CN107583100B - A kind of preparation method and application of Si based polyurethanes medical adhesive - Google Patents
A kind of preparation method and application of Si based polyurethanes medical adhesive Download PDFInfo
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- CN107583100B CN107583100B CN201710879156.5A CN201710879156A CN107583100B CN 107583100 B CN107583100 B CN 107583100B CN 201710879156 A CN201710879156 A CN 201710879156A CN 107583100 B CN107583100 B CN 107583100B
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Abstract
The invention discloses the preparation methods and application of a kind of Si based polyurethanes medical adhesive, first, with silicon oxygen (Si-O) for the compound of main chain, end group containing active hydrogen functional group, it is reacted with the compound containing isocyanates (NCO) functional group, obtains the predecessor that end group is isocyanates；Then predecessor is reacted with the crosslinking agent containing active hydrogen functional group, can be obtained required isocyanate-terminated Si based polyurethanes medical adhesive, by changing crosslink density, the modulus that can be realized Si based polyurethanes medical adhesive is adjusted.And Si based polyurethanes medical adhesive obtained is nontoxic, biocompatibility is good, has extensive chemical adhesion strength to tissue, can be used for that different human body is soft, reparations of sclerous tissues.
Description
Technical field
The present invention relates to the technical fields of medical glue, refer in particular to a kind of preparation side of Si based polyurethanes medical adhesive
Method and application.
Background technique
The reparation means of existing human tissue wound have surgical thread suture, medical adhesive tape and commercial biological glue, surgical thread
Suture causes Principle of Pain, the reparation for being difficult to use in Micro trauma, easily causes infection when using.Medical adhesive tape intensity is too low, to multiple
Miscellaneous surface of a wound adaptability is poor.Commercial biological glue mainly has fibrin glue, a-cyanoacrylate etc., fibrin glue
Biological safety is good, but bonding force is general and expensive；Although a-cyanoacrylate curing rate is fast, intensity is high, tool
There are certain bio-toxicity, modulus to be difficult to be adapted to tissue greatly.Accordingly, it is desirable to can develop, a kind of biological safety is good, modulus
It is adjustable to different tissues suitability is good, adhesion strength is high medical glue.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of systems of Si based polyurethanes medical adhesive
Preparation Method and application can realize that the modulus of Si based polyurethanes medical adhesive is adjustable by this method, and Si base obtained is poly-
Urethane medical adhesive is nontoxic, biocompatibility is good, has extensive chemical adhesion strength to tissue, can be used for different people
Body is soft, sclerous tissues reparations.
To achieve the above object, technical solution provided by the present invention is as follows:
A kind of preparation method of Si based polyurethanes medical adhesive, firstly, using silicon oxygen as main chain, end group function containing reactive hydrogen
The compound of group, reacts with the compound containing isocyanate functional group, obtains the predecessor that end group is isocyanates；Then will before
It drives object to react with the crosslinking agent containing active hydrogen functional group, can be obtained the required isocyanate-terminated medical gluing of Si based polyurethanes
Agent, by changing crosslink density, the modulus that can be realized Si based polyurethanes medical adhesive is adjusted.
The main chain is the compound of silicon oxygen, end group containing active hydrogen functional group, averagely number containing reactive hydrogen >=2.
The main chain is compound of the silicon oxygen end group containing active hydrogen functional group by NH2-(CH2)m-O-(Si(CH3)2-O)n-
(CH2)m-NH2、HO-(CH2)m-O-(Si(CH3)2-O)n-(CH2)m-OH、HS-(CH2)m-O-(Si(CH3)2-O)n-(CH2)m-SH
One or more of composition, wherein limit chemical formula in m=3~6, n=1~4.
Average functionality >=2 of the compound containing isocyanate functional group are NCO by the ratio between reactant functional group:
XH=1.3~1.9, wherein X is one of N, O, S.
The compound containing isocyanate functional group (NCO) is by lysine diisocyanate (LDI), three isocyanide of lysine
Acid esters (LTI), ethyl ester of lysine diisocyanate (LEEDI), ethyl ester of lysine triisocyanate (LEETI), toluene diisocyanate
One or more of acid esters (TDI), methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI) composition.
Averagely number containing the active hydrogen functional group > 2 of the crosslinking agent, by the ratio between functional group are as follows: activity H in crosslinking agent: forerunner
NCO=0.2~0.7 in object.
The crosslinking agent is by one or more of glycerol, trimethylolpropane (TMP), melamine, hyper-branched polyester
Be dissolved in solvent composition, the solvent by dimethyl sulfoxide (DMSO), n,N-Dimethylformamide (DMF), tetrahydrofuran (THF),
One or more of glycol dimethyl ether composition.
The Si based polyurethanes medical adhesive of above-mentioned preparation is as soft, sclerous tissues the reparations for human body of medical glue.Make
The surface of a wound is first done simple disinfection treatment by the used time, Si based polyurethanes medical adhesive is then coated in wound, at this time the poly- ammonia of Si base
Isocyanate group in ester medical adhesive will be crosslinked with the water in tissue reacts, and rapid curing closes surface of a wound mouth
It closes, to reach repairing effect.
Depending on final purpose, Si based polyurethanes medical adhesive can contain the addition such as antioxidant, desiccant, catalyst
Agent.
Compared with prior art, the present invention have the following advantages that with the utility model has the advantages that
It finally can get a kind of adjustable Si based polyurethanes medical adhesive of modulus, preparation process by the method for the invention
Simply, process control is good, repeated height, Si based polyurethanes medical adhesive obtained is nontoxic, biocompatibility is good,
There is extensive chemical adhesion strength to tissue, can be used for that different human body is soft, reparations of sclerous tissues, have a large promotion value.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1
The preparation method of Si based polyurethanes medical adhesive provided by the present embodiment, specifically: firstly, based on silicon oxygen
The compound of chain, end group containing active hydrogen functional group, reacts with the compound containing isocyanate functional group, and acquisition end group is isocyanic acid
The predecessor of ester；Then predecessor is reacted with the crosslinking agent containing active hydrogen functional group, is can be obtained required isocyanate-terminated
Si based polyurethanes medical adhesive, by change crosslink density, can be realized the modulus tune of Si based polyurethanes medical adhesive
Section.Wherein, main chain is the compound of silicon oxygen, end group containing active hydrogen functional group, averagely number containing reactive hydrogen >=2, by NH2-
(CH2)m-O-(Si(CH3)2-O)n-(CH2)m-NH2、HO-(CH2)m-O-(Si(CH3)2-O)n-(CH2)m-OH、HS-(CH2)m-O-
(Si(CH3)2-O)n-(CH2)mOne or more of-SH composition, wherein limiting m=3~6 in chemical formula, n=1~4；Containing different
Average functionality >=2 of the compound of cyanate functional group (NCO), by the ratio between reactant functional group be NCO:XH=1.3~
1.9, wherein X is one of N, O, S, and the compound containing isocyanate functional group (NCO) is by lysine diisocyanate
(LDI), lysine triisocyanate (LTI), ethyl ester of lysine diisocyanate (LEEDI), ethyl ester of lysine triisocyanate
(LEETI), toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), in hexamethylene diisocyanate (HDI)
One or more of compositions；Averagely number containing the active hydrogen functional group > 2 of crosslinking agent, by the ratio between functional group are as follows: active in crosslinking agent
H: NCO=0.2~0.7 in predecessor, crosslinking agent is by glycerol, trimethylolpropane (TMP), melamine, hyper-branched polyester
One or more be dissolved in solvent composition, the solvent is by dimethyl sulfoxide (DMSO), n,N-Dimethylformamide (DMF), four
One or more of hydrogen furans (THF), glycol dimethyl ether composition.
It is below the preferred embodiment of the above-mentioned Si based polyurethanes medical adhesive preparation of the present embodiment, concrete condition is as follows:
In a logical N2, 2.36gLDI is added in temperature is 60 DEG C, stirring rate is 2000rpm two mouthfuls of round-bottomed flasks, lead to
It crosses the mode being slowly added dropwise and 0.55gNH is added in 1 hour2-(CH2)3-O-Si-O-(CH2)3-NH2, before reaction obtains for 2 hours
Drive object；0.22g glycerine is dissolved in 1.5mlTHF, reaction temperature is 20 DEG C, is added in 1 hour by way of being slowly added dropwise
Enter, then react again 3 hours, resulting adhesive is sealed under the conditions of room temperature inflated with nitrogen.In use, adhesive is applied
It overlays in two panels wet tissue, applies pressure about 1 minute, can be obtained good bonding effect.
Embodiment 2
The present embodiment is in a logical N unlike the first embodiment2, temperature be 60 DEG C, two mouthfuls that stirring rate is 2000rpm
1.68gHDI is added in round-bottomed flask, 1.29gNH is added in 1 hour by way of being slowly added dropwise2-(CH2)6-O-(Si
(CH3)2-O)4-(CH2)6-NH2, react 2 hours and obtain predecessor；0.20g glycerine, 0.02g melamine are dissolved in
In 1.5mlTHF, reaction temperature is 20 DEG C, is added, is then reacted again 3 hours in 1 hour by way of being slowly added dropwise, will
Resulting adhesive is sealed under the conditions of room temperature inflated with nitrogen.In use, adhesive is coated in two panels wet tissue, apply
Pressure about 1 minute, it can be obtained good bonding effect.
Embodiment 3
The present embodiment is in a logical N unlike the first embodiment2, temperature be 60 DEG C, two mouthfuls that stirring rate is 2000rpm
2.36gLDI is added in round-bottomed flask, 1.04gNH is added in 1 hour by way of being slowly added dropwise2-(CH2)3-O-(Si
(CH3)2-O)4-(CH2)3-NH2, react 2 hours and obtain predecessor；0.18g glycerine, 0.02g melamine are dissolved in
In 1.5mlTHF, reaction temperature is 20 DEG C, is added, is then reacted again 3 hours in 1 hour by way of being slowly added dropwise, will
Resulting adhesive is sealed under the conditions of room temperature inflated with nitrogen.In use, adhesive is coated in two panels wet tissue, apply
Pressure about 1 minute, it can be obtained good bonding effect.
Embodiment 4
The present embodiment is in a logical N unlike the first embodiment2, temperature be 60 DEG C, two mouthfuls that stirring rate is 2000rpm
2.36gLDI is added in round-bottomed flask, 1.42gNH is added in 1 hour by way of being slowly added dropwise2-(CH2)3-O-Si-O-
(CH2)3-NH2, react 2 hours and obtain predecessor；0.06g glycerine is dissolved in 1.5mlTHF, reaction temperature is 20 DEG C, is passed through
The mode being slowly added dropwise is added in 1 hour, then reacts again 3 hours, by resulting adhesive under the conditions of room temperature inflated with nitrogen
It is sealed.In use, adhesive is coated in two panels wet tissue, applies pressure about 1 minute, can be obtained good bonding
Effect.
The examples of implementation of the above are only the preferred embodiments of the invention, and implementation model of the invention is not limited with this
It encloses, therefore all shapes according to the present invention, changes made by principle, should all be included within the scope of protection of the present invention.
Claims (6)
1. a kind of preparation method of Si based polyurethanes medical adhesive, it is characterised in that: firstly, containing by main chain, end group of silicon oxygen
The compound of active hydrogen functional group is reacted with the compound containing isocyanate functional group, obtains the forerunner that end group is isocyanates
Object；Then predecessor is reacted with the crosslinking agent containing active hydrogen functional group, it is poly- can be obtained required isocyanate-terminated Si base
Urethane medical adhesive, by changing crosslink density, the modulus that can be realized Si based polyurethanes medical adhesive is adjusted；
Wherein the main chain is compound of the silicon oxygen end group containing active hydrogen functional group by NH2-(CH2)m-O-(Si(CH3)2-O)n-
(CH2)m-NH2、HO-(CH2)m-O-(Si(CH3)2-O)n-(CH2)m-OH、HS-(CH2)m-O-(Si(CH3)2-O)n-(CH2)m-SH
One or more of composition, wherein limit chemical formula in m=3~6, n=1~4；The chemical combination containing isocyanate functional group
Object is by lysine diisocyanate, lysine triisocyanate, ethyl ester of lysine diisocyanate, three isocyanic acid of ethyl ester of lysine
One or more of ester, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexamethylene diisocyanate composition；Institute
Averagely number containing the active hydrogen functional group > 2 of crosslinking agent is stated, and by glycerol, trimethylolpropane, melamine, hyper-branched polyester
One or more be dissolved in solvent composition.
2. a kind of preparation method of Si based polyurethanes medical adhesive according to claim 1, it is characterised in that: the master
Chain is the compound of silicon oxygen, end group containing active hydrogen functional group, averagely number containing reactive hydrogen >=2.
3. a kind of preparation method of Si based polyurethanes medical adhesive according to claim 1, it is characterised in that: described to contain
Average functionality >=2 of the compound of isocyanate functional group are isocyanate functional group: XH=by the ratio between reactant functional group
1.3~1.9, wherein X is one of N, O, S.
4. a kind of preparation method of Si based polyurethanes medical adhesive according to claim 1, it is characterised in that: the friendship
Join agent by the ratio between functional group are as follows: activity H in crosslinking agent: isocyanate functional group=0.2~0.7 in predecessor.
5. a kind of preparation method of Si based polyurethanes medical adhesive according to claim 1, it is characterised in that: described molten
Agent is made of one or more of dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, glycol dimethyl ether.
6. a kind of application for the Si based polyurethanes medical adhesive that preparation method according to claim 1 obtains, it is characterised in that:
As soft for human body, hard tissue repair medical glue.
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| CN201710879156.5A CN107583100B (en) | 2017-09-26 | 2017-09-26 | A kind of preparation method and application of Si based polyurethanes medical adhesive |
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| CN201710879156.5A CN107583100B (en) | 2017-09-26 | 2017-09-26 | A kind of preparation method and application of Si based polyurethanes medical adhesive |
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| CN107583100B true CN107583100B (en) | 2019-08-20 |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3884995B2 (en) * | 2002-05-29 | 2007-02-21 | 日東電工株式会社 | Adhesive sheet for skin application |
| US7858835B2 (en) * | 2007-06-27 | 2010-12-28 | Tyco Healthcare Group Lp | Foam control for synthetic adhesive/sealant |
| DE102008009407A1 (en) * | 2008-02-15 | 2009-08-20 | Bayer Materialscience Ag | adhesive |
| RS57933B1 (en) * | 2011-12-20 | 2019-01-31 | Adhesys Medical Gmbh | Isocyanate functional pre-polymer for a biodegradable tissue adhesive |
| CN105461889B (en) * | 2015-12-16 | 2018-07-20 | 华南理工大学 | Medical transparent high-strength polyurethane adhesive of one kind and preparation method thereof |
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Effective date of registration: 20220711 Address after: 511466 floor 11, building 9 (Building 7), No. 6, Nanjiang Second Road, Zhujiang street, Nansha District, Guangzhou City, Guangdong Province (office only) Patentee after: Guangzhou Xunhe Medical Technology Co.,Ltd. Address before: 510640 No. five, 381 mountain road, Guangzhou, Guangdong, Tianhe District Patentee before: SOUTH CHINA University OF TECHNOLOGY |
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