CN102702509A - Silver-containing nylon 6-based composite resin material and preparation method thereof - Google Patents
Silver-containing nylon 6-based composite resin material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silver-containing nylon 6-based composite resin material and a preparation method thereof. The silver-containing nylon 6-based composite resin material is prepared by caprolactam, soluble silver salt, polyvinylpyrrolidone, ascorbic acid aqueous solution, ammonia, a alkaline catalyst and solvent as raw materials by using an in situ polymerization method. The amount of each component is as below : the soluble silver salt is 0.3-3 wt% of the weight of caprolactam, the polyvinylpyrrolidone is 0.3-1.0 wt% of the weight of caprolactam, the weight ratio of the ascorbic acid and the soluble silver salt is 1.2-1.5:1, the weight ratio of the soluble silver salt and the ammonia is 1-3:1. The nylon 6 / Ag composite resin material provided by the invention not only maintains the mechanical property of the original nylon 6, but also has excellent antibacterial property and permanent antimicrobial property. The preparation method provided by the invention has the advantages of simple process, short preparation period, low cost, and no pollution, and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of nylon-6 matrix compound resin and preparation method thereof.
Background technology
In recent years, the anti-biotic material of preparing through an amount of antiseptic-germicide of interpolation in macromolecular material has caused the extensive concern of industry.Patent (application number 02110160.4) " a kind of method of manufacture of antibacteria fiber containing nano particles " discloses a kind of nanoparticle prepares antibacterial fiber as antibiotic bactericide method of in the solvent spinning process, adding.It is the method for carrying out spinning after the blend granulation behind the nano inorganic MOX surface modification with dispersion agent and nylon 6 slice with silver that patent (application number 101705527) " antibiosis antistatic multifunctional nylon 6 fiber and preparation thereof and application " discloses a kind of.But aforesaid method all is to add blend in the polymeric matrix to nanoparticle, is difficult to reach the homodisperse of nanoparticle in matrix, and nanoparticle reunites easily, thereby loses the special dimensional effect of nanoparticle.
Summary of the invention
The purpose of this invention is to provide a kind of argentiferous nylon-6 matrix composite resin material and preparation method thereof, to overcome the defective that existing blending technology exists.
Argentiferous nylon-6 matrix composite resin material provided by the invention is to be raw material with hexanolactam, soluble silver salt, Vinylpyrrolidone polymer, aqueous ascorbic acid, ammoniacal liquor, basic catalyst and solvent, adopts the in-situ polymerization preparation;
The consumption of each component is:
Soluble silver salt is the 0.3-3wt% of hexanolactam weight, preferred 0.3～1.0%;
Vinylpyrrolidone polymer is 0.3 ~ 1.0wt% of hexanolactam weight, preferred 0.3 ~ 0.85%;
Xitix: soluble silver salt=1.2～1.5: 1, weight ratio;
In the above-mentioned ratio, be the ratio of xitix and soluble silver salt, rather than aqueous ascorbic acid;
Said aqueous ascorbic acid concentration is 0.5 ~ 1.5mg/ml, preferred 0.7 ~ 1.3mg/ml, optimum 1mg/ml;
Soluble silver salt: ammoniacal liquor=1 ~ 3:1, weight ratio;
NH in the ammoniacal liquor
3Weight concentration is 25～28%;
Described soluble silver salt is selected from Silver Nitrate AgNO
3, tachyol AgF or silver perchlorate AgClO
4
The K value of described Vinylpyrrolidone polymer PVP is 30, and molecular-weight average is 4000;
Said basic catalyst is selected from sodium Metal 99.5, NaOH, NaHCO
3Or K
2CO
3, weight consumption is 0.1～3% of a hexanolactam;
Wherein, ammoniacal liquor is made solvent, and Vinylpyrrolidone polymer is a stablizer;
Aqueous ascorbic acid, soluble silver salt and ammonia soln constitute reductive agent;
The preparation method of argentiferous nylon-6 matrix composite resin material of the present invention comprises the steps:
(1) with Vinylpyrrolidone polymer, add ammoniacal liquor, dissolving back, adding soluble silver salt, stirring and dissolving adds aqueous ascorbic acid then, and ultrasonic concussion 10～35min obtains colloidal sol;
(2) product with step (1) adds the fused hexanolactam, mixes, under nitrogen protection; Add basic catalyst and carry out polymerization, polymerization pressure is 0 ~ 1MPa, and polymerization temperature is 200 ~ 280 ℃; Polymerization time is 2～8 hours, then under the reaction end temperature, and the anhydrous discharge of reaction system in decompression dehydration to the polymeric kettle; Vacuum tightness is 0.1～3MPa, obtains nylon 6/Ag composite resin material;
Preferably, in the different steps of polymerization process, adopt different polymerization pressure and temperature; 0～2 hour, polymerization pressure was 0.1 ~ 0.8MPa, and polymerization temperature is 200 ~ 220 ℃; 2～6 hours, polymerization pressure was 0.8 ~ 3MPa, and polymerization temperature is 220 ~ 280 ℃; 6～8 hours, polymerization pressure was 0.1 ~ 1.2MPa, and polymerization temperature is 220 ~ 280 ℃;
Above-mentioned pressure is gauge pressure.
Among the present invention, in the silver of preparation/ammoniacal liquor colloidal sol, silver particles is uniformly dispersed in the PVP/ ammonia soln, and median size is between 10 ~ 200nm, and particle diameter can be regulated through controlling concn, reaction times.In the nylon 6/Ag composite resin material for preparing among the present invention, silver particles is uniformly dispersed in polymeric matrix, and median size is between 20 ~ 250nm.
Adopt the present invention to prepare the reaction process and the 6 synthetic not significantly differences of pure nylon of nylon 6/Ag composite resin material, therefore need not change polymerization technique.
The method that the present invention prepares nylon 6/Ag composite resin material has the following advantages:
The generation of Nano silver grain is carried out in position among the present invention; Nylon 6/Ag composite resin material by present method preparation; Not only mechanical mechanics property can keep the performance of former nylon 6; And have excellent anti-microbial property, and can image surface do not apply the method that kind that contains silver material and in use lose anti-microbial property gradually, permanent bacterinertness had.The inventive method technology is simple, and preparation cycle is short, and production cost is low, and is pollution-free, is applicable to large-scale industrial production.
Embodiment
Embodiment 1
(1) with the 1g weight concentration is 28% ammoniacal liquor, adds 3g Vinylpyrrolidone polymer K30 dissolving, add Silver Nitrate 3g; Stir 10min; Form yellow solution, add the aqueous ascorbic acid that concentration is 0.5mg/ml then, the gross weight that xitix adds is 3.6g; Stir, ultrasonic concussion 35min obtains colloidal sol;
(2) with mixing in the above-mentioned colloidal sol adding 997g fused hexanolactam; Add 1 gram NaOH as catalyzer; Under nitrogen protection, carry out polymerization; The anhydrous discharge of reaction system in 220 ℃ of following decompression dehydration to polymeric kettles of reaction end then, vacuum tightness is 0.5MPa, obtains nylon 6/Ag composite resin material;
Polymerization pressure is 1MPa, and polymerization temperature is 280 ℃;
The method that adopts document In situ synthesis of silver nano-particles in polymethylmethacrylate (Materials Chemistry and Physics, V104,2-3, P 367-372) to provide detects, and the result is following:
Silver particles is uniformly dispersed in polymeric matrix, and median size is between 20 ~ 250nm;
Adopt QB/T2591-2003 " antibiotic plastic---anti-microbial property TP and antibacterial effect " to detect, anti-microbial property is following: the nylon 6/Ag composite resin material of preparation, antibiotic rate is 90.2%.
Adopt T1039-1992 plastics mechanical test method general provisions, GB/T1040-1992 plastic tensile method for testing performance and GB/T1041-1992 plastics compression performance TP to detect; Mechanical mechanics property is following: tensile strength is 75MPa, and ultimate compression strength is 107MPa.
Embodiment 2
(1) with the 5g weight concentration is 25% ammoniacal liquor, adds 5g Vinylpyrrolidone polymer K30 dissolving, add Silver Nitrate 5g; Stir 30min; Form yellow solution, add the aqueous ascorbic acid that concentration is 1mg/ml then, the gross weight that xitix adds is 7.5g; Stir, ultrasonic concussion 65min obtains colloidal sol;
(2) with mixing in the above-mentioned colloidal sol adding 995g fused hexanolactam; Add 5 gram NaOH as catalyzer; Under nitrogen protection, carry out polymerization; The anhydrous discharge of reaction system in 220 ℃ of following decompression dehydration to polymeric kettles of reaction end then, vacuum tightness is 0.7MPa, obtains nylon 6/Ag composite resin material;
Polymerization pressure is 2MPa, and polymerization temperature is 275 ℃;
The method that adopts document In situ synthesis of silver nano-particles in polymethylmethacrylate (Materials Chemistry and Physics, V104,2-3, P 367-372) to provide detects, and the result is following:
Silver particles is uniformly dispersed in polymeric matrix, and median size is between 50 ~ 200nm;
Adopt QB/T2591-2003 " antibiotic plastic---anti-microbial property TP and antibacterial effect " to detect, anti-microbial property is following: the nylon 6/Ag composite resin material of preparation, antibiotic rate is 92.4%.
Adopt T1039-1992 plastics mechanical test method general provisions, GB/T1040-1992 plastic tensile method for testing performance and GB/T1041-1992 plastics compression performance TP to detect; Mechanical mechanics property is following: tensile strength is 72MPa, and ultimate compression strength is 105MPa.
Embodiment 3
(1) with the 4gNH3 weight concentration is 25 ~ 28% ammoniacal liquor, adds 8g Vinylpyrrolidone polymer K30 dissolving, add Silver Nitrate 8g; Stir 60min; Form yellow solution, add the aqueous ascorbic acid that concentration is 1.5mg/ml then, the gross weight that xitix adds is 7.5g; Stir, ultrasonic concussion 95min obtains colloidal sol;
(2) with mixing in the above-mentioned colloidal sol adding 992g fused hexanolactam; Add 5 gram NaOH as catalyzer; Under nitrogen protection, carry out polymerization; The anhydrous discharge of reaction system in 220 ℃ of following decompression dehydration to polymeric kettles of reaction end then, vacuum tightness is 0.3MPa, obtains nylon 6/Ag composite resin material;
Polymerization pressure is 0.7MPa, and polymerization temperature is 260 ℃;
The method that adopts document In situ synthesis of silver nano-particles in polymethylmethacrylate (Materials Chemistry and Physics, V104,2-3, P 367-372) to provide detects, and the result is following:
Silver particles is uniformly dispersed in polymeric matrix, and median size is between 120 ~ 250nm;
Adopt QB/T2591-2003 " antibiotic plastic---anti-microbial property TP and antibacterial effect " to detect, anti-microbial property is following: the nylon 6/Ag composite resin material of preparation, antibiotic rate is 94.7%.
Adopt T1039-1992 plastics mechanical test method general provisions, GB/T1040-1992 plastic tensile method for testing performance and GB/T1041-1992 plastics compression performance TP to detect; Mechanical mechanics property is following: tensile strength is 72MPa, and ultimate compression strength is 104MPa.
Claims (9)
1. argentiferous nylon-6 matrix composite resin material; It is characterized in that; Be to be raw material with hexanolactam, soluble silver salt, Vinylpyrrolidone polymer, aqueous ascorbic acid, ammoniacal liquor, basic catalyst and solvent, adopt the in-situ polymerization preparation, the consumption of each component is:
Soluble silver salt is the 0.3-3wt% of hexanolactam weight, and Vinylpyrrolidone polymer is 0.3 ~ 1.0wt% of hexanolactam weight, xitix: soluble silver salt=1.2～1.5: 1, and weight ratio;
Soluble silver salt: ammoniacal liquor=1 ~ 3:1, weight ratio;
NH in the ammoniacal liquor
3Weight concentration is 25～28%.
2. argentiferous nylon-6 matrix composite resin material according to claim 1 is characterized in that soluble silver salt is 0.3～1.0% of a hexanolactam weight; Vinylpyrrolidone polymer is 0.3 ~ 0.85% of a hexanolactam weight.
3. argentiferous nylon-6 matrix composite resin material according to claim 1 is characterized in that said aqueous ascorbic acid concentration is 0.5 ~ 1.5mg/ml.
4. argentiferous nylon-6 matrix composite resin material according to claim 1 is characterized in that described soluble silver salt is selected from Silver Nitrate AgNO
3, tachyol AgF or silver perchlorate AgClO
4
5. argentiferous nylon-6 matrix composite resin material according to claim 1 is characterized in that the K value of described Vinylpyrrolidone polymer PVP is 30, and molecular-weight average is 4000.
6. argentiferous nylon-6 matrix composite resin material according to claim 1 is characterized in that said basic catalyst is selected from sodium Metal 99.5, NaOH, NaHCO
3Or K
2CO
3, weight consumption is 0.1～3% of a hexanolactam.
7. according to each described argentiferous nylon-6 matrix composite resin material of claim 1～6, it is characterized in that silver particles median size in polymeric matrix is 20 ~ 250nm.
8. prepare the method for each described argentiferous nylon-6 matrix composite resin material of claim 1～7, it is characterized in that, comprise the steps:
(1) with Vinylpyrrolidone polymer, add ammoniacal liquor, dissolving back, adding soluble silver salt, stirring and dissolving adds aqueous ascorbic acid then, and ultrasonic concussion 10～35min obtains colloidal sol;
(2) product with step (1) adds the fused hexanolactam, mixes, under nitrogen protection; Add basic catalyst and carry out polymerization, polymerization pressure is 0 ~ 1MPa, and polymerization temperature is 200 ~ 280 ℃; Polymerization time is 2～8 hours, then under the reaction end temperature, and the anhydrous discharge of reaction system in decompression dehydration to the polymeric kettle; Vacuum tightness is 0.1～3MPa, obtains nylon 6/Ag composite resin material.
9. method according to claim 8 is characterized in that, in the different steps of polymerization process, adopts different polymerization pressure and temperature; 0～2 hour, polymerization pressure was 0.1 ~ 0.8MPa, and polymerization temperature is 200 ~ 220 ℃; 2～6 hours, polymerization pressure was 0.8 ~ 3MPa, and polymerization temperature is 220 ~ 280 ℃; 6～8 hours, polymerization pressure was 0.1 ~ 1.2MPa, and polymerization temperature is 220 ~ 280 ℃.
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| CN103042227A (en) * | 2012-12-18 | 2013-04-17 | 广东省微生物研究所 | Nano-silver sol antibacterial agent and preparation method thereof |
| CN108424514A (en) * | 2018-06-04 | 2018-08-21 | 东华大学 | A kind of method that PA6 meso-porous nano material@Ag composite antibacterial resins are prepared in situ in one-step method |
| CN108659525A (en) * | 2018-06-04 | 2018-10-16 | 东华大学 | A method of PA6/ meso-porous nano material@Ag composite antibacterial fibres are prepared based on situ aggregation method |
| CN108912325A (en) * | 2018-07-18 | 2018-11-30 | 安徽江淮汽车集团股份有限公司 | A kind of preparation method of antibacterial PA66 composite material |
| CN110818893A (en) * | 2019-09-26 | 2020-02-21 | 江阴市强力化纤有限公司 | Polymerization production method of antibacterial nylon 6 slices |
| CN111560170A (en) * | 2019-02-14 | 2020-08-21 | 上海凯赛生物技术股份有限公司 | Antibacterial polyamide and preparation method and application thereof |
| CN114179474A (en) * | 2021-12-14 | 2022-03-15 | 厦门长塑实业有限公司 | Antibacterial high-barrier biaxially-oriented polyamide film and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103042227A (en) * | 2012-12-18 | 2013-04-17 | 广东省微生物研究所 | Nano-silver sol antibacterial agent and preparation method thereof |
| CN108424514A (en) * | 2018-06-04 | 2018-08-21 | 东华大学 | A kind of method that PA6 meso-porous nano material@Ag composite antibacterial resins are prepared in situ in one-step method |
| CN108659525A (en) * | 2018-06-04 | 2018-10-16 | 东华大学 | A method of PA6/ meso-porous nano material@Ag composite antibacterial fibres are prepared based on situ aggregation method |
| CN108424514B (en) * | 2018-06-04 | 2020-10-23 | 东华大学 | Method for preparing PA6 mesoporous nanomaterial @ Ag composite antibacterial resin in situ by one-step method |
| CN108912325A (en) * | 2018-07-18 | 2018-11-30 | 安徽江淮汽车集团股份有限公司 | A kind of preparation method of antibacterial PA66 composite material |
| CN111560170A (en) * | 2019-02-14 | 2020-08-21 | 上海凯赛生物技术股份有限公司 | Antibacterial polyamide and preparation method and application thereof |
| CN110818893A (en) * | 2019-09-26 | 2020-02-21 | 江阴市强力化纤有限公司 | Polymerization production method of antibacterial nylon 6 slices |
| CN114179474A (en) * | 2021-12-14 | 2022-03-15 | 厦门长塑实业有限公司 | Antibacterial high-barrier biaxially-oriented polyamide film and preparation method and application thereof |
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| CN102702509B (en) | 2013-09-18 |
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Application publication date: 20121003 Assignee: Ningbo Shuaitelong Group Co., Ltd. Assignor: Shanghai Shitian Engineering Plastic Co.,Ltd. Contract record no.: 2013330000417 Denomination of invention: Silver-containing nylon 6-based composite resin material and preparation method thereof Granted publication date: 20130918 License type: Exclusive License Record date: 20131230 |
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Application publication date: 20121003 Assignee: Ningbo Shuaitelong Group Co., Ltd. Assignor: Shanghai Shitian Engineering Plastic Co.,Ltd. Contract record no.: 2013330000417 Denomination of invention: Silver-containing nylon 6-based composite resin material and preparation method thereof Granted publication date: 20130918 License type: Exclusive License Record date: 20131230 |
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