CN106189185A - A kind of TPU nano antibacterial agent and preparation method thereof - Google Patents
A kind of TPU nano antibacterial agent and preparation method thereof Download PDFInfo
- Publication number
- CN106189185A CN106189185A CN201610608206.1A CN201610608206A CN106189185A CN 106189185 A CN106189185 A CN 106189185A CN 201610608206 A CN201610608206 A CN 201610608206A CN 106189185 A CN106189185 A CN 106189185A
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- antibacterial agent
- nano antibacterial
- tpu
- antibacterial
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
A kind of TPU nano antibacterial agent and preparation method thereof.The mass fraction of the described each raw material of TPU nano antibacterial agent consists of: 5 20wt% water-soluble poly guanidine inorganic acid salt aqueous solutions 10 30 parts, zinc chloride 5 10 parts, white mica powder 30 70, diluent 5 20 parts, amino silicane coupling agent 2 10 parts.The antibacterial of the present invention joins and has not only reached good antibacterial effect in TPU, and does not affect the mechanical performances such as toughness and the tear strength of whole polymeric material.
Description
Technical field
The invention belongs to antibacterial field, particularly relate to a kind of TPU nano antibacterial agent and preparation method thereof.
Background technology
TPU (Thermoplastic polyurethanes) material is a kind of Thermoplastic polyurethane elastomer material, has
The advantages such as hardness range width, wear-resistance and oil-resistance, transparent, good springiness, therefore lead at article of everyday use, sports goods, toy, ornament materials etc.
Being used widely in territory, and has the trend progressively replacing PVC to meet more and more field environmental requirement.Therefore, TPU material is
A kind of novel material with broad mass market prospect.But owing to TPU material itself does not possess antibiotic and sterilizing performance, at some
The field that antibacterial requirement is higher cannot be obtained and use widely.To this end, the research of TPU antibacterial is arisen at the historic moment.
The antibacterial that TPU material is conventional has mineral-type, metal oxide-type, organic.
Mineral-type antibacterial is usually the antibacterial of metal ion (the metal ion class such as silver, copper, zinc).Metal ion
Inorganic salt or the inorganic antiseptic kind of complex most, purposes is also most, and yield is the most maximum.It is characterized in antibiotic property and peace
Quan Xinggao, heat-resist, antibacterial range is wide, and effect duration is long.Mineral-type antibacterial passes through the method such as Physical Absorption or ion exchange
Inorganic antibacterial composition (all kinds of inorganic oxides and the metal ion of inorganic metal salt) is fixed on carrier and makes.Carrier
Material mainly has: zeolite system, silica gel system, glass system, series of calcium phosphate, zirconium phosphate system, silicate, titanium oxide base, whisker system etc..
The Antibacterial Mechanism of mineral-type antibacterial is that 1. heavy metal ion is reacted by the sulfydryl (-SH) with protein, destroys the thin of antibacterial
The activity of born of the same parents' synzyme makes cell loss schizogamy ability and dead；2. anionic metal is combined with antibacterial, is just destroying antibacterial
Often metabolism, causes microorganism dead or suppresses it to breed.
The oxide in metal-oxide with antibacterial activity has magnesium oxide (MgO), calcium oxide (CaO), zinc oxide (ZnO)
And calcium preparation, it can burn till in powder and natural crystal etc. at pottery, Concha Ostreae, fan tool etc. and find.
Organic antibacterial can be divided into chemosynthesis antibacterial and the big class of natural antibacterial agent two.Chemosynthesis antibacterial is main
For all kinds of organic nitrogen-containing ionic compounds, organo-silicon compound, organic tin compound, amino acids metal salt and all kinds of containing season
Ammonium salt, season phosphonium salt, guanidine salt groups graft polymers etc., and anilid class, imidazoles, thiazoles, isothiazolone derivative,
Double croak classes, phenols etc..What application was relatively conventional at present has quaternary ammonium salt, quaternary salt and pyridine salt organic antibacterial agent.Natural antibacterial
Agent such as chitin, mustard, Oleum Ricini, Wasabia japonic (Euterma Wasabi) etc. are from the extract of natural animal-plant.
The initial sterilizing power of organic system antibacterial is strong, sterilization i.e. effect and broad-spectrum antibacterial property is good；Technology maturation, price is also the most just
Preferably.But organic system antibacterial poor chemical stability, thermo-labile；Heat, light or water etc. are readily volatilized, it is difficult to realize long-acting.?
Under the many high temperature of high polymer, high pressure, high shear processing conditionss, easy decomposition failure, even produces poisonous catabolite.Especially
Easily migrating when being and use in the plastic, cause antimicrobial lifetime short (service life only has 2-3), cost is high.
Although prior art occurring in that many materials being added with antibacterial in urethane composition, but it being antibacterial
Poor-performing, especially poor to common escherichia coli and staphylococcus aureus antibacterial effect, simultaneously antibacterial by adding
Make the hardness of whole polymeric material, toughness and tear strength etc. occur reducing after component, have a strong impact on whole polyurethane
The serviceability of elastomeric material.
Summary of the invention
For solving the problems referred to above, it is an object of the invention to provide a kind of TPU nano antibacterial agent.The antibacterial of the present invention adds
Enter in TPU and do not only reached good antibacterial effect, and do not affect toughness and the tear strength etc. of whole polymeric material
Mechanical performance.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
A kind of TPU nano antibacterial agent, the mass fraction of each raw material consists of:
Water-soluble poly guanidine inorganic acid salt aqueous solution for example, 12 parts, 14 parts, 17 parts, 21 parts, 24 parts, 28 parts etc..
Zinc chloride for example, 7 parts, 8.5 parts, 9 parts etc..
White mica powder for example, 33 grade, 36 etc., 39 etc., 42 etc., 47 etc., 51 etc., 56 etc., 59 etc., 63 etc., 68 etc..
Diluent for example, 7 parts, 8.5 parts, 9 parts, 12 parts, 14 parts, 17 parts etc..
Amino silicane coupling agent for example, 2.5 parts, 4 parts, 7 parts, 8.5 parts, 9 parts etc..
The present invention makes the TPU prepared by the combination of 5-20wt% water-soluble poly guanidine inorganic acid salt aqueous solution and zinc chloride
Not only achieve good antibacterial effect with nano antibacterial agent, and mechanical performance such as the hot strength of the TPU product prepared with
Elongation at break still and is added without the antibacterial holding of the present invention quite.
As preferably, the TPU nano antibacterial agent of the present invention, the mass fraction of each raw material consists of:
As preferably, described poly-guanidine inorganic acid salt is polyhexamethylene (double) guanidine hydrochloride, polyhexamethylene (double) guanidine third
In hydrochlorate, polyhexamethylene (double) guanidine stearate, polyhexamethylene (double) guanidine laruate, polyoxyethylene groups guanidine hydrochloride
One kind or two or more combination.
As preferably, described diluent is ethylene glycol and/or propylene glycol.
As preferably, described amino silicane coupling agent is γ-aminopropyltrimethoxysilane and/or γ-aminopropyl three second
TMOS.
Preferably, described amino silicane coupling agent is γ-aminopropyltrimethoxysilane and-aminopropyl triethoxysilane
Combination.
Preferably, described amino silicane coupling agent is mol ratio 1:0.5-2, for example, 1:0.7,1:0.9,1:1.2,1:
1.4, the γ-aminopropyltrimethoxysilane of 1:1.6,1:1.8 etc. and the combination of-aminopropyl triethoxysilane, above-mentioned scope
Amino silicane coupling agent be under mol ratio so that the mechanicalness of antibacterial prepared is retainable more preferably, be preferably mole
γ-aminopropyltrimethoxysilane than 1:1 and the combination of-aminopropyl triethoxysilane.
An object of the present invention also resides in the preparation method providing TPU nano antibacterial agent of the present invention, including
Following steps:
(1) by zinc chloride, white mica powder mix homogeneously, mixed powder is obtained；
(2) step (1) gained mixed powder is mixed with remaining raw material stirring i.e. obtain described TPU nano antibacterial agent.
The antibacterial of the present invention joins and has not only reached good antibacterial effect in TPU, bacteriostasis rate reach 99.5% with
On, and whole polymeric material still has the machineries such as the toughness suitable with the antibacterial being added without the present invention and tear strength
Performance.
Detailed description of the invention
For the present invention is better described, it is simple to understand technical scheme, the present invention's is typical but non-limiting
Embodiment is as follows:
Embodiment 1
A kind of TPU nano antibacterial agent, the mass fraction of each raw material consists of:
Amino silicane coupling agent is γ-aminopropyltrimethoxysilane and the-aminopropyl-triethoxy silicon of mol ratio 1:1.5
The combination of alkane.
Embodiment 2
A kind of TPU nano antibacterial agent, the mass fraction of each raw material consists of:
Amino silicane coupling agent is γ-aminopropyltrimethoxysilane and the-aminopropyl triethoxysilane of mol ratio 1:2
Combination.
Embodiment 3
A kind of TPU nano antibacterial agent, the mass fraction of each raw material consists of:
Amino silicane coupling agent is γ-aminopropyltrimethoxysilane and the-aminopropyl-triethoxy silicon of mol ratio 1:0.5
The combination of alkane.
Embodiment 4
A kind of TPU nano antibacterial agent, the mass fraction of each raw material consists of:
Amino silicane coupling agent is γ-aminopropyltrimethoxysilane and the-aminopropyl triethoxysilane of mol ratio 1:1
Combination.
Comparative example 1
A kind of TPU nano antibacterial agent, the mass fraction of each raw material consists of:
Amino silicane coupling agent is γ-aminopropyltrimethoxysilane and the-aminopropyl triethoxysilane of mol ratio 1:1
Combination.
Comparative example 2
A kind of TPU nano antibacterial agent, the mass fraction of each raw material consists of:
Amino silicane coupling agent is γ-aminopropyltrimethoxysilane and the-aminopropyl triethoxysilane of mol ratio 1:1
Combination.
Comparative example 3
A kind of TPU nano antibacterial agent, the mass fraction of each raw material consists of:
Amino silicane coupling agent is γ-aminopropyltrimethoxysilane and the-aminopropyl triethoxysilane of mol ratio 1:3
Combination.
Comparative example 4
A kind of TPU nano antibacterial agent, the mass fraction of each raw material consists of:
Amino silicane coupling agent is γ-aminopropyltrimethoxysilane and the-aminopropyl-triethoxy silicon of mol ratio 1:0.2
The combination of alkane.
The antibacterial that embodiment 1-4 and comparative example 1-4 prepare is joined Application No. by equal amount
201610403597.3 1 kinds of high durable TPU film and preparation method thereof prepare in embodiment 1 thin film.
According to QB/T 2591-2003A " antibiotic plastic Anti-microbial Performance Tests method and antibacterial effect ", detect with bacterium: large intestine
Escherichia ATCC25922, staphylococcus aureus ATCC6538 detect anti-microbial property.
And carry out physical property measurement by ASTMD412 (American Society Testing and Materials's standard).
The performance test results is as shown in table 1 below.
Table 1
As seen from Table 1, the antibacterial that the present invention prepares not only achieves good antibacterial effect in TPU goods, and
And tensile strength and elongation at break and to be added without the TPU product of antibacterial suitable.
From the comparison of embodiment 1-4 and comparative example 1-2 it can be seen that the present invention uses polyoxyethylene groups guanidine hydrochloride and chlorine
The effect of the combination acquirement changing zinc is substantially better than and is relatively used alone one of them effect obtained, i.e. the two cooperation can obtain association
With corresponding.
From the comparison of embodiment 1-4 and comparative example 3-4 it can be seen that in the range of the present invention uses mol ratio 1:0.5-2
The effect that the combination of γ-aminopropyltrimethoxysilane and-aminopropyl triethoxysilane obtains takes the most within the above range
The effect obtained is more preferable.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element
Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (9)
1. a TPU nano antibacterial agent, it is characterised in that the mass fraction of each raw material consists of:
TPU nano antibacterial agent the most according to claim 1, it is characterised in that the mass fraction of each raw material consists of:
TPU nano antibacterial agent the most according to claim 1 and 2, it is characterised in that described poly-guanidine inorganic acid salt is poly-six
Methylene (double) guanidine hydrochloride, polyhexamethylene (double) guanidine propionate, polyhexamethylene (double) guanidine stearate, polyhexamethylene
One kind or two or more combination in (double) guanidine laruate, polyoxyethylene groups guanidine hydrochloride.
4. according to the TPU nano antibacterial agent described in any one of claim 1-3, it is characterised in that described diluent is second two
Alcohol and/or propylene glycol.
5. according to the TPU nano antibacterial agent described in any one of claim 1-4, it is characterised in that described amino silane coupling
Agent is γ-aminopropyltrimethoxysilane and/or gamma-aminopropyl-triethoxy-silane.
6. according to the TPU nano antibacterial agent described in any one of claim 1-5, it is characterised in that described amino silane coupling
Agent is γ-aminopropyltrimethoxysilane and the combination of-aminopropyl triethoxysilane.
7. according to the TPU nano antibacterial agent described in any one of claim 1-6, it is characterised in that described amino silane coupling
Agent is γ-aminopropyltrimethoxysilane and the combination of-aminopropyl triethoxysilane of mol ratio 1:0.5-2, preferably rubs
Your γ-aminopropyltrimethoxysilane than 1:1 and combination of-aminopropyl triethoxysilane.
TPU nano antibacterial agent the most according to claim 7, it is characterised in that described amino silicane coupling agent is mole
γ-aminopropyltrimethoxysilane than 1:1 and the combination of-aminopropyl triethoxysilane.
9. the preparation method of the TPU nano antibacterial agent described in any one of claim 1-8, comprises the steps:
(1) by zinc chloride, white mica powder mix homogeneously, mixed powder is obtained；
(2) step (1) gained mixed powder is mixed with remaining raw material stirring i.e. obtain described TPU nano antibacterial agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610608206.1A CN106189185A (en) | 2016-07-28 | 2016-07-28 | A kind of TPU nano antibacterial agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610608206.1A CN106189185A (en) | 2016-07-28 | 2016-07-28 | A kind of TPU nano antibacterial agent and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110234673A (en) * | 2017-01-30 | 2019-09-13 | 路博润先进材料公司 | Antimicrobial thermoplastic polyurethane |
| CN111246891A (en) * | 2017-08-20 | 2020-06-05 | 环境特殊化学品公司 | Disinfectant composition for preventing and treating clostridium difficile spores |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102037988A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Composite antibacterial agent and preparation method thereof |
| CN102660114A (en) * | 2012-05-23 | 2012-09-12 | 福建越特新材料科技有限公司 | Preparation method of plastic antibacterial agent |
-
2016
- 2016-07-28 CN CN201610608206.1A patent/CN106189185A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102037988A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Composite antibacterial agent and preparation method thereof |
| CN102660114A (en) * | 2012-05-23 | 2012-09-12 | 福建越特新材料科技有限公司 | Preparation method of plastic antibacterial agent |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110234673A (en) * | 2017-01-30 | 2019-09-13 | 路博润先进材料公司 | Antimicrobial thermoplastic polyurethane |
| CN110234673B (en) * | 2017-01-30 | 2021-12-14 | 路博润先进材料公司 | Antimicrobial thermoplastic polyurethanes |
| CN111246891A (en) * | 2017-08-20 | 2020-06-05 | 环境特殊化学品公司 | Disinfectant composition for preventing and treating clostridium difficile spores |
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Application publication date: 20161207 |