CN109568679A - A kind of biodegradable polyurethane sheath and preparation method thereof with antibacterial functions - Google Patents
A kind of biodegradable polyurethane sheath and preparation method thereof with antibacterial functions Download PDFInfo
- Publication number
- CN109568679A CN109568679A CN201811370821.9A CN201811370821A CN109568679A CN 109568679 A CN109568679 A CN 109568679A CN 201811370821 A CN201811370821 A CN 201811370821A CN 109568679 A CN109568679 A CN 109568679A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- biodegradable
- sheath
- particle
- antibacterial functions
- 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.)
- Pending
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
Abstract
The invention discloses a kind of biodegradable polyurethane sheath and preparation method thereof with antibacterial functions.The main component of sheath includes: biodegradable polyurethane, mass percentage content 65%-90%；There is polyhydroxy structure modified antimicrobial particle is connected with the amphiphilic polymer of alkane structure simultaneously, mass percentage content is 10%-35%, the mass percentage content wherein simultaneously with the amphiphilic polymer of polyhydroxy structure and alkane structure is 35%-75%, and the mass percentage content of antimicrobial particle is 25%-65%.Be prepared the biodegradable polyurethane with antibacterial functions object lotion is made after, the additive that mass percentage is no more than 0.2% is added, condom manufacture technique routinely prepares biodegradable polyurethane sheath.The polyurethane condom not only has biodegradable, also has antibiotic effect, and preparation process is simple, and the content of the various additives such as vulcanizing agent, anti-aging agent, thickener is considerably less, has apparent production, application advantage.
Description
Technical field
The present invention relates to sheath technical field, in particular to a kind of biodegradable polyurethane with antibacterial functions is kept away
Pregnant set and preparation method thereof.
Background technique
Sheath is one of the tool for going to prevent to become pregnant in the form of non-drug, can also be effectively prevented from venereal diseases and aids etc.
The pathogeny body of disease is propagated.Therefore, sheath have double protection functions, can not only effectively practise contraception, and can prevent with
Disease of the sexual behaviour as route of transmission, prevents from infecting, and brings the happy free sexual experience of people.So sheath is also known as pacified
A full set, condom, condom etc., as it is simple, be effectively physically isolated contraceptive device, by countries in the world, government is promoted the use of.
Since sheath is a kind of tool being in close contact with human body sensitive part, the propagation for preventing disease can be played in use process
Function thus can more be led furthermore if material itself also has killing or inhibits the antibacterial functions such as various microorganisms, mould
Material is avoided to be infected in production, use process dynamicly.
Natural emulsion is current most popular condom material, but natural emulsion sheath itself has deficiency
Place: thermal conductivity is low, easy to oxidize, oil resistivity and poor solvent resistance；Containing ingredients such as anaphylaxis aqueous soluble protein matter in material, it is easy
So that some consumers is generated the allergic reactions such as erythema, itch, causes strong uncomfortable reaction；Asia can be also generated in sulfidation
This strong carcinogen of nitramine.
Polyurethane condom device has the advantages that nontoxic, intensity is high, prepares without allergic reaction, therefore with polyurethane material
Sheath is largely paid close attention to and is used widely.Such as Chinese invention patent 201510211717.5,
201510212375.9 reporting has good bio-compatible with chitosan, poly butyric ester blending and modifying natural emulsion
Property, Chinese invention patent 201710147978.4,201710147988.8 is reported to be prepared using organosilicon-modified acrylate
Multilayer sandwiched polyurethane condom has the characteristics that high barrier, high-intensitive, the report of Chinese invention patent 201610776510.7
A kind of sheath for women is developed with water-borne polyurethane bond, Chinese invention patent 201610776510.7 reports a kind of poly-
The polyurethane latex sheath of olefin material preparation, Chinese invention patent 201610959993.4,201611205662.8 are reported
Waterborne polyurethane resin and production technology etc..But the numerous sheaths reported at present are all not exclusively biodegradable materials
Material, from the point of view of the annual usage amount of sheath, this will certainly become another huge " white garbage ", the ring lived to us
Border pollutes, and also has a significant impact to the health of the mankind.
The research of the existing sheath with antibacterial action, such as Chinese patent 201610466374.1 are reported kuh-seng
The prevention and adjuvant treatment that can be used for the gynecological diseases such as cervical erosion, vagina mycotic infection is added in sheath lubricant in alkali,
Chinese patent 201611226925.3 reports the research that related nano zine oxide is added in rubber latex as auxiliary agent.But
It is that they have following shortcoming as the sheath with antibacterial functions:
1, the medicine with antibacterial and anti-inflammation functions is added in sheath, due to using limited time, drug is in the short time
It is difficult to play the role for the treatment of；And there is drug to cause the risks such as allergy, physiological stress.
2, unmodified antimicrobial particle is added into polymer, two-phase laminated flow, and particle will be detached from organic phase, sheath
Polymer mantle has perforation risk, and antibacterial action is also difficult to embody.
3, the matrix of this kind of polyurethane condom is synthesis high molecular material, is limited by the intrinsic chemical property of organic strand
It makes, the additives such as wetting agent, defoaming agent, anti-aging agent, dispersing agent, curing agent are added in component, since material itself does not have
There is killing or inhibit the antibacterial functions such as various microorganisms, mould, increases infection probability instead in production, use process.
Summary of the invention
The biodegradable polyurethane sheath and its preparation that the purpose of the present invention is to provide a kind of with antibacterial functions
Method.The sheath not only has biodegradable, also has antibiotic effect, and vulcanizing agent, anti-aging agent, thickener etc. are each
The content of class additive is considerably less, has fully demonstrated the multi-functional advantage of sheath.
Realize that the technical solution of the object of the invention is as follows:
A kind of biodegradable polyurethane sheath with antibacterial functions, comprises the following components in parts by weight:
(A) biodegradable polyurethane: 65%-90%；
(B) there is polyhydroxy structure to connect modified antimicrobial particle: 10%- with the amphiphilic polymer of alkane structure simultaneously
35%；The mass percentage content wherein simultaneously with the amphiphilic polymer of polyhydroxy structure and alkane structure is 35%-
75%, the mass percentage content of antimicrobial particle is 25%-65%；
The biodegradable polyurethane is polyurethane high molecule, average molecular weight 300000-2000000.
Further, the biodegradable polyurethane is natural Biodegradable high-molecular modified polyurethane or conjunction
At biodegradable polyurethane macromolecule.
Wherein, the natural Biodegradable high-molecular modified polyurethane specifically: cellulose modified polyurethane, shell are poly-
One of sugared modified polyurethane, starch conversion polyurethane, lignin modification polyurethane, tannin modified polyurethane.
Wherein, the synthesizing biological degradable polyurethane high molecule specifically: polylactic acid, polycaprolactone, poly- hydroxyl second
Acid, polybutene succinic acid, poly lactide-glycolide acid, PLA-PEG copolymer, polyethylencarbonate glycol,
Polyoxyethylene, polytetramethylene ether, polypropylene oxide, polyethylencarbonate glycol, lysine group diisocyanate, 1,6- oneself
One in diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate, Isosorbide-5-Nitrae-fourth diisocyanate
Kind.
Further, the antimicrobial particle refers to that nanometer or micron-sized inorganic antibacterial particle or organic quaternary ammonium salt are anti-
Bacterium particle.
Wherein, the inorganic antibacterial particle are as follows: one of gold, silver, silver oxide, titanium dioxide, zinc oxide are a kind of
Above mixture.
Wherein, the organic quaternary ammonium salt antimicrobial particle are as follows: cetyl trimethylammonium bromide, cetyl pyridinium chlorine
Change ammonium, tetradecyl benzyl dimethyl ammonium chloride, pyridine chlorine bi-quaternary ammonium salt, ammonium dihydrogen phosphate, polyethyleneimine, poly- (4- ethylene
Base) pyridine, one of methylacryoyloxyethyl-benzyl-dimethyl ammonium chloride or more than one mixture.
Further, the amphiphilic polymer with polyhydroxy structure and alkane structure while described is containing hydrophily
The alcohols of polyhydroxy structure, carbohydrate, acids organic molecule and the organic molecule for containing hydrophobic alkane structure, pass through chemistry
Synthetic reaction is had the grafting of hydrophilic segment and hydrophobic segment, block copolymer simultaneously.
A kind of preparation method of the biodegradable polyurethane sheath with antibacterial functions, including
A, biodegradable polyurethane, the amphiphilic polymer with polyhydroxy structure and alkane structure are dissolved respectively
It is distributed in distilled water in organic solvent, then by antimicrobial particle, sealing solution carries out ultrasonic wave or is dispersed with stirring；
B, antimicrobial particle aqueous solution is added dropwise in amphiphilic polymer solution with 1-3 drops/sec of rate, during dropwise addition
Mixing speed is maintained at 100-300 revs/min, is again sealed off solution after being added dropwise, and continues stirring no less than 0.5 hour, obtains
Mixed solution；
C, the b amphiphilic polymer walked and antimicrobial particle mixed solution are stirred to dispersibility, color and is become without obvious
Change, be then added dropwise in polyurethane solutions with 1-3 drops/sec of rate, during dropwise addition mixing speed be maintained at 200-400 turn/
Point, it is again sealed off solution after being added dropwise, 40 DEG C -80 DEG C is warming up to and continues to stir, no less than 0.5 hour, is obtained with antibacterial
The object of the biodegradable polyurethane of function；
D, after mixing evenly to the biodegradable polyurethane mixed system with antibacterial functions, mixing speed is dropped to
100-200 revs/min, temperature is maintained at the steady temperature between 10 DEG C -40 DEG C, the obtained production that lotion is made as sheath
Major ingredient；
E, it is made and the additive that mass percentage is no more than 0.2% is added in lotion, condom manufacture work routinely
Biodegradable sheath is prepared in skill.
Further, the organic solvent is specially acetone, methylene chloride, chloroform, tetrahydrofuran, petroleum ether, second
One of acetoacetic ester, dimethylformamide, dimethyl sulfoxide, pyridine, toluene.
The beneficial effects of the present invention are the surfaces of, antimicrobial particle by amphipathic with polyhydroxy structure and alkane structure
Polymer overmold connection, the organic molecule of connection is that had hydrophilic segment and hydrophobic segment simultaneously by chemosynthesis reaction
Grafting, block copolymer, the antimicrobial particle after cladding has excellent amphipathic, can fairly evenly be dispersed in polyurethane polyureas
It closes in object；The polyether polyols for being added to antimicrobial particle can significantly improve the property such as solidification, dispersion, film forming of sheath
Can, reduce the addition of other additives；Antimicrobial particle and biodegradable polyether polyols two-phase are tightly combined, material sheet
Body, which has, kills or inhibits the antibacterial functions such as various microorganisms, mould, enhances bacteriostasis in production, use process.
Specific embodiment
Below with reference to embodiment, the invention will be further described, is related to polyurethane, antimicrobial particle, amphiphilic polymer etc.
Component and additional proportion include but are not limited to by example.
Embodiment 1
Polyethylene glycol-polycaprolactone cladding connection Nano silver grain:
100 grams of polyethylene glycol-polycaprolactone amphiphilic polymers with polyhydroxy structure and alkane structure are dissolved in
In organic solvent dichloromethane；35 grams of silver-colored antimicrobial nano particle is distributed in distilled water, sealing solution carries out ultrasonic wavelength-division
It dissipates；Silver-colored antimicrobial nano particle aqueous solution is added dropwise to polyethylene glycol-polycaprolactone amphiphilic polymer with 1-3 drops/sec of rate
In solution, mixing speed is maintained at 100 revs/min during dropwise addition, is again sealed off solution after being added dropwise, and continues stirring and is no less than
0.5 hour, obtain mixed solution.Obtained mixed solution has coated polyethylene glycol-polycaprolactone amphiphilic polymer
The emulsion system of silver-colored antimicrobial nano particle, in order to keep cladding organic molecule silver-colored antimicrobial nano particle stability, lotion body
It ties up to and 100 revs/min of speed is maintained to stir under confined conditions, to compound in next step.
Composite modified Nano silver grain/polyaminoester emulsion:
350 grams, the biodegradable polycaprolactone that average molecular weight is 400000 are dissolved in dichloromethane solvent；
By the mixed solution of polyethylene glycol-polycaprolactone amphiphilic polymer that back obtains and silver-colored antimicrobial nano particle stir to point
Property, color are dissipated without significant change；Then it is added dropwise in polycaprolactone solution with 1-3 drops/sec of rate, stirs speed during being added dropwise
Degree is maintained at 300 revs/min；It is again sealed off solution after being added dropwise, is warming up to 40 DEG C and continues to stir, no less than 0.5 hour, obtains
The object of biodegradable polyurethane sheath with antibacterial functions.
Embodiment 2
This example is substantially the same manner as Example 1, and the different antimicrobial particles for being simply that addition is 1 gram of nanometer grade gold antibacterial
Particle.
Embodiment 3
This example is substantially the same manner as Example 1, and the different antimicrobial particles for being simply that addition is 60 grams of micron-sized silver oxides
Inorganic antibacterial particle.
Embodiment 4
This example is substantially the same manner as Example 1, and the different antimicrobial particles for being simply that addition is 40 grams of nanometer level silver oxides
With the inorganic composite antimicrobial particle of 1 gram of nanometer grade gold.
Embodiment 5
This example is substantially the same manner as Example 1, and the different antimicrobial particles for being simply that addition is 50 grams of nanometer-level silvers and 40
The inorganic composite antimicrobial particle of gram micron order zinc oxide.
Embodiment 6
This example is substantially the same manner as Example 1, and the different antimicrobial particles for being simply that addition is 30 grams of nanoscale titanium dioxides
Titanium, 30 grams of Nano-class zinc oxides, 30 grams of nanometer level silver oxides inorganic composite antimicrobial particle.
Embodiment 7
This example is substantially the same manner as Example 1, except that: the amphiphilic with polyhydroxy structure and alkane structure of addition
Property polymer be 100 grams of polyethylene glycol-polylactic acid amphiphilic polymers, and be dissolved in the solvent of chloroform, wait be completely dissolved
Afterwards, solution system is placed in and is dispersed with stirring under confined conditions.
Embodiment 8
This example is substantially the same manner as Example 1, it is different be simply that addition with polyhydroxy structure and alkane structure
Polyvinyl alcohol-polylactic acid polymer that amphiphilic polymer is 100 grams.
Embodiment 9
This example is substantially the same manner as Example 1, it is different be simply that addition with polyhydroxy structure and alkane structure
Polyvinyl alcohol-polycaprolactone polymer that amphiphilic polymer is 100 grams.
Embodiment 10
This example is substantially the same manner as Example 1, except that: the amphiphilic with polyhydroxy structure and alkane structure of addition
Property polymer be 100 grams of glucose-polycaprolactone polymer.
Embodiment 11
This example is substantially the same manner as Example 1, except that: the amphiphilic with polyhydroxy structure and alkane structure of addition
Property polymer be 100 grams of glucose-polylactic acid polymer.
Embodiment 12
This example is substantially the same manner as Example 1, except that: the amphiphilic with polyhydroxy structure and alkane structure of addition
Property polymer be 100 grams of sucrose-polycaprolactone polymer.
Embodiment 13
This example is substantially the same manner as Example 1, except that: the amphiphilic with polyhydroxy structure and alkane structure of addition
Property polymer be 100 grams of fructose-polylactic acid polymer.
Embodiment 14
This example is substantially the same manner as Example 1, except that: the amphiphilic with polyhydroxy structure and alkane structure of addition
Property polymer be 100 grams of starch-polycaprolactone polymer.
Embodiment 15
This example is substantially the same manner as Example 1, except that: the amphiphilic with polyhydroxy structure and alkane structure of addition
Property polymer be 100 grams of chitosan-polylactic acid polymer.
Embodiment 16
This example is substantially the same manner as Example 1, except that: compound synthesizing biological degradable polyurethane high molecule is
400 grams, the biodegradable polylactic acid that average molecular weight is 500000, are dissolved in acetone solvent.
Embodiment 17
This example is substantially the same manner as Example 1, except that: compound synthesizing biological degradable polyurethane high molecule is
450 grams, the biodegradable polyglycolic acid that average molecular weight is 200000.
Embodiment 18
This example is substantially the same manner as Example 1, except that: compound synthesizing biological degradable polyurethane high molecule is
400 grams, the biodegradable poly lactide-glycolide acid that average molecular weight is 400000.
Embodiment 19
This example is substantially the same manner as Example 1, except that: compound synthesizing biological degradable polyurethane high molecule is
400 grams, the biodegradable lysine group diisocyanate that average molecular weight is 600000.
Embodiment 20
This example is substantially the same manner as Example 1, except that: compound synthesizing biological degradable polyurethane high molecule is
400 grams, the biodegradable isophorone diisocyanate that average molecular weight is 500000.
Embodiment 21
This example is substantially the same manner as Example 1, except that: compound synthesizing biological degradable polyurethane high molecule is
400 grams, the biodegradable dicyclohexyl methyl hydride diisocyanate that average molecular weight is 400000.
Embodiment 22
This example is substantially the same manner as Example 1, except that: compound synthesizing biological degradable polyurethane high molecule is
380 grams, the modified cellulose-copolymer of poly lactic acid of the natural Biodegradable high-molecular that average molecular weight is 800000.
Embodiment 23
This example is substantially the same manner as Example 1, except that: compound synthesizing biological degradable polyurethane high molecule is
380 grams, the modified starch-polycaprolactone co-polymer of the natural Biodegradable high-molecular that average molecular weight is 1000000.
Embodiment 24
This example is substantially the same manner as Example 1, except that: compound synthesizing biological degradable polyurethane high molecule is
400 grams, the modified chitosan-polyvinyl alcohol copolymer of the natural Biodegradable high-molecular that average molecular weight is 600000.
Embodiment 25
This example is substantially the same manner as Example 1, except that: the biodegradable polyurethane macromolecule of compound synthesis is
450 grams, the modified lignin-ethylene glycol copolymer of the natural Biodegradable high-molecular that average molecular weight is 400000.
Embodiment 26
This example is substantially the same manner as Example 1, except that: compound synthesizing biological degradable polyurethane high molecule is
450 grams, the modified tannin-copolymer of poly lactic acid of the natural Biodegradable high-molecular that average molecular weight is 500000.
Embodiment 27
Polyethylene glycol-polycaprolactone cladding connection cetyl trimethylammonium bromide antimicrobial particle:
100 grams of polyethylene glycol-polycaprolactone amphiphilic polymers with polyhydroxy structure and alkane structure are dissolved in
In organic solvent dichloromethane；40 grams of cetyl trimethylammonium bromide antimicrobial particle is distributed in distilled water, is sealed molten
Liquid carries out ultrasonic wave dispersion；Cetyl trimethylammonium bromide antimicrobial particle aqueous solution is added dropwise to 1-3 drops/sec of rate poly-
In ethylene glycol-polycaprolactone amphiphilic polymer solution, mixing speed is maintained at 100 revs/min, after being added dropwise during dropwise addition
It is again sealed off solution, continues stirring no less than 0.5 hour, obtains mixed solution.Obtained mixed solution is to have coated poly- second
The emulsion system of glycol-polycaprolactone amphiphilic polymer cetyl trimethylammonium bromide antimicrobial particle, in order to keep wrapping
The stability of the cetyl trimethylammonium bromide antimicrobial particle of organic molecule is covered, emulsion system maintains 100 in confined conditions
Rev/min speed stirring, in next step it is compound.
Composite modified cetyl trimethylammonium bromide antimicrobial particle/polyaminoester emulsion:
350 grams, the biodegradable polycaprolactone that average molecular weight is 400000 are dissolved in dichloromethane solvent；
Polyethylene glycol-polycaprolactone amphiphilic polymer that back is obtained and cetyl trimethylammonium bromide antimicrobial particle it is mixed
Solution is closed to stir to dispersibility, color without significant change；Then it is added dropwise in polycaprolactone solution, is dripped with 1-3 drops/sec of rate
Mixing speed is maintained at 300 revs/min during adding；It is again sealed off solution after being added dropwise, is warming up to 40 DEG C and continues to stir, much
In 0.5 hour, the object of the biodegradable polyurethane sheath with antibacterial functions is obtained.
Embodiment 28
This example is substantially the same manner as Example 27, and the different organic quaternary ammonium salt antimicrobial particles for being simply that addition is 40
Gram methylacryoyloxyethyl-benzyl-dimethyl ammonium chloride organic anti-bacterial particle.
Embodiment 29
This example is substantially the same manner as Example 27, and the different organic quaternary ammonium salt antimicrobial particles for being simply that addition is 40
Gram cetyl pyridinium ammonium chloride organic anti-bacterial particle.
Embodiment 30
This example is substantially the same manner as Example 27, and the different organic quaternary ammonium salt antimicrobial particles for being simply that addition is 40
Gram tetradecyl benzyl dimethyl ammonium chloride organic anti-bacterial particle.
Embodiment 31
This example is substantially the same manner as Example 27, and the different organic quaternary ammonium salt antimicrobial particles for being simply that addition is 40
Gram pyridine chlorine bi-quaternary ammonium salt organic anti-bacterial particle.
Embodiment 32
This example is substantially the same manner as Example 27, except that: the organic quaternary ammonium salt antimicrobial particle of addition is 20 grams of phosphorus
The organic composite antibiotic particle of acid dihydride ammonium and 20 grams of polyethyleneimines.
Embodiment 33
This example is substantially the same manner as Example 27, except that: the organic quaternary ammonium salt antimicrobial particle of addition is 15 grams of phosphorus
The organic composite antibiotic particle of acid dihydride ammonium and 25 grams of poly- (4- vinyl) pyridine.
Embodiment 34
This example is substantially the same manner as Example 27, except that: the organic quaternary ammonium salt antimicrobial particle of addition is 10 grams
Tetradecyl benzyl dimethyl ammonium chloride and 30 grams of methylacryoyloxyethyl-benzyl-dimethyl ammonium chloride organic composite
Antimicrobial particle.
Embodiment 35
This example is substantially the same manner as Example 27, except that: the organic quaternary ammonium salt antimicrobial particle of addition is 10 grams
Ammonium dihydrogen phosphate, 10 grams of polyethyleneimine, 20 grams of cetyl pyridinium ammonium chloride organic composite antibiotic particle.
Embodiment 36
This example is substantially the same manner as Example 27, except that: the pyrrole that the organic quaternary ammonium salt antimicrobial particle of addition is 5 grams
Pyridine chlorine bi-quaternary ammonium salt, 15 grams of poly- (4- vinyl) pyridine, 15 grams of methylacryoyloxyethyl-benzyl-dimethyl ammonium chloride
Organic composite antibiotic particle.
Embodiment 37
This example is substantially the same manner as Example 27, except that: two with polyhydroxy structure and alkane structure of addition
Parent's property polymer is 100 grams of polyethylene glycol-polylactic acid amphiphilic polymers, and is dissolved in the solvent of chloroform, to completely molten
Solution system is placed in and is dispersed with stirring under confined conditions by Xie Hou.
Embodiment 38
This example is substantially the same manner as Example 27, it is different be simply that addition there is polyhydroxy structure and alkane structure
Amphiphilic polymer be 120 grams of polyvinyl alcohol-polylactic acid polymer.
Embodiment 39
This example is substantially the same manner as Example 27, except that: two with polyhydroxy structure and alkane structure of addition
Glucose-polylactic acid polymer that parent's property polymer is 110 grams.
Embodiment 40
This example is substantially the same manner as Example 27, except that: two with polyhydroxy structure and alkane structure of addition
Sucrose-polycaprolactone polymer that parent's property polymer is 100 grams.
Embodiment 41
This example is substantially the same manner as Example 27, except that: two with polyhydroxy structure and alkane structure of addition
Starch-polycaprolactone polymer that parent's property polymer is 130 grams.
Embodiment 42
This example is substantially the same manner as Example 27, except that: compound synthesizing biological degradable polyurethane high molecule is
400 grams, the biodegradable polylactic acid that average molecular weight is 400000, are dissolved in acetone solvent.
Embodiment 43
This example is substantially the same manner as Example 27, except that: compound synthesizing biological degradable polyurethane high molecule is
400 grams, the biodegradable lysine group diisocyanate that average molecular weight is 600000.
Embodiment 44
This example is substantially the same manner as Example 27, except that: compound synthesizing biological degradable polyurethane high molecule is
380 grams, the modified cellulose-copolymer of poly lactic acid of the natural Biodegradable high-molecular that average molecular weight is 800000.
Embodiment 45
Polyethylene glycol-polycaprolactone cladding connection silver oxide/cetyl trimethylammonium bromide composite antibacterial particle:
100 grams of polyethylene glycol-polycaprolactone amphiphilic polymers with polyhydroxy structure and alkane structure are dissolved in
In organic solvent dichloromethane；40 grams of silver oxide antimicrobial nano particle is distributed in distilled water, sealing solution carries out ultrasound
Wavelength-division dissipates；Separately 40 grams of cetyl trimethylammonium bromide antimicrobial particle is added in ethyl alcohol, dispersing and dissolving under magnetic agitation；
The mixed solution system of silver oxide antimicrobial particle and distilled water is added dropwise to cetyl trimethyl bromine with 1-3 drops/sec of rate
In the solution for changing ammonium, seals and mechanical stirring mixes, again ultrasonic disperse 30 minutes；Obtained silver oxide/cetyl front three
Base ammonium bromide composite antibacterial particle composite solution is added dropwise to the amphipathic polymerization of polyethylene glycol-polycaprolactone with 1-3 drops/sec of rate
In object solution, mixing speed is maintained at 100 revs/min during dropwise addition, is again sealed off solution after being added dropwise, and it is many to continue stirring
In 0.5 hour, mixed solution is obtained.Obtained mixed solution is to have coated polyethylene glycol-polycaprolactone amphiphilic polymer
Silver oxide/cetyl trimethylammonium bromide composite antibacterial particle emulsion system, in order to keep cladding organic molecule oxygen
Change silver/cetyl trimethylammonium bromide composite antibacterial particle stability, emulsion system maintain in confined conditions 100 turns/
The speed stirring divided, to compound in next step.
Composite antibacterial particle/polyaminoester emulsion:
350 grams, the biodegradable polycaprolactone that average molecular weight is 400000 are dissolved in dichloromethane solvent；
The polyethylene glycol-polycaprolactone amphiphilic polymer and silver oxide/cetyl trimethylammonium bromide that back is obtained are compound
The mixed solution of antimicrobial particle is stirred to dispersibility, color without significant change；Then it is added dropwise to 1-3 drops/sec of rate and gathers oneself
In lactone solution, mixing speed is maintained at 300 revs/min during dropwise addition；It is again sealed off solution after being added dropwise, is warming up to 40 DEG C
Continue to stir, no less than 0.5 hour, obtains the object of the biodegradable polyurethane sheath with antibacterial functions.
Embodiment 46
This example and embodiment 45 are essentially identical, except that: the organic quaternary ammonium salt antimicrobial particle of addition is 30 grams
Methylacryoyloxyethyl-benzyl-dimethyl ammonium chloride organic anti-bacterial particle, the nanometer that the inorganic antibacterial particle of addition is 40 grams
The silver-colored inorganic antibacterial particle of grade.
Embodiment 47
This example and embodiment 45 are essentially identical, except that: the organic quaternary ammonium salt antimicrobial particle of addition is 50 grams
Tetradecyl benzyl dimethyl ammonium chloride organic anti-bacterial particle, the Nano-class zinc oxide that the inorganic antibacterial particle of addition is 30 grams without
Machine antimicrobial particle.
Embodiment 48
This example and embodiment 45 are essentially identical, except that: the nanoscale oxygen that the inorganic antibacterial particle of addition is 20 grams
Change the inorganic composite antimicrobial particle of silver with 20 grams of Nano-class zinc oxide.First 20 grams of nanometer level silver oxide inorganic antibacterial particles are added
Enter into distilled water, disperses 30 minutes under ultrasonic wave and magnetic agitation；Continuously add 20 grams of Nano-class zinc oxide inorganic antibacterial grains
Son disperses 1 hour or more still under ultrasonic wave and magnetic agitation.By the mixed of the inorganic composite antimicrobial particle of silver oxide and zinc oxide
It closes solution system to be added dropwise in the solution of cetyl trimethylammonium bromide with 1-3 drops/sec of rate, seals and mechanical stirring is mixed
It closes, again ultrasonic disperse 30 minutes.It finally obtains: having coated polyethylene glycol-polycaprolactone amphiphilic with antibacterial functions
Property polymer oxidation silver/zinc oxide/cetyl trimethylammonium bromide composite antibacterial particle and polyurethane it is biodegradable
The object of sheath.
Embodiment 49
This example and embodiment 45 are essentially identical, except that: the nanoscale two that the inorganic antibacterial particle of addition is 10 grams
Titanium oxide, 10 grams of Nano-class zinc oxide, 10 grams of nanometer level silver oxide inorganic composite antimicrobial particle.Inorganic composite antimicrobial grain
Son solution preparation method are as follows: three kinds of inorganic antibacterial particles are added sequentially in distilled water, every time be added after, at least ultrasonic wave and
Magnetic agitation is dispersed 30 minutes, and second of antimicrobial particle is added.It finally obtains: having coated poly- second with antibacterial functions
Glycol-polycaprolactone amphiphilic polymer titanic oxide/zinc oxide/silver oxide/cetyl trimethylammonium bromide is compound anti-
The object of the biodegradable sheath of bacterium particle and polyurethane.
Embodiment 50
Condom manufacture experiment:
1000 grams of the titanium dioxide/cetyl trimethyl for having coated polyethylene glycol-polycaprolactone amphiphilic polymer
The composition polymer of ammonium bromide composite antibacterial particle and polycaprolactone is added in 5000 milliliters of toluene, at 150 revs/min
It is dissolved under mixing speed；Then 1 gram of defoaming agent, 0.5 gram of anti-aging agent are sequentially added；After all components are sufficiently mixed, cream is made
Liquid；Cover production procedure by conventional contraceptive, finally obtain with antibacterial functions to have coated polyethylene glycol-polycaprolactone amphipathic
The biodegradable contraception of the titanium dioxide of polymer/cetyl trimethylammonium bromide composite antibacterial particle and polycaprolactone
Set.
Application experiment:
In ingredient assessment, it is micro- less than 0.2 that the biodegradable sheath with antibacterial functions contains water soluble protein
Gram gram, the content of nitrosamine does not contain accelerator M BT less than 0.2 micro- gram gram；In the detection of performance, according to China
- 7544 detection method of sheath quality testing standard GB/T, electric-examination are not detected as pin hole, and explosion volume is greater than 28L, explosion
Pressure is greater than 3.0KPa, tensile strength 28MPa；In antibacterial experiment, the bacteriostasis rate of various microorganisms, mould is inhibited to reach
99.9% or more.
Claims (10)
1. a kind of biodegradable polyurethane sheath with antibacterial functions, which is characterized in that the group including following parts by weight
Point:
(A) biodegradable polyurethane: 65%-90%；
(B) there is polyhydroxy structure to connect modified antimicrobial particle: 10%- with the amphiphilic polymer of alkane structure simultaneously
35%；The mass percentage content wherein simultaneously with the amphiphilic polymer of polyhydroxy structure and alkane structure is 35%-
75%, the mass percentage content of antimicrobial particle is 25%-65%；
The biodegradable polyurethane is polyurethane high molecule, average molecular weight 300000-2000000.
2. a kind of biodegradable polyurethane sheath with antibacterial functions according to claim 1, which is characterized in that
The biodegradable polyurethane is natural Biodegradable high-molecular modified polyurethane or the poly- ammonia of synthesizing biological degradable
Ester macromolecule.
3. a kind of biodegradable polyurethane sheath with antibacterial functions according to claim 2, which is characterized in that
The natural Biodegradable high-molecular modified polyurethane specifically: cellulose modified polyurethane, chitin modified polyurethane,
One of starch conversion polyurethane, lignin modification polyurethane, tannin modified polyurethane.
4. a kind of biodegradable polyurethane sheath with antibacterial functions according to claim 2, which is characterized in that
The synthesizing biological degradable polyurethane high molecule specifically: polylactic acid, polycaprolactone, polyglycolic acid, polybutene amber
Acid, poly lactide-glycolide acid, PLA-PEG copolymer, polyethylencarbonate glycol, polyoxyethylene, poly- four
Methylene ether, polypropylene oxide, polyethylencarbonate glycol, lysine group diisocyanate, 1, it is hexamethylene-diisocyanate, different
One of isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate, Isosorbide-5-Nitrae-fourth diisocyanate.
5. a kind of biodegradable polyurethane sheath with antibacterial functions according to claim 1, which is characterized in that
The antimicrobial particle refers to nanometer or micron-sized inorganic antibacterial particle or organic quaternary ammonium salt antimicrobial particle.
6. a kind of biodegradable polyurethane sheath with antibacterial functions according to claim 5, which is characterized in that
The inorganic antibacterial particle are as follows: one of gold, silver, silver oxide, titanium dioxide, zinc oxide or more than one mixture.
7. a kind of biodegradable polyurethane sheath with antibacterial functions according to claim 5, which is characterized in that
The organic quaternary ammonium salt antimicrobial particle are as follows: cetyl trimethylammonium bromide, cetyl pyridinium ammonium chloride, myristyl
Dimethyl benzyl ammonium chloride, pyridine chlorine bi-quaternary ammonium salt, ammonium dihydrogen phosphate, polyethyleneimine, poly- (4- vinyl) pyridine, methyl-prop
One of alkene acyloxyethyl-benzyl-dimethyl ammonium chloride or more than one mixture.
8. a kind of biodegradable polyurethane sheath with antibacterial functions according to claim 1, which is characterized in that
Amphiphilic polymer with polyhydroxy structure and alkane structure while described is the alcohol containing hydrophilic polyhydroxy structure
Class, carbohydrate, acids organic molecule and the organic molecule for containing hydrophobic alkane structure, are obtained simultaneously by chemosynthesis reaction
Grafting, block copolymer with hydrophilic segment and hydrophobic segment.
9. a kind of preparation method of the biodegradable polyurethane sheath with antibacterial functions, which is characterized in that including
A, biodegradable polyurethane, the amphiphilic polymer with polyhydroxy structure and alkane structure have been dissolved separately in
In solvent, then antimicrobial particle is distributed in distilled water, sealing solution carries out ultrasonic wave or is dispersed with stirring；
B, antimicrobial particle aqueous solution is added dropwise in amphiphilic polymer solution with 1-3 drops/sec of rate, is stirred during being added dropwise
Speed is maintained at 100-300 revs/min, is again sealed off solution after being added dropwise, and continues stirring no less than 0.5 hour, is mixed
Solution；
C, the b amphiphilic polymer walked and antimicrobial particle mixed solution are stirred to dispersibility, color without significant change, so
It is added dropwise in polyurethane solutions with 1-3 drops/sec of rate afterwards, mixing speed is maintained at 200-400 revs/min during dropwise addition, drop
It is again sealed off solution after adding, is warming up to 40 DEG C -80 DEG C and continues to stir, no less than 0.5 hour, obtains that there are antibacterial functions
The object of biodegradable polyurethane；
D, mixing speed after mixing evenly to the biodegradable polyurethane mixed system with antibacterial functions, is dropped into 100-
200 revs/min, temperature is maintained at the steady temperature between 10 DEG C -40 DEG C, the obtained production master that lotion is made as sheath
Material；
E, it is made and the additive that mass percentage is no more than 0.2% is added in lotion, condom manufacture technique system routinely
It is standby to obtain biodegradable sheath.
10. a kind of preparation method of biodegradable polyurethane sheath with antibacterial functions according to claim 9,
It is characterized in that, the organic solvent be specially acetone, methylene chloride, chloroform, tetrahydrofuran, petroleum ether, ethyl acetate,
One of dimethylformamide, dimethyl sulfoxide, pyridine, toluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811370821.9A CN109568679A (en) | 2018-11-18 | 2018-11-18 | A kind of biodegradable polyurethane sheath and preparation method thereof with antibacterial functions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811370821.9A CN109568679A (en) | 2018-11-18 | 2018-11-18 | A kind of biodegradable polyurethane sheath and preparation method thereof with antibacterial functions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109568679A true CN109568679A (en) | 2019-04-05 |
Family
ID=65922760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811370821.9A Pending CN109568679A (en) | 2018-11-18 | 2018-11-18 | A kind of biodegradable polyurethane sheath and preparation method thereof with antibacterial functions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109568679A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204679A (en) * | 2019-05-20 | 2019-09-06 | 齐鲁工业大学 | A kind of preparation method of modified environment-friendly aqueous polyurethane and its polyurethane of preparation |
| CN111072902A (en) * | 2019-12-30 | 2020-04-28 | 眉山尤博瑞新材料有限公司 | Multilayer condom containing modified polyurethane raw material and preparation method thereof |
| CN113307932A (en) * | 2021-07-14 | 2021-08-27 | 四川轻化工大学 | Polyhydroxyacetic acid-based polyurethane and preparation method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0328421A2 (en) * | 1988-02-11 | 1989-08-16 | The Trustees Of Columbia University In The City Of New York | Infection-resistant compositions, medical devices and surfaces and methods for preparing and using same |
| CN101654499A (en) * | 2009-09-02 | 2010-02-24 | 陈煜� | Composite of natural macromolecule or amphiphilic grafting copolymer of water-soluble derivant and nanometer iodine and preparation method thereof |
| CN101735636A (en) * | 2008-11-12 | 2010-06-16 | 福建恒安集团有限公司 | Biodegradation time controlled plastic film and preparation method thereof |
| CN101851359A (en) * | 2010-06-04 | 2010-10-06 | 中国化工橡胶株洲研究设计院 | Antibacterial latex prophylactic and production method thereof |
| CN102671201A (en) * | 2012-05-21 | 2012-09-19 | 同济大学 | Antibacterial nano silver modified polymeric micelle and preparation method thereof |
| SG189569A1 (en) * | 2011-10-17 | 2013-05-31 | Pei Yong Chow | Nano-silver natural rubber (nr) condoms: preparation, characterization and antimicrobial activity |
| CN103585675A (en) * | 2013-11-21 | 2014-02-19 | 无锡中科光远生物材料有限公司 | Anti-bacterial composition as well as controlled-release anti-bacterial film and implant material prepared from same |
| CN104327297A (en) * | 2013-07-22 | 2015-02-04 | 中国人民解放军第三军医大学第一附属医院 | Porous nanometer silver polyurethane film applied to artificial skin and preparation method thereof |
| CN105001434A (en) * | 2015-08-26 | 2015-10-28 | 北京理工大学 | Chitosan-based multifunctional hemostasis microsphere |
| CN105419332A (en) * | 2015-12-24 | 2016-03-23 | 郑州欧姆康生物材料有限公司 | Antibacterial composite material, preparation method and application thereof |
| CN105754322A (en) * | 2016-02-26 | 2016-07-13 | 陈汝霖 | Polyurethane material and preparation method thereof |
| CN107325529A (en) * | 2017-08-15 | 2017-11-07 | 李俊杰 | A kind of composite ultra-thin flexible condom and preparation method thereof |
| US10080822B1 (en) * | 2017-04-21 | 2018-09-25 | Rulin Chen | Use of polyurethane material in the preparation of latex product |
-
2018
- 2018-11-18 CN CN201811370821.9A patent/CN109568679A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0328421A2 (en) * | 1988-02-11 | 1989-08-16 | The Trustees Of Columbia University In The City Of New York | Infection-resistant compositions, medical devices and surfaces and methods for preparing and using same |
| CN101735636A (en) * | 2008-11-12 | 2010-06-16 | 福建恒安集团有限公司 | Biodegradation time controlled plastic film and preparation method thereof |
| CN101654499A (en) * | 2009-09-02 | 2010-02-24 | 陈煜� | Composite of natural macromolecule or amphiphilic grafting copolymer of water-soluble derivant and nanometer iodine and preparation method thereof |
| CN101851359A (en) * | 2010-06-04 | 2010-10-06 | 中国化工橡胶株洲研究设计院 | Antibacterial latex prophylactic and production method thereof |
| SG189569A1 (en) * | 2011-10-17 | 2013-05-31 | Pei Yong Chow | Nano-silver natural rubber (nr) condoms: preparation, characterization and antimicrobial activity |
| CN102671201A (en) * | 2012-05-21 | 2012-09-19 | 同济大学 | Antibacterial nano silver modified polymeric micelle and preparation method thereof |
| CN104327297A (en) * | 2013-07-22 | 2015-02-04 | 中国人民解放军第三军医大学第一附属医院 | Porous nanometer silver polyurethane film applied to artificial skin and preparation method thereof |
| CN103585675A (en) * | 2013-11-21 | 2014-02-19 | 无锡中科光远生物材料有限公司 | Anti-bacterial composition as well as controlled-release anti-bacterial film and implant material prepared from same |
| CN105001434A (en) * | 2015-08-26 | 2015-10-28 | 北京理工大学 | Chitosan-based multifunctional hemostasis microsphere |
| CN105419332A (en) * | 2015-12-24 | 2016-03-23 | 郑州欧姆康生物材料有限公司 | Antibacterial composite material, preparation method and application thereof |
| CN105754322A (en) * | 2016-02-26 | 2016-07-13 | 陈汝霖 | Polyurethane material and preparation method thereof |
| US10080822B1 (en) * | 2017-04-21 | 2018-09-25 | Rulin Chen | Use of polyurethane material in the preparation of latex product |
| CN107325529A (en) * | 2017-08-15 | 2017-11-07 | 李俊杰 | A kind of composite ultra-thin flexible condom and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 段久芳 编著: "《天然高分子材料》", 30 September 2016 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204679A (en) * | 2019-05-20 | 2019-09-06 | 齐鲁工业大学 | A kind of preparation method of modified environment-friendly aqueous polyurethane and its polyurethane of preparation |
| CN110204679B (en) * | 2019-05-20 | 2021-08-31 | 齐鲁工业大学 | Preparation method of modified environment-friendly waterborne polyurethane and polyurethane prepared by same |
| CN111072902A (en) * | 2019-12-30 | 2020-04-28 | 眉山尤博瑞新材料有限公司 | Multilayer condom containing modified polyurethane raw material and preparation method thereof |
| CN111072902B (en) * | 2019-12-30 | 2020-09-08 | 眉山尤博瑞新材料有限公司 | Multilayer condom containing modified polyurethane raw material and preparation method thereof |
| CN113307932A (en) * | 2021-07-14 | 2021-08-27 | 四川轻化工大学 | Polyhydroxyacetic acid-based polyurethane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hu et al. | Formation of self-assembled polyelectrolyte complex hydrogel derived from salecan and chitosan for sustained release of Vitamin C | |
| CN109568679A (en) | A kind of biodegradable polyurethane sheath and preparation method thereof with antibacterial functions | |
| Bera et al. | Carboxymethyl fenugreek galactomannan-gellan gum-calcium silicate composite beads for glimepiride delivery | |
| CN103502356B (en) | The blend of poly(lactic acid) and water-soluble polymers | |
| WO2010015419A2 (en) | Continuous fiber layer comprising an active substance on the basis of bio-polymers, the use thereof, and method for the production thereof | |
| WO2017135498A1 (en) | Temperature sensitive hydrogel composition including nucleic acid and chitosan | |
| EP2323635A2 (en) | Fibrous surface structure containing active ingredients with controlled release of active ingredients, use thereof and method for the production thereof | |
| CN110200925A (en) | Oxycellulose microsphere and composition | |
| CN109957882A (en) | A kind of nano fibrous membrane and preparation method thereof | |
| Zhao et al. | Preparation and characterization of antibacterial poly (lactic acid) nanocomposites with N-halamine modified silica | |
| Bera et al. | Ziprasidone-loaded arabic gum modified montmorillonite-tailor-made pectin based gastroretentive composites | |
| Fink | Handbook of Engineering and Specialty Thermoplastics, Volume 2: Water Soluble Polymers | |
| CN102976660A (en) | Disposable disperse re-dispersible emulsion powder | |
| CN107298836A (en) | A kind of graphene crystal composite polylactic acid anti-biotic material and preparation method thereof | |
| CN101205304A (en) | Starch microspheres and method for preparing the same | |
| Chen et al. | Biocomposites with tunable properties from poly (lactic acid)-based copolymers and carboxymethyl cellulose via ionic assembly | |
| US9505916B2 (en) | Gel-like mass comprising natural or synthetic polymers and method for producing the gel-like mass | |
| Jena et al. | New strategies for the construction of eggshell powder reinforced starch based fire hazard suppression biomaterials with tailorable thermal, mechanical and oxygen barrier properties | |
| CN103289408A (en) | Method for preparing silicon rubber | |
| JP2004504445A (en) | Composition and film for capsule production | |
| DE60107555T2 (en) | Thermoplastic polyamic compounds with improved impact resistance | |
| CN102304259B (en) | Preparation method of fibroin blending material with gradually degrading performance | |
| CN101492560A (en) | Polyvinyl alcohol hydrogel releasing negative ion and method of producing the same | |
| CN101314650A (en) | Nano-scale chitosan and latex coblended antibiont and preparation method thereof | |
| CN109575379B (en) | starch grafted isocyanate modified natural latex condom and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190405 |
|
| RJ01 | Rejection of invention patent application after publication |