CN110509489A - A kind of manufacturing method of shield duct piece sealing strip - Google Patents
A kind of manufacturing method of shield duct piece sealing strip Download PDFInfo
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- CN110509489A CN110509489A CN201910697746.5A CN201910697746A CN110509489A CN 110509489 A CN110509489 A CN 110509489A CN 201910697746 A CN201910697746 A CN 201910697746A CN 110509489 A CN110509489 A CN 110509489A
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- China
- Prior art keywords
- hollow tube
- added
- duct piece
- sealing strip
- shield duct
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/1418—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the inserts being deformed or preformed, e.g. by the injection pressure
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
-
- 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
- C08G18/28—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
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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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
- C08G18/70—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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- 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
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- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/1418—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the inserts being deformed or preformed, e.g. by the injection pressure
- B29C2045/14237—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the inserts being deformed or preformed, e.g. by the injection pressure the inserts being deformed or preformed outside the mould or mould cavity
- B29C2045/14245—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the inserts being deformed or preformed, e.g. by the injection pressure the inserts being deformed or preformed outside the mould or mould cavity using deforming or preforming means outside the mould cavity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/26—Sealing devices, e.g. packaging for pistons or pipe joints
- B29L2031/265—Packings, Gaskets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
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- 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
Abstract
The invention discloses a kind of manufacturing method of shield duct piece sealing strip, include the following steps: that hollow tube performed polymer is made in polyethylene glycol, polypropylene glycol and MDI reaction；Liquid rubber, white carbon black, carbon fiber, anti-aging agent, bentonite, chlorinated paraffin, nanometer calcium carbonate is added in blank pipe performed polymer, chain extender is added and hollow tube is made；Hollow tube is fixed in the preformed groove of injection molding machine；Premix ethylene oxide and propylene oxide, pentaerythrite is added and high molecular polyether is made in potassium hydroxide reaction, TDI is added, filler performed polymer is made, liquid rubber, bentonite, anti-aging agent, white carbon black stirring is added, adds chain extender and filler is made in hydrophilic chain extender；Shield duct piece sealing strip is made in slow injection fillers object to hollow tube；Shield duct piece sealing strip is subjected to secondary microwave vulcanization.Shield duct piece sealing strip made of the present invention has double-layer structure, and mechanical property is good, and expansion rate of water absorption is high, and long service life can seal shield duct piece gap.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of manufacturing method of shield duct piece sealing strip.
Background technique
Shield method tunneling is used in subway engineering, after shield driving, shield duct piece is combined by the fissure of displacement
Ring forms the barrier of tunnel innermost layer.Shield duct piece subjects earth pressure, groundwater pressure and some special loads, because
The quality of this shield duct piece directly affects the quality and safety in tunnel.Since shield duct piece is to be spliced, shield duct piece it
Between the gap between shield duct piece can be blocked usually using solid sealing strip, to play good waterproof effect there are gap.
But shield duct piece on the market, due to mismachining tolerance and section of jurisdiction stitching error, the gap size of shield duct piece stitching portion is different
It causes, if will lead to gap with solid sealing strip can not be completely sealed, to cause water seepage of tunnel, seriously affects the safety in tunnel
Property.
Water-expandable polyurethane is a kind of common sealing strip material, and water-expandable polyurethane material is using active end group
Hydrophily oligomer or polymer are reacted with multicomponent isocyanate to be made, and high resiliency is derived from specific network structure, water suction
Ability is derived from Hydrophilicrto polyether block.It is connected on main chain since hydrophilic radical is embedding, water-expandable polyurethane material has uniform
Water suction not easily runs off moisture, and expansion uniformly, expands the advantages that sectional shape is small, and polyurethane material itself has elasticity
The features such as good, wear-resisting, oil resistant, corrosion-resistant, radiation hardness, therefore water-expandable polyurethane material is suitable for the sealing under various environment
Preventing leaking water engineering.
Summary of the invention
It can be sufficient filling with shield duct piece gap the object of the present invention is to provide a kind of, water-absorbent expanding multiple is big, plays sealing
The shield duct piece sealing strip of resistance to compression effect.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme:
A. hollow tube is manufactured:
A. hollow tube performed polymer is synthesized:
Methyl diphenylene diisocyanate (MDI) is added in pre- mixed polyethylene glycol and polypropylene glycol, hollow tube is made
Performed polymer；Wherein, in terms of mass fraction, 50~70 parts of polyethylene glycol, 30~40 parts of polypropylene glycol, diphenylmethane diisocyanate
20~40 parts of ester (MDI)；
B. hollow tube is synthesized:
(1) weigh a certain amount of hollow tube performed polymer be added liquid rubber, white carbon black, carbon fiber, anti-aging agent, bentonite,
Chlorinated paraffin, nanometer calcium carbonate are heated to 80~90 DEG C of stirring 0.5h；Wherein, in terms of mass fraction, hollow tube performed polymer 80~
100 parts, 5~10 parts of liquid rubber, 15~20 parts of white carbon black, 10~15 parts of carbon fiber, 1~5 part of anti-aging agent, bentonite 10~20
Part, 5~10 parts of chain extender, 2~6 parts of chlorinated paraffin, 1~3 part of nanometer calcium carbonate；
(2) chain extender of 110~125 DEG C of preheating is added, 1h is mixed；Manufactured hollow tube coarse fodder is put into extrusion
Machine, extruder are equipped with hollow tube extrusion die, are cut into hollow tube by microwave vulcanization after extrusion；
B. fix hollow tube: injection molding machine is equipped with hollow pipe die, and the hollow pipe die is equipped with preformed groove, hollow tube is put
Enter in preformed groove, the nozzle of injection molding machine is directed at hollow tube；
C. filler is manufactured:
A. high molecular polyether is synthesized:
Ethylene oxide, propylene oxide, pentaerythrite and potassium hydroxide are put into reaction kettle reaction, high molecular polyether is made；
B. filler performed polymer is synthesized:
(1) high molecular polyether that step a is obtained is added in reaction kettle, heats reaction kettle to 75~85 DEG C, toluene is added
Diisocyanate makes its reaction, and keeping temperature in the kettle is 95~105 DEG C, and pressure declines from 1kPa, and the reaction time is 3 hours；With
Mass fraction meter, 70~90 parts of high molecular polyether, 10~30 parts of toluene di-isocyanate(TDI) (TDI)；
(2) when pressure drops to 0 in kettle, blowing is packed when cooling to 50~60 DEG C, obtains filler performed polymer；
C. filler is synthesized:
(1) liquid rubber, bentonite, anti-aging agent, white carbon black, control temperature is added in the filler performed polymer for synthesizing step b
Degree is 80~90 DEG C, stirs 0.5h；In terms of mass fraction, 80~100 parts of filler performed polymer, 3~8 parts of liquid rubber, swelling
10~20 parts, 2~5 parts of anti-aging agent, 1~3 part of white carbon black, 5~15 parts of chain extender, 1~5 part of hydrophilic chain extender of soil；
(2) in the raw material that addition chain extender and hydrophilic chain extender are mixed to step c (1), 90~100 are maintained the temperature at
DEG C, filler coarse fodder is made in stirring 1h；
D. in injection fillers object to hollow tube: by filler coarse fodder manufactured in step C pour into injection molding machine in step B plus
In material mouth, filler coarse fodder is slowly injected to hollow tube by injection molding machine from bottom to top, and pouring temperature is maintained at 100 DEG C, will
The oven that mold is put into 110 DEG C is solidified, and extra filler is opened and cut off after 2h, shield duct piece sealing strip is made；
E. the shield duct piece sealing strip in step D is subjected to secondary microwave vulcanization.
Shield duct piece sealing strip outer layer hollow tube selects polyester polyurethane, and filler selects polyether polyurethane, because
Hollow tube is directly contacted with shield duct piece, and deformation degree is larger it is necessary to have preferable mechanical property, and filler then need compared with
Good water absorbing properties.In general polyester polyurethane is poly- better than polyether-type in terms of tensile strength, tearing strength and wearability
Urethane, while polyether polyurethane is better than polyester polyurethane in terms of hydrolysis, low temperature resistant, water absorbing properties.
Preferably, in step A-a, specific step is as follows for synthesis hollow tube performed polymer:
(1) polyethylene glycol and polypropylene glycol are heated to 100~140 DEG C of stirring 0.5h, keep temperature and vacuum defoamation 2h；
(2) polyethylene glycol of premix and polypropylene glycol are added in reaction kettle, it is different that diphenyl methane two is added in reaction kettle
Cyanate is simultaneously warming up to 80~90 DEG C, and when reactor pressure is slowly reduced to 0, vacuum defoamation 1h and drying obtain hollow tube
Performed polymer；
Preferably, in step C-a, synthesizing high molecular polyether, specific step is as follows:
(1) ethylene oxide and propylene oxide are pressed into the sealing container with stirring with ammonia, stirring 0.5h makes material
It mixes well；
(2) initiator pentaerythrite and catalyst potassium hydroxide are added in a kettle, in vacuum pump extraction kettle
Air, then pour nitrogen protection；
(3) reaction kettle is heated to 55~65 DEG C, is pressed into pre- mixed ethylene oxide and propylene oxide, makes its reaction；
(4) charging valve is adjusted, keeping reactor temperature is 100~120 DEG C, 4~5kPa of pressure, and is constantly water-cooled
Temperature in the kettle；
(5) after ethylene oxide and propylene oxide are added, temperature in the kettle is kept, so that its pressure is slowly fallen to 0, is made
Coarse fodder；
(6) above-mentioned coarse fodder is pressed into and is neutralized in kettle, neutralizer phosphoric acid and refining agent aluminium hydroxide is added, stir 1h, filtering
It is packaged to be high molecular polyether.
In terms of mass fraction, 80~90 parts of ethylene oxide, 10~20 parts of propylene oxide, 0.5~1 part of pentaerythrite, hydrogen-oxygen
Change 0.1~0.5 part of potassium, 0.3~0.5 part of neutralizer phosphoric acid, 0.3~0.7 part of refining agent aluminium hydroxide.
Preferably, increase a step between step A and step B: being mixed in hollow inside pipe wall even application polyester-polyether
Type aqueous polyurethane adhesive.Polyester-polyether mixed type watersoluble polyurethane adhesive can play excellent bonds hollow tube and fill out
The effect for filling object prevents filler in solidification since volume contraction leads to occur gap between hollow tube and filler.
Preferably, the manufacturing method of polyester-polyether mixed type watersoluble polyurethane adhesive is as follows:
(1) polyethylene glycol of 30~40 mass parts is put into reaction kettle, reaction kettle is warming up to 60~70 DEG C, is passed through nitrogen
The toluene di-isocyanate(TDI) of 5~10 mass parts is added afterwards, keeping reactor temperature is 100~110 DEG C, and polyester-type pre-polymerization is made
Body；
(2) 40~50 mass parts ethylene oxide are put into reaction kettle, reaction kettle is warming up to 80~90 DEG C, after being passed through nitrogen
The toluene di-isocyanate(TDI) of 5~10 mass parts is added, keeping reactor temperature is 110~120 DEG C, and polyethers is made after reacting 2h
Type performed polymer；
(3) 80~100 mass parts polyester prepolymers and polyether-type performed polymer is taken to be put into the sealing container with stirring,
It is stirred under vacuum 1h；
(4) chain extender of 1~3 mass parts and the hydrophilic chain extender of 2~5 mass parts, pre-polymerization 2h is added；
(5) salt forming agent that 0.3~0.5 mass parts are added neutralizes, and stirs 0.5h；The preferred triethylamine of salt forming agent；
(6) water is added to be emulsified, ultrasonic disperse 0.5h is finally made the bonding of polyester-polyether mixed type watersoluble polyurethane
Agent.
Preferably, hollow tube outer surface is equipped at least four grooves, and hollow pipe internal surface is equipped at least four protrusions, groove
It is corresponding with protrusion, hollow thickness of pipe wall 3mm.The groove of hollow pipe surface matches with shield duct piece side, hollow pipe internal surface
Protrusion increase the contact area between hollow tube and filler, connect filler with hollow tube even closer.
Preferably, microwave vulcanization process is that hollow tube or shield duct piece sealing strip sequentially enter microwave in step A and step E
Case, hot-air cure case, air cooled box and cutting machine, wherein microwave temperature is 140 DEG C in step A, and hot-air cure temperature is 150
DEG C, microwave temperature is 120 DEG C in step E, and hot-air cure temperature is 130 DEG C.
Preferably, chain extender be 1,4-butanediol, 1,6- hexylene glycol, glycerol, trimethylolpropane, diethylene glycol (DEG), triethylene glycol,
One of neopentyl glycol, sorbierite or a variety of mixtures；Hydrophilic chain extender is dihydromethyl propionic acid, dihydroxymethyl fourth
One of acid, 1,2- dihydroxy -3-N-morpholinopropanesulfonic acid sodium, ethylenediamine base sodium sulfonate, ethylenediamine base sodium sulfonate or a variety of mixtures.
Preferably, liquid rubber is liquid nitrile rubber, liquid butyl rubber, Liquid Ethylene Propylene Methylene, liquid polysulfide rubber
One of or a variety of mixtures.The mechanical performance of liquid rubber enhancing shield duct piece sealing strip.
Preferably, anti-aging agent is one of antioxidant BHT, anti-aging agent 405, anti-aging agent MDA or a variety of mixtures.
Due to the adoption of the above technical scheme, the invention has the following advantages:
1, shield duct piece sealing strip outer layer hollow tube is polyester polyurethane, has preferable tensile strength, tearing strength
And wearability, long service life；
2, shield duct piece sealing strip internal layer filler is polyether polyurethane, hydrolysis, low temperature resistant, water-absorbent expanding multiple
Greatly, rate of water absorption is high；
3, solidification, is completely embedded between hollow tube and filler, prevents gap after filler is injected into hollow tube；
4, hollow tube outer surface is equipped with groove, and groove matches with shield duct piece side, can more preferably seal shield duct piece it
Between gap；
5, hollow pipe internal surface is equipped with protrusion, increases the contact area between hollow tube and filler, enhances hollow tube
Connection between filler；
6, hollow inside pipe wall is coated with polyester-polyether mixed type watersoluble polyurethane adhesive, can prevent filler from solidifying
When lead to occur gap between hollow tube and filler due to volume contraction；
7, shield duct piece sealing strip passes through microwave vulcanization, and curing efficiency is high, and molding is reliable, the length of shield duct piece sealing strip
It can be needed and be cut according to product；
8, shield duct piece sealing strip good water absorption, sealing strip expands when touching underground water, fills up between shield duct piece
Gap prevents in seepage action of ground water to tunnel, guarantees the safety in tunnel.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of shield duct piece sealing strip.
Specific embodiment
Shield duct piece sealing strip as shown in Figure 1, outer layer are hollow tube 1, and internal layer is filler 2.1 outer surface of hollow tube is set
There are at least four grooves 3, groove 3 matches with shield duct piece side, so that shield duct piece sealing strip fitting shield duct piece be spelled
Seam gap.For 1 inner surface of hollow tube at least provided with four protrusions 4, protrusion 4 is corresponding with groove 3.Protrusion 4 increase hollow tube 1 with
Contact area between filler 2 enhances the connection between hollow tube and filler.
Raw material is as follows in embodiment:
A. polyethylene glycol: PEG-4000 B. polypropylene glycol: PPG-4000 C:MDI D1: liquid nitrile rubber D2: liquid
Butyl rubber D3: Liquid Ethylene Propylene Methylene E: white carbon black F: carbon fiber G: 405 H of anti-aging agent: bentonite I1:1,4- butanediol
I2:1,6- hexylene glycol I3: glycerol I4: trimethylolpropane I5: diethylene glycol (DEG) J: chlorinated paraffin K: nanometer calcium carbonate L: ring
Oxidative ethane M: propylene oxide N: pentaerythrite O: potassium hydroxide P: phosphoric acid Q: aluminium hydroxide R:TDI S1: dihydroxymethyl third
Sour S2: dimethylolpropionic acid S3:1,2- dihydroxy -3-N-morpholinopropanesulfonic acid sodium S4: ethylenediamine base sodium sulfonate S5: ethylenediamine base sulfonic acid
Sodium
Embodiment 1
The polypropylene glycol of the polyethylene glycol of 50 mass parts and 30 mass parts is heated to 110 DEG C of stirring 0.5h, keeps temperature
And vacuum defoamation 2h；The polyethylene glycol of premix and polypropylene glycol are added in reaction kettle, 20 parts of diphenyl is added in reaction kettle
Methane diisocyanate (MDI) is simultaneously warming up to 85 DEG C, and when reactor pressure is slowly reduced to 0, vacuum defoamation 1h and drying are obtained
To hollow tube performed polymer.
The liquid rubber of 5 mass parts, the white carbon black of 15 mass parts, 20 matter is added in the hollow tube performed polymer for weighing 80 mass parts
Measure the carbon fiber of part, the anti-aging agent 405 of 1 mass parts, the bentonites of 10 mass parts, the chlorinated paraffin of 2 mass parts, 1 mass parts
Nanometer calcium carbonate is heated to 80~90 DEG C of stirring 0.5h.The chain extender of 5 mass parts of 110 DEG C of preheating is added, 1h is mixed.
Manufactured hollow tube coarse fodder is put into extruder, extruder is equipped with hollow tube extrusion die, cuts after extrusion by microwave vulcanization
It cuts and hollow tube is made, microwave temperature is 140 DEG C, and hot-air cure temperature is 150 DEG C.
The polyethylene glycol of 35 mass parts is put into reaction kettle, reaction kettle is warming up to 65 DEG C, and 5 mass are added after being passed through nitrogen
The toluene di-isocyanate(TDI) of part, keeping reactor temperature is 100~110 DEG C, and polyester prepolymer is made.By 45 mass parts rings
Oxidative ethane is put into reaction kettle, and reaction kettle is warming up to 85 DEG C, is passed through the toluene di-isocyanate(TDI) that 5 mass parts are added after nitrogen, is protected
Holding reactor temperature is 110~120 DEG C, and polyether-type performed polymer is made after reacting 2h.Take 100 mass parts polyester prepolymers and
Polyether-type performed polymer is put into the sealing container with stirring, is stirred under vacuum 1h.The chain extender glycerol and 3.5 of 3 mass parts is added
The hydrophilic chain extender dihydromethyl propionic acid of mass parts, pre-polymerization 2h.It is added in the salt forming agent triethylamine of a certain amount of 0.3 mass parts
With stirring 0.5h.Water is added to be emulsified, ultrasonic disperse 0.5h is finally made the bonding of polyester-polyether mixed type watersoluble polyurethane
Agent.By polyester-polyether mixed type watersoluble polyurethane adhesive even application to hollow inside pipe wall.
Injection molding machine is equipped with hollow pipe die, and hollow pipe die is equipped with preformed groove, hollow tube is put into preformed groove, injection molding machine
Nozzle be aligned hollow tube.
The ethylene oxide of 80 mass parts and the propylene oxide of 10 mass parts nitrogen are pressed into the sealing container with stirring
In, stirring 0.5h mixes well material.The pentaerythrite and 0.1 mass parts of 0.5 mass parts of initiator are added in a kettle
Potassium hydroxide, take the air in reaction kettle away with vacuum pump, then pour nitrogen protection.Reaction kettle is heated to 55 DEG C, slowly presses
Enter the ethylene oxide of 90 mass parts and the premix material of propylene oxide, makes its reaction.Charging valve is adjusted, is remained in reaction kettle
Temperature is 110 DEG C, pressure 4kPa, and is constantly water-cooled temperature in the kettle.After premixing material addition, temperature in kettle is kept
Degree, makes its pressure slowly fall to 0.The coarse fodder indentation of end of reaction is neutralized in kettle, the neutralizer phosphoric acid of 0.3 mass parts is added
With the refining agent aluminium hydroxide of 0.3 mass parts, stirs 1 hour, filter and package to obtain high molecular polyether.
High molecular polyether after the purification of 7 mass parts is added in reaction kettle, heating makes the material in reaction kettle to 75 DEG C
When, the TDI for being slowly added into 10 mass parts makes its reaction, and keeping in mansion temperature is 100 DEG C, pressure from 1kPa automatically slowly under
Drop, reaction time are 3 hours.Blowing is packed when pressure drops to 0 in kettle, and when cooling to 50 DEG C, obtains extraordinary performed polymer.
By the extraordinary performed polymers of 80 mass parts be added the liquid butyl rubber of 3 mass parts, the bentonite of 10 mass parts, 2 mass parts it is anti-
Old agent 405,1 mass parts white carbon black, controlled at 80~90 DEG C, stir half an hour.Add 5 mass parts chain extender and
The hydrophilic chain extender of 1 mass parts maintains the temperature at 90~100 DEG C, stirs 1 hour.The above-mentioned manufactured coarse fodder of step is poured into
Casting machine, pouring temperature are maintained at 100 DEG C, demould after 3 hours, and filler coarse fodder is made.
Manufactured filler coarse fodder is poured into the feed opening of injection molding machine, during filler coarse fodder is slowly injected to by injection molding machine
Inside blank pipe, pouring temperature is maintained at 100 DEG C, and the oven that mold is put into 110 DEG C is solidified, be opened after 2h and cut off it is extra
Shield duct piece sealing strip is made in filler.
Shield duct piece sealing strip carries out secondary microwave vulcanization, and microwave temperature is 120 DEG C, and hot-air cure temperature is 130 DEG C.
The water-swelling property and mechanical property of the prepared shield duct piece sealing strip of test.
The manufacturing method of embodiment 2~5 is with embodiment 1, and only hollow tube and the specific composition proportion of filler are different, in
See Table 1 for details for the specific composition proportion of blank pipe, and see Table 2 for details for the specific composition proportion of filler.
Table 1: hollow tube composition proportion (being mass fraction in table)
| Embodiment | A | B | C | D | E | F | G | H | I | J | K |
| 1 | 40 | 24 | 16 | 5D1 | 15 | 10 | 1 | 10 | 5I1 | 2 | 1 |
| 2 | 56 | 32 | 32 | 7D1 | 17 | 12 | 3 | 12 | 7I2 | 3 | 2 |
| 3 | 50 | 30 | 20 | 8D2 | 18 | 13 | 4 | 15 | 8I3 | 5 | 3 |
| 4 | 60 | 45 | 30 | 10D2 | 20 | 15 | 5 | 20 | 10I4 | 6 | 3 |
| 5 | 70 | 40 | 40 | 15D2 | 30 | 22.5 | 7.5 | 30 | 15I5 | 9 | 4.5 |
Table 2: filler composition proportion (being mass fraction in table)
Shield duct piece sealing strip made of embodiment 1-5 is subjected to tensile stress-strain performance test and Shao Er A type hardness tester
Test, concrete outcome are as shown in table 3.
Table 3: the performance of shield duct piece sealing strip before absorbing water
Shield duct piece sealing strip made of embodiment 1-5 is put into the water suction of middle test sealing strip after 25 DEG C of distilled water 48h
Expansion rate, and sealing strip after water suction is subjected to tensile stress-strain performance test and the test of Shao Er A type hardness tester, concrete outcome such as table
Shown in 4.
Table 4: the performance of shield duct piece sealing strip after water suction
According to the data of table 3 and table 4, the expansion rate of water absorption and mechanical performance of shield duct piece sealing strip made of the present invention exist
Meet water before and after be above conventional water-swellable polyurethane material (conventional water-swellable polyurethane material expansion rate of water absorption >=360%,
Tensile strength >=4MPa, elongation at break >=500%), hollow tube and filler are completely embedded, water suction front and back hollow tube and filling
Do not occur gap between object, mechanical performance decline degree is small, and stability is high.
The above is only specific embodiments of the present invention, but technical characteristic of the invention is not limited thereto.It is any with this hair
Based on bright, to solve essentially identical technical problem, essentially identical technical effect is realized, made ground simple change, etc.
With replacement or modification etc., all it is covered by among protection scope of the present invention.
Claims (10)
1. a kind of manufacturing method of shield duct piece sealing strip, which comprises the steps of:
A. hollow tube is manufactured:
A. hollow tube performed polymer is synthesized:
Methyl diphenylene diisocyanate is added in pre- mixed polyethylene glycol and polypropylene glycol, hollow tube performed polymer is made；
B. hollow tube is synthesized:
(1) liquid rubber, white carbon black, carbon fiber, anti-aging agent, bentonite, chlorinated paraffin, nano-sized carbon is added in hollow tube performed polymer
Sour calcium is heated to 80~90 DEG C of stirring 0.5h；
(2) chain extender of 110~125 DEG C of preheating is added, 1h is mixed；Manufactured hollow tube coarse fodder is put into extruder, is squeezed
Machine is equipped with hollow tube extrusion die out, is cut into hollow tube by microwave vulcanization after extrusion；
B. fix hollow tube: injection molding machine is equipped with hollow pipe die, and the hollow pipe die is equipped with preformed groove, hollow tube is put into pre-
It stays in slot, the nozzle of injection molding machine is directed at hollow tube；
C. filler is manufactured:
A. high molecular polyether is synthesized:
Ethylene oxide, propylene oxide, pentaerythrite and potassium hydroxide are put into reaction kettle reaction, high molecular polyether is made；
B. filler performed polymer is synthesized:
(1) high molecular polyether that step a is obtained is added in reaction kettle, heats reaction kettle to 75~85 DEG C, it is different that toluene two is added
Cyanate makes its reaction, and keeping temperature in the kettle is 95~105 DEG C, and pressure declines from 1kPa, reaction time 3h；
(2) when pressure drops to 0 in kettle, blowing is packed when cooling to 50~60 DEG C, obtains filler performed polymer；
C. filler is synthesized:
(1) liquid rubber, bentonite, anti-aging agent, white carbon black is added in the filler performed polymer for synthesizing step b, controlled at
80~90 DEG C, stir 0.5h；
(2) in the raw material that addition chain extender and hydrophilic chain extender are mixed to step c (1), 90~100 DEG C is maintained the temperature at, is stirred
It mixes 1h and filler coarse fodder is made；
D. in injection fillers object to hollow tube: filler coarse fodder manufactured in step C is poured into the feed opening of injection molding machine in step B
Interior, filler coarse fodder is slowly injected to hollow tube by injection molding machine from bottom to top, and pouring temperature is maintained at 100 DEG C, by mold
It is put into 110 DEG C of oven to be solidified, extra filler is opened and cut off after 2h, shield duct piece sealing strip is made；
E. the shield duct piece sealing strip in step D is subjected to secondary microwave vulcanization.
2. a kind of manufacturing method of shield duct piece sealing strip according to claim 1, it is characterised in that:
In the step A-a, specific step is as follows for synthesis hollow tube performed polymer:
(1) polyethylene glycol and polypropylene glycol are heated to 100~140 DEG C of stirring 0.5h, keep temperature and vacuum defoamation 2h；
(2) polyethylene glycol of premix and polypropylene glycol are added in reaction kettle, diphenylmethane diisocyanate is added in reaction kettle
Ester is simultaneously warming up to 80~90 DEG C, and when reactor pressure is slowly reduced to 0, vacuum defoamation 1h and drying obtain hollow tube pre-polymerization
Body.
3. a kind of manufacturing method of shield duct piece sealing strip according to claim 1, it is characterised in that:
In the step C-a, synthesizing high molecular polyether, specific step is as follows:
(1) ethylene oxide and propylene oxide are pressed into the sealing container with stirring with ammonia, stirring 0.5h keeps material abundant
It mixes；
(2) it is added initiator pentaerythrite and catalyst potassium hydroxide in a kettle, the air in vacuum pump extraction kettle,
Nitrogen protection is poured again；
(3) reaction kettle is heated to 55~65 DEG C, is pressed into pre- mixed ethylene oxide and propylene oxide, makes its reaction；
(4) charging valve is adjusted, keeping reactor temperature is 100~120 DEG C, 4~5kPa of pressure, and is constantly water-cooled in kettle
Temperature；
(5) after ethylene oxide and propylene oxide are added, temperature in the kettle is kept, its pressure is made slowly to fall to 0, be made thick
Material；
(6) above-mentioned coarse fodder is pressed into and is neutralized in kettle, neutralizer phosphoric acid and refining agent aluminium hydroxide is added, stirred 1h, filter and package
Obtain high molecular polyether.
4. a kind of manufacturing method of shield duct piece sealing strip according to claim 1, it is characterised in that: the step A and institute
State one step of increase between step B: in hollow inside pipe wall even application polyester-polyether mixed type watersoluble polyurethane adhesive.
5. a kind of manufacturing method of shield duct piece sealing strip according to claim 4, it is characterised in that: the polyester-polyether
The manufacturing method of mixed type watersoluble polyurethane adhesive is as follows:
(1) polyethylene glycol is put into reaction kettle, reaction kettle is warming up to 60~70 DEG C, and toluene diisocynate is added after being passed through nitrogen
Ester, keeping reactor temperature is 100~110 DEG C, and polyester prepolymer is made；
(2) ethylene oxide is put into reaction kettle, reaction kettle is warming up to 80~90 DEG C, and toluene diisocynate is added after being passed through nitrogen
Ester, keeping reactor temperature is 110~120 DEG C, and polyether-type performed polymer is made after reacting 2h；
(3) polyester prepolymer and polyether-type performed polymer are put into the sealing container with stirring, are stirred under vacuum 1h；
(4) chain extender and hydrophilic chain extender, pre-polymerization 2h is added；
(5) salt forming agent is added to neutralize, stirs 0.5h；
(6) water is added to be emulsified, ultrasonic disperse 0.5h is finally made polyester-polyether mixed type watersoluble polyurethane adhesive.
6. a kind of manufacturing method of shield duct piece sealing strip according to claim 1, it is characterised in that: the hollow tube appearance
Face is equipped at least four grooves, and the hollow pipe internal surface is equipped at least four protrusions, and the groove is corresponding with the protrusion,
The hollow thickness of pipe wall 3mm.
7. a kind of manufacturing method of shield duct piece sealing strip according to claim 1, it is characterised in that: in step A and step E
Microwave vulcanization process is that hollow tube or shield duct piece sealing strip sequentially enter microwave box, hot-air cure case, air cooled box and cutting
Machine, wherein microwave temperature is 140 DEG C in step A, and hot-air cure temperature is 150 DEG C, and microwave temperature is 120 DEG C in step E, heat
Air cure temperature is 130 DEG C.
8. according to claim 1 or a kind of 5 manufacturing methods of shield duct piece sealing strip, it is characterised in that: the chain extender
For one in 1,4- butanediol, 1,6-HD, glycerol, trimethylolpropane, diethylene glycol (DEG), triethylene glycol, neopentyl glycol, sorbierite
Kind or a variety of mixtures；The hydrophilic chain extender is dihydromethyl propionic acid, dimethylolpropionic acid, 1,2- dihydroxy -3- third
One of sodium sulfonate, ethylenediamine base sodium sulfonate, ethylenediamine base sodium sulfonate or a variety of mixtures.
9. a kind of manufacturing method of shield duct piece sealing strip according to claim 1, it is characterised in that: the liquid rubber is
One of liquid nitrile rubber, liquid butyl rubber, Liquid Ethylene Propylene Methylene, liquid polysulfide rubber or a variety of mixtures.
10. a kind of manufacturing method of shield duct piece sealing strip according to claim 1, it is characterised in that: the anti-aging agent is
One of antioxidant BHT, anti-aging agent 405, anti-aging agent MDA or a variety of mixtures.
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