CN104744664A - Production method of nano-silver memory foams - Google Patents
Production method of nano-silver memory foams Download PDFInfo
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- CN104744664A CN104744664A CN201510160103.9A CN201510160103A CN104744664A CN 104744664 A CN104744664 A CN 104744664A CN 201510160103 A CN201510160103 A CN 201510160103A CN 104744664 A CN104744664 A CN 104744664A
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Abstract
The invention discloses a production method of nano-silver memory foams. According to the production method, nano-silver completely wraps polyurethane molecules by virtue of uniform dispersion to improve the interaction state among the polyurethane molecules, coordinate the interface effect of soft section and hard section molecules, improve the mechanical properties of the memory foams, and enhance the tensile strength and recovery accuracy of the memory foams; and the nano-silver memory foams have the functions of resisting bacteria, deodorizing, preventing mildews, preventing static electricity and the like.
Description
Technical field
The present invention relates to a kind of production method of nanometer silver memory sponge, described production method is nanometer silver cladding titanium dioxide sol-gel under the effect of coupling agent and chainextender, becomes memory sponge material, and be evenly distributed in memory sponge with polyurethane foam.
Background technology
Memory sponge belongs to the one of polyurethane material, is a kind of segmented copolymer, has the thermotropic shape memory function of comparative superiority, has the general character of plastics and rubber concurrently.From 20 century 70 US National Aeronautics and Space Administration to since polymer shape memory material research, shape-memory material is just with the functional extensive concern causing people of uniqueness.
The hard section polymer composition of the cotton soft section of polymer primarily of low thermal transition temperature of polyurethane memory and high thermal transition temperature, soft section of polymer is generally made up of polyester or polyether glycol, can anti-phase, hard section polymer is consisted of extremely strong interaction of hydrogen bond carbamic acid ester chain segment molecule, is stationary phase.Due to the difference of soft section and hard segment molecule structure in urethane, cause the two thermodynamically to have uncompatibility, produce microphase-separated, soft section different with the thermal transition temperature of hard segment molecule, make urethane have shape memory function at a certain temperature.By selection and the proportioning adjustable shape recovery temperature of raw material, the polyurethane memory cotton material with different memory temperature can be obtained.
Crystallization-the melting of cotton main soft section of the dependence of polyurethane memory realizes shape memory function.The chainextender kind, crosslinked group etc. of the kind of soft or hard segment molecule, ratio, introducing are the principal elements affecting the cotton memory function of polyurethane memory, result of study shows, lower molecular weight (molecular weight is in 1000 ~ 2000 scopes) soft section of polyurethane shape memory effectiveness comparison is poor, only can recover the deformation of about 20% ~ 30%, high molecular (molecular weight is in 3000 ~ 5000 scopes) soft section of polyurethane shape memory recovery rate is up to 93% ~ 95%; In urethane hard segment molecule content lower than 10 ~ 15% time shape recovery ratio only have 50 ~ 60%, but hard segment molecule content increase can suppress the crystallinity of soft segment molecule, when hard segment molecule content is greater than 50%, the fragility of polyurethane material increases, the mechanical property such as tensile strength, elongation at break can reduce, and memory function weakens.
Although existing polyurethane memory cotton material has a lot of excellent performance, but still there is many defects, as little in shape recovery force, reply that precision is low, mechanical property is not good enough, antistatic effect is poor, not antibacterial not mildew-resistant etc., it is applied in actual production life and is subject to certain restrictions.
Nano-Ag particles is the nanometer silver of common broad-spectrum antibiotics, particle diameter about 4nm, has strong suppression and killing action to tens of kinds of pathogenic microorganisms such as intestinal bacteria, gonococcus, chlamydia trachomatis, Ebolas.Antibacterial Mechanism is: nano-Ag particles acts on cell membrane protein, directly can destroy bacterial cell membrane, causes intracellular matter to ooze out, causes necrocytosis, suppresses it to grow.The charge effect of silver surface destroys the positive and negative charge balance of bacterium, causes bacterial death.
Nano titanium oxide, except being also usually applied in reinforced composite as photocatalyst, prepares antistatic and conductive polymer composite, wear-resisting antiskid material, electric wave absorbing materials, cushioning material, anti-ballistic materials, sound-proof material, ceramic composite, coating and antiseptic-germicide.
Summary of the invention
The object of the invention is to utilize nanometer silver and nano titanium oxide advantage separately, carry out organically-modified to memory sponge, provide a kind of nanometer silver memory sponge material producing method.
The present invention is dispersed by nanometer silver, complete has wrapped up polyurethane molecular, the interacting state between polyurethane molecular is improved with this, coordinate the interface interaction of soft section and hard segment molecule, improve the mechanical property of memory sponge material, strengthen tensile strength and reply precision, also there is the functions such as good comfortableness and antibacterial, deodorant mildew-proof, anti-electrostatic.
Technical scheme of the present invention comprises two steps:
1. the production of nanometer silver magma
1) with dehydrated alcohol and distilled water in mass ratio 100:60 be mixed with the mixing solutions of dehydrated alcohol/water, and with acetic acid regulator solution about the PH to 5.5 of mass concentration 36%.
2) take nano-silver powder, nanometer titanium dioxide titanium valve and polyvinylpyrrolidone that specification is 3-8nm, be 40:45:5 preparation, add in the mixing solutions of dehydrated alcohol/water according to mass ratio, at 40 DEG C of temperature, constant temperature stirring 4h presents collosol state to solution.
3) be the preparation of 9:1 according to colloidal sol and γ-(methacryloxypropyl) propyl trimethoxy silicane coupling agent mass ratio, stirred at ambient temperature 2h, namely obtains nanometer silver magma.
2. the production of nanometer silver memory sponge
1) DMF (DMF) is used 4A molecular sieve drying.
2) by soft segment molecule amount 3000 ~ 5000 poly adipate succinic acid ester (PBAG) and nanometer silver magma to prepare according to mass ratio 100 ~ 120: 5 ~ 7 and stir, and vacuumize dehydration under the condition of 80 ~ 100 DEG C.
3) get PBAG and the nanometer silver mixture of raw pulp of 3-5 weight part 2,4 toluene diisocyanate (TDI) and 100-110 weight part 70 DEG C of molten states, under 80 DEG C and nitrogen protection, rapid stirring reaction 2h obtains prepolymer.
4) in stirred reactor, add 40-50 weight part DMF (DMF) stir 2h.
5) BDO (BDO) (as hard section) adding 35-40 weight part carries out chain extending reaction, continues to stir 2.5h under 80 DEG C of conditions.
6) vacuumize the bubble removed in solution, and solution is transferred in mould, evaporation drying in 50 DEG C of-60 DEG C of vacuum drying ovens.
7) from baking oven, take out mould, after the demoulding, be cooled to normal temperature, natural aging 24 hours, be namely prepared into nanometer silver memory sponge material.
Beneficial effect of the present invention: the present invention adopts nanometer silver raw material, prepares nanometer silver cladding titanium dioxide by the method for sol-gel, under the effect of coupling agent and chainextender, with urethane soft or hard segment molecule synthesizing cross-linked type nanometer silver polyurethane memory cotton material.This material has the performance of good mechanical property, density is high, low resilience property retention lasting, has well antibacterial, deodorization, anti-electrostatic and good comfortableness simultaneously, can reach stimulate circulation, the function such as Ginseng Extract.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but non-limitation of the present invention.
The production method of nanometer silver memory sponge of the present invention, is achieved through the following technical solutions:
Embodiment 1:
1. the production of nanometer silver magma
1) with dehydrated alcohol and distilled water in mass ratio 100:60 be mixed with the mixing solutions of dehydrated alcohol/water, and with acetic acid regulator solution about the PH to 5.5 of mass concentration 36%.
2) take nano-silver powder, nanometer titanium dioxide titanium valve and polyvinylpyrrolidone that specification is 3nm, be 40:45:5 preparation, add in the mixing solutions of dehydrated alcohol/water according to mass ratio, at 40 DEG C of temperature, constant temperature stirring 4h presents collosol state to solution.
3) be the preparation of 9:1 according to colloidal sol and γ-(methacryloxypropyl) propyl trimethoxy silicane coupling agent mass ratio, stirred at ambient temperature 2h, namely obtains nanometer silver magma.
2. the production of nanometer silver memory sponge
1) DMF (DMF) is used 4A molecular sieve drying.
2) by soft segment molecule amount 3000 poly adipate succinic acid ester (PBAG) and nanometer silver magma to prepare according to mass ratio 100: 5 and stir, and vacuumize dehydration under the condition of 80 DEG C.
3) get PBAG and the nanometer silver mixture of raw pulp of 3 weight part 2,4 toluene diisocyanates (TDI) and 100 weight parts, 70 DEG C of molten states, under 80 DEG C and nitrogen protection, rapid stirring reaction 2h obtains prepolymer.
4) in stirred reactor, add 40 weight part DMFs (DMF) stir 2h.
5) BDO (BDO) (as hard section) adding 35 weight parts carries out chain extending reaction, continues to stir 2.5h under 80 DEG C of conditions.
6) vacuumize the bubble removed in solution, and solution is transferred in mould, evaporation drying in 50 DEG C of vacuum drying ovens.
7) from baking oven, take out mould, after the demoulding, be cooled to normal temperature, natural aging 24 hours, be namely prepared into nanometer silver memory sponge material.
Embodiment 2:
1. the production of nanometer silver magma
1) with dehydrated alcohol and distilled water in mass ratio 100:60 be mixed with the mixing solutions of dehydrated alcohol/water, and with acetic acid regulator solution about the PH to 5.5 of mass concentration 36%.
2) take nano-silver powder, nanometer titanium dioxide titanium valve and polyvinylpyrrolidone that specification is about 8nm, be 40:45:5 preparation, add in the mixing solutions of dehydrated alcohol/water according to mass ratio, at 40 DEG C of temperature, constant temperature stirring 4h presents collosol state to solution.
3) be the preparation of 9:1 according to colloidal sol and γ-(methacryloxypropyl) propyl trimethoxy silicane coupling agent mass ratio, stirred at ambient temperature 2h, namely obtains nanometer silver magma.
2. the production of nanometer silver memory sponge
1) DMF (DMF) is used 4A molecular sieve drying.
2) by soft segment molecule amount 5000 poly adipate succinic acid ester (PBAG) and nanometer silver magma to prepare according to mass ratio 120: 7 and stir, and vacuumize dehydration under the condition of 100 DEG C.
3) get PBAG and the nanometer silver mixture of raw pulp of 5 weight part 2,4 toluene diisocyanates (TDI) and 110 weight parts, 70 DEG C of molten states, under 80 DEG C and nitrogen protection, rapid stirring reaction 2h obtains prepolymer.
4) in stirred reactor, add 50 weight part DMFs (DMF) stir 2h.
5) BDO (BDO) (as hard section) adding 40 weight parts carries out chain extending reaction, continues to stir 2.5h under 80 DEG C of conditions.
6) vacuumize the bubble removed in solution, and solution is transferred in mould, evaporation drying in 60 DEG C of vacuum drying ovens.
7) from baking oven, take out mould, after the demoulding, be cooled to normal temperature, natural aging 24 hours, be namely prepared into nanometer silver memory sponge material.
Embodiment 3:
1. the production of nanometer silver magma
1) with dehydrated alcohol and distilled water in mass ratio 100:60 be mixed with the mixing solutions of dehydrated alcohol/water, and with acetic acid regulator solution about the PH to 5.5 of mass concentration 36%.
2) take nano-silver powder, nanometer titanium dioxide titanium valve and polyvinylpyrrolidone that specification is about 4nm, be 40:45:5 preparation, add in the mixing solutions of dehydrated alcohol/water according to mass ratio, at 40 DEG C of temperature, constant temperature stirring 4h presents collosol state to solution.
3) be the preparation of 9:1 according to colloidal sol and γ-(methacryloxypropyl) propyl trimethoxy silicane coupling agent mass ratio, stirred at ambient temperature 2h, namely obtains nanometer silver magma.
2. the production of nanometer silver memory sponge
1) DMF (DMF) is used 4A molecular sieve drying.
2) by soft segment molecule amount 4000 poly adipate succinic acid ester (PBAG) and nanometer silver magma to prepare according to mass ratio 110: 6 and stir, and vacuumize dehydration under the condition of 90 DEG C.
3) get PBAG and the nanometer silver mixture of raw pulp of 4 weight part 2,4 toluene diisocyanates (TDI) and 105 weight parts, 70 DEG C of molten states, under 80 DEG C and nitrogen protection, rapid stirring reaction 2h obtains prepolymer.
4) in stirred reactor, add 45 weight part DMFs (DMF) stir 2h.
5) BDO (BDO) (as hard section) adding 38 weight parts carries out chain extending reaction, continues to stir 2.5h under 80 DEG C of conditions.
6) vacuumize the bubble removed in solution, and solution is transferred in mould, evaporation drying in 55 DEG C of vacuum drying ovens.
7) from baking oven, take out mould, after the demoulding, be cooled to normal temperature, natural aging 24 hours, be namely prepared into nanometer silver memory sponge material.
For verifying the performance according to the nanometer silver memory sponge prepared by the present invention further, the present invention after prepared by memory sponge material, the density of test material; The means (crooked experiment) simultaneously adopting the shape-memory properties of shape memory alloy to test test the shape-memory properties of memory sponge material; Adopt the omnipotent strength tester of U.S.'s Instron 3367, sample length, width and height are respectively 50mm × 4mm × 0.5mm, and draw speed is that the mechanical property of 50mm/s to sample is tested; According to the moisture vapor permeability energy of ASTMD1653 standardized test specimen, test sample (be about 50 μm thick) is covered moisture-inhibiting gas test cup rim of a cup, and seals with paraffin, be positioned in the constant temperature and humidity instrument of temperature controllable, air velocity is 5m/s; Adopt the bactericidal property of inhibition zone method qualitative test memory sponge, take subtilis as sterilization object, with modification memory sponge for antiseptic-germicide raw material, by the beef extract-peptone solid medium prepared, data results is as follows:
| Density (D) | Response rate (%) | Tensile strength (MPa) | Elongation at break (%) | Moisture vapour transmission rate (g/m 2*day） | Antibacterial circle diameter (cm) | |
| Embodiment 1 | 105 | 100 | 32 | 480 | 3600 | 2.5 |
| Embodiment 2 | 109 | 100 | 36 | 520 | 3800 | 2.4 |
| Embodiment 3 | 107 | 100 | 35 | 520 | 3700 | 2.5 |
Claims (1)
1. a production method for nanometer silver memory sponge, is characterized in that the method comprises the production of nanometer silver magma and the large step of production two of nanometer silver memory sponge:
The production of described nanometer silver magma is specifically:
1) with dehydrated alcohol and distilled water in mass ratio 100:60 be mixed with mixing solutions, and regulate mixing solutions PH to 5.5 with the acetic acid of mass concentration 36%;
2) get nano-silver powder, nanometer titanium dioxide titanium valve and polyvinylpyrrolidone, be 40:45:5 preparation, add in above-mentioned mixing solutions according to mass ratio, at 40 DEG C of temperature, constant temperature stirring 4h presents collosol state to solution, and the specification of described nano-silver powder is 3-8nm;
3) be the preparation of 9:1 according to colloidal sol and γ-(methacryloxypropyl) propyl trimethoxy silicane coupling agent mass ratio, stirred at ambient temperature 2h, namely obtains nanometer silver magma;
The production of described nanometer silver memory sponge is specifically:
1) DMF is used 4A molecular sieve drying;
2) by soft segment molecule amount 3000 ~ 5000 poly adipate succinic acid ester and nanometer silver magma to prepare according to mass ratio 100 ~ 120:5 ~ 7 and stir, and vacuumize dehydration under the condition of 80 ~ 100 DEG C;
3) get PBAG and the nanometer silver mixture of raw pulp of 3-5 weight part 2,4 toluene diisocyanate and 100-110 weight part 70 DEG C of molten states, under 80 DEG C and nitrogen protection, rapid stirring reaction 2h obtains prepolymer;
4) in stirred reactor, add 40-50 weight part DMF stir 2h;
5) BDO adding 35-40 weight part carries out chain extending reaction as hard section, continues to stir 2.5h under 80 DEG C of conditions;
6) vacuumize the bubble removed in solution, and solution is transferred in mould, evaporation drying in 50 DEG C of-60 DEG C of vacuum drying ovens;
7) from baking oven, take out mould, after the demoulding, be cooled to normal temperature, natural aging 24 hours, be namely prepared into nanometer silver memory sponge material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106333575A (en) * | 2016-10-08 | 2017-01-18 | 东莞市邦达实业有限公司 | Sleep pillow containing modified MDI (diphenylmethane diisocyanate) foam |
| CN111440283A (en) * | 2020-05-29 | 2020-07-24 | 两者时尚商业(江苏)有限公司 | Antibacterial modified polyurethane memory cotton and preparation method thereof |
| EP3551241A4 (en) * | 2016-12-06 | 2020-08-12 | The Texas A&M University System | Antimicrobial shape memory polymers |
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Cited By (5)
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| CN106333575A (en) * | 2016-10-08 | 2017-01-18 | 东莞市邦达实业有限公司 | Sleep pillow containing modified MDI (diphenylmethane diisocyanate) foam |
| EP3551241A4 (en) * | 2016-12-06 | 2020-08-12 | The Texas A&M University System | Antimicrobial shape memory polymers |
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| CN111440283A (en) * | 2020-05-29 | 2020-07-24 | 两者时尚商业(江苏)有限公司 | Antibacterial modified polyurethane memory cotton and preparation method thereof |
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