CN1242781A - Graft polymer and moldings thereof for medical supply - Google Patents
Graft polymer and moldings thereof for medical supply Download PDFInfo
- Publication number
- CN1242781A CN1242781A CN 97181211 CN97181211A CN1242781A CN 1242781 A CN1242781 A CN 1242781A CN 97181211 CN97181211 CN 97181211 CN 97181211 A CN97181211 A CN 97181211A CN 1242781 A CN1242781 A CN 1242781A
- Authority
- CN
- China
- Prior art keywords
- graftomer
- carbonatoms
- moulded products
- quaternary ammonium
- medical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
A graft polymer comprising constituent units containing a quaternary ammonium group represented by general formula (A) wherein R2 and R3 represent each an alkyl group having 1 to 3 carbon atoms; R4 represents an alkyl group having 3 to 18 carbon atoms; and X represents at least one member selected from among halide, sulfate, hydroxide, and carboxylate ions, and an antimicrobial resin comprising the same. When the graft polymer is applied onto or incorporated into medical supplier to be retained for a long period of time, bacterial infection through the supplies can prevented.
Description
Technical field
The present invention relates to a kind of graftomer that can on polymer base material, be coated with, and the medical moulding product that use it.
Background technology
In medical field, caused infection disease was counted as one of complication during the medical instruments that macromolecular materials such as urethane are made inserted and be retained in intravital this section of patient.Past, the infection disease of causing in order to prevent to be accompanied by the indwelling of medical instruments, before using medical instruments, it is impregnated in the aqueous solution of the antiseptic-germicide that contains chloro hexedine or povidone-iodine etc. or sterilizing agent carries out disinfection, perhaps can replace continually for the medical instruments that can replace in the therapeutic process.But, understand, because the antiseptic-germicide sterilizing agent disappears from conduit (catheter) surface along with the prolongation of time, on sterilisation effect, there is not persistence, under the occasion of life-time service medical instruments, effect slowly reduces.In addition, the frequent substitution of medical instruments also makes medical worker's burden increase.Therefore, as one of means of further protecting from infection, can implement various antibiotic processing to medical instruments.As its representative, be main antiseptic-germicide with conduit in order to the chloro hexedine or be main metal or its surface of layer lining of containing its compound in order to silver, copper.In these conduits, adopt the system that slowly discharges material in vivo quantitatively, and compare under the occasion of disinfection conduit before using, demonstrate good effect with anti-microbial effect.
But, slowly discharge in the system of antimicrobial substance, still be restricted during use inevitably, render a service gradually and reduce.For metal or its compound of silver etc., in vivo dynamically not clear after slowly discharging is considered to harmful.And, remaining when silver in the medical instruments waste after the use, the special disposal that must when discarded, reclaim etc.
Therefore, as polymkeric substance non-slow release type, that itself have germ resistance, once relevant for the various motions of polymkeric substance (special public clear 54-17797, special public clear 54-18817) with quaternary ammonium group.But the poor in processability of these polymkeric substance can not be made the moulding product separately, therefore, must apply on the surface of the good forming polymer goods of mechanical characteristics, perhaps with this mixed with polymers moulding.Except the good substrate polymer of mechanical characteristics, poor with the intermiscibility of other polymkeric substance.If intermiscibility is poor, then the polymkeric substance of Tu Fuing is peeled off, and produces the crack.On the other hand, a kind of hydrogel is disclosed among the Te Kaiping 6-337378, wherein contain the polymer of monomers that has quaternary ammonium salt on polyalkylene glycol ethers (methyl) acrylate and the side chain, a kind of hydrogel is disclosed among the Te Kaiping 6-256424, wherein contain the monomer and the polymer of vinyl monomer that have quaternary ammonium salt on monomer with polyalkylene glycol ethers and the side chain, but all do not put down in writing graftomer in any patent, in these polymkeric substance, be subjected to optionally keeping the restriction of the characteristic of trunk composition and grafting composition.That is, still do not understand now and substrate polymer intermiscibility good antibacterial properties polymkeric substance.
Therefore, present inventors are in view of this problems of the prior art, for obtaining to form the such mantle of medical instruments that can be suitable for making complicated shape, and the germ resistance polymkeric substance good with intermiscibility, the binding property of various polymkeric substance carried out various researchs, found that, the one-tenth subdivision graft polymerization that will contain general formula (I) is to the polymkeric substance that contains vinylchlorid and intermiscibility, the binding property of polymkeric substance that forms and various polymkeric substance are good, and have very strong anti-microbial effect, thereby finish the present invention.That is, the objective of the invention is to, the medical moulded products that a kind of like this polymkeric substance is provided and uses this polymkeric substance, it can form mantle, can be suitable for making the base material of complicated shape.
Disclosure of an invention
The present invention relates to a kind of like this graftomer, it is characterized in that, it forms the formation unit graft polymerization that contains quaternary ammonium group shown in the general formula (A).
(R
2, R
3Be the alkyl of carbonatoms 1～3, R
4Alkyl for carbonatoms 3～18.X is selected from least a in halogen ion, sulfate ion, hydroxide ion and the carboxylic acid ion.)
Preferably, relating to a kind of formation unit that contains quaternary ammonium group shown in the general formula (A) that makes is to constitute unitary graftomer shown in the general formula (I) or make the formation unit that contains quaternary ammonium group and contain the graftomer that the unit graft polymerization of the unitary formation of polyalkylene glycol alkyl oxide composition shown in the general formula (B) forms:
(R
1For being selected from least a in hydrogen, methyl and the ethyl, n is 1～12 integer.A is for being selected from O, S or NR
5In at least a.R
5Alkyl for hydrogen or carbonatoms 1～12.)
-(R
5O)
nR
6(B) (n is 1～100 integer.R
5For the straight chain shape of carbonatoms 1～4 or have the alkylidene group of side chain, R
6For H or be selected from the straight chain shape of carbonatoms 1～4 or have at least a in the alkyl of side chain.)
The invention still further relates to a kind of in medical body, insert with moulded products on lining or mix above-mentioned graftomer and the medical moulded products that forms.
The preferred plan that carries out an invention
Below illustrate in greater detail the present invention.
Graftomer among the present invention has the functional group shown in the above-mentioned general formula (A).As formation unit with functional group shown in the general formula (A), can enumerate with ester bond, amido linkage, urea key, ehter bond, perhaps be bonded to the formation unit that forms on the main chain by alkylidene group, phenylene.Wherein, as formation unit,, preferably has the formation unit shown in the following general formula (I) from easy acquisition precursor with functional group shown in the general formula (A).
(R
1For being selected from least a in hydrogen, methyl and the ethyl, R
2, R
3Be the alkyl of carbonatoms 1～3, R
4Alkyl for carbonatoms 3～18.N is 1～12 integer.A is for being selected from O, S or NR
5In at least a.R
5Alkyl for hydrogen or carbonatoms 1～12.X is selected from least a in halogen ion, sulfate ion, hydroxide ion and the carboxylic acid ion.)
N is 1～12 integer, and this degree of freedom with antibiotic functional group is relevant, if too short, then functional group can not freely rotate, be difficult to contact with for example bacterium etc., and long, then because hydrophobicity strengthens, in the medium of the water system that contains bacterium, antibiotic functional group is difficult to contact with bacterium.
R
2, R
3Be alkyl, if carbonatoms is many, then hydrophobicity strengthens, and antibiotic functional group is difficult to contact with bacterium, and therefore, its carbonatoms is 1～3, and the minimum methyl of carbonatoms is best.
R
4Be the alkyl of carbonatoms 3～18, be preferably the alkyl of carbonatoms 8～12.These alkyl, if having side chain, then rotation is restricted, and therefore wishes to be the straight chain shape.
X is that sulfate ion is generally divalent under the occasion of sulfate ion, among the present invention, also can with the ion coordination of 1 valency.
In addition, A is for being selected from O, S or NR
5In at least a.
As being used to make the precursor vinyl compound that contains the formation unit graft copolymerization of quaternary ammonium group shown in the general formula (A), can use for example dimethyl amino ethyl methacrylate, dimethyl amino ethyl acrylate, diethylamino propyl methyl acid esters, dimethyl aminoethyl acrylamide, diethylamino ethyl acrylamide, consider from easy acquisition aspect, preferably use dimethyl amino ethyl methacrylate.If the amount of functional group is too much in the graftomer, screening characteristics variation then, under the occasion of wanting with other polymer blendings, intermiscibility may reduce.On the other hand, if very few, then anti-microbial property reduces.Therefore, among the graftomer 1g,, more preferably contain the formation unit of ammonium shown in the general formula (A) with the ratio more than 0.5 mmole, below 4 mmoles preferably with more than 0.1 mmole, below 4 mmoles.
Among the present invention, unqualified general formula (A) grafting composition in addition, consider from the aspect that easy and the aqueous solution and body fluid etc. mix, this material preferably uses hydrophilic composition, can use and contain like this that some constitute unitary hydrophilic composition, contain the polyalkylene glycol alkyl oxide shown in the general formula (B) in the said formation unit and become subdivision, for example methoxypolyethylene glycol, polyoxyethylene glycol ether, polypropylene glycol methyl ether, polypropylene glycol ether etc.
-(R
5O)
nR
6(B) (n is 1～100 integer.R
5For the straight chain shape of carbonatoms 1～4 or have the alkylidene group of side chain, R
6For H or be selected from the straight chain shape of carbonatoms 1～4 or have at least a in the alkyl of side chain.)
Wherein, consider from easy acquisition and secure context, preferably by the one-tenth subdivision shown in the following formula general formula (II).
(R
1Be hydrogen or methyl, n is 1～100 integer.R
7For the straight chain shape of carbonatoms 1～4 or have the alkylidene group of side chain, R
8For H or be selected from the straight chain shape of carbonatoms 1～4 or have at least a in the alkyl of side chain.A is for being selected from O, S or NR
9In at least a (R
9Alkyl for hydrogen or carbonatoms 1～12))
As the vinyl compound of graft copolymerization precursor, its specific examples can be enumerated for example methoxypolyethylene glycol methacrylic ester, methoxypolyethylene glycol acrylate, polyethylene glycol methacrylate-styrene polymer etc.If the amount of hydrophilic composition is too much in the graftomer, screening characteristics variation then in addition, is wanted under the occasion with other polymkeric substance copolymerization, and intermiscibility can reduce.On the other hand, if very few, then be difficult to be dissolved in the body fluid etc., live body adaptability reduces.Therefore, among the graftomer 1g,, more preferably contain the formation unit of polyalkylene glycol alkyl oxide shown in the general formula (B) with the ratio more than 0.1 mmole, below 1 mmole preferably with more than 0.01 mmole, below 5 mmoles.
Among the present invention, there is no particular limitation for the trunk polymkeric substance of formation graft copolymerization, has halogen atom, particularly chlorine bond thing on the preferred side chain, specifically, and the preferred polymkeric substance that contains vinylchlorid that uses.As the polymkeric substance except that polyvinyl chloride, the polymkeric substance for vinylchlorid and vinyl acetate between to for plastic has again, as the third composition, for example can use the polymkeric substance with acrylate, methacrylic ester, vinyl alcohol, vinylbenzene, vinyl cyanide; The polymkeric substance of grafting vinyl chloride, these mixture of polymers or in these polymkeric substance, be mixed with the various polymkeric substance or the mixtures such as polymkeric substance of softening agent or stablizer in the ethene-vinyl acetate polymkeric substance.Carrying out under the blended occasion, mixing, be highly suitable for using as medical moulded products with for example urethane, natural rubber, silicone resin, polyvinyl chloride, polymeric amide, synthetic rubber etc.The content of this vinylchlorid in these polymkeric substance and mixture can be 0.1～100%, can select aptly according to purpose.
The molecular weight of graftomer of the present invention is unqualified, and number-average molecular weight is approximately more than 3000, is preferably 5000～1,000,000, and more preferably about 30,000～100,000.
The manufacture method of graftomer of the present invention is arbitrarily, below illustrates.
Graftomer can make like this: the polymkeric substance that will constitute main chain carries out grafting and activating to be handled, and adds the unitary precursor vinyl compound of formation that contains general formula (A) then, adopts suitable polymerization process that it is polymerized.
As the method that grafting and activating is handled, the preferred method of using is, for example by rayed etc., replaces the chlorine atom in the polymkeric substance that contains vinylchlorid with the dithiocarbamate groups that provides free radical easily.
In order to obtain quaternary ammonium group, can be to use the unitary precursor vinyl compound of the formation that contains general formula (A) to carry out graft polymerization, carry out quaternizedly then with haloalkane, also can be to use and carry out quaternised precursor vinyl compound with haloalkane in advance and carry out graft polymerization.
Graftomer of the present invention is very suitable for as medical resin, wherein, because the excellent amount of germ resistance is well suited for as the germ resistance resin and uses.
Can carry out surface applied by the antimicrobial resin, go for to prevent on any medical instruments of infectation of bacteria.
In the middle of the medical instruments, effective especially under the occasion of insertion moulded products in being used for medical body.Raw material as inserting goods in the medical body preferably uses urethane, natural rubber, silicone resin, polyvinyl chloride, polymeric amide, synthetic rubber etc.
Insert in the middle of the moulded products in the medical body, can be applicable to effectively and for example keep somewhere for a long time in intravital conduit, transplant fixing device, pipe (drainage tube), cuff (cuff), joint (tube stub), inspection port (access port), endoscopy lid, apocenosis bag, blood circuit etc.Compare with the material of slow delivery systme, very safe owing to antibiotic functional group is fixed in the graftomer by covalent linkage to human body, have the persistence effect.
In addition, for the medical moulded products that graftomer of the present invention and above-mentioned urethane, natural rubber, silicone resin etc. are mixed, can be used for effectively and same purposes such as above-mentioned conduit, transplant fixing device, pipe.
Below, be described more specifically the present invention with embodiment, but the present invention is not subjected to the qualification of this embodiment.Embodiment 1
With the polymerization degree is that 550 polyvinyl chloride 120g is dissolved in 2 liters of dimethyl formamides, add 2.704g Thiocarb salt, reacted 3 hours down, use the methyl alcohol redeposition at 50 ℃, dry then, obtain photo-grafting activation polyvinyl chloride (being designated hereinafter simply as the DTC chlorinated polynvinyl chloride (CPVC)).
80g is dissolved in the 1250ml tetrahydrofuran (THF) with this DTC chlorinated polynvinyl chloride (CPVC), add 200g methoxypolyethylene glycol methacrylic ester (polymerization degree of polyalkylene glycol moiety is 20～23) and 80g dimethyl amino ethyl methacrylate, in light source internal penetration type apparatus for photoreaction, shone 9.5 hours down at 30 ℃ with 100W high pressure mercury vapour lamp (ゥ シ ォ motor UM-102), carry out the photo-grafting polymerization thus.The composition of this graftomer is vinylchlorid 54%, methoxypolyethylene glycol methacrylic ester 30%, dimethyl amino ethyl methacrylate 16% by weight.Embodiment 2
Graftomer 5g shown in the embodiment 1 is dissolved among the tetrahydrofuran (THF) 50ml, adds butyl bromide 1.1ml then, reacted 4 hours down at 50 ℃.Be poured in the saturated aqueous common salt, make its precipitation, water and washing with alcohol, drying then obtain to have the anti-bacterial material of the quaternary ammonium group that contains chain alkyl (carbonatoms is 4).Quaternary ammonium group import volume among the graftomer 1g is 0.15 mmole.Embodiment 3
In 10% solution of the anti-bacterial material shown in the embodiment 2, flood the pipe of urethane along its length, on pipe, be coated with anti-bacterial material, drying.To be suspended with bacterial concentration be 10 with being coated with the pipe ethanol disinfection of anti-bacterial material, being impregnated into then
4In the normal saline solution of the intestinal bacteria of individual/ml (MC1061 strain), left standstill 24 hours.After 24 hours, measure attached to the bacterial count on the pipe.In contrast, the urethane pipe that does not apply anti-bacterial material is carried out same operation.Its result, the particle-bound bacteria number of the urethane pipe of uncoated anti-bacterial material is 534, being coated with on the pipe of anti-bacterial material is 137.Embodiment 4
Graftomer 5g shown in the embodiment 1 is dissolved among the tetrahydrofuran (THF) 50ml, adds hexyl bromide 1.4ml then, under 50 ℃, make its reaction 4 hours.Be poured in the saturated aqueous common salt, make its precipitation, water and washing with alcohol, drying then obtain to have the anti-bacterial material of the quaternary ammonium group that contains chain alkyl (carbonatoms is 6).Quaternary ammonium group import volume among the graftomer 1g is 0.11 mmole.Embodiment 5
In 10% solution of the anti-bacterial material shown in the embodiment 4, flood the pipe of urethane along its length, on pipe, be coated with anti-bacterial material, drying.Experimentize similarly to Example 3, its result, the particle-bound bacteria number of the urethane pipe of uncoated anti-bacterial material is 534, being coated with on the pipe of anti-bacterial material is 125.Embodiment 6
Graftomer 5g shown in the embodiment 1 is dissolved among the tetrahydrofuran (THF) 50ml, adds n-octyl bromide 1.7ml then, under 50 ℃, make its reaction 4 hours.Be poured in the saturated aqueous common salt, make its precipitation, water and washing with alcohol, drying then obtain to have the anti-bacterial material of the quaternary ammonium group that contains chain alkyl (carbonatoms is 8).Quaternary ammonium group import volume among the graftomer 1g is 0.30 mmole.Embodiment 7
In 10% solution of the anti-bacterial material shown in the embodiment 6, flood the pipe of urethane along its length, on pipe, be coated with anti-bacterial material, drying.Experimentize similarly to Example 3, its result, the particle-bound bacteria number of the urethane pipe of uncoated anti-bacterial material is 534, being coated with on the pipe of anti-bacterial material is 126.Embodiment 8
Graftomer 5g shown in the embodiment 1 is dissolved among the tetrahydrofuran (THF) 50ml, adds decyl bromide 2.1ml then, under 50 ℃, make its reaction 4 hours.Be poured in the saturated aqueous common salt, make its precipitation, water and washing with alcohol, drying then obtain to have the anti-bacterial material of the quaternary ammonium group that contains chain alkyl (carbonatoms is 10).Quaternary ammonium group import volume among the graftomer 1g is 0.16 mmole.Embodiment 9
In 10% solution of the anti-bacterial material shown in the embodiment 8, flood the pipe of urethane along its length, on pipe, be coated with anti-bacterial material, drying.Experimentize similarly to Example 3, its result, the particle-bound bacteria number of the urethane pipe of uncoated anti-bacterial material is 534, being coated with on the pipe of anti-bacterial material is 71.Embodiment 10
Graftomer 5g shown in the embodiment 1 is dissolved among the tetrahydrofuran (THF) 50ml, adds lauryl bromide 2.4ml then, under 50 ℃, make its reaction 4 hours.Be poured in the saturated aqueous common salt, make its precipitation, water and washing with alcohol, drying then obtain to have the anti-bacterial material of the quaternary ammonium group that contains chain alkyl (carbonatoms is 12).Quaternary ammonium group import volume among the graftomer 1g is 0.18 mmole.Embodiment 11
In 10% solution of the anti-bacterial material shown in the embodiment 10, flood the pipe of urethane along its length, on pipe, be coated with anti-bacterial material, drying.Experimentize similarly to Example 2, its result, the particle-bound bacteria number of the urethane pipe of uncoated anti-bacterial material is 534, being coated with on the pipe of anti-bacterial material is 38.Embodiment 12
Graftomer 5g shown in the embodiment 1 is dissolved among the tetrahydrofuran (THF) 50ml, adds myristyl bromine 2.7ml then, under 50 ℃, make its reaction 4 hours.Be poured in the saturated aqueous common salt, make its precipitation, water and washing with alcohol, drying then obtain to have the anti-bacterial material of the quaternary ammonium group that contains chain alkyl (carbonatoms is 14).Quaternary ammonium group import volume among the graftomer 1g is 0.19 mmole.Embodiment 13
In 10% solution of the anti-bacterial material shown in the embodiment 12, flood the pipe of urethane along its length, on pipe, be coated with anti-bacterial material, drying.Experimentize similarly to Example 3, its result, the particle-bound bacteria number of the urethane pipe of uncoated anti-bacterial material is 534, being coated with on the pipe of anti-bacterial material is 151.Embodiment 14
Graftomer 5g shown in the embodiment 1 is dissolved among the tetrahydrofuran (THF) 50ml, adds myristyl bromine 2.7ml then, under 50 ℃, make its reaction 4 hours.Be poured in the saturated aqueous common salt, make its precipitation, water and washing with alcohol, drying then obtain to have the anti-bacterial material of the quaternary ammonium group that contains chain alkyl (carbonatoms is 18).Quaternary ammonium group import volume among the graftomer 1g is 0.24 mmole.Embodiment 15
In 10% solution of the anti-bacterial material shown in the embodiment 14, flood the pipe of urethane along its length, on pipe, be coated with anti-bacterial material, drying.Experimentize similarly to Example 3, its result, the particle-bound bacteria number of the urethane pipe of uncoated anti-bacterial material is 534, being coated with on the pipe of anti-bacterial material is 211.Embodiment 16
1% solution of the anti-bacterial material shown in the embodiment 10 is dripped on the cover glass coating anti-bacterial material or polyvinyl chloride or urethane on cover glass, drying.That side of coating anti-bacterial material is placed cover glass up, drips thereon and contains 10
3～10
4The intestinal bacteria of individual/ml or green dense bacterium or staphylococcus aureus or staphylococcus epidermidis or enterococcal serum or urine are placed one piece of cover glass thereon again, make that side of its coating anti-bacterial material clamp bacterium liquid down, place 24 hours down at 37 ℃.After cleaning cover glass, nestle on the nutrient agar, the bacterium that will adhere to shifts, and after cultivating, judges the formation that has or not bacterium colony.Its result is coated with on the cover glass of polyvinyl chloride or urethane, no matter be in serum or the urine, all forms bacterium colony for whole bacteriums, in contrast, be coated with in the cover glass of anti-bacterial material, and for whole bacteriums, the bacterium colony that does not form.Embodiment 17
The DTC chlorinated polynvinyl chloride (CPVC) 160g of embodiment 1 record is dissolved in the 2500ml tetrahydrofuran (THF), the dimethyl amino ethyl methacrylate that adds 400g methoxypolyethylene glycol methacrylic ester (mean polymerisation degree of polyalkylene glycol moiety is 90) and 160g, in light source internal penetration type apparatus for photoreaction, shone 9.5 hours down at 30 ℃ with 100W high pressure mercury vapour lamp (ウ シ ォ motor UM-102), carry out the photo-grafting polymerization thus.The composition of this graftomer is vinylchlorid 64%, methoxypolyethylene glycol methacrylic ester 21%, dimethyl amino ethyl methacrylate 15% by weight.Embodiment 18
Graftomer 30g shown in the embodiment 17 is dissolved among the dimethyl formamide 300ml, adds lauryl bromide 40ml then, under 60 ℃, make its reaction 18 hours.Pour in the mixed solvent of entry and methyl alcohol, make its precipitation, washing, drying then obtain to have the anti-bacterial material of the quaternary ammonium group that contains chain alkyl (carbonatoms is 12).Quaternary ammonium group import volume among the graftomer 1g is 1 mmole.Embodiment 19
In 3% solution of the anti-bacterial material shown in the embodiment 17, flood the pipe of urethane along its length, on pipe, be coated with anti-bacterial material, drying.To be suspended with bacterial concentration be 10 with being coated with the pipe ethanol disinfection of anti-bacterial material, being impregnated into then
4In the normal saline solution of the staphylococcus epidermidis of individual/ml, left standstill 24 hours.After 24 hours, measure attached to the bacterial count on the pipe.In contrast, the urethane pipe that does not apply anti-bacterial material is carried out same operation.Its result, the particle-bound bacteria number of the urethane pipe of uncoated anti-bacterial material is 967, being coated with on the pipe of anti-bacterial material is 0.Embodiment 20
In 3% solution of the anti-bacterial material shown in the embodiment 17, flood vinylbenzene-iso-butylene synthetic rubber sheet material along its length, on sheet material, be coated with anti-bacterial material, drying.Be immersed in the water after making drying, the intensity of coating is not for can peel off for 20 times with the nail scratching yet.
Utilize possibility on the industry
Graft polymers of the present invention can be applied to plastic products, particularly doctor at an easy rate Treat on the apparatus, even bacterium is dense, also demonstrate good antibacterial ability, its effect Last very long. Have again since the functional group of performance anti-microbial property etc. by covalent bonding and Can not be come out by elution, therefore, can the long term maintenance anti-microbial property, and harmless.
Claims (19)
1. a graftomer is characterized in that, it forms the formation unit graft polymerization that contains quaternary ammonium group shown in the general formula (A),
R
2, R
3Be the alkyl of carbonatoms 1～3, R
4Alkyl for carbonatoms 3～18; X is selected from least a in halogen ion, sulfate ion, hydroxide ion and the carboxylic acid ion.
2. the graftomer described in the claim 1 is characterized in that, wherein, the formation unit that contains quaternary ammonium group shown in the general formula (A) is the formation that contains quaternary ammonium group shown in the general formula (I)
R
1For being selected from least a in hydrogen, methyl and the ethyl, n is 1～12 integer; A is for being selected from O, S or NR
5In at least a; R
5Alkyl for hydrogen or carbonatoms 1～12.
3. the graftomer described in the claim 1 is characterized in that, contains the above formation unit that contains this quaternary ammonium group of 0.1 mmole.
4. the graftomer described in the claim 1 is characterized in that, makes this formation unit graft polymerization that contains quaternary ammonium group in the polymkeric substance that contains vinylchlorid.
5. the graftomer described in the claim 1 is characterized in that, makes this formation unit that contains quaternary ammonium group and contains the unit graft polymerization of the unitary formation of polyalkylene glycol alkyl oxide composition shown in the general formula (B):
-(R
6O)
nR
7(B) n is 1～100 integer, R
6For the straight chain shape of carbonatoms 1～4 or have the alkylidene group of side chain, R
7For H or be selected from the straight chain shape of carbonatoms 1～4 or have at least a in the alkyl of side chain.
6. the graftomer described in the claim 5 is characterized in that, contains the unitary formation of the polyalkylene glycol alkyl oxide composition unit shown in the general formula (B), is the formation unit shown in the general formula (II):
R
1Be hydrogen or methyl, n is 1～100 integer.A is for being selected from O, S or NR
5In at least a, R
5Alkyl for hydrogen or carbonatoms 1～12.
7. the graftomer described in the claim 5 is characterized in that, wherein contain 0.01 mmole above contain the unitary formation of this polyalkylene glycol alkyl oxide composition unit.
8. the graftomer described in the claim 1 is characterized in that, this R
4Carbonatoms be 8～12.
9. germ resistance resin that contains polymkeric substance described in the claim 1 and form.
10. one kind with the graftomer described in the claim 1 lining or be mixed in the substrate polymer and the medical moulded products that forms.
11. the medical moulded products described in the claim 10 is characterized in that, it is to insert in the medical body to use moulded products.
12. insert in the medical body described in the claim 11 and use moulded products, it is characterized in that substrate polymer is to be selected from least a in polyurethanes, natural rubber class, silicone resin class, polyvinyl chloride, polyamide-based, the synthetic rubber class.
13. insert in the medical body described in the claim 12 and use moulded products, it is characterized in that substrate polymer is a polyurethanes.
14. insert in the medical body described in the claim 12 and use moulded products, it is characterized in that substrate polymer is the natural rubber class.
15. insert in the medical body described in the claim 12 and use moulded products, it is characterized in that substrate polymer is the silicone resin class.
16. insert in the medical body described in the claim 12 and use moulded products, it is characterized in that substrate polymer is a polyvinyl chloride.
17. insert in the medical body described in the claim 12 and use moulded products, it is characterized in that substrate polymer is polyamide-based.
18. insert in the medical body described in the claim 12 and use moulded products, it is characterized in that substrate polymer is the synthetic rubber class.
19. the medical moulded products described in the claim 10 is characterized in that, it is conduit, pipe, shell, transplant fixing device, cuff, tube stub, inspection port, apocenosis bag, endoscopy lid or blood circuit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97181211 CN1200956C (en) | 1997-11-04 | 1997-11-04 | Graft polymer and moldings thereof for medical supply |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97181211 CN1200956C (en) | 1997-11-04 | 1997-11-04 | Graft polymer and moldings thereof for medical supply |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1242781A true CN1242781A (en) | 2000-01-26 |
| CN1200956C CN1200956C (en) | 2005-05-11 |
Family
ID=5178161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97181211 Expired - Fee Related CN1200956C (en) | 1997-11-04 | 1997-11-04 | Graft polymer and moldings thereof for medical supply |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1200956C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106029115A (en) * | 2014-02-20 | 2016-10-12 | 贝克顿·迪金森公司 | Antimicrobial inserts for medical devices |
| US10792399B2 (en) | 2014-02-20 | 2020-10-06 | Becton, Dickinson And Company | Antimicrobial inserts for medical devices |
| US10994118B2 (en) | 2014-04-23 | 2021-05-04 | Becton, Dickinson And Company | Antimicrobial stopcock medical connector |
| US11077293B2 (en) | 2015-01-27 | 2021-08-03 | Becton, Dickinson And Company | Antimicrobial inserts for stopcock medical connectors |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419332B (en) * | 2015-12-24 | 2018-08-07 | 郑州欧姆康生物材料有限公司 | A kind of antimicrobial form composite material and its preparation method and purposes |
-
1997
- 1997-11-04 CN CN 97181211 patent/CN1200956C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106029115A (en) * | 2014-02-20 | 2016-10-12 | 贝克顿·迪金森公司 | Antimicrobial inserts for medical devices |
| US10792398B2 (en) | 2014-02-20 | 2020-10-06 | Becton, Dickinson And Company | Antimicrobial inserts for medical devices |
| US10792399B2 (en) | 2014-02-20 | 2020-10-06 | Becton, Dickinson And Company | Antimicrobial inserts for medical devices |
| US11291749B2 (en) | 2014-02-20 | 2022-04-05 | Becton, Dickinson And Company | Antimicrobial inserts for medical devices |
| US11931483B2 (en) | 2014-02-20 | 2024-03-19 | Becton, Dickinson And Company | Antimicrobial inserts for medical devices |
| US10994118B2 (en) | 2014-04-23 | 2021-05-04 | Becton, Dickinson And Company | Antimicrobial stopcock medical connector |
| US11077293B2 (en) | 2015-01-27 | 2021-08-03 | Becton, Dickinson And Company | Antimicrobial inserts for stopcock medical connectors |
| US11554259B2 (en) | 2015-01-27 | 2023-01-17 | Becton, Dickinson And Company | Antimicrobial inserts for stopcock medical connectors |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1200956C (en) | 2005-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6497868B1 (en) | Graft polymer and moulded medical articles employing this | |
| US8809411B2 (en) | Hydrophilic coating | |
| JP3253082B2 (en) | Methods for reducing microbial adhesion | |
| CN111471202B (en) | Antibacterial silicon rubber material and preparation method and application thereof | |
| CN1612804A (en) | Microbe-resistant medical device, microbe-resistant polymeric coating and methods for producing same | |
| JP5406719B2 (en) | Method for treating a surface containing Si-H groups | |
| US11160276B2 (en) | Built-in antimicrobial plastic resins and methods for making the same | |
| CN110862680B (en) | Preparation method of fluorine-containing polyacrylic acid copolymer antibacterial composite material, obtained product and application | |
| US9155301B2 (en) | Antimicrobial agent comprising a cysteine component covalently bound to a substrate in particular by binding through an S-S bridge via a spacer molecule | |
| EP2245083A1 (en) | Coating compositon comprising an antimicrobial copolymer | |
| CN1200956C (en) | Graft polymer and moldings thereof for medical supply | |
| CN113797399B (en) | Use of non-releasing antimicrobial adhesion coating in antimicrobial medical devices | |
| JP3541627B2 (en) | Graft polymer and molded article for medical use using the same | |
| JPH1199200A (en) | Dialyzing catheter and its manufacture | |
| CN116041768A (en) | PH-responsive ultra-smooth antibacterial silicone rubber and preparation method thereof | |
| Hamid et al. | Synthesis of Acrylamide-Graphene Oxide Polymer for Antibacterial Application | |
| Balakrishnan et al. | Chemical modification of poly (vinyl chloride) using poly (ethylene glycol) to improve blood compatibility | |
| CA2276680C (en) | Graft polymer and moulded medical articles employing this | |
| CN105555806B (en) | Medical or beast medical apparatus surface modification | |
| JP2021531394A (en) | Antibacterial plastic, gas passages for breathing equipment including it and its manufacturing method | |
| Andersen | Antimicrobial Polymers for Catheter Coatings | |
| JPH10101828A (en) | Antibacterial molded product | |
| JP2004024418A (en) | Antibacterial composition | |
| Wu | Design of anti-biofilm coating on medical catheters | |
| JP3422151B2 (en) | Antibacterial material and antibacterial molded product using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050511 Termination date: 20141104 |
|
| EXPY | Termination of patent right or utility model |