CN101302345A - Modified water-soluble organosilicon for latex catheter and preparation thereof - Google Patents

Modified water-soluble organosilicon for latex catheter and preparation thereof Download PDF

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Publication number
CN101302345A
CN101302345A CNA2007100404522A CN200710040452A CN101302345A CN 101302345 A CN101302345 A CN 101302345A CN A2007100404522 A CNA2007100404522 A CN A2007100404522A CN 200710040452 A CN200710040452 A CN 200710040452A CN 101302345 A CN101302345 A CN 101302345A
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Prior art keywords
latex
parts
organic silicon
coating
water
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胡若明
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SHANGHAI XILIKANG HI-TECH PARTNER Co
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SHANGHAI XILIKANG HI-TECH PARTNER Co
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Abstract

The invention discloses water-soluble organic silicon latex used for surface modification of a latex catheter and a method for preparing the same. The compositions by weight portion of the water-soluble organic silicon latex are: 75 to 85 portions of coating agent latex AR, 10 to 15 portions of accelerant BR, and 5 to 10 portions of catalyst CR. The water-soluble organic silicon latex can be used for coating treatment of organic silicon materials of the latex catheter. The water-soluble organic silicon latex which is an aqueous coating agent has the advantages of convenient and safe technological operation without the three wastes pollution, suitable coated interlinkage with good adhesiveness and stretchability, smooth surface without pastiness, crack or shedding, better smoothness, easy insertion and less irritability, good biocompatibility, blockage prevention and no adverse effect to a patient if the latex is reserved in a body.

Description

Be used for waterborne organic silicon emulsion of latex catheter surface modification and preparation method thereof
Technical field
The present invention relates to a kind of latex catheter and preparation method thereof, relate in particular to a kind of latex catheter of surface modification.
Background technology
The natural emulsion conduit is that hospital a kind of medical apparatus, particularly severe and operation patients usage rate commonly used are very big.
Yet the pros and cons when self material of latex catheter and production technique thereof have determined that it uses: raw material sources are abundant.Cheap, goods have physical strength preferably.But the technology of the ion pickling process that generally adopts at present production conduit has been added auxiliary agents such as peptizer, vulcanizing agent in process of production, and having caused in the goods human body being had irritating soluble material increases greatly., keep somewhere easily and stop up in patient's use as latex catheter, tissue reaction is big, and patient is difficult to stand, and is easy to generate side effect.
People synthetic plastics successively occurred in this medicine equipment development to medical catheter, the conduit of various material such as pure silicon rubber.But the plastic catheter material is harder, and poor flexibility is used very inconvenient.The pure silicon rubber catheter is at tearing toughness, and tensile strength etc. are all not as the natural emulsion conduit, and price is managed slightly, adopt disposable conduit in current opinion especially, in order to avoid the age of superinfection, the pure silicon rubber catheter obviously can not be as first-elected product above the price of 2 to 3 times in natural emulsion conduit.
In recent years, there is report to adopt organic silicon coating that latex catheter is carried out surface treatment abroad, do the mechanical property that can keep the natural emulsion excellence like this, the market value that can compete, can make full use of the peculiar excellent biological compatibility of organosilicon material again, nonpoisonous and tasteless, to performance such as human body is non-stimulated, someone once did the work of a large amount of this respects, explored and did basic material with silicon rubber, was mixed with the slurry of solvent type condensation or add-on type, adopting silicone couplet is middle bridge, increase the adhesiveproperties with the latex surface, on the latex catheter surface and internal layer coated silicon materials, work has obtained certain progress.But its weak point is conspicuous: surface lubrication is poor, and coating easily comes off, conduit that can't coated band air bag.Its elongation is more than 700% when expanding because of the air bag position, and general silicon rubber is unapproachable.Showing as coating cracking can't normally use.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of waterborne organic silicon emulsion that is used for the latex catheter surface modification and preparation method thereof, to overcome the above-mentioned defective that prior art exists, satisfy the needs in relevant field.
Said waterborne organic silicon emulsion, its component and parts by weight comprise:
The coating-forming agent latex A R75~85 parts
Promotor emulsion B R10~15 parts
Catalyzer C R5~10 parts
Said catalyzer C RBe selected from a kind of in sodium hydroxide, Platinic chloride, Tetramethylammonium hydroxide or the dibutyl tin dilaurate;
Said coating-forming agent latex A RComponent and parts by weight comprise:
20~30 parts of coating-forming agent A
Emulsifying agent E 13~10 parts
Emulsifying agent E 23~5 parts
Dispersion agent D 11~5 part
60~70 parts in water
Said promotor emulsion B RComponent and parts by weight comprise:
20~30 parts of accelerant B
Emulsifying agent E 13~10 parts
Emulsifying agent E 23~5 parts
60~70 parts in water
Said emulsifying agent E 1Be selected from a kind of in Sodium dodecylbenzene sulfonate, bromogeramine, octyl phenol polyene ether (OP-10) or the sorbitan list olein Soxylat A 25-7 oxygen second, can adopt the commercially available prod, help the product of fine chemistry industry company as auxiliary reagent factory, Shanghai, sky, Tianjin;
Said emulsifying agent E 2Be selected from a kind of in Sodium dodecylbenzene sulfonate, bromogeramine, octyl phenol polyene ether (OP-10) or the sorbitan list olein Soxylat A 25-7, can adopt the commercially available prod, help the product of fine chemistry industry company as auxiliary reagent factory, Shanghai, sky, Tianjin;
Emulsifying agent E 1With emulsifying agent E 2Do not adopt with a kind of material;
Said dispersion agent D 1Be selected from dispersion agent WA, fatty alcohol-polyoxyethylene ether (IW), cellulose sulfuric acid ester and receive a kind of product in (dispersing agent C S) as auxiliary reagent factory, Shanghai, Earthquake of Anyang station in Henan auxiliary reagent factory.
The general structure of said coating-forming agent A is as follows:
Figure A20071004045200081
Wherein: x=2~4, n=1~2, m=20~50;
Rs is NH 2, H, CH=CH 2Or SH;
The general structure of said coating-forming agent B is as follows:
Figure A20071004045200091
R TBe NH 2, H, CH=CH 2Or SH; N=1~5, p=30~80;
Said coating-forming agent A is preparation like this:
To be with active group R 1Siloxanes oligopolymer (1) and octamethylcyclotetrasiloxane (2), reaction in the presence of basic catalyst, obtain intermediate, temperature of reaction is 60~80 ℃, and the reaction times is 1~2 hour, then with hexamethyldisiloxane (3), reaction in the presence of basic catalyst, temperature of reaction is 90~110 ℃, and the reaction times is 2~3 hours, obtains coating-forming agent A;
Said band active group R 1The siloxanes oligopolymer can adopt the commercially available prod, as the product of spark chemical plant, Jiangxi, Zhejiang Xinan Chemical Industry Group Co.Ltd;
Said basic catalyst is selected from a kind of in sodium hydroxide, potassium hydroxide, the Tetramethylammonium hydroxide;
The mol ratio of reaction raw materials is:
Band active group R sThe siloxanes oligopolymer: octamethylcyclotetrasiloxane=1: 60~80;
Band active group R SThe siloxanes oligopolymer: hexamethyldisiloxane=1: 5~10;
The add-on of basic catalyst is respectively band active group R SSiloxanes oligopolymer weight 0.5~1.5%;
Reaction expression is as follows:
Figure A20071004045200101
Wherein: x=2~4, n=1~2, m=20~50;
Rs is NH 2, H, CH=CH 2Or SH;
Said accelerant B is preparation like this:
To be with active group R TSiloxanes oligopolymer and dimethyldichlorosilane(DMCS), the tri-methyl-chlorosilane cohydrolysis stirs and to drip sour water down, obtains intermediate.Add an acidic catalyst then, reaction, temperature of reaction is 90~100 ℃, the reaction times is 2~3 hours.Obtain accelerant B;
Said an acidic catalyst is selected from hydrochloric acid, sulfuric acid, Glacial acetic acid or Platinic chloride;
Band active group R TThe siloxanes oligopolymer can adopt the commercially available prod, as the product of spark chemical plant, Jiangxi, Zhejiang Xinan Chemical Industry Group Co.Ltd;
The mol ratio of reaction raw materials is:
Band active group R TThe siloxanes oligopolymer: dimethyldichlorosilane(DMCS): tri-methyl-chlorosilane==1: 40~50: 5~10;
The add-on of an acidic catalyst is band active group R TSiloxanes oligopolymer weight 2~5%;
Reaction expression is as follows:
Figure A20071004045200111
Wherein: R TBe NH 2, H, CH=CH 2Or SH; N=1~5, p=30~80;
The coating-forming agent latex A RPreparation comprise the steps:
With coating-forming agent A, emulsifying agent E 1, E 2, dispersion agent D 1And water, by homogenate pump homogenate, obtain the coating-forming agent latex A R
The pH value is 8~10, and its centrifugal stability is: under the 3000r/min whizzer, 15min is not stratified;
Promotor emulsion B RPreparation
With accelerant B, emulsifying agent E 1, E 2Pass through homogenate pump homogenate with water, obtain promotor emulsion B R
The pH value is 4~6, and its centrifugal stability is: under the 3000r/min whizzer, 15min is not stratified;
With the coating-forming agent latex A R, promotor emulsion B RCR proportionally mixes with catalyzer, promptly obtains waterborne organic silicon emulsion of the present invention.
Waterborne organic silicon emulsion of the present invention, the organosilicon material coated that can be used for latex catheter is handled, and using method is as follows:
(1) latex catheter that will need coated to handle impregnated in the treatment solution, (chlorinated lime: hydrochloric acid: deionized water=0.8: 1.0: 98.2), take out behind 3~4min and be placed on rinse in the water, drying;
(2) coated is handled:
It is 4%~5% that above-mentioned waterborne organic silicon emulsion is diluted with water to the weight solid content, then step (1) be impregnated in wherein 2~3min through pretreated latex catheter, make treatment solution fully enter in the tube chamber, take out the surplus liquid of drip-dry, behind the room temperature surface drying, 130~140 ℃ solidify 2~4min, and cooling gets final product.
Waterborne organic silicon emulsion of the present invention, be the water aqua type coating-forming agent, technological operation convenience, safety, three-waste free pollution, the coating interlinkage is appropriate, tack, stretchiness are good, smooth surface is not clamminess, not chapping comes off, and the latex catheter oilness behind the coated is better, insertion is easy, pungency is littler, good biocompatibility, keep somewhere and be difficult for obstruction in the body, the patient does not have bad reflection.
Embodiment
Embodiment 1
200g is with active group R sSiloxanes oligopolymer (1) and 1700g octamethylcyclotetrasiloxane (2), 150g hexamethyldisiloxane (3) is reacted in the presence of 3 gram basic catalyst Tetramethylammonium hydroxide, 90~110 ℃ of temperature of reaction, the reaction times is to obtain coating-forming agent A in 3`4 hour;
X=3 wherein; R SFor-NH 2, n=1, m=45;
With 28 kilograms of above-mentioned coating-forming agent A, 1.4 kilograms of emulsifying agent E 1Octyl phenol polyene ether (OP-10) and 1 kilogram of E 2Sorbitan list olein Soxylat A 25-7,5 kilograms of dispersion agent D 1IW and 80 kg of water by homogenate pump homogenate, obtain the coating-forming agent latex A RWhite milk sap does not have mechanical impurity, and the pH value is 8~10, and its centrifugal stability is: under the 3000r/min whizzer, 15min is not stratified.
Emulsifying agent E 1Octyl phenol polyene ether (OP-10) adopts the product of Shanghai Assistant Agent Factory Co., Ltd.;
E 2Sorbitan list olein Soxylat A 25-7 adopts the product of Shanghai Assistant Agent Factory Co., Ltd.;
Dispersion agent D 1Adopt the product of Shanghai Assistant Agent Factory Co., Ltd..
Embodiment 2
40g is with active group R 2Siloxanes oligopolymer and 2000g dimethyldichlorosilane(DMCS), 250g tri-methyl-chlorosilane cohydrolysis, under the room temperature, the limit is stirred the limit fast and is dripped 0.1N salt sour water 500g, dropwises in 0.5 hour, keeps 1 hour, leaves standstill 2 hours, divides disacidify water.
Wherein: R TBe NH 2N=2, p=60;
Add 10g an acidic catalyst (98% sulfuric acid) reaction then, temperature of reaction is 90 ℃, 4 hours reaction times.Cooling is washed to the neutral accelerant B that obtains;
With 20 kilograms accelerant B, the emulsifying agent E of 1.2 kilograms of examples 1 1, the E of 0.8 kilogram of example 1 2Pass through homogenate pump homogenate with 80 kilograms water, obtain promotor emulsion B R
PH value 4.2, centrifugal stability, 15min, 3000r/min is not stratified.
Embodiment 3
Coating-forming agent latex A with 40g embodiment 1 R, 10g embodiment 2 promotor emulsion B RWith 5g catalyzer C RThe dibutyl tin dilaurate emulsion is mixed, and promptly obtains waterborne organic silicon emulsion of the present invention.
(1) latex catheter that will need coated to handle impregnated in the treatment solution, (chlorinated lime: hydrochloric acid: deionized water=0.8: 1.0: 98.2), take out behind the 3min and be placed on rinse in the water, drying;
(2) coated is handled:
It is 5% that above-mentioned waterborne organic silicon emulsion is diluted with water to the weight solid content, then step (1) be impregnated in wherein 3min through pretreated latex catheter, makes treatment solution fully enter in the tube chamber, take out the surplus liquid of drip-dry, behind the room temperature surface drying, 135 ℃ solidify 3min, cooling gets final product.Adopt following method to detect:
(1) air bag expansion partly detects
Latex catheter after the coating is injected air with syringe, and making air bag expansion is 30mL (20ch), and 50mL (20ch) looks coating and has or not the cracking dropping situations, and the result shows all do not have the cracking obscission.(2) latex catheter coating front and rear surfaces tension variation situation
SILICONE COATING AGENT is handled and untreated conduit, put into deionized water simultaneously and flood 1min, take out and observe catheter surface water-wet situation, the results are shown in Table 1.
Table 1
Numbering Organosilicon was handled Handled without organosilicon
1 Water does not launch on the surface, becomes the globule Water launches fully on the surface, and is moistening
2 Water does not launch on the surface, becomes the globule Water launches fully on the surface, and is moistening
3 Water does not launch on the surface, becomes the globule Water launches fully on the surface, and is moistening
4 Water does not launch on the surface, becomes the globule Water launches fully on the surface, and is moistening
(3) the latex catheter organic silicon coating is handled back dissolution fluid analysis
Coated is crossed two in the conduit of silicon coating agent, and (surface-area is about 250cm 2) with the deionized water washing, put into 500mL ground Erlenmeyer flask after drying, add 200mL distilled water, soak 1h at 121 ℃ ± 1 ℃, (or in 70 ℃ ± 1 ℃ baking oven, soak 24h, and soak 72h in 50 ℃ ± 1 ℃ baking oven) take out, the room temperature cooling detects the following project of dissolution fluid, the results are shown in Table 2:
Table 4
Project The result
Outward appearance Water white transparency, clarification
PH value <1
Chlorion, PPm <2.5
Ammonium ion, PPm <2.5
Heavy metal, PPm <1
Uv-absorbing liquid (λ=220nm, 1=10mm) ≤0.3
*The difference of pH value and blank sample.

Claims (8)

1. waterborne organic silicon emulsion that is used for the latex catheter surface modification is characterized in that its component and parts by weight comprise:
The coating-forming agent latex A R75~85 parts
Promotor emulsion B R10~15 parts
Catalyzer C R5~10 parts
Said catalyzer C RBe selected from a kind of in sodium hydroxide, Platinic chloride, Tetramethylammonium hydroxide or the dibutyl tin dilaurate;
Said coating-forming agent latex A RComponent and parts by weight comprise:
20~30 parts of coating-forming agent A
Emulsifying agent E 13~10 parts
Emulsifying agent E 23~5 parts
Dispersion agent D 11~5 part
60~70 parts in water
Said promotor emulsion B RComponent and parts by weight comprise:
20~30 parts of accelerant B
Emulsifying agent E 13~10 parts
Emulsifying agent E 23~5 parts
60~70 parts in water
Said emulsifying agent E 1Be selected from a kind of in Sodium dodecylbenzene sulfonate, bromogeramine, octyl phenol polyene ether (OP-10) or the sorbitan list olein Soxylat A 25-7 oxygen second;
Said emulsifying agent E 2Be selected from a kind of in Sodium dodecylbenzene sulfonate, bromogeramine, octyl phenol polyene ether (OP-10) or the sorbitan list olein Soxylat A 25-7;
Emulsifying agent E 1With emulsifying agent E 2Do not adopt with a kind of material;
Said dispersion agent D 1Be selected from dispersion agent WA, fatty alcohol-polyoxyethylene ether (IW), cellulose sulfuric acid ester and receive a kind of in (dispersing agent C S);
The general structure of said coating-forming agent A is as follows:
Figure A2007100404520003C1
Wherein: x=2~4, n=1~2, m=20~50;
Rs is NH 2, H, CH=CH 2Or SH;
The general structure of said coating-forming agent B is as follows:
Figure A2007100404520003C2
R TBe NH 2, H, CH=CH 2Or SH; N=1~5, p=30~80
Wherein: R TBe NH 2, H, CH=CH 2Or SH.
2. the waterborne organic silicon emulsion that is used for the latex catheter surface modification according to claim 1 is characterized in that, said coating-forming agent A is preparation like this:
To be with active group R 1Siloxanes oligopolymer (1) and octamethylcyclotetrasiloxane (2), reaction in the presence of basic catalyst, obtain intermediate, temperature of reaction is 60~80 ℃, and the reaction times is 1~2 hour, then with hexamethyldisiloxane (3), reaction in the presence of basic catalyst, temperature of reaction is 90~110 ℃, and the reaction times is 2~3 hours, obtains coating-forming agent A.
3. the waterborne organic silicon emulsion that is used for the latex catheter surface modification according to claim 2 is characterized in that, said basic catalyst is selected from a kind of in sodium hydroxide, potassium hydroxide, the Tetramethylammonium hydroxide.
4. the waterborne organic silicon emulsion that is used for the latex catheter surface modification according to claim 3 is characterized in that the mol ratio of reaction raw materials is:
Band active group R sThe siloxanes oligopolymer: octamethylcyclotetrasiloxane=1: 60~80;
Band active group R SThe siloxanes oligopolymer: hexamethyldisiloxane=1: 5~10;
The add-on of basic catalyst is respectively band active group R SSiloxanes oligopolymer weight 0.5~1.5%.
5. the waterborne organic silicon emulsion that is used for the latex catheter surface modification according to claim 1 is characterized in that, said accelerant B is preparation like this:
To be with active group R TSiloxanes oligopolymer and dimethyldichlorosilane(DMCS), the tri-methyl-chlorosilane cohydrolysis stirs and to drip sour water down, obtains intermediate.Add an acidic catalyst then, reaction, temperature of reaction is 90~100 ℃, the reaction times is 2~3 hours.Obtain accelerant B;
Said an acidic catalyst is selected from hydrochloric acid, sulfuric acid, Glacial acetic acid or Platinic chloride.
6. the waterborne organic silicon emulsion that is used for the latex catheter surface modification according to claim 5 is characterized in that the mol ratio of reaction raw materials is:
Band active group R TThe siloxanes oligopolymer: dimethyldichlorosilane(DMCS): tri-methyl-chlorosilane==1: 40~50: 5~10;
The add-on of an acidic catalyst is band active group R TSiloxanes oligopolymer weight 2~5%.
7. the described method that is used for the waterborne organic silicon emulsion of latex catheter surface modification of preparation claim 1 is characterized in that, comprises the steps: the coating-forming agent latex A R, promotor emulsion B RCR proportionally mixes with catalyzer, promptly obtains the waterborne organic silicon emulsion.
8. the described application method that is used for the waterborne organic silicon emulsion of latex catheter surface modification of claim 1 comprises the steps:
(1) latex catheter that will need coated to handle impregnated in the treatment solution, (chlorinated lime: hydrochloric acid: deionized water=0.8: 1.0: 98.2), take out behind 3~4min and be placed on rinse in the water, drying;
(2) coated is handled:
It is 4%~5% that above-mentioned waterborne organic silicon emulsion is diluted with water to the weight solid content, then step (1) be impregnated in wherein 2~3min through pretreated latex catheter, make treatment solution fully enter in the tube chamber, take out the surplus liquid of drip-dry, behind the room temperature surface drying, 130~140 ℃ solidify 2~4min, and cooling gets final product.
CNA2007100404522A 2007-05-09 2007-05-09 Modified water-soluble organosilicon for latex catheter and preparation thereof Pending CN101302345A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108853602A (en) * 2018-07-27 2018-11-23 董子强 A kind of intestinal lavage for animals, bowel lavage conduit coating

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108853602A (en) * 2018-07-27 2018-11-23 董子强 A kind of intestinal lavage for animals, bowel lavage conduit coating

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Open date: 20081112