CN107828044A - A kind of degradable double J pipe - Google Patents

A kind of degradable double J pipe Download PDF

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Publication number
CN107828044A
CN107828044A CN201711133349.2A CN201711133349A CN107828044A CN 107828044 A CN107828044 A CN 107828044A CN 201711133349 A CN201711133349 A CN 201711133349A CN 107828044 A CN107828044 A CN 107828044A
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China
Prior art keywords
parts
agent
added
pipe
double
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Chinese (zh)
Inventor
何国荣
林孝坤
陈聪德
刘平
张华�
赵鸣
赵一鸣
李仲荣
李育梅
胡小叶
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Second Affiliated Hospital and Yuying Childrens Hospital of Wenzhou Medical University
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Second Affiliated Hospital and Yuying Childrens Hospital of Wenzhou Medical University
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Priority to CN201711133349.2A priority Critical patent/CN107828044A/en
Publication of CN107828044A publication Critical patent/CN107828044A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/02—Applications for biomedical use
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention discloses a kind of degradable double J pipe, methyl diphenylene diisocyanate is dissolved completely in acetone first, then polyethylene glycol, cornstarch, cellulose, 1 methoxyl group 2 methyl 1 (trimethylsiloxy group) propylene, trimethyl silicane trimethylsilyl acetate, 3,3 dimethacrylate trimethylsilyl groups, ammonium lactate and catalyst are added in acetone and form prepolymer；After reaction completely, catechin and lignin are added to prepolymer solution, then add chain extender and carry out chain extending reaction again, then wash, alcohol is washed and then dried, and after drying and auxiliary agent is added to extruding pelletization in extruder, extrusion molding in extruder is put into the particle produced, then cut, the processing such as modification, final finished product.The double J pipe that the present invention prepares has good degradation capability, beneficial to sustainable development；But also with mechanical properties such as higher tensile strengths and bending strength, still there is higher tensile strength and bending strength under urine environment.

Description

A kind of degradable double J pipe
Technical field
The present invention relates to a kind of double J pipe, more particularly to a kind of degradable double J pipe.
Background technology
Double J pipe, it is referred to as pigtail catheter or ureter rack tube also or D-J is managed, be often applied to Urology Surgery In operation, suitable for the Upper urinary tract operations such as kidney stone, ureteral calculi, uronephrosis, kidney transplant, kidney and ureter benign tumour with And in the therapeutic process such as expansion of stone crusher rubble, ureterostenosis, it be implanted into ureter after can play drainage of urine, prevent it is defeated The narrow important function blocked with adhesion of urinary catheter.Widely used due to double J pipe, demand is big, and major producer all produces in succession Manufacture, but double J pipe is disposable product, and traditional double J pipe is made up of polyurethane high molecule material, common polyurethane material Material is difficult degradation and decomposition under field conditions (factors), is disorderly put so as to result in the double J pipe after a large amount of uses and left about, occupied substantial amounts of Space, and be difficult processed, or even certain influence, it is necessary to which the substantial amounts of manpower and materials of consumption could solve is caused on environment Certainly, financial cost is too high.
In the prior art, a kind of biodegradable polyurethane of Application No. CN201010288729.5 Chinese patent and Its preparation method, the inventive method reacting balance is easy to control, and the polyurethane prepared has the spies such as good biological degradability Point, it is difficult degradation and decomposition to solve the problems, such as conventional polyurethanes, at the same its double J pipe prepared also have preferable tensile strength and The mechanical properties such as modulus of elasticity；But because double J pipe is applied primarily in urological surgery, it is necessary in specific urine environment Lower work, when double J pipe works under urine environment made of the polyurethane, the mechanical property such as its tensile strength can significantly drop It is low.
The content of the invention
In view of the deficienciess of the prior art, it is an object of the invention to provide a kind of degradable double J pipe, the double J pipe is not But there is good degradability, and there is the mechanical properties such as good tensile strength later after urine is soaked.
To achieve the above object, the invention provides following technical scheme：A kind of degradable double J pipe, including following weight Part composition：
Acetone：180 parts
Methyl diphenylene diisocyanate：150 parts
Polyethylene glycol：65 parts
Cornstarch：70 parts
Cellulose：60 parts
Catechin：25 parts
Lignin：20 parts
Chain extender：15 parts
Coupling agent：5 parts
Anti-wear agent：3 parts
Conditioning agent：6 parts
Stabilizer：2 parts
Hardening agent：1 part
Thickener：1 part
Catalyst：3 parts
1- methoxyl group -2- methyl isophthalic acids-(trimethylsiloxy group) propylene：4 parts
Trimethyl silicane trimethylsilyl acetate：3 parts
3,3- dimethacrylate trimethylsilyl groups：2 parts
Ammonium lactate：3 parts.
The chain extender is the mixture of 4- aminobenzoyl amido ethanol and glycerophosphate, and its mass ratio is 1: 1.
The coupling agent is 3- (acryloxy) propyl trimethoxy silicane.
The anti-wear agent is hexadecyl trimethoxy silane.
The conditioning agent is tributyl 2-acetylcitrate, 4.4 '-bis- (α α-dimethylbenzyls) diphenylamines and N, N- diformazan The mixture of base glycine amide, its mass ratio are 2: 1: 3.
The stabilizer is the mixture of epoxidized soybean oil and potassium stearate, its mass ratio 1: 3.
The hardening agent is cetearyl alcohol alcohol sulfuric ester potassium.
The thickener is hydroxymethyl cellulose.
The catalyst is organic zinc class catalyst.
Another goal of the invention as the present invention provides a kind of preparation method of degradable double J pipe：
Step 1：Acetone is first added first in reactor as solvent, methyl diphenylene diisocyanate is added, stirs Mix uniformly, be passed through nitrogen, be warming up to 50-80 DEG C, after methyl diphenylene diisocyanate is completely dissolved in acetone, be subsequently added into Polyethylene glycol, cornstarch, cellulose, 1- methoxyl group -2- methyl isophthalic acids-(trimethylsiloxy group) propylene, trimethyl silicane acetic acid three Methyl estersil, 3,3- dimethacrylates trimethylsilyl group, ammonium lactate and catalyst reaction 2-4 hours, obtain prepolymer solution；
Step 2：First by catechin and lignin dissolution in acetone, it is then added to after being completely dissolved in step 1 In prepolymer solution, mixing speed 1000-3000r/min, 10-20 minutes are stirred, add chain extender and carry out chain extension, continued anti- Answer 1.5-2 hours；
Step 3：Product in step 2 is placed on soaked overnight in water, is washed with water 2-3 times, then is soaked 1 day with ethanol After be eluted with water, place into after drying substantially in 50 DEG C of vacuum drying oven and fully to dry；
Step 4：The material after constant weight and coupling agent, anti-wear agent, conditioning agent, stabilizer, hardening will be dried in step 3 Agent and thickener are added in extruder together carries out extruding pelletization, and then the particle produced is put into extruder, squeezes Go out shaping；
Step 5：Product in step 4 processing, the final finished product such as sheared to, modified.
Beneficial effects of the present invention：A kind of degradable double J pipe of the present invention, it is situated between using acetone as reaction dissolvent with reaction Matter by the way that methyl diphenylene diisocyanate is dissolved completely in acetone, then by polyethylene glycol, cornstarch, cellulose, 1- methoxyl group -2- methyl isophthalic acids-(trimethylsiloxy group) propylene, trimethyl silicane trimethylsilyl acetate, 3,3- dimethacrylates Trimethylsilyl group, ammonium lactate and organic zinc class catalyst are added in acetone, are reacted to each other between these materials, form pre-polymerization Thing, wherein cornstarch and cellulose are all the materials that some are easily degraded, and polyethylene glycol can provide soft segment structure, it with Diphenyl diisocyanate reacts the hardness that can improve product, and improves tensile strength to a certain degree；, will after reaction completely A certain amount of catechin and lignin are added in prepolymer solution, and catechin and lignin rise as two kinds of small molecule polyols To the effect of preliminary chain extension, and catechin and lignin are also the material easily degraded, and then add chain extender and carry out again Chain extending reaction, beneficial to the product of the good mechanical performances such as tensile property, bending strength is obtained, then washed then by washing, alcohol Drying, after drying and some auxiliary agents are added to extruding pelletization in extruder, are put into extruder and are extruded into the particle produced Type, then cut, the processing such as modification, final finished product.The double J pipe that the present invention prepares has degraded energy well Power, easily it is degraded, it is very environmentally friendly beneficial to sustainable development；But also with power such as higher tensile strengths and bending strength Performance is learned, still there is higher tensile strength and bending strength under urine environment.
As the key of the present invention, 1- methoxyl group -2- methyl isophthalic acids-(trimethylsiloxy group) propylene, trimethyl silicane are added This 4 kinds of materials of trimethylsilyl acetate, 3,3- dimethacrylates trimethylsilyl group, ammonium lactate, in the common work of this 4 kinds of materials Under, the mechanical properties such as the overall tensile strength of double J pipe and bending strength can not only be improved, and in urine environment still With very high tensile strength and bending strength, it ensure that obtained double J pipe can be applied in urological surgery well, hair Wave its effect.
The conditioning agent selected in the present invention is tributyl 2-acetylcitrate, 4.4 '-bis- (α α-dimethylbenzyls) diphenylamines And the mixture of N, N- dimethylglycylamide, under the collective effect of these materials, certain plastication can be played, is increased The strong pliability of double J pipe, also allows for processing, can also improve ageing resistance to a certain extent.
The stabilizer selected in the present invention is the mixture of epoxidized soybean oil and potassium stearate, in the common of both materials Under effect, ensure that various auxiliary agents all have preferable stability, can normally play and work；In addition epoxidized soybean oil is easy to drop Solution, degradability is fine, and potassium stearate can also improve the tensile strength and modulus of elasticity of double J pipe to a certain extent.
Embodiment
Embodiment 1：A kind of degradable double J pipe, including following parts by weight composition：
Acetone：180 parts
Methyl diphenylene diisocyanate：150 parts
Polyethylene glycol：65 parts
Cornstarch：70 parts
Cellulose：60 parts
Catechin：25 parts
Lignin：20 parts
Chain extender：15 parts
Coupling agent：5 parts
Anti-wear agent：3 parts
Conditioning agent：6 parts
Stabilizer：2 parts
Hardening agent：1 part
Thickener：1 part
Catalyst：3 parts
1- methoxyl group -2- methyl isophthalic acids-(trimethylsiloxy group) propylene：4 parts
Trimethyl silicane trimethylsilyl acetate：3 parts
3,3- dimethacrylate trimethylsilyl groups：2 parts
Ammonium lactate：3 parts.
The chain extender is the mixture of 4- aminobenzoyl amido ethanol and glycerophosphate, and its mass ratio is 1: 1.
The coupling agent is 3- (acryloxy) propyl trimethoxy silicane.
The anti-wear agent is hexadecyl trimethoxy silane.
The conditioning agent is tributyl 2-acetylcitrate, 4.4 '-bis- (α α-dimethylbenzyls) diphenylamines and N, N- diformazan The mixture of base glycine amide, its mass ratio are 2: 1: 3.
The stabilizer is the mixture of epoxidized soybean oil and potassium stearate, its mass ratio 1: 3.
The hardening agent is cetearyl alcohol alcohol sulfuric ester potassium.
The thickener is hydroxymethyl cellulose.
The catalyst is organic zinc class catalyst.
Another goal of the invention as the present invention provides a kind of preparation method of degradable double J pipe：
Step 1：Acetone is first added first in reactor as solvent, methyl diphenylene diisocyanate is added, stirs Mix uniformly, be passed through nitrogen, be warming up to 50-80 DEG C, after methyl diphenylene diisocyanate is completely dissolved in acetone, be subsequently added into Polyethylene glycol, cornstarch, cellulose, 1- methoxyl group -2- methyl isophthalic acids-(trimethylsiloxy group) propylene, trimethyl silicane acetic acid three Methyl estersil, 3,3- dimethacrylates trimethylsilyl group, ammonium lactate and catalyst reaction 2-4 hours, obtain prepolymer solution；
Step 2：First by catechin and lignin dissolution in acetone, it is then added to after being completely dissolved in step 1 In prepolymer solution, mixing speed 1000-3000r/min, 10-20 minutes are stirred, add chain extender and carry out chain extension, continued anti- Answer 1.5-2 hours；
Step 3：Product in step 2 is placed on soaked overnight in water, is washed with water 2-3 times, then is soaked 1 day with ethanol After be eluted with water, place into after drying substantially in 50 DEG C of vacuum drying oven and fully to dry；
Step 4：The material after constant weight and coupling agent, anti-wear agent, conditioning agent, stabilizer, hardening will be dried in step 3 Agent and thickener are added in extruder together carries out extruding pelletization, and then the particle produced is put into extruder, squeezes Go out shaping；
Step 5：Product in step 4 processing, the final finished product such as sheared to, modified.
Embodiment 2：A kind of degradable double J pipe, including following parts by weight composition：
Acetone：180 parts
Methyl diphenylene diisocyanate：150 parts
Polyethylene glycol：65 parts
Cornstarch：70 parts
Cellulose：60 parts
Catechin：25 parts
Lignin：20 parts
Chain extender：15 parts
Coupling agent：5 parts
Anti-wear agent：3 parts
Conditioning agent：6 parts
Stabilizer：2 parts
Hardening agent：1 part
Thickener：1 part
Catalyst：3 parts
1- methoxyl group -2- methyl isophthalic acids-(trimethylsiloxy group) propylene：4 parts
Trimethyl silicane trimethylsilyl acetate：3 parts
3,3- dimethacrylate trimethylsilyl groups：2 parts
Ammonium lactate：3 parts.
The chain extender is 4- aminobenzoyl amido ethanol.
The coupling agent is 3- (acryloxy) propyl trimethoxy silicane.
The anti-wear agent is hexadecyl trimethoxy silane.
The conditioning agent is tributyl 2-acetylcitrate.
The stabilizer is potassium stearate.
The hardening agent is cetearyl alcohol alcohol sulfuric ester potassium.
The thickener is hydroxymethyl cellulose.
The catalyst is organic zinc class catalyst.
Another goal of the invention as the present invention provides a kind of preparation method of degradable double J pipe：
Step 1：Acetone is first added first in reactor as solvent, methyl diphenylene diisocyanate is added, stirs Mix uniformly, be passed through nitrogen, be warming up to 50-80 DEG C, after methyl diphenylene diisocyanate is completely dissolved in acetone, be subsequently added into Polyethylene glycol, cornstarch, cellulose, 1- methoxyl group -2- methyl isophthalic acids-(trimethylsiloxy group) propylene, trimethyl silicane acetic acid three Methyl estersil, 3,3- dimethacrylates trimethylsilyl group, ammonium lactate and catalyst reaction 2-4 hours, obtain prepolymer solution；
Step 2：First by catechin and lignin dissolution in acetone, it is then added to after being completely dissolved in step 1 In prepolymer solution, mixing speed 1000-3000r/min, 10-20 minutes are stirred, add chain extender and carry out chain extension, continued anti- Answer 1.5-2 hours；
Step 3：Product in step 2 is placed on soaked overnight in water, is washed with water 2-3 times, then is soaked 1 day with ethanol After be eluted with water, place into after drying substantially in 50 DEG C of vacuum drying oven and fully to dry；
Step 4：The material after constant weight and coupling agent, anti-wear agent, conditioning agent, stabilizer, hardening will be dried in step 3 Agent and thickener are added in extruder together carries out extruding pelletization, and then the particle produced is put into extruder, squeezes Go out shaping；
Step 5：Product in step 4 processing, the final finished product such as sheared to, modified.
Comparative example 1：A kind of degradable double J pipe, including following parts by weight composition：
Acetone：180 parts
Methyl diphenylene diisocyanate：150 parts
Polyethylene glycol：65 parts
Cornstarch：70 parts
Cellulose：60 parts
Catechin：25 parts
Lignin：20 parts
Chain extender：15 parts
Coupling agent：5 parts
Anti-wear agent：3 parts
Conditioning agent：6 parts
Stabilizer：2 parts
Hardening agent：1 part
Thickener：1 part
Catalyst：3 parts.
The chain extender is 4- aminobenzoyl amido ethanol.
The coupling agent is 3- (acryloxy) propyl trimethoxy silicane.
The anti-wear agent is hexadecyl trimethoxy silane.
The conditioning agent is tributyl 2-acetylcitrate.
The stabilizer is potassium stearate.
The hardening agent is cetearyl alcohol alcohol sulfuric ester potassium.
The thickener is hydroxymethyl cellulose.
The catalyst is organic zinc class catalyst.
Another goal of the invention as the present invention provides a kind of preparation method of degradable double J pipe：
Step 1：Acetone is first added first in reactor as solvent, methyl diphenylene diisocyanate is added, stirs Mix uniformly, be passed through nitrogen, be warming up to 50-80 DEG C, after methyl diphenylene diisocyanate is completely dissolved in acetone, be subsequently added into Polyethylene glycol, cornstarch, cellulose and catalyst reaction 2-4 hours, obtain prepolymer solution；
Step 2：First by catechin and lignin dissolution in acetone, it is then added to after being completely dissolved in step 1 In prepolymer solution, mixing speed 1000-3000r/min, 10-20 minutes are stirred, add chain extender and carry out chain extension, continued anti- Answer 1.5-2 hours；
Step 3：Product in step 2 is placed on soaked overnight in water, is washed with water 2-3 times, then is soaked 1 day with ethanol After be eluted with water, place into after drying substantially in 50 DEG C of vacuum drying oven and fully to dry；
Step 4：The material after constant weight and coupling agent, anti-wear agent, conditioning agent, stabilizer, hardening will be dried in step 3 Agent and thickener are added in extruder together carries out extruding pelletization, and then the particle produced is put into extruder, squeezes Go out shaping；
Step 5：Product in step 4 processing, the final finished product such as sheared to, modified.
Comparative example 2：A kind of degradable double J pipe, including following parts by weight composition：
Acetone：180 parts
Methyl diphenylene diisocyanate：150 parts
Polyethylene glycol：65 parts
Cellulose：60 parts
Catechin：25 parts
Lignin：20 parts
Chain extender：15 parts
Coupling agent：5 parts
Anti-wear agent：3 parts
Conditioning agent：6 parts
Stabilizer：2 parts
Hardening agent：1 part
Thickener：1 part
Catalyst：3 parts
Trimethyl silicane trimethylsilyl acetate：3 parts
3,3- dimethacrylate trimethylsilyl groups：2 parts.
The chain extender is 4- aminobenzoyl amido ethanol.
The coupling agent is 3- (acryloxy) propyl trimethoxy silicane.
The anti-wear agent is hexadecyl trimethoxy silane.
The conditioning agent is tributyl 2-acetylcitrate.
The stabilizer is potassium stearate.
The hardening agent is cetearyl alcohol alcohol sulfuric ester potassium.
The thickener is hydroxymethyl cellulose.
The catalyst is organic zinc class catalyst.
Another goal of the invention as the present invention provides a kind of preparation method of degradable double J pipe：
Step 1：Acetone is first added first in reactor as solvent, methyl diphenylene diisocyanate is added, stirs Mix uniformly, be passed through nitrogen, be warming up to 50-80 DEG C, after methyl diphenylene diisocyanate is completely dissolved in acetone, be subsequently added into Polyethylene glycol, cellulose, trimethyl silicane trimethylsilyl acetate, 3,3- dimethacrylates trimethylsilyl group and catalyst reaction 2-4 hours, obtain prepolymer solution；
Step 2：First by catechin and lignin dissolution in acetone, it is then added to after being completely dissolved in step 1 In prepolymer solution, mixing speed 1000-3000r/min, 10-20 minutes are stirred, add chain extender and carry out chain extension, continued anti- Answer 1.5-2 hours；
Step 3：Product in step 2 is placed on soaked overnight in water, is washed with water 2-3 times, then is soaked 1 day with ethanol After be eluted with water, place into after drying substantially in 50 DEG C of vacuum drying oven and fully to dry；
Step 4：The material after constant weight and coupling agent, anti-wear agent, conditioning agent, stabilizer, hardening will be dried in step 3 Agent and thickener are added in extruder together carries out extruding pelletization, and then the particle produced is put into extruder, squeezes Go out shaping；
Step 5：Product in step 4 processing, the final finished product such as sheared to, modified.
Comparative example 3：A kind of degradable double J pipe, including following parts by weight composition：
Acetone：180 parts
Methyl diphenylene diisocyanate：150 parts
Polyethylene glycol：65 parts
Cornstarch：70 parts
Catechin：25 parts
Chain extender：15 parts
Coupling agent：5 parts
Anti-wear agent：3 parts
Conditioning agent：6 parts
Stabilizer：2 parts
Hardening agent：1 part
Thickener：1 part
Catalyst：3 parts
1- methoxyl group -2- methyl isophthalic acids-(trimethylsiloxy group) propylene：4 parts
Ammonium lactate：3 parts.
The chain extender is 4- aminobenzoyl amido ethanol.
The coupling agent is 3- (acryloxy) propyl trimethoxy silicane.
The anti-wear agent is hexadecyl trimethoxy silane.
The conditioning agent is tributyl 2-acetylcitrate.
The stabilizer is potassium stearate.
The hardening agent is cetearyl alcohol alcohol sulfuric ester potassium.
The thickener is hydroxymethyl cellulose.
The catalyst is organic zinc class catalyst.
Another goal of the invention as the present invention provides a kind of preparation method of degradable double J pipe：
Step 1：Acetone is first added first in reactor as solvent, methyl diphenylene diisocyanate is added, stirs Mix uniformly, be passed through nitrogen, be warming up to 50-80 DEG C, after methyl diphenylene diisocyanate is completely dissolved in acetone, be subsequently added into Polyethylene glycol, cornstarch, cellulose, 1- methoxyl group -2- methyl isophthalic acids-(trimethylsiloxy group) propylene, trimethyl silicane acetic acid three Methyl estersil, 3,3- dimethacrylates trimethylsilyl group, ammonium lactate and catalyst reaction 2-4 hours, obtain prepolymer solution；
Step 2：First by catechin and lignin dissolution in acetone, it is then added to after being completely dissolved in step 1 In prepolymer solution, mixing speed 1000-3000r/min, 10-20 minutes are stirred, add chain extender and carry out chain extension, continued anti- Answer 1.5-2 hours；
Step 3：Product in step 2 is placed on soaked overnight in water, is washed with water 2-3 times, then is soaked 1 day with ethanol After be eluted with water, place into after drying substantially in 50 DEG C of vacuum drying oven and fully to dry；
Step 4：The material after constant weight and coupling agent, anti-wear agent, conditioning agent, stabilizer, hardening will be dried in step 3 Agent and thickener are added in extruder together carries out extruding pelletization, and then the particle produced is put into extruder, squeezes Go out shaping；
Step 5：Product in step 4 processing, the final finished product such as sheared to, modified.
Comparative example 4：Application No. CN201010288729.5 a kind of biodegradable polyurethane of Chinese patent and its system Preparation Method
Embodiment 1 gathers polyethylencarbonate-L-type that weight average molecular weight fully dry 0.001mol is 2000g/mol Lactic acid block copolymer glycol is put into the 50ml reaction bulbs equipped with 2ml chloroforms, and the six of 0.002mol is added after to be dissolved Methylene diisocyanate (HDI), repetition vacuumize rear nitrogen charging and operated 5 times, and holding pressure is after being passed through nitrogen for the last time 0.05MPa；60 DEG C of backflow 0.1h of heating, then add chain extender BDO, its molal quantity added is HDI and poly- carbonic acid The difference of the molal quantity of alkylene carbonate-polylactic-acid block copolymer glycol, repeat and vacuumize rear nitrogen charging and operate 5 times, last time is logical Holding pressure is 0.05MPa after entering nitrogen, continues to react 0.1h, product filtration drying after precipitation process, finally gives molecule The polyurethane for being 1.81 for 10Kg/mol, molecular weight distribution is measured, the polyurethane material prepared with embodiment 1 is made corresponding double J is managed.
Comparative example 5：Production unit is the magnificent Medical Devices Co., Ltd. in Zhangjiagang, model 4.5-12# double J pipe.It is raw Thing degradation property is tested as follows：Sample is placed in pH=8 phosphate buffer solution, soaked at 37 DEG C, Mei Geyi Fix time and take out sample, constant mass is dried under vacuum under the conditions of 40 DEG C/1kPa, calculate sample mass loss late：
12h 1 day 10 days 30 days 60 days 90 days
Embodiment 1 0.03% 0.08% 1% 5% 13% 25%
Embodiment 2 0.02% 0.07% 0.9% 4.5% 12% 23&
Comparative example 1 0 0.02% 0.3% 2% 6% 12%
Comparative example 2 0.01% 0.04% 0.6% 3.5% 9% 17%
Comparative example 3 0 0.03% 0.4% 3% 8% 15%
Comparative example 4 0.02% 0.06% 0.8% 4% 11% 22%
Comparative example 5 0 0 0 0 0 0.2%
Respective standard sample is made according to various standards in product made from embodiment and comparative example, is then tested：
Performance Method of testing Unit
Tensile strength GB/T1040-1992 MPa
Elongation at break GB/T1040-1992 %
Bending strength GB/T9341-2000 MPa
Bending modulus GB/T9341-2000 MPa
Wearability GB/T 1689-1998 G
Modulus of elasticity HG/T 3321-2012 MPa
Urine titer is configured, it is often aqueous in 100ml：96.55%, urea：1.8% uric acid：0.05%, glucose： 0.5%, inorganic salts：1.1%；
After each sample is soaked 24 hours under the urine titer environment for being placed on configuration, first wash 2 times, then washed with ethanol 2 times, then dry, corresponding mechanical property is detected again according to various standards；
A kind of degradable double J pipe of the present invention, using acetone as reaction dissolvent and reaction medium by by diphenylmethyl Alkane diisocyanate is dissolved completely in acetone, then by polyethylene glycol, cornstarch, cellulose, 1- methoxyl group -2- methyl - 1- (trimethylsiloxy group) propylene, trimethyl silicane trimethylsilyl acetate, 3,3- dimethacrylates trimethylsilyl group, ammonium lactate It is added in acetone with organic zinc class catalyst, is reacted to each other between these materials, forms prepolymer, wherein cornstarch and fibre Dimension element is all the material that some are easily degraded, and polyethylene glycol can provide soft segment structure, and it is anti-with diphenyl diisocyanate The hardness of product should be able to be improved, and improve tensile strength to a certain degree；After reaction completely, by a certain amount of catechin and wood Quality is added in prepolymer solution, and catechin and lignin play a part of preliminary chain extension as two kinds of small molecule polyols, And catechin and lignin are also the material easily degraded, then add chain extender and carry out chain extending reaction again, beneficial to obtaining The product of the good mechanical performances such as tensile property, bending strength, then by washing, alcohol wash then dry, after drying and some Auxiliary agent is added to extruding pelletization in extruder, is put into extrusion molding in extruder with the particle produced, is then cut, repaiied The processing such as decorations, final finished product.The double J pipe that the present invention prepares has good degradation capability, is easily degraded, beneficial to can Sustainable development, it is very environmentally friendly；But also with mechanical properties such as higher tensile strengths and bending strength, even in urine environment Under still there is higher tensile strength and bending strength.
As the key of the present invention, 1- methoxyl group -2- methyl isophthalic acids-(trimethylsiloxy group) propylene, trimethyl silicane are added This 4 kinds of materials of trimethylsilyl acetate, 3,3- dimethacrylates trimethylsilyl group, ammonium lactate, in the common work of this 4 kinds of materials Under, the mechanical properties such as the overall tensile strength of double J pipe and bending strength can not only be improved, and in urine environment still With very high tensile strength and bending strength, it ensure that obtained double J pipe can be applied in urological surgery well, hair Wave its effect.
The conditioning agent selected in the present invention is tributyl 2-acetylcitrate, 4.4 '-bis- (α α-dimethylbenzyls) diphenylamines And the mixture of N, N- dimethylglycylamide, under the collective effect of these materials, certain plastication can be played, is increased The strong pliability of double J pipe, also allows for processing, can also improve ageing resistance to a certain extent.
The stabilizer selected in the present invention is the mixture of epoxidized soybean oil and potassium stearate, in the common of both materials Under effect, ensure that various auxiliary agents all have preferable stability, can normally play and work；In addition epoxidized soybean oil is easy to drop Solution, degradability is fine, and potassium stearate can also improve the tensile strength and modulus of elasticity of double J pipe to a certain extent.
Described above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned implementation Example, all technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It should be pointed out that for the art Those of ordinary skill for, some improvements and modifications without departing from the principles of the present invention, these improvements and modifications It should be regarded as protection scope of the present invention.

Claims (10)

  1. A kind of 1. degradable double J pipe, it is characterised in that：Formed including following parts by weight：
    Acetone：180 parts
    Methyl diphenylene diisocyanate：150 parts
    Polyethylene glycol：65 parts
    Cornstarch：70 parts
    Cellulose：60 parts
    Catechin：25 parts
    Lignin：20 parts
    Chain extender：15 parts
    Coupling agent：5 parts
    Anti-wear agent：3 parts
    Conditioning agent：6 parts
    Stabilizer：2 parts
    Hardening agent：1 part
    Thickener：1 part
    Catalyst：3 parts
    1- methoxyl group -2- methyl isophthalic acids-(trimethylsiloxy group) propylene：4 parts
    Trimethyl silicane trimethylsilyl acetate：3 parts
    3,3- dimethacrylate trimethylsilyl groups：2 parts
    Ammonium lactate：3 parts.
  2. A kind of 2. degradable double J pipe according to claim 1, it is characterised in that：The chain extender is 4- aminobenzoyls The mixture of aminoethanol and glycerophosphate, its mass ratio are 1: 1.
  3. A kind of 3. degradable double J pipe according to claim 2, it is characterised in that：The coupling agent is 3- (acryloyl-oxies Base) propyl trimethoxy silicane.
  4. A kind of 4. degradable double J pipe according to claim 3, it is characterised in that：The anti-wear agent is cetyl front three TMOS.
  5. A kind of 5. degradable double J pipe according to claim 4, it is characterised in that：The conditioning agent is acetyl tributyl citrate three The mixture of butyl ester, 4.4 '-bis- (α α-dimethylbenzyls) diphenylamines and N, N- dimethylglycylamide, its mass ratio are 2: 1: 3。
  6. A kind of 6. degradable double J pipe according to claim 5, it is characterised in that：The stabilizer be epoxidized soybean oil and The mixture of potassium stearate, its mass ratio 1: 3.
  7. A kind of 7. degradable double J pipe according to claim 6, it is characterised in that：The hardening agent is cetostearyl alcohol sulphur Acid esters potassium.
  8. A kind of 8. degradable double J pipe according to claim 7, it is characterised in that：The thickener is hydroxymethyl cellulose.
  9. A kind of 9. degradable double J pipe according to claim 8, it is characterised in that：The catalyst is catalyzed for organic zinc class Agent.
  10. A kind of 10. preparation method of degradable double J pipe as described in claim 1 to 9, it is characterised in that：
    Step 1：Acetone is first added first in reactor as solvent, adds methyl diphenylene diisocyanate, stirring is equal It is even, nitrogen is passed through, is warming up to 50-80 DEG C, after methyl diphenylene diisocyanate is completely dissolved in acetone, is subsequently added into poly- second Glycol, cornstarch, cellulose, 1- methoxyl group -2- methyl isophthalic acids-(trimethylsiloxy group) propylene, trimethyl silicane acetic acid trimethyl Estersil, 3,3- dimethacrylates trimethylsilyl group, ammonium lactate and catalyst reaction 2-4 hours, obtain prepolymer solution；
    Step 2：First by catechin and lignin dissolution in acetone, the pre-polymerization that is then added to after being completely dissolved in step 1 In liquid solution, mixing speed 1000-3000r/min, 10-20 minutes are stirred, add chain extender and carry out chain extension, continue to react 1.5-2 hour；
    Step 3：Product in step 2 is placed on soaked overnight in water, is washed with water 2-3 times, then is used after being soaked 1 day with ethanol Water is cleaned, and is placed into after drying substantially in 50 DEG C of vacuum drying oven and is fully dried；
    Step 4：To be dried in step 3 the material after constant weight and coupling agent, anti-wear agent, conditioning agent, stabilizer, hardening agent with And thickener is added in extruder and carries out extruding pelletization together, and then the particle produced is put into extruder, is extruded into Type；
    Step 5：Product in step 4 processing, the final finished product such as sheared to, modified.
CN201711133349.2A 2017-11-15 2017-11-15 A kind of degradable double J pipe Pending CN107828044A (en)

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