute, mix with above-mentioned calcium propionate, lauric acid amide of ethanol, rise high-temperature and be 80-85 DEG C, the hydrochloric acid of dropping 1-2mol/l, regulation pH is neutral, it is incubated 10-20 minute, is cooled to room temperature, obtains antimicrobial emulsion.
The preparation method of a kind of described antimicrobial nano earth silicon material, comprises the following steps:
(1) take above-mentioned polyamide wax micropowder, join in the dehydrated alcohol of its weight 10-13 times, stir, send in the water-bath of 80-90 DEG C, be incubated 4-5 minute, discharging, add gamma-aminopropyl-triethoxy-silane, stirring, to room temperature, obtains silanol solution；
(2) above-mentioned nano silicon is joined in the dehydrated alcohol of its weight 100-120 times, ultrasonic 40-50 minute, drip above-mentioned butyl titanate, rise high-temperature after dropping and be 50-60 DEG C, insulated and stirred 20-30 minute, is sent to equipped with in the reactor of polytetrafluoroethylliner liner, insulation reaction 4-5 hour at 180-190 DEG C, discharging, cooling, filters, and precipitation is washed 2-3 time, at 60-70 DEG C, vacuum drying completely, obtains titanium doped nano silicon；
(3) above-mentioned polyisoprene is taken, join in the dehydrated alcohol of its weight 100-160 times, stir, add double decyl dimethyl ammonium bromide, rise high-temperature and be 70-75 DEG C, mix with above-mentioned silanol solution, stir, add above-mentioned titanium doped nano silicon, rise high-temperature and be 80-90 DEG C, insulated and stirred 1.7-2 hour, obtains amino modified titanium doped nano silicon；
(4) take above-mentioned caprolactam, ethanedioic acid, mix with amino modified titanium doped nano silicon, add the distilled water of compound weight 10-18 times, it is sent in reactor, rise high-temperature and be 220-300 DEG C, insulation reaction 3-5 hour, slowly cool to room temperature, add antimicrobial emulsion and remain each raw material, 70-100 rev/min is stirred 10-17 minute, is filtered to remove filtrate, precipitation is dried, grind to form fine powder, obtain antimicrobial nano earth silicon material.
The invention have the advantage that
First the present invention uses silane treatment nano silicon, obtain the nano silicon that amino is contained on surface, then during caprolactam polymerization, caprolactam open-loop products aminocaproic acid is utilized to react with the amino of nano-silica surface, the polymeric material of high dispersive can be obtained, the present invention is also added into polybenzimidazoles, calcium propionate, isothiazolone etc., can effectively improve the anti-microbial property of finished-product material.
Detailed description of the invention
A kind of antimicrobial nano earth silicon material, it is made up of the raw material of following weight parts:
γ aminopropyl triethoxysilane 0.4, nano silicon 10, caprolactam 70, ethanedioic acid 20, butyl titanate 5, double decyl dimethyl ammonium bromide 0.6, antimicrobial emulsion 10, dibasic lead phosphite 0.06, polyisoprene 2, polyamide wax micropowder 0.5.
Described a kind of antimicrobial nano earth silicon material, described antimicrobial emulsion is made up of the raw material of following weight parts:
Calcium ricinoleate 1.4, hydrolytic polymaleic anhydride 0.2, allyl polyglycol 1, polybenzimidazoles 0.7, calcium propionate 0.1, isothiazolone 0.2, lauric acid amide of ethanol 1, deionized water 80；
(1) taking the 30% of above-mentioned deionized water weight, add hydrolytic polymaleic anhydride, rising high-temperature is 60 DEG C, adds above-mentioned calcium ricinoleate, the sodium hydroxide of dropping 3mol/l, regulation pH is 10, insulated and stirred 10 minutes, adding isothiazolone, stirring, to room temperature, obtains antibacterial liquid；
(2) by above-mentioned polybenzimidazoles, calcium propionate mixing, join in remaining deionized water, stir, add allyl polyglycol, antibacterial liquid, 100 revs/min are stirred 3 minutes, mixing with above-mentioned calcium propionate, lauric acid amide of ethanol, rising high-temperature is 80 DEG C, the hydrochloric acid of dropping 1mol/l, regulation pH is neutral, it is incubated 10 minutes, is cooled to room temperature, obtains antimicrobial emulsion.
The preparation method of a kind of described antimicrobial nano earth silicon material, comprises the following steps:
(1) take above-mentioned polyamide wax micropowder, join in the dehydrated alcohol of its weight 10 times, stir, send in the water-bath of 80 DEG C, be incubated 4 minutes, discharging, add γ aminopropyl triethoxysilane, stirring, to room temperature, obtains silanol solution；
(2) above-mentioned nano silicon is joined in the dehydrated alcohol of its weight 100 times, ultrasonic 40 minutes, drip above-mentioned butyl titanate, rising high-temperature after dropping is 50 DEG C, insulated and stirred 20 minutes, is sent to equipped with in the reactor of polytetrafluoroethylliner liner, insulation reaction 4 hours at 180 DEG C, discharging, cooling, filters, and precipitation is washed 2 times, at 60 DEG C, vacuum drying completely, obtains titanium doped nano silicon；
(3) above-mentioned polyisoprene is taken, join in the dehydrated alcohol of its weight 100 times, stirring, add double decyl dimethyl ammonium bromide, rising high-temperature is 70 DEG C, mix with above-mentioned silanol solution, stirring, add above-mentioned titanium doped nano silicon, rising high-temperature is 80 DEG C, insulated and stirred 1.7 hours, obtains amino modified titanium doped nano silicon；
(4) take above-mentioned caprolactam, ethanedioic acid, mix with amino modified titanium doped nano silicon, add the distilled water of compound weight 10 times, it is sent in reactor, rising high-temperature is 220 DEG C, and insulation reaction 3 hours slowly cools to room temperature, add antimicrobial emulsion and remain each raw material, 70 revs/min are stirred 10 minutes, are filtered to remove filtrate, precipitation are dried, grind to form fine powder, obtain antimicrobial nano earth silicon material.
Claims (3)
1. an antimicrobial nano earth silicon material, it is characterised in that it is made up of the raw material of following weight parts:
Gamma-aminopropyl-triethoxy-silane 0.4-1, nano silicon 10-13, caprolactam 70-84, ethanedioic acid 20-23, butyl titanate 5-7, double decyl dimethyl ammonium bromide 0.6-1, antimicrobial emulsion 10-13, dibasic lead phosphite 0.06-0.1, polyisoprene 2-4, polyamide wax micropowder 0.5-1.
A kind of antimicrobial nano earth silicon material the most according to claim 1, it is characterised in that described antimicrobial emulsion is made up of the raw material of following weight parts:
Calcium ricinoleate 1.4-2, hydrolytic polymaleic anhydride 0.2-0.3, allyl polyglycol 1-2, polybenzimidazoles 0.7-1, calcium propionate 0.1-0.3, isothiazolone 0.2-0.4, lauric acid amide of ethanol 1-2, deionized water 80-100；
(1) take the 30-40% of above-mentioned deionized water weight, add hydrolytic polymaleic anhydride, rise high-temperature and be 60-70 DEG C, add above-mentioned calcium ricinoleate, the sodium hydroxide of dropping 3-5mol/l, regulation pH is 10-13, insulated and stirred 10-14 minute, adding isothiazolone, stirring, to room temperature, obtains antibacterial liquid；
(2) by above-mentioned polybenzimidazoles, calcium propionate mixing, join in remaining deionized water, stir, add allyl polyglycol, antibacterial liquid, 100-200 rev/min is stirred 3-5 minute, mix with above-mentioned calcium propionate, lauric acid amide of ethanol, rise high-temperature and be 80-85 DEG C, the hydrochloric acid of dropping 1-2mol/l, regulation pH is neutral, it is incubated 10-20 minute, is cooled to room temperature, obtains antimicrobial emulsion.
3. the preparation method of an antimicrobial nano earth silicon material as claimed in claim 1, it is characterised in that comprise the following steps:
(1) take above-mentioned polyamide wax micropowder, join in the dehydrated alcohol of its weight 10-13 times, stir, send in the water-bath of 80-90 DEG C, be incubated 4-5 minute, discharging, add gamma-aminopropyl-triethoxy-silane, stirring, to room temperature, obtains silanol solution；
(2) above-mentioned nano silicon is joined in the dehydrated alcohol of its weight 100-120 times, ultrasonic 40-50 minute, drip above-mentioned butyl titanate, rise high-temperature after dropping and be 50-60 DEG C, insulated and stirred 20-30 minute, is sent to equipped with in the reactor of polytetrafluoroethylliner liner, insulation reaction 4-5 hour at 180-190 DEG C, discharging, cooling, filters, and precipitation is washed 2-3 time, at 60-70 DEG C, vacuum drying completely, obtains titanium doped nano silicon；
(3) above-mentioned polyisoprene is taken, join in the dehydrated alcohol of its weight 100-160 times, stir, add double decyl dimethyl ammonium bromide, rise high-temperature and be 70-75 DEG C, mix with above-mentioned silanol solution, stir, add above-mentioned titanium doped nano silicon, rise high-temperature and be 80-90 DEG C, insulated and stirred 1.7-2 hour, obtains amino modified titanium doped nano silicon；
(4) take above-mentioned caprolactam, ethanedioic acid, mix with amino modified titanium doped nano silicon, add the distilled water of compound weight 10-18 times, it is sent in reactor, rise high-temperature and be 220-300 DEG C, insulation reaction 3-5 hour, slowly cool to room temperature, add antimicrobial emulsion and remain each raw material, 70-100 rev/min is stirred 10-17 minute, is filtered to remove filtrate, precipitation is dried, grind to form fine powder, obtain antimicrobial nano earth silicon material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380986A (en) * | 2016-11-07 | 2017-02-08 | 芜湖市鸿坤汽车零部件有限公司 | Whisker-type antibacterial leather paint and preparation method thereof |
| CN108559259A (en) * | 2018-05-22 | 2018-09-21 | 温州市赢创新材料技术有限公司 | A kind of waste rubber powder doping nylon plastic material and preparation method thereof |
| CN113105788A (en) * | 2021-03-04 | 2021-07-13 | 安徽千鑫通讯科技有限公司 | Antibacterial coating on surface of mobile phone and spraying process thereof |
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| CN105778489A (en) * | 2016-05-21 | 2016-07-20 | 夏百庆 | Polyamide modified nano silicon dioxide material and preparation method thereof |
| CN105778351A (en) * | 2016-04-26 | 2016-07-20 | 安徽玉发塑业有限公司 | Antibacterial polyvinyl chloride plastic tube and preparation method thereof |
| CN105778490A (en) * | 2016-05-24 | 2016-07-20 | 夏百庆 | Hard nano silica material and preparation method thereof |
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2016
- 2016-08-05 CN CN201610636546.5A patent/CN106009653A/en active Pending
Patent Citations (5)
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| JPH0782473A (en) * | 1993-09-14 | 1995-03-28 | Teijin Ltd | Antimicrobial polyamide composition excellent in light resistance |
| CN103910996A (en) * | 2014-04-02 | 2014-07-09 | 合肥杰事杰新材料股份有限公司 | Antibacterial masterbatch, nano antibacterial super-tough plastic added with antibacterial masterbatch and preparation and application of plastic |
| CN105778351A (en) * | 2016-04-26 | 2016-07-20 | 安徽玉发塑业有限公司 | Antibacterial polyvinyl chloride plastic tube and preparation method thereof |
| CN105778489A (en) * | 2016-05-21 | 2016-07-20 | 夏百庆 | Polyamide modified nano silicon dioxide material and preparation method thereof |
| CN105778490A (en) * | 2016-05-24 | 2016-07-20 | 夏百庆 | Hard nano silica material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380986A (en) * | 2016-11-07 | 2017-02-08 | 芜湖市鸿坤汽车零部件有限公司 | Whisker-type antibacterial leather paint and preparation method thereof |
| CN108559259A (en) * | 2018-05-22 | 2018-09-21 | 温州市赢创新材料技术有限公司 | A kind of waste rubber powder doping nylon plastic material and preparation method thereof |
| CN113105788A (en) * | 2021-03-04 | 2021-07-13 | 安徽千鑫通讯科技有限公司 | Antibacterial coating on surface of mobile phone and spraying process thereof |
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