CN109293925A - Cross-linking guanidine bactericides and the application in the mould proof organic silicon rubber of long acting antibiotic - Google Patents
Cross-linking guanidine bactericides and the application in the mould proof organic silicon rubber of long acting antibiotic Download PDFInfo
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- CN109293925A CN109293925A CN201811131961.0A CN201811131961A CN109293925A CN 109293925 A CN109293925 A CN 109293925A CN 201811131961 A CN201811131961 A CN 201811131961A CN 109293925 A CN109293925 A CN 109293925A
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/10—Block- or graft-copolymers containing polysiloxane sequences
Abstract
The present invention relates to cross-linking guanidine bactericides and the applications in the mould proof organic silicon rubber of long acting antibiotic.Cross-linking guanidine bactericides have general formula structure (AaBCc)n, wherein A is end functionalization organosilicon polymer, and B is guanidine oligomer, and C is the reaction containing vinyl/crosslinking functional compounds VL or the reaction containing alkoxyl silicone/crosslinking functional compounds AO, a is the integer of 0-8, and c is the integer of 1-8, and n is the integer of 1-10.Cross-linking guanidine bactericides I and cross-linking guanidine bactericides II can be respectively used in high temperature vulcanized organic silicon rubber and room temperature vulcanization organosilicon rubber, realize safety without dissolution, the mould proof target of long acting antibiotic.The antibacterial and mouldproof organic silicon rubber that the present invention obtains is other than having the characteristics that safe, long-acting, wide spectrum, cross-linking guanidine bactericides additive amount is small, good dispersion in organic silicon rubber, the original performance of silicon rubber is not influenced, especially suitable for building sealing silicone adhesive and medical supplies, daily necessity, the mother and baby's articles of organic silicon rubber material etc..
Description
Technical field
The invention belongs to rubber processing or chemical modification technique field, more particularly, to a kind of cross-linking guanidine bactericides and
Application in the mould proof organic silicon rubber of long acting antibiotic.
Background technique
Organic silicon rubber has excellent high-low temperature resistant characteristic, weatherability, electrical insulation properties, physiological inertia and comfortable
The features such as feel, thus be widely used, serve not only as the extraordinary material in aerospace, defence and military and sophisticated technology
Material, and it has been also applied to each department of national economy, such as building, electric, automobile, weaving, machinery, chemical industry light industry, medical treatment
With daily necessity etc..In order to meet the application of different occasions, organic silicon rubber has derived dimethyl silicone rubber, methyl ethylene
The kinds such as silicon rubber, fluorine silicone rubber, phenyl siloxane rubber, nitrile silicone rubber, each kind have many trades mark again.From machine-shaping angle
It divides, organic silicon rubber is divided into high-temperature silicon disulfide rubber and room temperature vulcanized silicone rubber, and room temperature vulcanized silicone rubber, which is also known as liquid, to be had
Machine silicon rubber, silicone adhesive etc..Currently, the production of global silicon rubber is at 400,000 tons or so, room temperature vulcanized silicone rubber accounts for total amount
65% or so, and about 70% room temperature vulcanized silicone rubber be used for building sealant.
The sealing strip that frequent visible kitchen, toilet, window edge etc. black in life, the silicone actually to mildew
Sealant.Silicone adhesive itself does not have the function of antibacterial and mouldproof, and the most use environment of silicone adhesive is moister, bacterium mould compared with
It is more, it is very easy to mouldy, not only influences beautiful, reduce the service life of sealant, and prestige is also brought to human health
The side of body.In recent years, the life product of organic silicon rubber material quickly entered market, the gloves of silicone rubber material, glass holder, heat insulating mattress,
Nipple of feeding bottle, tableware, shoulder belt, watchband, slippers, insole, toy etc. are seen everywhere, and inevitably contact greasy dirt in use, are grown
Endophytic bacteria and mould cause the propagation of disease, bring serious harm.In medicine and hygiene fields, many medical conduits, hand
Set, silicone filler body etc., if bacterial infection, caused by lose it is even more inestimable.Therefore, preparation has antibacterial and antimildew function
Organic silicon rubber material has important practical value.
The processing of antibacterial can be carried out after product molding to surface by obtaining antibacterial and mouldproof organic silicon rubber, can also be preparatory
Antibacterial agent is added in silastic material.Obvious the latter has apparent advantage from operability and durable antibacterial effect.
Common antibacterial agent is divided into several classes such as natural antibacterial agent, inorganic antiseptic and organic synthesis antibacterial agent.Patent CN
201410387525.5 disclose a kind of antimildew and antibacterial glass cement, using the method for addition argentiferous or the inorganic antiseptic of zinc.It should
Method has good effect to bacteriums such as Escherichia coli, staphylococcus aureuses, but anti-mold effect is not significant.Patent CN
201610526742.7 disclosing a kind of glass cement for using Cocoamidopropyl betaine as antibacterial mildew inhibitor, glass can be prevented
The mouldy blackening of glass glue, however the antibacterial agent is added in glass cement by way of blending, there is antibacterial agent dissolution and is lost
The problem of, it cannot achieve the effect that permanent antibacterial and mouldproof.Patent CN201210049244.X discloses one kind and is received by addition
Rice silver-zirconium phosphate antimicrobial obtains a kind of good mechanical properties, while also with the medical grade silicon rubber material of anti-microbial property.It should
Method additive amount is big, at high cost, and the antibacterial agent for adding mass parts 40% is 98% to the bacteriostasis rate of Escherichia coli.Key is to rely on
Silver ion exudation reaches antibacterial effect, extremely dangerous to people.Patent CN201310415685.1 discloses a kind of silicon of antibacterial
Rubber composite material, antibacterial agent used are the antibacterials of Cefuroxime Sodium or benzoic methyl nitroazole.This method higher cost, and
It and is selective antibiotic.It is neither long-acting and dangerous by drug release to reach antibacterial, and non-refractory, it is not used to high temperature
Sulphurated siliastic.Patent CN 201110195614.6 discloses the organic silicon rubber material and preparation method of a kind of long acting antibiotic,
Using inorganic nano-particle or trifluoroacetic acid as antibacterial agent, under organic solvent, low surface energy polymeric and crosslinking agent auxiliary
Crosslinking achievees the effect that long-term antibacterial, but the antibacterial of inorganic nano-particle and trifluoroacetic acid antibacterial agent in matrix or surface
Ability is poor, does not also provide the test effect of antibacterial and mouldproof in patent, and it is even more impossible to state its long-acting reason.In short, existing
Patent is mainly in two aspect Shortcomings: first is that dangerous, second is that antibacterial agent is easy to run off, antibacterial effect is not lasting；Second is that anti-
Bacterium ability is weak, it is difficult to broad-spectrum antiseptic and mould proof.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide cross-linking guanidine bactericides,
The preparation method of cross-linking guanidine bactericides and cross-linking guanidine bactericides are in safety without the dissolution mould proof organosilicon rubber of long acting antibiotic
Application in glue.
Guanidine bactericides with broad-spectrum antibacterial and anti-mildew function are bonded to organic silicon rubber by chemical method by the present invention
In cross-linked network, the long-acting persistence of antibacterial and mouldproof performance is realized, while by silicone oligomer and guanidine bactericides pre-reaction,
Realize that antibacterial agent is evenly dispersed in organic silicon rubber.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of cross-linking guanidine bactericides, the general formula with formula (1):
(AaBCc)n (1)
Wherein, A is end functionalization organosilicon polymer, and B is guanidine oligomer, and C is the reaction containing vinyl/crosslinking function
Can compound VL or reaction containing alkoxyl silicone/crosslinking functional compounds AO, a be the integer of 0-8, c is the integer of 1-8, and n is
The integer of 1-10.
Further, the cross-linking guanidine bactericides are cross-linking guanidine bactericides I or cross-linking guanidine bactericides II,
When the cross-linking guanidine bactericides are cross-linking guanidine bactericides I, C is reaction/crosslinking containing vinyl
Functional compounds VL,
When the cross-linking guanidine bactericides are cross-linking guanidine bactericides II, C is reaction/friendship containing alkoxyl silicone
Join functional compounds AO.
The cross-linking guanidine bactericides I is to react/friendship with containing vinyl by end functionalization organosilicon polymer
The organosilicon function additive that connection functional compounds VL and guanidine oligomer are obtained by chemical reaction.
Cross-linking guanidine bactericides II is by end functionalization organosilicon polymer and reaction/crosslinking function containing alkoxyl silicone
The function additive containing alkoxyl silicone that energy compound AO and guanidine oligomer are obtained by chemical reaction.
Further, guanidine oligomer shown in B, structural formula in formula (1) are as follows:
Wherein, R1For-H or CH2SxCH2NH2；
CH2SxCH2NH2Middle S is CH2、CH2OCH2Or CH2NHCH2In any one or its it is compound, x is the integer of 0-12；
G is HCl or H3PO4, y=2-20.
Further, end functionalization organosilicon polymer, structural formula shown in A in formula (1) are as follows:
R2[Si(CH3)R3O]pR2
Wherein R2For-CH2CH2CH2NH2、-CH2CH2CH2NHCH2CH2NH2、-
CH2CH2CH2SH or-CH2CH2CH2NCO；
R3For-H ,-CH3、-CH2CH2CF3,-CH=CH2、-C6H5、-CH2CH2CN、-OCH3Or-OCH2CH3In it is any one
Kind；P is the integer of 3-500.
Further, the reaction containing vinyl/crosslinking functional compounds VL shown in C in formula (1), is selected from metering system
One or more of acid glycidyl ester, allyl glycidyl ether, allylamine, maleic anhydride, acrylic acid or acryloyl chloride
Mixing, preferably glycidyl methacrylate and allyl glycidyl ether.
Further, the reaction containing alkoxyl silicone/crosslinking functional compounds AO shown in C in formula (1), selected from 2- (3,
4- epoxy cyclohexane) ethyl trimethoxy silane, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl triethoxysilane, 3- glycidol
Ether oxygen base propyl trimethoxy silicane, 3- glycidyl ether oxypropyltriethoxysilane, 3- glycydoxy
Methyldiethoxysilane, N- (2- aminoethyl) -3- aminopropyl trimethoxysilane, three second of N- (2- aminoethyl) -3- aminopropyl
Oxysilane, N- (2- aminoethyl) -3- aminopropyltriethoxy diethoxy silane, 3- aminopropyl trimethoxysilane, 3- aminopropyl
One in triethoxysilane, 3- isocyanate group propyl trimethoxy silicane or 3- isocyanate group propyl-triethoxysilicane
Kind or several mixing.
The present invention also provides the preparation methods of the cross-linking guanidine bactericides.
When the cross-linking guanidine bactericides are cross-linking guanidine bactericides I, the preparation step of cross-linking guanidine bactericides I
It is rapid as follows:
End functionalization organosilicon polymer, the reaction containing vinyl/crosslinking functional compounds VL and guanidine oligomer are pressed
According to participation reactive functionality molar ratio (0-1): (0.1-1): 1 is added in reactor, reacts at 0-100 DEG C in a solvent
Then 0.1-24h removes solvent and obtains cross-linking guanidine bactericides I；
When the cross-linking guanidine bactericides are cross-linking guanidine bactericides II, the preparation of cross-linking guanidine bactericides II
Steps are as follows:
End functionalization organosilicon polymer, the reaction containing alkoxyl silicone/crosslinking functional compounds AO and guanidine oligomer
According to participation reactive functionality molar ratio (0-1): (0.1-1): 1 is added in reactor, anti-at 0-120 DEG C in a solvent
0.1-24h is answered, solvent is then removed and obtains cross-linking guanidine bactericides II.
The solvent is selected from methanol, ethyl alcohol, isopropanol, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl
The mixing of one or more of sulfoxide or acetonitrile.
The present invention also provides the application of the cross-linking guanidine bactericides, the cross-linking guanidine bactericides I is as function
Additive is mixed into high-temperature silicon disulfide rubber, and mixed method is the common processing method of high temperature vulcanized organic silicon rubber, such as
Using mixer, kneader or open mill, while vulcanization process is also conventional practices, and details are not described herein；
The cross-linking guanidine bactericides II is mixed into room temperature vulcanized silicone rubber as functional additive, and mixed method is
The common processing method of room temperature vulcanization organosilicon rubber, while curing process method is also conventional practices, it is no longer superfluous herein
It states.
The present invention also provides a kind of non-mould proof organic silicon rubber of dissolution long acting antibiotic of safety, including the non-dissolution of safety are long-acting anti-
The mould proof high temperature vulcanized organic silicon rubber of bacterium and the non-mould proof room temperature cured organic silicon rubber of dissolution long acting antibiotic of safety,
The mould proof high temperature vulcanized organic silicon rubber of the non-dissolution long acting antibiotic of safety, is made of following components and proportion:
The mould proof room temperature cured organic silicon rubber of the non-dissolution long acting antibiotic of safety, is made of following components and proportion:
The organic silicon rubber matrix includes methyl vinyl silicone rubber, fluorine silicone rubber, copolymerization fluorine silicone rubber, phenyl silicon rubber
Glue or nitrile silicone rubber.
The vulcanizing agent is the high temperature vulcanized common vulcanizing agent of organic silicon rubber；
The crosslinking agent is the common crosslinking agent of room temperature cured organic silicon rubber；
The catalyst is the common catalyst of room temperature vulcanized silicone rubber；
Other described auxiliary agents include heat-resistant agent, fire retardant, pigment, release agent or dispersing agent.Heat-resistant agent, fire retardant, pigment,
Release agent or dispersing agent are organic silicon rubber usual auxiliaries.
The present invention by broad-spectrum high efficacy antibacterial, antimildew function guanidine oligomer and end functionalization organosilicon polymer respectively with
Reaction containing vinyl/crosslinking functional compounds VL and/crosslinking functional compounds AO is reacted with containing alkoxy silane
It is chemically reacted, respectively obtains cross-linking guanidine bactericides I and cross-linking guanidine bactericides II, high temperature sulphur will be respectively used to
Change in organic silicon rubber and room temperature vulcanization organosilicon rubber, participating in of guanidine bactericides is made in the vulcanization of rubber or solidification
Cross-linking system is learned, realizes safety without dissolution, the mould proof target of long acting antibiotic.Obtained antibacterial and mouldproof organic silicon rubber is in addition to having
Except safe, long-acting, wide spectrum feature, cross-linking guanidine bactericides additive amount is small, the good dispersion in organic silicon rubber, not shadow
The original performance of silicon rubber is rung, especially suitable for building sealing silicone adhesive and the medical supplies of organic silicon rubber material, life
Articles, mother and baby's articles etc.
Compared with prior art, the present invention has the following advantages and beneficial effect:
1, since cross-linking guanidine bactericides participate in cross-linking reaction in Vulcanization Process of Rubber, to be bonded to rubbery system
In, thus have the characteristics that antibacterial agent is not oozed out, is not lost, effect is lasting for antibacterial and mouldproof.
2, guanidine oligomer has the characteristics that wide spectrum, efficient antibacterial, does not destroy antibacterial agent knot when being linked to rubbery system
Structure, therefore assign organic silicon rubber excellent antimildew and antibacterial effect.
3, contain part silicone segment in cross-linking guanidine bactericides, thus can be evenly dispersed in organic silicon rubber,
In addition antibacterial agent additive amount is small, to not influence the original performance of silicon rubber.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
Embodiment 1:
Prepare cross-linking guanidine bactericides I: by 100 parts by weight end epoxy silicon oils (epoxide number is 0.1mol/100g), 52 parts
Polyhexamethylene guanidine hydrochloride (x=6, y=5) and 35 parts of glycidyl methacrylate, are dissolved in 200 parts of N, N- dimethyl methyl
In amide, constant temperature stirs 8h at 50 DEG C, and then vacuum drying removes solvent, obtains cross-linking guanidine bactericides I -1.
Prepare the mould proof high-temperature silicon disulfide rubber of long acting antibiotic: by 100 parts by weight blue star medical grade silicon rubber HCRU4460,6
Cross-linking I -1 and 1 part of bis 25 vulcanizing agent of guanidine bactericides of part is uniformly mixed on a mill, is then sulfided into a mold
Type obtains the mould proof high-temperature silicon disulfide rubber product of long acting antibiotic.
Antibacterial test and long-term effect are tested: 2591 antibiotic plastics of establishing criteria QB/T-Anti-microbial Performance Tests method and antibacterial
Effect carries out anti-microbial property test, and test is golden yellow staphylococcus and Escherichia coli with bacterium.After tested, resist obtained in implementation 1
Bacterium silicon rubber is respectively 99.9%, 99.9% to the antibiotic rate of golden yellow staphylococcus, Escherichia coli.Antimicrobial silicon rubber sample is soaked
Not in water, every 48h changes a water, follow-on test 1 month, finds to the antibiotic rate of golden yellow staphylococcus, Escherichia coli still
It is 99.9%, 99.9%.
Mildew resistance test: 2591 Appendix B antibiotic plastic Anti-mildew capability test method of establishing criteria QB/T carries out mould proof survey
Examination selects aspergillus niger and ball hair shell as detection strain, test sample and blank control sample at 28 DEG C of temperature, relative humidity
It is cultivated 28 days under conditions of 90%RH or more, the mould proof grade for obtaining antibacterial silicon rubber in embodiment 1 is 1 grade.
Embodiment 2:
Prepare cross-linking guanidine bactericides I: by the double amido silicon oil CM-226 of 100 parts by weight, (ammonia value is about 0.1mol/
100g), 30 parts of polytetramethylene guanidine hydrochlorides (x=4, y=5) and 15 parts of allylamines, are dissolved in 200 parts of dimethyl sulfoxides,
Constant temperature stirs 8h at 120 DEG C, and the ammonia generated with dilute sulfuric acid come absorbing reaction, then vacuum drying removes solvent, obtains to hand over
Join guanidine bactericides I -2.
Prepare the mould proof high temperature vulcanized fluorine silicone rubber of long acting antibiotic: by 100 parts by weight Jurong Fu Saier fluorine silicone rubber FSIR-
0260,5 parts of cross-linking guanidine bactericides, I -2 and 1 part of bis 25 vulcanizing agent is uniformly mixed on a mill, then sulphur in a mold
Chemical conversion type obtains the mould proof high temperature vulcanized fluorine silicone rubber product of long acting antibiotic.
Antibacterial test and long-term effect are tested: 2591 antibiotic plastics of establishing criteria QB/T-Anti-microbial Performance Tests method and antibacterial
Effect carries out anti-microbial property test, and test is golden yellow staphylococcus and Escherichia coli with bacterium.After tested, resist obtained in implementation 1
Bacterium silicon rubber is respectively 99.5%, 99.5% to the antibiotic rate of golden yellow staphylococcus, Escherichia coli.Antimicrobial silicon rubber sample is soaked
Not in water, every 48h changes a water, follow-on test 1 month, finds to the antibiotic rate of golden yellow staphylococcus, Escherichia coli still
It is 99.0%, 99.0%
Mildew resistance test: 2591 Appendix B antibiotic plastic Anti-mildew capability test method of establishing criteria QB/T carries out mould proof survey
Examination selects aspergillus niger and ball hair shell as detection strain, test sample and blank control sample at 28 DEG C of temperature, relative humidity
It is cultivated 28 days under conditions of 90%RH or more, the mould proof grade for obtaining antibacterial silicon rubber in embodiment 1 is 1 grade.
Embodiment 3:
Prepare cross-linking guanidine bactericides I: by 100 parts by weight end ring oxygen methyl vinyl silicon oils, (epoxide number is 0.1mol/
100g, contents of ethylene 0.1mol%), 40 parts of polyhexamethylene guanidine hydrochlorides (x=6, y=5), be dissolved in 200 parts of acetonitriles,
Constant temperature stirs 20h at 50 DEG C, and then vacuum drying removes solvent, obtains cross-linking guanidine bactericides I -3.
Prepare the mould proof high-temperature silicon disulfide rubber of long acting antibiotic: by 100 parts by weight Dow Coming phenyl silicon rubber RBB-2060-
50,4 parts of cross-linking guanidine bactericides, I -3 and 1 part of bis 25 vulcanizing agent is uniformly mixed on a mill, is then vulcanized in a mold
Molding, obtains the mould proof high temperature vulcanized phenyl siloxane rubber product of long acting antibiotic.
Antibacterial test and long-term effect are tested: 2591 antibiotic plastics of establishing criteria QB/T-Anti-microbial Performance Tests method and antibacterial
Effect carries out anti-microbial property test, and test is golden yellow staphylococcus and Escherichia coli with bacterium.After tested, resist obtained in implementation 1
Bacterium silicon rubber is respectively 99.9%, 99.9% to the antibiotic rate of golden yellow staphylococcus, Escherichia coli.Antimicrobial silicon rubber sample is soaked
Not in water, every 48h changes a water, follow-on test 1 month, finds to the antibiotic rate of golden yellow staphylococcus, Escherichia coli still
It is 99.5%, 99.5%
Mildew resistance test: 2591 Appendix B antibiotic plastic Anti-mildew capability test method of establishing criteria QB/T carries out mould proof survey
Examination selects aspergillus niger and ball hair shell as detection strain, test sample and blank control sample at 28 DEG C of temperature, relative humidity
It is cultivated 28 days under conditions of 90%RH or more, the mould proof grade for obtaining antibacterial silicon rubber in embodiment 1 is 1 grade.
Embodiment 4:
Prepare cross-linking guanidine bactericides II: by the double amido silicon oil CM-226 of 100 parts by weight, (ammonia value is about 0.1mol/
100g), 25 parts of poly- eight methylene guanidine hydrochlorides (x=8, y=6) and 20 parts of 2- (3,4- epoxycyclohexyl) ethane ethyl triethoxy silicanes
Alkane is dissolved in 200 parts of isopropanols, and for 24 hours, then vacuum drying removes solvent for constant temperature stirring at 30 DEG C, obtains cross-linking guanidine
Class antibacterial agent II -1.
It prepares the mould proof room temperature vulcanized silicone rubber of long acting antibiotic: being 20000mpa.s room temperature vulcanization 107 by 100 parts by weight viscosity
Silicon rubber, 5 parts of cross-linking II -1,5 part of tetraethyl orthosilicates of guanidine bactericides and 1 part of dibutyl tin dilaurate mix in kneader
It closes uniformly, then places curing molding for 24 hours in a mold, obtain the mould proof room temperature vulcanized silicone rubber product of long acting antibiotic.
Antibacterial test and long-term effect are tested: 2591 antibiotic plastics of establishing criteria QB/T-Anti-microbial Performance Tests method and antibacterial
Effect carries out anti-microbial property test, and test is golden yellow staphylococcus and Escherichia coli with bacterium.After tested, resist obtained in implementation 1
Bacterium silicon rubber is respectively 99.8%, 99.7% to the antibiotic rate of golden yellow staphylococcus, Escherichia coli.Antimicrobial silicon rubber sample is soaked
Not in water, every 48h changes a water, follow-on test 1 month, finds to the antibiotic rate of golden yellow staphylococcus, Escherichia coli still
It is 99.6%, 99.6%
Mildew resistance test: 2591 Appendix B antibiotic plastic Anti-mildew capability test method of establishing criteria QB/T carries out mould proof survey
Examination selects aspergillus niger and ball hair shell as detection strain, test sample and blank control sample at 28 DEG C of temperature, relative humidity
It is cultivated 28 days under conditions of 90%RH or more, the mould proof grade for obtaining antibacterial silicon rubber in embodiment 1 is 1 grade.
Embodiment 5:
Prepare cross-linking guanidine bactericides II: by 100 parts by weight Amino End Group silicone oil (epoxide number is 0.1mol/100g), 32
Part polyhexamethylene guanidine hydrochloride (x=6, y=6) is dissolved in 200 parts of n,N-dimethylacetamide, and in 120 DEG C of reaction 8h, use is dilute
The ammonia that sulfuric acid absorption reaction generates.It is cooled to room temperature, 30 parts of 3- isocyanates propyl trimethoxy silicanes are added, at 30 DEG C
Constant temperature stirs for 24 hours, and then vacuum drying removes solvent, obtains cross-linking guanidine bactericides II -2.
It prepares the mould proof room temperature vulcanized silicone rubber of long acting antibiotic: being 10000mpa.s room temperature vulcanization benzene by 100 parts by weight viscosity
Base silicon rubber, 6 parts of cross-linking II -2,5 part of triethoxysilanes of guanidine bactericides and 1 part of dibutyl tin dilaurate are in kneader
In be uniformly mixed, then place curing molding for 24 hours in a mold, obtain the mould proof RTV phenyl-containing silicone rubber system of long acting antibiotic
Product.
Antibacterial test and long-term effect are tested: 2591 antibiotic plastics of establishing criteria QB/T-Anti-microbial Performance Tests method and antibacterial
Effect carries out anti-microbial property test, and test is golden yellow staphylococcus and Escherichia coli with bacterium.After tested, resist obtained in implementation 1
Bacterium silicon rubber is respectively 99.9%, 99.7% to the antibiotic rate of golden yellow staphylococcus, Escherichia coli.Antimicrobial silicon rubber sample is soaked
Not in water, every 48h changes a water, follow-on test 1 month, finds to the antibiotic rate of golden yellow staphylococcus, Escherichia coli still
It is 99.8%, 99.5%
Mildew resistance test: 2591 Appendix B antibiotic plastic Anti-mildew capability test method of establishing criteria QB/T carries out mould proof survey
Examination selects aspergillus niger and ball hair shell as detection strain, test sample and blank control sample at 28 DEG C of temperature, relative humidity
It is cultivated 28 days under conditions of 90%RH or more, the mould proof grade for obtaining antibacterial silicon rubber in embodiment 1 is 1 grade.
Embodiment 6:
Prepare cross-linking guanidine bactericides II: by 100 parts by weight end ring oxygen methyl methoxy base silicone oil, (epoxide number is
0.1mol/100g, methoxyl content 5mol%), 40 parts of polyhexamethylene guanidine hydrochlorides (x=6, y=6) be dissolved in 200 parts of first
In alcohol, for 24 hours, then vacuum drying removes solvent for constant temperature stirring at 30 DEG C, obtains cross-linking guanidine bactericides II -3.
It prepares the mould proof room temperature vulcanized silicone rubber of long acting antibiotic: being 10000mpa.s room temperature vulcanization 107 by 100 parts by weight viscosity
Silicon rubber, 4 parts of cross-linking II -3,5 part of tetraethyl orthosilicates of guanidine bactericides and 1 part of dibutyl tin dilaurate mix in kneader
It closes uniformly, then places curing molding for 24 hours in a mold, obtain the mould proof room temperature vulcanized silicone rubber product of long acting antibiotic.
Antibacterial test and long-term effect are tested: 2591 antibiotic plastics of establishing criteria QB/T-Anti-microbial Performance Tests method and antibacterial
Effect carries out anti-microbial property test, and test is golden yellow staphylococcus and Escherichia coli with bacterium.After tested, resist obtained in implementation 1
Bacterium silicon rubber is respectively 99.9%, 99.7% to the antibiotic rate of golden yellow staphylococcus, Escherichia coli.Antimicrobial silicon rubber sample is soaked
Not in water, every 48h changes a water, follow-on test 1 month, finds to the antibiotic rate of golden yellow staphylococcus, Escherichia coli still
It is 99.3%, 99.2%
Mildew resistance test: 2591 Appendix B antibiotic plastic Anti-mildew capability test method of establishing criteria QB/T carries out mould proof survey
Examination selects aspergillus niger and ball hair shell as detection strain, test sample and blank control sample at 28 DEG C of temperature, relative humidity
It is cultivated 28 days under conditions of 90%RH or more, the mould proof grade for obtaining antibacterial silicon rubber in embodiment 1 is 1 grade.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of cross-linking guanidine bactericides, which is characterized in that the general formula with formula (1):
(AaBCc)n (1)
Wherein, A is end functionalization organosilicon polymer, and B is guanidine oligomer, and C is the reaction containing vinyl/crosslinking functionalization
Closing object VL or reaction/crosslinking functional compounds AO, a containing alkoxyl silicone is the integer of 0-8, and c is the integer of 1-8, n 1-10
Integer.
2. cross-linking guanidine bactericides according to claim 1, which is characterized in that the cross-linking guanidine bactericides are that can hand over
Join guanidine bactericides I or cross-linking guanidine bactericides II,
When the cross-linking guanidine bactericides are cross-linking guanidine bactericides I, C is the reaction containing vinyl/crosslinking function
Compound VL,
When the cross-linking guanidine bactericides are cross-linking guanidine bactericides II, C is the reaction containing alkoxyl silicone/crosslinking function
It can compound AO.
3. cross-linking guanidine bactericides according to claim 1 or claim 2, which is characterized in that guanidine oligomerisation shown in B in formula (1)
Object, structural formula are as follows:
Wherein, R1For-H or CH2SxCH2NH2；
CH2SxCH2NH2Middle S is CH2、CH2OCH2Or CH2NHCH2In any one or its it is compound, x is the integer of 0-12；
G is HCl or H3PO4, y=2-20.
4. cross-linking guanidine bactericides according to claim 1 or claim 2, which is characterized in that hold functionalization in formula (1) shown in A
Organosilicon polymer, structural formula are as follows:
R2[Si(CH3)R3O]pR2
Wherein R2For-CH2CH2CH2NH2、-
CH2CH2CH2NHCH2CH2NH2、-CH2CH2CH2SH or-CH2CH2CH2NCO；
R3For-H ,-CH3、-CH2CH2CF3,-CH=CH2、-C6H5、-CH2CH2CN、-OCH3Or-OCH2CH3In any one；p
For the integer of 3-500.
5. cross-linking guanidine bactericides according to claim 1 or claim 2, which is characterized in that contain vinyl shown in C in formula (1)
Reaction/crosslinking functional compounds VL, be selected from glycidyl methacrylate, allyl glycidyl ether, allylamine, horse
Come the mixing of one or more of acid anhydrides, acrylic acid or acryloyl chloride, preferably glycidyl methacrylate and allyl contracting
Water glycerin ether.
6. cross-linking guanidine bactericides according to claim 1 or claim 2, which is characterized in that contain alkoxy shown in C in formula (1)
The reaction of silicon/crosslinking functional compounds AO is selected from 2- (3,4- epoxy cyclohexane) ethyl trimethoxy silane, 2- (3,4- rings
Oxygen cyclohexyl) ethyl triethoxysilane, 3- glycidyl ether oxypropyltrimethoxysilane, 3- glycidol ether oxygroup
Propyl-triethoxysilicane, 3- glycydoxy methyldiethoxysilane, N- (2- aminoethyl) -3- aminopropyl three
Methoxy silane, N- (2- aminoethyl) -3- aminopropyl triethoxysilane, N- (2- aminoethyl) -3- aminopropyltriethoxy diethoxy
Base silane, 3- aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane, 3- isocyanate group propyl trimethoxy silicane
Or one or more of 3- isocyanate group propyl-triethoxysilicane mixing.
7. the preparation method of cross-linking guanidine bactericides as claimed in claim 1 or 2, which is characterized in that
When the cross-linking guanidine bactericides are cross-linking guanidine bactericides I, the preparation step of cross-linking guanidine bactericides I is such as
Under:
End functionalization organosilicon polymer, the reaction containing vinyl/crosslinking functional compounds VL and guanidine oligomer are according to ginseng
With reactive functionality molar ratio (0-1): (0.1-1): 1 is added in reactor, reacts 0.1- at 0-100 DEG C in a solvent
For 24 hours, it then removes solvent and obtains cross-linking guanidine bactericides I；
When the cross-linking guanidine bactericides are cross-linking guanidine bactericides II, the preparation step of cross-linking guanidine bactericides II
It is as follows:
End functionalization organosilicon polymer, the reaction containing alkoxyl silicone/crosslinking functional compounds AO and guanidine oligomer according to
Participate in reactive functionality molar ratio (0-1): (0.1-1): 1 is added in reactor, reacts at 0-120 DEG C in a solvent
Then 0.1-24h removes solvent and obtains cross-linking guanidine bactericides II.
8. the application of cross-linking guanidine bactericides described in claim 2, which is characterized in that the cross-linking guanidine bactericides I makees
It is mixed into high-temperature silicon disulfide rubber for functional additive；
The cross-linking guanidine bactericides II is mixed into room temperature vulcanized silicone rubber as functional additive.
9. a kind of non-mould proof organic silicon rubber of dissolution long acting antibiotic of safety, which is characterized in that including the non-dissolution long acting antibiotic of safety
Mould proof high temperature vulcanized organic silicon rubber and the non-mould proof room temperature cured organic silicon rubber of dissolution long acting antibiotic of safety,
The mould proof high temperature vulcanized organic silicon rubber of the non-dissolution long acting antibiotic of safety, is made of following components and proportion:
The mould proof room temperature cured organic silicon rubber of the non-dissolution long acting antibiotic of safety, is made of following components and proportion:
Wherein, the cross-linking guanidine bactericides I is cross-linking guanidine bactericides I described in claim 2, the cross-linking guanidine
Antibacterial agent II is cross-linking guanidine bactericides II described in claim 2.
10. the mould proof organic silicon rubber of the non-dissolution long acting antibiotic of safety according to claim 7, which is characterized in that described organic
Silicone rubber matrix includes methyl vinyl silicone rubber, fluorine silicone rubber, copolymerization fluorine silicone rubber, phenyl siloxane rubber or nitrile silicone rubber.
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