CN105906778A - Environment-friendly high-intensity waterborne polyurethane slurry and preparation method thereof - Google Patents
Environment-friendly high-intensity waterborne polyurethane slurry and preparation method thereof Download PDFInfo
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- 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
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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
- 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
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
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- 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
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
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- 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
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- 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
- C08G18/58—Epoxy resins
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- 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
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Abstract
The invention discloses environment-friendly high-intensity waterborne polyurethane slurry and a preparation method thereof, and belongs to the field of adhesives. The environment-friendly high-intensity waterborne polyurethane slurry consists of a component A and a component B according to the mass ratio being 100:(10-100), wherein the component A contains the following components including 100 to 30 weight percent of polyoxyethylene polyoxypropylene block polyether type polyurethane prepolymers, 0 to 60 weight percent of polyoxyethylene ester type polyurethane prepolymers and 0 to 10 weight percent of liquid epoxy resin; the component B contains the following components including 30 to 90 weight percent of fatty aminepolyoxyethylene polyoxypropylenepolyether polyol and 70 to 10weight percent of polyoxyethylene polyoxypropylenepolyether polyolsuccinic acid ester. The environment-friendly high-intensity waterborne polyurethane slurry contains hydrophobicbenzene rings, PPO chain sections and hydrophilic PEO chain sections, tertiary amine base groups and tertiary amineorganic carboxylate; amphipathicself-emulsifying performing and better emulsifying dispersion with water can be realized; the curing speed of pure slurry or water-containing slurry gel is adjustable; an induration body has higher hardness.
Description
Technical field
The invention belongs to adhesive field, particularly to a kind of environment protection type high-strength aqueous polyurethane slurry and
Preparation method.
Background technology
Polyurethane grouting material is a kind of novel high polymer material, and its main component is polyurethane prepolymer,
It is characterized in that permeability is preferable, bond effect good, water resistance is good.The raw material used is different with technique, group
The effect becoming size performance, purposes, the character of solidfied material and acquirement is the most different, and the scope of application is very wide, as it can
To be applied to civil buildings, water conservancy and hydropower and the field such as subway tunnel and coal mining.
At present, China's polyurethane grouting material aspect has carried out research and application and development widely, mainly wraps
Include plain edition waterborne polyurethane grouting material, plain edition hydrophobic polyurethane grouting material, dual-component polyurethane are robbed
Danger reinforces grouting material, environment-protecting polyurethane grouting material and no-solvent type polyurethane grouting material etc., but they have
A little use solvent or plasticizer, hydrophilic solvent or auxiliary agents etc., be harmful to environment and human body, intensity phase
To relatively low, curing rate is difficult to regulate and control, and range of application is restricted.There is the controllable of amphipathic self emulsifying
The high-strength water-based polyurethane grouting material of bi-component environmental-protecting of curing rate there are no document report.
Summary of the invention
The primary and foremost purpose of the present invention is to overcome shortcoming and deficiency present in prior art, it is provided that a kind of environmental protection
The high-strength water-based polyurethane slurry of type.This environment protection type high-strength aqueous polyurethane pulp strength is high, has amphiphilic
Property self emulsifying and curing rate are adjustable.
Another object of the present invention is to provide the preparation method of described aqueous polyurethane slurry.
The purpose of the present invention is achieved through the following technical solutions: a kind of environment protection type high-strength aqueous polyurethane slurry,
It is made up of for 100:10～100 in mass ratio the first and second two kinds of components:
Described first component comprises following composition the most by weight percentage: 100～30wt% polyoxyethylene polyoxies third
Alkene block polyether-polyurethane prepolymer, 0～60wt% polyoxypropylene polyether type polyurethane prepolymer and 0～10wt%
Liquid epoxies.
Described polyoxyethylene polyoxypropylene block polyether-polyurethane prepolymer is preferably toluene diisocyanate list
Body TDI, liquefaction MDI MDI and the polyoxyethylene polyoxy third at least containing two terminal hydroxy groups
Alkene block polyether (or claiming block polyether polyol) contains work in what 50～90 DEG C of additive reaction 3～5 hours obtained
Property the line style of Carbimide. ester bond or branched EU prepolymer, described at least containing two terminal hydroxy groups
Polyoxyethylene polyoxypropylene block polyether be preferably molecular weight 1000～3000 PEO-PPO-PEO,
PPO-PEO-PPO tri-block linear polyether or many blocks ramiform polyethers, wherein EO accounts for the total matter of EO Yu PO
The 10～40wt% of amount；Isocyanate groups (-N=C=O) content in described prepolymer is preferably 3～7wt%；
Described at least polyoxyethylene polyoxypropylene block polyether containing two terminal hydroxy groups (or claim block polyether many
Unit's alcohol) preferably prepare with binary or polyhydric alcohol for initiator.
Described polyoxypropylene polyether type polyurethane prepolymer is preferably toluene diisocyanate monomer TDI, liquefaction
MDI and molecular weight 300～3000 and at least contain the polyoxypropylene polyether polyhydric alcohol of two terminal hydroxy groups in
70～100 DEG C of additive reaction 3～the EU prepolymer containing active isocyanate key obtained for 5 hours；
Isocyanate groups (-N=C=O) content in described prepolymer is preferably 4～10wt%.
Described liquid epoxies is preferably bisphenol A epoxide resin E-51 or E-44.
Described second component comprises following composition the most by weight percentage: 30～90wt% aliphatic amine polyoxyethylenes
Polyoxypropylene polyether polyhydric alcohol and 70～10wt% polyoxyethylene polyoxypropylene polyether polyol succinates.
Described aliphatic amine polyoxyethylene polyoxypropylene polyether polyhydric alcohol is at least to contain 1 tertiary amine group and extremely
The polyether polyol of few 2 terminal hydroxy groups；
Described aliphatic amine polyoxyethylene polyoxypropylene polyether polyhydric alcohol includes containing only EO chain link and 1 tertiary amine groups
The aliphatic amine polyoxyethylene ether dihydroxylic alcohols of group, preferably 18-amine. polyoxyethylene ether AC-1810,18-amine. are poly-
Oxygen vinyl Ether AC-1830, lauryl amine polyoxyethylene ether AC-1215；
Described aliphatic amine polyoxyethylene polyoxypropylene polyether polyhydric alcohol is more preferably with ethylenediamine, N-aminoethyl
Piperazine, diethylenetriamine, triethylene tetramine, TEPA be initiator prepare at least containing 2 tertiary amines
The aliphatic amine polyoxyethylene polyoxypropylene polyether polyhydric alcohol of group and at least 3 terminal hydroxy groups, wherein EO accounts for EO
It is preferably 25～50 with 0～40wt%, EO and PO chain link sum of PO gross mass.
Described polyoxyethylene polyoxypropylene polyether polyol succinate is by least containing 2 terminal hydroxy groups
Single-ended base monomester succinate that polyoxyethylene polyoxypropylene polyether polyol is obtained by succinic acid esterification and/or many
End group succinate；Described polyoxyethylene polyoxypropylene polyether polyol is preferably molecular weight 4000～400
PEO-PPO, PEO-PPO-PEO, PPO-PEO-PPO type block polyether, polyoxypropylene polyether polynary
Alcohol；In described PPO-PEO-PPO type block polyether, EO accounts for the 0～40wt% of EO Yu PO gross mass.
The preparation method of described environment protection type high-strength aqueous polyurethane slurry, comprises the following steps:
(1) by 100～30wt% polyoxyethylene polyoxypropylene block polyether-polyurethane prepolymers, 0～60wt%
Polyoxypropylene polyether type polyurethane prepolymer and 0～10wt% liquid epoxies
Uniform in mixed at room temperature, obtain first component；
(2) by 30～90wt% aliphatic amine polyoxyethylene polyoxypropylene polyether polyhydric alcohol and 70～10wt%
Polyoxyethylene polyoxypropylene polyether polyol or its succinate are uniform in mixed at room temperature, obtain second component；
(3) it is 100:10～100 in mass ratio by the second component of the first component of step (1), step (2)
After mix homogeneously, anhydrous or aqueous base material, aqueous slurry are irrigated or brush, cold curing, obtain ring
The high-strength water-based polyurethane slurry of guarantor's type.
The polyethers simultaneously containing hydrophilic group EO chain link and lipophilic group PO chain link in molecule is passed through by the present invention
Additive reaction is prepared has amphipathic polyurethane prepolymer as first component, easily realizes water emulsification, in advance
Isocyanate groups in polymers is the basis of further cross-linking reaction solidification.Fatty amine polyoxy in second component
Ethylene polyethenoxy ether does not contain only hydrophilic and catalysis isocyanate groups and hydroxyl in polyethers or the hydroxyl in water
The tertiary amine groups that base reacts, and strand contains multiple hydroxyl simultaneously, affinity is higher, reaction interval
Du Genggao, concretion body strength is bigger.Meanwhile, the polyoxyethylene polyoxypropylene block polyether succinum in second component
Acid esters contains the carboxylic acid of slow setting, and the weak acid and weak base that these carboxylic acids and tertiary amine interaction form hydrophilic higher has
Machine salt, on the one hand can regulate the gel solidification speed of serosity, on the other hand goes far towards polyurethane serosity
Amphipathic balance, rapid emulsion dispersion when meeting with aqueous phase, effectively in the solidification of isocyanate groups Yu hydroxyl
Reaction, induration has higher intensity simultaneously.Tertiary amine also contributes to the curing reaction of epoxy resin simultaneously,
It is favorably improved intensity and adhesive property.
The present invention has such advantages as relative to prior art and effect:
(1) present invention contain hydrophobic phenyl ring, PPO segment and hydrophilic PEO segment, tertiary amine group and
Tert-amine carboxylate's organic salt, has amphiphilic self emulsifying, can be with water emulsion dispersion well；
(2) present invention uses and contains catalysis urethane cures and the tertiary amine of catalysis epoxide group ring-opening reaction simultaneously
The polyethers succinate of group and many terminal hydroxy groups and deferred action, clean slurry or aqueous slurry gel solidification speed can
Adjusting, induration has higher intensity；
(3) present invention does not contains solvent or other poisonous and harmful auxiliary agent, is a kind of environment-friendly type slurry.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention do not limit
In this.
The preparation of embodiment 1 waterborne polyurethane prepolymer:
(1) in the there-necked flask of 5000mL, propanediol polyoxypropylene polyoxyethylene blocks polyethers L-61 is added
(mean molecule quantity is 2000 for Hai'an, Jiangsu petrochemical industry, HO-PEO-PPO-PEO-H type) 2000g,
Add toluene di-isocyanate(TDI) TDI 435g, after stirring, be warming up to 60 DEG C and react 5 hours, cool down standby
With, seal and preserve, numbered block polyether polyurethane prepolymer PU1.Sampling, measures by di-n-butylamine method
The content of the isocyanate groups (-N=C=O) going out PU1 is 4.9wt%.
(2) in the there-necked flask of 5000mL, polyoxyethylene polyoxypropylene block polyether RPE1740 is added
(mean molecule quantity is 2500 for BASF AG, HO-PPO-PEO-PPO-H type) 2500g, adds toluene
Diisocyanate TDI 382.8g, after stirring, is warming up to 70 DEG C and reacts 4 hours, cool down standby, close
Envelope preserves, numbered block polyether polyurethane prepolymer PU2.Sampling, measures PU2's by di-n-butylamine method
The content of isocyanate groups (-N=C=O) is 3.3wt%.
(3) in the there-necked flask of 5000mL, polyoxyethylene polyoxypropylene block polyether RPE1720 is added
(mean molecule quantity is 2000 for BASF AG, HO-PPO-PEO-PPO-H type) 2000g, adds liquefaction
MDI (MDI) (Yantai ten thousand China ,-N=C=O content is 28wt%) 660g, stirring
After Jun Yun, it is warming up to 80 DEG C and reacts 3 hours, cool down standby, seal and preserve, the poly-ammonia of numbered block polyether
Ester prepolymer PU3.Sampling, measures the containing of isocyanate groups (-N=C=O) of PU3 by di-n-butylamine method
Amount is 3.6wt%.
(4) in the there-necked flask of 5000mL, propanediol polyoxypropylene polyoxyethylene blocks polyethers L-43 is added
(mean molecule quantity is 1850 for Hai'an, Jiangsu petrochemical industry, HO-PEO-PPO-PEO-H type) 1850g,
Add TDI 487.2g, after stirring, be warming up to 50 DEG C and react 5 hours, cool down standby, seal and preserve,
Numbered block polyether polyurethane prepolymer PU4.Sampling, measures the isocyanates of PU4 by di-n-butylamine method
The content of group (-N=C=O) is 6.1wt%.
(5) reference " Dong monarch etc. the synthesis of block polymer demulsifier and demulsification rule. Chemical Engineering
Teacher, 2005, (9): 64-66 " prepare glycerol ramiform block polyether:
Initiator glycerol (glycerol) and catalyst potassium hydroxide are added in 0.5 liter of autoclave, uses
N2Fully scavenging pipeline and still, stir and be warming up to 90 DEG C, and evacuation also continues to heat up, to when 120 DEG C (about
0.5 hour) stop evacuation, drip oxirane, 125 ± 5 DEG C, react under≤0.3MPa, until
Initiator and molar ratio reach 1:15, obtain hydrophilic head.In autoclave, by identical
Operating procedure is warming up to 120 DEG C, drips expoxy propane, at 135 ± 5 DEG C ,≤0.4MPa after stopping evacuation
Lower reaction, adds expoxy propane until initiator and expoxy propane molar ratio reach 1:30, after 135 ±
5 DEG C are reacted 0.5 hour again, cooling, then use in the glacial acetic acid of equivalent and potassium hydroxide, obtain strand
Upper average EO and PO number is the polyethers shown in following formula, and this polyethers mean molecule quantity is 2492:
[H-(OP)10(OE)5]OCH2-CH[O(EO)5(PO)10-H]-CH2O[(EO)5(PO)10-H]
In the there-necked flask of 5000mL, add this polyethers 2492g, at room temperature add TDI 678.6g, stir
After mixing uniformly, being warming up to 90 DEG C and react 3 hours, cool down standby, seal and preserve, numbered block polyether gathers
Urethane prepolymer PU5.Sampling, the content measuring isocyanate groups (-N=C=O) by di-n-butylamine method is
6.0wt%.
(6) add in the there-necked flask of 5000mL polyoxypropylene polyether polyhydric alcohol N-210 (east, Shandong is big,
HO-PPO-H type, mean molecule quantity is 1000) (east, Shandong is big, and mean molecule quantity is for 1000g and N303
3000, three terminal hydroxy groups) 30g, add toluene di-isocyanate(TDI) TDI 520.6g, after stirring, heat up
React 5 hours to 70 DEG C, cool down standby, seal and preserve, numbered polyoxypropylene polyether prepolymer PU6.
Sampling, the content of the isocyanate groups (-N=C=O) measuring PU6 by di-n-butylamine method is 9.4wt%.
(7) add in the there-necked flask of 5000mL polyoxypropylene polyether polyhydric alcohol N-220 (east, Shandong is big,
HO-PPO-H type, mean molecule quantity is 2000) (east, Shandong is big, HO-(PPO-H) for 2000g and N-3302
Type, mean molecule quantity is 3000) 200g, add liquefaction MDI (MDI) (-N=C=O
Content is 28wt%) 858g, after stirring, it is warming up to 100 DEG C and reacts 3 hours, cool down standby, seal
Preserve, numbered polyoxypropylene polyether prepolymer PU7.Sampling, measures the isocyanide of PU7 by di-n-butylamine method
The content of acid esters group (-N=C=O) is 4.6wt%.
The preparation of embodiment 2 aliphatic amine polyoxyethylene polyoxypropylene polyether polyhydric alcohol:
With reference to " Zhang Jiehui etc. the synthesis of multi-block polyether, structure are studied with demulsification performance. oilfield chemistry,
1997,14 (4): 324-328 " prepare:
(1) initiator TEPA and catalyst acetic acid calcium, potassium hydroxide are added 0.5 liter of reaction under high pressure
In still, use N2Fully scavenging pipeline and still, stir and be warming up to 90 DEG C, and evacuation also continues to heat up, to 120 DEG C
Time (about 0.5 hour) stop evacuation, drip expoxy propane, 135 ± 5 DEG C, react under≤0.4MPa,
Until initiator and expoxy propane molar ratio reach 1:49, cooling, then neutralize with the glacial acetic acid of equivalent
Potassium hydroxide, obtains the TEPA that the reactive hydrogen on each N is the most averagely replaced by PPO shown in following formula
Polyethenoxy ether TEPAPPO1, TEPAPPO1 mean molecule quantity is 3031, containing 5 tertiary amines and 7
Terminal hydroxy group: [H-(OP)7]2N-[CH2CH2N[(PO)7-H]]3-CH2CH2N[(PO)7-H]2。
(2) initiator ethylenediamine and catalyst acetic acid calcium, potassium hydroxide are added in 0.5 liter of autoclave,
Use N2Fully scavenging pipeline and still, stir and be warming up to 90 DEG C, and evacuation also continues to heat up, during to 120 DEG C
(about 0.5 hour) stops evacuation, drips expoxy propane, 135 ± 5 DEG C, react under≤0.4MPa, directly
Reach 1:20 to initiator and expoxy propane molar ratio, obtain oleophylic head.In autoclave, by phase
Biconditional operation step is warming up to 120 DEG C, drips oxirane, at 125 ± 5 DEG C ,≤0.3MPa after stopping evacuation
Lower reaction, adds oxirane until initiator and molar ratio reach after 1:6 at 125 ± 5 DEG C
React again 0.5 hour, cooling, then use in the glacial acetic acid of equivalent and potassium hydroxide, obtain on each N
The ethylenediamine polyoxyethylene polyoxypropylene that the most averagely replaced by PPO-PEO diblock shown in following formula respectively of reactive hydrogen
Ether EDAPPOPEO2, EDAPPOPEO2 mean molecule quantity is 1484, containing 2 tertiary amines and 4 ends
Hydroxyl: [H-(OE)1.5(OP)5]2N-CH2CH2N[(PO)5(EO)1.5-H]2。
(3) initiator diethylenetriamine and catalyst acetic acid calcium, potassium hydroxide are added 0.5 liter of reaction under high pressure
In still, use N2Fully scavenging pipeline and still, stir and be warming up to 90 DEG C, and evacuation also continues to heat up, to 120 DEG C
Time (about 0.5 hour) stop evacuation, drip oxirane, 125 ± 5 DEG C, react under≤0.3MPa,
Until initiator and molar ratio reach 1:10, obtain hydrophilic head.In autoclave, press
Same operation step is warming up to 120 DEG C, stops dripping after evacuation expoxy propane, 135 ± 5 DEG C ,≤0.4
React under MPa, add expoxy propane until initiator and expoxy propane molar ratio reach 1:40, after
135 ± 5 DEG C are reacted 0.5 hour again, cooling, then use in the glacial acetic acid of equivalent and potassium hydroxide, obtain
The diethylenetriamine polyoxy that reactive hydrogen on each N is the most averagely replaced by PEO-PPO diblock shown in following formula
Ethylene polyethenoxy ether DETAPEOPPO3, DETAPEOPPO3 mean molecule quantity is 2863, containing 3
Individual tertiary amine and 5 terminal hydroxy groups: [H-(OP)8(OE)2]2N-CH2CH2N[(EO)2(PO)8
-H]CH2CH2N[(EO)2(PO)8-H]2。
The preparation of embodiment 3 polyoxyethylene polyoxypropylene block polyether succinate:
With reference to " Wu Jinchuan etc. live in the surface of fatty alcohol oxygen ethylene/oxypropylene segmentation polyethers mono succinate sodium sulfonate
Property. petrochemical industry, 1997,26 (9): 620～622 " prepare:
(1) in the there-necked flask of 5000mL add block polyether L-62 (Hai'an, Jiangsu petrochemicals,
Mean molecule quantity is 2500, and EO content is 20wt%) 2500g, add the maleic anhydride of 2mol,
Esterification 4h at 100 DEG C, cools down to be shown below the disuccinic acid monoesters containing two end carboxyl
MAPE1, standby: HOOCCH=CHCOO (EO)n(PO)m(EO)nOCCH=CHCOOH.
(2) in the there-necked flask of 5000mL add block polyether L-62 (Hai'an, Jiangsu petrochemicals,
Mean molecule quantity is 2500, and EO content is 20wt%) 2500g, add the maleic anhydride of 1.5mol,
Esterification 4h at 100 DEG C, cool down as shown in above formula containing two end carboxyl disuccinic acid monoesters and
Mixture M APE2 of the monomester succinate of 1 shown in following formula end carboxyl, standby:
HOOCCH=CHCOO (EO)n(PO)m(EO)nH。
(3) in the there-necked flask of 5000mL, add the glycerol block polyether prepared according to embodiment 2 method
[H-(OP)10(OE)5]OCH2-CH[O(EO)5(PO)10-H]-CH2O[(EO)5(PO)10-H] (molecular weight 2492)
2492g, adds the maleic anhydride of 3mol, is warming up to 120 DEG C and continues at 100 DEG C after esterification 2h
Continuous esterification 4h, cools down to be shown below the three monomester succinate MAPE3 containing three end carboxyl:
[HOOCCH=CHCO-(OP)10(OE)5]OCH2-CH[O(EO)5(PO)10-OCCH=CHCOOH]-CH2
O[(EO)5(PO)10-OCCH=CHCOOH].
Embodiment 4
A kind of environment protection type high-strength aqueous polyurethane slurry, is prepared by following steps:
(1) the prepared block polyether polyurethane prepolymer PU1 of 100g embodiment 1 is taken under room temperature as first group
Point, it is embedding that the prepared fatty amine polyethenoxy ether TEPAPPO1 of 9g embodiment 2 and 1g embodiment 3 prepare
Section polyethers succinate MAPE3 mix homogeneously is as second component, then rapidly by the first and second component mix homogeneously,
Carry out rapidly reverse mould, respectively clean surface solidification time, the 1 day comprcssive strength starched of test and tensile strength.
(2) same, take the block polyether polyurethane prepolymer PU1 work that 100g embodiment 1 prepares under room temperature
For first component, fatty amine polyethenoxy ether TEPAPPO1 and 1g embodiment 3 that 9g embodiment 2 prepares are made
Block polyether succinate MAPE3 mix homogeneously as second component, then rapidly by first and second liang of components and
55g water mix homogeneously, carries out rapidly reverse mould, tests the surface solidification time of aqueous slurry, 1 day resistance to compression respectively
Intensity.
Embodiment 5
A kind of environment protection type high-strength aqueous polyurethane slurry, is prepared by following steps:
(1) block polyether polyurethane prepolymer PU2,60g polyoxy that 30g embodiment 1 prepares is taken under room temperature
Propylene EU prepolymer PU6 and 10g epoxy resin E-44 mix homogeneously are as first component, 60g
Fatty amine block polyether EDAPPOPEO2,10g 18-amine. polyoxyethylene ether AC-1810 that embodiment 2 prepares
The block polyether succinate MAPE1 mixing that (Hai'an, Jiangsu petrochemical industry) and 30g embodiment 3 prepares is all
Even as second component, then rapidly by the first and second component mix homogeneously, carry out rapidly reverse mould, the respectively clean slurry of test
Surface solidification time, 1 day comprcssive strength and tensile strength.
(2) same, take block polyether polyurethane prepolymer PU2,60g that 30g embodiment 1 prepares under room temperature
Polyoxypropylene polyether type polyurethane prepolymer PU6 and 10g epoxy resin E-44 mix homogeneously as first component,
Fatty amine block polyether EDAPPOPEO2,10g 18-amine. polyoxyethylene ether that 60g embodiment 2 prepares
The block polyether succinate MAPE1 that AC-1810 (Hai'an, Jiangsu petrochemical industry) and 30g embodiment 3 prepare
Mix homogeneously, as second component, then rapidly by first and second liang of components and 100g water mix homogeneously, is carried out down rapidly
Mould, tests the surface solidification time of aqueous slurry, 1 day comprcssive strength respectively.
Embodiment 6
A kind of environment protection type high-strength aqueous polyurethane slurry, is prepared by following steps:
(1) block polyether polyurethane prepolymer PU2 and 60g polyoxy that 40g embodiment 1 prepares are taken under room temperature
Propylene EU prepolymer PU6 mix homogeneously is as first component, the fat that 30g embodiment 2 prepares
The block polyether succinate MAPE1 that amine block polyether EDAPPOPEO2 and 70g embodiment 3 prepare mixes
Close uniformly as second component, then rapidly by the first and second component mix homogeneously, carry out rapidly reverse mould, test respectively
Surface solidification time, the 1 day comprcssive strength of clean slurry and tensile strength.
(2) same, take under room temperature block polyether polyurethane prepolymer PU2 that 40g embodiment 1 prepares and
60g polyoxypropylene polyether type polyurethane prepolymer PU6 mix homogeneously is made as first component, 30g embodiment 2
The block polyether succinate that the fatty amine block polyether EDAPPOPEO2 obtained and 70g embodiment 3 prepare
MAPE1 mix homogeneously is as second component, then rapidly by first and second liang of components and 100g water mix homogeneously, fast
Speed carries out reverse mould, tests the surface solidification time of aqueous slurry, 1 day comprcssive strength respectively.
Embodiment 7
A kind of environment protection type high-strength aqueous polyurethane slurry, is prepared by following steps:
(1) block polyether polyurethane prepolymer PU3,45g polyoxy that 50g embodiment 1 prepares is taken under room temperature
Propylene EU prepolymer PU6 and 5g epoxy resin E-44 mix homogeneously are as first component, 25g
Fatty amine block polyether DETAPEOPPO3 and the prepared block of 25g embodiment 3 that embodiment 2 prepares gather
Ether succinate MAPE2 mix homogeneously is as second component, then rapidly by the first and second component mix homogeneously, rapidly
Carry out reverse mould, respectively clean surface solidification time, the 1 day comprcssive strength starched of test and tensile strength.
(2) same, take block polyether polyurethane prepolymer PU3,45g that 50g embodiment 1 prepares under room temperature
Polyoxypropylene polyether type polyurethane prepolymer PU6 and 5g epoxy resin E-44 mix homogeneously as first component,
It is embedding that the prepared fatty amine block polyether DETAPEOPPO3 of 25g embodiment 2 and 25g embodiment 3 prepare
Section polyethers succinate MAPE2 mix homogeneously is as second component, then rapidly by first and second liang of components and 75g water
Mix homogeneously, carries out rapidly reverse mould, tests the surface solidification time of aqueous slurry, 1 day comprcssive strength respectively.
Embodiment 8
A kind of environment protection type high-strength aqueous polyurethane slurry, is prepared by following steps:
(1) take prepared block polyether polyurethane prepolymer PU4 and 50g of 50g embodiment 1 under room temperature to gather
Oxypropylene EU prepolymer PU7 mix homogeneously is as first component, the fat that 25g embodiment 2 prepares
The block polyether succinate MAPE2 that fat amine block polyether DETAPEOPPO3 and 25g embodiment 3 prepare
Mix homogeneously, as second component, then rapidly by the first and second component mix homogeneously, carries out rapidly reverse mould, surveys respectively
Surface solidification time, the 1 day comprcssive strength of the clean slurry of examination and tensile strength.
(2) same, take under room temperature block polyether polyurethane prepolymer PU4 that 50g embodiment 1 prepares and
50g polyoxypropylene polyether type polyurethane prepolymer PU7 mix homogeneously is made as first component, 25g embodiment 2
The block polyether succinate that the fatty amine block polyether DETAPEOPPO3 obtained and 25g embodiment 3 prepare
MAPE2 mix homogeneously is as second component, then rapidly by first and second liang of components and 75g water mix homogeneously, rapidly
Carry out reverse mould, test the surface solidification time of aqueous slurry, 1 day comprcssive strength respectively.
Embodiment 9
A kind of environment protection type high-strength aqueous polyurethane slurry, is prepared by following steps:
(1) the prepared block polyether polyurethane prepolymer PU5 of 100g embodiment 1 is taken under room temperature as first group
Point, the lauryl amine polyoxyethylene ether of fatty amine polyethenoxy ether TEPAPPO1,1g that 8g embodiment 2 prepares
The block polyether succinate MAPE3 that AC-1215 (Hai'an, Jiangsu petrochemical industry) and 9g embodiment 3 prepare
Mix homogeneously, as second component, then rapidly by the first and second component mix homogeneously, carries out rapidly reverse mould, surveys respectively
Surface solidification time, the 1 day comprcssive strength of the clean slurry of examination and tensile strength.
(2) same, take the block polyether polyurethane prepolymer PU5 work that 100g embodiment 1 prepares under room temperature
For first component, the lauryl amine polyoxy of fatty amine polyethenoxy ether TEPAPPO1,1g that 8g embodiment 2 prepares
The block polyether succinate that vinyl Ether AC-1215 (Hai'an, Jiangsu petrochemical industry) and 9g embodiment 3 prepare
MAPE3 mix homogeneously is as second component, then rapidly by first and second liang of components and 59g water mix homogeneously, rapidly
Carry out reverse mould, test the surface solidification time of aqueous slurry, 1 day comprcssive strength respectively.
The test result of table 1 embodiment 4～9
In test result table 1 from embodiment 4～9, aqueous polyurethane serosity mixing prepared by the present invention
Having curing rate faster after solidification, clean slurry induration has the highest comprcssive strength and tensile strength, and
And slurry to have hydrophilic and oleophilic amphipathic, on the one hand accelerating with solidification in water mixed process, on the other hand containing
The water yield be 33% (the first and second mixed serums are 2:1 with the mass ratio of water) time consolidated uniformly, still have
Higher comprcssive strength.Generally, tertiary amine catalytic solidification polyurethane (time the most aqueous) speed the most quickly,
Gel time when second component is not added with succinate, within 1 minute, then reaches 200 in embodiments of the invention
More than Miao, there is curing gel time lengthening and adjustable feature.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-mentioned enforcement
The restriction of example, the change made, modifies, replaces under other any spirit without departing from the present invention and principle
In generation, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (9)
1. an environment protection type high-strength aqueous polyurethane slurry, it is characterised in that by the first and second two kinds of components by matter
Amount forms than for 100:10～100:
Described first component comprises following composition the most by weight percentage: 100～30wt% polyoxyethylene polyoxies
Polypropylene block EU prepolymer, 0～60wt% polyoxypropylene polyether type polyurethane prepolymer and
0～10wt% liquid epoxies；
Described second component comprises following composition the most by weight percentage: 30～90wt% aliphatic amine polyoxyethylenes
Polyoxypropylene polyether polyhydric alcohol and 70～10wt% polyoxyethylene polyoxypropylene polyether polyol succinates.
Environment protection type high-strength aqueous polyurethane slurry the most according to claim 1, it is characterised in that institute
The polyoxyethylene polyoxypropylene block polyether-polyurethane prepolymer stated is toluene diisocyanate monomer TDI, liquefaction
MDI MDI with at least containing two terminal hydroxy groups polyoxyethylene polyoxypropylene block polyether in
50～90 DEG C of additive reaction 3～the line style containing active isocyanate key obtained for 5 hours or branched polyether-type gather
Urethane prepolymer, the described polyoxyethylene polyoxypropylene block polyether at least containing two terminal hydroxy groups is molecular weight
PEO-PPO-PEO, PPO-PEO-PPO 1000～3,000 tri-block linear polyether or many blocks branch
Type polyethers, wherein EO accounts for the 10～40wt% of EO Yu PO gross mass；Isocyanates in described prepolymer
Group content is 3～7wt%.
Environment protection type high-strength aqueous polyurethane slurry the most according to claim 1, it is characterised in that institute
The polyoxypropylene polyether type polyurethane prepolymer stated is toluene diisocyanate monomer TDI, liquefied mdi and molecule
Amount 300～3000 and at least to contain the polyoxypropylene polyether polyhydric alcohol of two terminal hydroxy groups anti-in 70～100 DEG C of additions
Answer the EU prepolymer containing active isocyanate key obtained 3～5 hours；In described prepolymer
Isocyanate content be 4～10wt%.
Environment protection type high-strength aqueous polyurethane slurry the most according to claim 1, it is characterised in that
Described liquid epoxies is bisphenol A epoxide resin E-51 or E-44.
Environment protection type high-strength aqueous polyurethane slurry the most according to claim 1, it is characterised in that institute
The aliphatic amine polyoxyethylene polyoxypropylene polyether polyhydric alcohol stated is at least to contain 1 tertiary amine group and at least 2
The polyether polyol of terminal hydroxy group.
Environment protection type high-strength aqueous polyurethane slurry the most according to claim 5, it is characterised in that institute
The aliphatic amine polyoxyethylene polyoxypropylene polyether polyhydric alcohol stated be 18-amine. polyoxyethylene ether AC-1810,18
Amine polyoxyethylene ether AC-1830 or lauryl amine polyoxyethylene ether AC-1215.
Environment protection type high-strength aqueous polyurethane slurry the most according to claim 5, it is characterised in that institute
The aliphatic amine polyoxyethylene polyoxypropylene polyether polyhydric alcohol stated is for ethylenediamine, N-aminoethyl piperazine, divinyl
Triamine, triethylene tetramine, TEPA be initiator prepare at least containing 2 tertiary amine groups and at least 3
The aliphatic amine polyoxyethylene polyoxypropylene polyether polyhydric alcohol of individual terminal hydroxy group, wherein EO accounts for EO Yu PO gross mass
0～40wt%, EO and PO chain link sum be 25～50.
Environment protection type high-strength aqueous polyurethane slurry the most according to claim 1, it is characterised in that institute
The polyoxyethylene polyoxypropylene polyether polyol succinate stated is by the polyoxy second at least containing 2 terminal hydroxy groups
Single-ended base monomester succinate that alkene polyoxypropylene polyether polyhydric alcohol is obtained by succinic acid esterification and/or many end groups amber
Amber acid esters；Described polyoxyethylene polyoxypropylene polyether polyol be molecular weight 4000～400 PEO-PPO,
PEO-PPO-PEO, PPO-PEO-PPO type block polyether, polyoxypropylene polyether polyhydric alcohol；Described
In PPO-PEO-PPO type block polyether, EO accounts for the 0～40wt% of EO Yu PO gross mass.
9. the preparation method of the environment protection type high-strength aqueous polyurethane slurry described in claim 1, including following
Step:
(1) by 100～30wt% polyoxyethylene polyoxypropylene block polyether-polyurethane prepolymers, 0～60wt%
Polyoxypropylene polyether type polyurethane prepolymer and 0～10wt% liquid epoxies
Uniform in mixed at room temperature, obtain first component；
(2) by 30～90wt% aliphatic amine polyoxyethylene polyoxypropylene polyether polyhydric alcohol and 70～10wt%
Polyoxyethylene polyoxypropylene polyether polyol or its succinate are uniform in mixed at room temperature, obtain second component；
(3) it is 100:10～100 in mass ratio by the second component of the first component of step (1), step (2)
After mix homogeneously, anhydrous or aqueous base material, aqueous slurry are irrigated or brush, cold curing, obtain ring
The high-strength water-based polyurethane slurry of guarantor's type.
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| WO2023069254A1 (en) * | 2021-10-21 | 2023-04-27 | Arkema France | Moisture curable adhesive composition |
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Denomination of invention: Environment-friendly high-intensity waterborne polyurethane slurry and preparation method thereof Effective date of registration: 20191121 Granted publication date: 20181002 Pledgee: China Co truction Bank Corp Guangzhou Tianhe subbranch Pledgor: Guangzhou Chemical Grouting Engineering Co., Ltd., Chinese Academy of Sciences Registration number: Y2019440000208 |
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Date of cancellation: 20210910 Granted publication date: 20181002 Pledgee: China Co. truction Bank Corp Guangzhou Tianhe subbranch Pledgor: GUANGZHOU CHEMICAL GROUTING Co.,Ltd. CAS Registration number: Y2019440000208 |